Exposure assessment of nanomaterials in consumer products

Exposure assessment of nanomaterials in consumer products

Appendix report to environmental project No. 1636, 2015

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Title:

Exposure assessment of nanomaterials in

consumer products

Editing:

Poul Bo Larsen, DHI

Frans Christensen, COWI

Keld Alstrup Jensen, NFA

Anna Brinch, COWI

Sonja Hagen Mikkelsen, COWI

Anne Juliane Clausen; COWI

Frank Leck, Flotel, DHI

Antti Joonas Koivisto, NFA

Asger W. Nørgaard, NFA

Published by:

The Danish Environmental Protection Agency

Strandgade 29

1401 Copenhagen K

Denmark

www.mst.dk/english

Year:

2015

Disclaimer:

When the occasion arises, the Danish Environmental Protection Agency will publish reports and papers concerning

research and development projects within the environmental sector, financed by study grants provided by the Danish

Environmental Protection Agency. It should be noted that such publications do not necessarily reflect the position or

opinion of the Danish Environmental Protection Agency.

However, publication does indicate that, in the opinion of the Danish Environmental Protection Agency, the content

represents an important contribution to the debate surrounding Danish environmental policy.

Sources must be acknowledged.

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Contents

Appendix 1 - Databases/inventories and reports relevant for consumer 1.

exposure to nanomaterials .................................................................................... 5

Appendix 2 - Selection of consumer exposure scenarios and important 2.

parameters for assessing exposure ........................................................................ 8

Appendix 3 - Identification of relevant existing 3.

databases/surveys/inventories on marketed nanomaterials ............................... 15

Appendix 4 - Tables with examples of nanoproducts ........................................... 27 4.

4.1 Food and beverages ............................................................................................................. 28 4.2 Cosmetics ............................................................................................................................. 33 4.3 Cleaning agents .................................................................................................................... 44 4.4 Coating, impregnation ......................................................................................................... 49 4.5 Maintenance products .......................................................................................................... 57 4.6 Textiles ................................................................................................................................. 66 4.7 Construction materials ......................................................................................................... 71 4.8 Medical devices ..................................................................................................................... 77 4.9 Air-cleaner sprays ................................................................................................................. 81 4.10 Fuel and lubrication oil additive ......................................................................................... 85 4.11 Electronic devices ................................................................................................................ 89 4.12 Appliances ............................................................................................................................ 94

Appendix 5 - Model reviews – Templates with assessment for each model 5.

against the model assessment criteria ................................................................. 99 5.1 NanoRiskCat ........................................................................................................................ 100 5.2 NanoSafer............................................................................................................................. 116 5.3 Stoffenmanager Nano version 1.0 ........................................................................................ 134 5.4 Stoffenmanager 5.1 .............................................................................................................. 149 5.5 The ANSES tool .................................................................................................................... 169 5.6 Swiss Precautionary Matrix ................................................................................................. 183 5.7 ECETOC TRA ........................................................................................................................ 193 5.8 ConsExpo .............................................................................................................................210 5.9 DREAM ................................................................................................................................ 232 5.10 Margin of Exposure ............................................................................................................. 247

Appendix 6 - Review of methodologies for assessment of chemical 6.

exposure from consumer products ..................................................................... 271 6.1 RIVM (2009) and key parameters for evaluating consumer exposure to

nanomaterials ..................................................................................................................... 271 6.2 REACH guidances on exposure assessment from chemical products and articles ......... 272

REACH guidance Chapter R.15: Consumer exposure estimation ......................273 6.2.1

REACH guidance Chapter R.14: Occupational exposure estimation ................ 278 6.2.2

REACH guidance Appendix R14-4: Recommendations for nanomaterials ..... 278 6.2.3

REACH Guidance on information requirements and chemical safety 6.2.4

assessment, Chapter D ........................................................................................ 279 REACH Guidance on requirements for substances in articles .......................... 280 6.2.5

6.3 SCCS guidance on nanomaterials in cosmetics ................................................................. 281

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6.4 EFSA guidance on nanomaterials in food ......................................................................... 282 6.5 Environmental Defense – DuPont approach .................................................................... 283 6.6 ECETOC TRA ..................................................................................................................... 284 6.7 ConsExpo ........................................................................................................................... 286 6.8 NanoSafer ........................................................................................................................... 289 6.9 NanoRiskCat ....................................................................................................................... 291 6.10 Stoffenmanager .................................................................................................................. 292 6.11 Stoffenmanager Nano ........................................................................................................ 295 6.12 ANSES ................................................................................................................................ 297 6.13 Swiss Precautionary matrix ............................................................................................... 298 6.14 Dream ................................................................................................................................. 299 6.15 Margin of exposure concept .............................................................................................. 300

Appendix 7 - Working table for overview of the various exposure scenarios 7.

to consider and from which to prioritise sceanrios for further in-depth

evaluation .......................................................................................................... 302

Appendix 8 - Exposure estimations of 20 selected examples of 8.

representative .................................................................................................... 328 8.1 Scenario 1 - Product: Chewing gum with TiO2 food additive (E171) ................................ 329 8.2 Scenario 2 - Product: Nano-Silica in food items .............................................................. 335 8.3 Scenario 3 - Product: Nano-Ag food supplement ............................................................. 340 8.4 Scenario 4 - Product: Food contact material containing Silica ........................................ 344 8.5 Scenario 5 - Product: Sun screen lotion ............................................................................ 348 8.6 Scenario 6 - Product: Sun screen containing nano-ZnO (pump spray) .......................... 356 8.7 Scenario 7 - Product: Mascara with Carbon Black ........................................................... 364 8.8 Scenario 8 - Product: Lipstick sun screen containing nano-TiO2 .................................... 369 8.9 Scenario 9 - Product: Face powder containing nano-silica ............................................... 375 8.10 Scenario 10a - Product: Paint containing nano-TiO2 ....................................................... 383 8.11 Scenario 10b - Product: Primer Paint containing nano-TiO2 .......................................... 389 8.12 Scenario 11 - Product: Paint with Nano-Ag....................................................................... 399 8.13 Scenario 12 - Product: Surface impregnation product with silica (silane/siloxane

technology?) ........................................................................................................................ 411 8.14 Scenario 13 - Product: Air conditioner and air purifier device containing nano-

silver ................................................................................................................................... 422 8.15 Scenario 14 - Product: Disinfectant pump spray containing nano-Ag ............................ 426 8.16 Scenario 15 - Product: Disinfectant multipurpose sanitizer with Nano-Ag

(Propellant spray) .............................................................................................................. 437 8.17 Scenario 16 – Product: T-shirt containing nano-Ag ......................................................... 445 8.18 Scenario 17 - Product: Cement containing nano-TiO2 ..................................................... 452 8.19 Scenario 18 - Product: Wound dressing containing nano-Ag .......................................... 460 8.20 Scenario 19 - Product: Nanocomposite product for dental replacement and

restoration containing nano-Zirconia and nano-silica..................................................... 465 8.21 Scenario 20 - Product: Golf club with CNT re-enforced shaft ......................................... 473

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Appendix 1 - 1.Databases/inventories and reports relevant for consumer exposure to nanomaterials

(*: INVENTORIES/ DATABASES)

*ANEC (European Association for the Co-ordination of Consumer

Representation in Standardisation) and BEUC (Bureau européen des unions de

consommateurs). ANEC/BEUC inventory of products claiming to contain

nanoparticles available on the EU market. (Excel file. can e.g. be downloaded

from here: http://www.beuc.org/Content/Default.asp?PageID=2142)

environmental NGO “Bund” nanoproduct database:

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuc

he/

Kortlægning af produkter der indeholder nanopartikler eller er baseret på nanoteknologi. Consumer

Survey No 81. Danish Environmental Protection Agency (in Danish)

*Danish EPA (2007b). Nanomaterials used in the Danish Industry- surveuy on production and

application. Environmental Project No. 1206, Danish Environmental Protection Agency.

Danish EPA (2011). Survey on basic knowledge about exposure and potential environmental and

health risk for selected nanomaterials. Environmental Project No. 1370, Danish Environmental

Protection Agency.

Danish EPA (2011). NanoRiskCat – A conceptual decision support tool for

nanomaterials. Environmental Project 1372,

Danish EPA (2012). Vurdering af de administrative konsekvenser for virksomheder ved

indberetning til en nanoproduktdatabase.

Danish EPA (2013). Muligheder for reduktion af danske virksomheders administrative byrder ved

indberetning til en nanoproduktdatabase: Miljøprojekt nr. 1462.

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/


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http://www2.mst.dk/Udgiv/publikationer/2013/01/978-87-92903-84-6.pdf

*Danish EPA (2013/2014a) On-going survey on nanomaterials on the Danish Market

(expected to be available in autumn 2013).

Danish EPA (2013/2014b). NanoDEN project and as available other on-going surveying activities (to

be discussed with the Danish EPA soon after initiation of the project)

ENRHES (2009). (Engineered Nanoparticles - Review of Health and

Environmental Safety). Final report.

http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report

*EU-Commission (2012). Communication from the Commission to the

European Parliament the Council and the European Economic And Social

Committee on the Second Regulatory Review on Nanomaterials. Brussels

3.10.2012 SWD(2012) 288final.

*Friends of the Earth (2008). OUT OF THE LABORATORY AND ON TO

OUR PLATES - Nanotechnology in Food & Agriculture;

(http://nano.foe.org.au/sites/default/files/Nanotechnology%20in%20food%20a

nd%20agriculture%20-%20text%20only%20version_0.pdf)

*Milieu / RPA (2009).Information from Industry on Applied Nanomaterials

and their Safety. http://www.nanomaterialsconf.eu/documents/Nanos-

Task1.pdf

Milieu / RPA (2010). Proposal for an EU Reporting System for

Nanomaterials. http://www.nanomaterialsconf.eu/documents/NanoReportingSystemFinalRep

ort-20Jun10.doc

Nanex (2010). Development of Exposure Scenarios for Manufactured

Nanomaterials). Work package 4 report on consumer exposure.

http://www.nanex-project.eu/mainpages/public-documents/doc_download/101-nanex-project-final-

report-.pdf

+ FP7 Nanex project (http://nanex-project.eu/) surveying

literature and existing exposure models to identify knowledge about consumer

exposure scenarios and assessment of nanomaterials

*Nanoforum (2006). Nanotechnology in Consumer Products.

http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechnology_in_consume

r_products.pdf

*Nanotechproject (2013). Inventory of the Project on emerging Nanotechnologies (formerly known

as the Woodrow Wilson database)

(http://www.nanotechproject.org/inventories/consumer/)

*NANOWERK (2012);

http://www.nanowerk.com/nanotechnology_databases.php

OECD (2012). Important issues on Risk Assessment of manufactured nanomaterials. Series on the

Safety of Manufactured Nanomaterials No. 33. ENV/JM/MONO(2012)8. OECD.

*RIVM (2006). Nanomaterials in consumer products - Availability on the

European market and adequacy of the regulatory framework. RIVM/SIR



http://www.nanex-project.eu/mainpages/public-documents/doc_download/101-nanex-project-final-report-.pdf


http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechnology_in_consumer_products.pdf

http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechnology_in_consumer_products.pdf

http://www.nanotechproject.org/inventories/consumer/


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Advisory report 11014 (IP/A/ENVI/IC/2006-193). Prepared for the European

Parliament. http://www.europarl.europa.eu/comparl/envi/pdf/externalexpertise/nanomater

ials_in_consumer_products.pdf

*RIVM (2007). Inventory of consumer products containing nanomaterials.

RIVM/SIR Advisory report 11124;

http://www.rivm.nl/bibliotheek/digitaaldepot/inventoryconsumerproducts.pdf

RIVM (2009). Exposure to nanomaterials in consumer products. Letter report 340370001/2009.

http://www.rivm.nl/bibliotheek/rapporten/340370001.pdf

*RIVM (2010a). Nanomaterials in consumer products. Update of products on

the European market in 2010. RIVM Report 340370003/2010.

http://www.nanogenotox.eu/files/PDF/rivm%20rapport%20nanomaterials%2

0in%20consumer%20products%2023-02-2011.pdf

RIVM (2010b). Development of an inventory for consumer products containing

nanomaterials. Final Report. 070307/2010/580587/SER/D3;

http://ec.europa.eu/environment/chemicals/nanotech/pdf/study_inventory.pdf

RIVM (2011). Nanomaterial in consumer products. Detection, characterisation and interpretation.

Report 320029001/2011.

*Tænk/ Forbrugerrådet (2013)."Nanodatabasen". (http://nano.taenk.dk/velkommen-tildatabasen)




http://nano.taenk.dk/velkommen-tildatabasen

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Appendix 2 - Selection of 2.consumer exposure scenarios and important parameters for assessing exposure

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RIVM (2006)/ EU Parliament report : Nanomaterials in consumer product

Potentially high exposures are expected from consumer products containing free nanoparticles with direct exposure of these nanoparticles to humans or environmental organisms. As a

result, cleaning products, personal care products and cosmetics are ranked as

products associated with high potential health and environmental exposures. On the

other hand, the following products likely do not contain free nanoparticles and are therefore ranked

as products with low potential exposures: electronics and computers (excluding ink

and paper), cooking utensils and kitchenware, exteriors of motor vehicles, sporting

goods, shoes, air filtration and purification, air conditioning and coatings. If the

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integrated nanomaterials in these products are not released during the use and disposal of these

products, the potential environmental exposures of these products will also be ranked as low.

Unfortunately, little is known with respect to the release of integrated nanomaterials during the use

or during the processing after disposal.

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RIVM (2009) Exposure to nanomaterials in consumer products

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1= high exposure 2= medium exposure 3= low exposure

The most important parameters for the exposure evaluation by the experts

were:

- Free/ fixed NM

- Product form

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- Direct/ indirect exposure

- Exposure route

- Indoor/outdoor exp.

Nanodatabasen

(DTU Environment, The Danish Ecological Council and Danish Consumer Council)

High exposure potential (red scoring) for:

- home and garden products e.g. coating/ paints / cleaners

(i.e. products (aerosols and liquids) for surface treatment and cleaning)

- food and beverages

- health and fitness (cosmetics sunscreen, personal care products)

- car care products (cleaning solvents, surface treatment, liquid and aerosols)

- various coatings

Conclusion

Products/ scenarios to be covered from:

Food and beverages

NM ingredients

Food supplements

NM in packaging (migration)

Cosmetics (spray, liquids, creme, lipstick, mascara…)

Cleaning agents

Liquids, spray, paste

Coatings/ impregnation

Liquids, spray, paints

Maintainance products (car, boats)

Liquids, spray, paste

Textiles

Construction materials

Cement/ concrete a.o

Starting point most relevant for Denmark would be “Nanodatabasen” and its

exposure grading based on NanoCatRisk combined with RIVM 2009

regarding most important parameters for exposure.

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Appendix 3 - Identification 3.of relevant existing databases/surveys/inventories on marketed nanomaterials

Short description of the databases/surveys/inventories

*ANEC (European Association for the Co-ordination of Consumer Representation in

Standardisation) and BEUC (Bureau européen des unions de consommateurs).

ANEC/BEUC inventory of products claiming to contain nanoparticles available on

the EU market. (Excel file. can e.g. be downloaded from here:

http://www.beuc.org/Content/default.asp?pageId=1120&searchString=inventory

Scope: The database is an inventory over consumer products claiming to contain

nanomaterials.

Content/ outcome: The database contains 475 products categorized into appliances,

automotive, cross-cutting, electronic and computers, food and beverage, goods for

children, health and fitness, and home and garden. Last update was October 21, 2010. The

information include information on nanosubstance, if known, and a helpful description of

the characteristics and nanoclaim. There is link-out to venders website. There are several

Danish products and most declared nanoproducts have AgNM. An update only on

nanosilver containing products was made in 2012.

Exposure: No direct information.

Relevance: Medium. Could be useful for finding nanoproducts with specific contents.

Also links to the web-site of the products

*Bund (2013). German environmental NGO “Bund” nanoproduct database:

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdate

nbank/produktsuche/ Scope: The database is intended as a database on consumer products with link-out to the producers. Content/Outcome: The data base covers 11 product categories and 44 subcategories. The product caregories are: Auto/cars; electronics; leasure; health; house and garden; household products;children; body care; food, textiles. Exposure: No indication of exposure potential

http://www.beuc.org/Content/default.asp?pageId=1120&searchString=inventory



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Relevance. Medium. The database may be relevant, however it is not practical to use in its search options. No consistent outputs when various search strategies options were used.

*Danish EPA (2007a). Kortlægning af produkter der indeholder nanopartikler eller

er baseret på nanoteknologi. Consumer Survey No 81. Danish Environmental

Protection Agency (in Danish).

Scope: To identify the consumer products on the Danish market containing NMs

Content/ outcome: 243 specific consumer products divided in 9 product categories were

identified based on the suppliers statement as a nano-product.

For each consumer product data on company names, production country, availability in

DK, ID of nanomaterial, product formulation were given.

Products claimed to contain ZnO, TiO2; Ag, CNT and fullerenes were identified. For 202

products no data on NM ID was available.

Exposure: Further the consumer exposure potential from the products was ranked into

“no possibility for consumer exposure” – “possible exposure” – “expected exposure”.

However, no distinction between exposure routes was given. The evaluation was done

based on data whether the nanomaterial in the use phase could be considered as fixed in a

solid matrix, surface bound, suspended in liquids, or as air borne.

Based on this, products for surface treatment (liquid and aerosols) and cosmetics

(sunscreen and facial creme) were considered as products with very high exposure

potential. Specific exposure scenarios were elaborated for facial creme, sunscreen (creme),

outdoor surface treatment with liquid product, indoor surface treatment with spray.

Relevance: Medium-High. Not up to date for the inventory part. However 4 specific

exposure scenarios was elaborated and an overall approach for screening the NM exposure

potential for a product was given.

Danish EPA (2007b). Nanomaterials used in the Danish Industry- survey on

production and application. Environmental Project No. 1206, Danish

Environmental Protection Agency.

Scope: To identify where NMs are used in Danish Industry, in which sectors for which

purpose and how they are treated with respect to environmental release and in the

occupational environmentand in which type of processes. Also the available knowledge

regarding specific data on the used NMs were collected.

Content/outcome: 24 companies working with NMs were identified. NMs were used

within the product categories: paint & inks; coatings, cosmetics,Pharm & biotech; optics;

sensors; catalysts, concrete and textile. No specifec data on NMs was in general available

Tonnages and uses were indicated For TiO2; Fe2O3, carbon black silica, ZnO, AG, Cu.

Exposure: In the industrial setting NMs was in general handled as fine dust

Relevance: Low. Not up to date, does not focus on use of products but on occupational

environment during the manufacture process

Danish EPA (2011). Survey on basic knowledge about exposure and potential

environmental and health risk for selected nanomaterials. Environmental Project

No. 1370, Danish Environmental Protection Agency.

Scope: To provide an overview of the existing knowledge of different nanomaterials,

including environmental and human health properties, uses of those nanomaterials and

possible exposure scenarios of both humans and the environment.

Content/outcome: Seven different nanomaterials (Titanium dioxide, Cerium dioxide,

Fullerenes, Silver, Zero-valent iron, Silicium dioxide and nanoclay) are chosen on

the basis of application volume, potential for human and environmental exposure

from consumer product and expected biological effects. Information on manufacturing,

uses, toxicological and eco-toxicological properties, exposure scenarios and risk profiles

are summarized for each NM.

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Exposure: Focus is on direct exposure of humans from consumer products and how

nanomaterials from consumer products may end up in the environment. Main consumer

applications are summarized and the level of consumer exposure, related to these

applications, is indicated (low, medium, high). The indications are based on how the NM is

incorporated in the matrix, e.g. fixed particles in a matrix is equal to low potential

consumer exposure.

Relevance: Low. Gives an overview of existing knowledge – largely based on results of the

ENRHES (2009) project/report. No quantitative data presented.

Danish EPA (2011). NanoRiskCat – A conceptual decision support tool

fornanomaterials. Environmental Project 1372.

Scope: NanoRiskCat is a tool enabling categorization and rapid communication in color-code of the known hazards and potential exposures to man and the environment. Content/Outcome: The user is guided through decision trees for both exposure and human risk assessment. The exposure assessment is based on the location of the nanomaterial in the nanoproduct combined a predefined color-coding of REACH use scenarios. The human hazard assessment is based on the hazard information on existing analogue materials and observed in vivo and in vitro toxicological effects for the specific nanomaterial in question. Exposure: In the report, the exposure assessment is based on the location of the nanomaterial in the nanoproduct combined a predefined color-coding of REACH use scenarios. Relevance: The procedure is highly relevant for the project. Examples of use is given in the report and the Danish Consumer Database has been assessed using this tool.

Danish EPA (2012). Vurdering af de administrative konsekvenser for virksomheder

ved indberetning til en nanoproduktdatabase. Miljøprojekt nr. 1451.


Scope : To evaluate the administrative burdens on Danish industry in connection with

obligatory notification of nanoproduct to a Danish nanoregistry.

Content/ outcome: How to notify into 8 product categories in the nanoregister and

evaluation of the administrative burden of this. Description of the productcategoris and

examples of nanomaterials (eg. TiO2, Fe2O3, Carbon, Silica, ZnO, Ag, Cu and pigments)

used in the various product categories.

Exposure: no consideration regarding exposure

Relevance: Low

Danish EPA (2013). Muligheder for reduktion af danske virksomheders

administrative byrder ved indberetning til en nanoproduktdatabase: Miljøprojekt

nr. 1462. http://www2.mst.dk/Udgiv/publikationer/2013/01/978-87-92903-84-6.pdf

Scope: To identify proposals for reducing the administrative burden for industry when

notifying nanoproduct to a nanodatabase.

Content/ outcome: Evaluates the administrative burden of the industry ion connection to

various levels on information request for notification of a nano product.

Exposure: no consideration regarding exposure

Relevance: Low

Danish EPA (on-going). Survey project on products/applications for which “nano”

is already regulated under EU law

We await a first draft report from Technological Institute. The project is between other

addressing medical devices, which might identify NMs in medical devices for consumer

use, which might potentially cause a risk.

Danish EPA (on-going). NanoDEN project. Project ongoing …



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Scope: To assess the whether ENMs are likely to present a risk for the Danish

Environment. 10 Nanomaterials are addressed: Photocatalytic TiO2, photo-stable TiO2,

ZnO, silver, Carbon Nanotubes, CuCO3, zero-valent Iron, Cerium dioxide, quantum

dots,,Carbon Black.

Content/outcome: As part of the ‘environmental load’ estimation, diffuse releases from

consumer products are estimated on a general level. This will partly be based on i) the

below described “survey project”, ii) on assumptions already made about use in “Western

countreis” in the Swiss model applied in the project, iii) survey activities as part of the

project.

Exposure: No human/consumer exposure estimations are performed.

Relevance: Medium. Project ongoing. Compared to existing surveys, the project might

provide new information about presence and quantity of NMs in consumer products on

the Danish marked. Currently, no new high exposure/risk exposure scenarios are

identified compared to those listed in Chapter Fejl! Henvisningskilde ikke fundet.. The final

report expected by the end of the year will be addressed in the further WP2 activities.

ENRHES (2009). (Engineered Nanoparticles - Review of Health and Environmental

Safety). Final report. http://ihcp.jrc.ec.europa.eu/whats-new/enhres-final-report

Scope: The overall aim of the project was to perform a comprehensive and critical scientific

review of the health and environmental safety of four classes of nanomaterials: fullerenes,

Carbon Nanotubes, metals and metals oxides. The review considers sources, pathways of

exposure and health and environmental issues.

Content/Outcome: The project, between others, describe general applications of the four

materials types, as well as more detailed human health assessment of fullerenes, CNTs,

nano-TiO2 and nano-silver.

Exposure: The human health exposure assessments largely focus on occupational

inhalation exposure, although some considerations are provided on nano-silver and

fullerene containing consumers products.

Relevance: Medium. Potential high risk applications of nano-sivler as wound dressings,

as anti-bacterial agents (e.g. in textiles), as non-invasive hair removal products and in

toothpaste are addressed. NB! Whether the two latter applications occur in Denmark is not

known. Toxicity has been observed following applications with wound dressings (argyria

and liver toxicity). Fullerenes is used in some face creams (apparently most in Asian

countries, but might be bought e.g. via the Internet by European consumers). Several well-

known applications of nano-TiO2 are described, including use as UV-filter in cosmetics

and white pigment in paints/coatings.

European Commission (2012). Communication from the Commission to the

European Parliament the Council and the European Economic And Social

Committee on the Second Regulatory Review on Nanomaterials. Brussels 3.10.2012,

including SWD (2012) 288 final.

Scope (of the Staff Working document - SWD): To present available information ontypes

and uses of NMs, including safety aspects and to discuss options for a harmonized

database for nanomaterials. Content/Outcome: The paper is divided into several parts, where the first section focuses on giving further explanations on the EU definition of nanomaterials. In the Second part an overview of the main types and uses of nanomaterials on the European market is given. This is further elaborated in appendix 2, where a structured, though not exhaustive, overview of nanomaterials on the EU market is given. The third section covers information on the health and safety aspects of the nanomaterials by reviewing literature currently available to the commission and in the fourth part issues and activities relating to the risk assessment of nanomaterials are analyzed. In the last section, information on existing databases on (or with relevance to) consumer products containing nanomaterials is


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compiled. Appendix 8 reviews the existing product databases on the basis of certain criteria.

The outcome of the discussion of the possibility of a harmonized European web platform

on types and uses of nanomaterials (incl. safety aspects) is that the Commission is ready to

host such inventory, and that the web platform should benefit from the results in the

recently concluded RIVM report "Development of an inventory for consumer products

containing nanomaterials" Exposure: Exposure is only covered in a general matter. An important factor in characterizing exposure, according to the paper, is whether the nanoparticles occuras free particles, whether they occur in aggregates or agglomerates, whether they are bound in a matrix or enclosed in equipment, or whether they are transformed during the production process in a way that they do not occur as nanoparticles in the finished product. The paper highlights nano-titanium dioxide and nano-zinc oxide (due to high potential exposure, in particular in their applications as UV-filters), carbon nanotubes (for the possible carcinogenicity of certain forms) and nano-silver (for possible ecotoxicity) applications of nanomaterials where significant exposure of workers, consumers or the environment may occur.

Relevance: Medium-High. The overview of NMs on the European market must be

assumed to address NMs/products, which can generally also be found on the Danish

marked. The initial review has not identified any new high exposure/risk exposure

scenarios than those described in Chapter Fejl! Henvisningskilde ikke fundet.. The

document with its broad scope may further be consulted and used in the various work

packages of the project.

*Friends of the Earth (2008). Out of the laboratory and on to our plates -

Nanotechnology in Food & Agriculture

(http://nano.foe.org.au/sites/default/files/Nanotechnology%20in%20food%20and%

20agriculture%20-%20text%20only%20version_0.pdf)

Scope: To elaborate how manufactured nanomaterials and nanotechnologies are used in

food and agriculture and which health related risks that are associated with this.

Content/Outcome: The report focuses on the issues associated with the intentional

addition of nanomaterials to foods, food packaging and agricultural products. The

report also focuses on regulation of nanomaterials in these products and

discusses issues following this. There are descriptions on how nanotechnology is used in

the different categories (i.e. processed food, food packaging, agriculture etc.) and potential

health effects following these uses are covered as well. Appendix A of the report contains a

list of agricultural and food products that were identified to contain manufactured

nanomaterials by the authors.

Exposure: There is no quantitative data on the amounts of nanomaterials in the products

and thus no considerations regarding exposure scenarios

Relevance: Medium. Provides some information about which NMs might be found in

which food products, however without quantification.

Milieu / RPA (2009).Information from Industry on Applied Nanomaterialsand their

Safety. http://www.nanomaterialsconf.eu/documents/Nanos-Task1.pdf

Scope:

Content/ outcome:

Exposure:

Relevance: MATERIAL NO MORE ACCESSIBLE THROUGH ANY LINKS FOUND IN

WEB SEARCH

http://nano.foe.org.au/sites/default/files/Nanotechnology%20in%20food%20and%20agriculture%20-%20text%20only%20version_0.pdf

http://nano.foe.org.au/sites/default/files/Nanotechnology%20in%20food%20and%20agriculture%20-%20text%20only%20version_0.pdf

http://www.nanomaterialsconf.eu/documents/Nanos-Task1.pdf

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Milieu / RPA (2010). Proposal for an EU Reporting System for Nanomaterials.

http://www.nanomaterialsconf.eu/documents/NanoReportingSystemFinalReport-20Jun10.doc

Scope:

Content/ outcome:

Exposure:

Relevance: MATERIAL NO MORE ACCESSIBLE THROUGH ANY LINKS FOUND IN

WEB SEARCH

Nanex (2010). Development of Exposure Scenarios for Manufactured

Nanomaterials. Work Package 4 Report on Consumer Exposure.

http://www.nanex-project.eu/mainpages/public-documents/doc_download/101-

nanex-project-final-report-.pdf

Scope: The objective of the consumer exposure part of the Nanex project (2010) was to

collect and review information in order to describe and characterize exposure for three

generic consumer exposure scenarios and to identify the needs to comply with EU

legislation.

Content/Outcome: The focus was on three generic exposure scenarios identified as

relevant for consumers. These were: i) nano-silver in textiles, ii) nano-TiO2 in cosmetics,

and iii) carbon nanotubes (CNTs) in composite materials used in consumer products.

23 references dealing with consumer exposure to nanomaterials were identified and

reviewed and this was supplemented with a review/analysis of generic consumer exposure

models available. Based on this information it was attempted to develop (worst-case)

exposure estimations for the three exposure scenarios. The reviewed tools and models for

consumer exposure estimations were the ConsExpo model, the ECETOC TRA model, the

RISKOFDERM (ROD) model and the Spray Paint model. These models were reviewed in

order to examine their applicability regarding consumer exposure to nanomaterials. The

overall evaluation of the models showed that for dermal exposure the existing models may

be used with caution for engineered NM as well. For inhalation exposure estimates the

models seemed less applicable, since they were found not to consider the nano-specific

properties of the materials. Considerations should also be paid to the fact that none of the

models were validated for NMs and that the exposure estimated are given in mass-based

metric.

Exposure: Exposure estimates were made for the three above mentioned generic exposure

scenarios, and where applicable, several exposure scenarios are built. Exposure routes for

the scenarios are also covered. The exposure scenarios are as follows:

Nano-Ag in textiles: In socks (worst 'worst-case')

In T-shirts (worst 'worst-case')

In wound dressings (reasonable worst-case)

CNT in textiles: Textile products with CNTs bound into the matrix

Nano-TiO2 in sunscreens: Creams and lotions

Sprays

Lipsticks

Relevance: Medium-High. Relevant for model evaluation in WP1. WP2:

Quantitative data is given for most of the scenarios.

Nanoforum (2006). Nanotechnology in Consumer Products.

http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechno

logy_inconsumer_products.pdf

http://www.nanomaterialsconf.eu/documents/NanoReportingSystemFinalReport-20Jun10.doc



http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechnology_inconsumer_products.pdf

http://www.innovationsgesellschaft.ch/images/fremde_publikationen/Nanotechnology_inconsumer_products.pdf

21

Scope: The focus of the report is consumer products on the European market which claim

to contain nanotechnology

Content/Outcome: The report describes in general how nanotechnology is and may be

used in consumer products. The report lists different effects and innovations, which are

considered as important factors contributing to the added value in consumer

products containing nanotechnology.

Different product categories are listed and examples of how nanotechnology is

Incorporated into the consumer products and the following beneficial effects are given.

These product categories are: textiles, health care products, electronic devices, sports

equipment, home improvement and household products. Examples of specific products

containing (or claiming) nanotechnology is given.

Exposure: No considerations regarding actual exposure. The report can give a general idea

of difference use patterns of products of different product categories, but no actual data on

exposure level or exposure scenarios and no quantitative data are given.

Relevance: Low. Reference does not seem to add any new information as compared to

other sources indicated with higher relevance.

*Nanotechproject (2013). Inventory of the Project on emerging Nanotechnologies

(formerly known as the Woodrow Wilson database)

(http://www.nanotechproject.org/inventories/consumer/)

Scope: The inventory is claimed to be an essential resource for consumers, citizens,

policymakers, and others who are interested in learning about how nanotechnology is

entering the marketplace.

Content/Outcome: At the present the inventory includes a total of 1317 products produced

by 587 companies, located in 30 countries. The last update was in October 2011.

The criteria for listing a product in the inventory are that:

It can be readily purchased by consumers, and

It is identified as nano-based by the manufacturer or another

source, and

The nano-based claims for the product appear reasonable.

Most products in the inventory satisfy these three criteria. However, some "generic"

products have been added as well, which are products that can be found in many places on

the market (e.g. computer processor chips). These are labeled in the inventory.

There have been no verification of the manufacturer's claim of the nanotechnology used in

the product and no independent testing of the products has been conducted prior to

listing.

The inventory is divided into 7 different categories and a "cross-cutting" category, and 34

subcategories:

Appliances (Batteries; heating, cooling and air; large kitchen appliances; laundry and clothing care)

Automotive (Exterior; maintenance and accessories; watercraft) Goods for Children (Basics; toys and games) Electronics and Computers (Audio; cameras and film; computer hardware;

display; mobile devices and communications; television; video) Food and Beverage (Cooking; food; storage; supplements) Health and Fitness (Clothing; cosmetics; filtration; personal care; sporting

goods; sunscreen)

http://www.nanotechproject.org/inventories/consumer/

22

Home and Garden (Cleaning; construction materials; home furnishings; luxury; paint, luggage, pets)

Cross-Cutting (Coatings)

Exposure: No considerations regarding exposure.

Relevance: Medium-high. The inventory provides information on the possible (based on

claims) content of NMs in a range of consumer products. The inventory provides some

information about the identity of the NMs in the products. The inventory gives no

quantitative information. Very good options for targeted search in the register. Has very

recently been updated (November 2013). Contains also European nano products, thus

contain also products from the Nanodatabase (DTU Environment, The Danish Ecological

Council and Danish Consumer Council). May be relevant for supplemental search due to

good search options. l

*NANOWERK (2012)

http://www.nanowerk.com/nanotechnology_databases.php http://www.nanowerk.com/phpscripts/n_dbsearch.php http://www.nanowerk.com/products/products.php http://www.nanowerk.com/products/products.php#ixzz2eWH0sUVe

Scope: The Nanowerk product database, is not comprehensive and still in progress. The purpose of this database is to give an idea of how and where in industry nanoscale materials, devices, structures and processes are being used. Content/Outcome: The database link out to companies producing the different nano-based products. Exposure: There is no information on exposure Relevance: Low to moderate. Check of the database may give the user inspiration on potentially new products.

OECD (2012). Important issues on Risk Assessment of manufactured nanomaterials.

Series on the Safety of Manufactured Nanomaterials No. 33.

ENV/JM/MONO(2012)8. OECD.

Scope: Examines and identifies critical issues (where specific nano-material data are

required) in relation to performance of risk assessment.

Content/outcome: Focus on the hazard assessment part, where data on the ID and

characterization of the NM was stressed.

Exposure: 14 issues in relation to exposure assessment is shortly mentioned, however in

and overall and general manner

Relevance: Low-Medium (mostly for WP1 and WP5)

RIVM (2006). Nanomaterials in consumer products - Availability on the European

market and adequacy of the regulatory framework. RIVM/SIR Advisory report

11014 (IP/A/ENVI/IC/2006-193). Prepared for the European Parliament.

http://www.europarl.europa.eu/comparl/envi/pdf/externalexpertise/nanomaterial

s_in_consumer_products.pdf

Scope: The report describes the uses of NMs in consumer products and discusses the

human exposure and risk for human health. Further it analyses the adequacy of the

current legislation.

Content/ outcome: 8 overall categories divided in 29 subcategories and generic examples

of products within the subcategories was given (table 2.7 in the report). Also, a table

indicating use of 21 different nanomaterials within the various product subcategories

(table 3.1 in the report).


http://www.nanowerk.com/phpscripts/n_dbsearch.php

http://www.nanowerk.com/products/products.php

http://www.nanowerk.com/products/products.php#ixzz2eWH0sUVe

http://www.europarl.europa.eu/comparl/envi/pdf/externalexpertise/nanomaterials_in_consumer_products.pdf

http://www.europarl.europa.eu/comparl/envi/pdf/externalexpertise/nanomaterials_in_consumer_products.pdf

23

Exposure: Main characteristics for exposure potential (as well as for hazard potential) was

given, table 3.2 (and table 3.3). Ranking of exposure potential was given for the various

product subcategories (in: high, medium, low, unknown), table 3.4 . Not divided in

exposure routes but oral, dermal, and inhalation route was noted as important for

consumer products. High exposure potential was especially concluded for cosmetics and

cleaning products.

Relevance: High. The approach is further used and developed in the following RIVM

reports.

*RIVM (2007). Inventory of consumer products containing nanomaterials.

RIVM/SIR Advisory report 11124;


Scope: To make an updated list/ inventory with specific products that claim to contain

NMs and which may be available on the Dutch market.

Content/ outcome: From available other databases, from web-search and from contacts to

manufactures a list of 143 named consumer products claimed to contain NMs was

established. The products were divided in 12 product categories covering: - Appliances; -

Electronics & computers; - Home furnishing & household products, - Motor vehicles; -

Food packaging; - Personal care products & cosmetics; - Health; - Sporting Goods; -

Textile; - Toys & Games; - Cross-cutting (multifunctional e.g. coatings); - Miscellaneous.

Most products were found in cleaning products (21), coating/paints (12), other coating

(28), skin care (12), construction materials (10), clothing (12). Sporting goods (10)

Exposure: The matrices for the claimed NMs were given: solid, coating, fluid, spray,

creme, paste, paint, foam, gel, textile. NM ID was given for only few products: silver,

silica, poymers, carbon. titanium, CNT, silicon oxide, calcium. Exposure routes are

discussed on an overall level. Liquids and aerosols considered to be of high exposure

potential, thus cleaning and coating products would constitute high potential for dermal

and inhalational exposure.

Relevance: Medium, relevant categories are given, however, no further specific grading of

exposure is given. Not up to date.

RIVM (2009). Exposure to nanomaterials in consumer products. Letter report

340370001/2009. http://www.rivm.nl/bibliotheek/rapporten/340370001.pdf

Scope: To update the RIVM NM inventory from 2007 and to give a market value analysis.

Further to make expert consultation on defining relevant important exposure parameters

and to grade exposure potential from the various product categories and product

formulations .

Content/ outcome: The trend in increased amount of products containing NMs was given,

however, no specific figure on number of products on the Dutch market were given.

Products were divided into 8 product categories: - motor vehicles,- electronics and

computer, - miscellaneous,- household products and home improvement,- personal care

and cosmetics, - sporting goods, - textiles and shoes, -

filtration/purification/neutralization/ sanitization.

Further divided into 28 product subcategories.

More than 20 NMs and the use in various types of products were listed (table 4.4 in the

report)

(e.g. aluminia, CNT, carbon black, nanoclay, iron oxide, polymer, silica, silver, TiO2,

precious metals)

Exposure: Expert panel identified the following parameters to be important for exposure :

NM ID; shape of NM in product; product form (e.g. solid, spray, liquid , powder etc.) ;

free/fixed NM, concentration; direct or indirect exposure; indoor/outdoor use; event

duration; event frequency, exposure route, numbers of the population (table 5.1).



24

The parameters fixed/ free NM; direct or indirect exposure; product form, and exposure

route were considered to be the most import parameters for characterising the product in

relation to its exposure characteristics.

From these parameters the various types of products was assessed for their consumer

exposure potential in the categories (high, medium, low exposure). High exposure

potential for: sun cosmetics; toothpaste; health care products; fuel; coatings, cleaning

products with NMs such as ZnO, TiO2; hydroxyapatite; silver; cerium oxide; polymers;

aluminia. (table 5.2). Low exposure potential for electronics and computers, sportoing

goods, lighting; precoated surfaces.

Relevance: High. Provides the most detailed assessment of characteristics of importance

for exposure evaluation and identifies spec ific product types with high potential for

consumer exposure.

*RIVM (2010a). Nanomaterials in consumer products. Update of products on the

European market in 2010. RIVM Report 340370003/2010.

http://www.nanogenotox.eu/files/PDF/rivm%20rapport%20nanomaterials%20in%

20consumer%20products%2023-02-2011.pdf

Scope: To make an update of products containing NMs on the European market based on

internet search and consultation of available databases and recent reports.

Content/ outcome: A total of 858 named products were listed. The products were divided

in 12 product categories: -appliances (20);- electronics and computers (9); -home

furnishing and household products (108),- motor vehicles (103 mainly coating cleaning

products) ; - packages (incl. food pack.) (1); - personal care products and cosmetics (304), -

health (8); - sporting goods(40); - textile (81); - toys and games (2); - cross-cutting

(especially coatings) (30); - miscellaneous (9).

Exposure: Important parameters for assessing the potential for consumer exposure was

given (identical to RIVM (2009), see above). No data on product form or ID for

nanomaterial was given.

Relevance: medium, the inventory gives a rather updated view on the European market

for products containing NMs and the importance of each of the product categories is

indicated on the number of products pertaining to the category. However, no further

product information is given except links to warehouse or product web-site.

RIVM (2010b). Development of an inventory for consumer products containing

nanomaterials. Final Report. 070307/2010/580587/SER/D3;


Scope: To develop a methodology to set up a database on NMs in consumer products and

to populate the database with examples of approx. 200 consumer products

Content/ outcome: The report reviews available databases and literature (as this project!).

In the proposed set up for a database the products were suggested to be divided into the

following 10 product categories: : -appliances;- electronics and computers; -home

furnishing and household products ,- motor vehicles ; - packages (incl. food pack.); -

personal care products and cosmetics, - health; - sporting goods; - textile and shoes; - toys

and games.

Exposure: No considerations regarding exposure is indicated

Relevance: Low, however the further use of the defined product categories may be

considered (very comparable to RIVM 2010a).

RIVM (2011). Nanomaterial in consumer products. Detection, characterisation and

interpretation. Report 320029001/2011.

Scope: To use analytical methods to verify the ID and content of NMs in consumer

products claimed as nano-products.


25

Content/ outcome: 25 products were selected and analysed. Several products claimed to

contain NMs did not contain substances in nanoform. In several silver products nano-

silver was not found. In some products not claiming as nano-products NMs were found . A

number of claimed nano-products contained organic “soft” nanomaterials i.e. not solid

and unsoluble NMs.

NMs were found in diaper cream, lip balm, shoe cream, wall paint, anti-wrinkle cream,

facial mask, socks, sunscreen, wound dressing, leather maintainance product, anti-dirt

spray,

The following NMs were positively identified in the products: ZnO; Ti; Si; Ag; Zn; organic

NM;

Exposure: No considerations regarding exposure

Relevance: Low, however the outcome to the project causes great uncertainty concerning

the existence of NMs in products claimed to contain NMs.

*Tænk/ Forbrugerrådet (2013)."Nanodatabasen".

(http://nano.taenk.dk/velkommen-tildatabasen)

Scope: In a continuous process to register Nano-products that are available on the Danish

market and provide relevant information to the consumers regarding type of product and

nanomaterial and the potential for NM exposure and potential hazard of the NMs.

Content/ outcome: Currently 1236 products with product information have been

registered in the database. The products are registered within 9 product categories and 32

product subcategories. Product information and use formation on the named products are

available on the database and an evaluation according to the NanoRiskCat scheme is made

for each product.

Information regarding formulation of the product, location and ID of the NMs are given if

available.

The 9 product categories are: - appliances; - electronics & computers; - home & garden; -

food & beverages; - health & fitness; - automotive; - cross cutting (coatings); - goods for

children; - not categorized.

The potential for hazardous properties of the nanomaterial both in relation to human

health and in relation to environment is graded in “high, medium, low and unknown”

according to the criteria and the colour codes described in the NanoRiskCat scheme.

Search can be made in the database in relation to product name; manufacturer;

nanomaterial, product type (category and subcategory), and production country.

Exposure: The exposure potential towards consumers, workers and the environment is for

each category graded in” high, medium, low, unknown” according to the criteria and the

colour codes described in the NanoRiskCat scheme. From the database high consumer

exposure potential (red scoring) can be seen for:

- home and garden products e.g. coating/ paints / cleaners (i.e. products (aerosols

and liquids) for surface treatment and cleaning)

- food and beverages

- health and fitness (cosmetics sunscreen, personal care products)

- car care products (cleaning solvents, surface treatment, liquid and aerosols)

- various coatings

Relevance: High. Related to the Danish market. Continuously updated. Ranking of

exposure (and hazard ) potential.

Overall evaluation

Databases/ inventories

For the inventories/databases, the Danish “Nanodatabasen” seems as the most relevant

database as it is a living database with detailed information and evaluation of each

product. Thus this should be the first-choice database when extracting data from products

from various product categories. Secondary databases for WP 2.3 would be the BUND

http://nano.taenk.dk/velkommen-tildatabasen

26

database (also a living database) and the ANEC/BEUC database (last update 2012 with

nanosilver products) covering to a great extent the same product categories as the

Nanodatabase. Also Friend of the Earth´s listing of nanoproduct s in food and agriculture

from 2008 may be of importance in extracting data from products in the product category

food and food packing.

Exposure information

With respect to a framework for screening of the exposure potential for NMs through the

use of consumer products, the RIVM (2009) approach seems most developed in

pinpointing relevant parameters for exposure estimation. Furthermore, RIVM

recommends to differentiate between the various exposure routes in the exposure

assessment. NanoCatRisk uses a more simplistic approach predominantly based on the

matrix effects and the potential of release of the NM from the matrix as an indicator for

exposure and do furthermore not differentiate between the various exposure routes when

assessing the exposure potential.

Thus, the parameters identified by RIVM (2009) seems to be a good starting point for the

relevant exposure parameters to look for when looking for and extracting product

information in the databases in WP 2.3.

With respect to description of detailed specific exposure scenarios for marketed products

the reports from Danish EPA (2007) and Nanex (2010) may contribute to WP2.4, however

further search for additional specific exposure scenarios would be needed.

27

Appendix 4 - Tables with examples 4.

of nanoproducts

28

Food and beverages 4.1

Food and beverages (intended, direct exposure by use)

1

Product name, volume and

type

2

Formulation/ matrix

Liquid/Aerosol/ Crème/Paste/ Powder/Solid

Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure

route(s)/ (secondary exposure

route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/ outdoor

All

ages/Children/ Adults/Sportsm

en/Hobby

Oral/ Dermal/

Inhalation

The Danish Nanodatabase contains reference to 51 products belonging to food and beverages category. The nanomaterial are not known for most of the products, the known materials are mainly silver but also zinc, palladium, iridium and platinum are used. A supplementary survey of products on the Danish market containing nanomaterials (Danish EPA, 2013,draft) highlights that the Danish Veterinary and Food Administration have not yet received inquiries from companies to use nanomaterials in food and feed products. However the survey have identified following approved food additives which may be considered as nanomaterials; silicon dioxide, titanium dioxide, calcium carbonate, and carbon black. Iron, calcium and silver and oxides thereof are being marketed as food supplements but are not approved as food additives. For use in food contact material nanomaterials such as silicon dioxide, titanium dioxide and titanium nitride have been approved for use. The ANEC-BEUC inventory contains a food and drink category. The products are however similar to the products in the Danish nanodatabase, but some additional food supplements are identified The BUND database contains about 130 products in the food and beverage category. No products have been selected for this table as products are considered covered by the Danish nanodatabase. The Nanotech project database contains 199 products in the food and beverage category, most are already covered by the products selected above and no additional products have been selected. Product category/Products: Food and beverages

29


1


type

2

Formulation/ matrix

Liquid/Aerosol/ Crème/Paste/

Powder/Solid Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure

route(s)/ (secondary

exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Solgar CQ10,

60 capsules,

Food suppl.

Specified Suspension in liquid CoQ10 molecules

as micelle

1 capsule daily Oral http://www.nutritioncentre.co.uk/products/485-solgar-nutri-

nano-coq10-with-alpha-lipoic-acid

http://nanodb.dk/da/products/

solgar-cq10

Estimated <1% <1g Hours Adults

Colloidal

Silver, 15 ml

Food suppl.

Specified Suspension in liquid Silver 500 ppm

(0,05%)

Daily Oral http://www.fairvital.com/produ

ct_info.php?products_id=77

Estimated <1g Hours Adults

Mesozinc

500 ml

(1 month

supply)

Food suppl.

Specified Suspension in liquid zinc 30 ppm (0.003%)

5 -20 ml Daily Oral http://www.purestcolloids.com/mesozinc.php

Estimated Hours Adults

http://www.nutritioncentre.co.uk/products/485-solgar-nutri-nano-coq10-with-alpha-lipoic-acid




30


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Sovereign

Silver (8oz) 10

ppm Nano

Hydrosol

(Liquid) Food

suppl.

Specified Suspension in liquid Silver 10 ppm (0.001%)

Oral http://www.amazon.co.uk/Sovereign-Silver-Hydrosol-Liquid-Bottles/dp/B002RGCX32/ref=sr

_1_51?ie=UTF8&qid=1321453507&sr=8-51 Estimated <1g hours Daily/Weekly Adults

MesoPlatinum,

250 ml-3800 ml

Food suppl.

Specified Suspension in liquid Platinum 10 ppm (0.001%)

5-20 ml Daily Oral http://www.purestcolloids.com/mesoplatinum.php

Estimated Hours Adults

MesoPaladium

250 ml-3800 ml

Specified Suspension in liquid Paladium 10 ppm

(0.001%)

5-20 ml Daily Oral http://www.purestcolloids.com/mesopalladium_price_list.php

31


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Food suppl. Estimated Hours Adults

Allergy

Research

Group,

Mucolyxir

Nanotech

Nutrients 12 ml,

Food suppl.

Specified Suspension in liquid DNA from pacific

salmon

0.3 µg/drop (0.05 ml)

Oral http://www.allergyresearchgroup.com/Mucolyxir-Nanotech-

Nutrients-12-ml-liquid-p-151.html Estimated <1g Hours Daily Adults

Muscle tech

Nano Vapor tm

Body building

Food suppl.

Specified Powder

NI NI >10g (13g) Oral http://www.wholesalefitness.co.nz/site/ViewItem.aspx?pageModuleItemId=982300

Estimated Minutes/hours

Daily Sportsmen

Bionic Joint

Support

Specified Suspended in liquid Hyalu- ronic

nano-

NI Oral http://www.life-enhancement.com/shop/produ

ct/bjs-bionic-joint-support

http://www.allergyresearchgroup.com/Mucolyxir-Nanotech-Nutrients-12-ml-liquid-p-151.html




http://www.life-enhancement.com/shop/product/bjs-bionic-joint-support



32


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

pheres The product is also present in

the Danish nanodatabase, but presented with unknown nanomaterial.

However from the product website it seems likely that the

actual nanomaterial is the carrier system for the identified

substance

Estimated 1-10g Minutes/hours

Daily Sportsmen

NI: not indicated

Overall findings

All the identified products are food supplements. The food supplement products contain a wide range of elements, such as silver, platinum, palladium and gold, but also

different organic substances apparently in the nano size are used. Among the identified NM a concentration level up to 500 ppm is indicated (for silver). Uses of NM in food

products have not been presented in the databases, and therefore not included in the table. However, silicon dioxide, titanium dioxide, calcium carbonate, and carbon black

which may be considered as nanomaterials are all approved food additives for colouring , anticaking etc..

33

Cosmetics 4.2

Cosmetics (intended, direct exposure by use)

1


type

2

Formulation/

matrix Liquid/Aerosol/

Crème/Paste/ Powder/Solid

Application

method

3

NM

ID

4

Conc. of

NM in product

5

Volume of

product per use

6

Duration

per event

7

Use

frequency and site of

use

8

Consumer

group.

9

Primary

exposure route(s)/

(secondary exposure

route)

10

Comments/ web-links

Exact value or range

[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day

Daily/ Weekly/ Monthly/

Yearly/

Indoor/ outdoor

All ages/Children/

Adults/Sportsmen/Hobby

Oral/ Dermal/ Inhalation

The Danish Nanodatabase contains 63 cosmetic products. Only few products with identified nanomaterials, typically silver. Many of the products is also found in the Nanotechproject database as non-European products. A supplementary survey of products on the Danish market containing nanomaterials (Danish EPA, 2013,draft) nanomaterials were identified in cosmetics as colorants and UV filters, the identified nanomaterials were titanium dioxide, carbon black, iron oxides and aluminium hydroxide. The nanomaterials were present in up to 5%. In the BUND database contain 100 products under the category körperpflege of which identification of the nanomaterial is given for 64 products. The majority contain siliciumdioxide and titaniumdioxide The ANEC-BEUC inventory contains nearly 100 cosmetics products- the majority having no nano ID. Nano ID mostly titanium dioxide, silver and fullerenes The Nanotechproject database contains 198 cosmetic and sunscreen products of which ID of the NM is given for for 99 products. Nearly all products are from non-European countries.

Product category/Products: Cosmetics

34


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Mydelko

naturalne

Soap,100 g

Specified silver http://nanodb.dk/products/mydelko-naturalne-natural-soap-0

http://www.mydelkonaturalne.com.pl/en/product/how-was-

natural-soap-created.html

Estimated Suspended in liquid

Applied on skin, Rinse off product

<1% <1g / 1-10 g minutes daily All dermal

Nanolia pure

silver Anti-

Redness

50 ml body gel

specified Suspended in gel

Applied on skin, leave on

silver http://nanodb.dk/products/body-gel-cosmetic-nanolia-pure-

silver-anti-redness http://intouch.nanolia.com/info

/index.php?p=88

estimated <1% <1g / 1-10 g Hours Daily All dermal

Silber-Crème

50-500 ml

specified Suspended in cremel

Applied on skin, leave on

Colloidal silver

http://nanodb.dk/products/silber-creme http://www.schuhma-

naturprodukte.de/naturkosmetik/silber-creme/

estimated <1% <1g / 1-10 g Hours Daily All dermal

http://nanodb.dk/products/mydelko-naturalne-natural-soap-0

http://nanodb.dk/products/mydelko-naturalne-natural-soap-0

http://www.mydelkonaturalne.com.pl/en/product/how-was-natural-soap-created.html



http://nanodb.dk/products/body-gel-cosmetic-nanolia-pure-silver-anti-redness



http://intouch.nanolia.com/info/index.php?p=88

http://intouch.nanolia.com/info/index.php?p=88

http://www.schuhma-naturprodukte.de/naturkosmetik/silber-creme/



35


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Silber-

DeoSpray

120 ml

Specified Liquid / aerosol Colloidal silver

http://nanodb.dk/products/silver-deo http://www.schuhma-naturprodukte.de/naturkosmeti

k/silber-deo-spray/

estimated Applied on skin by pump spray, leave on

<1% <1g / 1-10 g hours daily all Dermal (inhalation)

Dentasil Gel

Approx. 100 ml

specified Suspended in liquid silver http://nanodb.dk/products/den

tasil-gel estimated For flushing of the

oral cavity <1% <1g / 1-10g minutes daily all Oral, dermal

Nano Gold 24

Hour Facial

Cream

20-100 ml

Specified Suspension in liquid gold

http://nano.taenk.dk/da/products/nano-gold-24-hour-cream

Estimated Applied on skin, leave on

<1% <1 g /1-10g hours daily adults dermal

LEOREX Anti-

Aging Face-

specified Silicon

http://nano.taenk.dk/da/products/leorex-cosmetics

http://nanodb.dk/products/silver-deo

http://nanodb.dk/products/silver-deo

http://www.schuhma-naturprodukte.de/naturkosmetik/silber-deo-spray/



http://nanodb.dk/products/dentasil-gel

http://nanodb.dk/products/dentasil-gel





36


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Renewal

Cream, 60 ml

Estimated 1-10%

<1 g /1-10g

hours Daily Adults Dermal

LEOREX™ Eye

Gel Gold

30 ml

Specified Liquid/gel Silicon

oxide

http://www.leorex-

cosmetics.com/products/LEOREX%E2%84%A2+Eye+Gel+Gol

d.html Estimated Applied on skin

around eye leave on

1-10% < 1g hours daily women Dermal (eye)

Neosine Spray

Forte 50ml

specified Suspended in liquid in pump spray

silica https://www.neosino.at/products/gesichtspflege/spray-forte-

50ml

estimated Sprayed on skin, leave on

1-10% <1g/1-10 g hours Daily all Dermal, (inhalation)

http://www.leorex-cosmetics.com/products/LEOREX%E2%84%A2+Eye+Gel+Gold.html




https://www.neosino.at/products/gesichtspflege/spray-forte-50ml



37


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Platinum Silver

Nanocolloid

Cream

antiwrinkle,

40g

specified Crème Applied on skin,

leave on

Plati-num and Silver

http://nano.taenk.dk/da/products/platinum-silver-nanocolloid-cream

http://www.dhccare.com/DHC/ProductDetail.aspx?ProductID=

3002

Estimated <1%

<1g/1-10g

hours daily adults dermal

Sircuit White

Out

15 ml

specified Suspension in liquid Fullere-ne

http://nano.taenk.dk/da/products/sircuit-white-out

http://www.amazon.com/Sircuit-Skin-White-Out-0-

5/dp/B000NPWJZG

Estimated Applied on skin

around eyes, leave on

<1% <1g/1-10g hours daily Adults dermal (eye)




http://www.dhccare.com/DHC/ProductDetail.aspx?ProductID=3002





http://www.amazon.com/Sircuit-Skin-White-Out-0-5/dp/B000NPWJZG



38


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Revite,

NANOTECHNO

LOGY Hair

Growth

Stimulating

Shampoo, 190

ml

Specified Suspended in liquid Nano copper Peptides

http://nano.taenk.dk/da/products/revite-nanotechnology-hair-growth-stimulating-

shampoo

http://www.makemeheal.com/mmh/product.do?id=93034&ut

m_source=google&utm_medium=product&utm_campaign=go

ogleproduct

Estimated Applied to skin and hair

Wash-off

<1%

1-10g/>10g

Minutes Daily Adults Dermal

Doctor

Gunderson's

Rãahj Nano

Copper Facial

Spray, Pump

spray 28 g

specified Suspension in liquid,

Copper Direct leave on

http://nano.taenk.dk/products/doctor-gundersons-raahj-nano-

copper-facial-spray

Estimated Spray onto hands face,

leave on

1%/1-10% <1g/1-10g hours Daily Adults Dermal/ Inhalation

http://nano.taenk.dk/da/products/revite-nanotechnology-hair-growth-stimulating-shampoo




http://www.makemeheal.com/mmh/product.do?id=93034&utm_source=google&utm_medium=product&utm_campaign=googleproduct





http://nano.taenk.dk/products/doctor-gundersons-raahj-nano-copper-facial-spray



39


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Soltan® Facial

Sun Defence

Cream -

Optisol® >100

ml

Specified Suspended in liquids

Titanium dioxide

http://www.nanotechproject.org/cpi/products/soltan-r-facial-sun-defence-cream-optisol-r/

Estimated Applied onto the skin, leave on

1-10% 1-10g/ >10g hours daily All Dermal (oral)

“Face

powder” 15 g

Specified powder Titanium

dioxide

*Example based on data from Danish EPA (draft 2013),

without specific naming

Estimated Applied in skin by brush or cotton pad

Up to 3% <1 g hours daily Women Dermal (inhalation, oral)

Nano-Peptide,

Natural

Eyelash

Conditioner

5ml

Specified Nano-peptides

http://www.lashfood.com/r/productsp.php?p=28


Applied to the

eyelash by brush, leave on

<1% <1 g Minutes/ho

urs

Daily women dermal, eye






40


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Lash food

conditioning

drama mascara

waterproof ,8

ml

Specified Nano-peptides


Estimated Suspended in paste

Applied on eye lashes by brush ,

leave on

<1% < 1g hours Daily Women Dermal, eye

“Mascara”*

10 ml

Specificied Suspended in a

paste

Carbon

black

Up to 5%

*Example based on data from Danish EPA (draft 2013),

without specific naming

Estimated Applied by brush, leave-on

<1g hours daily women Dermal. eye

Daylong Kids

SPF 30

100, 200 ml

Specified Suspended in liquid zinkoxid http://www.bund.net/nc/themen_und_projekte/nanotechnolo

gie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_

pi1%5Bitem%5D=1206&kategorie=10&unterkat=48&msb_pr

oduct_submit=suchen

Estimated Applied on skin,

Leave on

(1-10%) >10g hours daily children Dermal, oral



http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=1206&kategorie=10&unterkat=48&msb_product_submit=suchen







41


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Daylong

extreme Stick

SPF 50+

Apprx 10-20

ml

Specified Supended in stick; semisolid matrix,

Titanium dioxide

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/pro

duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=1204&kateg

orie=10&unterkat=48&msb_product_submit=suchen

Estimated Applied on the facial skin incl. lips,

leave on

1-10% <1g hours daily all Dermal., oral

NIVEA SUN

Kids

Pflegendes

Sun Spray

LF50+

specified Suspended in liquid Siliziumdioxid,

Titandioxid

http://www.bund.net/nc/themen_und_projekte/nanotechnolo


pi1%5Bitem%5D=510&offset=3&kategorie=10&unterkat=48

&msb_product_submit=suchen

estimated Sprayed on hands/

body, leave on

1-10% >10g hours daily children Dermal, oral

(inhalation)

Swiss Dent –

Nanowhite-

specified Suspended in creme

Calciumperoxide










http://www.bund.net/themen_und_projekte/nanotechnologie/nanomaterialien/siliziumdioxid/

http://www.bund.net/themen_und_projekte/nanotechnologie/nanomaterialien/siliziumdioxid/

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=510&offset=3&kategorie=10&unterkat=48&msb_product_submit=suchen







http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=424&freitext=zahncreme&kategorie=10&unterkat=48&msb_product_submit=suchen




42


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

ning -

Zahncreme

100ml

estimated <1%/1-10% <1g/1-10g minutes Daily adults Oral (dermal) pi1%5Bitem%5D=424&freitext=zahncreme&kategorie=10&unterkat=48&msb_product_subm

it=suchen

http://shop.essenza-nobile.de/kosmetik-online-

shop/Swiss-Dent-Dental-Cosmetics/Swiss-Dent-

Nanowhitening-Zahncreme.html?cSEOid=8b0320c9d1140cd79ba03a2315ff2b

4c





http://shop.essenza-nobile.de/kosmetik-online-shop/Swiss-Dent-Dental-Cosmetics/Swiss-Dent-Nanowhitening-Zahncreme.html?cSEOid=8b0320c9d1140cd79ba03a2315ff2b4c








43

Overall findings

In the examples found in the table the following nanomaterials have been found in the cosmetic products:

Silver: in soap/ creams/ gels/ lotions for dermal application. Also in mouth wash solution and in toothpaste

Gold: in cream for facial dermal use

Platinium: in cream

Fullerenes: in cream at dermal application in eye region

Nano-peptides: in mascara for eye lashes

Silicium dioxide: in sunscreen cream and in liquid preparations for application in face and eye region

Zinkoxide: in sunscreen

Titanium dioxide: in sunscreen, face powder

Calciumperoxide: in toothpaste

Copper & copper peptides: in shampoo and facial liquid preparations

Carbon black: mascara

For the far majority of the products the primary exposure route is the dermal route, whereas secondary routes are in relation to oral, inhalational and eye exposure. For

mouthwash solution (silver) and toothpaste (calciumperoxide) the primary route is the oral route.

For cosmetics the exposure is intended and the whole volume of a cosmetic is normally intended for e.g. dermal or oral exposure. For product that are ´leave on´ the products

stays on the body whereas most of the use volume from `rinse-off` products is washed off (e.g. soaps and shampoos) and exposure is limited to a much shorter duration.

It may be surprising that although pigments are used in a variety of cosmetics (e.g. mascara, lip stick, eye shadow, face powder etc.) this content seems not to have led to

inclusion of any cosmetics into the nanodatabases, although pigments are known to contain particles in nano size. Only few toothpastes occur in the databases even though it

has often been stated that they in general contain nanoparticles e.g. silica and titanium dioxide.

44

Cleaning agents 4.3

Cleaning agents (not intended, indirect exposure by use)

1


type

2

Formulation/ matrix


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product per

use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/ outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Nanotechproject database contains 115 products with specified nanomaterials belonging to the category Home and garden ‘cleaning’ subcategory. The Danish Nanodatabase contains reference to 129 products containing nanomaterials in the ‘Cleaning’ subcategory under ‘Home and garden’. The ANEC-BEUC inventory contains the subcategory ‘Home & garden’. The products are already identified in the two databases referred to above, and thus the inventory therefore does not provide additional information to the table. Product category/Products: Home and garden

Laundry Detergent – Irin

2 kg

Skin Care fabric softener for baby

clothes and underwear

Specified Suspended in liquid

Silver http://aekyung.en.ec21.com/Laundry_Detergent_Irin--

2_1586347.html

http://nanodb.dk/da/products/laundry-detergent-irin-0

Estimated <1% > 10g Minutes weekly

Indoor

All ages Dermal

(inhalation, oral)

http://aekyung.en.ec21.com/Laundry_Detergent_Irin--2_1586347.html





45


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

NanoCover bath + tiles 75 ml

Sealing- and

cleaning product for bathrooms and

tiles

Specified Liquid 10-25 ml pr. m²

http://www.nanocover.dk/shop/nanocover-bad-fliser-180p.html

http://www.nanotechproject.or

g/cpi/products/bath-and-tilling-cleaner/

Estimated Applied with cloth

or alternative product with pump

spray

Unknown <1% Minutes to

Hours

Monthly/Yearly

Indoor

Adults Dermal

(inhalation/oral)

Poprang fabric

Softener with aroma capsules

1L (uncertain)

Textile softener for laundry

Specified

Suspended in liquid

Handling of Liquid

Silver http://www.nanotechproject.or

g/cpi/products/fabric-softener-nano-silver-650-poprang/

http://poprang.en.ec21.com/Fabric_Softener_Nano_Silver_6

50--952338_952354.html

Estimated <1% > 10g Minutes (handling

of product) / Whole

day (textile)

weekly

Indoor

Adults Dermal (oral, inhalation)

Flooring

treatment Vol?

Specified

Suspended in liquid Silica http://nanosafeguard.com/floo

ring_treatment.html http://www.nanotechproject.or




http://www.nanotechproject.org/cpi/products/bath-and-tilling-cleaner/



http://www.nanotechproject.org/cpi/products/fabric-softener-nano-silver-650-poprang/



http://poprang.en.ec21.com/Fabric_Softener_Nano_Silver_650--952338_952354.html



http://nanosafeguard.com/flooring_treatment.html

http://nanosafeguard.com/flooring_treatment.html

http://www.nanotechproject.org/cpi/products/flooring-treatment-absorbant-surfaces/

46


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Hydrophobic treatment, Coatings, and

Antimicrobial protection (form

of product unclear)

Estimated Procedure for application not specified (cloth,

sponge or spray)

Possibly additional material

as it is claimed

antibac-terial.

<1%/1-10% > 10g Minutes to Hours

Yearly Indoor

Adults Dermal (inhalation, oral)

g/cpi/products/flooring-treatment-absorbant-surfaces/

NanoLotus

Antidew Universal

100 – 500 ml Hydrophobic

treatment and cleaning in pump

spray

Specified

Suspended in liquid http://nanolotus.dk/forside/alle

-produkter/antidug-universal/

http://www.nanotechproject.org/cpi/products/glass-cleaner-universal/

Estimated Aerosol Unknown <1%/1-10% > 10g Minutes Weekly to

Monthly

Indoor

Adults Dermal (oral)

Nano Silver Wet Wipes

Wet wipes for

personal cleaning of all ages as well as any surface

Specified

Surface bound particles

Silver Dermal http://www.ecplaza.net/product/nano-silver-wet-wipes--

58974-344650.html

http://www.nanotechproject.org/cpi/products/nano-silver-wet-wipes/

Estimated Skin and surfaces <1% 1 - 10g Minutes Daily

Indoor

All ages



http://nanolotus.dk/forside/alle-produkter/antidug-universal/

http://nanolotus.dk/forside/alle-produkter/antidug-universal/




http://www.ecplaza.net/product/nano-silver-wet-wipes--58974-344650.html






47


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

nanoCotz Colloidal Cleaner 0.5-10 l

Cleaning agent

with wide application areas

Specified

Suspended in liquid Unspeci-fied Nano micelles

https://www.facebook.com/Nanocotz

http://www.nanotechproject.org/cpi/products/nanocotztm-

colloidal-cleaner/ Estimated Application as liquid

using cloth or

sponge

<1%/1-10% > 10g Minutes Weekly

Indoor/outdoor

Adults Dermal (oral)

SGG BIOCLEAN

Photocatalytic titania coating embedded in self-

cleaning surface of outdoor window

glass.

Specified

embedded in window glass

Titanium dioxide

Outdoor http://uk.saint-gobain-glass.com/product/670/sgg-

bioclean http://www.nanotechproject.or

g/cpi/products/sgg-bioclean/ Estimated <1%/1-10% > 10g Minutes Monthly/Yearly Adults Dermal (oral,

inhalation)

NANOTEC -

Sanitizer NPS 200

Anti-bacterial

cleaning agent in pump spray with wide application

areas

Specified

Suspended in liquid Silver http://www.nanotec.pl/en/inde

x.php?go=produkty&id=nanotec_sanitizer

http://docshare.beuc.org/Com

mon/GetFile.asp?ID=44567&mfd=off&LogonName=Guesten

http://nanodb.dk/products/nan

Estimated Aerosol <1% > 10g Minutes Weekly

Indoor

Adults inhalation (dermal, oral)



http://www.nanotechproject.org/cpi/products/nanocotztm-colloidal-cleaner/



http://uk.saint-gobain-glass.com/product/670/sgg-bioclean



http://www.nanotechproject.org/cpi/products/sgg-bioclean/

http://www.nanotechproject.org/cpi/products/sgg-bioclean/

http://www.nanotec.pl/en/index.php?go=produkty&id=nanotec_sanitizer



http://docshare.beuc.org/Common/GetFile.asp?ID=44567&mfd=off&LogonName=Guesten



http://nanodb.dk/products/nanotec-sanitizer-nps-200

48


1


type

2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

otec-sanitizer-nps-200

Overall findings In the area of cleaning agents, three different product types were observed: liquid, spray, and cloth/wipe-based products. The identified active nanomaterial ingredients were either silver (Ag), TiO2, silica, and micelles. Since the nanomaterials were reported in many of these products, the concentrations may exceed 1 wt%, in spite less than 1 wt% is expected in most Ag-based nanomaterial products. The most important exposure routes were inhalation and possibly dermal and subsequent accidental oral exposure. The volume expected to be used during use of the products is typically greater than 10 g. The typical exposure duration will last minutes, but in some cases the post application stage can result in exposure for days. This is especially the case with treated textiles.

http://nanodb.dk/products/nanotec-sanitizer-nps-200

49

Coating, impregnation 4.4

Coating, impregnation such as liquids, sprays, cloths and paint (not intended, indirect exposure by use)

1

Product name, volume and type

2

Formulation/ matrix*

Application method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/ outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Danish Nanodatabase contains reference to 22 products belonging to the coatings and impregnations category. The nanomaterials are not known for most of the products, the only identified material is silver. In the BUND database coatings and impregnation products are not grouped together but can be found in categories such as “leisure” or “paint and laquers”, which contains coating and impregnation products mostly also identified in the Danish database. The ANEC-BEUC inventory contains a subcategory coating under the crosscutting category. For most of the products, the nanomaterials are not identified. The identified nanomaterials are mostly silver. The inventory therefore does not add any additional information to the table. The Nanotechproject database contains 86 products under the coating category of which 29 products with named nanomaterial of which many of these were pre-surface treated devices or impregnation products found out-site Europe. Product category/Products: Coatings/Impregnation

WoodProtector

Coating, 1000 ml

Specified Liquid

NI http://nano.taenk.dk/da/produ

cts/woodprotector http://www.jamestowndistribut

http://nano.taenk.dk/da/products/woodprotector

http://nano.taenk.dk/da/products/woodprotector

http://www.jamestowndistributors.com/userportal/product.do?part=142947&BASE

50


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Surface treatment of teak on boats

Estimated Applied as liquid <1%/1-10% > 10g Minutes/ Hours

Monthly/ Yearly

outdoor

Sportsmen/hobby/All ages

Dermal ors.com/userportal/product.do?part=142947&BASE

Percenta AG

Nano Synthetic Material Sealant,

1000 ml, Easy to clean

surface

specified Liquid Titanium

dioxide Pr. P

Size:2.0 nm.Sec. P Size: 6.0 nm. Anatase.

http://shop.percenta.com/nano

-plastics-coating-50ml-nanotechnology-

60.html?shop=373a71bf445ee32d334f4fe5f68b8228

estimated Is sprayed <1; 1-10% >10 g minutes Monthly/ yearly

indoor

adults Dermal-inhalation

Nano waffenspray

100 -200 ml Gun oil

specified Liquid/ aerosol Teflon; polytetra

fluoroethylene

http://www.cs-nanoshop.de/product_info.php

?products_id=38

estimated Is sprayed <1; 1-10% 1-10 g minutes Monthly

indoor

sportsmen Dermal- inhalation



51


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

NanoSafeguard Countertop Treatment

Apprx 1 L Easy to clean

surface

Specified Liquid silicondioxide

http://www.nanosafeguard.com/countertop_treatment.html

estimated Is sprayed <1; 1-10% 1-10 g/ > 10 g

minutes Monthly indoor

adults Dermal-inhalation

NanoSafeguard Self-Cleaning Window

Treatment, apprx 60 ml

Specified liquid Titanium dioxide

http://www.nanotechproject.org/cpi/products/self-cleaning-

window-treatment/ http://nanosafeguard.com/self

_cleaning_window_treatment.html

estimated Is sprayed <1; 1-10% 1-10 g/ > 10 g

minutes Monthly

outdoor

adults dermal

TextileProof+

active Water proofing

250 -1000 ml

Specified Liquid/ aerosol

NI

http://nano.taenk.dk/da/produ

cts/textileproofactive http://www.bike-

discount.de/shop/a6393/textile-proof-active-250ml.html?lg=en

Estimated Is sprayed <1%/1-10% 1-10 g/>10g Hours Monthly/ Yearly

indoor

Sportsmen/hobby

Inhalation-dermal

http://www.nanotechproject.org/cpi/products/self-cleaning-window-treatment/



http://nanosafeguard.com/self_cleaning_window_treatment.html



http://nano.taenk.dk/da/products/textileproofactive

http://nano.taenk.dk/da/products/textileproofactive

http://www.bike-discount.de/shop/a6393/textile-proof-active-250ml.html?lg=en




52


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Select Super

Protector with

Nano Particles Shoeshine

(200 g)

Specified Liquid/aerosol

Nanoparticles indicated

http://nano.taenk.dk/da/products/select-super-protector-with-nano-particles

http://www.kiwishoeshine.com/KIWI-Select-Super-Protector-

with-Nano-Particles-7-oz_p_479.html

Estimated Is sprayed <1%/1-10% <1g/1-10g minutes Weekly/ Monthly

indoor

Adults Inhalation-dermal

NoFog+clean 20 ml

Anti-fog treatment

on goggles and windows

Specified

Liquid/aerosol NI http://nano.taenk.dk/da/products/nofogclean

http://www.bike-discount.de/shop/a50024/no-

fog-clean-20ml.html?lg=en

Estimated Is sprayed

<1/1-10% <1g/1-10g

minutes Weekly

indoor

Adults/ sportsmen

Inhalation-dermal

Nanowax Ski

wax 50 ml

Specified Liquid/aerosol NI


cts/nanowax http://www.tesmasport.si/pro-

3 Estimated Is sprayed <1/1-10% <1g/1-10g minutes Weekly

indoor

Adults Inhalation -dermal




http://www.kiwishoeshine.com/KIWI-Select-Super-Protector-with-Nano-Particles-7-oz_p_479.html




http://nano.taenk.dk/da/products/nofogclean

http://nano.taenk.dk/da/products/nofogclean

http://www.bike-discount.de/shop/a50024/no-fog-clean-20ml.html?lg=en



http://nano.taenk.dk/da/products/nanowax

http://nano.taenk.dk/da/products/nanowax

http://www.tesmasport.si/pro-3

http://www.tesmasport.si/pro-3

53


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Nano Glass & Ceramics Coating

100 ml

Specified Liquid/aerosol NI http://shop.percenta.com/nano-glass-ceramics-coating-

100ml-nanotechnology-10.html?shop=820901dba8671

aa8c75346eb102ef65a%20[Page%20visited%20on%204%20

August%202010]

Estimated Is sprayed <1%/1-10% >10g minutes Monthly /yearly

indoor


Nanotol the

universal

nano sealant 250 ml, 1000ml

For all smooth

surfaces e.g. cars, boats, indoor

Specified Liquid NI http://nano.taenk.dk/da/products/nanotol-the-universal-

nano-sealant

http://www.cenano.de/shop/Nanotol-sealant-for-all-smooth-

surfaces/Nano-vitrification-nanotol::320.html

Estimated Applied as liquid <1%/1-10% >10g Minutes/ho

urs

Monthly/

yearly

indoor

Adults dermal

Antibacterial

shoe deodorizer with silver ions

Specified Liquid/aerosol Silver http://nano.taenk.dk/da/produ

cts/antibacterial-shoe-deodorizer-with-silver-ions

http://shop.percenta.com/nano-glass-ceramics-coating-100ml-nanotechnology-10.html?shop=820901dba8671aa8c75346eb102ef65a%20%5bPage%20visited%20on%204%20August%202010







http://nano.taenk.dk/da/products/nanotol-the-universal-nano-sealant



http://www.cenano.de/shop/Nanotol-sealant-for-all-smooth-surfaces/Nano-vitrification-nanotol::320.html




http://nano.taenk.dk/da/products/antibacterial-shoe-deodorizer-with-silver-ions



54


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Estimated Is sprayed <1% <1g Minutes Weekly/ monthly

indoor


Product could not be found on

the cenano.de website Several similar products exists on the market

Product category/Products: Paint

Herbol

Symbiotec, Farbe Outdoor

paint 5L; 12.5 L

Specified Liquid

Rolling/ spraying

Silicium

dioxide

http://www.bund.net/nc/them

en_und_projekte/nanotechnologie/nanoproduktdatenbank/pro

duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=177&unterk

at=14&msb_product_submit=suchen

http://www.herbol.de/produkte/symbiotec.htm

Estimated 1-10% >>10g hours Monthly/ yearly

outdoor

Adults, Mainly

professionals, consumer cannot be

excluded.

dermal

Bioni

HYGIENIC®Multifunktionale

Innenbeschich-

Specified Liquid

Rolling/ spraying

silver

http://www.bioni.de/daten/PDB%20Bioni%20Hygienic.pdf

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=177&unterkat=14&msb_product_submit=suchen











55


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

tung Indoor paint 5L; 10 L

Estimated <1% >>10g hours Yearly indoor

adults Mainly professionals,

consumer use cannot be

excluded.

dermal

TP2220 Primer Indoor/ outdoor primer paint 5 L Mainly for spray

application.

Specified Liquid

Spraying/ rolling

Titanium

dioxide particles

< 3nm

0.7-0.9%



pi1%5Bitem%5D=837&offset=1&unterkat=14&msb_product_submit=suchen

http://titanprotect.de/file/pdfs/

neu/PDB/PDB%20TP2221.pdf

Estimated >>10g hours Yearly

Indoor/outdoor

Adults Mainly

professionals, consumer use cannot be

excluded.

Inhalation- dermal

Product category/Products: Impregnation cloth

http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=837&offset=1&unterkat=14&msb_product_submit=suchen







http://titanprotect.de/file/pdfs/neu/PDB/PDB%20TP2221.pdf


56


1


2


Application

method

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group.

9

Primary exposure


exposure route)

10

Comments/ web-links

Liquid/Aerosol/


Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Nano lotus Cloths for sealing of car windows,

Repelling dirt and droplets

Specified

NI http://shop.bilvask.nu/nano-bilruder-1stk

Estimated Textile/ paper towel

containing impregnation

<1% <1g/1-10g minutes Monthly/yearly

outdoor

adults dermal

Overall findings

For many of the products identified, no specification of the actual nanomaterial could be found. The most abundant nanomaterial seems to be titanium dioxide, but also

silicium dioxide, silver and Teflon has been is observed. Only one product specifies the actual concentration of the nanomaterial, for the remaining products the estimated

concentrations are less than 10 %, with the most products estimated to have less than 1%. Duration of use of the products is estimated to minutes to hours, and frequency

estimated to monthly to yearly. The primary exposure routes for the NM exposure is the dermal routes and for products that are sprayed also the inhalation route.

http://shop.bilvask.nu/nano-bilruder-1stk

http://shop.bilvask.nu/nano-bilruder-1stk

57

Maintenance products 4.5

Maintenance products such as liquids, sprays, cloths and paint for cars and boats (not intended, indirect exposure by use)

1


2

Formulation/ matrix


Powder/Solid

Application method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/ Indoor/

outdoor

All ages/Children/



The Nanotechproject database contains 18 products with specified nano materials belonging to the categories ‘Automotive-maintenance and accessories’, ‘Automotive-Watercraft’ and ‘Automotive-exterior’. The Danish Nanodatabase contains reference to 6 products belonging to maintenance and accessories category for automotive. For 3 of the products the nanomaterials are not known, and for the remaining 3 products the identified material is silver and titan. In the BUND database maintenance and accessory 165 products can be found under the category “auto/Motorräder” which contains maintenance and accessory products for cars and boats. Some of the products are already identified in the Danish database. Also some products for car maintenance are categorized as ‘other’. For most of the products the nanomaterial is not known and only silicium dioxide and silver is identified in 3 products. The ANEC-BEUC inventory contains the subcategory ‘maintenance and accessories’ under the ‘automotive’ category. The products are already identified in the Danish database, and thus the inventory therefore does not provide additional information to the table. Another product has been found on a company web-site referred to in the databases. Product category/Products: Maintenance products

58


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Top Efekt KOK

NANO

450-1000 ml Anti-reflecting

cleaning agent for cockpits, car

interior and other plastic surfaces

Specified Suspended in liquid Energetically mix

about 1 minute before use and then

spray

Silver http://nano.taenk.dk/da/produ

cts/topefektr-kok-nano

http://en.tenzi.pl/artyku%C5%82y/assortment/nanotechnolog

y/top-efekt-kok-nano Estimated <1% > 10g Minutes Monthly/

Yearly

Indoor

Adults Inhalation

(Dermal)

Textil Prot

NANO

500 -1000 ml Impregnates

textile and leather surface


Used as spray

Silver http://nano.taenk.dk/da/produ

cts/textil-prot-nano-silver

http://en.tenzi.pl/artyku%C5%

82y/assortment/nanotechnology/textil-prot-nano

Estimated

<1% >10g Minutes Monthly/

Yearly Indoor/Outdoor

Adults Inhalation

(Dermal)

http://nano.taenk.dk/da/products/topefektr-kok-nano

http://nano.taenk.dk/da/products/topefektr-kok-nano

http://en.tenzi.pl/artyku%C5%82y/assortment/nanotechnology/top-efekt-kok-nano



http://nano.taenk.dk/da/products/textil-prot-nano-silver

http://nano.taenk.dk/da/products/textil-prot-nano-silver

http://en.tenzi.pl/artyku%C5%82y/assortment/nanotechnology/textil-prot-nano



59


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

FIBRIL nanotubes

Plastic compounds that are molded into automotive

parts

USA

Specified

Suspended in solid Carbon nanotubes

10 nm and length over 10 microns

Dermal http://www.nanotechproject.org/cpi/products/fibril-nanotubes/

http://hyperioncatalysis.com/a

utomotive2.htm

Estimated Solid matrix <1/1-10% <1/1-10g Minutes/H

ours

Monthly/Yearly

Indoor/Outdoor

Adults

Dermal/inhalation? Only

exposure from debris during

handling/ repair (is released during tear and

wear)

Nanoauto

Cockpit cleaner

100, 250 and 600

ml

Antimicrobial protection for

Specified

Silver http://www.nanotechproject.or

g/cpi/products/nanoauto-cockpit-cleaner/

http://nanoauto.eu/index.php?option=com_content&task=vie

w&id=108&Itemid=59


Already mixed and

used as spray

<1/1-10% 1-10g Minutes Monthly/Yearly

Indoor

Adults Inhalation/derm

al

http://www.nanotechproject.org/cpi/products/fibril-nanotubes/



http://hyperioncatalysis.com/automotive2.htm

http://hyperioncatalysis.com/automotive2.htm

http://www.nanotechproject.org/cpi/products/nanoauto-cockpit-cleaner/



http://nanoauto.eu/index.php?option=com_content&task=view&id=108&Itemid=59



60


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

plastic parts of car interior

Poland

S.drive Tire

Car tires

USA

Specified

Suspended in solid Silicon

dioxide(20 nm spheres)

Dermal http://www.nanotechproject.or

g/cpi/products/s.drive-tire/ http://www.streetdirectory.co

m/travel_guide/49548/car_parts/how_yokohama_tires_have_

made_use_of_innovative_nano_technology.html

Estimated Solid matrix Consumers

changing tires with hands

1-10% 1g/1-10g Hours Yearly Outdoor

Adults/car owners

Exposure related to release.

Highest for consumers

changing their own tyres.

Sonax xtreme Polish & wax 3

250-500 ml

Specified

Aluminium oxide

http://www.nanotechproject.org/cpi/products/sonax-xtreme-

polish-wax-3-nanopro/

http://www.nanotechproject.org/cpi/products/s.drive-tire/

http://www.nanotechproject.org/cpi/products/s.drive-tire/

http://www.streetdirectory.com/travel_guide/49548/car_parts/how_yokohama_tires_have_made_use_of_innovative_nano_technology.html





http://www.nanotechproject.org/cpi/products/sonax-xtreme-polish-wax-3-nanopro/



61


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Polish/coating for cars

Germany

Estimated Viscous solution (polish/wax)

Apply with sponge and microfiber cloth

<1/1-10% > 10 g Hours Monthly/Yearly Outdoor

Adults/car owners

Dermal (oral, inhalation)

http://www.sonax.com/Products/Xtreme-Series/%28search%29/1/%28s

o%29/1/%28node%29/12780/202100-SONAX-XTREME-

Polish-Wax-3

2C Auto Sealant

PRO

Apprx.100 ml

Sealant/coating and protection for cars

Specified

Liquid

Surface bound

particles after use

Energetically mix about 1 minute before use. Spray

or apply manually with sponge.

Silicon

dioxide

Yearly http://www.nanotechproject.or

g/cpi/products/auto-paint-gel-coat-treatments-2c-auto-

sealant-pro-fast-seal-2c-marine-sealant-pro/

http://nanosafeguard.com/auto_paint_gel_coat.html

Estimated <1/1-10% 1-10g/>10g Minutes/Hours

Yearly

Outdoor

Adults/car owners

Dermal /Inhalation

SI Extreme;

Versiegelung 20 ml

Specified

Nano-

ceramics



duktsuche/?tx_mspproductdb_

http://www.sonax.com/Products/Xtreme-Series/%28search%29/1/%28so%29/1/%28node%29/12780/202100-SONAX-XTREME-Polish-Wax-3






http://www.nanotechproject.org/cpi/products/auto-paint-gel-coat-treatments-2c-auto-sealant-pro-fast-seal-2c-marine-sealant-pro/







http://www.bund.net/nc/themen_und_projekte/nanotechnologie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=114&kategorie=5&attribute=10&msb_product_submit=suchen




62


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Maintenance for cars

Estimated Suspended in liquid <1/1-10% 1-10g/>10g Minutes/Hours

Monthly/Yearly Outdoor

Adults Dermal (oral, inhalation)

pi1%5Bitem%5D=114&kategorie=5&attribute=10&msb_product_submit=suchen

http://www.amazon.de/EXTRE

ME-Scheibenversiegelung-Car-fr%C3%BCher-

SichtKlar/dp/B001HIY3U2

Empox® 61

FreieSicht

Window coating for cars

Specified Silicium

dioxid



duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=959&kategorie=5&attribute=15&msb_produ

ct_submit=suchen

http://www.merkelcoatings.com/nano-spezial.htm

Estimated Suspended in liquid <1/1-10% 1-10g/>10g

Minutes/hours

Yearly Outdoor

Adults Dermal (inhalation)

Permanon car supershine

Bottle or large can

Specified Liquid

Apply as spray or suspended in liquid

Silicium dioxide

2-5% http://www.bund.net/nc/themen_und_projekte/nanotechnolo





http://www.amazon.de/EXTREME-Scheibenversiegelung-Car-fr%C3%BCher-SichtKlar/dp/B001HIY3U2

















63


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Permanon car shampoo

Estimated Apply with a sponge or spray

1-10g/>10g Minutes/hours

Monthly/Yearly Outdoor

Adults Dermal Inhalation

pi1%5Bitem%5D=860&kategorie=5&attribute=15&msb_product_submit=suchen

http://www.yacht-

pflege.com/kfz.html

BORPover®

Coating for the

motor protection unit

Specified Nano

Boron



duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=106&kategor

ie=5&attribute=16&msb_product_submit=suchen

http://www.nnt-nano.com/index.php?id=borpo

wer


Apply as spray

<1/1-10% <1g/1-10g Minutes/hours

Yearly

Outdoor

Adults Dermal

(Inhalation)

Odor OFF NANO

1L og 0,5L

Odor remover inside car

Specified Liquid

Energetically mix

about 1 minute before use and

apply as spray

Titanium

dioxide or silver

http://en.tenzi.pl/artyku%C5%

82y/assortment/nanotechnology/odor-off-nano




http://www.yacht-pflege.com/kfz.html

http://www.yacht-pflege.com/kfz.html








http://www.nnt-nano.com/index.php?id=borpower



http://en.tenzi.pl/artyku%C5%82y/assortment/nanotechnology/odor-off-nano



64


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5

Volume per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Estimated

<1/1-10% >10g Minutes/ hours

Monthly/Yearly Indoor

Adults Inhalation/ dermal

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in the maintenance products:

Silver: In anti-reflecting cleaning agent, textile impregnation, antimicrobial protection for plastic parts of car interior, odor remover inside car

Silicium dioxide: In window coating for cars, car shampoo

Silicon dioxide: Car tires, sealant/coating and protection for cars

Aluminium oxide: In polish/coating for cars

Nano boron: Coating for the motor protection unit

Nano ceramics: In maintenance for cars

Titanium dioxide: In odor remover inside car

Carbon nanotubes: In plastic compounds that are molded into automotive parts

65

For the far majority of the products the primary exposure route is the dermal route, whereas secondary routes are in relation to oral or inhalational exposure. However, for

spray/pump products such as textile impregnation and products where they require mixing before use, such as cockpit cleaner, the primary exposure route is inhalation. The

latter are also assumed to cause the highest consumer exposures.

For maintenance products the exposure is unintended, except for the silver products where the antibacterial effect is applied. The consumers exposed will mainly be adults and

car owners, who use the maintenance products. The frequency of use will mainly be monthly or yearly for the maintenance products and the duration of the event will be

minutes or hours depending on the application.

66

Textiles 4.6

Textiles (not intended, indirect exposure by use)

1


2

Formulation/ matrix


Application

method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/ outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Danish Nanodatabase contains reference to 3 textile products belonging to Home and furnishing category. The Health and fitness category contains 431 products, herein several textiles. The nanomaterials are not known for most of the products, the most commonly identified nanomaterial is silver. The clothing category contains 74 products. The nanomaterials are not known for most of the products, the most commonly identified nanomaterial is silver. One product is included as it also contains Titanium.

The BUND database contains about 130 products in the textile category. The nanomaterials are not identified in most of the products, silver is the most commonly used nanomaterial in the remaining products. No products have been selected for this table as products are considered covered by the Danish nanodatabase. The ANEC-BEUC inventory does not contain a separate textile category, textiles are presented under Health and fitness. The products are however similar to the products in the Danish nanodatabase.

The Nanotech project database contains 194 products in the clothing category, most are already covered by the products selected above, and when nanomaterial is identified, mainly

silver and titaniumdioxde is used. However in one product, Carbon nanotubes are reported, as used in a bullet proof safety west; Unisex centurion tactical vest, however the human

exposure is expected to be insignificant, therefore not included in the table.

Product category/Products: Textiles

67


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Night Therapy Mattress Toppers with

Nano Silver

Specified silver http://nanodb.dk/da/products/night-therapy-mattress-

toppers-with-nano-silver

product could not be found at;

http://www.daysmobility.co.uk/Night_Therapy_Mattress_Topp

ers_with_Nano_Silver.htm

Estimated Surface bound <1% <1g Hours Daily

Indoor

All ages Dermal

PowerImpregna

tion+care Textile impregnation

Specified Liquid/Aerosol NI http://shop.pinbax.com/index.

asp?selection=detailed&uid=33304&itemtitle=PowerImpregnation

Estimated Applied by spraying 1-10 <1g/1-10g Minutes Monthly All ages Inhalation, Dermal

Nano-Flow Pillow

Specified Surface bound NI http://www.ihealthproducts.com/scripts/prodView.asp?idprod

uct=134 The product has changed name

to Nano-Sphere Pillow - Regular

Estimated <1% < 1g Days daily

All ages Dermal (oral

small children)

http://nanodb.dk/da/products/night-therapy-mattress-toppers-with-nano-silver



http://shop.pinbax.com/index.asp?selection=detailed&uid=33304&itemtitle=PowerImpregnation




http://www.ihealthproducts.com/scripts/prodView.asp?idproduct=134



68


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

ASAT Elite Basic Layer Crew

Specified Surface bound Silver http://www.abbeyarchery.com.au/p/ASEBLC3XL/ASAT+Elite+Basic+Layer+Crew.html

Estimated <1 <1g Hours Daily Sportsmen/Hobby

Dermal

Antibacterial Socks

Specified Surface bound Silver http://www.agactive.com/socks.html

Estimated <1% <1g Hours Daily All ages Dermal

GreenYarn Eco-

Fabric Polo Shirt

Specified Surface bound Bamboo

charcoal

http://www.greenyarn.com/tec

hnology.htm

Estimated <1% <1g Hours Daily All ages Dermal

SPORT COMPRESSION SOCK - Black

Specified Surface bound Polytetrafluoroethylene

>10% http://nanodb.dk/da/products/sport-compression-sock-black

http://nanodb.dk/da/material/teflon



http://nanodb.dk/da/products/sport-compression-sock-black

http://nanodb.dk/da/products/sport-compression-sock-black

69


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Estimated <1g Hours Daily Adults/sportsmen

Dermal

Relaxed Plain Front Pant – Nanocare

Specified NI http://nanodb.dk/products/relaxed-plain-front-pant-nanocare

Estimated Surface bound <1g Hours Daily Adults Dermal

CW-X Conditioning

Wear Sports clothes

Specified Surface bound Silver Titanium

dioxide

Sportsmen http://nanodb.dk/products/cw-x-conditioning-wear

Estimated <1g Hours Daily Dermal

NI: not indicated

http://nanodb.dk/products/relaxed-plain-front-pant-nanocare

http://nanodb.dk/products/relaxed-plain-front-pant-nanocare

http://nanodb.dk/products/cw-x-conditioning-wear

http://nanodb.dk/products/cw-x-conditioning-wear

70

Overall findings

The most frequently used nanomaterial in textiles seems to be silver, due to the antimicrobial effect. A few products contain other nanomaterials such as bamboo charcoal,

Teflon and titanium dioxide, the latter as UV protection. For exposure to surface bound NMs it is difficult to express volume of exposure of product for use in a meaningful

manner and thus a value of <1 g is used in this table. The principal exposure route is the dermal route, however only low exposure levels may be assumed. Oral exposure may be

relevant for small children sucking the textile.

71

Construction materials 4.7

Construction materials (Indirect exposure)

1


2

Formulation/ matrix


3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


route)

10

Comments/web-links

Application method


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/

Indoor/outdoor

All ages/Children/



The Nanotechproject database contains 7 products belonging to the category ‘Home and garden – construction materials’. The products mainly contain silver, titanium dioxide and silicon dioxide. The Danish Nanodatabase contains 14 products in the category ‘construction materials’. The nanomaterial content is unknown for most of the products, but the identified nanomaterials are silver and phosphate. The BUND database contains 24 products in the category ‘baumaterialien’. The nanomaterial content is unknown for most of the products, but the identified nanomaterials are carbon nanotubes and silicium dioxide. The ANEC-BEUC inventory does not contain any of these products and thus does not contribute with information to the table. Other construction materials are found on the websites of companies.

Product category/Products: Construction materials

72


1


2

Formulation/ matrix


Powder/Solid

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Application method


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/

Indoor/outdoor

All ages/Children/



Pilkington ActivTM Self

Cleaning Glass,

Self-cleaning glass

UK

Specified Titanium dioxide


g/cpi/products/pilkington-

activtm-self-cleaning-glass-1/

http://www.pilkington.com/ Estimated Solid

Coating

1-10% <<1g Seconds/Minutes

(Consumer touches

glass)

Daily/Weekly/Monthly

Outdoor

All ages Dermal

Zement

Dyckerhoff Nanodur,

Cement

Specified Silicium

dioxide



duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=862&kategorie=1&unterkat=16&msb_produ

ct_submit=suchen

http://www.dyckerhoff.de/online/Home/Zement/Premium-

Zement/NANODUR.html


until end product where the cement

gets solid (suspended in solid

for the consumer)

1-10% >>10g Hours Daily/Weekly/Y

early

Outdoor/indoor

Mainly adults

consumers

Dermal,

inhalation

Floor, gap and

concrete sealer, Sealer


Used as spray

Unknow

n


floor-gap-and-concrete-sealer

http://www.nanonordisk.com/?

id=14598&product_item_id=10735&product_subcat_id=931

Estimated 1-10% 1-10g Minutes/Hours

Monthly/Weekly/yearly

Outdoor/indoor

Mainly adults Dermal, inhalation

http://www.nanotechproject.org/cpi/products/pilkington-activtm-self-cleaning-glass-1/



http://www.pilkington.com/








http://www.dyckerhoff.de/online/Home/Zement/Premium-Zement/NANODUR.html



http://nanodb.dk/da/products/floor-gap-and-concrete-sealer

http://nanodb.dk/da/products/floor-gap-and-concrete-sealer

http://www.nanonordisk.com/?id=14598&product_item_id=10735&product_subcat_id=931



73


1


2

Formulation/ matrix


Powder/Solid

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Application method


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/

Indoor/outdoor

All ages/Children/



Alphasoil-06 Bodenstabilisati

on, Soil stabilization

Specified Suspended in liquid Unknown

http://nanodb.dk/da/products/alphasoil-06-

bodenstabilisation-0 http://www.nanodaten.de/uplo

ads/data_sheets/6638a634e84cd29491e9e448395632cd.pdf

Estimated Application:

Stabilization and improvement of soil

in relation to construction work

etc.

1-10% >10g Minutes Monthly/yearly Adults Dermal

(Inhalation)

Nano Stone,

Hydrophobic

treatment 100-1000ml

Specified Suspended in liquid Silicon

dioxide

Dermal,

Inhalation, Oral


g/cpi/products/nano-steen-nano-stone/

http://www.nanotech-solutions.nl/nanoshop/nanocoa

ting-steen

Estimated Coating for protection of stones

and tiles

1-10% >10g Minutes Monthly/yearly Adults

EMACO®

NanoCrete R3 Reparaturmörtel

Mortar

25 kilo

Specified The nanostructures

are generated by adding

nanoparticles.

Unknow

n



duktsuche/?tx_mspproductdb_pi1%5Bitem%5D=1022&kateg

orie=1&unterkat=16&msb_product_submit=suchen

http://www.emaco-nanocrete.com/uploads/media/

NanoCrete_6-S_deutsch.pdf

Estimated 1-10% >>10g Minutes/H

ours

Monthly/yearly

Adults Dermal

(Inhalation)

http://nanodb.dk/da/products/alphasoil-06-bodenstabilisation-0



http://www.nanodaten.de/uploads/data_sheets/6638a634e84cd29491e9e448395632cd.pdf



http://www.nanotechproject.org/cpi/products/nano-steen-nano-stone/



http://www.nanotech-solutions.nl/nanoshop/nanocoating-steen










http://www.emaco-nanocrete.com/uploads/media/NanoCrete_6-S_deutsch.pdf



74


1


2

Formulation/ matrix


Powder/Solid

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Application method


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/

Indoor/outdoor

All ages/Children/



Bioni Perform,

Facade protection

10 L

Specified Silver http://www.bioni.de/index.php?page=produktprogramm_fass

adenbeschichtung&lang=de


Mixing before use

<1% >>10g Hours Yearly

Outdoor

Adults Dermal,

Inhalation

ECO-ACTIV,

Layer for roofs and pavements


http://www.icopal.de/

Estimated Suspended in solid 1-10% >>10g Hours Yearly

Outdoor

Adults Dermal

ThermoSan-

Fassadenputz NQG R und K,

Surface pus for buildings

20 kg

Specified Silicium

dioxide

(nano-quartz-

gitter)

http://www.caparol.de/produkt

e/putze-spachtelmassen/aussenputze/nqg-putze/thermosan-

fassadenputz-nqg.html

Estimated Suspended in liquid 1-10% >>10g Hours Yearly

Outdoor

Adults Dermal (Inhalation)

http://www.bioni.de/index.php?page=produktprogramm_fassadenbeschichtung&lang=de



http://www.icopal.de/

http://www.caparol.de/produkte/putze-spachtelmassen/aussenputze/nqg-putze/thermosan-fassadenputz-nqg.html





75


1


2

Formulation/ matrix


Powder/Solid

3

NM ID

4

Conc. of NM in

product

5

Volume of product

per use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Application method


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/

Indoor/outdoor

All ages/Children/



S-Pfanne mit ClimaLife,

Tile


http://www.nelskamp.de/no_cache/menue-

links/verarbeiter/produkte/dachsteine/s-pfanne-climalife.html?sword_list%5B%

5D=Pfanne

Estimated Suspended in solid 1-10% >> 10g Hours Yearly

Outdoor

Adults (Dermal)

Diamon-Fusion

Surface protection

Specified Suspended in liquid Unknow

n


diamon-fusion

Estimated 1-10% 1-10g Minutes Monthly/yearly Adults Dermal (Inhalation)

http://www.nelskamp.de/no_cache/menue-links/verarbeiter/produkte/dachsteine/s-pfanne-climalife.html?sword_list%5B%5D=Pfanne






http://nanodb.dk/da/products/diamon-fusion

http://nanodb.dk/da/products/diamon-fusion

76

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in the construction materials:

Silver: In facade protection

Silicium dioxide: In plaster, cement

Silicon dioxide: In coating for stone and tile protection

Titanium dioxide: In tiles, layer for roofs and pavements, self-cleaning glass

Unknown nanomaterials: In surface protection, mortar, sealing and soil stabilization

For all of the products the primary exposure route is the dermal route (for cement also the inhalational route), whereas secondary routes are for the majority of the products in

relation to inhalational and oral. Most of the nanomaterial content is unknown.

For construction materials, the exposure is unintended and the consumer will only be exposed to part of the volume of the product. The duration of the exposure depend on

whether the product is a protection spray, which is quickly sprayed on the surface or whether it is construction material requiring handling such as tile. Consumer exposure

must be assumed to be much higher for nanomaterials in powders and liquids than for nanomaterials in solid matrices.

77

Medical devices 4.8

Medical devices (Indirect exposure)

1


2



Application

method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Nanotechproject database contains 161 personal care products with specified nano materials. The products are not relevant for the medical devices.

The Danish Nanodatabase only contains ‘personal care’ products, where only wound dressing is relevant for the medical devices category.

The BUND database contains 12 products in the category ‘Gesundheit’. The nanomaterials are not known for 5 of the products, the identified materials are silver, titanium dioxide and calcium.

The ANEC-BEUC inventory only contains cosmetics and personal care products and no medical devices. Thus, the inventory therefore does not contribute with any additional information to the table.

The DRAFT report from Teknologisk Institut on ‘Supplementary survey of products on the Danish market containing nanomaterials’ contains several products on medical devices.

Product category/Products: Medical devices

Dental filling

Specified Zirconia,

Silicate

Zirconia

(1%) Silicate (10-

20%)

DRAFT report from Teknologisk

Institut

Estimated Solid/paste

Added by Dentist with dentist tools

1-10g Application:

Minutes/hours

Yearly

Indoor

All ages, except small children

Oral

78


1


2




method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

After

applications: 24-7

Acticoat Wound

dressing,

Wound dressing

Specified Surface bound Silver http://nanodb.dk/da/products/

acticoat-wound-dressings http://www.smith-

nephew.com/us/professional/products/featured-

products/acticoat/

Estimated Solid

Applied on skin to kill bacteria to

assist healing after burns

<1% 1g Minutes/Hours/Whol

e day

Yearly

Indoor

All ages Dermal

Hy ProtectTM,

Plasmabeschicht

ung für

Oberflächen von

medizinischen

Implantaten und

Instrumenten

Coating for

Specified Silver

<200 nm coating


gie/nanoproduktdatenbank/produktsuche/?tx_mspproductdb_pi1%5Bitem%5D=21&kategori

e=11&unterkat=0&msb_product_submit=suchen

http://www.bio-

gate.de/page.asp?lang=d&main=1&did=514&sec=1&third=1


Coating

<1% 1-10g (Application:

Minutes/hours)

The

consumer exposure

is after

Yearly

Indoor

All ages, mostly elderly

(Dermal)

“Systemic”

http://nanodb.dk/da/products/acticoat-wound-dressings

http://nanodb.dk/da/products/acticoat-wound-dressings

http://www.smith-nephew.com/us/professional/products/featured-products/acticoat/











http://www.bio-gate.de/page.asp?lang=d&main=1&did=514&sec=1&third=1



79


1


2




method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

implants impalnatati

on:: 24-7

Ostomy bags

Specified Copper <0,0001% DRAFT report from Teknologisk Institut

Estimated Solid

Applied on stomach skin

>10g Hours/whole day

Daily

Indoor

All ages, but more elderly

Dermal

80

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in the medical devices:

Silver: In wound dressing, coating for implants

Copper: In ostomy bags

Silicate: In dental filling

Zirconia: In dental filling

For the ostomy bags and would dressing the primary exposure route is the dermal route. For dental filling (silicate or zirconia) the primary route is the oral route. For coating

implants, the consumer exposure is “systemic”. The exposure conditions generally applies for all ages. However ostomy bags and implants will be used more often by elderly

people.

Except for dental fillings, the nanomaterials are added to enhance the antibacterial effect and thus the exposure is intended for the medical devices. For coating of implants and

dental filling the duration of the event is divided into ‘application’ and ‘after application’ since the dental filling or implants will be permanent embedded into the body.

However for the dentist or doctor the dermal exposure will be short term during application and during the coating of implants, only professionals will be exposed.

81

Air-cleaner sprays 4.9

Air-cleaner sprays (not intended, indirect exposure by use)

1


2

Formulation/ matrix


Powder/Solid

Application method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/ Indoor/

outdoor

All ages/Children/



The Nanotechproject database contains 96 products with specified nanomaterials belonging to category Home and garden ‘cleaning’ subcategory.

The Danish Nanodatabase contains reference to 129 products containing nanomaterials in the ‘Cleaning’ subcategory under ‘Home and garden’.

The ANEC-BEUC inventory contains the subcategory ‘Home & garden’. The products are already identified in the two databases referred to above, and thus the inventory therefore does not provide additional

information to the table.

Product category/Products: Home and garden

Odor Eliminator

4-12 Oz

(ca. 120-350 g) pump spray to

sprayed onto surface to prevent

bio-film formation and on treated

surfaces.

Specified Aerosol http://www.nanotechproject.or

g/cpi/products/g-scenttm-odor-eliminator/


g-scent-odor-eliminator

http://www.getg.com/G-CLEAN/odor_eliminator.php

Estimated sprayed into air Declared: Plant Oil

Fatty Acids

Plant Oils Vegetable Extracts

1-10%; > 10%

> 10g Minutes weekly

Indoor

Adults Dermal and inhalation

http://www.nanotechproject.org/cpi/products/g-scenttm-odor-eliminator/



http://nanodb.dk/da/products/g-scent-odor-eliminator

http://nanodb.dk/da/products/g-scent-odor-eliminator



82


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

A/C & indoor climate purifier

150 ml spray can for one-term use

by continuous release for air-

purification in A/C, cars and indoor

environments

Specified Aerosol 5 min release

followed by working

period ranging

from 0 to half a day

http://nanolotus.dk/forside/alle-produkter/auto-cleaner-klima-

rens/

Estimated sprayed into air Silver or similar

NM with biocidal activity

<1% 150g Rare (maybe between

monthly and yearly)

Indoor

Adults Dermal and inhalation

Quan Zhou Hu Zheng Nano

Technology Co., Ltd.

AC liquid spraying filter for

antibacterial and deodorant

Specified Aerosol Silver http://www.nanotechproject.or

g/cpi/products/quan-zhou-hu-zheng-nano-technology-co-ltd-

r-ac-filter-liquid-antibacterial-and-deodorant-spray/ http://www.china-

nano.cn/product/detail_8552.js

Estimated Apparently sprayed into air (unclear

product and use description)

<1% 1 - 10g Minutes to Whole

Days

daily Indoor

All ages Dermal and inhalation

http://nanolotus.dk/forside/alle-produkter/auto-cleaner-klima-rens/



http://www.nanotechproject.org/cpi/products/quan-zhou-hu-zheng-nano-technology-co-ltd-r-ac-filter-liquid-antibacterial-and-deodorant-spray/





83


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

treatment p

Oregon

Scientific Nano-Technology

Room Air Sanitizer

Nano-filtration

system

Specified Solid

http://www.nanotechproject.org/cpi/products/oregon-

scientific-r-nano-technology-room-air-sanitizer/

http://www.oregonscientific.com/us/en/Nano-Technology-

Room-Air-Sanitizer-WS907-P

Estimated Air-stream through filter

Silver <1%/ NA Hours to Daily

Daily for cleaned air; Every 3rd year

for filter replacement

Indoor

All ages Dermal (main exposure if filters are

changed manually)

Home Nano Tio2

Air Purification

4 stage catalytic home Nano TiO2 Air-purification

spray

Specified Aerosol Titanium

dioxide / Activated

Carbon

http://www.nanotechproject.org/cpi/products/home-nano-

tio2-air-purification/ http://www.alibaba.com/produ

ct-free/11848761/Home_ Nano_Tio2_Air_Purification.ht

ml

Estimated Sprayed into air <1%/1-10% < 10g Minutes weekly to yearly

Indoor

All ages Dermal and inhalation

http://www.nanotechproject.org/cpi/products/oregon-scientific-r-nano-technology-room-air-sanitizer/




http://www.oregonscientific.com/us/en/Nano-Technology-Room-Air-Sanitizer-WS907-P



http://www.nanotechproject.org/cpi/products/home-nano-tio2-air-purification/



http://www.alibaba.com/product-free/11848761/Home_%20Nano_Tio2_Air_Purification.html




84


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/

outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Air Sanitizer, Nano Silver Photocatalyst

100-1000 ml or

1.5 to 25 kg tank

Air-purification spray for indoor

office and households, as well as goods etc.

Specified Aerosol Silver dermal and inhalation

http://www.nanotechproject.org/cpi/products/air-sanitizer-nano-silver-photocatalyst/

http://web.archive.org/web/20

061004150907/http://www.aircleanermedium.com/Nano-

Silver-Photocatalyst.html

Estimated Sprayed into air or onto wetted

product

<1% from 1g to > 10g

Minutes weekly to yearly

Indoor

Adults

Overall findings In the area of air-cleaners and sprays, we find logically two principal technical types of nano-enabled products; namely solid state and spray-based air-cleaners. The active ingredients were either silver (Ag), TiO2, activated carbon or possibly plant oil fatty acids, plant oils vegetable extracts. Solid-state air-cleaning may be assisted by UV-light or ozone treatment. In two cases, other air-cleaning agents were reported. The most important exposure route were inhalation and dermal for sprays and dermal exposure for handling solid state air-cleaning systems (filters, filter changes). The typical volume used during use of the products is in the order of 1-10 g. In a few cases the actual exposure and exposure duration could be hours or longer.




85

Fuel and lubrication oil additive 4.10

Fuel and lubrication oil additive (Indirect exposure)

1


2

Formulation/ matrix


Application

method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Nanotechproject database contains 16 products with specified nano materials belonging to the category ‘Automotive-lubricants’ and ‘Automotive-maintenance and accessories’. The products mainly contain cerium oxide, gold and tungsten disulphide. The Danish Nanodatabase does not contain any of these products and thus does not contribute with information to the table. The BUND database does not contain any products in this category where the nanomaterial is known and thus does not contribute with information to the table. The ANEC-BEUC inventory does not contain any of these products and thus does not contribute with information to the table.

Product category/Products: Fuel and lubrication oil additive

EnviroxTM Fuel Borne Catalyst,

Diesel fuel additive

Specified Suspended in liquid Cerium oxide

5-10 ppm of cerium oxide in the fuel

Dermal, fuelling (Inhalation,

combustion product)


g/cpi/products/enviroxtm-fuel-

borne-catalyst/

http://www.nanotechproject.org/cpi/products/enviroxtm-fuel-borne-catalyst/



86


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

(catalyst)

UK

Estimated >10g Minutes/

Daily/Weekly

Outdoor

Mainly persons

>18 years

http://web.archive.org/web/20

070220222935/http://www.oxonica.com/energy/energy_envirox_intro.php

Nanostellar Catalyst

Materials,

Catalyst

Specified Gold http://www.nanotechproject.or

g/cpi/products/nanostellar-

catalyst-materials/

http://californiananoeconomy.org/content/nanostellar-0


Added in fuel

1-10% <10g Minutes Daily/Weekly

Outdoor

Mainly persons >18 years

Dermal, fuelling

(Inhalation, combustion

product)

NanoLub© RC-X Engine,

Lubricant for

engine oil

Specified Suspended in liquid Tungsten

disulfide

Nanofilms 30-

70nm

2-7%

Dermal, http://www.nanotechproject.org/cpi/products/nanolub-c-rc-x-

engine/

http://www.apnano.com/products/lubricants/

Estimated >10g Minutes Monthly/yearly

Indoor

(Garage)/Outdoor

Mainly persons

>18 years

http://web.archive.org/web/20070220222935/http:/www.oxonica.com/energy/energy_envirox_intro.php




http://www.nanotechproject.org/cpi/products/nanostellar-catalyst-materials/





http://www.nanotechproject.org/cpi/products/nanolub-c-rc-x-engine/





87


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Nano Engine Oil,

Engine oil (Taiwan)

Specified Suspended in liquid Gold

90nm

50 millions

Nano-bearing per sq. mm.


g/cpi/products/nano-engine-oil/

http://web.archive.org/web/20060822220459/http://www.ss

nano.net/ehtml/detail1.php?productid=78

Estimated >10g Minutes Monthly/Yearly

Indoor (Garage)/Outd

oor

All ages Dermal,

http://www.nanotechproject.org/cpi/products/nano-engine-oil/



http://web.archive.org/web/20060822220459/http:/www.ssnano.net/ehtml/detail1.php?productid=78




88

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in fuel and lubrication oil additive products:

Gold: in engine oil and as fuel catalyst

Cerium oxide: as diesel catalyst

Tungsten disulfide: as lubricant for engine oil

For all of the products the primary exposure route is the dermal route during fuelling/addition of oil. The product can be added either indoor in a garage or outside on a service

station.

The primary route related to combustion of the diesel would be the inhalational route. The latter is relevant for the general population (all ages) and not just the consumers

fuelling the vehicles.

The exposure to the products/combustion products is any case unintended.

Fuel is added regularly and the frequency of the exposure will be daily or weekly depending on the driving habits. Engine oil is added less frequently and the frequency of the

exposure is therefore monthly or yearly. Exposure to traffic exhaust is very frequent/almost continuous and this is covered in another section of this project.

89

Electronic devices 4.11

Electronic devices such as computers and smaller electronic devices (does not include appliance such as hair straighteners, washing machines etc.) (Indirect exposure)

1


type

2

Formulation/

matrix Liquid/Aerosol/ Crème/Paste/

Powder/Solid

3

NM

ID

4

Conc. of

NM in product

5

Volume

per use

6

Duration

per event

7

Use

frequency and site of use

8

Consumer

group

9

Primary

exposure route(s)/ (secondary

exposure route)

10

Comments/web-links

Application

method

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

The Nanotechproject database contains 40 products with specified nano materials belonging to the category ‘electronics and computers’. Most of the products contain NMs in solid matrices. It does not contribute with new exposure scenarios compared to the Danish Nanodatabase. The products mainly contain silicon, silicon dioxide, copper, carbon nanotubes, silver, titanium dioxide and cobalt. The Danish Nanodatabase contains reference to 62 products belonging to the ‘electronics and computers’ category. The nanomaterials are not known for most of the products, the identified materials are silver, silicium, lithium and titandioxid. The BUND database contains 12 electronics products. The nanomaterials are not known for most of the products, the identified materials are siliciumdioxide, silver and gold. The ANEC-BEUC inventory contains only one product in the subcategory electronics and this is categorized under the crosscutting category. The product contains nano silver and is already identified in the Danish database. Thus, the inventory therefore does not contribute with any additional information to the table.

Product category/Products: Electronic devices

90


1


type

2

Formulation/



3

NM

ID

4

Conc. of

NM in product

5

Volume

per use

6

Duration

per event

7

Use


use

8

Consumer

group

9

Primary

exposure route(s)/

(secondary exposure route)

10

Comments/web-links

Application

method

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Keyboard ‘Tasto’

waterproof, Waterproof

keyboard with antibacterial

properties

Specified Surface bound Silver Doctor’s offices,

hospitals, nursing homes, production

facilities, schools, hotels

and for demanding

consumers.


cts/keyboard-tasto-waterproof

http://www.yapii.de/VCM-

Tastatur-Tasto-1-wassserdicht-Weltneuheit-Preisvergleich-

159382.html

Estimated Solid <1% <<1g Hours Daily

Indoor

Dermal

Intel Pentium D

Processor

Specified Structured film Silicon http://nano.taenk.dk/da/produ

cts/intel-pentium-d-processor

http://www.amazon.com/Intel-

Pentium-3-4Ghz-Fsb800Mhz-Lga775/dp/B000IEO964

Estimated Solid

Silicon

dioxide

1-10% <1g Minutes/H

ours (but normally no contact

with processor)

Monthly/

Yearly (but normally no contact with

processor)

Indoor

Dermal (only in

case of consumer intervention in

the PC)

Product category/Products: Maintenance products for electronic devices

http://nano.taenk.dk/da/products/keyboard-tasto-waterproof

http://nano.taenk.dk/da/products/keyboard-tasto-waterproof

http://www.yapii.de/VCM-Tastatur-Tasto-1-wassserdicht-Weltneuheit-Preisvergleich-159382.html




http://nano.taenk.dk/da/products/intel-pentium-d-processor

http://nano.taenk.dk/da/products/intel-pentium-d-processor

http://www.amazon.com/Intel-Pentium-3-4Ghz-Fsb800Mhz-Lga775/dp/B000IEO964



91


1


type

2

Formulation/



3

NM

ID

4

Conc. of

NM in product

5

Volume

per use

6

Duration

per event

7

Use


use

8

Consumer

group

9

Primary

exposure route(s)/


10

Comments/web-links

Application

method

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Furutech Gold-

Silver Nano Liquid Kontaktvergröß-

erer

Appx, 10-20 ml

Maintenance and

protection coating

for metal surfaces

Germany

Specified Liquid

Gold and

silver 8nm


en_und_projekte/nanotechnolo

gie/nanoproduktdatenbank/pro

duktsuche/?tx_mspproductdb_

pi1%5Bitem%5D=444&kategor

ie=9&unterkat=0&msb_produc

t_submit=suchen

http://www.dienadel.de/Furute

ch+Gold-Silver+Nano+Liquid+Kontaktv

ergroesserer.htm

http://www.furutech.com/2013/01/18/1647/

Estimated Assumed to be applied by

consumer with a small brush or in

droplets

<1% <<1g Minutes Monthly/Yearly

Indoor

Adults Dermal

Ice Dragon Cooling

nanofluid

Specified Suspended in liquid Zinc Oxide

http://www.nanotechproject.org/cpi/products/ice-dragon-

cooling-nanofluid/ http://www.frozencpu.com/pro








http://www.dienadel.de/Furutech+Gold-Silver+Nano+Liquid+Kontaktvergroesserer.htm






http://www.nanotechproject.org/cpi/products/ice-dragon-cooling-nanofluid/



http://www.frozencpu.com/products/15033/ex-liq-203/Ice_Dragon_Cooling_Nanofluid_Coolant_White_Color_-_32oz.html

92


1


type

2

Formulation/



3

NM

ID

4

Conc. of

NM in product

5

Volume

per use

6

Duration

per event

7

Use


use

8

Consumer

group

9

Primary

exposure route(s)/


10

Comments/web-links

Application

method

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

32oz

Electronic cooling

liquid

USA

Estimated Assumed to be

applied by consumer from bottle

1-10% 1-10g Minutes Monthly/Yearly

Indoor

Adults Dermal

(Oral, inhalation)

ducts/15033/ex-liq-

203/Ice_Dragon_Cooling_Nanofluid_Coolant_White_Color_-_32oz.html





93

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in the electronic devices:

Silver: in computer keyboard and protection coating for metal

Gold: in protection coating for metal

Silicon dioxide: In processor

Zincoxide: in cooling liquid

It is also known that Carbon nanotubes are used in electronics (e.g. in semi-conductors and other solid matrices)

For all of the products, the primary exposure route is the dermal route, whereas secondary routes are in relation to oral and inhalational exposure.

For the cooling liquid, to be applied from the bottle, actual consumer exposure is expected. For the keyboard where the nanomaterials are added for antibacterial purposes,

exposure may also take place. The frequency of the exposure is expected to be monthly or yearly and thus limited, except for the keyboard, which will be used daily. The

consumer exposure to nanomaterials in solid matrices (e.g. the processor) would require consumer intervention into the computer.

94

Appliances 4.12

Appliances (include large appliances such as washing machines and smaller appliances such as hair straighteners) (Indirect exposure)

1


2

Formulation/ matrix


Powder/Solid

Application method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links


[<1, 1-10, >10%]


[<1g, 1-10g, >10g]

Minutes/ Hours/

Whole day


Yearly/ Indoor/outdoor

All ages/Children/



The Nanotechproject database contains 32 products with specified nano materials belonging to the category ‘appliances’. Most of the products contain NMs in solid matrices. It does not contribute with new exposure scenarios compared to the Danish Nanodatabase. The products mainly contain silver, titanium dioxide, iron, carbon, gold, titanate and cobalt. The Danish Nanodatabase contains reference to 54 products belonging to the ‘appliance’ category. The nanomaterials are not known for 4 of the products, the identified materials are silver, phosphate and gold. The BUND database contains 19 products in the category ‘Haushaltsgeräte’. The nanomaterials are not known for 8 of the products, the identified materials are silver, nano-ceramics, titanium dioxide and polyetherketon. The ANEC-BEUC inventory contains 47 products in the category ‘appliances’. All of the products contain nano silver. Thus, the inventory does not contribute with any additional information to the table.

Product category/Products: Appliances

Samsung Refrigerator,

Specified Surface bound

Coating on the inner surface of the

refrigerator

Silver http://nanodb.dk/da/products/

samsung-refrigerator

http://www.samsung.com/sg/c

http://nanodb.dk/da/products/samsung-refrigerator

http://nanodb.dk/da/products/samsung-refrigerator

http://www.samsung.com/sg/consumer/learningresources/silvernano/silvernano/refigerator.html

95


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Refrigerator

As air circulates, the coated surfaces allow the silver ions

to control the airborne bacteria.

onsumer/learningresources/silv

ernano/silvernano/refigerator.html

Estimated Solid, <1% <<10g Hours/Whole day

Daily

Indoor

All ages (Dermal) (oral)

LG Refrigerator Specified This nano-carbon

deodoriser with

Green Catechine is located at the air

circulation

Carbon http://www.lg.com/sg/support-product/lg-GR-M4924CPN

Estimated Solid matrix <1% <<10g Hours/Who

le day

Daily

Indoor

All ages (Dermal)

(oral)

Haier

Refrigerator

Specified Solid matrix

The ‘Nano Ferrite Filter’ inbuilt in the

refrigerator creates a magnetic field of Nano Ferrite, which

provides intelligent filtering

Iron http://www.businesswireindia.c

om/PressRelease.asp?b2mid=30471




96


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

Estimated ??? ??? Whole day Daily All ages Oral

Bielmeier

Luftbefeuchter BHG 558, Air humidifier

Specified Surface bound

Plastic parts are coated with nano-

silver

Silver http://nanodb.dk/da/products/

bielmeier-luftbefeuchter-bhg-

558

http://www.bielmeier-

hausgeraete.com/en/Air-Huidifier/BIELMEIER-Humidifier-BHG-558.html

Estimated Solid

<1% <<1g Minutes/H

ours

Monthly/

Yearly

Indoor

Inhalation

(Dermal)

Daewoo

Washing Machine,

Washing machine

Specified Silver http://nanodb.dk/da/products/

daewoo-washing-machine

http://www.daewooelectronics.com.au/about_dec.asp

Estimated Solid, probably as a

coating

<1% <<1g Hours Daily

Indoor

All ages (Dermal)

Alu pan "silver nano" - the

healthy pan Kitchen ware

Specified Solid Surface bound

Silver http://nanodb.dk/products/alu-pan-silver-nano-the-healthy-

pan

http://www3.westfalia.de/shops/haushalt/kochgeschirr/toepfe

_/?pid=728571

Estimated Minutes/hours

Daily All ages Oral

http://nanodb.dk/da/products/bielmeier-luftbefeuchter-bhg-558



http://www.bielmeier-hausgeraete.com/en/Air-Huidifier/BIELMEIER-Humidifier-BHG-558.html




http://nanodb.dk/da/products/daewoo-washing-machine

http://nanodb.dk/da/products/daewoo-washing-machine



http://nanodb.dk/products/alu-pan-silver-nano-the-healthy-pan



http://www3.westfalia.de/shops/haushalt/kochgeschirr/toepfe_/?pid=728571



97


1


2

Formulation/ matrix



method

3

NM ID

4

Conc. of NM in

product

5


use

6

Duration per event

7

Use frequency

and site of use

8

Consumer group

9

Primary exposure


exposure route)

10

Comments/web-links

Exact value

or range [<1, 1-10,

>10%]

Exact value

or range [<1g, 1-

10g, >10g]

Minutes/

Hours/ Whole day

Daily/ Weekly/

Monthly/ Yearly/

Indoor/outdoor

All


en/Hobby

Oral/ Dermal/

Inhalation

(currently not available at

webshop)

Nano-San® Anti-bacterial

gastronomy mat Kitchen ware

Specified Surface bound Silver http://www.nanotechnologie-

sozamex.com/gastronomie/45-nanosan-gastronomie-classe-

30.html

Estimated <1% Minutes/hours

Daily Adults Oral/Dermal

Primea Touch

Plus Cappucino

maker

Specified Surface bound silver http://www.bella-

italia.com/gondola/coffee/index19a.shtml

Estimated Hours Daily Adults Oral

http://www.nanotechnologie-sozamex.com/gastronomie/45-nanosan-gastronomie-classe-30.html




98

Overall findings

In the examples addressed in the table, the following nanomaterials have been found in the appliance products:

Silver: in refrigerator, air humidifier and in washing machine, and iron and carbon in refrigerators

For the far majority of the products the primary exposure route is the dermal route, whereas secondary routes are in relation to oral or inhalational exposure. This applies for

the refrigerators and the air humidifier.

For appliances, the use of silver as biocide will lead to some release of silver (as silver ions and perhaps as nano-silver) and thereby some exposure. The exposure is difficult to

estimate but assessed to be low, since e.g. for the washing machine <1mg of silver will be released during a washing event and also for when touching the refrigerator.

99

Appendix 5 - Model reviews – 5.

Templates with assessment for each

model against the model assessment

criteria

Each identified method/tool has been assessed against the model assessment criteria implemented

in a template. Thus, the sub-seqeunt 10 templates address:

NanoRiskCat (DTU and NRCWE)

NanoSafer (NRCWE, DTI)

Stoffenmanager Nano (TNO)

Stoffenmanager (TNO)

The ANSES tool

Swiss Precautionary Matrix (Swiss consortium)

ECETOC TRA

ConsExpo (RIVM)

DREAM (TNO and IOM)

Margin of Exposure (MOE) concept (The US Soap and Detergent Industries)

Each template consists of: A summary

An initial overview of the context of the method/tool (developed by whom, for which

purpose, etc.).

The actual evaluation of the tool, structured around four questionnaires:

o General input model for NM/product characteristics

o Exposure module(s)

o Hazard module

o Output / risk characterization / risk management module

Some questionnaires are not relevant for all methods/tools as for example hazards are not

addressed in all methods tools. In this case, the detailed questions have not been answered and

therefore deleted.

100

NanoRiskCat 5.1 The tool is available from: Hansen, SF, Jensen, KA, Baun, A. accepted. NanoRiskCat - A Conceptual Tool for Categorization

and Communication of Exposure Potentials and Hazards of Nanomaterials in Consumer Products.

Journal of Nanoparticle Research.

The first version was published by Hansen, S.F., Baun, A., and Jensen, K.A., 2011. NanoRiskCat. A

Conceptual Decision Support Tool for Nanomaterials. Environmental Project 1372, 86 pp.

In addition, the following background material is referred to in this template: Hansen, S.F., Larsen, B.H., Olsen, S.I., Baun,A., 2007. Categories and hazard identification scheme of nanomaterials. Nanotoxicology, 3, 243-250. Hansen, S.F., Michelson, E., Kamper, A., Borling, P., Stuer-Lauridsen, F., Baun, A., 2008. Categorization framework to aid exposure assessment of nanomaterials in consumer products. Ecotoxicology, 17/5, 438-447. Tran, C.L., Hankin, S.M., Ross, B., Aitken, R.J., Jones, A.D., Donaldson, K., Stone, V., Tantra, R., 2008. An outline scoping study to determine whether high aspect ratio nanoparticles (HARN) should raise the same concerns as do asbestos fibres. Report on Project CB0406, August 13, 55 pp. ECHA, 2010. Guidance on information requirements and chemical safety assessment. Chapter R12 Use descriptor system Version: 2. March 2010.

101

Summary

The tool covers/addresses (tick or leave empty):

A general input module

Exposure-dermal module

Exposure-oral module

Exposure – general inhalation

module

Exposure - spray module

Hazards module

Output module

No, as the system is not

a web-tool, the data are gathered as

information to follow the binary

“decision” logics of the system.

x (part of the generic modul) x (partly qualitative

as the quality and reliability of

the scientific information sometimes

has to be evaluated)

x Colour-scaled Risk

Categorization assessing potential

exposure to professional end-user,

consumers and the environment

as well as ranking of the known hazard

of the nanomaterial in the product

1. Type of tool

NanoRiskCat is a not a risk assessment tool and therefore the tier level may be preceeding tier 0. It is

a risk categorization tool that can be applied for screening purposes and communication of knowledge

in between producers and authorities as well as consumers if needed.

2. Input parameters

The system follows a systematic approach and requests a clear description of the product, the

nanomaterial therein and the use of the product.

For exposure assessment, a simple categorization of the possibility for exposure is made according to

the physical location and state of the nanomaterial as described in Hansen et al. (2007; 2008) and

assessment of the potential release and exposure during intended use and potential manipulation of

the product/article. Based on this procedure, the possibility for exposure is selected from 4 predefined

categories: Unknown, low, medium, and high exposure potential for the professional end-user,

consumers, and the environment, respectively. If release or exposure data do exist these data shall

be used for the qualitative categorization. The final output agglomerates all exposure scenarios into

one dot, but a written explanation should be accompanied the assessment to explain which scenarios

and exposure routes that have been assessed and the outcome of these assessments.

For human hazard assessment, the user is required to answer 5 questions, where only one: is the

nanomaterial classified as a high aspect ratio nanomaterial? is related to the physico-chemical

characteristics and properties of the nanomaterial. The other input parameters are related to the

toxicity of the nanomaterial: does the bulk material have a CLP classification for selected severe

irreversible toxicological effects? does the bulk material have a CLP classification for less severe

reversible toxicological effects? is the nanomaterial associated with any acute effects from scientific

literature? is there any scientific evidence suggesting that the nanomaterial is associated with

genotoxic, mutagenic, carcinogenic, respiratory, cardiovascular neurotoxic or reproductive effects in

humans and/or laboratory animals or has organ-specific accumulation been documented?

The method also contains a module for ecotoxicological assessment, which is not reported in this

evaluation.

3. Matrices/scenarios

The method has no limitation in general, i.e. all types of generic matrixes categories can be

assessed. The model is based on the nanomaterial substance in the product.

All scenarios listed in 2.1/1.1 could principally be addressed.

4. Overview

102

The model addresses all potential hazards related to the nanomaterial, including dermal,

oral, and inhalation exposure, however, limited to what hazards are known about the bulk

form and data from scientific literature. The hazard model uses a binary approach, where

the user is guided through a decision tree with predefined color categorization depending

on the answers. The output is qualitative and the background for the final hazard

categorization is explained using one out of 20 NanoRiskCat standard human health hazard

phrases. The method is not focused on metrics. It is focused on the indications and

evidence of hazard.

5. Tool targeted at nano?

NanoRiskCat is intended to be used on nanomaterials as well as products and articles

including nanomaterials only.

103

Description and evaluation

Context of the method/tool

Who developed the tool/method?

The method was developed by Steffen Foss Hansen and Anders Baun from the Technical

University of Denmark (DTU), Lyngby, Denmark and Keld Alstrup Jensen from the National Research Centre for the Working Environment, Copenhagen, Denmark.

For which purpose, products and/or processes:

NanoRiskCat was developed as a procedure to categorize and communicate the knowledge on the potential exposure and hazard of nanomaterials in consumer products. Due to the

flexibility of the system, there are no immediate limitations on which types of products or even raw nanomaterials that can be assessed.

Has the tool been validated for NMs?

The method has not been validated and it cannot be done at this point in time. The method

may not need evaluation as such, as it is a tool intended to enable assessment of the present knowledge, the exposure potentials of nanomaterials and products with “nano-claims” and the knowledge on hazard for the specific nanomaterials therein. However, if knowledge appears

that suggest that the categorization criteria are not sufficiently rigid, modification of the method would be warranted.

If not, what is the potential for testing/validating within this project?

The tool can probably not be evaluated as part of this project as it requires validated data on exposure and a full hazard assessment of the nanomaterial in question.

Describe the level of quantification of the algorithms of the different modules of the method/tool:

All the algorithms are binary and qualitative assessments of literature data on for the hazard assessment

How are uncertainties addressed in the algorithms of the different modules of the method/tool:

Uncertainties are not quantified. The uncertainties in the method are anticipated to be mainly

linked with the qualitative assessments on knowledge on the hazard of the nanomaterial.

Describe the level of quantification of the output of the method/tool:

The output is qualitative and given as five dots, which can have four different colors

describing the likelihood for exposure and the level of knowledge on hazard of the bulk compound and the nanomaterial specifically.

How are uncertainties addressed in the output of the method/tool:

Uncertainties are not quantified. The criteria for the decisions are to be communicated in writing in a supplemental document, which will enable the reader to discuss agreement on the conclusions.

Describe level of expertise needed to use the method/tool, is it an expert tool?

104

The method is intended for professionals, who have the ability to access and evaluate scientific literature on exposure science and nanotoxicology.

105

Questionnaire 1: General input module

List the NM/product characteristics required as input parameters: There is no module for general input parameters, but two key physicochemical input parameters are required by NanoRiskCat as listed in Table 1

Table 1 Overview of the input parameters on the nanomaterial and the nanomaterial-based product/article.

Is the nanomaterial categorized as a HARN

(aspect ratio > 10 and follow the criteria in Tran et al. (2008)

What is the matrix and location of the nanomaterial in the product

yes/no

Fixed or embedded in a solid (matrix),

Surface-bound nanomaterial, Nanomaterial in Liquid dispersions,

Nanomaterial as free powder

106

Questionnaire 2: Exposure module

General issues Is background exposure taken into account, including whether this has been considered relevant for consumer exposure:

Background exposure is not taken into account.

Are exposure based waiving principles applied (e.g. in relation to NMs bound in solid matrices or others):

Yes, the assumed exposure potential during intended use is low when embedded in a solid.

Is exposure assessment based on worst case or average values for the various input parameters?

The exposure assessment is entirely based on guided judgment considering the physical

location of the nanomaterial in a product/article and the user’s assessment on the potential of exposure during the intended and likely use(s) and manipulation of the product or article.

Other relevant issues: If there is too little information available on where the nanomaterial occurs in a product/article, it is possible to categorize the likelihood of exposure to unknown.

Is the REACH methodology for describing product categories and exposure scenarios used?

No, this is not the case in the accepted scientific publication. In the first version published by the Danish EPA (Hansen et al., 2011), the exposure categorization was predefined for

REACH process and use categories (ECHA, 2010). However, this procedure was later evaluated to potentially result in too many errors, because the user would not consider the likelihood of exposure to the specific product, but blindly follow the process and use

categories.

Is banding of exposure potential used?

The system is a categorization tool of the exposure potential or likelihood of exposure to a

nanomaterial in a product. Depending on the tools, the risk categorization is somewhat comparable the exposure banding in the simplest qualitative control banding tools.

107

Dermal exposure

Which input parameters are required (including whether they are taken from a possible general input module) (dermal: dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

There are no specific input parameters. The procedure for exposure assessment is entirely

based on the location of the nanomaterial in the product/article according to Hansen et al. (2007; 2008) and an assessment of the potential for exposure to the nanomaterial in the product or article during intended use and expected modification (e.g., sanding a surface or

drilling a hole). The final output agglomerates all exposure scenarios into one dot, but a written explanation should be accompanied the assessment to explain which scenarios and exposure routes that have been assessed and the outcome of these assessments.

Are specific product types and/or scenarios addressed? Which? (compare with Activity 2.1/1.1 list):

Specific product types/scenarios are not addressed in the method. The method is deliberately not isolated to specific material or product groups to enable general applicability.

Are default factors applied (e.g. for default scenarios)? Which?

As above with the same arguments, default factors are not applied.

Are default calculations applied (e.g. for default scenarios)? Which?

There are no calculations to be made due to the categorization paradigm depending on the location of the nanomaterial in the product/article.

Which “matrix effects” are addressed (powder, dispersion/solution, solid matrix, etc.):

All types of generic matrixes categories can be assessed.

Is dermal exposure following aerosol deposition and condensation of vapours addressed?

This is not considered, unless the evaluator brings this issue into the evaluation.

Which metric (mass, number, surface area…) is applied (relevant if quantitative exposure estimates are derived)

The method is not limited by which metric to be used and the assessment is not quantitative.

Is the effect of implemented risk management measures taken into account? Which/how?

There is no risk management module.

108

Inhalation exposure Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation, etc.):

There are no specific input parameters. The procedure for exposure assessment is entirely

based on the location of the nanomaterial in the product/article according to Hansen et al. (2007; 2008) and an assessment of the potential for exposure to the nanomaterial in the product or article during intended use and expected modification (e.g., sanding a surface or

drilling a hole). The final output agglomerates all exposure scenarios into one dot, but a written explanation should be accompanied the assessment to explain which scenarios and exposure routes that have been assessed and the outcome of these assessments.


Specific product types are not addressed in the method. The method is deliberately not

isolated to specific material or product groups to enable general applicability.


As above with the same arguments, default factors are not applied.


There are no calculations to be made due to the categorization paradigm depending on the

location of the nanomaterial in the product/article.

Is aggregation/agglomeration in product and aerosol dynamics addressed? How?:

No, because the categorization is solely qualitative, aggregation/agglomeration is not considered.


All types of generic matrixes categories can be assessed.

Is evaporation-condensation processes addressed and if so how:

No; only if the evaluator takes this into consideration in the qualitative assessment. Which metric (mass, number, surface area…) is applied (relevant if quantitative exposure estimates are derived)

The method is not limited by which metric to be used and the assessment is not quantitative.


There is no risk management module.

109

Inhalation spray Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation):

As above under inhalation exposure.

Are specific product types and/or scenarios addressed? Which? (compare with Activity 2.1/1.1 list)

As above under inhalation exposure. Are default factors applied (e.g. for default scenarios)? Which?



As above under inhalation exposure. Is aggregation/agglomeration in product and aerosol dynamics addressed? How?:

As above under inhalation exposure. Which “matrix effects” are addressed (powder, dispersion/solution, solid matrix, etc.):








110

Oral exposure Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use,):

As above under inhalation and dermal exposure.



Is dissolution in different gastric compartments addressed? If so how?

Dissolution of the nanomaterial is only considered of the evaluators takes this into their

specific assessment.





111

Questionnaire 3: Hazards Module

Is this module estimating hazards or is the hazard/hazard profile typed into the module to be used in a subsequent risk assessment:

The module estimates the hazard category.

What are the input parameters for the hazard module? (including whether they are taken from a possible general input module). This would include characterisation/physchem parameter used for identifying hazards, classification, quantitative dose descriptors (NOAELs, BMDs, OELs…):

The method assesses the hazard category based on 1 to 5 questions to be answered along a flow-chart (Table 2; Figure 1). Because the method is not an established computer-

based tool, there is not a general input module.

. Table 2 Input parameters used for hazard assessment in the NanoRiskCat hazard module

Is the nanomaterial

categorized as a HARN

(aspect ratio > 10

and follow the

criteria in Tran et al. (2008)

Is the bulk form of the

nanomaterial known/suspected to cause any severe and possibly irreversible detrimental

toxicological effects in its

CLP classification?

Is the bulk form of the

nanomaterial known/suspected to cause less severe and reversible toxicological effects in its

CLP classification?

Is the specific

nanomaterial known to be acute toxic?

Are there indications that the

nanomaterial causes genotoxic, mutagenic, carcinogenic,

respiratory, cardiovascular, neurotoxic, or reproductive effects in humans and/or

laboratory animals or has organ-specific accumulation?

yes/no yes/no yes/no yes/no yes/no

Is the model/tool generally advised not to be used for certain substances/substance groups; e.g. is it advised not to use the model/tool for CMR substances?:

112

No; the method is applicable to all nanomaterials, products and articles.

Are hazard-based grouping principles applied, e.g. banding according to classification or selected hazard end-point; high hazard potential for high aspect ratio materials; regular hazard potential for water-soluble NMs; nano at least as toxic as bulk/macro, etc.:

Yes, the module categorizes products and articles with high-aspect ratio nanomaterials that

fulfill the paradigm given by Tran et al. (2008) as well as CMAR endpoints for the analogue bulk materials. In addition categorization is made based on lack of data.

Figure 1 Flow-chart decision tree for assigning a NanoRiskCat color code for the potential hazard

of a nanomaterial in a product/article.

Does the tool/model suggest use of alternative hazard data, e.g. use of scaling (e.g. from bulk or other nano-sizes or based on physico-chemical properties), QSAR/QSAR-like systems, in vitro data, etc.:

The tool requires mandatory review of scientific literature to include information from toxicological studies on the nanomaterials in the products/articles. However, this is again a qualitative assessment including results from both in vivo and in vitro experiments.

113

Are (specific) hazards linked to the relevant exposure route (e.g. lung inflammation to lung exposure?):

No, due to the intended precautionary approach and traffic-light approach, the method uses hazards to any organ (or in vitro cell study) for the final hazard categorization. Therefore,

subsequent assessment is required to assess the relevance of the reported hazard category. However, the inclusion of all end-points and exposure routes in the final hazard assessment dot may on the other help to identify data where read-across between exposure routes is

possible and are included in the report.

Which metric (mass, number, surface area…) is applied (relevant if a quantitative dose descriptor e.g. NOAEL/DNEL is applied)

The model does not calculate dose. It uses hazard data qualitatively.

114

Questionnaire 4: Output / risk characterization / risk

management module

How are the results communicated? (e.g. qualitatively, control banding, risk management guidance, semi-quantitative, as risk characterization ratios, probabilistic or fully quantitative). Describe if differences among various exposure routes and hazard categories.

The risk category is communicated in a three colored dots, representing the potential exposure for professional end-users, consumers, and the environment, respectively and two

colored dots, representing the potential hazard to humans and the environment (see Figure 2). The colors rank red (high), yellow (medium), green (low), and gray (unknown due to lack

of information), similar to a traffic-light, the potential level of exposure and hazard. The colors

red and gray would normally prompt further investigation. In this review, the environmental exposure and hazard is not taken into consideration.

Figure 2 Example of a graphical report of the risk categorization in NanoRiskCat. From the left, the first three dots represent the potential exposure to professional end-users, consumers and the environment. The next two dots, represent the hazard categorization for humans and the environment.

The color-code output is to be accompanied by a more elaborate written explanation and

argumentation of the decisions leading to the categories. Are risks evaluated in relation to specific exposure routes? Which/how?

Not directly, the exposure categorization can in the elaborated description consider specific

exposure routes and use-description.

Is there a facility to address combined exposures?

No, this is not discussed in the method.

Are there any risk communication facilities (e.g. High-Medium-Low-Unknown/Uncertain, grading, grouping, colour codes…..):

Yes, the tool has a color-coded risk categorization system as described above.

Is the outcome related to any risk management recommendations? Which/how?

Not directly. However, action for risk management would normally be prompt by gray and red categorizations.

Are uncertainties presented/addressed in the output? How?

No, uncertainties are not considered in the qualitative categorization output. Variables can be

discussed in the elaborate background documentation to be given together with the

categorization.

115

116

NanoSafer 5.2 The tool is available from: http://nanosafer.i-bar.dk/

In addition, the following background material has been reviewed for filling in this template: Scientific paper in preperation

Jensen, KA, Saber AT, Kristensen HV, Koponen IK, Wallin H (in prep) NanoSafer v 1.1: A web-based precautionary risk assessment tool for manufactured nanomaterials using first order modelling.

The web-page (http://nanosafer.i-bar.dk/) and supporting documents available from the web-page.

http://nanosafer.i-bar.dk/


117

Summary





Exposure – general inhalation module


Hazards module

Output module

x x (x; not reactions)

X (considers OEL of bulk analogue materials and physico-chemical properties of MN)

x (Control/Risk Banding)

1. Type of tool

NanoSafer is an advanced tier 0 to tier 1 tool. The tool is intended for worker representatives,

company safety teams, and first assessment for professionals and usage of the tool does not require

training beyond introduction or study of the written manual.

2. Input parameters

The tool follows a systematic approach and requests specific nanomaterial characteristics, hazard

data and the occupational exposure limit of the nearest chemical bulk analogue and user-specific

input parameters on the contextual information and specifics on the work process to enable a

scenario and user-specific risk assessment. The input parameters and are listed in Tables 1 to 3.


Only powders are addressed in the current tool. The tool is developed for fugitive

emissions, point source emission and powder handling. Exposure waiving is not applied as

such. However, the user can define the emission potential as “0”, which will allow using the

tool for hazard assessment alone.

The model is based on substance.

NanoSafer can be used for scenarios where dust/particles or chemicals are released to the

air. These processes include powder handling and spraying in downstream user and

consumer exposure situations. However, it should be noted that, the model does not

consider evaporation and condensation processes. NanoSafer may be applied in the

following scenarios identified in activity 2.1/1.1:

*Cosmetics

Spray Cleaning agents

Spray Coatings/ impregnation

Spray Maintenance products (car, boats)

Spray Cement/ concrete a.o

Powder handling

Air-cleaners Sprays

Construction materials

Spray applications

118

4. Overview

The model addresses all hazards related to occupational inhalation exposure. The model

assesses the potential hazard of the nanomaterial as a function of water solubility, aspect

ratio (i.e. high-aspect ratio materials), uncertainty ascribed to coatings, and already

identified hazards of the specific chemical compound as a bulk material expressed by the

occupational exposure limit and specific hazard sentences. Assessment of combined

exposures is not possible.

The hazard model uses a quantitative algorithm. Various hazard contributions are multiplied

using an asymptotic multiplication function to ensure that individual low-hazard

contributions; say irritation of both eye, skin and airways, will not immediately result in a

high hazard score.

The algorithms applied for final risk assessment is quantitative, but the quantitative

assessment is scaled and used in the context of Control-Banding/Risk Management

Banding due to the inability to validate the assessments. The final output is an integrated

risk assessment for Acute (15 min) and 8-hour Near-Field and Far-Field exposure. The risk

scaling is based on compilation of hazard data and hazard indicators as explained above

and estimated exposure levels scaled according to a nanomaterial-specific theoretical

occupational exposure limit adjusted to by the ratio between the volume-specific surface

area of the nearest analogue bulk (reference at 200 nm size) and the nanomaterial in

question. Overviews of the input parameters are listed in Tables 1 to 3. The exposure and

hazard models are illustrated in Figures 1 and 2, respectively.

The risk assessment is based on the occupational exposure limit, which is given as a mass-

concentration (mg/m3) and adjustments considering the volume-specific surface area

(m2/cm

3) of the nanomaterial under evaluation. The adjustment of volume-specific surface

area is applied in the scaling of the potential exposure level.


NanoSafer is intended for risk assessment of occupational inhalation exposure during

process-specific manufacturing and handling of nanomaterials, which result in inhalation

exposure to free MN. The underlying

quantitative model can be applied to more sophisticated variations of scenarios. For

example assuming that a

release from a process, such as grinding release dust with a fraction of MN.

119




The web-based tool, including basic e-learning resources was developed by the National

Research Centre for the Working Environment and the Danish Technological Institute, Denmark


NanoSafer was developed specifically for SME’s and the assessment of inhalation risk. The

system can be applied to processes where MN emissions are generated as free nano-objects and their agglomerates and aggregates. The primary scenarios are powder handling and fugitive sources, where emissions can be either continuous or episodic. The current version

of NanoSafer is not developed for handling exposures to composite debris particles.


Neither the hazard nor the exposure modules have yet been evaluated. This is due to lack of

hazard data on a larger suite of nanomaterials as well as lack of good workplace data where immediate emissions are described in sufficient detail and where there at the same time has been good control of the far-field contributions. Internal evaluations were made to investigate

that the exposure and hazard scaling had sufficient precautionary effect.


The tool cannot be evaluated as part of this project as it is based on quantitative input

parameters and does not take products, articles and consumer products in general into consideration.

Further as noted above, validation would require good exposure data and hazard data on a larger suite of nanomaterials using a harmonized test approach.


All the algorithms are quantitative following the hypothesis and paradigms of the model. The

exposure assessment is based on calculation of the potential exposure concentrations in the Near-Field and Far-Field. The hazard is estimated using a multiplicative asymptotic hazard accumulation function.


Uncertainties are not quantified.


The algorithms are quantitative. The risk scaling is based on compilation of hazard data, hazard indicators and estimated exposure levels.


Uncertainties are not quantified. However, the approach in control banding is to try and take

uncertainty into consideration by application of a precautionary principle.

120


The user does not require training beyond introduction or study of the written manual. Understanding and application of the algorithms behind the interface, however, requires expert level. The tool is intended for worker representatives, company safety teams, and first

assessment for professionals.

121


List the NM/product characteristics required as input parameters:

Table 3 summarizes the physicochemical input parameters required by NanoSafer.

Table 3 Overview of the input parameters on the nanomaterial and hazard.

Material name

(optional)

CAS number

(optional)

EINICs Number

(optional)

Nano-specific word or

term

(yes/no)

Coated or surface modified

nanomaterial

(yes/no)

Dimension of the

nanomaterial

(a≤b≤c)

Specific density

(g/cm3)

Is the naomaterial

water

soluble

(yes/no)

The specific surface

area

(m2/g)

text text text NANO Rcoat a,b,c So SSA

122



As this procedure is following a conventional compound specific risk assessment, background exposure is not taken into account.


Exposure waiving is not applied as such. However, the user can define the emission potential

as “0”, which will allow using the tool for hazard assessment alone.


The exposure assessment is intended to be based on a worst case scenario for the specific

work situation. The results are currently only given as a control- / risk management out-put not taking existing

LEV into consideration.

Other relevant issues:

No


No


Yes, banding is used and the ranking (EXPi) of the acute and 8-hour exposure is calculated

based on the ratio between the estimated respirable dust concentration and a surface area modified specific exposure limit for the specific material under investigation (OELnano)

Equation 1 to 3 below.

Equation 1)

nano

AcuteAcute

OEL

CEXP

2 and Equation 2)

nano

hourhour

OEL

CEXP

88 ,

where

Equation 3)

nano

nanoSSA

OELOEL

130

, where nmSSA200

130

The reference OEL200nm is the OEL of the nearest analogue bulk material, where the bulk reference size has been defined to be 200nm, which has a Volume-Specific-Surface Area of

30 m2/cm

3. The specific density () is assumed to be the same of both the bulk and the

nanomaterial.

123

The values for EXPi can vary from 0 to infinite, In the control banding scheme, the exposure

risk level increases in five steps at 0.1, 0.25, 0.5, and 1.0, where the value 1 means that the exposure level exceeds OELnano (please see Figure 5 for the schemes of the control banding

output).

The calculations performed to reach the exposure scaling are made using a two-box instant mixing exposure model for calculating the scenario-specific exposure levels. The emission

rate (Ei) for this calculation is made using either dustiness data (Eo) adjusted for the activity energy (h) and applied mass-flow (dM/dt) or a constant release rate (Ei,o). The fundamental principles in this calculation in illustrated in Figure 3.

A) B)

Figure 3 A) Illustration of the release rate module, where the Emission rate (Ei) is given by a constant release rate (Ei,o) or the dustiness multiplied with mass-flow rate (kg/min) and a scenario-specific default handling energy factor (hi). B) Illustrates the two-box near-field (NF) and far-field (FF) instant mixing exposure model. The aerosol transfer and decay rates in the NF and FF volumes were calculation based on equations in Schneider et al. (2004).

Dermal exposure (not addressed)


Table 4 lists the eleven key input requirements for the inhalation exposure module.

Air-exchange in the near-field (QNF)

QNF = QFF x (VNF/VFF)+ ; = 10

CNF

QNF

CNF

QNF

Source

Emission rate:

Ei = Ei,c or Eo x h x dM/dt

Concentration in the near-field

CNF = (Ei + NFFF->NF - NFNF->FF + NFresidual) / VNF

CNF

QNF

CNF

QNF

EEii

QFF,in

QFF,out

V1,in

V1,out

QFF,in

QFF,out

V1,in

V1,out

CFF

CFF = (NFNF->FF - NFFF->NF + FFresidual) / VFF

CFF

CFF = (NFNF->FF - NFFF->NF + FFresidual) / VFF

CNF = (Ei + NFFF->NF - NFNF->FF + NFresidual) / VNF

124

Table 4 Overview of the input parameters on the nanomaterial and hazard.

Constant Release

rate

(kg/min)

Respirable

dustiness

(mg/kg)

Handling

energy factor

(0 - 1)

Amount Product Used per

work cycle

(kg/cycle)

Amount used per transfer

(kg/transfer)

Duration of work cycle

(min)

Duration of

transfer

(min)

Number of work cycles

(n)

Pause between

work cycles

(min)

Volume of work room

(m3)

Air-exchange

rate

(h-1)

dM/dt DI Hi M m tduration ttransfer n tpause V Q

Are specific product types and/or scenarios addressed? Which? (compare with Activity 2.1/1.1 list): The scenarios addressed in the model includes only release during powder handling and fugitive sources


Default scenarios are not applied


No, the calculations are always based on the contextual information, process description, and material input data.


No, aggregation/agglomeration is not considered.


Only powders are addressed in the current model.

125


No.


The model bases its calculation on the mass-concentration of airborne respirable dust in the near-field and far-field. The values are subsequently scaled using the volume-specific surface area.


No, risk management measures are not taken into account in the calculations. However, they are taken into account when setting the final risk bands.

Inhalation spray (Generally not applicable): Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation):

NanoSafer is not intended for application of general spray exposure assessment, unless the

product does or can be assumed to emit a stable mass-concentration in the air. It does not consider reaction chemistry, evaporation and condensation. If these assumptions are made, the model can be used as described above.


No specific scenarios addressed.


No.


No, the calculations are always based on the contextual information, process description, and

material input data.


No, aggregation/agglomeration is not considered.


Only powders are addressed in the current model.


No.

126


The model bases its calculation on the mass-concentration of airborne respirable dust. The values are subsequently scaled using the volume-specific surface area.


No, risk management measures are not taken into account in the calculations. However, they are taken into account when setting the final risk bands.

Oral exposure (not addressed)



The module estimates the hazard based on the input parameters and use this information for subsequent control banding.


The input parameters relevant for hazard assessment are listed in

127

Table 5 and Figure 3 illustrates the use and values of the hazard grouping parameters.

128

Table 5 Input parameters used for hazard assessment in the NanoSafer hazard module.

Is the naomaterial

water soluble

(yes/no)

Dimension of the

nanomaterial

(a≤b≤c)

Coated or surface

modified nanomaterial

(yes/no)

Occupational exposure

limit for

analogue bulk

material

(mg/m3)

Risk sentences for general

toxicity/irritation for analogue bulk material

(0-1)

Risk sentences for

carcinogenicity for analogue bulk material

(0-1)

Risk sentences

for reprotoxicity

for analogue

bulk material

(0-1)

Risk sentences

for neurotoxicity

for analogue

bulk material

(0-1)

Risk sentences for

allergy and sensibilization for analogue bulk material

(0-1)

So a,b,c Hcoat HOEL Rtox,i Rtox,i Rtox,i Rtox,i Rtox,i

129

Figure 4 Flow chart for hazard assessment in NanoSafer. Note that the key input parameters include water solubility (So), particle dimensions (length and diameter), information on inorganic/organic coatings, the OEL for the nearest bulk analogue, and risk phrases from safety data sheet. Calculation of the hazard levels are shown in Equation 4 and 5.

The hazard levels are estimated using equation 5 and 6 and consequently take values

between 0.2 and 1.

Equation 4)

ij j

n

i icarc RRH 11

, example of risk end-point for cancer

Equation 5) jij

n

i itot HHH 11 , total hazard score for all hazard

indicators.


No. The module is applicable to all nanomaterials.


Yes, the module categorizes: 1) all high-solubility nanomaterials as regular chemicals, 2) high-aspect nanomaterials (using the WHO fiber definition) as potentially highly toxic

(carcinogenic or asbestos like), 3) nanomaterials where the nearest analogue bulk compound has a high OEL as low toxic nanomaterials,

4) nanomaterials with coatings or surface modifications to have elevated hazard potential (at least level 2 out 4)

“nanorelevance”

NM with low

solubility (So < 1 g/L)

Is the NM a HARN

(a < 3 µm c > 5 µm

c/a > 3)

traditional risk

assessment is suggested

Htot = 1.00

Hcoat = 0.45

yes

no

yes

yes

yes

no

Are there any R-phrases

for the analogue bulk material

HOEL = 0.20

no

yes

Is the OEL for the analogue

bulk material < 1 mg/m3?

Is the NM surface modified

with an inorganic

and/or organic compound?

no

no

Calculate Htot

HOEL = 0.26

Calculate accumulated

HR from R-values

“nanorelevance”

NM with low

solubility (So < 1 g/L)

Is the NM a HARN

(a < 3 µm c > 5 µm

c/a > 3)

traditional risk

assessment is suggested

Htot = 1.00

Hcoat = 0.45

yes

no

yes

yes

yes

no

Are there any R-phrases

for the analogue bulk material

HOEL = 0.20

no

yes

Is the OEL for the analogue

bulk material < 1 mg/m3?

Is the NM surface modified

with an inorganic

and/or organic compound?

no

no

Calculate Htot

HOEL = 0.26

Calculate accumulated

HR from R-values

130


Yes, as described above.


Yes. The selected risk sentences are selected based on direct or indirect relevance for inhalation exposure.


The model does not calculate dose. The hazard level is associated to the OEL given in mg/m

3.

131

Questionnaire 4: Output / risk characterization / risk management module


A semi-quantitative risk level is estimated and given in the format of a 4 by 5 level control banding for the near-field, far-field acute (15 min) and daily (8-hour) exposure with

recommendation on applicable risk management measures. The control banding chart has 4 hazard bands and 5 exposure bands (Figure 5).

Figure 5 The control banding output format from NanoSafer where a control banding diagram is made for four specific scenarios: NF and FF acute and NF and FF chronic exposure, respectively.

NF

Acu

teF

F A

cu

te

NF

Ch

ron

icF

F C

hro

nic

5544332211

5544332211

44 33 22 11

NF

Acu

teF

F A

cu

te

NF

Ch

ron

icF

F C

hro

nic

5544332211

5544332211

5544332211

5544332211

44 33 22 1144 33 22 11

132

Are risks evaluated in relation to specific exposure routes? Which/how?

Yes. The tool only addresses inhalation exposure and air-way toxicity.


No. This is not possible.


Yes, the tool has a colour-coded risk management guidance as well as e-learning tools with introduction and some recommendations for risk management.


Yes. Risk management actions are recommended for each risk level and are listed below

(Table 6) in the same colour codes as applied in Figure 5 with increasing risk level moving from white to dark blue.

133

Table 6 Recommended risk management actions

Potentially highly hazardous nanomaterial and/or moderate to very high exposure potential. Separate the

process, work in fume-hoods or similar. Respirators or high efficiency filter masks (P3 or better) may be used

as supplemental personal respiratory protection and in case of accidents. Expert consultancy is

recommended.

Potentially high hazard and/or high exposure potential. Conduct the work in a fume-hood, enclusure or

glove box or similar. High efficiency filter masks (P3 or better) should be readily available for personal

respiratory protection in case of accidents.

Moderate hazard potential and/or moderate exposure potential. The work should be conducted in a fume-

hood or with good local exhaust ventilation in combination with personal high efficiency respiratory

protection equipment (P3 or better). High efficiency filter masks (P3 or better) should be readily available

for personal respiratory protection in case of accidents.

Presumably low-hazardous nanomaterial and/or low exposure potential. The exposure level is probably

acceptable. The work should be conducted under local exhaust ventilation or in a fume hood or similar. High

efficiency filter masks (P3 or better) should be readily available for personal respiratory protection in case of

accidents.


Uncertainties are not considered in the output. However, it is considered, by the use of

default scores for e.g., insoluble fibers, MN with coating/functionalization and attempting to

follow a “reasonable” precautionary level in hazard scoring.

134

Stoffenmanager Nano version 1.0 5.3

The tool is available from: http://nano.stoffenmanager.nl

In addition, the following background material has been reviewed for filling in this template: Fransman W, Verbist K, Stuurman B, Vink S, Heussen H, Brouwer D, van Niftrik M (n.d.).

Development of Stoffenmanager Nano (www.stoffenmanager.nl). TNO. Available online:

http://www.nanosafe.org/home/liblocal/docs/Nanosafe%202010/2010_poster%20presentations/P1b

-1_van%20Niftrik.pdf (accessed 30.10.13)

Schneider T, Brouwer DH, Koponen IK, Jensen KA, Fransman W, Duuren-Stuurman B, Van

Tongeren M, Tielemans E (2011). Conceptual model for assessment of inhalation exposure to

manufactured nanoparticles.Journal of Exposure Science and Environmental Epidemiology, 21, pp.

450-463.

Van Duuren-Stuurman B, Vink SR, Verbist KJM, Heussen HGA, Brouwer, DH, Kroese, DED, Van

Niftrik, MFJ, Tielemans, E, Fransman, W (2011a): Stoffenmanager Nano Version 1.0: A Web-

Based Tool for Risk Prioritization of Airborne Manufactured Nano Objects. Ann. Occup. Hyg. pp 1-

17.

Van Duuren-Stuurman B, Vink SR, Brouwer DH,Kroese DED, Heussen HGA, Verbist KJM, Tielemans E , Van Niftrik MFJ, , Fransman W (2011b). Stoffenmanager Nano: Description of the conceptual control banding model.TNO Report V9216. The Netherlands.

http://nano.stoffenmanager.nl/

http://www.stoffenmanager.nl/

http://www.nanosafe.org/home/liblocal/docs/Nanosafe%202010/2010_poster%20presentations/P1b-1_van%20Niftrik.pdf

http://www.nanosafe.org/home/liblocal/docs/Nanosafe%202010/2010_poster%20presentations/P1b-1_van%20Niftrik.pdf

135

Summary


A general

input

module

Exposure-

dermal

module

Exposure-

oral module

Exposure –

general

inhalation

module

Exposure -

spray

module

Hazards

module

Output

module

()*

*the tool does not cover a specific spray module, but it is included in the general inhalation module.

1. Type of tool

The Stoffenmanager Nano is a tier 1 occupational model, which is developed to be used by (non-

experts in) SMEs.

2. Input parameters

The exposure parameters needed to run the model are (for inhalation exposure only):

Concentration of nano component in the product

Characterisation of task

Duration of task

Frequency of task

Is the task being carried out in the breathing zone of an employee

Daily cleaning of working room

Monthly inspection/maintenance of machinery/ancillary products

Volume of the working room

Ventilation of the working room

The tool is tailored requiring further input depending on what is selected as primary inputs. See further

details in Questionnaire 1.

136

The estimate of the potential inhalation exposure is calculated on the basis of the following algorithm (Schneider et al. 2011)

Parameter Concentration (score)

due to near-field exposure

Concentration (score) due

to far-field exposure

Background Concentration (score) due to

diffusive sources

Multiplier for the

reduction of

exposure due to control

measures as the worker

Multiplier for the

reduction of exposure due to use of personal protective equipment

Multiplier for

duration of the

handling

Multiplier for

frequency of the

handling

Exposure score

Algorithm [(Cnf + Cff + Cds)] x Ƞimm x Ƞppe x Th x tf

Where

Cnf = E x H x Ƞlc_nf x Ƞgv_nf; Cnf = E x H x Ƞlc_ff x Ƞgv_ff; Cds = E x a and

E =intrinsic emission multiplier; a = multiplier for the relative influence of background sources; H =

handling (or task) multiplier; ƞlc = multiplier for the effect of local control measures; ƞgv_nf = multiplier for the effect of general ventilation in relation to the room size on the exposure due

to near-field sources; and ƞgv_ff = multiplier for the effect of general ventilation in relation to the room size on the exposure due to far-field sources.

3. Matrices/Scenarios

The tool addresses powders, granules/flakes and particles dispersed in a liquid. Exposure based waiving principles are not explicitly addressed, but solid matrices are as a starting point

implicitly excluded.

The Stoffenmanager nano is developed for use in an occupational setting, and the consumer exposure scenarios from activity 2.1/1.1 are therefore not addressed as consumer scenarios.

However, some of the inhalation scenarios could probably be generically addressed, in particular inhalation exposures resembl ing some of the source domains used in the tool (e.g.

dispersion of (solid or liquid) intermediates or ready-to-use MNO-containing products).

137

4. Overview

The hazard module of the tool uses a hazard band approach, where a hazard band (A-E, where A is

the lowest hazard and E is the highest) is assigned on the basis of input parameters for the

nanomaterials or characterisation from the parent material, if the MNO-specific hazard is unknown.

The input parameters for the hazard module are:

Does the product contain fibers/fiber-like particles? (Y/N). If yes hazard band E

(see below for more detail) (taken from a general input module concerning product characteristics)

(Inhalation) hazard input is based on classification: o Unknown o Mutagenic (and possibly carcinogenic) and/or sensitizing (hazard band

E) o Carcinogenic (not mutagenic), reprotoxic and/or very toxic (hazard band

D)

o Toxic, corrosive and/or respiratory allergens (hazard band C) o Harmful and/or irritating (hazard band B) o Non-hazardous (hazard band A)

The tool is only applicable for inhalation exposure, and it is not possible to address combined exposures. The exposure module uses a semi-quantitative approach, since the algorithm used for calculating a relative exposure score includes different multipliers for various modifying factors. The

exposure score is transferred into an exposure band and combined with the hazard band in a final qualitative output.


The Stoffenmanager nano tool is targeted at nanomaterials.

138




The tool was developed by TNO (contract with the Dutch House of Representatives (advised by the Social Economic Council (SER)). Stoffenmanager nano is a nano-specific module

within the generic Stoffenmanager risk-banding tool (NB! The generic Stoffenmanager tool is assessed separately in this project)


Stoffenmanager nano was developed for employers and employees handling manufactured nano objects (MNO) in order to protect workers and minimize exposure to nanoparticles. The model only assesses occupational exposure through inhalation.

Applicability of the tool: The Stoffenmanager nano applies to substances that consists of MNOs with a primary size between 1 and 100 nm and/or to products with specific surface area of ≥ (1/ρ) 60m

2 g-

1.

Water solubility also affects the applicability of the model, since nano-specific properties are expected to be lost when particles are in solution (Van Duuren-Stuurman et al. (2011a). For water soluble MNOs, the user is redirected to the generic Stoffenmanager tool.


Version 1.0 of the model has not been validated for NMs. A future aim is to test and refine the inhalation model based on measurement data published in the open literature and in

NANOSH (EU FP7 project), as was previously done for validating the generic Stoffenmanager tool (Fransman et al. (n.d)


Although not a real validation, we might be able to compare (i.e. benchmark) results from Stoffenmanager nano with those of other tools/information found in literature


The exposure banding module is based on a semi quantitative approach, since the algorithm

used for calculating a relative exposure score includes different multipliers for various modifying factors.


Uncertainties are not explicitly addressed in the algorithms. However, the model is claimed to be underpinned by the precautionary principle due to the limited knowledge about exposure and hazards of NMs. Due to these uncertainties, high exposure should be avoided and therefore high exposure bands automatically lead to high risk priorities for all hazard bands

(except hazard band 'A'). Currently, no MNOs will be assigned hazard band A and B due to lack of information. This means, that in order to achieve a low risk priority band, the lowest exposure band must be assigned to the scenario.

Describe the level of quantification of the output of the method/tool: The output of the exposure module is qualitative, since the exposure scores calculated from

the algorithm are converted into an exposure band. The output of the hazard banding module is also qualitative, since it is based on properties of the MNO and hazard classification. Thus, the final output of the model is qualitative.

139


Uncertainties within the model are not addressed in the reviewed literature for the Stoffenmanager nano tool and uncertainties are not presented along with the output.


Stoffenmanager nano is not an expert tool - it is intended to be used by (non-experts in) SMEs and user friendliness is of major importance. Input parameters to the assessment are

selected on the basis of the availability of these parameters, e.g. from the Safety Data Sheets.

140



Source domain o Release of primary particle during actual synthesis

o Handling of bulk aggregated/agglomerated nanopowders o Spraying or dispersion of a ready-to-use nanoproduct

Product type:

Intermediate

Ready-use-product

o Fracturing and abrasion of MNO-embedded end products Redirected to the generic Stoffenmanager

Product name

Product appearance

o Powder Dustiness (unknown, medium (50-150 mg/kg), high (150-500

mg/kg), very high (>500 mg/kg)) Moisture content (dry product (<5% moisture content), 5-10%

or >10% moisture content)

o Granules/flakes

Dustiness (granules/flakes, firm granules/flakes)

Moisture content (dry product (<5% moisture content), 5-10% or >10% moisture content)

o Particles dispersed in a liquid Viscosity of the liquid (liquids with low viscosity (like water),

liquids with medium viscosity (like oil), liquids with high

viscosity (like paste or syrup) ) Name of the nano component Is the exact concentration of the nano component in the product known? (Y/N)

Does the product contain fibers/fiber-like particles? (Y/N)

Depending on the input parameter/characteristic that is chosen, different input information is required. E.g. for liquids the specific input parameters could be as follows:

Source domain: Spraying or dispersion of a ready-to-use nano product

Product appearance: Particles dispersed in a liquid

Viscosity of the liquid (low, medium, high)

Is the direct dilution of the product with water known? (Y/N) (optional) o If no: choose between unknown, undiluted, concentrated, moderately

diluted, diluted, very diluted or extremely diluted

Characterization of task: o Handling of liquids at high pressure resulting in substantial generation of

visible mist or spray/haze o Handling of liquids on large surfaces or large workpieces o Handling of liquids using low pressure, low speed with large or medium

quantities o Handling of (almost) undisturbed liquids (very low speed), very small

quantities (under controlled conditions) of liquids in tightly closed

containers.

Whereas if another source domain is chosen, other input parameters for e.g. product

appearance and characterization of task will appear. Please refer to the actual tool (http://nano.stoffenmanager.nl) for details.

http://nano.stoffenmanager.nl/

141



Background exposure is taken into account as it is included in the exposure algorithm

("background concentration from diffuse sources (Cds)"). Background concentration (score) is calculated as Cds = E*a,

where E= intrinsic emission multiplier (determines the intrinsic emission potential of a substance, e.g. dustiness for a particulate agent and volatility for liquids (Schneider et al.

(2011)) and a = multiplier for the relative influence of background sources. The reviewed background literature does not address whether the background exposure

function is relevant for consumers as the tool is developed for occupational settings.


Not explicitly addressed.

However, in the fourth source domain, solid matrices are not directly covered by the tool – only in the case where release of MNOs following fracturing/abrasion (e.g. by sanding of surfaces) of MNO-embedded end products is expected by the assessor (source domain 4).

I.e. solid matrices are as a starting point implicitly excluded. If this source domain/exposure scenario is chosen (fracturing/abrasion), the Stoffenmanager Nano tool cannot yet assess the exposure, and the user is redirected to the generic Stoffenmanager.


Not explicitly addressed in reviewed literature, although the impression is that assessments are based on worst case.

When values or information are missing, worst-case values/categories are assigned (van Duuren-Stuurman et al. 2011)


No


Yes, the tool will calculate an overall exposure score using an exposure algorithm. This score is not used directly (as the score itself does not represent a quantitative exposure level), but

score/result of the algorithm is use to assign a qualitative exposure band (1-4) on the logarithmic scale (similar to the generic Stoffenmanager) (see Table 7 below).

142

Table 7: Stoffenmanager Nano exposure bands (table adopted from van Duuren-Stuurman et al. 2011)

6. Exposure band

7. Range Stoffenmanager Nano scores

8. 1 9. <0.002

10. 2 11. 0.002-0.2

12. 3 13. 0.2-20

14. 4 15. >20

Dermal exposure (Not addressed)


Exact concentration of nano component in the product known? (Y/N) (taken from

the general input module) o If yes, the concentration in % is entered

o If no, following options can be chosen Pure product (100%) Main component (50-99%

Substantial (10-50%) Small (1-10%) Very small (0.01-0.1%)

Unknown

Characterisation of task (depending on whether the object is a solid or a liquid and

which source domain that is chosen)

Duration of task

Frequency of task

Is the task being carried out in the breathing zone of an employee (distance head-

product <1 m) (Y/N)

Daily cleaning of working room (Y/N)

Monthly inspection/maintenance of machinery/ancillary products (Y/N)

Volume of the working room (<100 m3, 100-1000 m3, >1000 m3, work done

outside)

Ventilation of the working room (no ventilation, mechanical or natural ventilation or

spraying booth).


Stoffenmanager nano should ideally be applicable to all types of occupational inhalation

exposure scenarios (it is not clear whether the future versions of the tool is supposed to be applicable to e.g. consumer exposure scenarios as well). Currently the tool distinguishes between four general source domains:

1. Point or fugitive emission during the production phase prior to harvesting the bulk

material (e.g. leaks through connections, seals, etc. during MNO synthesis/incidental release)

2. Handling and transfer of bulk powdered MNOs (e.g. bagging or dumping of

powder) 3. Dispersion of (solid or liquid) intermediates or ready-to-use MNO-containing

products (e.g. spraying, pouring liquids)

4. Activities resulting in fracturing and abrasion of MNO-containing end products (e.g. sanding of surfaces).

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Since the Stoffenmanager nano is developed for use in an occupational setting, the consumer exposure scenarios from activity 2.1/1.1 are not addressed as consumer scenarios, but some of the inhalation scenarios could probably be generically addressed, in

particular inhalation exposures resembling above source domain 3 (Dispersion of (solid or liquid) intermediates or ready-to-use MNO-containing products (e.g. spraying, pouring liquids)). Potentially also source domain 4 (Activities resulting in fracturing and abrasion of

MNO-containing end products (e.g. sanding of surfaces)) could be addressed; however, as noted earlier this is not yet implemented in Stoffenmanager nano (use directed to generic Stoffenmanager).


See below


Default calculation algorithms with default parameters and input parameters are applied (see

above). Default decision rules depending on input parameters are applied.


Seemingly not addressed (no information on this issue in reviewed literature)


o Powder

o Granules/flakes

o Particles dispersed in a liquid


Not addressed (no information in reviewed literature)


NA, no quantitative exposure estimates are derived.


Yes, different risk management measures are a part of the modifying factors affecting the

final exposure score. Different multipliers are given depending on the different local control measures. The different input parameters are:

Working area:

Is the working room being cleaned daily (Y/N)?

Are inspections and maintenance of machines/ancillary equipment being done at least monthly to ensure good condition and proper functioning and performance (Y/N)

Volume of working area (<100 m3, 100-1000 m3, >1000 m3, work done outside)

Ventilation of the working room (no ventilation, mechanical or natural ventilation or

spraying booth).

Local control measures and personal protective equipment:

Local control measures o No control measures at the source

o Use of a product that limits the emission o Local exhaust ventilation o Containment of the source

o Containment of the source with local exhaust ventilation o Glove boxes/bags

144

Is the employee situated in a cabin? o The worker does not work in a cabin

o The worker works in a cabin without specific ventilation system o The worker works in a separated cabin with independent clean air supply

Is personal protective equipment applied

o None o Filter mask P2 (FFP2)

o Filter mask P3 (FFP3) o Half-mask respirator with filter, type P2L o Half-mask respirator with filter, type P3L

o Full-face respirator with filter, type P2L o Full-face respirator with filter, type P3L o Half-/full-face powered air respirator TMP1 (particulate cartridge)

o Half-/full-face powered air respirator TMP2 (particulate cartridge) o Half-/full-face powered air respirator TMP3 (particulate cartridge) o Full-face powered air respirator TMP3 (particulate cartridge)

o Hood or helmet with supplied air system TH1 o Hood or helmet with supplied air system TH2 o Hood or helmet with supplied air system TH3

An example of how the different risk management measures results in different multiplying

factors are given in Table 8 below.

145

Table 8 Stoffenmanager Nano multipliers for reduction by general ventilation for near-field (A) and far-field sources (B). The score is given to a combination of room volume in cubic meter and ventilation type. No far-field exposure is assumed in

a spraying booth, due to the special conditions in a spraying booth (table adapted from van Duurman-Stuurman et al. 2011).

146

Inhalation spray Inhalation spray is addresses in the inhalation module (see above)




The module is using a hazard band approach, where a hazard band (A-E, where A is the

lowest hazard and E is the highest) is assigned on the basis of the input parameters for the nanomaterials or characterisation from the parent material (see below).


Does the product contain fibers/fiber-like particles? (Y/N). If yes hazard band E

(see below for more detail) (taken from a general input module concerning product characteristics)

(Inhalation) hazard input is based on classification:

o Unknown o Mutagenic (and possibly carcinogenic) and/or sensitizing (hazard band

E) o Carcinogenic (not mutagenic), reprotoxic and/or very toxic (hazard band

D)

o Toxic, corrosive and/or respiratory allergens (hazard band C) o Harmful and/or irritating (hazard band B) o Non-hazardous (hazard band A)

"As the hazard of the MNOS is currently unknown, the hazard band is determined by expert judgement (for commonly used particles) or the classification of the parent material (other

particles)" (van Duuren-Stuurman et al., 2011b)


No, the model is aimed to be applicable for all types of non-soluble manufactured nano objects.


Hazard banding is done in a stepwise manner, and is based on the properties of the MNO. Step 1 concerns the water solubility of the MNO, which determines the applicability of the

Stoffenmanager nano tool. If a MNO is considered water soluble, the user is redirected to the generic Stoffenmanager tool. If the water solubility is unknown, the MNO is considered non-soluble.

In step 2 a distinction of persistent nanofibers (defined as (insoluble) nanofibers with a length > 5000nm, with the two other dimensions in the nano range) is needed. Because of the

147

uncertainty regarding the risk of nanofibers, persistent nanofibers are always classified in the highest hazard category (E). MNOs are treated as nanofibers when there is an indication for fiber-like properties. When no information is available, MNO are considered non-fibers.

In step 3 classification based on MNO-specific hazards is conducted, if information on the hazard of the particle itself is available. See above for input parameters.

If there is insufficient toxicological data for the given MNO, then classification can be made based on the hazardous potential of the parent material in step 4. Input parameters for this

step are type of MNO (chosen from a list consisting widely used MNOs (published by RIVM)) and primary particle diameter. The MNO are considered at least as toxic as the parent material, and in most cases it is classified in a higher hazard band than the bulk material.

When no data is available on the parent material, the highest hazard band (E) is assigned for precautionary purposes.


When no data on the toxicological properties for the MNO is available, hazard data for the

parent material is used (see above).


NA, the tool only addresses inhalation exposure.


NA, no quantitative dose descriptor is used.


management module


The tool provides more of a risk prioritization instead of a real control banding. The output of the model combines the results from the exposure and hazard banding in a risk matrix, which gives a risk priority band. These risk bands provide a relative ranking of risks for activities for

individual workers. Since both the exposure and hazard bands are based on qualitative measures, no quantitative output is given.


Yes, only inhalation is covered in this tool.


The algorithm of the tool combines exposure from near-field, far-field and background

inhalation exposure into a single exposure score. It is not possible to address combined exposure from e.g. inhalation and dermal exposure in the model as only inhalation is addressed.


148

The output is a risk priority band, which gives three different bands with different colour codes:

1 = high priority (red)

2 = medium priority (yellow) 3 = low priority (green)

See Table 9 below.

Table 9 Risk priority bands in Stoffenmanager (adapted from van Duurman-Stuurman et al. 2011)

Hazard band

Exposure band

A B C D E

1 3 3 3 2 1

2 3 3 2 2 1

3 3 2 2 1 1

4 2 1 1 1 1


After assigning a risk priority band, the tool enables the user to design a risk reduction scenario. A list with possible control measures that can be implemented to reduce exposure is presented. Subsequently, a new calculation of the risk priority band is completed

(implementation of a reduction scenario might not directly lead to a lower priority category though).

These control measures covers local control measures, control measures in the area directly around the source, control measures affecting the worker's wide surroundings, adaption of the worker situation and personal protective equipment. After completing this, an action plan

is provided to the user.


Uncertainties are not presented along with the output.

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Stoffenmanager 5.1 5.4

The tool is available from: https://stoffenmanager.nl/

In addition, the following background material has been reviewed for filling in this template: ECHA (2012): Guidance on information requirements and chemical safety assessment. Chapter R.14:

Occupational exposure estimation. Version 2.1. Available online; http://echa.europa.eu/documents/10162/13632/information_requirements_r14_en.pdf (Accessed 12.11.13)

Marquart H, Heussen H, Le Feber M, Noy D, Tielemans E, Schinkel J, West J, van der Schaaf D (2008). 'Stoffenmanager', a web-based control banding tool using an exposure process model. Ann. Occup. Hyg., 52(6), pp. 429-441

1

MILJOE (2003). Risk Assessment for Occupational Dermal Exposure to Chemicals RISKOFDERM Project QLK4-CT-1999-01107. Deliverable 48: Toolkit for Dermal Risk Assessment and Management. Available online:

http://www.insht.es/InshtWeb/Contenidos/Documentacion/FICHAS%20DE%20PUBLICACIONES/EN%20CATALOGO/Aip%20en%20catalogo/AIP%20203%20RISKOFDERM/Toolkit%20Paper%20Version.pdf (Accessed 14.11.13)

Oppl R, Kalberlah F, Evans PG, van Hemmen JJ (2003). A Toolkit for Dermal Risk Assessment and Management: An Overview. Ann. Occup. Hyg., 47(8), pp. 629-640.

Tielemans E, Noy D, Schinkel J, Heussen H, Van der Schaaf D, West J, Fransman W (2008). Stoffenmanager Exposure Model: Development of a Quantitative Algorithm. Ann. Occup. Hyg. 52(6), pp. 443-454.

TNO (2006). The RISKOFDERM Dermal Exposure Model Version 2.0 – Guidance Document. Available online: http://www.google.dk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=4&ved=0CEYQFjAD&url=http%3A%2F%2Fw

ww.tno.nl%2Fdownloads%2FThe%2520RISKOFDERM%2520Dermal%2520Exposure%2520Model%2520-%2520Guidance%2520document.doc&ei=W_KFUp-8EYi44AT_h4GwDg&usg=AFQjCNGZ6UU7EPVHPdl2ktOX8HQZYdX0IA&bvm=bv.56643336,d.bGE&cad=rja

(Accessed 15.11.13)

1 NB. It is important to note, that this background material refer to an older version of the Stoffenmanager (ver.

3.5).

https://stoffenmanager.nl/

http://echa.europa.eu/documents/10162/13632/information_requirements_r14_en.pdf

http://www.google.dk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=4&ved=0CEYQFjAD&url=http%3A%2F%2Fwww.tno.nl%2Fdownloads%2FThe%2520RISKOFDERM%2520Dermal%2520Exposure%2520Model%2520-%2520Guidance%2520document.doc&ei=W_KFUp-8EYi44AT_h4GwDg&usg=AFQjCNGZ6UU7EPVHPdl2ktOX8HQZYdX0IA&bvm=bv.56643336,d.bGE&cad=rja




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Summary


A general

input

module

Exposure-

dermal

module

Exposure-

oral module

Exposure –

general

inhalation

module

Exposure -

spray

module

Hazards

module

Output

module

()

1. Type of tool:

The Stoffenmanager is an occupational tool and has two different routes: a control banding/risk

prioritizing for both dermal and inhalation exposure (tier 1) and a quantitative assessment for

inhalation exposure (tier 1+). It is a non-expert tool developed for assessment of occupation

exposures especially in SMEs. The tool is not developed for consumer exposure and control banding

and thus do not contain methods for assessing oral exposure or exposure of subgroups e.g. children.

2. Input parameters:

General input parameters are data from the Safety Data Sheets (SDS). The input parameters for

exposure assessment are:

Dermal exposure

Product (chose from the products entered as described in Questionnaire 1 for the general input module with data from the SDS)

Dilution (if relevant)

Characterisation of the type of activity

o Handling objects or surfaces with (possible) presence of the product o Manuel dispersion of the product without a hand-held tool, but e.g. with

hands, cloth or sponge

o Dispersion of product with hand-held tool, e.g. brush, roller, scoop, broom or bucket

o Spray dispersion of product

o Immersing or dipping objects in product o Mechanical treatment of solid objects or product

Different input parameters are then required, depending on the activity chosen. If 'Spray dispersion of product' is chosen as an example (with a liquid substance), following input parameters are then required:

How is the liquid best described? Does spraying create fine mist (Y/N)

What is the distance to the source? Is the workroom small, narrow or enclosed (e.g. toilet) (Y/N) What is the working height during an activity?

How much product is used per quarter of an hour? Is the source segregated (Y/N) Is local exhaust ventilation used (Y/N)

Does workers wear working clothes (provided by employer) during the activity (Y/N) What is the total duration of the activity? What uncovered parts of the body are exposed?

151

Inhalation Exposure

Is the product a solid or liquid


Duration of task

Frequency of task

Distance to task

Is personal protective equipment applied? (Y/N)

Volume of working room

Characterization of type of general ventilation

Daily cleaning of working room (Y/N)?

Are inspections and maintenance of machines/ancillary equipment being done at

least monthly to ensure good condition and proper functioning and performance (Y/N)?

The tool is tailored requiring further input depending on what is selected as primary inputs. See further details in Questionnaire 2.

See point 4 below in relation to hazard input.


Stoffenmanager is applicable to liquids and solids and no exposure based waiving principles are

applied. The Stoffenmanager assesses exposure to products. These may be preparations (e.g. a

paint), but can also be pure substances. The Stoffenmanager is developed for use in an occupational

setting, and the consumer exposure scenarios from activity 2.1/1.1 are therefore not addressed as

consumer scenarios. However some of the scenarios/activities that are covered within the tool may

also apply to the scenarios from activity 2.1/1.1 (e.g. dermal and inhalation exposures from sprays,

paints, coatings etc.).

4. Overview

The hazard assessment is based on the R-phrases (or H-sentences) for the substance/product, and

these are then converted into a hazard band according to the COSHH Essential scheme2. The tool is

assessing inhalation and dermal exposure separately, and it has not been identified whether

combined exposure assessment is possible. Different levels of quantification are found for the

different assessment routes. For the risk prioritizing module, dermal and inhalation exposures can be

assessed and the outcome is qualitative in the form of a risk band. For inhalation exposures, a

quantitative assessment is also possible, where the output is giving exposure concentrations of tasks

in mg/m³.


Stoffenmanager is not targeted towards nanomaterials. It possible applicability for nanomaterials shall

be seen in the light of the specific “Stoffenmanager nano” developed (assessed in a separate

template). In general, we assess that Stoffenmanager can be used with caution e.g for dermal for

scenarios not addressed by the Stoffenmanager nano tool (currently focusing on inhalation).




The tool is developed by TNO as a part of the so-called 'VASt programme', established by the Safe and Healthy Work Department of the Ministry of Social Affairs and Employment of

Netherlands.

For which purpose, products and/or processes: The tool was developed to assist SMEs without specific expertise in chemical risk

assessment to prioritize the potential risk of chemicals handled and to indicate the types of

2 http://www.hse.gov.uk/coshh/essentials/index.htm

http://www.hse.gov.uk/coshh/essentials/index.htm

152

exposure controls that could lower these risks. At the moment the tool is available in Dutch, Finnish and English.


No


Although not a real validation, we might be able to compare (i.e. benchmark) results from

Stoffenmanager with those of other tools/information found in literature


For the dermal module, default potential exposure rates are assigned to the different exposure situations (see section for 'dermal exposure' below). These are multiplied with different modifying scores which gives a quantitative exposure rate as a result (Oppl et al.,

2003) (But not a quantitative exposure estimate).

For the control banding/risk prioritizing module for inhalation exposure, the exposure banding module is based on a semi quantitative approach, since the algorithm used for calculating a relative exposure score includes different multipliers for various modifying factors

For the quantitative inhalation assessment, the underlying algorithm is evidently quantitative.

The hazard “algorithm” is qualitative/decision-based categorising based on the classification.


Some information about model uncertainties is given for the quantitative inhalation model in Tielemans et al. (2008), which is stated to apply to 'reasonable worst case' scenarios.

For the dermal module it is also the impression that assessments are based on reasonable worst case. See Questionnaire 2 for details.

The banding approach is generally considered to be conservative.


The output consists of a qualitative control banding/risk prioritizing.

For inhalation, also a quantitative exposure estimate is provided ( in mg/m³).


Presentation of the banding output does not explicitly address uncertaintites. Regarding the quantitative inhalation exposure estimate output: "The variation in the model is included in the exposure assessment output, which enables the use of different percentiles of the exposure distribution. The estimated exposure distribution is also visualized in a graph" (ECHA, 2012)


The tool is developed to be used in SMEs by employers who are non-experts in occupational hygiene. In some parts of the calculations, user-friendliness was prioritised over precision (Marquart et al., 2008)

153


The tool has been recommended by REACH as a tier 1+ model in Chapter R14 (part

R14.5.1) in the Guidance on information requirements and chemical safety assessment (ECHA, 2012). The quantitative inhalation exposure module in the tool has also been recognized as method to evaluate dangerous substances at the workplace by the Dutch

Labour Inspectorate (De Arbeidsinspectie).


List the NM/product characteristics required as input parameters: Input parameters – product (data from the SDS)

Name of the product

Publication date of the SDS

Supplier

Whether the substance is a solid or a liquid

o For a solid: the dustiness Objects

Solid granules/grains/flakes Granules/grains/flakes Coarse dust

Fine dust Extremely dusty products

o For a liquid, the vapour pressure

If vapour pressure is unknown, the vapour pressure of water at 20°C is used as default value

Health and safety information

o R- and S-phrases or H-and P-phrases [R/S phrases for the product (i.e. not for the individual components), according to the SDS]

Composition of the product, according to the SDS o The different substances the product is composed of o Concentration of the substances within the product

Hazard categories (i.e. symbols according to the SDS)

Personal protective equipment (PPE) and ventilation needed (according to the SDS)

154


An illustrative overview of the tool (version 3.5) is given in Figure 6 below

Figure 6 Overview of Stoffenmanager, including risk banding and other important elements (Adapted from Marquart et al., 2008

155



For the inhalation modules, background exposure is taken into account as it is included in the exposure algorithm ("background concentration from diffuse sources (Cds)"). Background

concentration (score) is calculated as Cds = E*a,

where E= intrinsic emission multiplier (determines the intrinsic emission potential of a substance, e.g. dustiness for a particulate agent and volatility for liquids (Schneider et al., 2011) and a = multiplier for the relative influence of background sources.

It is a basic assumption in the model that the exposure (and the background score) has to be related to the intrinsic emission of the product (e.g. background emission of a high volatile substance is higher than for a low volatile substance) (Marquart et al., 2008)

The background documentation does not evaluate whether this should be considered

relevant for consumer exposure, as the model only concerns occupational exposure. Based on the information reviewed, background is not addressed for the dermal exposure

module.


No


For the RISKOFDERM model: "The model always calculates the median (50th percentile) of the output distribution appropriate to the input (…) You can indicate an additional percentile to be calculated in the input screen for the chosen "process"" (TNO, 2006). NB! It is not entirely

clear whether this option is available in the Stoffenmanager. For the assessment of internal exposure "‘reasonably worst case’ assumption of complete

percutaneous absorption, had to be used within this toolkit, and the internal exposure then

equals the actual exposure or is of the same order of magnitude. Except for a limited number of chemicals with low skin penetration, the toolkit considers internal exposure to be less than actual exposure" (Oppl et al., 2008)

For the risk prioritizing part of the inhalation assessment this issue is not explicitly addressed in the literature reviewed, although the impression is that assessments are based on worst

case. For the quantitative inhalation exposure assessment the mixed-effect regression model may

be used for assessment of reasonable-worst-case scenarios (Tielemans et al. 2008). "Depending on how conservative the inputs provided are, a higher or lower percentile should be used as an estimator of the reasonable worst case. If more or less typical values are

provided for all inputs, the 90th percentile of the output distribution is recommended for use in risk assessment. If conservative values are used for all Inputs, the 75th percentile of the output distribution is recommended for use in risk assessmen"t (ECHA,2012)


No

156


Yes, for the risk prioritizing part of the inhalation module the tool will calculate an overall

exposure score using an exposure algorithm. This score is not used directly (as the score itself does not represent a quantitative exposure level), but the score/result of the algorithm is used to assign a qualitative exposure band (1-4) on the logarithmic scale (see Table 7

below). For the dermal module, two different outputs are given: one health risk that refer to local

health effects and another health risk that refers to systemic effects after percutaneous uptake. In the algorithm peak actual exposure scores and internal exposure scores are calculated for local and systemic health effects, respectively, and these are then converted to

a banding scheme that indicates the significance of the exposure (Oppl et al. 2003) (See

Table 11 and Table 12 below)

Table 10: Assignment of exposure scores to exposure bands. (Marquart et al., 2008)

16. Exposure

band

17. Minimum

exposure score

18. Maximum

exposure score

19. 1 20. 0 21. 0.00002

22. 2 23. 0.00002 24. 0.002

25. 3 26. 0.002 27. 0.2

28. 4 29. 0.2 30. 20

Table 11 Peak actual exposure (AE) scores (for substances with local health effects) (Adopted from Oppl et al., 2003)

AEDPEAKscore x EBA score Actual exposure

AEPEAK scores

0.002 or less Negligible

>0.002-0.02 Low

>0.02-0.2 Moderate

>0.2-2 High

>2-20 Very high

>20 Extreme

AEDPEAK score = AERPEAK score x AT score, where AEDPEAK is the actual exposure dose,

AERPEAK is the actual exposure rate and AT is the activity time. EBA = exposed body area (cm

2). For further detail and information about the assignment of different scores, please refer

to Oppl et al. (2008).

157

Table 12 Internal exposure (IE) scores (for substances with systemic health effects after uptake) (Adopted from Oppl et al., 2003)

ED score x EBA score Relative IE score IE score

0.5 or less 0.007 or less Negligible

>0.5-5 >0.007-0.07 Low

>5-50 >0.07-0.7 Moderate

>50-500 >0.7-7 High

>500-5000 >7-70 Very high

>5000 >70 Extreme

ED score = ER score x AT score, where ED is the exposure dose score, the ER score is the exposure rate score and the AT score is the activity time score. The IE score = ED score x EBA score, where EBA is exposed body area. The relative IE score = IE score / 70 (related to

the standard body weight of 70 kg). The IE scores are then transformed into a banding scheme that indicates the significance of the internal exposure.

Dermal exposure The dermal module is incorporating the RISKOFDERM Toolkit (TNO). "Because of the integration in the total tool, some questions that are in the RISKOFDERM Toolkit do not appear in the dermal part of Stoffenmanager

because they are already covered in the general hazards part or the inhalation exposure part. This does not influence the actual risk assessment for dermal exposure" (Marquart et al., 2008). It is not entirely clear whether

RISKOFDERM is incorporated in its full form or if some modifications other that those cited have been made for

the version included in Stoffenmanager. Some parts of the evaluation of the dermal exposure module are therefore made on the basis of literature for the RISKOFDERM tool.

Which input parameters are required (including whether they are taken from a possible general input module) (dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

Location/department

Product (chose from the products entered as described in Questionnaire 1 for the

general input module)

Dilution (if relevant)

Characterisation of the type of activity o Handling objects or surfaces with (possible) presence of the product

o Manuel dispersion of the product without a hand-held tool, but e.g. with hands, cloth or sponge

o Dispersion of product with hand-held tool, e.g. brush, roller, scoop,

broom or bucket o Spray dispersion of product o Immersing or dipping objects in product

o Mechanical treatment of solid objects or product

Different input parameters are then required, depending on the activity chosen. If 'Spray dispersion of product' is chosen as an example (with a liquid substance), following input parameters are then required:

How is the liquid best described?

o Like water, included foam

o Like solvent o Like oil or grease o Like solvent suspension (for example glues, paints, gels, pastes, and tars

with solvents) Does spraying create fine mist (Y/N) What is the distance to the source?

o One arm's length or less o More than one arm's length (including length of the hand tools)

Is the workroom small, narrow or enclosed (e.g. toilet) (Y/N)

158

What is the working height during an activity? o Mostly at waist level o Mostly below waist level

o Mostly at or above shoulder level How much product is used per quarter of an hour?

o Less than 0.9L/quarter

o About 4.5. L/quarter o More than 22.5 L/quarter

Is the source segregated (Y/N)

Is local exhaust ventilation used (Y/N) Does workers wear working clothes (provided by employer) during the activity (Y/N) What is the total duration of the activity?

o Less than 6 minutes a day o 6-30 minutes a day o 30-60 minutes a day

o 1-4 hours a day o More than 4 hours a day

What uncovered parts of the body are exposed? (chose one or more options)

If a solid substance is chosen instead, other input parameters are required. Please refer to the actual tool (http://stoffenmanager.nl) for details.


The Stoffenmanager is developed for use in an occupational setting, and therefore are the consumer exposure scenarios from activity 2.1/1.1 not addressed as consumer scenarios.

However, by-and-large, it is assessed that the dermal exposure resulting from the scenarios/activities that are covered within the tool could be used with caution to assess the scenarios from activity 2.1/1.1 (eg. handling of cleaning agents, coatings/impregnation or

maintenance products where dermal exposure is expected)


Exposure: Yes, default factors/calculations are used to estimate an exposure score, then again assigned an exposure band.

Hazards: Yes, default factors/algorithms are used to convert Hazards phrases to hazard bands.


See above


Liquids Solids (including powders)


Included, but mechanisms not entirely clear how this is incorporated in the algorithms of the tool. It is stated that "potential dermal exposure may occur via three different routes of exposure: direct contact with the chemical, contact with contaminated surfaces (e.g. tools, tables, walls), and contact with an aerosol after deposition onto the body" (Oppl et al. 2003).

And if choosing 'Spray dispersion of product' in characterising the type of activity, an input parameter is required stating: 'Does spraying create fine mist (Y/N)', which is the closes

parameter that resembles an input requirement regarding aerosol formation.

http://stoffenmanager.nl/

159


NA, no quantitative exposure estimates are given in the dermal module


Yes, different risk management measures are part of the modifying factors affecting exposure estimate. The effect of degree of automation, segregation, containment and ventilation is taken into account (MILJOE, 2003) (see Table 13)

Table 13 Correction factors for Control-related modifiers describing the typical effectiveness of control actions applied. The values in the Table are the modifier factors MFDC, MFSC, MFDEP


Location/department

Is the product a solid or liquid

o If solid: does the situation concern shaping by removing or cutting of material (Y/N)?

If yes: what kind of dust is released

Wood

Stone

If no: choose product (from the products entered as described in Questionnaire 1 for the general input module)

o If liquid:

Select product (from the products entered as described in Questionnaire 1 for the general input module)

160

Select dilution


o If solid: No shaping by removing or cutting of material

Handling of products in closed containers

Handling of products in negligible amounts

Handling of products in very small amounts or situations where release is highly unlikely

Handling of products in small amount or in situations

where only low quantities of products are likely to be released

Handling of products with low speed or with little force in medium quantities

Handling of products with a relatively high speed/force which may lead to some dispersion of dusts

Handling of products or treatment of objects, where due to high pressure, speed or high force, large

quantities of dust are generated and dispersed

Handling of very large amounts of product

Shaping by removing or cutting of material

If wood is chosen

o Mechanical sanding of woods o Mechanical sanding of woods resulting in

fine dusts o Mechanical sanding of woods resulting in

coarse dusts or chips o Manual sanding of woods

o Low energy mechanical handling of wood resulting in less dusts

o Other mechanical handling of wood

If stone is chosen o Mechanical sawing and sanding of stone

o Mechanical handling and demolition of stone resulting in fine dusts

o Low energy mechanical handling of stone

o Low energy mechanical handling of stone resulting in less dusts

o If liquid:

Handling of liquids in tightly closed containers Handling negligible amounts of product Handling of liquids where only small amounts of product may

be released Handling of liquids at small surfaces or incidental handling of

liquids

Handling of liquids using low pressure, low speed and on medium-sized surfaces

Handling of liquids on large surfaces or large work pieces

Handling of liquids (using low pressure but high speed) without creating a mist or spray/haze

Handling of liquids at high pressure resulting in substantial

generation of mist or spray/haze

Duration of task

o 1-30 minutes a day o 0.5-2 hours a day o 2-4 hours a day

o 4-8 hours a day

Frequency of task o 1 day a year

o 1 day a month o 1 day per 2 weeks o 1 day a week

o 2-3 days a week o 4-5 days a week

Distance to task

o Is the task being carried out in the breathing zone of an employee (distance head-product <1m) (Y/N)?

o Is there more than one employee carrying out the same task simultaneously (Y/N)?

o Is the task followed by a period of evaporation, drying or curing (Y/N)?

Protection of employee o Is personal protective equipment applied? (Y/N)

If yes, different options can be selected

161

Volume of working room

Characterization of type of general ventilation

o Spraying booth o General ventilation (open windows)

o General ventilation (mechanical) o No general ventilation

Daily cleaning of working room (Y/N)?

Are inspections and maintenance of machines/ancillary equipment being done at least monthly to ensure

good condition and proper functioning and performance (Y/N)?


"The Stoffenmanager prioritizes exposure to products. These may be preparations (e.g. a

paint), but can also be pure substances. Basic data on the products can be entered manually or (largely) from a database with product information, using a standard exchange format"

(Marquart et al., 2008). Thus, Stoffenmanager applies to products, where basic data from the

SDS are available. Since Stoffenmanager is developed for use in an occupational setting the consumer exposure

scenarios from activity 2.1/1.1 are not addressed as consumer scenarios. However some of the scenarios/activities that are covered within the inhalation module may also apply to the scenarios from activity 2.1/1.1 (e.g. handling of cleaning products, coatings/impregnation or

maintenance products where inhalation exposure is expected)


Exposure: Yes, default factors/calculations are used to estimate an exposure score, then

again assigned an exposure band. Hazards: Yes, default factors/algorithms are used to convert Hazards phrases to hazard

bands.


See above.


No, not a nano tool.


Solids (including powders, but also solid objects)

Liquids


No.


Mass is used as metric for the quantitative exposure concentration. Output: mg/m³.

162


Yes, different risk management measures are a part of the modifying factors affecting the final exposure score. Different multipliers are given depending on the different local control

measures. An example of the scores for local control measures is given in Table 14. The different input parameters are:

Size of the working room Type of general ventilation Daily cleaning of working room (Y/N)

Are inspections and maintenance of machines/ancillary equipment being done at least monthly to ensure good condition and proper functioning and performance? (Y/N)

Available control measures: o No control measures at the source o Use of a product that limits the emission

o Local exhaust ventilation o Containment of the source o Containment of the source with local exhaust ventilation

Is the employee situated in a cabin? o The employee does not work in a cabin o The employee is situated in an open or closed cabin without specific

ventilation system o The worker is in a separated (control) room with independent clean air

supply Is personal protective equipment applied

o No protection o Filter mask P2 (FFP2) o Filter mask P3 (FFP3)

o Half-mask respirator with filter, type P2L o Half-mask respirator with filter, type P3L o Full-face respirator with filter, type P2L

o Full-face respirator with filter, type P3L o Half-/full-face powered air respirator TMP1 (particulate cartridge) o Half-/full-face powered air respirator TMP2 (particulate cartridge)

o Half-/full-face powered air respirator TMP3 (particulate cartridge) o Full-face powered air respirator TMP3 (particulate cartridge) o Hood or helmet with supplied air system TH1

o Hood or helmet with supplied air system TH2 Hood or helmet with supplied air system TH3

163

Table 14 Scores for local controls.

164


For the quantitative inhalation module, it is also possible to calculate a daily average

concentration. Inputs are:

Do you want to perform the calculation for vapours or for inhalable/Respirable

dust? o Liquid o Dust

Pick of (performed) risk assessment, for which you want to calculate daily average concentration

Duration (min)

Output is then an daily worst-case concentration (in mg/m³)

Figure 2 shows the applicability of the qualitative exposure module.

Product

Activity

Gas Volatile

liquids

Non-

volatile

liquids

Powders Fibers Objects

Moving and agitating n.a.

Gravitational transfer n.a.

Spreading and immersion n.a.

Air dispersive techniques n.a.

Hot work techniques n.a.

Abrasion and impact n.a. n.a. n.a. n.a. n.a.

Figure 7 The applicability domain for the qualitative inhalation exposure model (from https://stoffenmanager.nl/Public/Explanation.aspx#/#referenties (accessed 12.11.13)

Green = Falls in the applicability domain.

Red = Falls out of the applicability domain.

Orange = Applicability of this combination is unsure.

n.a. = Not applicable; this situation cannot occur.

Inhalation spray (not addressed):


https://stoffenmanager.nl/Public/Explanation.aspx#/

165



The hazard characterisation is done on the basis of the R/H-phrases of the product or substance according to the COSHH Essentials scheme

3


The R- and S-phrases or H- or P-phrases from the Safety Data Sheet for the substance or product is entered as the input parameter.


The risk prioritization part of the Stoffenmanager is not suitable for substances or products without SDS or products for which R-phrases are unknown or not available. If the tool must

be used for such substances, determination of the R-phrases should be done with the help of an expert.

The dermal module of the tool is not suitable for risk characterization of products containing substances which are labelled as both (very) toxic and corrosive.

The applicability of the quantitative inhalation exposure tool is pictured in Figure 7. It is

advised not to use this part of the tool for fibers, gases or substances released into the air as a result of hot working techniques.

Are hazard-based grouping principles applied, e.g. banding according to classification or selected hazard end-point; high hazard potential for high aspect ratio materials; regular hazard potential for water-soluble NMs; nano at least as toxic as bulk/macro, etc.: Yes, a hazard band is given for each substance on the basis on the R-phrases (or H-sentences according to the

CLP-GHS) entered according to the COSHH Essential scheme – see below:

3 http://www.coshh-essentials.org.uk/assets/live/CETB.pdf (accessed 12.11.13)

http://www.coshh-essentials.org.uk/assets/live/CETB.pdf

166

Table 15 Allocation of R-phrases or GHS phrase to Hazard Group; concentration range (from http://www.coshh-essentials.org.uk/assets/live/CETB.pdf (accessed 12.11.13))


No


No, hazards are only linked to the R-phrases (or H-statements) for the substance.


NA, no quantitative dose descriptor applied.

http://www.coshh-essentials.org.uk/assets/live/CETB.pdf

167


management module


The tool was developed as a control banding tool, and the results from the dermal exposure module are

qualitative. The output of the model combines the results from the exposure and hazard banding in a risk matrix, which gives a risk priority band (1, 2 and 3). For inhalation exposures, the tool contains a quantified and validated exposure model for estimating

inhalation exposure to both inhalable dust and vapour. Thus, for inhalation exposures the output can be both quantitative (giving exposure concentrations of tasks in mg/m³) and control banding.


Yes, inhalation and dermal exposure is covered in the tool.


Not identified in reviewed material


The output for the control banding module is a risk priority band, which gives three different

bands with different colour codes: 1 = high priority (red) 2 = medium priority (yellow)

3 = low priority (green) See Table 9 below.

Table 16 Risk priority bands in Stoffenmanager (adapted from van Duurman-Stuurman et al. 2011)

Hazard band

Exposure band

A B C D E

1 3 3 3 2 1

2 3 3 2 2 1

3 3 2 2 1 1

4 2 1 1 1 1

168


After assigning a risk priority band, the tool enables the user to design a risk reduction scenario. A list of generic exposure control measures can be evaluated for their possibility to reduce exposures/risks. Subsequently, a new calculation of the risk priority band is completed

(implementation of a reduction scenario might not directly lead to a lower priority category though).

These control measures are presented in order of the 'STOP-principle' (substitution, technical measures, operational measures and personal protection). After completing the risk reduction scenario, an action plan is provided to the user. In addition the Stoffenmanager can be used to generate workplace instruction cards that are more readable and user-friendly than the

SDSs. For users from The Netherlands, Stoffenmanager can also help with building up registry for

CMR-substances (legally required in The Netherlands). Information for storage of dangerous substances and explosion safety can also be evaluated via Stoffenmanager.


No.

169

The ANSES tool 5.5 The tool is available from: Not available as web-tool.

In addition, the following background material has been reviewed for filling in this template: ANSES (2010). Development of a specific Control Banding Tool for Nanomaterials. Request

N°2008-SA-0407 relating to Control Banding. Expert Committee (CES) on Physical Agents. French

agency for food, environmental and occupational health and safety.

Brouwer D. H. (2012). Control Banding Approaches for Nanomaterials, Ann. Occup. Hyg., Vol. 56,

no. 5 pp. 506-514, Oxford University Press

Riediker M., Ostiguy C., Triolet J., Troisfontaine P., Vernez D., Bourdel G., Thieriet N. and Cadène

A. (2012). Development of a Control Banding Tool for Nanomaterials, Research article, Journal of

Nanomaterials, Volume 2012, Article ID 879671, 8 pages

170

Summary


A general

input

module

Exposure-

dermal

module

Exposure-

oral module

Exposure –

general

inhalation

module

Exposure -

spray

module

Hazards

module

Output

module

*the tool does not cover a specific spray module, but it is included in the general inhalation module.

1. Type of tool

ANSES is a tier 0 control banding tool, which is developed to be used by in relation to laboratory and industrial

production environments. The tool is developed for use for persons with a sufficient level of expertise within the

fields of chemical risk prevention. The concept of the tool shall be seen in light of the French activities in ISO TC

229 (ISO technical committee addressing nanomaterials). It is noted in the reviewed literature that is has been

forwarded to ISO, but the outcome of this process is not evident. Further, to our knowledge, the tool has not yet

been implemented in a web-tool, making the assessment in this document somehow limited.

2. Input parameters

The input parameters for the exposure assessment are:

Physical form – matrix in which nanomaterial is used (Solid matrix, in suspension/liquid, as powder,

as free NM/aerosol)

In addition for solid matrices:

o Friable solids (release of NM under low stress)

o Dust generated by external forces (e.g. mechanical, electrical, laser forces)

o Melting?

o Dispersion in liquid

Liquids/suspensions:

o Highly volatile liquids (possibly generating NM powder – if so dustiness is required)

o Spraying?

o Generation of aerosol during process?

Powder

o Dustiness

o Spraying?

The input parameters for the hazard assessment (all parameters not always needed):

Does the product contain nanomaterials?

Is the nanomaterials classified (CLP)

Is it a biopersitent fibre?

If NM not classified: Classification of bulk (preferred) of analogues materials

Solubility

Reactivity

It is noted that the following parameters are not taken into account:

Quantity of products used

Duration

Frequency of exposure


As can be seen above, the tool addresses four categories of physical forms of nanomaterials: in solid matrices,

in liquid, suspensions, as powder and as aerosols, listed in order of increasing emission potential affecting the

exposure score. Exposure based waiving principles based on matrix are thus implicitly addressed.

171

The ANSES is developed for use in an occupational setting, and the consumer exposure scenarios from activity

2.1/1.1 are therefore not directly addressed. The method might however be applied for possible consumer

inhalation related to all the scenarios identified in activity 2.1/1.1.

4. Overview

The tool focuses on reducing the risks associated with occupational inhalation exposure. Hazards are largely

based on classification (of NM or bulk/analogues substances) also taking into account possible fibre like

properties as well as solubility and reactivity.

Algorithms used are decision-based and not quantitative.

Output are qualitative exposure and hazard bands combined into risk bands, which in turn trigger various risk

control strategies (focusing on engineering control measure and explicitly not addressing personal protective

equipment).


The ANSES methodology is targeted at nanomaterials and has quite some analogy to the Stoffenmanager nano

tool, in particular on the hazard side.

172




The methodology was developed by an interdisciplinary and international expert team in

request to the French Ministry of Health, in agreement with the Ministries for the Environment and Labour, who had requested that ANSES conduct a collective expert appraisal specifically on Control Banding applied to manufactured nanomaterials. In turn the methodology should

via the French standardisation organisation be feed into the ISO process. The progress in ISO has not been evident from reviewed literature. ANSES is a nano-specific Control Banding tool.


The ANSES control banding method was developed as an alternative to quantitative risk assessment, considered uncertain for NMs. The method focused on a qualitative approach

focusing on risk prevention to protect workers exposed via inhalation to manufactured nanomaterials. Classifying manufactured nanomaterials in hazard bands will ultimately provide producers and users of these substances with input data for risk management

according to control levels, or ‘Control Banding’. Applicability of the tool: The output data from the tool should only be used for risk management if the regulatory

environment in force in the country considered has been taken into account. The control banding method requires regular updating of scientific and technical knowledge in order to better adapt the means of prevention implemented.

The method is not adapted to extreme situations, for example (ANSES, 2010):

If the nanomaterials are an extremely diluted component of the product used,

Or when handling large volumes, which requires special expertise.


“... the approach was not yet extensively tested and still needs to be validated to be truly

practical for the proposed group of users” (Riediker et al., 2012).


Although not a real validation, we might be able to compare (i.e. benchmark) results from of this tool with those of other tools/information found in literature.


The algorithms of the methodology are yes/no decision based and thus not quantitative. Thus, no quantitative algorithms are used.


The algorithms generally use higher bands if exposure could be higher and higher hazards than those of bulk/analogues substances are always assigned.


The output of the hazard banding module and the exposure banding module is qualitative. Thus, the final risk and control banding output of the model is qualitative.

173


This functionality is difficult to judge given the lacking web-application, but from the reviewed

literature, it is not obvious that the output will describe the uncertainty (considered implicitly covered in the control banding approach).


ANSES is developed to be used by a person ‘adequately qualified in chemical risk prevention’ (Brouwer, 2012) and it is intended to be used in industrial companies, SMEs and academic

institutions. Input parameters to the assessment are selected on the basis of the availability of these parameters and only a few parameters are applied, e.g. from the Safety Data Sheets.

However, though the tool seems easy and simple to apply for managing the risks of individual workplaces, the CB method applied to manufactured nanomaterials requires assumptions to

be formulated on information that is desirable but unavailable (Riediker et al., 2012). To be able to obtain the necessary parameters for this CB, the user should be proficient in chemical risk prevention and have some basic knowledge on nanomaterials and nanotoxicology

(Riediker et al., 2012). Also the output generated by the CB will have an impact on other processes of the overall

management system defined by the employer and a ‘central support’ that overlooks the risk management strategy and that provides risk assessment expertise is essential.

174




Physical form – matrix in which nanomaterial is used (Solid matrix, in

suspension/liquid, as powder, as free NM/aerosol)


o Friable solids (release of NM under low stress) o Dust generated by external forces (e.g. mechanical, electrical, laser

forces)

o Melting? o Dispersion in liquid



o Spraying?


Powder

o Dustiness o Spraying?






Solubility

Reactivity

It is noted that the following parameters are not taken into account:

Quantity of products used

Duration


175



Not addressed in reviewed literature


Implicitly addressed via considering NMs in different matrices having different exposure potentials.


Exposure bands are assigned taking into account potential for release of free nanoparticles. This could be considered a general conservative approach is used in assigning exposure

bands.


No


The module is using an emission potential band approach qualitatively estimate an overall

emission potential (see Figure 8 below). ANSES covers the emission potential by initial banding based on physical state of the material, ranging from solid (exposure band 1) to aerosol (exposure band 4). Further modification of the bands (increments) is possible either

due to the substance emission potential or due to the process operations (activity emission potential) (Brouwer, 2012). ANSES covers the source domains 2-4; however, it is unclear whether the emission during synthesis (domain 1) may be covered as well (Brouwer, 2012).

Dermal exposure (not addressed)



Physical form – matrix in which nanomaterial is used (Solid matrix, in

suspension/liquid, as powder, as free NM/aerosol)


o Friable solids (release of NM under low stress) o Dust generated by external forces (e.g. mechanical, electrical, laser

forces)

o Melting? o Dispersion in liquid


176


o Spraying?


Powder

o Dustiness o Spraying? o

It is noted that the quantity of the products used, the duration and the frequency of the exposure are not taken into account. The input parameters are all quantitative and in the

figure below the banding of the emission potential can be seen. How input parameters affect the exposure band is shown in Figure 8

Figure 8: ANSES exposure bands (figure adopted from ANSES (2010))


The ANSES methodology is developed for use in an occupational setting, and the consumer

exposure scenarios from activity 2.1/1.1 are therefore not directly addressed. The method might however be applied for possible consumer inhalation related to the scenarios identified in activity 2.1/1.1.


No default factors are applied, since all input parameters are qualitative.


No default calculations are applied, since all input parameters are qualitative.


The tool does not assess aggregation/agglomeration in the product. Aerosols are incorporated as one of the categories in the exposure bands and modification of the bands is

177

possible either due to the substance emission potential or due to the process operation (Brouwer, 2012), see also above figure.


The following four matrices are addressed, listed in order of increasing emission potential affecting the exposure score:

Solid

Liquid

Powder

Aerosol


Evaporation is qualitatively assessed under EP2, liquids. Highly volatile liquids are assigned 1 extra band as powders could be generated.


No quantitative estimates are used.


No, but the output are suggestions of risk management measures.

Inhalation spray (no specific module, but part of above inhalation module):




The module is using a hazard band approach, where a hazard band (HB1-HB5, where HB1 is

the lowest hazard and HB5 is the highest) is assigned on the basis of the input parameters for the nanomaterials or the characterisation from the parent material (see below).

HB1 = Very low: No significant risk to health

HB2 = Low: slight hazard – slightly toxic effects rarely requiring specific medical

follow-up

HB3 = Moderate: moderate to significant health effects requiring specific medical

follow-up HB4 = High: unknown health effects or serious hazard: material highly toxic, sensitising, or with unknown effects on health or the environment. Emission

or exposure in the environment requires a specific survey.

HB5 = Very high: severe hazard requiring a full hazard assessment by an expert.

In the figures (Figure 9 and Figure 10) below the interactive decision-making (based on input parameters) and the hazard banding can be seen.

178

Figure 9: A flowchart showing the input parameters and the hazard banding (figure adopted from ANSES (2010)).

179

Figure 10: Hazard banding according to classification and labeling (figure adopted from

ANSES (2010))







Solubility

Reactivity

Size as such is not considered to be a separate hazard parameter (Brouwer, 2012).


The tool is suitable for any type of nanomaterial, as long as the amount handled are neither

too diluted nor of excessive volume. However, for the highest risk/control band, the user is advised to conduct a full risk

assessment


180

The ANSES methodology uses the CLP classification, as the starting point for the hazard banding process if the MNM is not a biopersistent fibre. Hazard parameters such as dissolution time and reactivity may increase the hazard band (Brouwer, 2012).


If information on the toxicology of the nanomaterial or product containing is incomplete or non-existent, the substance that is chemically closest to the nanomaterial should be

considered: bulk material, analogous material (ANSES, 2010). When the bulk material exists, it takes precedence over the analogous material (ANSES, 2010). Finally if there are several choices for the same bulk (analogous) material, the most toxic one shall be taken into account (ANSES, 2010).


The methodology focuses on inhalation.


Not relevant as no quantitative dose descriptor applied.

181


management module


The tool provides qualitative risk control banding. The output of the model combines the

results from the hazard and emission potential bands in a matrix of control classes. Each control level corresponds to technical solutions for collective prevention to be implemented at the work station (ANSES, 2010).


The methodology addresses inhalation exposure


Not addressed in reviewed literature.


The output is a matrix of control classes, which gives five different bands with different colour codes:

CL1 = Natural or mechanical general ventilation (white)

CL2 = Local ventilation: extractor hood, slot hood, arm hood, table hood, etc.(light

grey)

CL3 = Enclosed ventilation: ventilated booth, fume hood, closed reactor with

regular opening (dark grey)

CL4 = Full containment: continuously closed systems (light green)

CL5 = Full containment and review by a specialist required: seek expert advice (dark green)

See Table 9 below.

Table 17 Matrix of control classes in ANSES (adapted from ANSES 2010)


Yes, the outcome is qualitative technical solutions for collective prevention to be implemented at the work station. It should be noted that the wearing of personal protective equipment has deliberately not been taken into account (ANSES, 2010). Furthermore the result of the

approach should be reviewed as soon as circumstances change (process modifications, development of scientific knowledge or state of the art, etc.) (ANSES, 2010).

182


Uncertainties within the model are not addressed in the reviewed literature for the ANSES tool.

183

Swiss Precautionary Matrix 5.6 The tool as a web-tool is available from: http://www.bag.admin.ch/nanotechnologie/12171/12174/12175/index.html?webgrab_path=aHR0cDovL3d

3dy5iYWctYW53LmFkbWluLmNoL25hbm9yYXN0ZXIvcG9ydGFsX2VuLnBocD9tb2Q9YSZsYW5nPWVu&lang=en

and the guide: Wegleitung zum Vorsorgeraster für Synthetische Nanomaterialien BAG/BAFU 2011, Version 3.0, 16.09.2013

Available from: http://www.bag.admin.ch/nanotechnologie/12171/12174/index.html?lang=en

- at present only as a German version

In addition, the following background material has been reviewed for filling in this template: Guidelines on the Precautionary Matrix for Synthetic Nanomaterials Version 2.1, 2011

http://www.bag.admin.ch/nanotechnologie/12171/12174/12175/index.html?webgrab_path=aHR0cDovL3d3dy5iYWctYW53LmFkbWluLmNoL25hbm9yYXN0ZXIvcG9ydGFsX2VuLnBocD9tb2Q9YSZsYW5nPWVu&lang=en



http://www.bag.admin.ch/nanotechnologie/12171/12174/index.html?lang=en

184

Summary


A general

input

module

Exposure-

dermal

module

Exposure-

oral module

Exposure –

general

inhalation

module

Exposure -

spray

module

Hazards

module

Output

module

x (x) (x) (x) x x

(x) exposure addressed but not on specific exposure route level

1. Type of tool The Swiss Precautionary Matrix for Synthetic Nanomaterials is a scoring tool considering exposure potential, hazard potential and level on information for evaluating whether further precautionary actions are

needed in relation to consumers, workers or the environment for the current/ intended use of a nanomaterial. Can be considered as a tier 0 level tool. The tool shall only be used if the substance has nano relevant properties, e.g. primary particles < 500 µm or e.g. fulfil the EU definition as a nanomaterial.

2+3: Input parameters + matrices/scenarios Input data pertain to:

Physico-chemcial characteristics regarding primary particles size, specific surface area, no of particles in the nano-range, agglomeration in order to evaluate whether the substance can be identified as nano relevant e.g. in relation to the EU definition of a nanomaterial. The nano relevance is extended to a cut-off

point of 500 nm for primary particles in the approach Then the following information has to be used as input for grading at 3-4 different levels for each parameter:

- Information level of the nanomaterial (0- 3-5 points for each of four types of information) - Reactivity of the NM (1-5-9 points) - Lifetime (stability) in the body of the NM (1-5-9 points) (-here information concerning coating

is also requested) - Matrix description (various categories from aerosols to solid matrices) (0.0001- 0.01- 0.1-1

points)

- Volume of NM to which the consumer is in contact per event (1-5-9 points) - Frequency (1-5-9 points)

No specific product types are addressed in the approach so in principle it includes all products/ scenarios identified in WP 1.1/2.1.

4. Overview Hazard is evaluated based on the reactivity of the nanomaterial (redox potential; ROS generation; (photo-) catalytic properties; potential for inflammation) and on the degree of persistency in the human body (hours;

days/weeks; months). Consumer exposure is evaluated (scored) based on consideration of liberation from the matrix (four

graduations from 0.0001 to 1) and an estimation of the total volume (three graduations: < 1.2 mg; < 12 mg; >12 mg) of nanomaterial per day that the consumer may be exposed to from the product/ article. Also frequency (three graduations: monthly; weekly; daily) of exposure is included in the overall exposure

score. Further, an additional scoring is added if the information level is low and data for e.g. lack of ID of NM, lack

on data on physicochemical parameters or impurities.

For the overall evaluation the exposure scores are multiplied with the hazard scores and to this figure

scores for the lack of information is added.

If the overall score is above 20, further precautionary measures are recommended whereas a score of 20

or below does not call for further action.

A high degree of precaution is built into the tool as input with “unknown” for a specific parameter results in

a default scoring at the highest level. 5. Tool targeted at nano? Although developed for nanomaterials the approach in its exposure scoring procedure take only account of

mass based dose metrics.

185

For the purpose of our project, some aspects may be considered for further use e.g. how to evaluate (or score) matrix effects, reactivity, persistence in the body (stability) or how to treat lack of information.

186




Federal Office of Public Health in Switzerland


To help industry with a framework for responsible handling of nanomaterials. The tool

enables risk banding in two classes (A or B) for either occupational risk, consumer risk or environmental risk. Class A indicates no concern whereas class B indicate that further action is needed regarding risk management measures or collection of further information.


Specifically developed for nanomaterials (validation of this is not specif ied in reviewed literature/material)


Although not a real validation, the project might at a later stage decide to compare outcome with that of other tools.

Describe the level of quantification of the algorithms of the different modules of the method/tool: Various parameters are given semi-quantitative estimates divided in 3-4 different levels.

E.g.:

Consumer exposure (Ev) = Matrix effect (E1A,V ) x dose (E2.4) x frequency (E2.5) Matrix effect scores, e.g.: 1 (free in air); 0.1 (in liquid); 0.01 (solid matrix but migration of

NM); 0.0001 (solid matrix non-migrable NM) Dose: <1.2 mg (score 1); <12 mg (score 5); >12 mg (score 9)

Frequency: monthly (score 1); weekly (score 5); daily (score 9)

Hazard (WA,V) = reactivity (W1) x stability (W2A,V ) Reactivity: low (score 1); medium score (score 5); high (score 9) with respect to either redox

activity, ROS generation or (photo-) catalytic effects or potential for inflammation Stability: persistence in the human body of hours (score 1), days/weeks (score 5), or months

(score 9)

Precautionary need (VV ) = Nanodef (N A,V ) x (exposure (Ev) x hazard (WA,V)+ information level(I) )

Information level:

Nano ID known (score 0); Nano ID known to some extent (score 3); No information (score 5)

+ score for level of physic-chemical characteristics. Sufficient data (score 0), some data (score 3), no data (score 5) + score for impurities or other factors of influence. Sufficient data (score 0), uncertain data

(score 3), no data (score 5) If the overall score is below 20 the substance is in class A (no concern). Scores at 20 and

higher means the substance is placed in class B which mean further actions in relation to risk management or further collection of data.

187


Uncertainties are addressed in a precautionary manner as lack of information or ticking in the “unknown” box for a specific parameter by default results in worst case assumption with a maximum score. .


The output is a qualitative ranking at two different levels: class A (no further precautionary actions needed) and class B (further precautionary action is needed for reducing uncertainty or risk In addition to this the overall calculated score can be seen and it can be seen which

fraction of the score is due to “unknowns”.


Uncertainties in terms of lack of knowledge (I) or ticking in “unknown” for a parameter

increase the scoring due to default worst case scoring. The fraction of the overall scoring that pertains to “unknown” scoring can be seen in the output.


Some experience with interpretation/evaluation of physico-chemical properties in relation to characteristics for nanodefinition and in relation to evaluation of reactivity and stability is

needed otherwise the tool is an non-expert tool


The approach addresses the NM as such but does not provide guidance on specific uses or product categories

188



Before the approach is used several criteria for definition of a nanomaterial has to be fulfilled e.g. if primary particles of the material < 500 nm or it complies with the EU nano-definition Nano ID and a series of physico-chemical characteristics should if available be identified.



No


Graduation of exposure is made. No exposure based waiving.


No specific methods for evaluating the exposure but exposure assessment should be made whether exposure per day is <1.2 mg NM; 1.2-12 mg NM; >12 mg NM


Matrix factors are used e.g. a matrix factor of 10

-4 is used for a solid matrix and 0.1 for a liquid

matrix whereas a factor of 1 is used for aerosols < 10 µm. In relation to aerosols the

inhalation route is specifically mentioned as relevant, otherwise exposure routes are not further specified.

Although developed for nanomaterials the approach take only account of mass based dose

metrics (e.g. exposure to xx mg NM/ day).No other metrics such as surface area or particle

number are addressed.


No


Yes banding within each of the parameters: four levels of matrix effects; three levels of daily exposure; and three levels for frequency of use.

Dermal exposure (not explicitly addressed)

189


Inhalation is mentioned as the cause for the high scoring of aerosols but otherwise not further addressed

Inhalation spray (not specifically addressed):

Oral exposure (not specifically addressed)

190



The tool is estimating hazard in terms of reactivity (scored with 1-5-9 points) multiplied by the stabilbity/ persistence of the nanomaterial (scored with 1-5-9 points)


Nano ID; characterisation of physico-chemical parameters; redox activity; ROS generation; (photo) catalytic properties; inflammation potential; stability in humans (hours/ days/ months)


No limitations indicated as long as the criteria for the nano relevance apply. No specific considerations regarding fibres.


Reactivity is scored with either 1-5-9 points based on a table where specific well-known nanomaterials have been scored. Stability/ persistence in the body have to be scored on case

by case assumptions and allocated 1-5-9 points if the particle is persistent in the body for hours, days/weeks, or months.


No mentioning of how to use data on bulk form


No


No metrics applied to the hazard parameters

191


management module

How are the results communicated? (e.g. qualitatively, control banding, risk management guidance, semi-quantitative, as risk characterization ratios, probabilistic or fully quantitative). Describe if differences among various exposure routes and hazard categories. Below is given an example of the output. A precautionary triangle is made with the scoring for consumer (VV) at the top of the triangle. A table indicate the level of scoring and another table indicate how much scorings due to

“un known” input influence the overall scoring.


No

192


No


Output is class A (no concern) or class B (further measures/considerations have to be taken),

see also output above.


In general no specific risk managements are recommended other than trying to achieve further knowledge if scoring is highly dependent on lack of data and unknowns. However one example is given as how to proceed:


Se output figure above indicating scoring due to “unknowns”.

193

ECETOC TRA 5.7

ECETOC TRA version 3

The tool is available from: http://members.ecetoc.org/Documents/Document/20120705110808-ConsumerTRA_Ver3_2May2012.zip

In addition, the following background material has been reviewed for filling in this template: ECETOC 2004. Targeted Risk Assessment, Technical Report No. 93

ECETOC 2009. Addendum to Targeted Risk Assessment Report No. 93. Technical Report No 107. ECETOC 2012. ECETOC TRA version 3: Background and rationale for the improvements. Technical Report No. 114.

http://members.ecetoc.org/Documents/Document/20120705110808-ConsumerTRA_Ver3_2May2012.zip

194

Summary


A general

input

module

Exposure-

dermal

module

Exposure-

oral module

Exposure –

general

inhalation

module

Exposure -

spray

module

Hazards

module

Output

module

x x x x (x) X (possibility

to enter

reference or

DNEL-values)

x

(X) as a part of the inhalation module

1. Type of tool

The Ecetoc Tra tool for consumer exposure is a conservative tool for estimating exposure and risk. It is a tier 0

and tier 1 tool for exposure assessment as the tool operates with a high level of default values, but several

possibilities for using specific values exists. The tool is made by experts/ specialists but is not an expert tool.

Some experience regarding exposure estimation is needed for using the tool and get meaningful output.

2. Input parameters:

Input parameters are:

Mandidatory parameters:

Vapour pressure

References value (e.g. DNELs) for the various exposure routes

Select product subcategory and type of use

Optional parameters (otherwise default values used):

Concentration in the products

Amount of product used per event

Skin contact area (adult/ children)

Oral Contact area (of product adult/children)

Dermal or oral transfer factor


The tool can be used for getting a rough and conservative quantitative output in terms of exposure and risk for

preselected products and articles. The included products and articles (see attachment for the products articles

that are covered) covers various kinds of matrices (e.g. liquids; aerosols; pastes; solids; textiles, paper,

plastics).

Overall, most of the use scenarios/ product categories identified in WP 1.1/2.1 are covered by the product/

article t categories in ECETOC TRA tool. However, food/ beverages; cosmetics; medical devices and

construction materials are not included in the ECETOC TRA model. See Table 18 for product categories and

article categories included in the model.

4. Overview

195

Both dermal, inhalational and oral exposure routes are considered but from the start it is anticipated for each of

the product subcategories whether exposure via a specific exposure route is it all relevant and also whether

children may be exposed or not.

196

For the dermal exposure the following algorithm is used for calculating exposure:

Parameter Produc

t Ingredi

ent

(g/g)

Contact

Area (cm

2)

Transfer

Factor (unitless)

FreQuenc

y of use (events /

day)

Thickness

of Layer (cm)

Density

(g/cm3)

Conve

rsion Factor (mg/g)

Body

Weight (kg)

Exposure

(mg/kg/day)

Algorithm (PI x CA x TF x FQ x TL x D x 1000) / BW

For inhalational exposure the following algorithm is used for calculating exposure:

Product

Ingredient

(g/g)

Amount Product Used per Application

(g/event)

FreQuency of use

(events / day)

Fraction Released

to Air3

(g/g)

Dilution Fraction (unitless)

Exposure Time

(hr)

(PI x A x FQ x F x DF x ET x

Inhalation

Rate (m

3/hr)

Conversion

Factor

Room

Volume (m

3)

Body

Weight (kg)

Inhalation Exposure

Estimate

(mg/kg/day)

Inhalation

Exposure

Estimate

(mg/m3)

Basis for inhalation exposure

IR x 1000) / (V x BW) SVC=saturated vapour

concentration

197

For oral exposure the following algorithm is used for calculating exposure:

Parameter:

Product

Ingredient (g/g)

Volume of

product swallowed

(cm3)

Transfer Factor

(unitless)

FreQuency of

use (events / day)

Density

(g/cm3)

Conversion

Factor (mg/g)

Body

Weight (kg)

Exposure

(mg/kg/day)

Algorithm: (PI x V x TF x FQ x D x 1000) / BW

The estimated dermal, oral and inhalational exposure is in the output module compared to a reference value for hazard (in REACH termed as a DNEL value) and a risk characterisation ratio, RCR is

calculated. There is, however, no tool for development of the reference value and the value should be known from beforehand and as a start be given as an input to the model.

Overall, the ECETOC TRA is a rough tool and a tool at a screening level for consumer exposure. There is a great overlap of the parameters in the WP 2.3 template and in ECETOC TRA tool (e.g.)

concentration.; dose per use; frequency, matrix effects; differentiation in the various exposure route. ). However differences also exist:

- with respect to frequency of use this refers to number of uses per day and thus ECETOC TRA does not take into account of frequency in a larger time scale e.g. weekly/ monthly or yearly.

- for dermal exposure calculation the ECETOC TRA takes into account how large a skin area that may be exposed from the various products categories, the thickness of the product layer on the

skin and how large a fraction of the substance that is actually available for exposure from the matrix (a default value of 100% is used).

- for inhalation exposure the amount of product liberated in to air is considered, the dilution factor for this amount (room volume and ventilation rate) and the respiratory rate of the consumer.


The ECETOC TRA is a tool using mass based dose metrics and it can be used for estimating the mass based exposure to an ingredient e.g. a nanomaterial from a product. It is not possible to

include and consider further nano relevant metrics such as particle size distributions, agglomeration, surface area or partic le number and use these parameters for exposure estimation.

198




Developed by ECETOC - one of Europe’s leading industry association for developing and

promoting science in human and environmental risk assessment of chemicals. Members include the main companies with interests in the manufacture and use of chemicals, biomaterials and pharmaceuticals, and other organisations active in these fields.


To develop a tool for evaluating consumer and worker (and environmental) exposure. Developed as a tier 1 tool for making exposure scenarios under REACH. ECETOC has

developed the so-called TRAM program, which enables the users to prepare exposure scenarios under REACH. This TRAM program includes both the calculation modules for consumers, workers and the environment. The user can enter all identified uses throughout

the life-cycle, and do all relevant calculations


The tool has to our knowledge not been validated as such, but is regulatory accepted via

inclusion in the REACH guidance.

In the Nanex project (2010), the ECETOC TRA tool and its models were evaluated and it was

concluded that the tool in principle was applicable for estimating consumer exposure from

products (in relation to mass based exposure). However, the tool cannot take into account

nano-specific information/properties such as particle size distributions, agglomeration,

surface area or particle number which especially may be important for inhalation exposure.

If not, what is the potential for testing/validating within this project? The tool can be considered applicable within the framework of this project when mass based information is given for the content of nanomaterials in the products and for a mass based

outcome of the exposure. The tool is, however, not applicable for handling nanospecific information such as particle size distributions, agglomeration, surface area or particle number which especially may be important for inhalation exposure. May be validated to other tools

where using mass based metrics.


See algorithms in summary section. Point estimates are used for the parameters in the quantitative algorithms


Not specifically addressed. However, default assumptions for the exposure estimations are

considered as conservative i.e. above an average exposure and the model would in most cases overestimate exposure when compared to higher tiered models.


Output as quantitative point estimate in relation to exposure or the RCR value


199

Uncertainty is not addressed in the output


It is not an expert tool. Some experience regarding exposure estimation is needed for

using the tool and get meaningful output.



The Product category and subcategory has to be selected in order to use the right default factors for exposure estimation (see attachment). Further specific data on concentration, contact areas (oral, dermal), amount can be chosen instead of default values. Vapour

pressure and molecular weight are further parameters for input data.



No Are exposure based waiving principles applied (e.g. in relation to NMs bound in solid matrices or others):

Starting assumptions/ conclusions whether exposure by a specific exposure route is relevant

for a specific product category is relevant or not has to be taken. Thus some exposure based adaptation is built in.


Conservative default parameters are used so the exposure assessment may be considered as worst case


Yes


No

200

Dermal exposure Which input parameters are required (including whether they are taken from a possible general input module) (dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

The following algorithm is used for estimating dermal exposure:

Parameter Product Ingredie

nt (g/g)

Contact Area (cm

2)

Transfer Factor

(unitless)

FreQuency of use

(events / day)

Thickness of Layer

(cm)

Density (g/cm

3)

Conversion

Factor (mg/g)

Body Weight

(kg)

Exposure (mg/kg/day)

Algorithm (PI x CA x TF x FQ x TL x D x 1000) / BW

Various default parameters are given for the various product types.


Overall, most of the use scenarios/ product categories identified in WP 1.1/2.1 are covered by the Product categories in ECETOC TRA tool. However, food/ beverages; cosmetics;

medical devices and construction materials are not included in the ECETOC TRA model.


Tables with various default factors are given. Also specific default factors for the various product types/article types are given.


Default scenarios given for all the product and articles categories according to the algorithms, however options for modifying some of the factors are given

201


With relation to the transfer factor (i.e. the fraction of the dose that is available for exposure)

this is dependent of the matrix. The default factor is 100% unless another factor can be justified and used.

For products leading to dermal exposure the viscosity of the matrix may either lead to a default thickness layer on the skin layer of either 0.01 cm or 0.001 cm


No


Mass based metrics


No, not in the consumer tool of ECETOC TRA


202

The following algorithm is used for estimating inhalation exposure:

Product

Ingredient

(g/g)


Application (g/event)

FreQuency of use

(events / day)

Fraction Released to Air3 (g/g)


Exposure Time (hr)


Inhalation Rate

(m3/hr)

Conversion Factor

Room Volume

(m3)

Body Weight

(kg)

Inhalation Exposure Estimate

(mg/kg/day)

Inhalation Exposure Estimate (mg/m3)


IR x 1000) / (V x BW) SVC=saturated

vapour concentration


Are specific product types and/or scenarios addressed? Which? (compare with Activity 2.1/1.1 list): Overall, most of the use scenarios/ product categories identified in WP 1.1/2.1 are covered by the Product categories in ECETOC TRA tool. However, food/ beverages; cosmetics;

medical devices and construction materials are not included in the ECETOC TRA model.

203


Tables with various default factors are given. Also specific default factors for the various product types/article types are given.


Default scenarios given for all the product and articles categories according to the algorithms, however options for modifying some of the factors is given


No


Vapour pressure of substance is used as input in order to model fractions of evaporation

during use. However, for nanomaterials it would be the vapour pressure of the matrix/solution that is important for exposure rather than the vapour pressure of the nanomaterial itself


See reply to above question


Mass based metric i.e. mg/m3 and mg/kg bw/d


No

Inhalation spray (not specific spray module, addressed under inhalation): Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation):

For spray scenarios the amount released to air is set to 100% is considered to be homogeneously mixed into the air of a room. Spray scenarios is otherwise not specifically

addressed, - so the questions below are not further addressed.

204

Oral exposure Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use):

The following algorithm is used for estimating dermal exposure:

Parameter: Product

Ingredient (g/g)

Volume of product

swallowed (cm3)

Transfer Factor

(unitless)

FreQuency of use

(events / day)

Density (g/cm3)

Conversion Factor (mg/g)

Body Weight

(kg)

Exposure (mg/kg/day)

Algorithm: (PI x V x TF x FQ x D x 1000) / BW



Overall, most of the use scenarios/ product categories identified in WP 1.1/2.1 are covered by the Product categories in ECETOC TRA tool. However, food/ beverages; cosmetics; medical devices and construction materials are not included in the ECETOC TRA model


No


Tables with various default factors are given e.g. childrens mouthing of an object with a default surface of 10 cm

2. Also specific default regarding where oral exposure is relevant or

not for the specific products.

205


With relation to the transfer factor (i.e. the fraction of the dose that is available for exposure) this is dependent of the matrix. The default factor is 100% unless another factor can be

justified and used


Mass based metrics are used


No



Reference values (e.g. DNEL values should be used for input for making risk

characterisation. The value should be known as an input parameter from the start as no tool is available in the ECETOC TRA model for deriving the reference value. In the ECETOC (2004) report DNEL derivation is described, however using lower default assessment factors

than REACH


DNEL,TDI, ADI; toxic reference values.


May be used for all chemicals allowed in consumer products and should therefore not be

used for CMR substances category 1A or 1B


No


No

206


No


Mass based metrics…mg/kg bw/d and mg/m3


management module


Based on the estimated exposure and the reference value for hazard (e.g. DNEL values),

quantitative risk characterisation ratios (RCRs) are calculated for dermal, inhalational, and oral exposure,


The RCR values are calculated for each specific exposure route


Also the cumulated RCR (the RCR´s for the various exposure routes are added) is given.


No


No


No

207

Table 18 Product categories and article categories included in ECETOC TRA:

PC1:Adhesives, sealants Glues, hobby use

Glues DIY-use (carpet glue, tile glue, wood parquet glue)

Glue from spray

Sealants

PC3:Air care products Aircare, instant action (aerosol sprays)

Aircare, continuous action (solid & liquid)

PC9a: Coatings, paints, thinners, removers

Waterborne latex wall paint

Solvent rich, high solid, water borne paint

Aerosol spray can

Removers (paint-, glue-, wall paper-, sealant-remover)

PC9b: Fillers, putties, plasters,

modelling clay Fillers and putty

Plasters and floor equalizers

Modelling clay

PC9c: Finger paints Finger paints

PC12:Fertilizers Lawn and garden preparations

PC13:Fuels Liquids

PC24: Lubricants, greases, and release products

Liquids

Pastes

Sprays

PC31:Polishes and wax blends Polishes, wax / cream (floor, furniture, shoes)

Polishes, spray (furniture, shoes)

208

PC35:Washing and cleaning products (including solvent based products)

Laundry and dish washing products

Cleaners, liquids (all purpose cleaners, sanitary products, floor

cleaners, glass cleaners, carpet cleaners, metal cleaners )

Cleaners, trigger sprays (all purpose cleaners, sanitary products, glass cleaners)

AC5:Fabrics, textiles and apparel Clothing (all kind of materials), towel

Bedding, mattress

Toys (cuddly toy)

Car seat, chair, flooring

AC6: Leather articles Purse, wallet, covering steering wheel (car)

Footwear (shoes, boots)

Furniture (sofa)

AC8: Paper articles Diapers

Sanitary towels

Tissues, paper towels, wet tissues, toilet paper

Printed paper (papers, magazines, books)

AC10: Rubber articles Rubber handles, tyres

Flooring

Footwear (shoes, boots)

Rubber toys

AC11: Wood articles Furniture (chair)

Walls and flooring (also applicable to non-wood materials)

Small toys (car, train)

Toys, outdoor equipment

209

AC13: Plastic articles Plastic, larger articles (plastic chair, PVC-flooring, lawn mower, PC)

Toys (doll, car, animals, teething rings)

Plastic, small articles (ball pen, mobile phone)

210

ConsExpo 5.8

ConsExpo version 5 (beta-version), evaluation

The tool is available from: http://www.rivm.nl/en/Documents_and_publications/Scientific/Models/Download_page_for_ConsEx

po_software

Note: A ConsExpo version 4.1 is also available from the above site. However, it appears not possible to install

the program on a 64-bit computer.

In addition, the following background material has been reviewed for filling in this template: D.E. Delmaar, M.V.D.Z. Park, J.G.M. van Engelen: ConsExpo 4.0. Consumer Exposure and Uptake Models. Program Manual. RIVM report 320104004/2005

http://www.rivm.nl/en/Documents_and_publications/Scientific/Models/Download_page_for_ConsExpo_software

http://www.rivm.nl/en/Documents_and_publications/Scientific/Models/Download_page_for_ConsExpo_software

211

Summary


A

general

input

module

Exposure-

dermal

module

Exposure-

oral

module

Exposure –

general

inhalation

module

Exposure

- spray

module

Hazards

module

Output module

x x x x x

(X), exposure estimation as

output, no risk

assessment/characterisation

1. Type of tool

ConsExpo is an exposure estimation tool, which can both be used as a low tier tool and a higher tier tool at tier

2 level. In order to run the model, some training is needed even though it is quite user friendly. If the tool is on

the higher tier level, involving more detailed calculations, some expert knowledge is required in order to specify

the input data properly.

2. Input parameters

ConsExpo has defined a number of use scenarios involving selecting the product category (e.g. paint, cleaning

agents, cosmetics). There is no direct link between the use scenarios defined in ConsExpo and the PC/AC-

categories used for characterisation of uses in connection with REACH registration.

212

Overall, main identified use characteristics/ parameters are handled in the algorithms used in ConsExpo:

Exposure route Concen-

tration in

product

Contact

Area

Duration Frequenc

y of use

Amount Thickness

of Layer

Density Body

Weight

Operator x x (if

relevant)

X (decrease in

concentration with time

is considered)

X (Is used

to

calculate

d daily

average

exposure

level)

x x x /

ConsExpo takes into account if the substance is a part of the product, i.e. the concentration of the substance in the product is considered.

The use scenarios include the required parameters for carrying out oral, dermal and inhalation calculations. The parameters needed for doing higher tier calculations depend on the actual use

scenario, see below:

Exposure

route

Model

Parameters Model expression

All All General:

use frequency

body weight (Wbody)

product amount (A) or concentration (wf)

213

weight fraction compound (wf)

Molecular weight

Octanol-water partition coefficient

Vapor pressure

Inhalation Vapour

Instantaneous release

mode

exposure duration

room volume (V or Vroom)

ventilation rate (q)

(application duration) (tr)

(release area)

(mass transfer rate) (K)

(molecular weight matrix)

qtA

C

V

wfo

aire

Constant rate release

mode

t<tr (tr=release duration):

/(1 )

qtA w to f rC e

air qV

t>tr

/( )

(1 )

A to r qt q t tr r

C e eair

qV

wf

214

Evaporation release

mode

Differential equations (Aair: amount in air;

Aprod:amount of substance in product; Peq:

saturated concentration in air; Pair: actual

concentration)

( )air room

dAairP P Q Ceqdt

K Vair

( ) /air

dAP Peqdt

prodK A T w

tot app f

Spray spray duration

room height

(cloud volume)

mass release rate (Rspray)

airborne fraction (fairborne)

density solvent + non-volatile

particle distribution

inhalation cut-off diameter

The algorithm is to complex to write down.

The model is relevant to use for spray-

applied non-volatile substances. A droplet

size distribution of the aerosols is included.

Only droples with a size enabling penetration

to the alveolar region is considered to give

rise to inhalation exposure.

Dermal Instant application exposed area D: external dose

/D A wf Wprod body

Constant rate contact rate (R)

/D R t w Wbodyf

Rubbing off transfer coefficient (Rtrans) /D S F Warea dislodge body

wf

215

dislodgeable amount (Fdislodge)

contact time (t)

rubbed surface (Sarea)

max( , )maxS R t Sarea trans

Migration leachable fraction (Fleach)

skin contact factor (Scontact)

/D A S F Wo contact leach body

Diffusion compound concentration

diffusion coefficient (D)

layer thickness

exposure time

Diffusion equation

2( , )( , )

2

C x tD C x t

t x

Ingestion Direct oral intake ingested amount (A) /D A wf

Wbody

Constant rate ingestion rate (R)

exposure time (t)

/D R w t Wf body

Migration exposure time (t)

contact area (S)

initial migration rate (Rm)

/ (1 exp( ))R SmW t

body A wfD A w

f

Migration from

packaging material

thickness package

contact area

package amount

/consfood body

pack

AD A W

A

max( , )food migr compA R t A

216

ingested amount

storage time (t)

migration rate (Rm)

amount of packaged food (Apack)

amount of consumed food (Acons)

amount of compound in food (Afood)

217


Matrix effects are not directly addressed in ConsExpo. However, the defined used scenarios include a pre-evaluation if the product is a liquid or a solid. A pre-assessment whether specific exposure routes are relevant

to include has been included in the pre-defined use scenarios in ConsExpo.

The below table addresses which scenarios identified in activity 2.1/1.1 are addressed in ConsExpo. It is seen

that not all scenarios are included. It is however possible to define and add new scenarios to ConsExpo. This

required expert knowledge.

Products/scenarios ConsExpo use

scenarios

Dermal

exposure

considered?

Inhalation

considered?

Oral exposure

considered?

Food and beverages No direct use

scenarios included

in ConsExpo

- - -

Cosmetics Hair care cosmetics Yes Yes No

Bath- shower

products Yes No No

Skin care cosmetics Yes No No

Makeup cosmetics Yes Yes Yes

Deodorant

cosmetics Yes Yes No

Oral care cosmetics No No Yes

Foot care products Yes No No

Fragrance products Yes Yes No

Cleaning agents Laundry products Yes Yes No

Dishwashing

products Yes Yes Yes

All-purpose

cleaners Yes Yes No

Abrasives Yes Yes No

Sanitary products Yes Yes No

Floor, carpet and

furniture products Yes Yes Yes

Miscellaneous

cleaning and

washing products

Yes Yes No

Coatings/impregnation

Maintenance products

Textiles No direct use

scenarios included

in ConsExpo

- - -

218

Construction material No direct use

scenarios included

in ConsExpo

- - -

4. Overview

No hazard module is included in ConsExpo, so any risk assessment has to be carried out outside ConsExpo.

ConsExpo includes all exposure routes. It calculates both the external dose and internal exposure (systemic).

So it has models included for the calculation of the uptake into the body. In addition it also calculates combined

exposure, I.e. accounting for both oral, dermal and inhalative exposure.

The results of a ConsExpo exposure calculation can be presented in different ways: as point values, as a graph

over (exposure) time, as a distributed result from a Monte Carlo simulation, and in a textual report. In addition,

sensitivity analysis of the exposure assessments can also be carried out in ConsExpo.

Exposures and doses are presented both per route and integrated over all routes. Per route various exposure

measures are calculated:

External inhalation exposure is calculated as the air concentration during exposure.

Different measures are: mean air concentration during a single exposure event; mean

air concentration on the day of exposure and year average air exposure.

Internal inhalation doses calculated are: the acute (amount taken up during one event

per kg bodyweight) and chronic (daily average of the amount taken up per kg

bodyweight) dose.

External dermal exposure is calculated as dermal load (amount of compound per cm2 of

exposed skin) or as external dose (the amount that can potentially be taken up per kg

bodyweight).

Internal dermal doses calculated are: the acute (amount taken up during one event per

kg bodyweight) and chronic (daily average of the amount taken up per kg bodyweight)

dose.

External oral exposure is calculated as external dose (the amount that can potentially be

taken up per kg bodyweight).

Internal doses are: the acute (amount taken up during one event per kg bodyweight) and

chronic (daily average of the amount taken up per kg bodyweight) dose.

The integrated doses are the summations of the corresponding doses per route

When one or more parameters have been specified as a distribution, ConsExpo can perform a distributed

(Monte Carlo) calculation. The program will draw a set of random numbers from the specified distributions for

distributed parameters and calculates the endpoint of choice with this set. For the non-distributed parameters

the specified point value is taken. The calculated exposure measure for the set is stored. This procedure is

repeated for a user-specified number of times (the number of Monte Carlo samples). The result of this

procedure is a distributed set of calculated exposures. Some characteristics of the distribution such as median,

standard deviation 90- and 99-percentile of the calculated distribution are reported.

The ConsExpo report gives an overview of the exposure calculation. It displays all parameter values and the

calculated exposures in the mass metric. The text can be saved to (text-) file or can be printed directly from

ConsExpo.

5. Tool targeted at nano? Even though ConsExpo is not targeted at nanomaterial exposure it can be used for mass based consumer

exposure assessment to nano-materials– with caution. As a tier 1 and tier 2 tool, the tool may be highly relevant

219

for use in his project e.g. to evaluate specific exposure scenarios further and also for evaluation of semi-quantitative exposure assessments in our project. If the standard use scenarios included in ConsExpo should be updated/modified so they better respond to the

characteristics of nano-materials inclusion of other dose metrics e.g. particle number exposure or particle

surface exposure may be considered in addition with further consideration on the liberation of free nanoparticles

from a product during use. Furthermore, it should be assessed if the uptake models should be modified, to

better account for the special behaviour of nano-materials.

It should be mentioned that RIVM is running a project looking on the suitability of ConsExpo to handle NM and if

any modifications should be introduced into ConsExpo. Currently we do not have any estimate of when this

project will be published.

220




ConsExpo is developed by RIVM - one of Europe’s leading institutes for assessing environmental and consumer exposure.


To develop a tool for evaluating consumer exposure to chemical substances. It has been used extensively by REACH registrants for preparing consumer exposure assessments.


The ConsExpo (version 4.1) was addressed in the Nanex project (2010). The tool was

concluded that is should be used with caution for estimating the external exposure in relation to inhalation; dermal exposure and oral exposure from products containing NMs as a part of the product and only in relation to its weight based fraction. The tool does not consider nano-

specific properties like particle size distributions, agglomeration, surface area or particle

number which especially may be important for inhalation exposure.. If not, what is the potential for testing/validating within this project?

The tool has to our knowledge not been validated as such, but is regulatory accepted via inclusion in the REACH guidance.

As a tier 1 and tier 2 tool, the tool may be highly relevant for use in his project e.g. to evaluate specific exposure scenarios further and also for evaluation of semi-quantitative exposure assessments in our project.


The algorithms used for the calculations are all described in the manual and all results in

specific mass based exposure values. For the levels of detail in the calculation see the tables

in summary description .


It is possible to specify uncertainties in a number of the input parameters, and ConsExpo can carry out a Monte-Carlo based uncertainty analysis, so certain percentiles, e.g. 95% can be

chosen for the safety assessment.


The results of a ConsExpo exposure calculation can be presented in different ways: as point

values, as a graph over (exposure) time, as a distributed result from a Monte Carlo

simulation, and in a textual report. In addition, sensitivity analysis of the exposure

assessments can also be carried out in ConsExpo.

Exposures and doses are presented both per route and integrated over all routes. Per route

various exposure measures are calculated:

External inhalation exposure is calculated as the air concentration during exposure.

Different measures are: mean air concentration during a single exposure event; mean

air concentration on the day of exposure and year average air exposure.

221

Internal inhalation doses calculated are: the acute (amount taken up during one event

per kg bodyweight) and chronic (daily average of the amount taken up per kg

bodyweight) dose.

External dermal exposure is calculated as dermal load (amount of compound per cm2 of

exposed skin) or as external dose (the amount that can potentially be taken up per kg

bodyweight).

Internal dermal doses calculated are: the acute (amount taken up during one event per

kg bodyweight) and chronic (daily average of the amount taken up per kg bodyweight)

dose.

External oral exposure is calculated as external dose (the amount that can potentially be

taken up per kg bodyweight).

Internal doses are: the acute (amount taken up during one event per kg bodyweight) and

chronic (daily average of the amount taken up per kg bodyweight) dose.


When one or more parameters have been specified as a distribution, ConsExpo can perform

a distributed (Monte Carlo) calculation. The program will draw a set of random numbers from

the specified distributions for distributed parameters and calculates the endpoint of choice

with this set. For the non-distributed parameters the specified point value is taken. The

calculated exposure measure for the set is stored. This procedure is repeated for a user-

specified number of times (the number of Monte Carlo samples). The result of this procedure

is a distributed set of calculated exposures. Some characteristics of the distribution such as

median, standard deviation 90- and 99-percentile of the calculated distribution are reported.

The ConsExpo report gives an overview of the exposure calculation. It displays all parameter

values and the calculated exposures. The text can be saved to (text-) file or can be printed

directly from ConsExpo.


The results of a Monte Carlo analysis are reported in the output of the tool (if required), see above


If the user only wants to use the standard use scenarios defined in the ConsExpo tool, then it is relatively straight-forward to run the model. However, the interpretation of the output

requires knowledge, not necessarily on expert level.


The metric for exposure is weight based, so other relevant exposure metrics e.g. particle

number, surface area or considerations regarding the liberation of free nanoparticles during used are not taken into account.

222



If using the one of the default use scenarios included in ConsExpo, the product category has

to be selected in order to use the right default factors for exposure estimation. Not all NM product types are defined in the ConsExpo these have to be defined. This includes setting amount, concentration in product, exposure duration, contact areas, frequency for the various

exposure routes. Further specific data on vapour pressure, octanol-water partition coefficient and molecular

weight are further parameters for input data.



No


It has been evaluated in the standard use scenarios included in ConsExpo, if the various

exposure routes are relevant to consider. See below table.


Different possibilities to assess the variability and uncertainty of the estimated exposure

levels are included in ConsExpo.

For some exposure assessments, the available information on the product use and/or the

compound of interest or the exposed consumer may be very limited. In these cases, a worst case exposure can be estimated by using first tier screening models requiring a minimum amount of information. The required parameters can also be filled out using worst case single

point values. It is also possible to calculate a more realistic worst case exposure for example by using of

parameter distributions instead of point values. This is based on Monte Carlo simulations as described above.


No.


No

223

Dermal exposure (fill only in if addressed) Which input parameters are required (including whether they are taken from a possible general input module) (dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

Model

Parameters

General input parameters General:

use frequency

body weight

product amount or concentration

weight fraction compound

(physicochemical properties)

Molecular weight

Octanol water partition coefficient

Vapor pressure

Instant application exposed area

Constant rate contact rate

Rubbing off transfer coefficient

dislodgeable amount

contact time

rubbed surface

Migration leachable fraction

skin contact factor


diffusion coefficient

layer thickness

exposure time

224


ConsExpo includes a number of default use scenarios. These are defined in an Access database. It is relatively straight-forward to include new use scenarios in the database. The following scenarios for the identified NM-product types identified in WP1.1/2.1 are

included.

Products/scenarios ConsExpo use scenarios

Food and beverages No direct use scenarios included in ConsExpo

Cosmetics Hair care cosmetics

Bath- shower products

Skin care cosmetics

Makeup cosmetics

Deodorant cosmetics

Oral care cosmetics

Foot care products

Fragrance products

Cleaning agents Laundry products

Dishwashing products

All-purpose cleaners

Abrasives

Sanitary products

Floor, carpet and furniture products

Miscellaneous cleaning and washing products

Coatings/impregnation Painting products

Do-it-your-self-products

Maintenance products Painting products


Textiles No direct use scenarios included in ConsExpo

Construction material No direct use scenarios included in ConsExpo. The below

use scenarios may in some cases be useful.

Painting products



225

When selecting a use scenario, then default parameters are defined, and the user does not need to specify any further parameters.




Matrix effects are not directly addressed. However, the default use scenarios have included a setting of the matrix (liquid, solid)


No


The models operate with mass based metrics, so other nanomaterial relevant parameters

such as particle number or particle surface area exposure cannot be used.


Not directly, but it is possible by changing some of the parameters (e.g. contact area) to include some risk management measure.

226

Inhalation exposure (fill only in if addressed) Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation, etc.):

Model

Parameters

All General:

use frequency

body weight




Molecular weight


Vapor pressure

Inhalation of vapour

Vapour

exposure duration

room volume

ventilation rate

(application duration)

(release area)

(mass transfer rate)



See previous answer on dermal exposure.




When selecting a use scenario, then default parameters are defined, and the user does not

need to specify any further parameters.

227


No




No





Not directly, but it is possible by changing some of the parameters (e.g. air retention time in

room) to include some risk management measure.


-

Inhalation spray (fill in if a specific spray module is part of the tool): Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use, indoor/outdoor, room volume/ventilation):

228

Model

Parameters

All General:

use frequency

body weight




Molecular weight

Octanol water partition coefficient

Vapor pressure

All inhalation models:

Inhalation - Spray spray duration

room height

(cloud volume)

mass release rate

airborne fraction

density solvent + non-volatile




ConsExpo includes a number of default use scenarios. These are defined in an Access database. It is relatively straight-forward to include new use scenarios in the database.

Some scenarios for the identified NM-product types are included. See table in summary.





Is aggregation/agglomeration in product and aerosol dynamics addressed? How?

No

229


Matrix effects are not directly addressed. However, the default use scenarios have included a setting of the matrix (liquid, solid).


No





Not directly, but it is possible by changing some of the parameters (e.g. contact area) to include some risk management measure.


-

Oral exposure (fill only in if addressed) Oral exposure and uptake from compounds in consumer products may occur for example due

to mouthing objects or exposed hand to mouth contact. ConsExpo provides two models for

oral exposure: exposure through direct ingestion of the product (direct intake, constant rate,

migration from a mouthed product) containing the compound and a secondary exposure

model to estimate exposure from compounds in packaging material that migrate to food.

The oral model calculates the external dose as a measure of external exposure. The external

dose equals the maximum possible (potential) dose of the exposure event.

Internal exposure is calculated using the oral uptake models as the internal (systemic) dose,

i.e. the total amount of compound taken up into the blood per kilogram bodyweight.

230

Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use):

Type of

oral

exposure

Direct ingestion

Packaging

material

Sub-type of

oral

exposure

direct intake constant rate migration from a

mouthed

product

Packaging

material

Input Concentration

Amount

ingested

Concentration

Ingestion rate

Exposure

duration

Product amount

Exposure

duration

Concentration

Contact area

Initial migration

rate

Concentration

Package amount

Ingested amount

Thickness

package

Contact area

Output External dose

Internal

exposure

External dose

Internal

exposure

External dose

Internal

exposure

External dose

Internal exposure


See previous answer on dermal exposure.


No






The models operate with mass based metrics, so other nanomaterial relevant parameters such as particle number or particle surface area exposure cannot be used.

231


Effects of implemented ris management measures are not directly taken into account. But is possible to include the effects, e.g. by reducing contact area or similar.

Questionnaire 3: Hazards Module (not addressed in tool)


management module


No risk characterisation is included in ConsExpo. Exposure estimates are given as output.


-


-


-


-


-

232

DREAM 5.9

DeRmal Exposure Assessment Method (DREAM)

The tool is available from: No online tool available. Van-Wendel-De-Joode B, Brouwer DH, Vermeulen R, Van Hemmen JJ, Heederik D, Kromhout H (2003). DREAM: A method for Semi-quantitative Dermal Exposure Assessment. Ann. Occup. Hyg. 47(1), pp. 71-87.

In addition, the following background material has been reviewed for filling in this template: Van-Wendel-De-Joode B, Van Hemmen JJ, Meijster T, Major V, London L, Kromhout H (2005). Reliability of a semi-quantitative method for dermal exposure assessment (DREAM). Journal of Exposure Analysis and Environmental Epidemiology. 15, pp. 11-120.

Van Duuren-Stuurman B, Pelzer J, Moehlmann C, Berges M, Bard D, Wake D, Mark D, Jankowska E, Bouwer D (2010). A Structured Observational Method to Assess Dermal Exposure to Manufactured Nanoparticles: DREAM as an Initial Assessment Tool. International Journal of Occupational and Environmental Health, 16(4), pp. 399-405(7). (Only abstract reviewed)

233

Summary







Hazards module

Output module

()

1. Type of tool

The tool is a tier 0 tool to be used by occupational health professionals when evaluating dermal

exposure in a workplace setting.

2. Input parameters

The method consists of two parts, an inventory and an evaluation part. The inventory part is the input

module, where a multiple choice questionnaire is filled out by a professional after observing the

worker(s). The input parameters are:

Company:

General information about the company and observer Department

Chemical or biological agents that occur in the work environment

Cleaning activities at the department

Agent Physical-chemical characteristics of the substance, e.g.

Concentration of active ingredient in the substance

Physical state

Boiling temperature

Viscosity

Formulation (powder, granules)

Dustiness

Stickiness

Job

Hygienic behaviour

Number of people with the job title

Task

Percentage of time that the task is performed

Number of people performing the task

Exposure to a substance assessed for a certain task

Probability and intensity of dermal exposure routes (emission, transfer

and deposition) (per body part)

Use of clothing (per body part) (covered vs. uncovered body parts,

clothing material, repeated use of clothing)

Contamination of work environment


It is possible to address solids (incl. powders/granules), liquids and vapours using DREAM. No

exposure based waving principles are used in this context. The method is used for exposure

assessments for chemical and biological agents. The scenarios from activity 2.1/1.1 are not covered

by the method, since no default scenarios are used. An occupational health professional defines

which activities the tasks comprise. It is an occupational tool, and no consumer scenarios are

therefore directly addressed. However, the method might be used for dermal consumer exposure

assessments more generally, since the determinants of exposure could be applied to consumer

scenarios as well.

234

4. Overview

Hazards are not assessed by the approach, only dermal exposures are assessed. The model

estimates potential and actual dermal exposure by summing contributions from emission from the

source, plus deposition and transfer processes, while taking account of the protection afforded by

clothing and gloves. The exposure algorithms are semi-quantitative, as they are based on weighted

effects of exposure determinants (on logarithmic scale). The output of the model is semi-quantitative

as it is given in DREAM units, which are categorized, ranging from low to extremely high exposure.

An overview of the evaluation part of DREAM is given in Figure 11 below.


The tool is not targeted nano, but might be relevant for dermal exposure to nanomaterials. However, a

shortened version of the tool has been demonstrated applicable for occupational dermal exposure in

the EU FP7 NANOSH project (Van Duuren-Stuurman et al., 2010)

Figure 11 Summary of the evaluation part of DREAM. Each estimate is determined by a set of underlying variables. The range of the estimates are in brackets (Adopted from Van-Wendel-de-Joode et al., 2010).

235



The method was developed by the Dutch TNO Chemistry, Department of Chemical Exposure Assessment and the Institute for Risk Assessment Sciences, Utrecht University, The Netherlands and the Division of Cancer Epidemiology and Genetics, National Cancer

Institute, USA based on a conceptual model developed by the National Insitute for Occupational Health, Denmark (now the National Research Centre for the Working Environment, Denmark).


The method was developed to assess and evaluate occupational dermal exposure to chemical agents.


No. But a shortened version of DREAM was used within the NANOSH project as an initial

method to assess dermal exposure and the results of the survey showed that it was feasible and useful to use the shortened version of DREAM for this purpose (Van Duuren-Stuurman et al. 2010)


Although not a real validation, we might compare with results from other tools/methods.


The exposure algorithms are semi-quantitative, as they are based on weighted effects of

exposure determinants (on logarithmic scale).


Not specified in the reviewed literature.


The evaluation algorithms result in numerical estimates for exposure levels on both the outside clothing layer and skin after taking into account the reductive effect of clothing, on the skin .The output is

given in DREAM units, ranging from 0-40545. The output can therefore be seen as semi-quantitative.


Not addressed


DREAM is an expert tool/method, since an occupational health professional need to fill out the input parameters in the inventory questionnaire, based on observations of the worker(s).

236


The DREAM method consists of two parts, an inventory and an evaluation part. In the

evaluation part both potential dermal exposure and actual dermal exposure for nine different body parts are evaluated, as well as total dermal exposure. Potential dermal exposure concerns exposure on clothing and uncovered skin, where actual exposure is defined as exposure on skin (Van-Wendel-De-Joode et al., 2003).



The inventory part comprises a hierarchically structured (multiple choice) questionnaire with

six modules:

1. Company:

General information about the company and observer 2. Department

Chemical or biological agents that occur in the work environment

Cleaning activities at the department

3. Agent

Physical-chemical characteristics of the substance , e.g.

i. Concentration of active ingredient in the substance ii. Physical state iii. Boiling temperature

iv. Viscosity v. Formulation (powder, granules) vi. Dustiness

vii. Stickiness 4. Job

Hygienic behaviour

Number of people with the job title 5. Task

Percentage and of time that the task is performed

Number of people performing the task

6. Exposure to a substance assessed for a certain task

Probability and intensity of dermal exposure routes (emission, transfer

and deposition) (per body part)

Use of clothing (per body part) (covered vs. uncovered body parts,

clothing material, repeated use of clothing)

Contamination of work environment

Each of the answers to the questionnaire corresponds to a pre-assigned value that is subsequently put into the evaluation algorithm.

237



Seems not addressed based on the reviewed literature


No


Not specified in reviewed literature


In the DREAM model, evaluation of exposure takes place at task level, assessing both potential and actual dermal exposure. Potential exposure concerns exposure on clothing and

uncovered skin, and the potential exposure estimate is a product of dermal exposure due to three different exposure routes: emission, transfer and deposition.

Actual exposure is defined as exposure on skin, and is the potential exposure multiplied with the clothing protection factor (see Table 21).

The exposure route estimates are the products of probability and intensity of each exposure route, assessed for each body part, and multiplied by estimates of intrinsic emission. Intrinsic emission concerns physical and chemical characterisations of the substance, see Table 19

below.

238

Table 19 Determinants for 'intrinsic emission' estimate (Adopted from van-Wendel-de-Joode et al., 2010)


No


The calculated dream score lead to inclusion in exposure potential bands.

Dermal exposure (fill only in if addressed) Which input parameters are required (including whether they are taken from a possible general input module) (dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

The exposure module is a part of the general input module ("inventory"). The input parameters that contribute to the exposure estimate are:

1. Emission to clothing and uncovered skin; and immersion of skin into agent

Unlikely

Occasionally

Repeatedly

Almost constantly 2. Intensity (= amount of agent) of emission

Small amount

Medium amount

Large amount 3. Exposure route factors

Emission

Deposition

Transfer

239

4. Probability of deposition on clothing and uncovered skin

Unlikely

Occasionally

Repeatedly

Almost constantly

5. Intensity of deposition on clothing and uncovered skin

Small amount

Medium amount

Large amount

6. Transfer to clothing and uncovered skin : Contact with surfaces, or tools, occurs:

Unlikely

Occasionally

Repeatedly

Almost constantly 7. Intensity of transfer: Contamination level of contact surface

Not contaminated

Possibly contaminated

< 50% of contact surface

≥ 50% of contact surface 8. Body surface factor

Head

Upper arm

Forearm

Hands

Torso front

Torso back

Lower body part

Lower leg

Feet

See

Table 20 for more information, including assigned values.

240

Table 20 Exposure module – exposure routes: direct emission, transfer and deposition (Adopted from Van-Wendel-De-Joode et al., 2003)

241

242


No, an occupational health professional defines which activities the tasks comprise and no default scenarios are used. It is an occupational tool, and no consumer scenarios are

therefore directly addressed. However, the method may be used for consumer exposure assessments more generally, since the determinants of exposure could be applied to consumer scenarios as well.


Yes, each exposure determinant is assigned with a default value that decrease and increase on a log scale, see Table 19. The direction of the default values (increasing vs. decreasing exposure) are derived from the literature and expert judgment.


See above.


Solids (including powders/granules), liquids and vapours are addressed.


Deposition is taken into account in the exposure model: "Deposition in skin or clothing describes mass transport from air. In this case, the contaminant mass (e.g. small particles

with aerodynamic diameter of <100 µm, such as vapours, mists) is first released into the air and subsequently deposited on skin or clothing" (Van-Wendel-De-Joode et al., 2003)


Not applicable, only semi-quantitative exposure estimates are derived.


The effect of protective personal equipment (clothing or gloves) is taken into account as specified in Table 21 below. Different values are assigned depending on the clothing used, and these values are then used in the evaluation part.

243

Table 21: Exposure module – determinants of 'clothing' estimate (Adopted from Van-Wendel-De-Joode et al., 2003)

244

245

Inhalation exposure (not addressed)

Inhalation spray (not addressed):


Questionnaire 3: Hazards Module (not addressed)


management module


The results from the exposure assessment are semi-quantitative exposure estimates. The output is in DREAM units (ranging from 0-40545).

"The DREAM estimates form an initial assessment of dermal exposure at task level, which allows the ranking of tasks, or (groups of) workers, by grouping them according to their

DREAM estimate; for example, when aiming at 'hazard evaluation or control." (Van-Wendel-De-Joode et al., 2003)


Risks are not evaluated.


No, only dermal exposure is covered by the tool. However, it is possible to calculate exposure estimates for a specific task by summing combined exposure to different individual body

parts.


The output is given in DREAM units, which are grouped into DREAM categories:

0 = no exposure

0-10 = very low

10-30 = low

30-100 = moderate

100-300 = high

300 – 1000 = very

high

> 1000 = extremely high

246


No


No

247

Margin of Exposure 5.10

Margin of Exposure in: Consumer Product Ingredient Safety: Exposure

and Risk Screening Methods for Consumer Product Ingredients

The tool is available from: Not a tool/web-tool

In addition, the following background material has been reviewed for filling in this template: Key reference: American Cleaning Institute: Consumer Product Ingredient Safety: Exposure and Risk Screening Methods for Consumer Product Ingredients 2nd Edition, 2010, American Cleaning Institute, Washington DC

248

Summary







Hazards module

Output module

(x) (x) (x) (x) (x) (x) (x)

1. Type of tool

Not a tool as such, but an approach/framework (i.e. more “guidance type”), developed by the

American Cleaning Institute to "present methodologies and specific consumer exposure information

that can be used for screening-level risk assessments of environmental and human exposures to high

production volume (HPV) chemicals through the manufacturing and use of consumer products, mainly

laundry, cleaning, and personal care products" (American Cleaning Institute, 2010). The intended

users are chemical risk assessors in government agencies, businesses, and stakeholder groups, and

a certain level of experience within the fields of consumer product exposure and risk assessment is

needed.

2. Input parameters

The algorithm used for calculating the margin of exposure (MOE) is:

𝑀𝑂𝐸 =𝐷𝑜𝑠𝑒 − 𝑅𝑒𝑠𝑝𝑜𝑛𝑠𝑒 𝑡ℎ𝑟𝑒𝑠ℎ𝑜𝑙𝑑

(𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝐸𝑥𝑝𝑜𝑠𝑢𝑟𝑒(𝑃𝐸) ∗ 𝐼𝑛𝑔𝑟𝑒𝑑𝑖𝑒𝑚𝑡 𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝐼𝐶)

Input parameters for estimation of PE are listed below and the PE estimates are based on several

screening exposure concentrations.

For inhalation exposure, the following parameters are used to estimate PE (not all are relevant for all product types):

Product use frequency (use/day)

Product amount used per use (g/use)

Airspace volume (m³)

Respirable product concentration in breathing zone (mg/m³)

Exposure duration (hr)

Bioavailable fraction (%)

Respirable fraction (%)

Body weight (kg)

Product exposure (mg/kg/day)

Model equation/formula

For dermal exposure, the following parameters are used to estimate PE (not all are relevant for all product types):



Product amount used per day (g/day)

Product use concentration (%)

Product use concentration (g/cm3)

Contact area (cm2)

Product retained (%)

Film thickness (cm)

Transfer to skin (%)

Dermal absorption (%)

Body weight (kg)

Scaling: Duration of exposure



For oral exposure, the following parameters are used to estimate PE (not all are relevant for all product types):


249



Product retained (ml/cm2)

Dish area containing food (cm2)

Fraction ingested (%)

Body weight (kg)



In order to obtain PE estimates, a data matrix has been constructed for several categories of

consumer products:

"The data matrix provides exposure factors (e.g. frequency of use, duration of use, amount of use per

occasion) and equations used to estimate oral, inhalation, and dermal exposures for the key

scenarios of each consumer product category. It should be noted that the exposure estimates are

provided in terms of product, not specific chemical substance."

These exposure factors result in a PE value for that route of exposure and type of exposure scenario.

An example of the data matrix for obtaining PE estimates is shown in Table 22 below.

250

Table 22 Summary of model equations used to calculate Product Exposure (PE) for dermal, oral and inhalation exposure routes (Adopted from American Cleaning institute, 2010)

251

252

The Ingredient Concentration (IC) estimates are based on information from industry surveys from companies that produce the products in question. The information collected from the

surveys was compiled to develop a minimum and maximum IC (in %) for each product category.

The selection of the dose-response threshold is based on the No Adverse Effect Level (NOAEL). The most sensitive repeated-exposure toxicity endpoint (i.e., lowest NOAEL when a

range of values is available) is chosen as default for the initial screening-level risk characterization. In the consulted background literature, it is not specified how to address non-threshold

substances (without a NOAEL).


The approach is used for evaluating substances as a part of a consumer product. Some of the scenarios from activity 2.1/1.1 are possible to address using the tool, in particular the

scenarios concerning cosmetics, cleaning agents and possibly textiles as well (e.g. dermal exposure from wearing clothes). However, "the approach can be applied generally to other

consumer products when information on how consumers use the products is available" (American Cleaning Institute).

4. Overview

Hazards are evaluated on the basis of the lowest NOEAL (in mg/kg bw per day). In order to evaluate exposures both inhalation, dermal and oral exposure routes are considered. In

general, the PE estimates are based on a 60kg body weight for women. However, for products designed for a specific target population (e.g. men or children), representative body weights

for those populations are used. It is possible to address combined exposures, since the exposure estimates (PExIC) may be aggregated either within each product category or across

product category. The level of quantification for both algorithms and output is quantitative.


The tool is not a nano-tool, but might be used with caution or modified for the scenarios to be addressed in this project.

253




American Cleaning institute (formerly: The Soap and Detergent Association (SDS))

For which purpose, products and/or processes: "(…) to present methodologies and specific consumer exposure information that can be used for screening-level risk assessments of environmental and human exposures to high

production volume (HPV) chemicals through the manufacturing and use of consumer products, mainly laundry, cleaning, and personal care products" (American Cleaning Institute,

2010). The main purpose of this framework is to serve as a priority-setting tool for future work

on the basis of their hazards and exposure potential.

Has the tool been validated for NMs? No


Although not a validation, result from using the approach might be compared with results from other methods/tools.


The algorithms are quantitative.


The algorithms are conservative, since they use worst case assumptions about exposure, "including default assumptions of high-end PE estimates, ingredient concentration ranges for

the category applied to all product types irrespective of the actual chemical concentration, and the use of the lowest NOAEL" (Amercian Cleaning Institute, 2010)


The output of the tool is a margin of expose (MOE), based on quantitative data on dose-

response thresholds, and exposure estimates.


The output MOEs are based on worst-case values. "The assumptions are deliberately

designed to be conservative in order to avoid risk decisions based on “false negatives.”"

(American Cleaning Institute, 2010)


The framework is targeted chemical risk assessors in government agencies, businesses and stakeholder groups, and therefore a certain level of expertise is required.

254



The input for the MOE/screening-level risk characterization algorithm are Product Exposure

(PE), Ingredient Concentration (IC, %) and NOAEL. The PE component is an estimate of exposure to the consumer product (mgproduct/kg BW/day).

A PE data matrix has been constructed, which provide exposure factors (e.g. frequency of use, duration, amount of use per occasion, etc.) and equations used to estimate exposures (both inhalation, dermal and oral) for the key scenarios of each consumer product category.

The exposure estimates provided are in terms of product, not specific chemical substance. Table 23 shows an example of the inhalation exposure parameters for estimating PE, including default high-end input values.

255

Table 23 Inhalation Exposure Parameters to Estimate Screening Exposures to Consumer products – Europe (Adopted from American Cleaning institute, 2010)

For dermal exposure, the following parameters are used to estimate PE (not all are relevant for all product types):






Contact area (cm2)


Film thickness (cm)



Body weight (kg)




256








Body weight (kg)





No


No


Worst case estimates are used for the exposure estimates.


No


No

Dermal exposure Which input parameters are required (including whether they are taken from a possible general input module) (dermal area exposed, amount/concentration, duration and frequency of use, indoor/outdoor, etc.):

For dermal exposure, the following parameters are used to estimate PE (not all are relevant

for all product types):






Contact area (cm2)


Film thickness (cm)

257



Body weight (kg)





Yes, products within the categories

Soap and detergents (including all-purpose cleaners) (scenario is relevant compared to activity 2.1/1.1. list)

Personal care and cosmetics (scenario is relevant compared to activity 2.1/1.1. list)

Baby care products

Fragrances (See Table 24 for more details)


Yes, default factors for exposure parameters used to estimate PE for are applied. See Table 24.

258

Table 24 Dermal Exposure Parameters to Estimate Screening Exposures to Consumer products – Europe (Adopted from Amercian Cleaning institute, 2010)

259

260


Yes, see above


<…….>


No


Mass based metric is applied


No


For inhalation exposure, the following parameters are used to estimate PE (not all are relevant for all product types):



Airspace volume (m³)

Respirable product concentration in breathing zone (mg/m³)

Exposure duration (hr)

Bioavailable fraction (%)

Respirable fraction (%)

Body weight (kg)




Yes, products within the categories:

Soap and detergents (including all-purpose cleaners) (scenario is relevant

compared to activity 2.1/1.1. list)


Fragrances

Miscellaneous

o Paints (scenario is relevant compared to activity 2.1/1.1. list) o Lubricants (scenario is relevant compared to activity 2.1/1.1. list)

o Paper products and processing o Other – pharmaceuticals o Other – metal working fluid

(See Table 23 for more details)

261


Yes, default factors for exposure parameters used to estimate PE for are applied. See Table 23.


See above


No


<…….>


No


Mass based metric applied


No

Inhalation spray (fill in if a specific spray module is part of the tool):

Sprays are addressed as explained above for inhalation exposure.

Oral exposure (fill only in if addressed) Which input parameters are required (including whether they are taken from a possible general input module) (amount/concentration, duration and frequency of use):








Body weight (kg)

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Yes, products within the categories:

Soap and detergents (including all-purpose cleaners) (scenario is relevant

compared to activity 2.1/1.1. list)


Food and food additives (scenario is relevant compared to activity 2.1/1.1. list)


No


Yes, default factors for exposure parameters used to estimate PE for are applied. See

263

Table 25 below.

264

Table 25 Oral Exposure Parameters to Estimate Screening Exposures to Consumer products – Europe (Adopted from Amercian Cleaning institute, 2010)


<…….>


Mass is applied as metric


No

265



Hazards are evaluated on the basis of NOAELs, which are entered into the risk

characterization algorithm.


Hazards are evaluated on the basis of NOAELs. The selection of the appropriate NOAEL (or LOAEL) should be based on following considerations:

The most sensitive repeated-exposure toxicity endpoints (i.e., lowest NOAEL of all

the repeated-dose endpoints evaluated when a range of values is available)

Routes of exposure relevant to the product exposure scenarios (i.e., dermal, oral,

or inhalation)

The quality of available experimental study data


In the consulted background literature, it is not specified how to address non-threshold

substances (without a NOAEL).


No


No


Implicitly yes as the NOAEL has to be relevant for the exposure route for which the MoE is calculated.


Mass-based metrics are applied: mg/kg bw/day (or mg/m

3) is applied as metric for the

NOAEL

266


management module


The output of the approach is a number of screening-level MOEs for each product category,

for each possible route of exposure. A hypothetical output from a screening risk characterization is shown in

267

Table 26 below.

268

Table 26 Hypothetical outputs from a screening risk characterization (Adopted from American Cleaning Institute, 2010)


Yes, see

269

Table 26 above.


It is possible to address combined exposures, since the exposure estimates (PExIC) may be aggregated either within each product category or across product category.


Not directly, but the MoE in itself indicate if exposure is close to or well below the NOAEL. If the calculated MOE ≥ 1000, an initial default decision of "not of concern and no further

refinement" is considered adequate (American Cleaning Institute, 2010)


No

270


No, not explicitly addressed.

Other information/issues

List/describe any other identified information deemed relevant for this project:

The framework is not an actual tool, rather a guidance for exposure/risk assessment.

However, the elements of the approach are useful for the project.

271

Appendix 6 - Review of 6.

methodologies for assessment of

chemical exposure from consumer

products

RIVM (2009) and key parameters for evaluating consumer 6.1

exposure to nanomaterials Scope The scope of the RIVM (2009) report was to get more insight in the possible exposure of consumers to nanomaterials in consumer products. A panel of nano- and exposure experts was consulted in order to identify and estimate the most relevant exposure characteristics within the different product categories. The aim was to identify the exposure potential for the different product categories and to identify product categories with a high priority for future exposure studies. Input The sources of information for the work were data from market reports and inventories describing nanomaterial use and consumer product categories in which nanomaterials may occur. Outcome An expert panel then identified the most important exposure characteristics for a consumer product in order to evaluate the potential for nanomaterial exposure from use of the product, see table 4-1.

272

TABLE 6-1. MAIN CHARACTERISTICS FOR HUMAN EXPOSURE TO NANOMATERIALS FROM CONSUMER PRODUCTS (RIVM 2009)

When using these characteristics to assess the potential for exposure from various product

categories, the experts found that following most important for assessing and characterising the

exposure:

Nanomaterial free or fixed inside the matrix of the product

Application expected to lead to direct or indirect exposure via release of particles out of the

product

Exposure route: dermal, oral, inhalation (or a combination of these)

REACH guidances on exposure assessment from chemical 6.2

products and articles

The REACH guidance on Information Requirements and Chemical Safety Assessment (ECHA,

2012) contains several chapters addressing various types of exposure assessment, including some

specific recommendations regarding nanomaterials. Relevant part of this guidance will be

addressed in the following. The guidance is intended for assisting REACH registrants in eventually

documenting in their safety assessments that risks are controlled. The guidance also forms the basis

for exposure estimation/assessment in other REACH processes addressing risks.

273

REACH guidance Chapter R.15: Consumer exposure estimation 6.2.1

Scope

The guidance provides a procedure/guidance for the estimation of consumer exposure to

substances on their own, in mixtures or in articles at a Tier 1 level. The estimation of consumer

exposure deals with consumer products and articles that can be purchased from retail outlets by

members of the general public.

Input data Exposure of consumers to chemical substances should generally be characterized by:

1. The different routes of exposure, separately or in combination 2. The identification of the different phases of activity in handling the consumer product or

article (including post-application) 3. The duration and frequency of exposure.

Inhalation exposure

The guidance recommends that inhalation exposure is expressed in terms of external exposure, as a

concentration, usually as mg/m3. For measurement of exposure to nanomaterials, information in

relation to number concentration (especially for fibres) and surface area concentration are also

considered to be of benefit (i.e. n/m³ or cm2/m3).

The method presented in the guidance is applicable for calculating exposure to all substances

released into a standard room as a gas, vapour or airborne particulate.

The method has not yet been validated for use with nanomaterials. If the output of the model is

used to estimate exposure for nanomaterials, this should preferably be supported by measured data.

The two essential input parameters are:

Amount of product used

Fraction of substance in the product (concentration).

Other input parameters, used in the algorithm for estimating the air concentration and resulting

inhalatory dose of the product are shown in .

TABLE 6-2. SPECIFIC INPUT PARAMETERS FOR CONSUMER INHALAITON EXPOSURE ESTIMATION

ALGORITMS

Input parameter Description Units

Qprod Amount of product used [g]

Fcprod Weight fraction of substance in product [g/gprod]

Vroom Room size (default 20 m3) [m³]

Fresp Respirable fraction of inhaled substance (default 1)

[-]

IHair Ventilation rate of person [m³/d]

Tcontact Duration of contact per event (default 1 day)

[d]

BW Body weight [kg]

N Mean number of events per day [/d]

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Output parameter Description

Cinh Concentration of substance in air of room

[mg/m3]

Dinh Inhalatory dose (intake) of substance per day and body weight

[mg/kg bw d]

And the algorithms are:

The concentration in air, Cinh in mg/m3 after using an amount Qprod of the product becomes:

Cinh = Qprod ∗ fcprod

Vroom

The daily dose, Dinh in mg/kg bw per day becomes:

Dinh = Fresp ∗ Cinh ∗ IHair ∗ Tcontact

BW∗ N

When the inhalable and/or respirable fraction is known, it should be taken into account. If the

product contains releasable nanomaterials then the assumption should be made that it is entirely

within the respirable fraction if not otherwise known.

Dermal exposure

The guidance recommends that dermal exposure is expressed as mg/cm2 (local effects) or as mg/kg

BW/day (systemic effect). No specific recommendation for dermal exposure to nanomaterials is

provided.

Calculation of dermal exposure is given for two different scenarios:

A. The substance is contained in a mixture

B. Substance migrating from an article.

Dermal scenario A: Instant application of a substance contained in a mixture

The essential parameters used for this model are:

Weight fraction compound: the fraction of the compound in the total product

Amount of product: the amount of total product applied to the skin

The surface area of the exposed skin.

Other input parameters, used in the algorithm for estimating dermal load and external dose in

scenario A are shown in Table 6.

TABLE 6-3. SPECIFIC INPUT PARAMETERS FOR CONSUMER DERMAL EXPOSURE ESTIMATION

ALGORITMS (INSTANT APPLICATION)


Cprod Concentration of substance in product before dilution g/cm3

D Dilution factor (If not diluted, D =1) [-]

RHOprod Density of product before dilution [g/cm3]


Fcprod Weight fraction of substance in product before dilution

[-]

275

Vprod Volume of product used before dilution [cm3]

Vappl Volume of diluted product actually contacting the skin [cm3]

THder Thickness of product layer on skin (default 0.01 cm) [cm]

Askin Surface area of the exposed skin [cm2]

BW Body weight [kg]

n Mean number of events per day [/d]

Output Description

Cder Dermal concentration of substance on skin [mg/cm3]

Lder Amount of substance on skin area per event [mg/cm2]

Dder Amount of substance (external dose) that can potentially be taken up (account later for actual dermal absorption) per body weight

[mg/kg bw d]

Further applications Description (see the text below)

V*appl Volume of diluted product actually remaining on the skin

[cm3]

Fcder Fraction of the applied product remaining on the skin [-]

The dermal load, Lder in mg/cm2 is calculated as:

and the external dose Dder in mg/kg bw d as

In cases where the substance is contained in a liquid into which certain parts of the body are

dipped, the equation is not based on the mass of the substance applied to a certain area of skin, but

rather on the concentration of the substance in the mixture that is in contact with the skin. First, the

concentration Cder of a substance in contact with skin is calculated. Depending on how the

parameters are provided, three analogous calculations are used:

The total dermal load, Lder is then calculated by:

And the dermal dose, Dder (mg/kg bw d) derived as

The above dermal equations also apply to:

a non-volatile substance in a medium used without further dilution. In this case the

dilution factor (D) is set to 1;

a non-volatile substance contained in an undiluted medium removed from the skin by, for

example, wiping or rinsing and drying (e.g., liquid soap). Recalculate the V*appl “real”

276

volume of application based on volume of application (Vappl) as V*appl=Vappl x Fcder; where

Fcder is the fraction of the product remaining on the skin;

a non-volatile substance in a volatile medium. The concentration Cder is only valid at the

very beginning of exposure. However, this concentration can still be used to calculate Lder,

because the substance is non-volatile.

Dermal scenario B: A non-volatile substance migrating from an article


Weight fraction compound: the fraction of the compound in the total product

Amount of product: the total amount of product applied to the skin

The surface area of the exposed skin

The migration rate of the substance

The contact time of the substance

Skin contact factor (set at 1 for default), a factor that can be used to account for the fact

that the product is only partially in contact with the skin.

Other input parameters, used in the algorithm for estimating dermal load and dermal dose in

scenario B are shown in .

TABLE 6-4. SPECIFIC INPUT PARAMETERS FOR CONSUMER DERMAL EXPOSURE ESTIMATION

ALGORITMS (MIGRATION FROM AN ARTICLE)

Input parameter Description Unit


Fcprod Weight fraction of substance in product [g/gprod]

Fcmigr Rate (fraction) of substance migrating to skin per unit time

[g/(gprod x t)]

Fcontact Fraction of contact area for skin, to account for the fact that the product is only partially in contact with the skin (default = 1)

[cm2/cm2]

Tcontact Contact duration between article and skin [d]

SDprod Surface density (mass per unit area) [mg/cm2]

Askin Area of contact between product and skin [cm2]

Cder Dermal concentration of substance on skin [mg/cm3]

BW Body weight [kg]


Output Description

Lder Dermal load on the skin that is expected due to migration

[mg/cm2]

Dder Dermal dose per day and body weight [mg/kg bw d]

The dermal load Lder in mg/cm-2 is calculated as:

277

In case a surface density, SDprod for an article is available (in mass per unit area), the equation

reverts to:

The external dermal dose, Dder in mg/(kg bw d) is then calculated as

Oral exposure

Oral exposure is expressed as external dose (mg/kg bw).

Calculation of oral exposure is given for two different scenarios:

A. Substance in a product unintentionally swallowed during normal use

B. Substance migrating from an article; applicable for example when a substance migrates

from a pen, cutlery or textile

Oral scenario A: Unintentional swallowing of a substance in a product during normal use


Weight fraction compound: the fraction of the compound in the product

Concentration in the product as swallowed (if diluted)

Amount ingested: the total amount of product swallowed

Other input parameters used in the algorithm for estimation of concentration in the product as

swallowed and the oral dose are shown in Table 6-5:

TABLE 6-5. SPECIFIC INPUT PARAMETERS FOR CONSUMER ORAL EXPOSURE ESTIMATION ALGORITMS

(UNINTENTIONAL SWALLOWING – NORMAL USE)


Cprod Concentration of substance in product before dilution

[g/cm3]

D Dilution factor [-]

RHOprod Density of product before dilution [g/cm3]

Qprod Amount of product before dilution [g]

Fcprod Weight fraction of substance in product before dilution

[g/gprod1]

Vprod Volume of product before dilution [cm3]

Vappl Volume of diluted product per event in contact with mouth

[cm3]

Foral Fraction of Vappl that is ingested (default = 1) [-]

BW Body weight [kg]


Output

Coral Concentration in ingested product [mg/m3]

Doral Intake per day and body weight [mg/kg bw d)]

The concentration mg/m3 in the product as swallowed is calculated from:

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and the oral dose in mg/kg bw per day is then given by:

If an undiluted product is swallowed, D = 1.

These equations may also be used to estimate exposures arising from ingestion of the non-

respirable fraction of inhaled airborne particulates.

Oral scenario B: Substance migrating from an article

For articles that may be taken into the mouth or sucked on (mouthing) as part of reasonable

foreseeable misuse, substances can migrate into saliva or (through it) to skin. This could be limited

to a few classes of articles.

For a screening assumption on migration, the Tier 1 oral exposure model A can be used. In a higher

tier model, the release rate of the substance from a product can be measured and the exposure time

assessed, to obtain a more reliable estimate of substance released from the article. The amount of

ingested substance can then be calculated. (From REACH guidance chapter R17)

Comment

The presented Tier 1 equations for consumer exposure estimations are implemented in the ECETOC

TRA model and the ConsExpo model, which are also addressed elsewhere in this chapter. We will

further down address how this guidance has been evaluated in relation to assessing exposure from

nanomaterials.

REACH guidance Chapter R.14: Occupational exposure estimation 6.2.2

Scope

Provides a procedure/guidance for occupational exposure estimation. It describes what information

is needed for the assessment at the different levels (Tiers) and how to deal with it.

Input data

The guidance document does not provide any additional information regarding input

parameters/determinants for exposure estimation than those covered by the different occupational

exposure models already reviewed (e.g. Stoffenmanager and DREAM addressed elsewhere in this

chapter).

REACH guidance Appendix R14-4: Recommendations for nanomaterials 6.2.3

Scope

To provide advice to registrants preparing their registration dossiers for nanomaterials. The content

of the appendix implements the advice provided by the REACH Implementation Project on

Nanomaterials 3 (RIP-oN 3) on exposure assessment and risk characterization. Main focus is on

exposure measurements and not on input parameters for modeling.

Input data

The appendix does not recommend specific input parameters/determinant of exposure to be taken

into account as there is not yet consensus on what such parameters should be. On the other hand,

current guidance e.g. in relation to methods and tools should only be used if scientifically justified

279

to be relevant. Thus implicitly the registrant is advised to carefully consider a given exposure

scenarios as a specific case. Some advices are given regarding metric to be used for description of

nanomaterial inhalation exposure:

"Inhalation exposure can be described by the concentration of the substance in air and the

duration and frequency of exposure. It is generally expressed in ppm (parts per million) or

amount per unit air volume inhaled, averaged over the duration of the relevant task or shift (e.g.

mg/m3 8hr Time Weighted Average (TWA)). For measurement of exposure to nanomaterials,

information in relation to number concentration (especially for fibres) (i.e. n/m3) and surface

area concentration are also considered to be of benefit (i.e cm2/m3)."

REACH Guidance on information requirements and chemical safety 6.2.4

assessment, Chapter D

Scope

The module regarding exposure scenario building explains how to conduct exposure assessment

covering the development of exposure scenarios and exposure estimation. The main focus of this

module is on how exposure scenarios (ES) can be developed.

An overview of the core information to be taken into account when developing exposure scenarios is

given.

Input data

Examples of determinant of exposure are given in Table 6-6.

280

TABLE 6-6. EXAMPLES OF DETERMINANTS OF EXPOSURE (ADOPTED FROM REACH GUIDANCE ON

INFORMATION REQUIREMENTS AND CHEMICAL SAFETY ASSESSMENT. CHAPTER D: EXPOSURE

SCENARIO BUILDING)

Outcome

The determinants of exposure are used in the development of the final exposure scenario for a given

substance and in turn for estimating the exposure.

Comments

According to the guidance document: "Generalisation of exposure scenarios for nanomaterials, as with other substances, will always need to be justified. For nanomaterials this would not just be based on substance composition but would also need to take account of other parameters such as particle size distribution".

REACH Guidance on requirements for substances in articles 6.2.5

Scope

This guidance addresses implementation of REACH article 7 (notification and registration of substances in articles) and 33 (duty to communicate information on substances in articles) and does thus not address exposure estimation (ECHA 2011).

281

SCCS guidance on nanomaterials in cosmetics 6.3

Scope

The aim of the "Guidance on the Safety Assessment of Nanomaterials in Cosmetics" from the

Scientific Committee on Consumer Safety (SCCS 2012a) was to develop a guidance on the essential

elements that would be required in safety dossiers for manufactured nanomaterials in order to

document safe use of the nanomaterials in cosmetics.

Outcome

In the exposure section of the guidance document it is stated that there is currently no indication

that the use of consumer/cosmetic products that contain nanomaterials is likely to be any different

from the use of other products that contain conventional ingredients. As a consequence , this means

that default values in relation to exposure e.g. used amounts, will be the same.

The following factors are mentioned to be important exposure factors in connection with use of a

cosmetic product:

- class of cosmetic product(s) in which the ingredient may be used,

- method of application: rubbed-on, sprayed, applied and washed off, etc.,

- concentration of the ingredient in the finished cosmetic product,

- quantity of the product used at each application,

- frequency of use,

- total area of skin contact,

- duration of exposure

- foreseeable misuse which may increase exposure,

- consumer target groups (e.g., children, people with sensitive, damaged or

compromised skin) where specifically required

- quantity likely to enter the body (fraction absorbed),

- application on skin areas exposed to sunlight,

- use area (indoors/outdoors) and ventilation

- all routes of exposure (dermal, oral and inhalation exposure) should be considered in

view of the intended use of the product

In addition to this, further guidance is given on how to calculate the internal exposure by

accounting for dermal absorptions factors expressed either as percent of the applied dose of the

substances or as absorption per cm2 skin surface area. For oral exposure it may be especially

relevant to apply a retention factor as e.g. for toothpaste where only a fraction of the used volume is

considered to be swallowed. For inhalational exposure from e.g. spray products the guidance refers

to the ConsExpo model.

However, it is stated that the spray module in the model calculates the exposure based on the

inhalable fraction of the generated aerosols. For conventional substances it is assumed that these

are homogeneously distributed over the generated aerosols, on a mass basis. For that reason, in the

experiments carried out for the calibration of the model, aerosols with a size <1 μm are not be taken

into account. It should be noted that the mass of aerosol droplets <1 μm is negligible compared to

the aerosols present in the inhalable fraction of 1-20 μm. Key parameters in the calculation of the

inhalation exposure are:

- room volume, - spray duration, - ventilation rate, - exposure duration - mass generation rate,

and product specific parameters, such as:

282

- airborne fraction, - aerosol size distribution - weight fraction of the ingredient.

Further it is noted that the applicability of ConsExpo spray module to nanoparticles has not yet

been determined. Therefore, for spray application of products with nanomaterial, a careful

characterisation is needed of the droplet size and the nanomaterial distribution in the droplets.

Determination of the generated droplet size distribution is not sufficient, but needs to be

complemented by the size distribution of the dried residual aerosol particles. Exposure patterns

during consumer use (e.g. in terms of variable particle size distribution) might be different from

exposure patterns in experimental settings (e.g. stable particle size distribution). However, factors

such as particle size and size distribution/ agglomeration state of nanomaterials are known to be

important in determining the hazard, however more specific guidance on how to account for this is

not given.

In the description above, the parameters important for quantitative exposure assessment have been

highlighted in bold.

In the SCCS’s Notes of guidance for the testing of cosmetic substances and their safety evaluation 8th revision 2012 (SCCS 2012b), specific values are given for key exposure parameters for the various types of cosmetic product covering:

- Identification of part of the body exposed - Skin surface area exposed (cm2) - Frequency of application (times per day) - Estimated daily amount applied (g/day) - Relative amount applied (mg/kg bw day) - Retention factor (unitless) - Calculated daily exposure (estimated daily amount applied x the retention

factor) - Calculated relative daily exposure (relative amount applied x the retention

factor)

EFSA guidance on nanomaterials in food 6.4

Scope

The aim of the EFSA ”Guidance on the risk assessment of the application of nanoscience and

nanotehcnologies in the food and feed chain” EFSA (2011a), was to develop a practical approach for

assessing potential risks arising from applications of nanoscience and nanotechnologies in food and

feed chain.

Outcome

In the rather short and overall section regarding exposure assessment the guidance states, that…

“basically, the principles of exposure assessment of ENM* (via food and feed) will be the same as

in exposure assessment of non-nanoform materials.

Issues like food/feed sampling and variability within composite samples and variation in

concentrations between samples are not different from the exposure assessment of

micro/macroscale or dissolved chemicals.

On the basis of the available consumption data, the anticipated average and high intakes in

various population groups of the ENM food/feed must be estimated. Probabilistic methods may be

useful to determine ranges of plausible values rather than point estimates. If possible, particular

sections of the population with an expected high exposure should be identified and this should be

considered in the risk assessment. There is limited information on the consumption (amounts and

frequency) of food supplements. Data on import and production quantities could provide

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additional information for the exposure assessment. Any assumptions made in the exposure

assessment should be described.

A central aspect of exposure assessment is the determination of the amount and characterisation

of the ENM present in the food or feed as consumed. In most cases, the starting point for

determining the amount of ENM currently has to rely on information on the material added or

that is in contact with food/feed. The initial characteristics of the added ENM can be assessed and

used as an assumption in the exposure assessment, however, currently it is not possible to

routinely determine ENM in situ in the food or feed matrix that increases the uncertainty in the

exposure assessment. The structure of the ENM in food/feed may be changed in the food/feed

production chain during processing or storage because of their interactions with proteins, lipids

and other substances present in the food/feed matrices. Hence, ENM should be analysed at an

early stage of the food chain, and effects of processing and storage and the stability of the ENM

should be considered in the exposure assessment. Also, effects of digestion or other causes of

degradation of the matrix on ENM characteristics need to be considered.

For ENM added to feed, the potential carry over to food should be considered for human exposure,

which could be determined by measurement of the ENM in relevant animal tissue or products.

In the absence of exposure data, and where it is not possible to determine the nanoform in the

food/feed matrix, it should be assumed that all added ENM is present, ingested and absorbed in

the nanoform, although the structure/properties of the ENM remain undetermined and therefore

difficult to relate to the structure/properties of the ENM used in the toxicity studies”

*ENM: Engineered nanomaterial

Environmental Defense – DuPont approach 6.5

Scope The Environmental Defense – DuPont Nano Risk Framework (Environmental Defense – DuPont, 2007) is developed as a process to identify and address potential environmental, health and safety risks of engineered nanomaterials across the whole lifecycle of a product. The Framework is targeted organizations (e.g. companies or public and private research institutes) that are working with nanomaterials and developing associated products. The Framework should be applicable for a broad audience, and expert knowledge does not seem to be required. Input data The framework consists of six steps:

1. Describe materials and application 2. Profile lifecycle(s) 3. Evaluate Risks 4. Assess Risk Management 5. Decide, Document and Act 6. Review and adapt

Exposure assessment lies within “Profile Lifecycle(s)”, where the potential for human and environmental exposures across the full product life cycle is identified and characterised. According to the Framework, following types of questions should be considered when assessing potential for human exposure:

What are the potential routes of human exposure (e.g. inhalation, ingestion, and eye or dermal penetration)?

Are the nanomaterials present in a consumer product?

Can the nanomaterials have direct or indirect contact with food?

Can the nanomaterials be present in water used for drinking or recreational purposes?

Can the nanomaterials be present in the ambient air or surfaces of the workplace, home,

and other locations where people may be exposed?

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What sensitive populations (e.g., children, elderly persons) may be exposed?

The base set of exposure data required when investigating human exposure in the use phase is as follows:

- Commercial or consumer product types (e.g., paints and coatings, soaps, and detergents) in which the substance is used or present

- Specific commercial or consumer products in which the substance is used or present

- The percent of production volume associated with each commercial or consumer use

- Trade names of the products

- Settings for use (e.g., in manufacturing sites, in homes, outdoors)

- Use patterns (e.g., description of products or applications and how they are used)

- Numbers of commercial users (including workers) working with the substance and consumers using the product

- Maximum concentration of the substance in each commercial or consumer product

- Indication of whether the products are intended for use by children or other sensitive populations

- Indication of whether the substance is intended for release during use or can reasonably be anticipated to be released. If so, what are the magnitude, frequency, duration, and mode (e.g., to air) of the expected release?

- Indication of whether there is potential for exposure to the substance in the product through inhalation, ingestion, skin absorption, or ocular uptake

- Required or recommended controls for use (e.g., training, engineering controls, personal protective equipment)

- Recovery/recall techniques (e.g., in case of misuse or new hazard data)

Outcome

The framework does not provide algorithms for calculation of exposure.

ECETOC TRA 6.6

Scope

The ECETOC TRA tool for consumer exposure is a conservative tool for estimating exposure and

risk for consumers. It is a tier 0 / tier 1 tool for exposure assessment as the tool operates with a high

level of default values, but several possibilities for using specific values exists. The tool is not an

expert tool, but some experience regarding exposure estimation is needed for using the tool and get

meaningful output.

Input data

Mandatory parameters:

Vapour pressure

References value (e.g. DNELs) for the various exposure routes

Select product subcategory and type of use

Optional parameters (otherwise default values used):

Concentration in the products

Amount of product used per event

Skin contact area (adult/ children)

Oral Contact area (of product adult/children)

Dermal or oral transfer factor

Overall, most of the use scenarios/product categories identified in chapter 2-4 are covered by the

product/article categories in ECETOC TRA tool. The included products and articles covers various

kinds of matrices (e.g. liquids; aerosols; pastes; solids; textiles, paper, plastics). However, food/

285

beverages, cosmetics, medical devices and construction materials are not included in the ECETOC

TRA model.

Both dermal, inhalational and oral exposure routes are considered, but from the start it is

anticipated for each of the product subcategories whether exposure via a specific exposure route is

relevant and also whether children may be exposed for the product.

Dermal exposure

For the dermal exposure, the following algorithm is used for calculating exposure:

TABLE 6-7: ALGORITHM FOR DERMAL CONSUMER EXPOSURE, ECETOC TRA.

Product Ingredi

ent (g/g)

Contact Area (cm2)

Transfer Factor

(unitless)

FreQuency of use

(events / day)

Thickness

of Layer (cm)

Density (g/cm3)

Conversion

Factor (mg/g)

Body Weig

ht (kg)

Exposure (mg/kg/

day)

(PI x CA x TF x FQ x TL x D x 1000) /

BW

Where the transfer factor is the fraction of the chemical content in the product matrix that is available for exposure.

Inhalation

For inhalational exposure, the following algorithm is used for calculating exposure:

TABLE 6-8: ALGORITHM FOR INHALATIONAL CONSUMER EXPOSURE, ECETOC TRA

Product

Ingredient

(g/g)


Application (g/event)

FreQuency of use

(events / day)

Fraction

Released to

Air3

(g/g)


Exposure Time (hr)


Inhalation Rate

(m3/hr)

Conversion Factor

Room Volume

(m3)

Body Weight

(kg)

Inhalation

Exposure

Estimate

(mg/kg/day)

Inhalation

Exposure

Estimate

(mg/m3)


IR x 1000) / (V x BW) SVC=saturate

d vapour concentration

Oral exposure

For oral exposure, the following algorithm is used for calculating exposure:

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TABLE 6-9 : ALGORITHM FOR ORAL CONSUMER EXPOSURE, ECETOC TRA

Product Ingredient (g/g)

Volume of product

swallowed (cm3)

Transfer Factor

(unitless)

FreQuency of use

(events / day)

Density (g/cm3)

Conversion Factor (mg/g)

Body Weight

(kg)

Exposure (mg/kg/ day)

(PI x V x TF x FQ x D x 1000) / BW

Output

When using the default values for the parameters the tool can be used for getting a rough and

conservative quantitative output in terms of exposure and risk for preselected products and articles.

However, more refined estimates may be obtained if case specific input values are available and can

be used. In the output module of ECETOC TRA, the estimated dermal, oral and inhalational

exposure is compared to a reference value for hazard (in REACH termed as a DNEL value) and a

risk characterisation ratio, RCR is calculated.

Comments

Overall, the ECETOC TRA is a tool at a screening level for consumer exposure. There is a great

overlap of the exposure parameters identified in chapter 2 from the RIVM (20009) report and in

the ECETOC TRA tool, e.g. concentration.; dose per use; frequency, matrix effects;

differentiation in the various exposure route. However differences also exist:

- with respect to frequency of use this refers to number of uses per day and thus ECETOC

TRA does not take into account frequency in a larger time scale e.g. weekly/ monthly or

yearly.

- for dermal exposure calculation the ECETOC TRA takes into account further parameters

such as - how large a skin area that may be exposed from the various products categories;

the thickness of the product layer on the skin, and how large a fraction of the substance

that is actually available for exposure from the matrix (a default value of 100% is used).

- for inhalation exposure the amount of product liberated into the air is considered, the

dilution factor for this amount (room volume and ventilation rate) and the respiratory rate

of the consumer are also taken into account. Thus for dermal an inhalation exposure it is

possible to consider more details in the exposure assessment.

The ECETOC TRA is a tool using mass based dose metrics and it can be used for estimating the

mass based exposure to an ingredient e.g. a nanomaterial from a product. It is not possible – and

the tool is not designed for including nano-relevant metrics such as particle size distributions,

agglomeration, surface area or particle number, and use these parameters in the exposure

estimation.

ConsExpo 6.7

Scope

ConsExpo is a consumer exposure estimation tool, which can both be used as a low tier tool and a

higher tier tool at tier 2 level. In order to run the model, some training is needed even though it is

quite user friendly. If the tool is on the higher tier level, involving more detailed calculations, some

expert knowledge is required in order to specify the input data properly.

Input data

ConsExpo has defined a number of use scenarios involving selecting the product category (e.g.

paint, cleaning agents, cosmetics). There is no direct link between the use scenarios defined in

287

ConsExpo and the PC/AC-categories used for characterisation of uses in connection with REACH

registration.

Overall, main identified use characteristics/ parameters are handled in the algorithms used in ConsExpo:

TABLE 6-10. MAIN PARAMETERS FOR EXPOSURE ASSESSMENT, CONSEXPO

Exposure

route

Concen-

tration

in

product

Contact

Area

Duration Frequency

of use

Amoun

t

Thickness

of Layer

Density Body

Weight

Operator x x (if

relevant)

X (decrease in

concentration

with time is

considered)

x x x x /

ConsExpo takes into account if the substance is a part of the product, i.e. the concentration of the substance in the product is considered.

The use scenarios include the required parameters for carrying out oral, dermal and inhalation

calculations. The parameters needed for doing higher tier calculations depend on the actual use

scenario, see below:

TABLE 6-11. FURTHER PARAMETERS IN RELATION TO EXPOSURE ROUTE SPECIFIC USE SCENARIOS;

CONSEXPO

Exposure

route

Model

Parameters

All All General: use frequency

body weight (Wbody) product amount (A) or concentration (wf)

weight fraction compound (wf)

Molecular weight


Vapour pressure

Inhalation Vapour

(Instantaneous release mode,

Constant rate release mode,

Evaporation release mode)

exposure duration room volume (V or Vroom)

ventilation rate (q)

(application duration) (tr)

(release area)

(mass transfer rate) (K)


Spray spray duration

room height

(cloud volume)

mass release rate (Rspray)

airborne fraction (fairborne) density solvent + non-volatile



droplets size distribution

Dermal Instant application exposed area

Constant rate contact rate (R)

288

Rubbing off transfer coefficient (Rtrans)

dislodgeable amount (Fdislodge)

contact time (t) rubbed surface (Sarea)

Migration leachable fraction (Fleach)

skin contact factor (Scontact)


diffusion coefficient (D)

layer thickness exposure time

Ingestion Direct oral intake ingested amount (A)

Constant rate ingestion rate (R) exposure time (t)

Migration exposure time (t)

contact area (S)

initial migration rate (Rm)

Migration from packaging

material

thickness package

contact area package amount

ingested amount

storage time (t)

migration rate (Rm)

amount of packaged food (Apack)

amount of consumed food (Acons) amount of compound in food (Afood)

Matrix effects are not directly addressed in ConsExpo. However, the defined use scenarios include a pre-evaluation if the product is a liquid or a solid. A pre-assessment whether specific exposure routes are relevant to include has been included in the pre-defined use scenarios in ConsExpo.

Output

ConsExpo includes all exposure routes. It calculates both the external dose and internal exposure

(systemic). So it has models included for the calculation of the uptake into the body. In addition it

also calculates combined exposure, i.e. accounting for combined oral, dermal and inhalative

exposure.

The results of a ConsExpo exposure calculation can be presented in different ways: as point values,

as a graph over (exposure) time, as a distributed result from a Monte Carlo simulation, and in a

textual report. In addition, sensitivity analysis of the exposure assessments can also be carried out

in ConsExpo.

Exposures and doses are presented both per route and integrated over all routes. Per route various

exposure measures are calculated:

External inhalation exposure is calculated as the air concentration during

exposure. Different measures are: mean air concentration during a single

exposure event; mean air concentration on the day of exposure and year

average air exposure.

Internal inhalation doses calculated are: the acute (amount taken up during

one event per kg bodyweight) and chronic (daily average of the amount taken

up per kg bodyweight) dose.

External dermal exposure is calculated as dermal load (amount of compound

per cm2 of exposed skin) or as external dose (the amount that can potentially

be taken up per kg bodyweight).

Internal dermal doses calculated are: the acute (amount taken up during one

event per kg bodyweight) and chronic (daily average of the amount taken up

per kg bodyweight) dose.

External oral exposure is calculated as external dose (the amount that can

potentially be taken up per kg bodyweight).

289

Internal doses are: the acute (amount taken up during one event per kg

bodyweight) and chronic (daily average of the amount taken up per kg

bodyweight) dose.


When one or more parameters have been specified as a distribution, ConsExpo can perform a

distributed (Monte Carlo) calculation. The program will draw a set of random numbers from the

specified distributions for distributed parameters and calculates the endpoint of choice with this

set. For the non-distributed parameters the specified point value is taken. The calculated exposure

measure for the set is stored. This procedure is repeated for a user-specified number of times (the

number of Monte Carlo samples). The result of this procedure is a distributed set of calculated

exposures. Some characteristics of the distribution such as median, standard deviation 90- and 99-

percentile of the calculated distribution are reported.

The ConsExpo report gives an overview of the exposure calculation. It displays all parameter values

and the calculated exposures in the mass metric. The text can be saved to (text-) file or can be

printed directly from ConsExpo.

Comments Even though ConsExpo is not targeted at nanomaterial exposure it can be used for mass based consumer exposure assessment to nanomaterials– with caution. As a tier 1 and tier 2 tool, the tool may be highly relevant for use in his project e.g. to evaluate specific exposure scenarios further and also for evaluation of semi-quantitative exposure assessments in our project. If the use scenarios included in ConsExpo in future should be updated/modified so they better

respond to the characteristics of nanomaterials, inclusion of other dose metrics would be necessary

e.g. particle number exposure or particle surface exposure may be considered in addition with

further consideration on the liberation of free nanoparticles from a product during use.

Furthermore, the uptake models probably would have to be modified, to better account for the

special behaviour of nanomaterials.

It should be mentioned that RIVM is running a project looking on the suitability of ConsExpo to

handle nanomaterials and whether any modifications should be introduced into ConsExpo.

Currently we do not have any estimate of when that project will be published.

NanoSafer 6.8

Scope

NanoSafer is an advanced tier 0 to tier 1 modelling-based control banding tool for assessment and

precautionary management of potential risks associated with occupational inhalation exposure to

nano-objects and their agglomerates and aggregates during specific nanomaterial release and

handling activities. NanoSafer is available at http://nanosafer.i-bar.dk/ and a full description is

given in Jensen et al. (submitted). Use of the web-based NanoSafer does not require training

beyond introduction or study of the written manual.

Inhalation exposure assessment procedure

For estimation of the exposure levels, the NanoSafer uses specific nanomaterial characteristics,

user-specific input parameters on the contextual information and specifics on the work process.

Ranking (banding) of the exposure level is done for estimated acute (15 min) and 8-hour work-day

exposure levels in the near-field (activity site) and far-field (outside of the activity site). The ranking

is made for each of the four pre-defined assessment situations based on the estimated exposure

levels, the occupational exposure limit of the nearest chemical bulk analogue, and the specific

surface area of the nanomaterial and the bulk reference value. The potential exposure levels used

for setting the near-field and far-field exposure bands are estimated using a two-box instant mixing

aerosol model. Uncertainties are not quantified. However, the approach in control banding is to try


290

and take uncertainty into consideration by using conservative assumptions and application of a

precautionary approach.

Input data

The required input data should primarily be available from Safety Data Sheets (SDS), presumably of

the nearest analogue bulk analogue, and the producers Technical Data Sheets (TDS) on the

nanomaterials. Suggested default values in the guidance manual are to be used when data does not

exist, but the user is free to enter other values if other data are thought to be more suitable for the

specific assessment. The input parameters used for the exposure assessment are listed in Tables 6-

12 and 6-13.

TABLE 6-12. OVERVIEW OF THE INPUT PARAMETERS ON THE PHYSICOCO-CHEMICAL NANOMATERIAL

CHARACTERISTICS.

Material name

(optional)

CAS number

(optional)

EINICs Number

(optional)

Nano-specific

word or term

(yes/no)

Coated or surface

modified nanomaterial

(yes/no)

Dimension of the

nanomaterial

(nm)

Specific density

(g/cm3)

Is the nanomaterial

water soluble

(yes/no)

The specific

surface area

(m2/g)

text text text NANO Rcoat a≤b≤c So SSA

TABLE 6-13. OVERVIEW OF THE INPUT PARAMETERS FOR EXPOSURE ASSESSMENT/RANKING.

Constant Release

rate

(kg/min)

Respirable

dustiness

(mg/kg)

Handling

energy

factor

(0 - 1)


work cycle

(kg/cycle)

Amount used per transfer

(kg/transfer)

Duration of work cycle

(min)

Duration of

transfer

(min)

Number of work cycles

(n)

Pause between

work

cycles

(min)

Volume of work room

(m3)

Air-exchange

rate

(h-1)

Occupational

exposure

limit for

analogue bulk

material

(mg/m3)

dM/dt DIresp Hi M m tduration ttransfer n tpause V Q

OEL

Algorithm

The near- and far-field exposure/risk bands (EXPi) are determined for the acute and daily exposure

according to equation 1.2.8.1 and 1.2.8.2

Equation 1.2.8.1:

nano

AcuteAcute

SSAOEL

CEXP

130

2

Equation 1.2.8.2:

nano

hourhour

SSAOEL

CEXP

130

88

thus incorporating the specific surface area and specific density; i.e. specific nano-properties.

291

In both calculations the Acute (Cacute) and 8-hour (C8-hour) exposure concentrations are the

respirable nanomaterial dust mass-concentration calculated following the procedure in equation

1.2.8.3:

Equation 1.2.8.3:

QVVttt

dt

dMorMmHDIfC FFNFpausedurationtransferirespresp ,,,,,),(),(,,

In addition to mass, these calculations can also be made according to particle number or surface

area concentrations, but not from the web-based resource.

Suitability of procedure for exposure assessment for consumer products

NanoSafer was made to assess the potential risks associated with worker inhalation exposure.

However, the control banding tool can also be applied for consumer products, where the exposure is

considered to be dominated by free of readily accessible nano-objects and the aggregates and

agglomerates. This could include release from processes, such as spraying, grinding, and sanding.

NanoSafer uses many of the parameters applied for assessment nanomaterial exposure in the RIVM

(2009) study.

NanoRiskCat 6.9

Scope

NanoRiskCat is a risk categorization tool that can be applied for screening purposes and

communication of knowledge in between producers and authorities as well as consumers if needed.

It is therefore not a risk assessment tool as such and therefore the tier level may precede tier 0.

However, the assessment paradigm for the exposure categorization may contain concepts useful for

future developments. A full description of the categorization tool is published in Hansen et al.

(2014). The procedure has been used for categorization of more than 1235 products claimed to

contain nanomaterials in the Danish nano database hosted by “Forbrugerrådet Tænk”

(http://nanodb.dk).

Exposure assessment procedure

The basic exposure assessment procedure is solely based on the physical state and occurrence of the

nanomaterial in the product (Hansen et al. (2007; 2008). Clear information is requested on the

product, the nanomaterial therein, and the intended use. The possible exposure situations are

identified and evaluated qualitatively. Based on this procedure, the possibility for exposure is

selected from 4 predefined categories: Unknown, low, medium, and high exposure potential for the

professional end-user, consumers, and the environment, respectively. If release or exposure data do

exist these data shall be used for the qualitative categorization. The final output pool all exposure

scenarios into one dot, but a written explanation should be accompanied with the assessment to

explain which scenarios and exposure routes that have been assessed and the outcome of these

assessments.

Input data

The information requirement is either official documentation on the exposure levels that can result

in a verified exposure categorization or a qualitative assessment based on where the nanomaterial

occurs in the product/article:

Bulk solid composite with nanostructured matrix

Surface: nanomaterial on a surface

Nanoparticles (nano-objects, editor)

o Nano-objects dispersed/adhered onto a surface

http://nanodb.dk/da

292

o Nano-objects dispersed in a liquid

o Nano-objects embedded/dispersed in solid matrix

o Nano-objects in powder or aerosol form

Algoritm

There is no algorithm for calculation.

Comments

The approach considers all potential exposure routes, which are agglomerated into one general

statement for the consumer and professional end-user in the short form. Further reading into the

written background information is intended to give further insight. It is important to note that NRC

used the assessed potential for release of the nanomaterial from the product as a surrogate for

exposure. Using the type of product and physical location of the nanomaterial in the product as an

exposure indicator may be a useful parameter to take into account in further development of an

exposure assessment paradigm for nanomaterial-based products.

Stoffenmanager 6.10

Scope

Stoffenmanager is a non-expert occupational tool used for inhalation and dermal exposure

assessments. The tool was initially developed to help SMEs to prioritize and control risks of

handling chemical products. It is a tier 1+ tool used for qualitative risk banding for dermal and

inhalation exposures as well as for quantitative exposure assessment for inhalation exposure.

Input data

General input parameters are provided from the Safety Data Sheet (SDS) for the product:

- Name of the product

- Whether the substance is a solid or a liquid

o For a solid: the dustiness

o For a liquid, the vapour pressure

- Health and safety information (according to R- and S-phrases)

- Composition of the product

o The different substances the product is composed of

o Concentration of the substances within the product

- Hazard categories (i.e. symbols)

- Personal protective equipment (PPE) and ventilation needed

Input parameters for dermal exposure assessment:

- Product

- Dilution (if relevant)

- Characterisation of the type of activity

o Handling objects or surfaces with (possible) presence of the product

o Manuel dispersion of the product without a hand-held tool, but e.g. with hands,

cloth or sponge

o Dispersion of product with hand-held tool, e.g. brush, roller, scoop, broom or

bucket

o Spray dispersion of product

293

o Immersing or dipping objects in product

o Mechanical treatment of solid objects or product

The tool is tailored requiring further input depending on what is selected as primary inputs. If -

'Spray dispersion of product' -is chosen as an example of activity (with a liquid substance), following

input parameters are then required (other input parameters are needed if e.g. a solid is chosen):

- How is the liquid best described? (like water, solvent, oil, grease or solvent

suspension)

- Does spraying create fine mist (Y/N)

- What is the distance to the source?

- Is the workroom small, narrow or enclosed (e.g. toilet) (Y/N)

- What is the working height during an activity?

- How much product is used per quarter of an hour?

- Is the source segregated (Y/N)

- Is local exhaust ventilation used (Y/N)

- Does workers wear working clothes (provided by employer) during the

activity (Y/N)

- What is the total duration of the activity?

- What uncovered parts of the body are exposed? (chose one or more

options)

Input parameters for inhalation exposure assessment:

- Is the product a solid or liquid

o If solid: does the situation concern shaping by removing or cutting of material

(Y/N)?

o If liquid: select product and dilution

- Characterisation of task (depending on whether the product is a liquid or a solid)

- Duration of task

- Frequency of task

- Distance to task

o Is the task being carried out in the breathing zone of an employee (distance head-

product <1m) (Y/N)?

o Is there more than one employee carrying out the same task simultaneously

(Y/N)?

o Is the task followed by a period of evaporation, drying or curing (Y/N)?

- Protection of employee

o Is personal protective equipment applied? (Y/N)

- Volume of working room

- Characterization of type of general ventilation

- Daily cleaning of working room (Y/N)?

- Are inspections and maintenance of machines/ancillary equipment being done at least

monthly to ensure good condition and proper functioning and performance (Y/N)?

294

The estimate of potential inhalation exposure is calculated using the algorithm in Table 6-14, which

gives a semi-quantitative exposure score, which is converted to an exposure band for a qualitative

inhalation exposure assessment.

TABLE 6-14. ALGORITH FOR ESTIMATING POTENTIAL INHALATION EXPOSURE

Parameter

Concentration

(score) due to near-field

exposure

Concentration (score) due to far-

field exposure

Background Concentration (score) due to diffusive

sources

Multiplier for the reductio

n of exposure

due to control

measures as the

worker

Multiplier for the

reduction of

exposure due to use of

personal protectiv

e equipme

nt

Multiplier for

duration of the

handling

Multiplier for

frequency of the

handling

Exposure

score

Algorithm

[(Cnf + Cff + Cds)] x Ƞimm x Ƞppe x th x fh B

Where

Cnf = E x H x Ƞlc_nf x Ƞgv_nf; Cnf = E x H x Ƞlc_ff x Ƞgv_ff; Cds = E x a and E =intrinsic emission

multiplier; a = multiplier for the relative influence of background sources; H =handling (or task)

multiplier; ƞlc = multiplier for the effect of local control measures; ƞgv_nf = multiplier for the effect

of general ventilation in relation to the room size on the exposure due to near-field sources; and

ƞgv_ff = multiplier for the effect of general ventilation in relation to the room size on the exposure

due to far-field sources.

The algorithm for the quantitative exposure assessment is as follows:

�̌�𝑠𝑜𝑙𝑖𝑑 = 𝐸𝑥𝑝 (1.55 + 0.69 ∗ ln 𝐶𝑡)

�̌�𝑙𝑖𝑞𝑢𝑖𝑑 = 𝐸𝑥𝑝 (6.17 + 0.87 ∗ ln 𝐶𝑡)

Where Ct = total personal exposure score = (Cnf + Cff + Cds) * Ƞimm and Y = geometric mean exposure

level.

The tool takes matrix effects into consideration and addresses liquids (including solvent

suspension) and solids (including powders).

Output

For the control banding module: The tool calculates an overall exposure score using the above

mentioned algorithm. This score is converted into an exposure band (1-4).

For inhalation exposures, the tool contains a quantified and validated exposure model for

estimating inhalation exposure to both inhalable dust and vapour (giving exposure concentrations

of tasks in mg/m³). Thus, for inhalation exposures the output can be both quantitative and

qualitative (control banding).

Comments

Stoffenmanager is not targeted towards nanomaterials and its possible applicability for

nanomaterials shall be seen in the light of the specific tool "Stoffenmanager nano” developed.

However, since Stoffenmanager Nano is only applicable for inhalation exposure, the generic

Stoffenmanager may be used with caution for e.g. some of the dermal exposure scenarios identified

in chapter 3 (such as use of cleaning agents, coatings/impregnation or maintenance products where

dermal exposure is expected). Stoffenmanager is, however, an occupational tool and the use

scenarios from chapter 3 cannot directly be addressed as consumer scenarios.

295

There is a great overlap of the exposure parameters identified by RIVM (2009) and in

Stoffenmanager tool (e.g.) concentration; duration and frequency of task, matrix effects;

differentiation in the various exposure route.

The tool takes additional input parameters into account, which may be relevant – especially if it is

an indoor exposure scenario:

For inhalation exposure:

- distance to task

- use of personal protection equipment

- volume of room

- ventilation of room

For dermal exposure:

- Amount of product used per quarter of an hour

- What uncovered parts of the body are exposed

Stoffenmanager Nano 6.11

Scope

The Stoffenmanager Nano is a tier 1 tool to be used in relation to occupational settings. The tool is

developed to be used by non-experts users, especially in SMEs.

The Stoffenmanager Nano applies to substances that consist of non-water soluble nanomaterials

with a primary size between 1 and 100 nm and/or to products with specific surface area of ≥ 60 m2

/g.

Input data

The general input parameters are:

- Source domain:

o Release of primary particle during actual synthesis

o Handling of bulk aggregated/agglomerated nanopowders

o Spraying or dispersion of a ready-to-use nanoproduct

(intermediate or ready-use-product)

o Fracturing and abrasion of MNO-embedded end products

(redirected to the generic Stoffenmanager tool)

- Product name

- Product appearance

- Name of nano component

- Does the product contain fiber/fiber-like particles?

- Inhalation hazard

The input parameters for exposure estimates are:

- Concentration of nano component in the product

- Characterisation of task

- Duration of task

- Frequency of task

- Is the task being carried out in the breathing zone of an employee?

- Daily cleaning of working room

- Monthly inspection/maintenance of machinery/ancillary products

- Volume of the working room

- Ventilation of the working room

The tool is tailored requiring further input depending on what is selected as primary inputs.

296

Only inhalation exposure is considered in Stoffenmanager Nano. The estimate of potential

inhalation exposure is calculated using the algorithm in Table 6-15.

TABLE 6-15. INHALATION EXPOSURE ALGORITHM

Paramet

er

Concentra

tion

(score)

due to

near-field

exposure

Concentrati

on (score)

due to far-

field

exposure

Background

Concentration

(score) due to

diffusive

sources

Multiplier

for the

reduction

of

exposure

due to

control

measures

as the

worker

Multiplier

for the

reduction

of

exposure

due to use

of personal

protective

equipment

Multiplier

for

duration

of the

handling

Multiplier

for

frequency

of the

handling

Exposu

re

score

Algorith

m [(Cnf + Cff + Cds)] x Ƞimm x Ƞppe x th x fh B

Where Cnf = E x H x Ƞlc_nf x Ƞgv_nf; Cnf = E x H x Ƞlc_ff x Ƞgv_ff; Cds = E x a and E = intrinsic emission

multiplier; a = multiplier for the relative influence of background sources; H =handling (or task)

multiplier; ƞlc = multiplier for the effect of local control measures; ƞgv_nf = multiplier for the effect

of general ventilation in relation to the room size on the exposure due to near-field sources; and

ƞgv_ff = multiplier for the effect of general ventilation in relation to the room size on the exposure

due to far-field sources. The multipliers are modifying factors which depend on the different local

control measures reflected by the input parameters listed above.

The tool takes matrix effects into consideration and addresses powders, granules/flakes and

particles dispersed in a liquid.

Output

The tool calculates an overall exposure score using the above mentioned algorithm. This score is

converted into an exposure band (1-4).

Comments

Stoffenmanager nano is directly targeted nanomaterial exposure, however, only for occupational

exposure. Since Stoffenmanager nano is developed for use in an occupational setting, the use

scenarios/product categories identified in chapter 3 will not be addressed as consumer scenarios.

The tool may, however, be used to generically address some of the use scenarios from chapter 3, if

the use resembles some of the source domains required as input parameters in the tool (see above).

The most relevant source domain is 'spraying or dispersion of a ready-to-use nano-product

(intermediate or ready-use-product)', which could be used to assess inhalation exposure within use

scenarios/product categories such as cleaning agents (spray products), coatings/impregnation

(spray products), maintenance products (sprays) and air cleaner sprays.

Stoffenmanager Nano uses many of the same exposure parameters as identified by RIVM (2009),

e.g. product form, matrix effects, concentration, duration of event and frequency of

event

297

ANSES 6.12

Scope

The tool is a tier 0 control banding tool and it is intended to be used in companies (incl. SMEs) and

academic institutions. The tool is an occupational tool and is developed to be used by persons with

a sufficient level of expertise within the field of chemical risk prevention.

Input data


Physical form – matrix in which nanomaterial is used (Solid matrix, in suspension/liquid,

as powder, as free nanomaterial/aerosol)


- Friable solids (release of nanomaterial under low stress)

- Dust generated by external forces (e.g. mechanical, electrical, laser forces)

- Melting?

- Dispersion in liquid


- Highly volatile liquids (possibly generating nanomaterial powder – if so dustiness

is required)

- Spraying?

- Generation of aerosol during process?

Powder

- Dustiness

- Spraying?

Only inhalation exposure is considered in the ANSES tool. The tool addresses four categories of

physical forms of nanomaterials: in solid matrices, in liquids, suspensions, as powders and as

aerosols. The algorithms are qualitative and decision-based.

Output

The tool provides qualitative risk control banding. Exposure is given as an overall emission

potential, which is converted to emission potential bands based on the physical state of the material

ranging from solid (exposure band 1) to aerosol (exposure band 4).

Comments

The ANSES methodology is directly targeted nanomaterials, but for use in an occupational setting.

There are fewer required input parameters compared with the other models/approaches assessed,

and these input parameters differ from those identified in chapter 2 and 4 in the way that focus is

mainly on the matrix in which the nanomaterial is used (for exposure assessment) and

physiochemical properties of the material (for hazard assessment). Parameters such as quantity of

the product used, duration and frequency of use are not taken into account. And even though the

tool is targeted nanomaterials, size as such is not considered to be a separate hazard parameter

(Brouwer , 2012).

The tool is an occupational tool, and the scenarios relevant for the product categories identified in

chapter 2 will therefore not be addressed as consumer scenarios. The applicability of the ANSES

tool for assessment of the identified consumer scenarios for nanomaterial exposure is somewhat

unknown, since no actual tool is available and the reviewed background documentation lacks

information regarding this. It is, however, assessed that the tool may, with caution, be used for

product categories such as cosmetics, cleaning agents, coatings and impregnation, maintenance

products, air cleaners, fuel and lubricants where inhalation exposure is expected.

298

Swiss Precautionary matrix 6.13

Scope

The Swiss Precautionary Matrix for Synthetic Nanomaterials is a scoring tool considering exposure

potential, hazard potential and level on information for evaluating whether further precautionary

actions are needed in relation to consumers, workers or the environment for the current/ intended

use of a nanomaterial. The approach may be considered as a tier 0 tool. The tool is only to be used if

the substance has nano relevant properties, e.g. primary particles < 500 µm or e.g. fulfil the EU

definition as a nanomaterial.

Input data

The input data pertain to:

Physico-chemcial characteristics regarding primary particles size, specific surface area, number of

particles in the nano range, agglomeration in order to evaluate whether the substance can be

identified as nano relevant e.g. in relation to the EU definition of a nanomaterial. However, the

nano relevance is extended to a cut-off point of 500 nm for primary particles in the approach.

The following information has to be used as input ranked into one of 3-4 different levels for each

parameter:

- information level of the nanomaterial (0-3-5 points for each of four types of information)

- reactivity of the nanomaterial (1-5-9 points) (surrogate for hazard)

- lifetime (stability) in the body of the nanomaterial (1-5-9 points) (here information concerning

coating is also requested)

- matrix description (various categories from aerosols to solid matrices) (0.0001- 0.01- 0.1-1 points)

- volume of nanomaterial to which the consumer is in contact per event (1-5-9 points)

- frequency (1-5-9 points)

No specific product types are addressed in the approach so in principle it includes all the selected

products/ scenarios identified in chapter 2-4.

Consumer exposure is then evaluated (scored) based on consideration of liberation from the matrix

(four graduations from 0.0001 to 1) and an estimation of the total volume (three selection levels: <

1.2 mg; < 12 mg; >12 mg) of nanomaterial per day that the consumer may be exposed to from the

product/ article. Also frequency (three levels: monthly; weekly; daily) of exposure is included in the

overall exposure score.

An additional scoring is added if the information level is low and data for e.g. lack of ID of

nanomaterial, lack on data on physicochemical parameters or impurities.

Output

For the overall precautionary evaluation, the exposure scores are multiplied with the hazard scores

and to this figure, scores for the lack of information is added. If the overall score is above 20, further

precautionary measures are recommended whereas a score of 20 or below does not call for further

action.

Comments

A high degree of precaution is built into the tool, as input with “unknown” for a specific parameter

results in a default scoring at the highest level.

Although developed for nanomaterials the approach in its exposure scoring procedure take only

account of mass based dose metrics.

For the purpose of this project, some aspects may be considered for further use in the exposure

estimation e.g. how to evaluate (or score) matrix effects or how to treat lack of information. The tool

can be used for a rough relative semi-quantitative exposure evaluation of nanomaterials, if the

299

hazard scoring is not considered by using a fixed identical scoring for the reactivity (hazard)

scoring.

Dream 6.14

Scope

DREAM is a tier 0 tool to be used by occupational health professionals when evaluating dermal

exposure in a workplace setting. It is an expert tool/method, since the input is given by an

occupational health professional based on observations of the worker(s).

Input data

The DREAM method consists of two parts, an inventory and an evaluation part. The inventory part

comprises a hierarchically structured (multiple choice) questionnaire with six modules:

7. Company: - General information about the company and observer

8. Department - Chemical or biological agents that occur in the work environment - Cleaning activities at the department

9. Agent Physical-chemical characteristics of the substance, e.g.

- Concentration of active ingredient in the substance - Physical state - Boiling temperature - Viscosity - Formulation (powder, granules) - Dustiness - Stickiness

10. Job - Hygienic behaviour - Number of people with the job title

11. Task - Percentage of time that the task is performed - Number of people performing the task

12. Exposure to a substance assessed for a certain task - Probability and intensity of dermal exposure routes

(emission, transfer and deposition) (per body part) - Use of clothing (per body part) (covered vs. uncovered body

parts, clothing material, repeated use of clothing) - Contamination of work environment

Each of the answers to the questionnaire corresponds to a pre-assigned value that is subsequently

put into the evaluation algorithm.

The exposure module is a part of the general input module ("inventory part"). The input parameters

that contribute to the exposure estimate are:

9. Emission to clothing and uncovered skin; and immersion of skin into agent (unlikely, occasionally, repeatedly, almost constantly)

10. Intensity (= amount of agent) of emission 11. Exposure route factors (= either emission, deposition, transfer) 12. Probability of deposition on clothing and uncovered skin 13. Intensity of deposition on clothing and uncovered skin 14. Transfer to clothing and uncovered skin : Contact with surfaces, or tools,

occurs: 15. Intensity of transfer: Contamination level of contact surface 16. Body surface factor

Each of the above mentioned exposure determinants are assigned with a default value (weighted

effect).

Output

300

The results from the exposure assessment are semi-quantitative exposure estimates given in DREAM units, which in turn are grouped into DREAM categories (ranging from low to extremely high exposure). This can subsequently be used in hazard evaluation or control, since the categorisation allows ranking of tasks according to the exposure potential. Comments DREAM is not targeted towards nanomaterials, but might be relevant for dermal exposure to nanomaterials. A shortened version of the tool has been demonstrated applicable for assessment of occupational dermal exposure to nanomaterials in the EU FP7 NANOSH project (Van Duuren-Stuurman et al., 2010). There are some similarities in exposure parameters between DREAM and those identified by RIVM (2009), such as concentration; matrix effects; duration of event; direct/indirect exposure and number of people performing the task. Since an occupational health professional defines which activities the tasks comprise, no default scenarios are used. It is an occupational tool, and no consumer scenarios are therefore directly addressed. However, the method may be used for the dermal exposure scenarios identified in chapter 3 more generally, since the determinants of exposure could be applied to consumer scenarios as well.

Margin of exposure concept 6.15

Scope A concept operationalised e.g. by the American Cleaning Institute, which provides methodologies and specific consumer exposure information that can be used for screening-level risk assessments of exposures to chemicals through the manufacture and use of consumer products. It is therefore not a model/tool as such, but a guidance-type approach or framework. A sufficient level of knowledge within the fields of consumer exposure and risk assessments is needed in order to use the concept. Input data Both inhalation, dermal and oral exposure are considered. Product exposure (PE) is determined from following input parameters (however, not all parameters are relevant for all product types): Inhalation exposure:

- Product use frequency (use/day) - Product amount used per use (g/use) - Airspace volume (m³) - Respirable product concentration in breathing zone (mg/m³) - Exposure duration (hr) - Bioavailable fraction (%) - Respirable fraction (%) - Body weight (kg)

Dermal exposure:

- Product use frequency (use/day) - Product amount used per use (g/use) - Product amount used per day (g/day) - Product use concentration (%) - Product use concentration (g/cm3) - Contact area (cm2) - Product retained (%) - Film thickness (cm) - Transfer to skin (%) - Dermal absorption (%) - Body weight (kg) - Scaling: Duration of exposure

Oral exposure:

- Product use frequency (use/day) - Product amount used per use (g/use) - Product use concentration (g/cm3) - Product retained (ml/cm2) - Dish area containing food (cm2) - Fraction ingested (%) - Body weight (kg)

301

In order to obtain exposure estimates (PE), a data matrix has been constructed for several categories of consumer products. The data matrix provides values for the exposure factors mentioned above and together with equations for estimation of oral, inhalation, and dermal exposures for the key scenarios of each consumer product category. These exposure factors result in a PE value for that route of exposure and type of exposure scenario. Output The exposure output of the approach is based on worst-case estimations. Comments The concept is not targeted to nanomaterials and no specific product characteristics are required as input parameters from the exposure assessment, other than the ingredient concentration. Some overlap between exposure parameters between those identified by RIVM (2009) and MOE concept is found, i.e. Frequency of use (on a daily basis, however), duration of exposure (dermal exposure only) differentiation of exposure route and ingredient concentration. Some of the product categories covered in the MOE concept are similar to those identified in chapter 3 (however, not all exposure routes are possible to assess within all product categories)

- Soap and detergents (dermal, inhalation and oral) - Personal care and cosmetics (dermal, inhalation and oral) - Paints (inhalation) - Lubricants (inhalation) - Food and additives (oral)

For each product category there is a set of default values for each of the relevant input parameters

mentioned above, which may be of use for the project.

302

Appendix 7 - Working table for 7.

overview of the various exposure scenarios to consider and from which to prioritise sceanrios for further in-depth evaluation

Selection of representative consumer exposure scenarios. The below working table has been elaborated based on the information on

nanomaterials in consumer products identified in:

- WP2, activity 2.3 (data from nano-inventories and nanodatabases);

- WP2, activity 2.4 (identification of important exposure parameters and description of

specific exposure scenarios, including literature review), and

- WP3 (bioavailability and hazards of NM in consumer products).

The working table provides in column 1-4 an overview of product categories, product

types, product matrix, and all the contained nanomaterials identified so far in WP2 and

WP3. In the various product categories a total of approximately 20 products will be

selected based on the criteria indicated below (next page).

Yellow highlights represent our initial proposal for selection:

Column 4-8 can be seen as justification for the choices and as a working platform in order

to provide information and tools to the risk assessment work in WP5, thus:

Column 4 : indicates the selected nanomaterial

Column 5: indicates selection of a specific product within the product category (found

either from product tables in appendix 4 or from descriptions in the literature review in

chapter 5).

Column 6: indicate the relevant exposure routes to be assessed and also indicate the

most relevant consumer target group to consider

Column 7: indicates comments/ reasoning for the selection with respect to e.g. expected

high or low exposure potential and/or toxicological concern (as identified in WP3) and to

indicate specific selection criteria

Column 8: refer to relevant literature found in WP2 and WP3 work to be used in the risk

assessment in WP5

Column 9: indicate proposals for risk assessment tools that might be used in WP5

303

In choosing/highlighting these, it was attempted to strive for:

- Coverage of the various product categories and type of use

- Coverage of various formulations and matrices of the

products/ articles

- Coverage of various type of use/ application methods

- Coverage of low as well as high quantitative use of the

product

- Coverage of high/ low/ uncertain exposure potential

- Coverage of use of specific user target groups in the

population

- Coverage of all relevant exposure routes (dermal, oral,

inhalation and eye)

- Coverage of uses of nanomaterials that may be of

toxicological concern

- Coverage of most used nanomaterials

304

Working table for selection of nanoproducts for describing representative exposure scenarios for consumers 1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

305

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Food and

beverages

Food additives Food matrix,

free

Silica

CaCO3

TiO2

??overall

exposure??

Chewing

gum

children

Oral

oral

NB! Only CaCO3 and

silica allowed in the

nanoform in the EU.

Chen et al paper: Over

93% of TiO2 in chewing

gum (6 brands tested) is

nanoTiO2 and most of

the TiO2 was liberated

during chewing

EFSA (2011)

on CaCO3

SCCS (2013)

on TiO2

Tox data on

nanoTiO2 in

chewing gum

(Chen et al.,

2013)

306

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

"Food supplements"

(kosttilskud)

Liquid,

free

Silver

Platinum

Palladium

Zinc

Colloid

silver

500ppm, 15

ml

oral SCENIHR

2013

Food contact materials/

leakage of silver from

refrigerator/food containers

Solid matrix,

matrix bound

Silver?

CNT

References on Ag

migration

SCENIHR

2013

307

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Cosmetics Sunscreen Liquid,

free

Nano-TiO2

or

NanoZnO

Silica

Products

up to 25%

content

(children)

Dermal/oral High exposure Nanex (2010)

MST(2007)

SCCS

(2013a)/

SCCS (2012)

Lorenz 2011

Consexpo

ECETOC TRA

MoE

308

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Spray ,

free

Nano-TiO2

or

NanoZnO

Silica

Products

up to 25%

content

(children)

Inh/Dermal/oral High exposure

Inh tox?

Nanex (2010)

MST(2007)

SCCS

(2013a)/

SCCS (2012)

Lorenz 2011

Consexpo

ECETOC TRA

MoE

Powder,

free

Nano-TiO2

NanoZnO

Silica

309

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Lipstick (semi

solid),

free

Nano-TiO2

NanoZnO

Silica

Products

up to 25%

content

(children)

oral High exposure SCCS 2013a

Lorenz 2011

Consexpo

ECETOC TRA

MoE

Anti-perspirant Spray,

free

Nano-silver

Mascara "Semisolid, paste"

free

Carbon Black

Nano-peptides

Up to 10% Eye/ dermal Abs?/Tox? SCCS 2013b

Lorenz 2011

310

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Other

creams/emulsions/gels/lotions

Liquid/crème/gel

free

Nanosilver

Fullerenes

Nanogold

Nanoplatinum

Nanocopper

Nano copper

peptides

Various

women

Dermal/ eye Tox of nanomaterials SCENIHR

2013 (Ag)

Consexpo

ECETOC TRA

MoE

Soaps Liquid and solid

free

Nanosilver

311

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Face powder Powder

free

Nano-TiO2 Up to 3%??

Women

Inh/dermal Inh tox? SCCS 2013a

Nazarenko

2012

Lorenz 2011

Consexpo

ECETOC TRA

MoE

Nanosafer

Stoffenmanager-

nano

312

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Toothpaste Semisolid/paste

free

Silica

or

TiO2

Nanosilver

Calcium peroxide

??

children

oral Exposure levels? SCCS 2013a

Lorenz 2011

Consexpo

ECETOC TRA

MoE

Mouth spray Spray,

free

Nanosilver

Mouth wash solutions Liquid,

free

Nanosilver

Cleaning Various cleaning Liquid Nanosilver Dermal

313

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

agents products/disinfectants free

Silica

Nano-TiO2

Unknown

(Inhalation – if

becomes airborne)

314

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Spray

free

Nanosilver

Silica

Nano-TiO2

Unknown

Dermal

Inhalation

Eye

High inh. exp. potential Hagendorfer

et al. (2010) -

500 ml

Nazarenko et

al. (2011)

Quadros and

Marr (2011)

Michel et al.

(2013 – silica

– one spray

shot about 2

g)

315

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Surface

treatment

Paints/coatings, including self-

cleaning surfaces

Liquids

free?

Nano-TiO2

Nanoclays

Silica

Carbon Black

Aluminium-oxide?

Nanocopper

Nanosilver

NanoZnO

Nanopolymer

particle dispersion

(acrylic ester based

polymer)

Unknown

Nanoceramics

NanoBoron

Paint

Paint

Dermal/ roller

appl

Inh/ spray appl

Large product volume (5

L), high nanomaterial

content, high exposure

potential.

Large product volume

(10L), long exposure

duration per event; high

exposure potential.

/Toxicity (inh)

Product table

WP2.3

(“TP2220

Primer”)

Nanex 2010

paint

scenario.

/SCCS 2013a

opinion

…

Product table

WP2.3

(“Bioni”)

Nanex 2010

paint

scenario

/SCENIHR

2013

preliminary

opinion Ag

ECETOC TRA;

Consexpo;

MoE

ECETOC TRA;

Consexpo;

MoE

316

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Sprays Nano-TiO2 or

Silica/Nanoclays

Carbon Black

Aluminium oxide

Nanocopper

Nanosilver

NanoZnO

(Silane

(condensated

duringuse)Siloxane

(condensated

during use))

Nanopolymer

particle dispersion


polymer)

Unknown

Easy-to

clean/ self-

cleaning

surface

Inh / spray Large product volume

(1L), large surfaces

treated in small rooms;

high inh. exposure

/tox inh

Product table

WP2.3

(“Percenta

AG”)

MST (2007)

self-cleaning

bathroom

surface;

…

Consexpo

ECETOC TRA

MoE

Nanosafer

Stoffenmanager-

nano;

317

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

After application:

"Solid" surface -

possible release

during due to

wear/ tear and

abrasion/sanding

Nano-TiO2

Nanoclays

Silica

Carbon Black

Aluminiumoxide

Nanocopper

Nanosilver

NanoZnO

Nanopolymer

particle dispersion


polymer)

Unknown

Nanoceramics

NanoBoron

318

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Textile/shoe impregnation/

shoes polish

Spray

free

ZnO

Silica/nanoclay?

Nanosilver

??

Liquid/paste

free

Silica/nanoclay?

??

After application:

Solid matrix with

possible release

ZnO

Silica/nanoclay

??

319

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Textiles Cuddley toy Solid matrix

Nanosilver Children Oral

Dermal

Various: Socks, t-shirts, shoe-

soles…

Solid matrix

Nanosilver

Nano-TiO2

(CNT-bamboo

charcoal?)

(Teflon?)

Unknown

Dermal

Widespread use of

nanosilver in textiles

Longterm dermal

contact

Danish EPA

(2012)

Nanex (2010)

Benn and

Westerhoff

(2008)

Goetz et al.

(2013)

Quadros et al

(2013)

320

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Construction

materials

Concrete/cement When applying:

Powder, liquid

suspension

free

Silica

CNT

Metal oxides

Unknown

Dermal

Inhalation

Eye

van

Broekhuizen

et al. 2010,

Nano

Connect

Scandinavia,

2012.

NanoForum,

2006

321

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

After use:

Possible release

from tear/wear

and

drilling/sanding

Free/debris

Silica

CNT

Metal oxides

Dermal

Inhalation

Steel alloys Solid matrix

Matrix bound

“Carbon”

“Iron”

Dermal

322

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Glass Solid

matrix/surface

Matrix bound

Tungsten oxide

Silica

Metal oxides

Nanosilver

Carbon fluorine

Polymers

NanoTiO2

Dermal

323

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Medical

devices

Wound dressings Solid matrix,

Free?

Nanosilver

Nanoclay

Dermal

High exposure

Case reports that this has

lead to toxicity

Nanex (2010)

Vlachou et al.

(2007)

Trop et al.,

2006

Rigo et al.

(2012)

Roman et al.

2013

324

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Coatings for implants Solid matrix

Matrix bound

Nanosilver "Systemic"

(Dermal)

Ostomy bags Solid matrix

Matrix bound

Nanocopper Dermal

325

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Dental fillings When applied:

Liquid/ paste

Free?

After treatment:

Solid

One of the

following:

Silica

Zirconia

Nanocomposite

(nanopolymer)

resin used as root-

end filling material

Oral (during and

after appications)

Inhalaiton (During

polishing/sanding)

/Moulding and

abrasion

Potential long-term oral

exposure

Van Landyot

et al. (2012)

Air cleaners Air conditions etc. Solid matrix

Matrix bound

Nanosilver

TiO2

(Activated carbon)

Inhalation Potential for long term

inhalation if released

326

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Fuel and

lubrication

oil additives

Additives Liquid

free

Gold

CeO2

Tungsten

disulphide

"Nanofilm"

Dermal

(Inhalaiton)

Electronic

devices /

products

Various Solid matrix

Matrix bound

Nanosilver

NanoZnO

Nanogold

Silica

Dermal

327

1

Product

category

2

Product type

3

Matrix

Including

assumptions

regarding

release

potential: free

or matrix

bound

4

Nanomaterials

5

Specific

product

(here the

chosen

product is

indicated)

+ (target

group)

6

Exposure route/

application

7

Comments/reasoning

for selection

Relevant exposure

parameters (WP2)

for high –low

exposure potential/

Toxicological

concern (WP3)

(see selection

criteria)

8

References/

data

WP2/ WP3

9

Other

potential

models for

contributing

to exposure/

risk assess

Appliances Washing machines,

refrigerators

Solid matrix,

Matrix bound

Nanosilver

NanoIron

“Carbon”

Dermal

Composite

(see also

"surface

treatment")

Various reinforced

matrices/polymers

Solid matrix –

possible release

from tear/wear

and

abrasion/sanding

CNT

Nanoclay

Inhalation

(Dermal)

Sports equipment Solid matrix –

possible release

from tear/wear

and

abrastion/sanding

CNT Inhalation

(Dermal)

328

Appendix 8 - Exposure 8.estimations of 20 selected examples of representative

Consumer scenarios with respect to nanomaterial exposure

329

Scenario 1 - Product: Chewing gum with TiO2 food additive (E171) 8.1

Description of product:

TiO2 in the form of E171 in chewing gum, i.e. in an elastomer matrix.

Description of exposure scenario:

Several types of chewing gum exist and it is assumed that most population groups (except

babies and very small children) might use chewing gum.

Step 1

Product and exposure relevant information established in chapter 4 is filled in below, supplemented

with additional information when necessary.

Parameter Specified data* Estimated* Comments/

References

Product category Food/candy with

food additive

Type of Product Chewing gum

ID of nanomaterial TiO2 with a nano-

TiO2 fraction

Weir et al.: 36% of

particles are in nanoform

Chen et al (2013): 18-44

% of particles below 100

nm

More than 93% of the

particles below 200 nm.

(based on TEM and SEM)

Physical matrix/form of

product

Elastomer matrix

Package design, volume Typically 10

pieces of

chewing gum

in a chewing

gum back

Application/use/ handling Chewing the

chewing gum

leading to

swallowing of

released TiO2

Chen et al. (2013)

Location of nanomaterial eg.

free/ matrix-bound

In an elastomer

Direct/ indirect exposure Intended oral; i.e.

direct exposure

Indoor/ outdoor use Both, but

irrelevant for

this

assessment

Generation of nanomaterial

during use

Unlikely But release during use

(Chen et al., 2013)

Specific target group (children,

teenagers etc.)

All population

groups except

babies and very

330

young children

Forseeable misuse Possibly

individual

swallowing

the chewing

gum.

Possibly

individuals

chewing large

amounts

Site of contact/ exposure Gastrointestinal

tract

Primary exposure route(s) Oral

Concentration of

nanomaterial in product

>1 mg/g

1.7 – 3.9 mg/g

Weir et al (2012)

Chen et al (2013)

Volume of product used,

exposed to

Each gum

contains 2.4 mg -

7.5 mg TiO2

As a realistic

worst case, we

assume intake

of 20 pieces of

chewing gum

per day

Chen et al. (2013)

Body area exposed to NA

Retention rate on body

surface

NA

Migration/liberation rate of

nanomaterial from matrix

> 95% Chen et al. (2013)

Ingested amount All of the

released

Volume of product released

to air / concentration in air

NA

Duration of exposure Almost all TiO2 is

released during

the first ten

minutes

Some users

may use

chewing gum

during the

whole day

Chen et al. (2013) shows

that

Frequency of exposure Some users

may

frequently

take a new

piece of

chewing gum

* Use “ - “ if not given or not relevant

In addition key information from relevant references described in chapter 5 (or found elsewhere in

connection with the project) are presented.

Step 2

331

Based on the availability of data the most relevant algorithms are generated/ selected for

estimation of the exposure (algorithms for various purposes and at various tiers are

described in chapter 4, section 4.2) :

Exposure route Algorithms used Comments/

References

Inhalation exposure

NA

Dermal exposure

NA

Oral exposure

Total TiO2 intake (mg): N * Rel * M (mg)/ BW (kg)

N: Number of gums per day

Rel: Fraction released

M: Mass of TiO2 per gum (mg)

BW: Body weight (kg)

Nano- TiO2 intake: Fnano * Total TiO2

Fnano: Fraction of TiO2 in nanoform

No source. Own

equation based o

mass-based

considerations

Eye exposure

NA

Step 3

For the identified target population relevant values for anatomical/physiological parameters are

selected. As information sources the following may be consulted:

REACH guidance R15, 2012: Consumer exposure assessment.


Nordic Council of Ministers, 2011: Existing default values amd recommendaqtions for exposure

assessment. http://www.norden.org/en/publications/publikationer/2012-505/

Target population: xxx

Anatomical /Physiological

parameters

Specified Estimated Comments/

References

Body weight Children: 18.6

kg

Mean for 3-6 years old

children


332

Adult: 60 kg

Recommended for adult

women

Source: Nordic council of

Ministers (2011)

Other relevant parameters for use in the algorithms are estimated based on the available

information and from default assumptions when necessary.

Exposure routes Specific parameters Comments/ References

Inhalation exposure

NA

Dermal exposure NA

Oral N:20 pieces

Rel: 1 (100%)

M: 7.5 mg TiO2/piece of gum

Fnano: 0 - 1

Assumed worst case

Worst case based on Chen

et al. (2013). It is assumed

that this released amount I

swallowed

Worst case based on Chen et

al. (2013)

See below discussion

Eye NA

Step 4

Total TiO2 intake:

Daily:

Child: 20 pieces/day * 1 (release fraction) * 7.5 mg TiO2 per piece / 18.6 kg bw= 8.1 mg TiO2/kg

bw/day

Adult: 20 pieces/day * 1 (release fraction) * 7.5 mg TiO2 per piece / 60 kg bw = 2.5 mg TiO2/kg

bw/day

Total annual dose:

Child and adult: 365 days/year * 20 pieces/days * 7.5 mg TiO2 per piece = 54,750 mg/year =

Approx. 55 g TIO2/year.

A very rough assumption would be to assume that all TiO2 is nano.

However Weir et al. (2012) notes that about 36% of the E171 TiO2 particles could be in the

nanoform and Chen et al. (2013) notes that the figure is around 18-44%.

These numbers are fractions of the particles, thus the fraction of the mass would be considerably

lower, but depend on the size distribution. Chen et al. (2013) notes that about 93% of the particles

333

are below 200 nm, thus the distribution does not seem to be skewed too much towards larger

particles.

Overall, it seems that a very conservative estimate would be that 20% of the mass is in the nanoform

(if the distribution is skewed towards smaller particles, otherwise much less). This would give:

Daily nano-TiO2 intake:

Child: 0.20 * 8.1 mg/kg bw/day = 1.62 mg nanoTiO2/kg bw/day

Adult: 0.20 * 2.5 mg/kg bw/day = 0.50 mg nanoTiO2/kg bw/day

Total annual nano-TiO2 intake:

Child and adult: 0.1 * 55 = 5.5 g nano-TiO2/year

Step 5

Uncertainties of the described exposure scenario:

Overall the estimates are considered very conservative. As a starting point, these estiates will be

used in the risk assessment (first tier). If this indicates a risk, we will iteratie the risk assessment

with more detailed and reasonable exposure estiamtes (second tier).

EFSA in an assessment of whether the rutile form could be used in addition to the anatase forms of

TiO2 for food additives, estimated the following rutile TiO2 intakes (EFSA, 2004) for adults:

Proposed Use Use-Level Estimated Intake1

Medicinal Product Tablet 0.4% 0.25 mg/kg bw/day

Food Supplement Tablet 0.4% 0.625 mg/kg bw/day

Confectionery2

0.068% 0.407 mg/kg bw/day

Total 1.282 mg/kg bw/day

i.e. about 1mg/kg bw/day (0.407 mg/kg bw/day from confectionaries and 0.625 mg/kg bw/day for

food supplements). EFSA (2014) assumes that about 20% is the consumed food additive amount is

rutile. Thus the remaining 80% would be anatase. Thus the total TiO2 volume would 5*1 mg/kg

bw/day equalling about 5 mg/bw/day. Weir et al. (2012) estimated that realistic average food intake exposures for the UK population was

2-3 mg TiO2/kg bw/day for children under the age of 10 years, whereas exposure for higher age

groups were estimated to about 1 mg TiO2/kg bw/day.

These figures support that our total TiO2 estimates of 8.1 (child) and 2.5 (adult) mg TiO2/kg bw/day

just for chewing gum can be considered rather conservative estimates.

Further, the estimated nano fraction is considered further conservative given the assumed mass

fraction in the nanosize. See above discussion.

Step 6 (for use in WP5)

E171 as such does not meet the nanodefinition, which is line with the legal situation where nano-

TiO2 has not been assessed in relation to the food additive positive list entry for TiO2 (E171).

However, still the consumer would be exposed to nanoparticles below 100 nm due to the nanotail

constituting about 20-40% of the number particle size distribution. Further, the 100 nm cut-off is

rather arbitrary and it is worth noting that an estimated 93% of the particles are below 200nm.

Combined exposure from other food source are likely.

Weir et al. (2012) notes that candies with hard chocolate shell have similar contents of E171 as

chewing gum, about 1 mg/g. Some consumers of such candies could perhaps (very conservatively)

eat up to 500 grams of such candies per day equalling 500 mg/day or about 27 mg TiO2/kg bw/ day

for children or 3.7 mg nanoTiO2/kg bw/day! But again this is very conservative.

334

As can be seen from the EFSA (2004) a small fraction of E171 might result from intake via medical

product tablets.

Overall, it is suggested that WP3 toxicity (oral) considers food grade TiO2 as such rather than the

contained nano-fraction below 100nm.

References:

Weir A, Westerhoff P, Fabricius L, Hristovski K, and Goetz NV. 2012. Titanium Dioxide

Nanoparticles in Food and Personal Care Products. Environ. Sci. Technol 46, 2242-2250

EFSA. 2004. Opinion of the Scientific Panel on Food Additives, Flavourings, Processing Aids and

materials in Contact with Food on a request from the Commission related to the safety in use of

rutile titanium dioxide as an alternative to the presently permitted anatase form - Question N°

EFSA-Q-2004-103. Adopted on 7 December 2004. The EFSA Journal (2004) 163:1-12

Chen X-X, Cheng B, Yang Y-X, Cao A , Liu J-H, Du L-J, Liu Y, Zhao Y, Wang H. Characterization

and Preliminary Toxicity Assay of Nano-Titanium Dioxide Additive in Sugar-Coated Chewing Gum.

Small , 9 (9–10), 1765–1774. DOI: 10.1002/smll.201201506

335

Scenario 2 - Product: Nano-Silica in food items 8.2

Description of exposure scenario

SiO2 in its amorphous form is currently authorised under Directive 95/2/EC as an additive (E551)

other than colours and sweeteners (e.g. as an anticacking agent). E551 is e.g. used in various powder

food items, dry cereals, in tablets and in some cheese. It may be used in a concentration up to 10 g

/kg (and for some items e.g in tablets in quantum satis amounts). Manufactured nano-silica is

according to Kesteren et al. (2014) also known as synthetic amorphous silica (SAS).

Further specifications of commercial available qualities of E551 on the market indicate that the food

additive contain nanoparticles.

Step 1



Parameter Specified data* Estimated* Comments/

References

Product category Food

Type of Product Various food

items

Dekkers et al. (2011).

ID of nanomaterial Silica

Characterisation e.g. size distr. Amorphous silica.

From analysis of two silica

(E551) qualities (Aerosil

200F and Aerosil 380F)

specific surface areas of

199 m2/g and 388 m2/g

were determined (BET

nitrogen adsorption

method). Primary particle

size diameters of 12 nm

and 7 nm were

determined using

transmission electron

microscopy, however,

most of the primary

particles formed larger

aggregates and

agglomerates. (Dekkers et

al. 2011)


product

various Powders,

pills/tablets,

salt, cakes etc.

Package design, volume Various food

items

Application/use/ handling ingestion


free/ matrix-bound

Mixed in the food

item or surface

attached

Direct/ indirect exposure direct

Indoor/ outdoor use -


during use

No

336


teenagers etc.)

All

Forseeable misuse -

Site of contact/ exposure Gastrointestinal

tract

Primary exposure route(s) oral

Concentration of


Up to 10 g/kg

(1%)

For some formulations

e.g. tablets even higher

concentrations


exposed to (1)

Up to more than

100 grams

Body area exposed to oral


surface (1)

1



Up to 100%

migration

Ingested amount See below

Concentration in air/


into air

Duration of exposure - -

Frequency of exposure daily

“ - “ if not given or not relevant

The available information of the cumulated exposure to nano-silica derives from the study by

Dekkers et al. (2011). Dekkers et al. (2011) made a detailed assessment of nano-silica (synthetic

amorphous silica also sometimes denoted silicon dioxide, SiO2) in food.

The total concentrations of silica in 26 products containing E551 were found to be in the range of 0 -

13.7 mg/g. The nano-silica content was determined in seven products (sauce, soup, coffee cream,

pancake mix, seasoning products and spicy rubs) and was in the range of <0.1 - 1 mg/g with the

highest content found in coffee creamer. The highest relative content of nano-silica of 33%

(compared to the total silica content) was found in instant asparagus soup, however, this product

had an overall low total silica content of 0.6%.

It was determined that when 2 g of the coffee cream was added to 200 ml coffee the ready to drink

content of nano-silica was 22 mg/L.

EFSA (2009) in their opinion on silicon dioxide/ silicic gel indicated that for food supplements the

recommended dose is about 1500 mg silicon dioxide /day (corresponding to about 21-25 mg/kg

bw/d)

337

Step 2 Algorithms

Based on the availability of data the most relevant algorithms are generated/ selected for estimation

of the exposure (algorithms for various purposes and at various tiers are described in chapter 4,

section 4.2) :


References

Inhalation exposure

-

Dermal exposure

-

Oral exposure

Doral (mg/kg bw/d) = A x C x Fnano / BW

A: amount of a food item ingested per day (g/d)

Worst case estimates of the daily intake (A) were made

by Dekkers et al. (2011) based on food intake rates

from the Dutch Food Consumption Survey combined

with expert judgements.

C: Concentration of substance (mg/g)

Fnano: Fraction of nano-particles of the substance

BW: bodyweight

Eye exposure

-

Step 3 Target group





Nordic Council of Ministers, 2011: Existing default values and recommendations for exposure


338

Target population: adults


parameters


References

Body weight 70 kg used by Dekkers et al.

(2011)

Inhalation rate

Skin surface (site of contact)

Specific behaviour (duration for

e.g. mouthing of children)

Others

Step 4 Exposure estimation

Adults

Dekkers et al. (2011) made estimates (for adults) of the daily intake of nano-silica from 14 food

products containing E551.

Mean concentrations of silica contents and nano-silica contents were used instead of worst case

because concentrations will average out over time.

Information on portion sizes was derived from packing and manufacturer information.

Worst case assumptions about number of portions were used. Thus it was assumed that every day

one portion of pancakes, one portion of instant noodles, one portion of asparagus soup, four

vitamin C pills, two cakes and six cups of coffee with creamer was consumed. In addition, every five

days a portion of lasagne, minced meat with seasoning mix and cheese sauce, vegetables with rub, a

Mexican-style dish with taco and guacamole and burrito seasoning, and Indonesian–style rice with

meat and vegetables with nasi rames seasoning mix were consumed.

From these estimates daily exposures to nano-silica of 33 mg, 20 mg and 15 mg were found from

intake of coffee creamer, seasoning mix and cheese sauce, respectively. A total daily consumption of

124 mg nano-silica per day (corresponding to 1.8 mg/kg bw d) was estimated from intake

from the total of the 14 different food products (for seven of the products not analysed for the nano-

silica fraction (products such as e.g. vitamin products, other seasoning mixes and a cake) a worst

case assumption of a relative amount of nano-silica of 50% in E551 was assumed).

No further data has been found to refine or adjust this exposure estimate by Dekkers et al. (2011).

In specific cases much higher silica exposure of 1500 mg/day may occur when consuming food

supplements as indicated by EFSA (2009). If the nano-fraction is e.g. 10% this would result in a

daily consumption of 150 mg nano-silica/d which exceeds the estimate from Dekkers et al.

(2011).

Children

When exposed through food small children are often on a weight basis exposed to a higher degree

compared to adults (about a factor of two) because of higher energy demand per kg bodyweight.

Based on the data by Dekkers et al. (2011) it is considered very difficult to make a child estimate

regarding nano-silica exposure as many of the products containing nano-silica are more addressed

to adults than children (e.g. coffee creamer, various seasoning etc.). Thus no exposure estimation

for children is performed.

339

Step 5 Uncertainties of the described exposure scenario

No uncertainty pertain to that E551 contain nano-sized particles (mainly as agglomerates). However

the relative content of the nano-sized silica particles may vary a lot.

The exposure assessment is made on a very high level based on analytical data and of expert

knowledge concerning intake rates of various food items. As indicated by Dekkers et al. (2011) the

calculated daily intake of nano-SiO2 should be considered as a worst case estimate due to worst

caseintake rates of the analysed food items and due an assumed high default level of 50% for the

relative content of nano-silica in food-items where the non-size fraction was not analytically

determined.

On the other hand the study may have over-looked some food items with contents of E551 (e.g

cereals that may be especially relevant for exposure of children).

Step 6 (for WP5)

Other exposure to nano-silica may result from cosmetics as there is not regulatory limit for the use

of silica in cosmetics. Both oral (e.g. toothpaste), dermal (e.g. creams) and inhalational nano-SiO2

exposure (e.g. face powder) may occur. Use of other types of products e.g. surface treatment sprays

and liquids may result in inhalational as well as dermal exposure to nano-SiO2.

In relation to the use of silica in food contact material EFSA (2013 and 2014) concluded that no

migration/ exposure is expected to occur from these uses.

References

Dekkers S, Krystek P, Peters RJB, Lankveld DPK, Bokkers BGH, Hoeven-Arentzen PHv,

Bouwmeester H, and Oomen AG. (2011). Presence and risks of nanosilica in food products.

Nanotoxicology 5(3), 393-405.

EFSA (2009). Calcium silicate and silicon dioxide/silicic acid gel added for nutritional purposes to

food supplements. Scientific Opinion of the Panel on Food Additives and Nutrient Sources added to

Food. The EFSA Journal (2009) 1132, 1-24

EFSA (2013). SCIENTIFIC OPINION. Scientific Opinion on the safety evaluation of the active

substances iron, sodium chloride, water, silica gel, activated carbon, monosodium glutamate,

potassium acid tartrate, powdered cellulose, malic acid, chabazite, hydroxypropyl cellulose,

potassium carbonate, sodium thiosulfate, propylene glycol, glycerin, polyethyleneglycol sorbitan

monooleate, sodium propionate and clinoptilolite for use in food contact materials. EFSA Journal

2013;11(4):3155

EFSA (2014). SCIENTIFIC OPINION. Statement on the safety assessment of the substance silicon

dioxide, silanated, FCM Substance No 87 for use in food contact materials. EFSA Journal

2014;12(6):3712

van Kesteren PC, Cubadda F, Bouwmeester H, van Eijkeren JC, Dekkers S, de Jong WH, Oomen AG

(2014) Novel insights into the risk assessment of the nanomaterial synthetic amorphous silica,

additive E551, in food. Nanotoxicology July 18:1-10.

http://www.ncbi.nlm.nih.gov/pubmed?term=van%20Kesteren%20PC%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=Cubadda%20F%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=Bouwmeester%20H%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=van%20Eijkeren%20JC%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=Dekkers%20S%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=de%20Jong%20WH%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed?term=Oomen%20AG%5BAuthor%5D&cauthor=true&cauthor_uid=25033893

http://www.ncbi.nlm.nih.gov/pubmed/25033893

340

Scenario 3 - Product: Nano-Ag food supplement 8.3 Description of exposure scenario Several nano-Ag supplements products have been found in the inventories of nano consumer products. Step 1 Product and exposure relevant information established in chapter 4 is filled in below, supplemented with additional information when necessary. Parameter Specified

data* Estimated* Comments/ References

Product category Food Type of Product Food

supplement

ID of nanomaterial Colloidal Ag

http://www.fairvital.com/product_info.php?products_id=77

Characterisation e.g. size distr.

0.65 nm http://www.purestcolloids.com/mesosilver.php This seems to be a very small particle size. Depending of the liquid matrix and the production methods the particle size of colloid silver may vary greatly within the range of 1-100 nm. https://www.silverinstitute.org/site/wp-content/uploads/2014/04/EPA_SAP_SNWGpresentation_Nov2009.pdf

Physical matrix/form of product

liquid

Package design, volume

15 - 500 ml http://www.fairvital.com/product_info.php?products_id=77 http://www.purestcolloids.com/mesosilver.php

Application/use/ handling

ingestion

Location of nanomaterial eg. free/ matrix-bound

Dissolved/ suspended in liquid

Direct/ indirect exposure

direct

Indoor/ outdoor use - Generation of nanomaterial during use

-

Specific target group (children, teenagers etc.)

adult

Forseeable misuse - Site of contact/ exposure

Gastrointestinal tract

Primary exposure route(s)

oral

Concentration of nanomaterial in product

500 mg/l; 10 mg/l

http://www.fairvital.com/product_info.php?products_id=77 http://www.purestcolloids.com/mesosilver.php

Volume of product used, exposed to

Up to 60 ml; 1.25 ml

http://www.purestcolloids.com/mesosilver.phphttp://www.fairvital.com/product_info.php?products_id=77

Body area exposed to (1)

oral

Retention rate on body surface (1)

1



http://www.purestcolloids.com/mesosilver.php

https://www.silverinstitute.org/site/wp-content/uploads/2014/04/EPA_SAP_SNWGpresentation_Nov2009.pdf












341

Migration/liberation rate of nanomaterial from matrix

100%

Ingested amount 60 ml; 1.25 ml

http://www.purestcolloids.com/mesosilver.phphttp://www.fairvital.com/product_info.php?products_id=77

Concentration in air/ Volume of product released into air

-

Duration of exposure

-


Daily

-


In relation to ingesting of colloid silver either as food supplement or as (alternative) medicine several cases have demonstrated visible effects. After absorption of silver from the preparations the persons have developed a bluish-gray discoloration of the skin and eyes (argyria). Thus, Kim et al. (2009) recently described a case in which a woman during 16 months had ingested about 1 liter of colloid silver solution. The woman developed blue-gray discoloration of mucous membranes and skin, especially in the head and on the hands, i.e. areas getting sun-exposed. The serum silver concentration was highly elevated (381 ng Ag/ml compared to a reference level of <15 ng Ag/ml). Step 2 Algorithms

- Based on the availability of data the most relevant algorithms are generated/ selected for estimation of the exposure (algorithms for various purposes and at various tiers are described in chapter 4, section 4.2) :

- - Exposure

route - Algorithms used - Comments/

References - Inhalation

exposure - - - - - - -

- - -

- Dermal exposure

- - - - - -

- - -

- Oral exposure - - - - - - -

- Doral (mg/kg bw d) = A x C x Fnano / BW

- - A: amount of a food supplement

ingested per day (g/d) - C: Concentration of substance

(mg/g) - Fnano: Fraction of nano-particles

of the substance - BW: bodyweight -

-

- Eye exposure

- - -




342

Step 3 Target groups For the identified target population relevant values for anatomical/physiological parameters are selected. As information sources the following may be consulted: REACH guidance R15, 2012: Consumer exposure assessment. http://echa.europa.eu/documents/10162/13632/information_requirements_r15_en.pdf Nordic Council of Ministers, 2011: Existing default values amd recommendaqtions for exposure assessment. http://www.norden.org/en/publications/publikationer/2012-505/

- Target population: adult female - - - Anatomical

/Physiological parameters

- Specified - Estimated - Comments/ References

- Body weight (adult, woman)

- 60 kg - - REACH guidance R15

- Inhalation rate

- - -

- Skin surface (site of contact)

- - -

- - - - - Specific

behaviour (duration for e.g. mouthing of children)

- - -

- Others - - -

Step 4 Exposure estimations

Doral (mg/kg bw d) = A x C x Fnano / BW A: amount of a food supplement ingested per day (g/d) For the high concentration product a daily dose of 1.25 ml is recommended. The bottle is intended to deliver the liquid drop-wise, however it may be difficult to control such small volumes. As some consumers further may use increased doses compared to recommended doses a daily dose of 2.5 ml is used as a worst case assumption. C: Concentration of substance (mg/g) 0.5 mg/ml Fnano: Fraction of nano-particles of the substance 100% (colloid silver) BW: bodyweight 60 kg Doral (mg/kg bw d) = 2.5 ml x 0.5 mg nano-Ag/ml x 1 / 60 kg = 0.021 mg nano-Ag/kg bw/d.

Thus, this exposure corresponds to an ingestion of a total dose of 1.2 mg nano-Ag per day. It should be noted that these doses are daily doses that may occur over a duration of years.


http://www.norden.org/en/publications/publikationer/2012-505/

343

Step 5 Uncertainties of the described exposure scenario: No great uncertainty pertains to the exposure estimate as the estimate is based on given information on concentration and recommended dose to use. However it may be considered as a worst case scenario for nano-Ag exposure from food supplements as the highest found concentration of nano-Ag among the products is used and as the daily dose is assumed to be a factor 2 higher than the recommended dose. Regard the colloid size of silver in these products this may vary a lot, but most probably within the size range of the EU-definition of nanomaterials (1-100 nm). Step 6 (for use in WP5) Although nano-silver may be used in a lot of various consumer products (cosmetics; surface treatment, air cleaner spray) the exposure in relation to food supplement preparations may constitute the far highest exposure. Several cases of argyria (discoloration of skin and eyes due to deposition of silver) have been reported due to absorption of silver (either as colloids or ionic silver) after excessive oral exposure from food supplement or self-medication with colloid silver. Dermal exposure may further be relevant in connection with use of cosmetics containing nano-Ag (eg. soap and cream) and in connection with use of surface treatment with liquids/ sprays. Also dermal exposure from the use of nano-silver in wound dressings may occur. Inhalation may especially be relevant in connection spray applications e.g. surface treatment of spray paint. Further the use of biocides with nano-Ag as the active component and use of medical devices e.g. wound-dressing may lead to additional exposure. References Height (2009). Evaluation of Hazard and Exposure Associated with Nanosilver and Other Nanometal Oxide Pesticide Products. Presentation at the FIFRA SCIENTIFIC ADVISORY PANEL (SAP) OPEN CONSULTATION MEETING November 3 - 6, 2009 Arlington VA. https://www.silverinstitute.org/site/wp-content/uploads/2014/04/EPA_SAP_SNWGpresentation_Nov2009.pdf Kim et al. (2009). A case of generalised argyria after ingestion of colloid silver solution. Am J Ind Med 52, 246-250. Product specifications: http://www.fairvital.com/product_info.php?products_id=77 http://www.purestcolloids.com/mesosilver.php





344

Scenario 4 - Product: Food contact material containing Silica 8.4


Exposure in relation to migration of silica from food contact material into food

Step 1



Parameter Specified

data*

Estimated* Comments/

References

Product category Food and

beverages

Type of Product Food contact

material

No specific product found

ID of nanomaterial Silica gel (FCM

no 504)

Silicon dioxide,

silanated (FCM

no 87)

EFSA (2013)

EFSA (2014)

Characterisation e.g. size distr. See below**

EFSA (2013)

EFSA (2014)

Physical matrix/form of product Plastic materials

and articles in

contact with

food


Application/use/ handling Packing

material, food

container


free/ matrix-bound

Embedded in

polymer matrix

Direct/ indirect exposure Indirect



during use

-


teenagers etc.)

All

Forseeable misuse, alternative

use

-

Site of contact/ exposure Oral

Primary exposure route(s) Oral

Concentration of


No restriction

e.g. 3% w/w

EFSA (2014)


exposed to

-

Body area exposed to -


surface

-

345



no migration EFSA (2013); EFSA (2014)

Ingested amount -



into air

-

Duration of exposure -

Frequency of exposure -

* “ - “ if not given or not relevant in a specific context

** Silica gel (silicon dioxide): is authorised as additive or monomer for plastic materials and articles in

contact with foods (Regulation (EU) No 10/2011). The use is restricted to: Synthetic amorphous

silicon dioxide: primary particles of 1 – 100 nm which are aggregated to a size of 0.1 – 1 μm which

may form agglomerates within the size distribution of 0.3 μm to the mm size (FCM Substance No

504). It is also listed in Regulation (EU) No 1129/2011 amending Annex II to Regulation (EC) No

1333/2008 9of the European Parliament and of the Council by establishing a Union list of Food

Additives, with a specific maximum level of 10g/kg or higher, depending on the foodstuffs (E 551).

EFSA (2013).

Silicon dioxide, silinated:. Using TEM (transmission electron microscopy) analysis of the additive in

powder form, the primary particles were estimated to be ca. 12 nm in size and they were all

aggregated in the range 100-300 with some evidence of larger agglomerates. No isolated primary

particles were observed in the many TEM images recorded and analysed. Using AF4-MALS

(asymmetric-flow field flow fractionation with multi-angle light scattering detection) the particle

size distribution of the powder product (dispersed in ethanol to allow injection onto the system) was

estimated to be about 160 – 600 nm, peaking at about 300 nm. EFRS (2014)

Step 2 Algorithms



section 4.2) :

Exposure route Algorithms to use Comments/

References

Inhalation exposure

-

Dermal exposure

-

Oral exposure -

346

Eye exposure

-

Step 3 Target group







Target population: adult, infant, child, teenager etc.


parameters


References

Body weight

Inhalation rate

Skin surface (site of contact)



Others



Exposure routes Specific parameters Comments/

References

Inhalation exposure

Room volume

Air exchange rate (room ventilation)

Distance from breathing zone

Particle size distribution

Dustiness

Etc.

Dermal exposure Film thickness on skin

Viscosity


347

Etc

Oral

Eye


Calculations/ estimations

According to EFSA (2013) and EFSA (2014) opinions no migration and thus no consumer

exposure is to be expected from the use of silica (including nano-silica) in food contact

materials.

Migration testing of low density polyethylene (LDPE) containing up to 3% of silicon dioxide,

silanated found no detectable migration of the substance (detection limit of 0.3-0.6 µg/kg simulant

(i.e. 0.3-0.6 ppb)) (EFSA 2014).

Step 5 Uncertainties of the described exposure scenario:

In the specific case of migration testing no migration was found even at very low limits of detection.

The conclusion by EFSA (2014) is based on migration tests on one type of LDPE polymer. Some

uncertainty remains to whether these data would be representative for other polymers as well.


References

EFSA (2013). SCIENTIFIC OPINION. Scientific Opinion on the safety evaluation of the active

substances iron, sodium chloride, water, silica gel, activated carbon, monosodium glutamate,

potassium acid tartrate, powdered cellulose, malic acid, chabazite, hydroxypropyl cellulose,

potassium carbonate, sodium thiosulfate, propylene glycol, glycerin, polyethyleneglycol sorbitan

monooleate, sodium propionate and clinoptilolite for use in food contact materials. EFSA Journal

2013;11(4):3155

EFSA (2014). SCIENTIFIC OPINION. Statement on the safety assessment of the substance silicon

dioxide, silanated, FCM Substance No 87 for use in food contact materials. EFSA Journal

2014;12(6):3712

348

Scenario 5 - Product: Sun screen lotion 8.5

Description of product: Sun screen containing nano-TiO2

Description of product: Sun screen containing nano-TiO2

Description of exposure scenario: Dermal application of sun screen

Step 1



Parameter Specified

data*

Estimate

d*

Comments/ References

Product

category

Cosmetic

Type of Product Sun Screen

ID of

nanomaterial

Nano-TiO2 SCCS (2013a). OPINION ON Titanium Dioxide (nano form).

http://ec.europa.eu/health/scientific_committees/consumer_safety/d

ocs/sccs_o_136.pdf

Characterisatio

n e.g. size distr.

Size

Particles

Aspect ratio

Volume specific

surface area

Crystal form

Purity

Coating

Crystals:

9-21 nm

(XRD)

1.5 and up

to 4.5

192-460

m2/cm3

Rutile with

max. 15 %

anatase

≥99.5%

Yes

The below is based on industry data submitted to SCCS.

SCCS (2013a)

SCCS (2013a): The median particle sizes of the different materials

range from ~44 nm to 354 nm on volume weighted basis, and ~34 nm

to ~99 nm on number weighted basis. The lower size cut offs range

between 17 nm and 73 nm.

SCCS (2013a)

SCCS (2013a)

SCCS (2013a)

SCCS (2013a)

See table 1 in SCCS (2013a). Includes the following types of coatings:

alumina/silica, methicone/silica, aluminium hydroxide and

dimethicone/methicone copolymer, trimethyloctylsilane,

alumina/silicone and alumina/silica/silicone, dimethicone,

simethicone, stearic acid, glycerol, dimethoxydiphenylsilane,

triethoxycaprylylsilane

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_o_136.pdf


349

Physical

matrix/form of

product

Liquid

Package design,

volume

≤ 500 ml Larger sizes can be found but are typically not on the Danish market

Application/use

/ handling

Leave-on

product,

manual

Location of

nanomaterial

eg. free/

matrix-bound

In liquid

matrix

Direct/ indirect

exposure

Direct,

intended,

leave-on

Indoor/

outdoor use

Mainly

outdoor

Can be applied indoor

Generation of

nanomaterial

during use

No, but

possible

de-agglo-

meration

SCCS (2013a)

Specific target

group (children,

teenagers etc.)

All

Forseeable

misuse

May be

used on

the lips

Site of contact/

exposure

Whole

body

Primary

exposure

route(s)

Dermal

(oral, eye)

Concentratio

n of

nanomaterial

in product

≤25%

containing

max. 15%

anatase

SCCS (2013a)

Volume of

product used,

exposed to

36 g/day in

DK

72 g/day

south of

DK

Based on Danish EPA (2014) recommendation:

- 2 times the amount suggested by SCCS (2012a) 36 g/day) as a worst

case scenario for Danish summer conditions and 4 times the amount

for a summer in the south, i.e. 72 g/day)

Or

- In Denmark: 1 application per days of the amount suggested in

European Commission (2006): 36 gram/day

- South: 2 applications per day, i.e. 2x36 = 72 gram/day

Body area

exposed to

Total body

area:

17500 cm2

SCCS (2012a): adult

Retention Assumed SCCS (2012a) (For body lotion and other leave-on products)

350

rate on body

surface

1

Migration/lib

eration rate

of

nanomaterial

from matrix

As worst

case it

must be

considere

d possible

for all

nano-

material

to reach

the skin

Ingested

amount

0.9 mg/kg

bw/day

For

children

an

additional

hand-to

mouth

amount

SCCS (2012a): Exposure from lipstick/lip salve (if the sunscreen is

used on the lips)

Concentratio

n in air/

Volume of

product

released into

air

NA

Duration of

exposure

16

hours/d

up to

24/hours/

d

Frequency of

exposure

25

days/year

2/day

Nanex (WP4), 2010: Estimated number of days per year: 25

SCCS (2013a): 2 applications per day




351

Step 2



section 4.2) :


References

Inhalation exposure

Not considered relevant in relation to sunscreen lotion

applied manually.

Dermal exposure

The dermal load is calculated as:

𝐿𝑑𝑒𝑟 =𝑄𝑝𝑟𝑜𝑑 × 𝐶𝑛𝑎𝑛𝑜 × 𝑅𝑅

𝐴𝑠𝑘𝑖𝑛

The external dermal dose is calculated as:

𝐷𝑑𝑒𝑟 =𝑛 × 𝑄𝑝𝑟𝑜𝑑 × 𝐴𝑠𝑘𝑖𝑛 × 𝐶𝑛𝑎𝑛𝑜 × 𝑅𝑅

𝐵𝑊

Daily amount: Qprod (Amount per application) * n

(number of applications)

Qprod: Amount per application (mg)

Cnano: Fraction of nano TiO2 in product (0.25)

Askin: Surface of exposed skin (cm2)


RR: Retention rate

n: number of applications (/day)

Oral exposure

Applications on lips (children, teenagers and adults): To

be calculated as for TiO2 in lipstick (scenario 8)

In addition for children (Conservatively assuming that

50% is sucking of 10 fingers):

𝐼𝑛𝑡𝑜𝑟𝑎𝑙 = 0.5𝑥𝐴𝑓𝑖𝑛𝑔𝑒𝑟𝑠

𝐴𝑏𝑜𝑑𝑦𝑥

𝑛 × 𝑄𝑝𝑟𝑜𝑑 × 𝐶𝑛𝑎𝑛𝑜

𝐵𝑊

Where:

Afingers: Area of 10 fingers

Abody: Area of body




SCCS (2012a)

352

n: number of applications (/day)

Eye exposure

Expected to be negligible compared to the full body

exposure

Step 3







Target population: Adults/ children


parameters


References

Body weight 60 kg (adult)

9.47 kg (13.5

months)

9.85 kg (1.5

year)

16.3 kg (4.5

years)

SCCS 2013a

Nordic Council of

Ministers (2011)

Skin surface (site of contact) 17500 cm2

(body adult)

4670 cm2

(body 13.5

months)

4800 cm2(1.5

year)

7090 cm2(body

4.5 years)

230cm2 (adult

fingers)

SCCS 2013a

Nordic Council of

Ministers (2011)

Idem

Idem

Idem

Dose which may be ingested 0.9 mg/kg

bw/day (adult)

SCCS (2012a)



Children may suck on e.g.

their fingers.

Others



353


References

Inhalation exposure

NA

Dermal exposure No additional parameters

Oral No additional parameters

Eye NA

Step 4

This section describes and explains the calculation of exposure:

DERMAL

Adult:

Dermal load (1: 36 g/day – i.e. 18 g/application):


𝐴𝑠𝑘𝑖𝑛=

18000 𝑚𝑔 × 0.25 × 1

17500 𝑐𝑚2≅ 𝟎. 𝟐𝟓𝟕

𝒎𝒈

𝒄𝒎𝟐




36000 𝑚𝑔 × 0.25 × 1

17500 𝑐𝑚2≅ 𝟎. 𝟓𝟏𝟒

𝒎𝒈

𝒄𝒎𝟐

External dermal dose (1):

𝐷𝑑𝑒𝑟 =𝐷𝑎𝑖𝑙𝑦 𝑎𝑚𝑜𝑢𝑛𝑡 𝑇𝑖𝑂

𝐵𝑊=

9000 𝑚𝑔 𝑇𝑖𝑂2

𝑑𝑎𝑦 × 60 𝑘𝑔= 𝟏𝟓𝟎 𝒎𝒈

𝑻𝒊𝑶𝟐

𝒌𝒈/𝒅𝒂𝒚



𝐵𝑊=

18000 𝑚𝑔 𝑇𝑖𝑂2

𝑑𝑎𝑦 × 60 𝑘𝑔= 𝟑𝟎𝟎 𝒎𝒈

𝑻𝒊𝑶𝟐


Children (4.5 years):

Dermal load (same applied amount/cm2 per application as for adults applied 36 g/day):

𝐿𝑑𝑒𝑟 = 𝟎. 𝟐𝟓𝟕𝒎𝒈

𝒄𝒎𝟐corresponding to a daily amount of 2

× 1820 𝑚𝑔 for a child with body surface area of 7090 𝑐𝑚2


𝐿𝑑𝑒𝑟 = 𝟎. 𝟓𝟏𝟒𝒎𝒈

𝒄𝒎𝟐 corresponding to a daily amount of 2


External dermal dose (same as adults applied 36 g/day):


𝐵𝑊=


𝑑𝑎𝑦 × 16.3 𝑘𝑔= 𝟐𝟐𝟑. 𝟑 𝒎𝒈

𝑻𝒊𝑶𝟐



354


𝐵𝑊=


𝑑𝑎𝑦 × 16.3 𝑘𝑔= 𝟒𝟒𝟔. 𝟔 𝒎𝒈

𝑻𝒊𝑶𝟐


ORAL

Adults

Application on lips (taken from scenario 8):

Adults, 2 applications: 14.3 mg TiO2/day / 60 kg = 0.24 mg TiO2/kg/day

Adults, 6 applications: 42.8 mg TiO2/day / 16.3 kg = 0.72 mg TiO2/kg/day



Child, 2 applications: 14.3 mg TiO2/day / 16.3 kg = 0.88 mg TiO2/kg/day


Licking on fingers:

NB! IT has not been possible to find a value for the area of children fingers.

Thus the fraction Afingers/Abody is calculated based on adult numbers:

Afingers: 230 cm2 ; Abody: 17,500 cm2

Thus for exposure in the south the oral intake from licking fingers can be calculated to:



𝑛×𝑄𝑝𝑟𝑜𝑑×𝐶𝑛𝑎𝑛𝑜

𝐵𝑊= 0.5𝑥

230 𝑐𝑚2

17500𝑐𝑚2𝑥

7280 𝑚𝑔 𝑇𝑖𝑂2∗/𝑑𝑎𝑦

16.3 𝑘𝑔 = 2.9 mg TiO2/ kg bw/day

Thus, a total daily oral intake of up to 2.6 + 2.9 = 5.5 mg TiO2/ kg bw/day

Step 5


Description of the validity and robustness of the exposure estimates

A concentration of 25 % is the maximum allowed concentration of nano-TiO2. Danish surveys have

indicated that this is a worst case scenario.

As a worst case it is assumed that 100% of the TiO2 in the sunscreen will reach the skin.

The estimated daily amounts of 36 g and 72 g (south) are considered reasonable worst case.

The oral exposure for children (including the hand-to-mouth behaviour) is considered worst case,

in particular the 50% intake assumption.

Exposure parameters

Are taken from SCCS(2012a) and SCCS (2013a) and are considered reasonable worst case.

355


Consumers may also be exposed from TiO2 from other sources of cosmetics, from textiles where

TiO2 is added as UV-filter, and from paints, inks and coatings.

The possible risk from combined exposure will be discussed in WP5 considering absorption and

hazard information identified in WP 3 on hazard assessment.

The uncertainties addressed under Step 5 should be considered in WP5.

References: European Commission (2006). COMMISSION RECOMMENDATION of 22 September 2006 on the efficacy of sunscreen products and the claims made relating thereto. 2006/647/EC. OJ L 265/39 Scientific Committee on Consumer Safety (SCCS). 2013a. Opinion on Titanium Dioxide (nano-form), 22 July 2013.

Scientific Committee on Consumer Safety (SCCS). 2012a. The SCCS's Notes of Guidance for testing

the Substances and their Safety Evaluation, 8th Revision, 11 December 2012.



Danish EPA (2014): Personal communication.

356

Scenario 6 - Product: Sun screen containing nano-ZnO (pump 8.6

spray)


Step 1



Background

The Scientific Committee for Consumer Safety (SCCS) has evaluated nano-ZnO as uv-filter in sunscreens. The industry submissions behind the opinion had submitted some data on droplets sizes using various fillers incl. TiO2 and ZnO. the data indicated on a weight based that droplets were generally rather large. However, the SCCS noted some uncertainties in the data (it was not always clear whether ZnO had been used and that results are very dependent on experimental parameters), and in any case concluded that complementary measurements of the size distribution of the dried residual aerosol particles are needed. The industry submission noted that they were curently not aware of such sunscreen spray products (propellant spray) on the EU marked. The SCCS opinion states that the opinion is not applicable for spray applications. However, it is not explicitly stated whether this statement related only to propellant sprays (discussed to some extend in the option) or also to pump sprays (not mentioned in the option). Although not stated explicitly, it is however assumed that the opinion should neither be applied to pump sprays. In any case, it is known from the current study (and visible in any shops selling sun screens) that pump spray sunscreens are avalilable on the marked. Thus, this scenario addresses pump sprays. It is assumed that the nano-ZnO forming part of pump sprays possess characteristics similar to the nano-ZnO in lotions addressed in the SCCS opinion.

Parameter Specifie

d data*

Estimat

ed*


Product

category

Cosmetic

Type of

Product

Sun

Screen

(pump

spray)

ID of

nanomaterial

Nano-

ZnO

NB! Even-though the Scientific Committee for Consumer Safety

(SCCS) has not evaluated and does not recommend spraying, it

is in this scenario assumed that the characteristics of the nano-

ZnO applied in pump-spray sun screens is similar to the nano-

ZnO in lotions.

SCCS (2013b). ADDENDUM to the OPINION SCCS/1489/12 on

Zinc oxide (nano form). Adopted 23 July 2013

SCCS (2012b). OPINION ON Zinc oxide (nano form).

SCCS/1489/12. Adopted 18 September 2012.

Characterisati

on e.g. size

distr.

SCCS (2013b) based on data submitted by industry:

357

Size

Aspect

ratio/morphol

ogy

Volume

specific

surface area

Crystal form

Purity

Coating

Solubility

Purity

D50

(number)

above 30

nm; D1

(number)

above

20nm

rod-like,

star-like

and/or

isometric

shapes

Wurtzite

≥96%

Yes or no

< 50 mg/l

Impuritie

s <1%

(except

water and

CO₂ )

ZnO nanoparticles with a median diameter (D50: 50% of the

number below this diameter) of the particle number size

distribution above 30 nm, and the D1 (1% below this size)

above 20nm.

Physical appearance as clusters

Wurtzite crystalline structure

ZnO nanoparticles that are either uncoated or coated with

triethoxycaprylylsilane, dimethicone,

dimethoxydiphenylsilanetriethoxycaprylylsilane cross-

polymer, or octyltriethoxy silane. Other cosmetic ingredients

can be used as coatings as long as theyare demonstrated to the

SCCS to be safe and do not affect the particle properties

related to behaviour and/or effects, compared to the

nanomaterials covered in the current opinion.

ZnO nanoparticles that have a comparable solubility to that

reported in the dossier,i.e. below 50 mg/L (approximately the

maximum solubility of the ZnO nanomaterials for which data

are provided in the dossier).

With impurities consisting only of carbon dioxide and water,

whilst any other impurities are less than 1% in total.

Physical

matrix/form

of product

Liquid

Package

design,

volume

≤ 200 ml According to findings in survey conducted in this product

Application/u

se/ handling

Spraying

onto

hand/ski

358

n and

then

distribut

ed over

the body

Location of

nanomaterial

eg. free/

matrix-bound

Free/as

clusters

in liquid

matrix

Direct/

indirect

exposure

Direct,

intended,

leave-on

Indoor/

outdoor use

Mainly

outdoor

Can be applied indoor

Generation of

nanomaterial

during use

No

Specific target

group

(children,

teenagers etc.)

All

Forseeable

misuse

May be

used on

the lips

or

accidenta

lly

sprayed

into the

eyes

Site of

contact/

exposure

Whole

body

Primary

exposure

route(s)

Dermal

and

inhalation

(oral, eye)

Concentrati

on of

nanomateri

al in product

≤25%

SCCS (2012b)

Volume of

product

used,

exposed to

36 g/day

in DK

72 g/day

south of

DK

Based on Danish EPA (2014) recommendation:

- 2 times the amount suggested by SCCS (2012a) ( 36 g/day)

as a worst case scenario for Danish summer conditions and 4

times the amount for a summer in the south, i.e. 72 g/day)

Or

- In Denmark: 1 application per days of the amount suggested

in European Commission (2006): 36 gram/day

- South: 2 applications per day, i.e. 2x36 = 72 gram/day

Body area

exposed to

Total

body

area:

SCCS (2012a): adult

359

17500

cm2

Retention

rate on body

surface

Assumed

1

SCCS (2012a) (For body lotion and other leave-on products)

Migration/li

beration

rate of

nanomateri

al from

matrix

As worst

case it

must be

consider

ed

possible

for all

nano-

material

to reach

the skin

Ingested

amount

0.9

mg/kg

bw/day

For

children

an

addition

al hand-

to mouth

amount

See Scenario 5

Concentrati

on in air/

Volume of

product

released

into air

NA

Duration of

exposure

16

hours/d

up to

24/hours

/d

Frequency

of exposure

25

days/year

2/day

Nanex (WP4), 2010: Estimated number of days per year: 25

SCCS (2013a): 2 applications per day




Step 2



section 4.2) :


360

References

Inhalation exposure

No data on ZnO sun screen pump spray exposure

during application have been identified and we have

not identified any model suitable of estimating pump

spray exposure.

Based on the literature reviewed in this project (see

Chapter 5), pump spraying generally produce larger

particles (according to SCCS (2013a) in general no

more than 1 wt % below 10µm) which readily settle

causing no/very low inhalation exposure.

Considering also that cosmetic formulation are

relatively highly viscous, it might be assumed that

pump spray exposure from such applications are even

lower than for formulations considered in the reviewed

literature. The data for propellant spray discussed in

SCCS (2012b) indicates that even propellant spraying

with cosmetic products might produce relatively large

droplets. On the other hand, possible addition of

surface active additives might influence the behaviour

of cosmetics formulation.

Overall, based on the currently available

knowledge, it is difficult to estimate the

inhalation exposure. Based on inhalation data

from other pump spray applications and

assuming that viscous formulation possibly

produce even less exposure, it is however

likely that exposure is minor/low. However, it

is recommended to proof such an assessment

by actual experiments.

Dermal exposure

It is assumed that the same amount as for sun screen

lotion is applied. As the nanomaterials concentration

is the same (25%), values calculated in scenario 5 is

also used in this scenario.

Scenario 5

Oral exposure

It is assumed that the same amount as for sun screen

lotion is applied. As the nanomaterials concentration

is the same (25%), values calculated in scenario 5 is

also used in this scenario.

Scenario 5

Eye exposure

Expected to be negligible compared to the full body

exposure

Accidental eye exposure possible as a result of misuse

361

Step 3 and Step 4

INHALATION

Based on the currently available knowledge, it is difficult to estimate the inhalation exposure. Based

on inhalation data from other pump spray applications and assuming that viscous formulation

possibly produce even less exposure, it is however likely that exposure is minor/low. However, it is

recommended to proof such an assessment by actual experiments.

¨

DERMAL (taken from scenario 5 by changing TiO2 with ZnO)

Adult:




18000 𝑚𝑔 × 0.25 × 1

17500 𝑐𝑚2≅ 𝟎. 𝟐𝟓𝟕

𝒎𝒈

𝒄𝒎𝟐




36000 𝑚𝑔 × 0.25 × 1

17500 𝑐𝑚2≅ 𝟎. 𝟓𝟏𝟒

𝒎𝒈

𝒄𝒎𝟐



𝐵𝑊=


𝑑𝑎𝑦 × 60 𝑘𝑔= 𝟏𝟓𝟎 𝒎𝒈

𝑻𝒊𝑶𝟐




𝐵𝑊=

18000 𝑚𝑔 𝑇𝑖𝑂2

𝑑𝑎𝑦 × 60 𝑘𝑔= 𝟑𝟎𝟎 𝒎𝒈

𝑻𝒊𝑶𝟐




𝐿𝑑𝑒𝑟 = 𝟎. 𝟐𝟓𝟕𝒎𝒈

𝒄𝒎𝟐corresponding to a daily amount of 2



𝐿𝑑𝑒𝑟 = 𝟎. 𝟓𝟏𝟒𝒎𝒈

𝒄𝒎𝟐 corresponding to a daily amount of 2




𝐵𝑊=


𝑑𝑎𝑦 × 16.3 𝑘𝑔= 𝟐𝟐𝟑. 𝟑 𝒎𝒈

𝑻𝒊𝑶𝟐




𝐵𝑊=


𝑑𝑎𝑦 × 16.3 𝑘𝑔= 𝟒𝟒𝟔. 𝟔 𝒎𝒈

𝑻𝒊𝑶𝟐


ORAL (taken from scenario 5 by changing TiO2 with ZnO)

362

Adults


Adults, 2 applications: 14.3 mg ZnO/ 60 kg = 0.24 mg ZnO/kg/day

Adults, 6 applications: 42.8 mg ZnO /day / 16.3 kg = 0.72 mg ZnO /kg/day



Child, 2 applications: 14.3 mg ZnO /day / 16.3 kg = 0.88 mg ZnO /kg/day

Child, 6 applications: 42.8 mg ZnO /day / 16.3 kg = 2.6 mg ZnO /kg/day

Licking on fingers:

NB! IT has not been possible to find a value for the area of children fingers.

Thus the fraction Afingers/Abody is calculated based on adult numbers:

Afingers: 230 cm2 ; Abody: 17,500 cm2

Thus for exposure in the south the oral intake from licking fingers can be calculated to:



𝑛×𝑄𝑝𝑟𝑜𝑑×𝐶𝑛𝑎𝑛𝑜

𝐵𝑊= 0.5𝑥

230 𝑐𝑚2

17500𝑐𝑚2𝑥

7280 𝑚𝑔 𝑍𝑛𝑂/𝑑𝑎𝑦

16.3 𝑘𝑔 = 2.9 mg ZnO/ kg bw/day

Thus, a total daily oral intake of up to 2.6 + 2.9 = 5.5 mg ZnO/ kg bw/day

Step 5



Inhalation:

As described in step 2, it has not been possible to quantitavely estimate inhalation exposure due to

lack of data and models. However, based on available evidence inhalation exposure is carefully

estimated to be low/minor, but it is recommended to follow this up with experimental proofs.

Dermal:

See scenario 5.

Oral:

See scenario 5.


Inhalation:

Uncertainty related to inhalation exposure (see above).

Current scenario applies to pump sprays, not to propellant sprays. Industry submission to SCCS

indicated that propellant spray applications are no known to them.

363

Dermal:

See scenario 5.

Oral:

See scenario 5.

References:

European Commission (2006). COMMISSION RECOMMENDATION of 22 September 2006 on the efficacy of sunscreen products and the claims made relating thereto. 2006/647/EC. OJ L 265/39 SCCS (2013a). Scientific Committee on Consumer Safety. Opinion on Titanium dioxide (nano form). SCCS/1516/13. 111 pp. SCCS (2013b). ADDENDUM to the OPINION SCCS/1489/12 on

Zinc oxide (nano form). Adopted 23 July 2013

SCCS (2012b). OPINION ON Zinc oxide (nano form). SCCS/1489/12. Adopted 18

September 2012.

Danish EPA (2014): Personal communication.

364

Scenario 7 - Product: Mascara with Carbon Black 8.7


Application of mascara in the eye region

Step 1



Parameter Specified

data*

Estimate

d*


Product category Cosmetics

Type of Product Mascara

ID of nanomaterial Carbon Black

Characterisation

e.g. size distr.

Primary particle size

distribution by

number

Aggregations/agglo

meration

Purity

Powder:

D50: 59 – 76

nm

Commercial

dispersion:

D50: 77 and

146 nm

See footnote4

> 97% Carbon

Four sample measurements with Transmission Electron

Microscopy (TEM) (SCCS, 2014)

D10: 41-48 nm, D90: 132-149 nm

Two samples measured with various methods (SCCS, 2014)

D10: 50 and 127 nm, D90: 143 and 259 nm

SCCS (2014)

SCCS (2014)

Physical

matrix/form of

product

Paste In line with how mascara is normally marketed

Package design,

volume

10 ml A similar product is supplied in 8 ml packaging (

http://www.lashfood.com/r/productsp.php?p=41#.U759S6

PU9aQ

Application/use/

handling

Leave-on

product for eye

lashes with

little skin

contact

Danish EPA (2014)

Location of

nanomaterial eg.

free/ matrix-bound

In a liquid

paste

matrix

Direct/ indirect Direct intended

4 SCCS (2014): "The SCCS has accepted that nanoparticles in carbon black materials exist mainly

as

aggregates and agglomerates. A few tests in the presence of emulsifiers have not shown complete dispersion of the agglomerates. However, further tests would be needed to

eliminate the possibility of deagglomeration to primary particles or nano-sized aggregates

under other conditions, e.g. in final formulations or when in the biological environment."

365

exposure leave on

Indoor/ outdoor use Both

Generation of

nanomaterial

during use

No, but

possibly

deagglomeratio

n

See footnote4

Specific target

group (children,

teenagers etc.)

Teenagers

and adults

Even in

rare cases

children

This may more frequently be the case for e.g. eye liners,

which also may contain Carbon Black

Forseeable misuse See

previous

line

Site of contact/

exposure

Eye lashes, Incidentall

y eye and

skin in the

eye region

Primary exposure

route(s)

Eye lashes,

Dermal, Eye

Concentration of

nanomaterial in

product

<3%

Up to 10% for

eye decorative

products

10% will be

assumed as a

worst case

Danish EPA (2014)

SCCS (2014)

Volume of

product used,

exposed to

0.025 grams

per day (= 25

mg/day)

I.e. 12.5

gram/applicati

on

SCCS (2012)

Body area

exposed to

1.6 cm2 SCCS (2012)

Retention rate on

body surface

1

Migration/liberat

ion rate of

nanomaterial

from matrix

1

Ingested amount NA

Concentration in

air/

Volume of

product released

into air

NA

Duration of Whole day

366

exposure 16

hours/day

up to 24

hours/day

as a worst

case

Frequency of

exposure

2 applications

per days

SCCS (2012)




Step 2

Based on the availability of data the most relevant algorithms are generated/ selected for

estimation of the exposure (algorithms for various purposes and at various tiers are

described in chapter 4, section 4.2):


References

Inhalation exposure

Considered negligible given amount used and

formulation (liquid paste)

Dermal exposure The dermal load is calculated as:




𝐷𝑑𝑒𝑟 =𝑛 × 𝑄𝑝𝑟𝑜𝑑 × 𝐶𝑛𝑎𝑛𝑜 × 𝑅𝑅

𝐵𝑊





RR: Retention rate

n: Number of applications per day (/day)

Oral exposure

NA

Eye exposure As a worst case it is assumed that eye exposure could be

20% of the applied amount: 0.2 * Daily amount

(mg/day) * Cnano (fraction)

367

Step 3







Target population: Children/ teenagers/ adults


parameters


References

Body weight Children: 18.6

kg

Teenagers:

56.8 kg

Adult: 60 kg

Mean for 3-6 years old

children

Mean for 11-16 years

Recommended for adult

women

Source: Nordic council of

Ministers (2011)

Skin surface (site of contact) 1.6 cm2 SCCS (2012)




References

Inhalation exposure

NA


Oral NA

Eye No additional parameters

Step 4

This section describes and explains the calculation of the exposure.

Dermal load:



12.5 𝑚𝑔 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 × 0.1 𝑚𝑔𝐶𝐵𝑚𝑔

𝑝𝑟𝑜𝑑𝑢𝑐𝑡 × 1

1.6 𝑐𝑚2= 𝟎. 𝟖 𝒎𝒈/𝒄𝒎𝟐

Dermal dose:

368

Children:


𝐵𝑊=

2/𝑑𝑎𝑦 × 12.5 𝑚𝑔 × 0.1 × 1

18.6 𝑘𝑔= 𝟎. 𝟏𝟑𝐦𝐠 𝐂𝐁 /𝐤𝐠 𝐛𝐰/𝐝𝐚𝐲

Teenagers:


𝐵𝑊=

2/𝑑𝑎𝑦 × 12.5 𝑚𝑔 × 0.1 × 1

56.8 𝑘𝑔= 𝟎. 𝟎𝟒𝟒 𝐦𝐠 𝐂𝐁 /𝐤𝐠 𝐛𝐰/𝐝𝐚𝐲

Adults:


𝐵𝑊=

2/𝑑𝑎𝑦 × 12.5 𝑚𝑔 × 0.1 × 1

60 𝑘𝑔= 𝟎. 𝟎𝟒𝟐 𝐦𝐠 𝐂𝐁 /𝐤𝐠 𝐛𝐰/𝐝𝐚𝐲

Eye exposure:

As a worst case estimate, 20% of the daily applied amount of 25 mg mascara (2.5 mg Carbon Black)

might end up in the eye: 0.2 * 2.5 mg Carbon Black/day = 0.5 mg Carbon Black / day

This amount is assumed to be applied twice daily, i.e. 0.25 mg Carbon Black per event

Step 5



As noted by SCCS (2012) there is some uncertainty on to which extent the consumer is solely

exposed to agglomerates/aggregates or also to primary particles. This is of importance with respect

to the potential ability of nanoparticles to penetrate skin.

Worst case assumptions has been used in relation to body weight and concentration of Carbon

Black in product (upper limit of 10% CB in cosmetics used – 3% might be more representative).

It is as a worst case assumed that 100% of the Carbon Black is released form the paste matrix.

Skin area exposed, amount of mascara used per day and number of daily applications are taken

from SCCS (2012) and can be considered reasonable worst case.

Overall, the estimated exposures can be considered worst case for mascara.

Exposure estimates can be further refined if needed during the risk assessment.


Consumers can also be exposed to Carbon Black from other sources of cosmetics, such as eyeliners,

eye pencils, eye shadows, blushers, brush-on-brow, foundations and nail enamels, as well as in

rinse-off skin products (SCCS, 2012). Thus, overall it can be assumed that dermal and eye Carbon

Black exposure could be considerably higher than what is estimated for mascara.

Actual risk from such combined exposure will be discussed in WP5 considering absorption and

hazard information identified in WP3 on hazard assessment.

References:

Scientific Committee on Consumer Safety (SCCS). 2012. The SCCS's Notes of Guidance for testing

the Substances and their Safety Evaluation, 8th Revision, 11 December 2012. Scientific Committee on Consumer Safety (SCCS). 2014. OPINION ON Carbon Black (nano-form). SCCS/1515/13. Adopted 12 December 2013. Published 27 March 2014. Danish EPA (2014). Supplementary Survey of Products on the Danish Market Containing Nanomaterials. Environmental Project No. 1581. Danish Environemntal Proctection Agency, Copenhagen.

369

Scenario 8 - Product: Lipstick sun screen containing nano-TiO2 8.8


Step 1



Parameter Specifie

d data*

Estimat

ed*


Product

category

Cosmetic

Type of

Product

Lipstick

Sun

Screen

ID of

nanomaterial

Nano-

TiO2

SCCS (2013a). OPINION ON Titanium Dioxide (nano form).

http://ec.europa.eu/health/scientific_committees/consumer_s

afety/docs/sccs_o_136.pdf

Characterisati

on e.g. size

distr.

Size

Particles

Aspect ratio

Volume

specific

surface area

Crystal form

Purity

Coating

Crystals:

9-21 nm

(XRD)

1.5 and up

to 4.5

192-460

m2/cm3

Rutile

with max.

15 %

anatase

≥99.5%

Yes

SCCS (2013a)

SCCS (2013a): The median particle sizes of the different

materials range from ~44 nm to 354 nm on volume weighted

basis, and ~34 nm to ~99 nm on number weighted basis. The

lower size cut offs range between 17 nm and 73 nm.

SCCS (2013a)

SCCS (2013a)

SCCS (2013a)

SCCS (2013a)

See table 1 in SCCS (2013a). Includes the following types of

coatings: alumina/silica, methicone/silica, aluminium

hydroxide and dimethicone/methicone copolymer,

trimethyloctylsilane, alumina/silicone and

alumina/silica/silicone, dimethicone, simethicone, stearic acid,

glycerol, dimethoxydiphenylsilane, triethoxycaprylylsilane

Physical

matrix/form

of product

Paste,

salve

Package ≤ 20 ml According to information found on the internet



370

design,

volume

Application/u

se/ handling

Leave-on

product

Location of

nanomaterial

eg. free/

matrix-bound

In a paste

matrix or

salve/oint

ment

Direct/

indirect

exposure

Direct,

intended,

leave-on

Indoor/

outdoor use

Indoor /

outdoor

Generation of

nanomaterial

during use

No, but

possible

de-agglo-

meration

SCCS (2013a)

Specific target

group

(children,

teenagers etc.)

All

Forseeable

misuse

NA May be

used for

other

dermal

areas

Site of

contact/

exposure

Lips

Primary

exposure

route(s)

Dermal

(oral)

Concentrati

on of

nanomateri

al in product

≤25%

containin

g max.

15%

anatase

SCCS (2013a)

Volume of

product

used,

exposed to

0.057

g/day

0.9

mg/kg

bw/day

SCCS (2012a)

Body area

exposed to

Lips: 4.8

cm2

SCCS (2012a)

Retention

rate on body

surface

Assumed

1

SCCS (2012a) (For body lotion and other leave-on products)

Migration/li

beration

rate of

As worst

case it

must be

371

nanomateri

al from

matrix

consider

ed

possible

for all

nano-

material

to reach

the lips

Ingested

amount

100% Worst case ingestion: 100%

Concentrati

on in air/

Volume of

product

released

into air

NA

Duration of

exposure

16

hours/d

up to

24/hours

/d

Frequency

of exposure

2/day

2-6/day

SCCS (2012a)

Nordic Council of Ministers (2011)




Step 2



section 4.2) :


References

Inhalation exposure

Not considered relevant in relation to sunscreen lotion

applied manually.

Dermal exposure





𝐷𝑑𝑒𝑟 =𝑄𝑝𝑟𝑜𝑑 × 𝐶𝑛𝑎𝑛𝑜 × 𝑛 × 𝑅𝑅

𝐵𝑊

372







RR: Retention rate

n: Number of applications per day (/day)

Oral exposure

Fing * Cnano * Qprod

Fing: Fraction ingested (assumed 1 (=100%) as worst

case)



n: number of applications/day

Amount per day: n*Qprod = 57 mg/day (based on n=2)

SCCS(2012a)

Eye exposure

NA

Step 3







Target population: Adults/ children


parameters


References


16.3 kg (child)

SCCS 2012a

Skin surface (site of contact) 4.8 cm2 (adult)

4.8 cm2 (child,

worst case)

SCCS 2012a

373

Dose which may be ingested =0.057 g/day

0.9 mg/kg

bw/day

SCCS (2012a)

(Based on two

applications and assuming

the total applied dose is

ingested. In that case,

there will be no dermal

dose)



NA

Others




References

Inhalation exposure

NA


Oral No additional parameters

Eye NA

Step 4

The exposure will be a combination between dermal and oral exposure. It is suggested that the risk

assessment addresses two scenarios: 100% dermal exposure and 100% oral exposure and selects the

worst case.


Dermal:

Dermal load:



28.5 𝑚𝑔 × 0.25 × 1

4.8 𝑐𝑚2≅ 𝟏. 𝟒𝟖

𝒎𝒈

𝒄𝒎𝟐

External dermal dose, 2 applications (adult):


𝐵𝑊=


𝑑𝑎𝑦 × 60 𝑘𝑔= 𝟎. 𝟗 𝒎𝒈

𝑻𝒊𝑶𝟐


External dermal dose, 2 applications (child):


𝐵𝑊=


𝑑𝑎𝑦 × 16.3 𝑘𝑔= 𝟑. 𝟓 𝒎𝒈

𝑻𝒊𝑶𝟐


External dermal dose, 6 applications (adult): 𝟐. 𝟕 𝒎𝒈𝑻𝒊𝑶𝟐


External dermal dose, 6 applications (child): 𝟏𝟎. 𝟓 𝒎𝒈𝑻𝒊𝑶𝟐


Oral:

374

The oral dose is the total applied daily dose suggested by SCCS (2012): 57 mg product/day equalling

14.3 mg TiO2/day based on two applications. If six applications are used the value is 42.8

mg TiO2/day. As no value for the surface area of lips are provided for children, the same daily dose

is used for children as a worst case.

This corresponds to:

Adults, 2 applications: 14.3 mg TiO2/day / 60 kg = 0.24 mg TiO2/kg/day

Adults, 6 applications: 42.8 mg TiO2/day / 16.3 kg = 0.72 mg TiO2/kg/day



Step 5



A concentration of 25 % is the maximum recommended concentration of nano-TiO2 by SCCS (based

on industry submissions). Danish surveys have indicated that this is a worst case scenario in the

case of lotions as concentrations are generally lower. No specific information has been identified for

sun screen lipstick.

It as a worst case assumed that 100% of the TiO2 in the sunscreen will reach the skin or be ingested.

The estimated daily amount of 0.057 g is the value provided by SCCS (2012a) for lipstick/lip salve

based on two applications. However, in the Nordic Council of Ministers (2011), 2 -6 applications are

suggested for lipstick. Thus 6 applications is considered worst case.

Exposure parameters besides numbers of applications are taken from SCCS (2012a) and SCCS

(2013a) and are considered realistic worst case.


Consumers may also be exposed to TiO2 from other sources of cosmetics, from textiles where TiO2 is

added as UV-filter, and from paints, inks and coatings.




References: Scientific Committee on Consumer Safety (SCCS). 2013a. Opinion on Titanium Dioxide (nano-form), 22 July 2013.

Scientific Committee on Consumer Safety (SCCS). 2012a. The SCCS's Notes of Guidance for testing

the Substances and their Safety Evaluation, 8th Revision, 11 December 2012.



375

Scenario 9 - Product: Face powder containing nano-silica 8.9


Brush application of face powder

Step 1

From the data collected and the conclusions in chapter 4, information regarding the parameters

listed below is filled in.

Parameter Specified

data*

Estimated* Comments/ References

Product

category

cosmetics

Type of Product Face powder

make-up

e.g.: http://eshiko.com/

ID of

nanomaterial

Silica

Characterisation

e.g. size distr.

10 nm

hydrated

silica particles

amorphous 10 nm indicated on specific products. http://eshiko.com/

Various types of nano-silica may be used in cosmetics.

According to notifications to the Commission: silica;

hydrated silica; silica sylilate and silica dimethyl silylate

are used in cosmetics.(The Commission has asked the SCCS

to prepare an opinion on the use of these four nano

substances).

http://ec.europa.eu/health/scientific_committees/consume

r_safety/docs/sccs_q_086.pdf

Physical

matrix/form of

product

Powder

Package design,

volume

Few grams 10 g

Application/use/

handling

By brush

Location of

nanomaterial

eg. free/ matrix-

bound

Mixed into

the powder

Direct/ indirect

exposure

Direct dermal

application

Indoor/ outdoor

use

Indoor

Generation of

nanomaterial

during use

No

Specific target

group (children,

teenagers etc.)

adult/

teenagers

Forseeable

misuse

-

Site of contact/ Skin surface,

http://eshiko.com/

http://eshiko.com/

376

exposure face

Primary

exposure

route(s)

Dermal Inhalation Oral and eye exposure may be relevant as well.

Concentration

of

nanomaterial

in product

1-10%

Volume of

product used,

exposed to (1)

0.51 g SCCS (2012) estimate for liquid foundation used for powder

make-up as well

Body area

exposed to (1)

Face 565 cm2 SCCS (2012). ½ the area of female head

Retention rate

on body

surface (1)

1 Leave-on product

Migration/libe

ration rate of

nanomaterial

from matrix

100% Nanomaterial not fixed to a matrix

Ingested

amount

- -

Concentration

in air/

Volume of

product

released into

air

Have to be measured/ calculated

Duration of

exposure

Inhalation: 15

minutes

Dermal: hours

Frequency of

exposure

Once daily

through the year

SCCS (2012)


(1) For cosmetics values can be found in section 4-2 in SCCS (2012) Notes of guidance for

the testing of cosmetic substances and their safety evaluation 8th revision 2012.

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_s_00

6.pdf

In chapter 5.3.2 the following characterization of the inhalation exposure from use of face powder

has been given:

Nazarenko et al. (2012) looked at the potential for nanoparticle inhalational exposure from use of

six cosmetic make-up powders, three of which were considered to contain nanomaterials (products

from the Woodrow Wilson database). Two of the nano-products and two of the regular products

had a content of silica. Exposure was simulated by applying the cosmetic powder preparation by

brush or pads to a female mannequin head and sampling air from the nostrils of the head at a

"breathing rate" of 11 liter air per minute. Using TEM microscopy, the exposure was predominantly

characterized (not quantified by mass) by agglomerates with sizes above 100 nm. Greater fractions

of primary particles in nano-size were observed in two of the nano-products as compared to the

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_s_006.pdf

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_s_006.pdf

377

three conventional products. During application of the make-up powder the particle concentrations

reached up to about 10,000 particles/cm3 for the 20 nm-size mode (reading from the size-

distribution plot) for both the conventional products and the products claimed to be nano-products

(the highest level was measured for a conventional product). Measurements were performed using

a scanning mobility particle sizer instrument. For one of the conventional products particle levels

up to 10,000 particles/cm3 were measured for particle sizes in the size range of 300-700 nm.

It was by Nazarenko et al. (2012) concluded that the release of particles > 100 nm (up to 20 μm in

diameter) indicates potential exposure to nanoparticle agglomerates, especially from products with

a high proportion of primary particles in the nano-size range. Exposure to nanomaterial(s) due to

the use of cosmetic powders will be predominantly in the form of agglomerates or nanomaterials

attached to larger particles in the micrometer range that would deposit in the upper airways of the

human respiratory system rather than in the alveolar and tracheobronchial regions of the lung, as

would be expected for the primary nanoparticles.

Form this it can be seen that use of nano-enabled face powder does not necessarily lead to higher

levels of free nano-particles in the air compared to conventional products. However, in our

exposure assessment also exposure to agglomerated particles are to be considered and therefor

exposure to nanoparticles cannot be based on measurements of free nanoparticles alone. Although

size distribution plots were given no estimations of the total number concentration of nanoparticles

in size modes below 100 nm were given by Nazarenko et al. (2012).

Step 2 Algorithms



section 4.2) :


References

Inhalation

exposure

Concentration air:

Cinh (mg/m3) = (PI x A x F x DF / V) x 1000 mg/g

PI: concentration of nano-ingredient in product (g/g)

A : amount of product used per event

F: fraction of product released into air

DF: dilution factor

V: Volume of air near the head/inhalation zone)

Inhalation Dose

Dinh = Fresp ∗ Cinh ∗ IHair ∗ Tcontact

BW∗ N

Parameter Description Units

Dinh Inhalation dose (intake) of

substance per day

[mg/kg bw d]

378

and body weight

Cinh Concentration of substance in air of

room

[mg/m3]


[-]

IHair Ventilation rate of person

[m³/d]

Tcontact Duration of contact per event

[d]

BW Body weight [kg]

N Mean number of events per day

[/d]

Dermal exposure

Dermal load:

The dermal load Lder in mg/cm2 is calculated as:

Dermal dose:

The external dermal dose, Dder in mg/kg /d) is then

calculated as

Dder (mg/g bw/d) = (Qprod/ d x FCprod / Bw) x

1000 mg/g

Where:

Qprod/ d : the amount of procut used per day (g/d)

FCprod: Fraction of nanomaterial in product

Askin: exposed skin surface (cm2)

Bw: body weight (kg)

Oral exposure

Oral exposure is to some part covered by calculation of the

inhaled dose as one fraction of this dose enter the deeper

part of the lung and is available for pulmonary absorption

and another part of the dose may be swallowed and be

available for gastrointestinal absorption.

A very small fraction of the applied face-powder may end-

up on the lips but more importantly oral exposure may

derive from licking the area surrounding the lips.

Eye exposure

No algorithm for deposition of airborne particles in the

eye has been found

Step 3 Target group

379







Target population: teenager

Teenagers are according to Lorenz et al. (2011) the consumer group using the

cosmetic products most heavily.


parameters


References

Body weight 56.8 kg Nordic Council of

Ministers, 2011

Inhalation rate 0.013 m3/min Nordic Council of

Ministers, 2011

Skin surface (site of contact) 565cm2 SCCS (2012)

Lips 4.8 cm2 SCCS (2112)

Eye surface 2 x 4 cm2 assumed



-

Others




References

Inhalation exposure

Room volume




Dustiness

Etc.


Viscosity

Etc

Oral

Eye

380


Teenager

Dermal load:

Lder (mg/cm2) = 0.51 g x 0.1 x 1000 (mg/g)/ 565 cm2 = 0.09 mg/cm2

Dermal exposure:

Dder (mg/g bw/d) = (Qprod/ d x FCprod / BW) x 1000 mg/g

Dder (mg/bw/d) = (0.51 g/d x 0.1 /56.8 kg) x 1000 mg/g = 0.90 mg/kg bw/d

Inhalation exposure:

Cinh (mg/m3) = (PI x A x F x DF / V) x 1000 mg/g

In this calculation it is assumed that a fraction of 1%* of the use face powder is released into the air

as respirable particles and it is a worst case considered that 10% is inhaled. I.e. a total of 1% of the

volume used is inhaled. With respect to the concentration it is assumed that the amount that is

inhaled is evenly distributed in volume of inhaled air during the application period:

Cinh (mg/m3) = (0.1 g/g x 0.51 g x 0.01 x 0.1 / (0.013 m3/min x 15 min) x 1000 mg/g = 0.26

mg/m3

This value should be considered as a 15 minutes peak value, as no inhalation exposure after the

application phase is considered to occur.

* Levin et al. (2014) made measurement of the dustiness of four different pharmaceutical nano-

powders. Using a rotation drum for dustiness measurements they found a dustiness index of 10000

mg/kg (1%) as the highest value for the powders. To use such a value for face powder is considered

as a conservative estimate as lower dusting index for face powders would be expected, as face

powders are designed to strongly adhere to surfaces.

Further, the Dinh - (mg/g bw/d) can be calculated as:

Dinh (mg/g bw/d) = PI x A x F x D/ BW x 1000 mg/g

Dinh (mg/g bw/d) = (0.1 g/g x 0.51 g x 0.01 x 0.1) / 56.8 kg x 1000 mg/g = 0.0009 mg/kg w/d

Particle number exposure

Nazarenko et al. (2012) measured a particle concentration of about 10,000 partilcles/cm3 for

particles with a diameter of 20 nm from a face-powder claimed as a nano-product, however, they

did not indicate an overall exposure level for 1-100 nm particles.

With a ventilation rate of 0.013 m3/min and a duration for 15 minutes this would lead to an

exposure of:

Dinh (#/d) = 10,000 particles/cm3 x 0.013 m3/ min x 15 min/d x 106 cm3/m3 = 2 x 109 particles

/d

or

Dinh (#/kg bw/d) = 2 x 109 particles /d / 56. 8 kg = 3.5 x 107 particles /kg bw/d

However, it has to be emphasized that for conventional face powders similar concentrations of 20

nm particle were measured. Further the particle numbers given are for 20 nm nanoparticles from

the whole products and its consituents and not only for nano-silica.

381

Eye exposure, teenager

No algorithm for eye exposure has been found. If it as a worst case is assumed that the surface load

of the eye is 1% of the surface load on the skin, then the eye surface load would be 0.0009 mg/cm2.

With an assumed surface of the eyes of 2 x 4 cm2, this would correspond to a daily dose of 0.0072

mg or 0.0001 mg/kg bw/d.

Oral exposure

As a worst case it is assumed that oral exposure may derive from licking around the lips from a

surface area corresponding to the area of the lips (4.8 cm2).

With a dermal load of 0.09 mg nano-silica/cm2 on this surrounding area this would lead to a daily

oral dose of:

Doral (total) = 4.8 cm2/d x 0.09 mg nano-silica/cm2 = 0.43 mg nano-silica/d

Doral (mg/kg bw/d) = = 0.43 mg nano-silica/d / 56.8 kg = 0.0077 mg nano-silica/kg bw/d

Step 5


Face powder may contain hydrated silica in nano-size as indicated in this example. Information on

the concentration in the product has not been given, but a content of 10% of nano-silica in the

product is considered a conservative estimate.

Based on this the dermal load that has been calculated based on SCCS (2012) exposure figures

seems to be conservative due to the high content of 10% nano-silica.

The inhalation exposure is based of liberation of 1% of the used amount of face powder into the air

and to inhalation of 10% of this fraction. This lead to a concentration of 0.26 mg/m3 of

nanomaterial corresponding to a total dust level of 2.6 mg/m3 in the inhaled air. Such an estimate

does not seem quite unrealistic, however it is still considered as worst case scenario.

The oral dose is estimated to be nearly a factor 10 higher than the inhalation dose, thus licking of

the skin area surrounding the lips covered with face powder may result in a significant exposure.

Although great uncertainties pertain to the estimate for eye exposure the figure indicates far lower

exposure compared to the dermal, oral and inhalational route.


There is no regulatory limit for the use of silica in cosmetics so other cosmetics product may

contribute to exposure to nano-silica (e.g. oral exposure from toothpaste or dermal exposure from

body cream). Use of other product categories may further contribute e.g. oral exposure from food

containing silica as food additive (or in food supplement) and inhalational exposure for the use of

surface treatment sprays. However, the exposure may pertain to various types of nano-silica in

cosmetics and the Commission has recently asked the SCCS for an opinion on four types of nano-

silica that are currently used.

References

Eshiko face powder website: http://eshiko.com/

Lorenz C, Goetz NV, Scheringer M, Wormuth M, and Hungerbühler K. 2011. Potential exposure of

German consumers to engineered nanoparticles in cosmetics and personal care products.

Nanotoxicology 5(1), 12-29.

http://eshiko.com/

382

Nazarenko Y, Zhen H, Han T, Lioy PJ, and Mainelis G. 2012. Potential for Inhalation Exposure to

Engineered Nanoparticles from Nanotechnology-Based Cosmetic Powders. Environmental Health

Perspectives 120(6), 885-892.

SCCS 2012b. The SCCS´S notes to Guidance for the testing of Cosmetic substances and their safety

evaluation. Scientific Committee on consumer safety, SCCS/1501/12.

Commissions request on nano-silica (2014).

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_q_086.pdf

http://ec.europa.eu/health/scientific_committees/consumer_safety/docs/sccs_q_086.pdf

383

Scenario 10a - Product: Paint containing nano-TiO2 8.10

Description of exposure scenario: Roller application of paint

Step 1



Parameter Specifie

d data*

Estimat

ed*


Product

category

Surface

treatment

/ coatings

Type of

Product

Paint

ID of

nanomaterial

Nano-

TiO2

Characterisati

on, e.g. size

distr.

Size

Crystal form

5-30 nm

Anatase

Patent information:

http://www.google.com/patents/EP2188125A1?cl=en

Due to the photocatalytic properties, it is assumed that anatase

is the major constituent.

Physical

matrix/form

of product

Liquid

matrix

Package

design,

volume

≤ 5 L

Application/u

se/ handling

Roller

applicatio

n

Location of

nanomaterial

eg. free/

matrix-bound

In liquid

matrix

Direct/

indirect

exposure

Direct

exposure

Indoor/

outdoor use

Indoor

and

outdoor

Generation of

nanomaterial

during use

No

Specific target

group

(children,

teenagers etc.)

Mainly

adults

Forseeable

misuse

No

http://www.google.com/patents/EP2188125A1?cl=en

384

Site of

contact/

exposure

Hands /

arms

Primary

exposure

route(s)

Dermal

(oral, eye)

Concentrati

on of

nanomateri

al in product

≤25%

Photocatalytic paints generally contain 5-10 % (Danish EPA, in

prep).

Volume of

product

used,

exposed to

5L –

7500 g

Body area

exposed to

Hands

and arms

SCCS (2012): adult

Retention

rate on body

surface

Assumed

1

SCCS (2012) (For body lotion and other leave-on products)

Migration/li

beration

rate of

nanomateri

al from

matrix

As worst

case it

must be

consider

ed

possible

for all

nano-

material

to reach

the skin

Ingested

amount

NA

Concentrati

on in air/

Volume of

product

released

into air

NA

Duration of

exposure

5L

applied

per day

Frequency

of exposure

Full day

for

several

days




385

Step 2



section 4.2) :


References

Inhalation exposure

Not considered relevant

Dermal exposure


𝐿𝑑𝑒𝑟 =𝑄𝑝𝑟𝑜𝑑 × 𝐹 × 𝐶𝑛𝑎𝑛𝑜 × 𝑅𝑅



𝐷𝑑𝑒𝑟 =𝑄𝑝𝑟𝑜𝑑 × 𝐶𝑛𝑎𝑛𝑜 × 𝐹 × 𝑛 × 𝑅𝑅

𝐵𝑊




F: Fraction which may come into contact with skin




RR: Retention rate (assumed 1)

Oral exposure

Not considered relevant

Eye exposure

Might happen during rolling, but no data to estimate

exposure.

386

Step 3







Target population: Young and adults

Anatomical

/Physiological

parameters

Specified Estimated Comments/ References

Body weight 60 kg

(adult)

43.9 (13.5

years)


Retention rate 1

Skin surface (site of

contact):

- arms and hands

(20% of body surface

– women

13.5 years)

50% of hands and

arms:

50%×20% of

19100 cm2

(woman)= 1910

cm2

50%×20% of

14000 cm2 (13.5

years)= 1400 cm2


(In ECHA (2012) it is estimated that the maximal

exposed area in relation to occupational roller painting is

960 cm2)

Density >1.0

1.5 g/cm3 (worst

case)

Example of photo-catalytic paint with density: 1.31

g/cm3:

http://www.auro.de/downloads/sicherheitsdatenblaetter

/328-SDB-Frischeweiss-AURO-Naturfarben.pdf

http://www.auro.de/downloads/technische-

merkblaetter/328-Technisches-Merkblatt-Frischeweiss-

AURO-Naturfarben.pdf

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Others




References

Inhalation exposure NA

http://www.auro.de/downloads/sicherheitsdatenblaetter/328-SDB-Frischeweiss-AURO-Naturfarben.pdf

http://www.auro.de/downloads/sicherheitsdatenblaetter/328-SDB-Frischeweiss-AURO-Naturfarben.pdf

http://www.auro.de/downloads/technische-merkblaetter/328-Technisches-Merkblatt-Frischeweiss-AURO-Naturfarben.pdf



387

Dermal exposure

Amount which may

get in contact with

skin through splashes

or direct contact.

0.1 % of product, i.e. 7500 mg / application (In ECHA (2012) it is

estimated that the

dermal exposure for

a professional is 1.37

mg/kg/day

corresponding to

82.2 mg/day for a

woman)

Oral NA

Eye NA

Step 4


Adult:

Dermal load:


𝐴𝑠𝑘𝑖𝑛= 𝐿𝑑𝑒𝑟 =

7500𝑔 × 0.001 × 0.25 × 1

1910 𝑐𝑚2= ≅ 𝟎. 𝟗𝟖

𝒎𝒈 𝑻𝒊𝑶𝟐

𝒄𝒎𝟐

External dermal dose:


𝐵𝑊=

7500𝑔 × 0.25 × 0.0001 × 1 × 1/𝑑𝑎𝑦

60 𝑘𝑔=

0.0031 g TiO2 / kg bw /day = 3.1 mg TiO2 /kg bw /day

Teenager (13.5 years):

Dermal load:


𝐴𝑠𝑘𝑖𝑛= 𝐿𝑑𝑒𝑟 =

7500𝑔 × 0.001 × 0.25 × 1

1400𝑐𝑚2= ≅ 1. 𝟑𝟒

𝒎𝒈 𝑻𝒊𝑶𝟐

𝒄𝒎𝟐

External dermal dose:


𝐵𝑊=

7500𝑔 × 0.25 × 0.0001 × 1 × 1/𝑑𝑎𝑦

43.9 𝑘𝑔=

0.0043 g TiO2 / kg bw /day = 4.3 mg TiO2 /kg bw /day

388

Step 5



A nanoTiO2 concentration of 25 % is considered a worst case. A Danish survey has found that the

concentration of photocatalytic TiO2 in paints on the Danish market is 5-10 %. (Occurrence and

effects of nanosized anatase titanium dioxide in consumer products (Danish EPA, in prep)).

The dermal exposure assessment is as a worst case assuming that 50 % of the surface of arms and

hands are exposed.

It is assumed that 0.1% of the product volume/weight gets in contact with the skin. This is taken

from ECHA guidance and might be a bit low.

Eye exposure is likely when rolling with paint. No data on this issue have been identified, but should

be qualitatively considered in WP5.


Consumers may also be exposed from nano-TiO2 from other sources such as cosmetics, from

textiles where TiO2 is added as UV-filter, and from other coatings and inks. Furthermore nano-TiO2

may be released from different articles/matrices.




References:



Danish EPA (in prep): Occurrence and effects of nanosized anatase titanium dioxide in consumer

products.

ECHA (2012): Guidance on information requirements and chemical safety assessment. Chapter

R.14: Occupational exposure estimation. Version: 2.1, November 2012

389

Scenario 10b - Product: Primer Paint containing nano-TiO2 8.11

Description of exposure scenario: Case 10b: Sanding UV-protective primer paint

Step 1


with additional information when necessary. Parameter Specified

data* Estimated*


Product category

Coating/impregnation


Type of Product Primer or UV-protective coating

This type of product can be used either as a primer before painting or as UV-protective coating. http://www.titanprotect.de/deu/4_Produkte/10_Beschichtungen/51_Produkt-TP2220.html

ID of nanomaterial

Nano-TiO2

Characterisation, e.g. size distr. Size Crystal form

<3 nm

Anatase

http://titanprotect.de/file/pdfs/neu/PDB/PDB%20TP2221.pdf Anatase is assumed due to the photocatalytic properties.


Hardened primer or UV-protective surface coating on absorbing surfaces



NA This assessment is of post-application aftertreatment


Sanding using electrical sander

This procedure was chosen as the evaluation scenario.


1) UV-resistant surface coating or 2) Primer under hardened paint

We assess case 1


Direct exposure

Indoor/ outdoor use

Indoor and outdoor

Generation of nanomaterial during use

Likely as the use phase in this case is sanding

This product type consists of nano-TiO2 dispersed in water (http://titanprotect.de/file/pdfs/neu/PDB/PDB%20TP2221.pdf); possibly added a minor amount of stabilizer. Consequently, a highly enriched layer of nanoTiO2 will form on the surface of the treated product during drying. This layer may be coated with paint when the product is used as a primer, but will occur as a direct surface coating if applied as a UV-protective coating.


Adults and teenagers

Forseeable Yes User may sand the surfaces under poorly ventilated conditions without




http://www.titanprotect.de/deu/4_Produkte/10_Beschichtungen/51_Produkt-TP2220.html

http://www.titanprotect.de/deu/4_Produkte/10_Beschichtungen/51_Produkt-TP2220.html




390

misuse PPE Site of contact/ exposure

Direct surface contact by hands and broader dust deposition

We assess only the dermal load by direct contact with palm of hands. Palms will often touch the surface during sanding to support and the operator as well as to feel the quality of the sanding. Finally, dust remaining on the surface will normally be cleaned of by vacuuming, washing and wiping. We assess the situation of dermal load after 1 touch of a 100% covered surface layer with 100% transferred to the skin. This is assumed to roughly saturate the dermal load.


Inhalation and dermal (oral, eye)


Surface layer with 0.70 g/m2

The surface or primer layer is assumed to consist of 100% NanoTiO2. The product contains 0.7-0.9% nanoTiO2 dispersed in water. http://titanprotect.de/file/pdfs/neu/PDB/PDB%20TP2221.pdf. After drying the primer or UV-coating will consist of TiO2 alone. With 1/13 L/m2 as found in the example below, the area concentration of NanoTiO2 is on the order of 0.70 g/m2:

Volume of product used, exposed to (1)

1 L/13 m2 Example taken from Aqua Titanium Primer: http://www.beckmann.dk/da-dk/shop/indend%C3%B8rs/tr%C3%A6--metal/grunder/grunder-aqua-titanium--primer.aspx?mode=3&nav=1300000@@SHOP5 This is assumed a reasonable worst case area concentration


Hands Nordic Council of Ministers (2011): adult Nordic Council of Ministers (2011): adult


Assumed 1

R.15 v. 2.1 (ECHA, 2012)


0.28 – 1.39 g/hour

Assuming use as 100% layer of UV-protective surface coating emission rates of 1.39 and 0.28 g/hour were reached at 100 and 20% removal, respectively.

Ingested amount

minor Not assessed


0.28 – 1.39 g/hour

According to the estimate give above


0.5 hour minutes to hours


1 per year Depending on application, the product may last for up to 10 years. http://titanprotect.de/file/pdfs/neu/PDB/PDB%20TP2221.pdf

* Use “ NA “ if not given or not relevant



Step 2



section 4.2) :

Cnano in product Density of product Amount nanoTiO2 Cnano of treated surface

wt% g/ccm g nanoTiO2/L g/m2

0.9 1.006 9.054 0.70

Rate of work

m2/hour

2 1.39 0.28

handheld sander 100% removal 20% removal

Emission rate

g/hour


http://www.beckmann.dk/da-dk/shop/indend%C3%B8rs/tr%C3%A6--metal/grunder/grunder-aqua-titanium--primer.aspx?mode=3&nav=1300000@@SHOP5




391

Exposur

e route

Algorithms used Comments

/

Reference

s

Inhalatio

n

exposure

Three studies give emission data that are relevant for the current

Primer product.

Chu and Chain (2007) observed 8-127 nm-size particle emissions on the

order 280,000 particles/min/m2 during scraping on a nanoTiO2

powder coating.

Göhler et al. (2010) determined that taper abrasion-induced emission

from treating of a 13 cm2 architectural powder coating in a 30 m3 room

with no ventilation and estimated a total worst case concentration of

620 particles/cm3 air. For a 1 m2 product surface this corresponds to an

end concentration of 476,926 particles/cm3 air. The sizes of nano-

coating emissions were bimodal with peaks in the 10-30 nm and 100-

200 nm range depending on the material (ZnO and Fe2O3)

Recently Gomez et al., (2014) determined the size-resolved emission

rates between ca. 3,000 and 8,000 particles/cm3/sec during machine

sanding two different nanoTiO2-rich doped experimental paints (36

wt%) in a 0.66 m3 steel chamber. The emissions were determined to be

dominated by matrix-composite dust particles with a wide size-

distribution peaking between 400 nm and ca. 1 µm. Assuming 0.5 hour

sanding in a 30 m3 room this results in end-concentrations of 158,400

to 422,400 particles/cm3, respectively

In table 4-16, we conclude that none of the REACH tools or nano-

specific CB-like tools are currently available to make a quantitative

exposure assessment based on particle number concentrations. None of

the tools appeared to be directly applicable for consumer assessment of

sanding coatings. Consequently, a conservative mass-based exposure

estimate is made using the Tier 1 estimation of inhaled dose in R.15

(ECHA, 2012):

nBW

TIHCFD

contactairinhresp

inh

Input parameter Description Units Cinh Concentration of

substance in air of room

[mg/m3]


[-]

IHair Ventilation rate of person (adult 2.75x10-

2; teenager 2.75x10-2

m3/min

[m³/d]


[d]

BW Body weight [kg]

N Mean number of [/d]

Chu and

Chain

(2007)

Göhler et al.

(2010)

Gomez et al.

(2014)

ECHA R.15

v 2.1 (2012)

392

events per day

Output parameter

Description


[mg/kg BW d]

aveinhC , (mg/m3) was calculated according to:

30/30

1

,

i

iaveinh

V

tRC

where R = emission rate [mg/min or n/min], ti = time [min], and

V = Room volume [m3].

Using the above-mentioned estimated release rates of 0.28 and 1.39

g/hour for 20 and 100% removal, respectively and assuming sanding

for 30 min in a 20 m3 un-ventilated room (according to R.15 version

2.1; 2012) as a worst case scenario and leaving the room immediately

after sanding the average aveinhC , reaches:

18 mg nanoTiO2/m3 (peak value = 34.75) at 100% removal of the UV-

protective coating from 1 m2 product.

and

3.6 mg nanoTiO2/m3 (peak-value 7.00) at 20% removal of the UV-

protective coating from 1 m2 product.

The concentration evolution plots for these two cases are shown below.

Dermal

exposure

The external dermal load (Lder) and dose (Dder) at direct contact the procedure

by ECETOC TRA Equation R.15-5, 15-6 and 15.7 (ECHA, 2012):

D

CCTHCcmmgL

prod

derderderder

1000/

BW

nALkgmgD skinder

BWder /

ECHA

(2012)

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25 30 35

Co

nce

ntr

atio

n (

mg/

m3)

Time (min)

C(t)100% (mg/m3)

C(t)20% (mg/m3)

393

Lder: Amount of substance on skin per event (mg/cm2)

Cder: Dermal concentration of substance on skin (mg/cm2)

Dder: Dermal dose (mg/kgBW)

THder: Thickness of product on layer (assumed 0.001 cm)

Cprod: Concentration of substance in product before dilution (g/cm3)

D: Dilution factor (1 if not diluted)


n: Mean number of events per day


Oral

exposure

Expected to be negligible compared to the full body exposure

Eye

exposure

Expected to be negligible compared to the full body exposure

Step 3



REACH guidance R.15 v. 2.1, 2012: Consumer exposure assessment.




Target population: Adults and teenagers

Anatomical

/Physiological

parameters



56.8 (11-<16

years)


Retention rate 1

Skin surface (site of

contact): palm of

hands (male, female

and 11-<16 years)

50% of hand

mean surface

area (m2)

Male: 0.0535

Fem: 0.0445

Teen: 0.0360




Density 3.9 g/cm3 http://webmineral.com/data/Anatase.shtml

Daily amount NA

Application per day 1/365

Amount which may

get in contact with

skin through

splashes or direct

contact.

NA


http://webmineral.com/data/Anatase.shtml

394

Concentration of

nano-TiO2 in

product

100%

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

0.001

1oo%

Other relevant parameters for not taken into consideration in the assessment.


References

Inhalation exposure

Ventilation rate

Size-distribution

Agglomeration (coagulation)

Surface deposition

Deposition efficiencies in the airways

Indoor or outdoor use

Schenider et al.

(2011)


Oral NA

Eye NA

395

Step 4


Inhaled Dose: Adult male: Respiration volume 0.028 m3/min for moderate intensity (Nordic Ministry Council, 2012) 100% removal:

daykg

mg

kg

dayday

m

m

mg

nBW

TIHCFD

adultbw

contactairinhresp

inh

,

3

3

216.0170

24

2

1

32.40181

20% removal:

daykg

mg

kg

dayday

m

m

mg

nBW

TIHCFD

adultbw

contactairinhresp

inh

,

3

3

0432.0170

24

2

1

32.406.31

Considering that this scenario is repeated once every year, the average annual exposure dose is also 0.216 and 0.0432 mg/kgbw,maleYear at 100 and 20% removal of the TiO2 coating, respectively.

For an adult female the all inhalation values will be 14.3% higher per kg bodyweight.

Teenager (11-<16 years):

Inhaled Dose: Respiration volume 0.025 m3/min for moderate intensity (Nordic Ministry Council,

2012)

100% removal:

daykg

mg

kg

dayday

m

m

mg

nBW

TIHCFD

teenagerbw

contactairinhresp

inh

,

3

3

238.018.56

24

2

1

36181

20% removal:

daykg

mg

kg

dayday

m

m

mg

nBW

TIHCFD

teenagerbw

contactairinhresp

inh

,

3

3

0475.018.56

24

2

1

44.376.31

396

Considering that this scenario is repeated once every year, the average annual exposure dose is also

0.238 and 0.0475 mg/kgbw,teenYear at 100 and 20% removal of the TiO2 coating, respectively.

Dermal exposure dose:

Dermal load is estimated considering exposure and 100% transfer to skin of a 0.1 mm thick sanding

debris entirely consisting of nanoTiO2

2

3

29.3

1

10009.3

001.01000

cm

mgcm

g

cmD

CCTHC

cm

mgL

prod

derderderder

Adult Male: Inner half of hand: 535 cm2; 70 kg according to Nordic Council of Ministers (2011)

maleBW

skinder

BW

derkg

mg

kg

cmcm

mg

BW

nAL

kg

mgD

,

2

2

81.2970

15359.3

Adult female: Inner half of hand: 445 cm2; 60 kg according to Nordic Council of Ministers (2011)

femaleBW

skinder

BW

derkg

mg

kg

cmcm

mg

BW

nAL

kg

mgD

,

2

2

93.2860

14459.3

Teenager: Inner half of hand: 535 cm2; 56.8 kg according to Nordic Council of Ministers (2011)

teenBW

skinder

BW

derkg

mg

kg

cmcm

mg

BW

nAL

kg

mgD

,

2

2

72.248.56

13609.3

In all cases, because the scenario is 1 time per year, the daily dermal dose is also the annual dose.

Summary Table: Estimated inhalation and dermal dose for females, males and teenagers during

sanding of nano-TiO2 product 100 and 20 %.

Nano-TiO2

covering

removal

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

Inhalation

[µg/kg]

Dermal

[mg/kg]

Oral

[mg/kg]

Inhalation

[µg/kg]

Dermal,

[mg/kg]

Oral

[mg/kg]

100 % f 247

m 216

f 28.93

m 29.81 NA 238 24.72 NA

20 % f 49.4

m 43.2

f 28.93

m 29.81 NA 47.5 24.72 NA

397

Step 5



Based on literature data on emission characteristics of sanding dust (e.g., Hsu and Chein, 2007;

Göhler et al., 2010; Gomez et al., 2014), it is assumed that all emitted particles are in the respirable

fraction and dominated by particles between 10 and 200 nm. However the deposition efficiency of

the respirable fraction is not 100% as it is assumed in Tier 1 of R.15 (ECHA, 2012). In addition, in

the inhalation scenarios, the airborne exposure concentrations are set very conservative by

assuming that the surface layer consists of 100% nanoTiO2 and dispersing the sanding emission

into 20 m3 volume of the standard small room recommended in R.15 without ventilation. Normally

sanding is expected to occur under better indoor ventilated conditions or outdoors with high rate of

ventilation and dilution and in both cases during use of personal respiratory protection. In small

rooms, it can be assumed that the ratio between near-field source exposure concentrations and the

average room concentrations of respirable particles approach unity.

If this type of process is conducted for extended durations of time or with higher frequency the

potential exposure increases dramatically. However, due to the modifying factors not considered in

this assessment, more advanced modelling is required to assess the potential exposure levels and

doses in such cases.

The dermal exposure was assessed for palms touching the sanded surface with 100% loose

NanoTiO2 resulting in a 0.001 cm layer transferred onto the skin. Dermal exposure from aerosol

deposition, changing sanding paper and cleaning the sanded surface etc. was not considered. Even

though the dermal deposition may be higher, it is assumed that at least the maximum possible palm

concentration was close to being reached in the given calculations. Additional dermal exposure will

occur on other skin surfaces accessible for dust. However, the assumption of the 100% efficient

transfer from the sanded surface to inner hand is a high estimate. The exact transfer and possible

load of nanoTiO2 and sanding dust is not known at this point as well as the deposition efficiency of

airborne dust onto accessible skin.

Direct oral exposure was assumed negligible. Oral uptake would come from NanoTiO2 deposited in

the nose and mouth as well as brought up along the mucusilary escalator from the respiratory tract.

(is implicitly covered by the inhaled dose). Some NanoTiO2 may also enter the gastro-intestinal

tract from lips and inadvertent hand to mouth dust transfer.

Overall, the assessment of daily dose should be used with caution as the results rely mostly on

model and worst case exposure considerations. It is, however, evident that this type of process is

associated with high risk of very high peak exposure concentrations to both airways and skin.


The calculated scenario is relevant for a sanding a specific group of surface coatings including

primer paints, particle-based or solid nanoscale surface coatings as well as paints with very high

loads of specific nanocompounds. The calculations are assumed to consider typical worst case

scenarious. However, quantitative measurements are still needed to buld the knowledge base and

perform more accurate exposure assessments.

It should also be noted that consumers may also be exposed from Nano-TiO2 from other sources

such as cosmetics, from textiles where TiO2 is added as UV-filter, and from other coatings and inks.

Furthermore nano-TiO2 may be released from different articles/matrices.

398




References:



ECHA (2012): Guidance on information requirements and chemical safety assessment. Chapter

R.14: Occupational exposure estimation. Version: 2.1, November 2012

Hsu LY, and Chein HM. 2007. Evaluation of nanoparticle emission for TiO2 nanopowder coating

materials. Journal of Nanoparticle Research 9 (1): 157-163.

Göhler D, Stintz M, Hillemann L and Vorbau M. 2010. Characterization of nanoparticle release

from surface coatings by the simulation of a sanding process. Annals of Occupational Hygiene

54(6), 615-624.

Gomez V, Levin M, Saber AT, Irusta S, Del Maso M, Hanoi R, Santamaria J, Jensen KA, Wallin H,

and Koponen IK, 2014. Comparison of dust release from epoxy and paint nanocomposites and

conventional products during sanding and sawing, Annals of Occupational Hygiene, 2014, 1-12 e-

pub ahead of print. doi:10.1093/annhyg/meu046.

Schneider T, Brouwer D, Koponen IK, Fransman W, Jensen KA, van Duuren-Stuurman B, van

Tongeren M & Tielemans E., 2011. Conceptual model for assessment of inhalation exposure to

Manufactured Nanoparticles. Journal of Exposure Science and Environmental Epidemiology 21,

450–463.

399

Scenario 11 - Product: Paint with Nano-Ag 8.12

Description of exposure scenario: Case 11: Spray painting surface

Step 1



Parameter Specified data*

Estimated*


Product category


http://www.bioni-living.de/MycoSolan

Type of Product

Antibacterial and fungicide paint


ID of nanomaterial

Ag-complex

NanoAg It is assumed that the Ag is added as NanoAg to the paint. The product data-sheet claims “Silber-Komplex”


NA NA NA

The product data-sheet claims “Silber-Komplex”, which may mean that the Ag is not present as ions and not as nanoparticles.


Acrylic paint matrix



5L; 10L http://www.bioni-living.de/MycoSolan


brush, roller, or spray

http://www.bioni-living.de/MycoSolan. Only the spray scenario is assessed in this evaluation.


Ag is in a liquid matrix


Direct exposure

Indoor/ outdoor use

Indoor The specific type of Ag-paint is intended for indoor use, but outdoor types also exist.


Unlikely The matrix is acrylic paint and consumers will typically apply brush or roller in indoor applications. In the worst case, a spray gun may be applied.



Forseeable misuse

Yes Application using spray gun and without requested use of gloves, glasses, mask, and ventilate the working area.

Site of contact/ exposure

Direct surface contact by unprotected

We assess the dermal load by direct dermal contact on hands and aerosol deposition of overspray.






400

hands, deposition of aerosol/ dripping/ splashes


Inhalation and dermal


1% http://www.bioni-living.de/MycoSolan does not report in any composition data. We assume that the concentration is lower than 1 wt% as a worst case assumption.


0.35 mL /m2

http://www.bioni-living.de/MycoSolan. This is the amount to be used according to the supplier example.


Face Hands

Nordic Council of Ministers (2011): adult Nordic Council of Ministers (2011): adult


Assumed 1

R.15 v. 2.1 (ECHA, 2012)


none It is not expected that nanoAg is liberated from the liquid paint matrix

Ingested amount

minor Not assessed


17.25 g/min

5 m2 can be painted in 12 min (600 ml chamber) when using a spray gun. http://byg1.dk/shop/bosch-pfs55-sproejtepistol-3132p.html. This gives a release rate of 600 mL/12 min = 50 mL/min (57.5 g/min at a density of 1.15 g/cm3 from http://www.bioni-living.de/MycoSolan) and a coverage rate of 5 m2/12 min = 0.417 m2/min. Using a default deposition efficiency for air-less spraying of 0.70 (Brouwer et al., 2001), the total paint overspray released to air becomes: (1.0-0.7) x 57.5 g/min = 17.25 g/min. It should be noted that this fraction is not only the inhalable paint dust, but also include the size-fraction that can not reach the airways.


0.5 hour Painting can take between minutes and hours. However, using the spray rate above and a 20 m3 standard room (R.15 v.2; ECHA, 2012) resulting in a wall area of 8.7 m2 (assuming ceiling height 2.3 m), the entire work duration is set to 8.7 m2/0.417 m2/min = 20.86 min + paint gun refilling time = 30 min.


once day every 5 years

Indoor paints can last for several years. Painting every 5 years is a conservative guess.






http://byg1.dk/shop/bosch-pfs55-sproejtepistol-3132p.html

http://byg1.dk/shop/bosch-pfs55-sproejtepistol-3132p.html


401

Step 2



section 4.2) :

Exposu

re route

Algorithms used Comment

s/

Reference

s

Inhalatio

n

exposure

One previous relevant exposure assessment of spray painting was

conducted in the NANEX project (2010) considering a water-based paint

with 25 wt% nanoTiO2. They found an average airborne concentration of

1.7 mg nanoTiO2/m3 (recalculated this equals 6.8 mg paint dust/m3)

using the ConsExpo model for 25 min application. The inhalational

exposure dose was estimated to be 0.0157 mg nanoTiO2/kgBW. The Ag-

doped paint considered here contains < 1 wt%. Therefore direct

conversion of the NANEX scenario would result in 0.068 mg Ag/m3 and

an inhaled dose of 0.000628 mg/kgBW, i.e. 0.638 µg Ag/kgBW.

There appears in general to be a lack of relevant exposure measurement

data on painter using sprays and on the number size-distribution

measurements of overspray aerosols from spray painting; i.e. the spray

droplets that are aeroslized but do not deposit on the intended object. No

studies were found to describe the overspray and mass- or particle size-

distributions from spraying nanoparticle-doped paints.

A relevant study by Sabty-Daily et al. (2005) showed that the Mass

Median Aerodynamic Diameter (MMAD) of overspray from a water-

reducing epoxy-paint primer varied from 8.22.4 µm at 6 psi to 7.23.1

µm at 10 psi, respectively. Hence, the overspray aerosol can be expected

to be inhalable and to some extent respirable. Results from an analysis

based on the overspray size-distributions in the Sabty-Daily study

suggested that 88% of the mass would deposit in airways of the head

region and 3-4% would deposit in the tracheo-brachio-alveolar region.

ConsExpo has previously been used to assess the inhalation exposure to

spray paint in the NANEX study. We converted the results from this

study to the current scenario above.

In addition, a more conservative mass-based assessment of the

inhalation exposure estimate is made using the traditional Tier 1

estimation of inhaled dose in R.15 (ECHA, 2011):

nBW

TIHCFD

contactairinhresp

inh



[mg/m3]


[-]

NANEX

(2010) /

ConsExpo

Sapty-Daily

et al.

(2005)

ECHA

(2011)

402

IHair Ventilation rate of person (adult 2.7x10-2; teenager 2.6x10-2

m3/min

[m³/d]


[d]

BW Body weight [kg] N Mean number of

events per day [/d]

Output parameter

Description


[mg/kg BW d]


30/30

1

,

i

iaveinh

V

tRC ,

where R = emission rate [mg/min or n/min], ti = time [min], and


Using the above-mentioned estimated release rate of 17.25 g/min and a

total exposure time of 0.5 hour (effective spraying for 20.8 minutes in a

20 m3 un-ventilated room (according to R.15 version 2.1; 2012)) adding 7

minutes for refilling time after first 600 ml use at ti = 16 to 22 min) as a

worst case scenario and leaving the room immediately after painting is

completed, the average aveinhC , reaches:

10,948 mg total paint dust/m3 (peak value = 19,665 mg/m3) after 30

min.

Assuming the Ag content to be 1 wt%, the Ag concentration is thus:

0.01 x 10,948 = 109.48 mg Ag/m3 (peak value = 196.65 mg Ag/m3).

These concentration values are rather high and as they are derived from

the overspray assumption the concentrations include the total size-

distribution of paint not adhering to the painted surface, including non-

inhalable large droplets. The fraction of respirable paint dust is not

known.

The temporal evolution in Cinh,ave is illustrated in the below.

Time-

weighed

average

exposure

concentrati

on

403

Dermal

overspra

y

depositio

n

O

DPWVVEVCTVM

sprayNTsprayCOI

TOT

01.01

MTOT: Emission rate onto painter (mg)

V: Volume rate of spraying (L/min)

T: Duration of spraying task (min)

CCOI: Concentration of compound of interest (mg/L)

product density multiplied with weight fraction of

compound

spray: Deposition efficiency of selected spray-technique (%; expressed as

decimals). Defaults:

compressed air spraying: 0.35

airless spraying: 0.70

electrostatic spraying: 0.80

EV: Evaporation rate (dimensionless factor)

Non-volatile compounds: 1

Volatile fractions in warm and high air-movement

conditions: 0.3

Volatile fractions in cold and low air-movement

conditions: 1

VNT: Ventilation factor (dimensionless factor). Defaults:

Enclosed spaces: 1

Natural/general ventilation: 0.3

Local exhaust ventilation: 0.1

WV: Worker orientation factor (dimensionless factor). Default values:

Air movement towards worker at 180° orientation: 3

Air movement to the side of the worker: 1

Brouwer et

al. (2009)

0

5000

10000

15000

20000

25000

0 10 20 30 40

Time (min)

C(t

) (m

g/m

3)

C(t) (mg/m3)

404

Dermal

overspra

y dose

Air movement at indefinite direction (90° orientation): 1

Air movement from the worker at a 180° orientation: 0.3

P: Posture factor (dimensionless factor). Defaults:

Stretched normal position: 1

Bent or 180 deviation: 0.3

Position aside air-stream: 0.1

D: Distance factor (dimensionless factor). Defaults:

Recommended spray distance: 1

Closer than recommended spray distance: 3

Further away than recommended spray distance: 0.3

O: Object factor (dimensionless factor for the shape of treated material).

Defaults:

Flat densely structured items: 1

Open-structure or absorbiong pieces: 3

Enclosed special-shaped opjects: 0.3

In this scenario a conservative value of 1 is chosen for all the

parameters

MTOT is thereafter adjusted to calculate the dermal dose per kgBW

adjusted to the normal worst-case un-covered dermal area (face and

hands).

BW

FQMkgmgD TOT

BWoversprayder /,

Following a simple adjustment of the procedure in ECETOC TRA in R.15.

v 2.1 (ECHA, 2012)

Dder,overspray: Dermal dose (mg/kgBW)

FQ: Surface of exposed skin (cm2)


Modificatio

n of

ECETOC

TRA

(ECHA,

2011)

Dermal

contact

exposure

The external dermal load (Lder) and dose (Dder) at direct contact the

procedure by ECETOC TRA Equation R.15-5, 15-6 and 15.7 (ECHA,

2012):

D

CCTHCcmmgL

prod

derderderder

1000/

BW

nALkgmgD skinder

BWder /



ECHA

(2011)

405








Oral

exposure

Relevant, but not assessed

Eye

exposure


Step 3

For the identified target population, relevant values for anatomical/physiological parameters are







Anatomical

/Physiological

parameters


Body weight 70 kg (male)

60 kg (female)

71.6 (16-<21

years)


Retention rate 1

Skin surface (hand,

head):

(male and female

41 - <51 years old;

teenager 16 - <21

years old)

50% of hand area

60% of head area

Total regional dermal areas

Nordi

c Council of Ministers (2011)

Dermal area

Men

40<50

Women

40<50

Teen 16-

21y

Hands (cm2) 1118.0 906.2 828.0

Head (cm2) 1419.0 1170.6 754.4

Total (cm2) 21500 18880 18400

Density 10.5 g/cm3 http://webmineral.com/data/Silver.shtml#.U_nII8XV9c

Q

Daily amount NA

Application per year 1 Only once every some years (1 time every 5 years in this

http://webmineral.com/data/Silver.shtml#.U_nII8XV9cQ

http://webmineral.com/data/Silver.shtml#.U_nII8XV9cQ

406

case)

Amount which may

get in contact with

skin through

splashes or direct

contact.

Assessed from the

area of hands and

film thickness.

Concentration of

nano-Ag in product

1% For assessment, a concentration of 1 wt% was used. The

true values are likely lower than 1 wt%. The mass-

concentration is 11.5 g/L at density 1.15 g/cm3

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

1 mm

100%

In accordance with R.15 v. 2.1 (ECHA, 2012)

Step 4


Male Adult (41 - <51):


2012).

daykgmgAgkg

dayday

m

m

mg

nBW

TIHCFD maleBW

contactairinhresp

inh ,

3

3

/314.1170

24

2

1

32.4048.1091

Dermal overspray dose:

O

DPWVVEVCTVM

sprayNTsprayCOI

TOT

01.01=

mgAgL

mgL

M AgTOT 188.251

1)7.001.0(11117.0111500min86.20min

05.0

,

maleBW

TOT

BWoversprayder kgmgAgkg

cm

cmcmmgAg

BW

FQMkgmgD ,

2

22

, /0236.070

21500

14196.011185.0188.25

/

In this exposure estimate the dermal area accessible for exposure is assumed to be 50% of hands

and 60% of head region. This exposure dose must be normalized for the entire body area as the

overspray considers the entire body.

407

Dermal contact dose (inner side of hands):

23

2 /115.001.01

10000115.01000/ cmmgcm

g

D

CCTHCcmmgL

prod

derderderder

maleBWskinder

BWder kgmgkg

cmcmmg

BW

nALkgmgD ,

22

/918.070

11185.0/115.0/

Female Adult (41 - <51):


2012)

daykgmgAgkg

dayday

m

m

mg

nBW

TIHCFD femaleBW

contactairinhresp

inh ,

3

3

/533.1160

24

2

1

32.4048.1091

Dermal overspray dose adult female:

O

DPWVVEVCTVM

sprayNTsprayCOI

TOT

01.01=

mgAgL

mgL

M AgTOT 188.251

1)7.001.0(11117.0111500min86.20min

05.0

,

femaleBW

TOT


cm

cmcmmg

BW

FQMkgmgD ,

2

22

, /0257.060

18880

6.11706.02.9065.0188.25

/

In this exposure estimate the dermal area accessible for exposure is assumed to be 50% of hands and 60% of head region. This exposure dose must be normalized for the entire body area as the overspray considers the entire body.


23

2 /115.001.01

10000115.01000/ cmmgcm

g

D

CCTHCcmmgL

prod

derderderder

BW

skinder

BWder kgmgkg

cmcm

mg

BW

nALkgmgD /868.0

60

2.9065.0115.0

/

2

2

Teenager (16 - <21 years):

408

Inhaled Dose: Respiration rate 0.026 m3/min for moderate intensity; body-weight = 71.6 kg

(Nordic Minister Council report; 2012):

daykgmgAgkg

daymm

mg

nBW

TIHCFD maleBW

contactairinhresp

inh ,

3

3

/193.116.71

24

2

2

44.3748.1091

Dermal overspray dose:

O

DPWVVEVCTVM

sprayNTsprayCOI

TOT

01.01

mgAgL

mgL

M AgTOT 188.251

1)7.001.0(11117.0111500min86.20min

05.0

,

teenagerBW

TOT


cm

cmcmmgAg

BW

FQMkgmgD ,

2

22

, /0167.06.71

18400

4.7546.08285.0188.25

/

In this exposure estimate the dermal area accessible for exposure is assumed to be 50% of hands

and 60% of head region. This exposure dose must be normalized for the entire body area as the

overspray considers the entire body.


BWskinder

BWder kgmgkg

cmcm

mg

BW

nALkgmgD /665.0

6.71

8285.0115.0

/

2

2


spray painting with a Nano-Ag paint

Nano-Ag

paint

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

(1621 years)

Inhalation

[mg/kg]

Dermal

overspray

[mg/kg]

Dermal

contact

[mg/kg]

Inhalation

[mg/kg]

Dermal

overspray

[mg/kg]

Dermal

contact

[mg/kg]

100 % f 1.533

m 1.314

0.0257

0.0236

0.869

0.918 1.193 0.0167 0.665

Step 5

409



It is not verified whether this product contains nanoparticulate or ionic silver and the concentration

is not specified. In the assessment, it is assumed that the product contains 1 wt% silver

nanoparticles. The amounts of Ag in paints is not thought to exceed 1 wt%. The amounts and

physical form of the Ag needs generally to be better clarified for this type of products and silver-

based products in general. The assumptions taken on the product and the exposure scenarios are

assumed to represent worst case sitations for the paint area covered. See below.

In the inhalation scenarios, the airborne exposure concentrations are set very conservative as the

exposure was assessed as a spray case (air-less), the ventilation was set to zero and the 20 m3

volume of the standard room in R.15 is rather small. Moreover, the consumer exposure was

assessed without taking into consideration that the user should wear gloves, mask/respirator and

eye-protection in addition to full-body suite. The existing exposure measurement data are scarce

and do not include measurement of Ag-containing paints applied using a spray gun. No data

appears to be available showing the entire size-distribution during spraying this type of paint in

different scenarios. In the exposure assessment, we assume no mask is used by the consumer and a

100% air-way deposition efficiency. If painting of significantly larger areas are to be assessed, it is

recommended to use more advanced modelling and obtain further data on the products.

The dermal contact exposure was assessed for overspray as well as inner hands touching a newly

painted surface with 100% transfer from the exposed area to the hand. This assumption appears to

be a worst case estimate.

Eye and oral exposure was assumed negligible. Oral uptake would come from NanoAg deposited in

the nose and mouth as well as brought up along the mucusiliary escalator from the respiratory tract

and finally by accidental uptake via hand-to-mouth transfer. The inhaled dose implicitly covers the

worst case gastro-intestinal exposure that could arise from the inhalation pathway. Some NanoAg

may also enter the gastro-intestinal tract from lips and inadvertent hand to mouth dust transfer.

This exposure is not accounted for in this assessment.


Consumers may also be exposed from nano-Ag from other sources such as jewellery, cosmetics,

textiles, humidifiers, and from other coatings and food supplements.




References:



ECHA, 2012. Guidance on information requirements and chemical safety assessment. Chapter R.15:

Consumer exposure estimation. Version: 2.1, November 2012.




410

Brouwer DH, Semple S, Marquart J, and Cherrie JW, 2001. A dermal model for spray

painters. Part I: Subjective exposure modelling of spray paint deposition. Annals of

Occupational Hygiene, 45/1. 15-23.

Micheletti C, Gerritsen R, Schmid K, Brouwer DH, Peters S, Gaelle U, Christensen F, 2010.

Development of Exposure Scenarios for Manufactured Nanomaterials. Work Package 4: Consumer

Exposure Scenarios. NANEX Project. 145 pp.




450–463.

411

Scenario 12 - Product: Surface impregnation product with silica 8.13

(silane/siloxane technology?)

Description of exposure scenario: Case 12: Coating counter-top surface by a spray

Step 1




Estimated*


Product category


http://www.nanosafeguard.com/cooktop_treatment.html http://www.nanocover.dk/shop/nanocover-bad-fliser-180p.html

Type of Product

Easy to clean; Impregnation


ID of nanomaterial

Silica? A critical review of the products listed as containing silica in the

Woodrow Wilson database and the Danish “nanodatabasen” at

“Tænk” reveals that there is no evidence of this group of house-hold

products to contain silica or silicon dioxide. At nanosafeguard, a label

reports S1O2 hydrophobic chemistry and that the ingredients

chemically bind to the surface. (The other reference is NanoCover

Denmark, but they do not claim that their product contains silica.

Instead they refer to chemical nanotechnology. This is in accord with

chemical analysis by Nørgaard et al. (2009) identifying siloxane and

fluorosilane as the active ingredients in this type of products and no

presence of silica was found. Hence, that these products for indoor

use are based on nanofilm technology rather than a nanoparticle

technology, even-though nanofilm technology with nanoparticles

may have better performance. In this assessment, we consider the

products to potentially contain silica. Characterisation, e.g. size distr. Size Crystal form

NA NA NA


Liquid matrix. Alcohol Ethanol



2 oz (2.835 g) 75ml to 1L



spray (recommended onto cloth or sponge) and then add to surface with

http://www.bioni-living.de/MycoSolan http://www.nanocover.dk/shop/nanocover-bad-fliser-180p.html

http://www.nanosafeguard.com/cooktop_treatment.html















412

wipe/ sponge


In liquid


Direct exposure

Indoor/ outdoor use

Indoor The specific type of product is intended for indoor use, but outdoor types also exist.


possibly Both alcohol and water-based “nano-pump-spray” have been shown to generate nanoparticles during use; both with and without presence of solid nanomaterials in dispersion (Nørgaard et al., 2009). A nanoTiO2-based product produced approximately the same amount and size-characteristics of airborne particles as silane- and siloxane-based products.


Adults

Forseeable misuse

Yes The spray may be misused for direct spray onto surfaces rather than spraying on a wipe or sponge for subsequent surface treatment.


Direct spray on unprotected hands or sponge and surface contact by un-protected hands

Dermal exposure may occur from aerosol deposition of overspray on wipe/sponge or (as unintended) on the surface to be treated as well as during wiping and polishing and direct surface contact, if the consumer is not wearing the recommended personal protection.




NA <1% This concentration is inferred, because the composition and concentration are not reported in the safety or technical data sheets. One of the products found is rather expensive (10.7 USD/ml) as compared to known silane/siloxane products (ca. 0.12 to 0.40 USD/ml) and it could be inferred that the loading in the expensive product is much higher or different than in less expensive products.


NA 2.6 - 200 mL

The volume product required depends entirely on the product type and size of the objects to be treated. As minimum volume observed, a cook-top treatment can be purchased in 2 oz pumps (ca. 2.8 mL) http://www.nanosafeguard.com/cooktop_treatment.html. This bottle is for treatment of 50 square-feet (5.4 m2). Another product in the same surface-treatment category requires 10-25 ml/m2. http://www.nanocover.dk/images/shopdownloadfiles/045.01.%20Bad%20+%20Fliser.V.pdf A third comparable product requires 25-50 ml/m2. http://www.nanocover.dk/images/shopdownloadfiles/045.10.


http://www.nanocover.dk/images/shopdownloadfiles/045.01.%20Bad%20+%20Fliser.V.pdf

http://www.nanocover.dk/images/shopdownloadfiles/045.01.%20Bad%20+%20Fliser.V.pdf

http://www.nanocover.dk/images/shopdownloadfiles/045.10.Tr%C3%A6%20+%20Sten.V.pdf

413

Tr%C3%A6%20+%20Sten.V.pdf We assume treatment of a 5 m2 counter top.

Body area exposed to

Hands Nordic Council of Ministers (2011): adult

Retention rate on body surface

Assumed 1

R.15 v. 2.1 (ECHA, 2012)


None

Ingested amount

NA Not assessed


unknown See discussion below


30 min 1 min

inhalation dermal (hand exposure); here the assumption is 50% coverage of hand once.


2 per year

The coatings may last from 1 to several years. It is recommended to make two treatments the first time and then treating the surface once a year.




Step 2



section 4.2) :

Exposure

route

Algorithms used Comments/

References

Inhalation

exposure

Nørgaard et al. (2009) analysed the particle and gas-phase

release to room air during use of nanoTiO2-, silane-, siloxane-

based nanofilm pump-spray products. They products were

intended for direct spray application onto surfaces using in

consumer-type pump-sprays. Particles measured 20 cm

behind the spray nozzle were in the respirable range with a

number peak-size around 100 nm and no particles larger than

3 µm were observed. The aerosol emission rate of the water-

solvent nanoTiO2 spray was ca. 3.1 108 particles/ml and it

showed a stable peak size at ca. 170 nm. A simple exposure

assessment showed that the particle concentration during use

could result in ca. 6103 particles/cm3 (authors’ correction)

after treating 7 m2 surface in a 17.4 m2 unventilated standard

room. For silane + siloxane products with 1 wt%, the emission

could in the worst case reach ca. 1.4 mg/m3 (authors’

correction) assuming no deposition of particles of chemicals.

Nørgaard et al.

(2009)

http://www.nanocover.dk/images/shopdownloadfiles/045.10.Tr%C3%A6%20+%20Sten.V.pdf

414

Converting these results to the silica spray products in this

study and treatment of 5 m2 countertop in 17.4 m3 room

would result in ca. 4300 particles/cm3 and a nanosilica

concentration of 1 mg/m3. However, it should be notified that

part of the silane / siloxane in the above-mentioned study is

volatile and the values for nanoTiO2 may therefore be lower.

Michel et al. (2013) performed a human and environmental

risk assessment of a commercial pump-spray glass-cleaner

with 0.09 wt% ca. 10 nm-size colloidal silica in water with

some additives. Spray tests performed to analyse the size-

distribution (lower size-limit 500 nm) of emission spray

droplets formed directly at spray head showed only large µm-

size droplets with 90 vol% of the spray droplets being larger

than 28-34 µm and a 50 vol% at 75-95 µm. An exposure

assessment was completed in ConsExpo 4.1 assuming 0.1 wt%

silica, 3 applications per day in use, mass-generation rate 2

g/sec (1 stroke per sec), 30 sec spray per room (60 g product),

exposure duration 10 min per room, room size 58 m2,

ventilation rate 0.5 h-1, median particle size 100 µm,

distribution coefficient 0.6, inhalation cut-off 100 µm, uptake

fraction 1 of the inhalable fraction, inhalation rate 32.9

m3/day (default for light exercise for 60 kg person). The result

from the ConsExpo scenario predicts an 10 min average silica

inhalation exposure level of 0.002 mg/m3 (peak

concentration 0.035 mg/m3). Direct spraying onto a person

would result in a 10 min average of 0.044 mg/m3.

Conversion to the 1 wt% product concentration used in this

assessment, and the use data by Michel et al. (2013) would

result in a 10 times higher exposure level. In addition,

reducing the room size to the 20 m3 typical for worst case

assessment, the concentration would finally reach on the

order of 0.06 mg silica/m3 for application of 60 mL product

(0.02 mg/mL).

The two case studies show differences with a factor greater

than 10 in the exposure levels estimated from read across.

For comparison with the above-mentioned indicative data,

the silica-based spray products mentioned above are assessed

for their inhalation dose using the traditional Tier 1

estimation of inhaled dose in R.15 (ECHA, 2011):

nBW

TIHCFD

contactairinhresp

inh

Input

parameter Description Units


[mg/m3]

Michel et al.

(2013)

ECHA (2011)

415


[-]


[m³/d]


[d]

BW Body weight [kg]


[/d]

Output parameter

Description


[mg/kg BW d]

For Cinh the two cases by Nørgaard et al. (2009) and Michel et

al. (2013) suggest that inhalable airborne concentrations

could reach 1 and 0.06 mg silica/m3, respectively. The

volumes required for treatments in these two cases, however,

appear to be very different. This is also the case for the

products found in the product description where between 2.5

and 200 mL is required to treat the same surface area. The

highest volume, is however, considered for materials with

some porosity, such as concrete. Due to apparent higher

product similarity with the Nanosafeguard product, we

assume that 2.5 mL is required for treatment of 5 m2 as this is

the product claimed to contain silica in the Woodrow Wilson

database. As a worst case, it is also assumed that the 2.5 mL

product is sprayed directly onto the countertop or onto

sponge with a similar distance between the nozzle and the

sponge in a room with no ventilation. The duration of

application is 10 min and the entire exposure duration is 30

min. The total concentration, aveinhC , was then 0.002125

mg/m3 calculated according to:

30/30

1

,

i

iaveinh

V

tRC ,

where R = emission rate [0.005 mg silica/min], ti = time

[min], and V = Room volume [20 m3].

The temporal evolution of the room concentration is shown

below.

416

Dermal

overspray

exposure

No applicable model

Dermal contact

exposure

The external dermal load (Lder) and dose (Dder) at direct

contact the procedure by ECETOC TRA Equation R.15-5, 15-6

and 15.7 (ECHA, 2012):

D

CCTHCcmmgL

prod

derderderder

1000/

BW

nALkgmgD skinder

BWder /





Cprod: Concentration of substance in product before dilution

(g/cm3)





ECHA (2011)

Oral exposure

Not assessed

Eye exposure


Step 3





0.E+00

5.E-04

1.E-03

2.E-03

2.E-03

3.E-03

3.E-03

0 10 20 30 40

Time (min)

C(t

) (m

g/m

3)

C(t) (mg/m3)

417




Anatomical

/Physiological

parameters



60 kg (female)

71.6 (16-<21

years)


Retention rate 1

Skin surface (hand,

head):

(male and female 41

- <51 years old;

teenager 16 - <21

years old)

50% of hand area Total regional dermal areas


Dermal area Men

40<50 Women 40<50

Teen 16-21y

Hands (cm2) 1118.0 906.2 828.0

Total (cm2) 21500 18880 18400

Density 2.25 g/cm3 Roberts (2006)

Daily amount NA once every year

Application per year 1 Once every year

Amount which may

get in contact with

skin through

splashes or direct

contact.

Assessed from the

area of the hands

Concentration of

nanomaterial in

product

1% For assessment, a concentration of 1 wt% was used.

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

0.1 mm

100%


418

Step 4




2012)

daykgµgkg

daymm

µg

nBW

TIHCFD maleBW

contactairinhresp

inh ,

3

3

/051.0270

24

2

1

32.40125.21


23

2 /01.0001.01

100001.01000/ cmmgcm

g

D

CCTHCcmmgL

prod

derderderder

maleBWskinder

BWder kgmgkg

cmcm

mg

BW

nALkgmgD ,

2

2

/080.070

11185.001.0

/

For all cases, the daily dose is also the annual dose.



2012)

daykgµgkg

daymm

µg

nBW

TIHCFD femaleBW

contactairinhresp

inh ,

3

3

/0595.0260

24

2

1

32.40125.21


23

2 /01.0001.01

1000/01.01000/ cmmg

cmg

D

CCTHCcmmgL

prod

derderderder

BWskinder

BWder kgmgkg

cmcmmg

BW

nALkgmgD /0755.0

60

2.9065.0/01.0/

22


419




daykgµgkg

daymm

µg

nBW

TIHCFD teenBW

contactairinhresp

inh ,

3

3

/0463.026.71

24

2

1

44.37125.21


BWskinder

BWder kgmgkg

cmcmmg

BW

nALkgmgD /056.0

6.71

8285.0/01.0/

22



treatment of a countertop using a (assumed) silica spray.

Nano-TiO2

covering

removal

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

(1621 years)

Inhalation

[µg/kg]

Dermal

overspray

[mg/kg]

Dermal

contact

[mg/kg]

Inhalation

[µg/kg]

Dermal

overspray

[mg/kg]

Dermal

contact

[mg/kg]

100 % f 0.0595

m 0.0510 NA

0.080

0.076 0.0463 NA 0.056

Step 5



This exposure assessment is highly uncertain and values range from 0.06 to 1 mg/m3 using read

across from a silica nanospray (Michel et al., 2013) and a nanoTiO2 spray (Nørgaard et al., 2009),

respectively to 0.0021 mg/m3 in a case-specific scenario based on published results on the silica

nanospray. However, the assessment has uncertainties on the formulation and concentration in the

product, the relevant scenario on product group level, the amount of product required to treat the

surface, the release characteristics.

First, it is doubtful that the specific products identified in the data bases, for which the current

scenario was build, do contain silica in suspension, at all. However, literature data does report silica

in relevant products on the European market (Michel et al., 2013). There are likely two groups of

products of which one may contain silica and the other only contain silanes or siloxanes. In neither

of the cases, there are explicit information on the amount of the ingredients in the products. The

amount of product required for treatment was found highly variable and ranging from 0.5 to 50

mL/m2. The variation may be related to the ingredients, but also to the type of surface treated. In

the case presented here, we assume 0.5 mL/m2 as this was the value for the most similar product in

Michel et al. (2013). However, the emission and exposure characteristics determined for this

420

product may not fully reflect reality as big controversy exist between the data for a silica pump

spray in Michel et al. (2013) and the nanoTiO2 pump spray in Nørgaard et al. (2009). Nørgaard

found that all airborne particles were respirable and below 4 µm in size with peaks in the nanosize

range as they measured the airborne particles behind the spray nozzle. However, the amount of

nanoTiO2 was not quantified. Michel et al. (2013) found that all airborne particles were inhalable

and above 10 µm in size as they measured the emission from the spray nozzle. Many differences

may be ascribed to different test methods and differences in the spray configurations. The

differences call for the need to have specific emission characteristics and source strengths from

specific products.

To consider the relevant worst case, the REACH-based consumer exposure assessment was

completed without taking into consideration that the user should wear gloves and mask and work in

a ventilated area. In the exposure assessment, we assume no mask is used by the consumer and a

100% air-way deposition efficiency, because the published data suggest that the entire airborne

fraction is surely inhalable. As discussed above high uncertainty still exist on the relevant size-

distribution.

The dermal contact exposure was assessed for as inner hands touching a newly treated surface (0.1

mm) with 100% transfer from the exposed area to the hand. This assumption is a worst case

estimate.

Eye and oral exposure was assumed negligible. Oral uptake would come from nanomaterial

deposited in the nose and mouth as well as brought up along the mucusiliary escalator from the

respiratory tract and finally by accidental uptake via inadvertent hand-to-mouth transfer. The

potential for oral exposure by inhalation is however in part covered by assuming 100% of the

inhalational dose (expressed in ug/kg bw/d) is swallowed. Still, the true oral dose may be greater

than the inhaled dose as the dermal dose to inner hand is about 1000 times higher than the inhaled

dose.


Consumers may also be exposed to silica from many other types of products.




References:

Nordic Council of Ministers, 2011: Existing default values and recommendations for

exposure assessment. http://www.norden.org/en/publications/publikationer/2012-505/

ECHA, 2012. Guidance on information requirements and chemical safety assessment.

Chapter R.15: Consumer exposure estimation. Version: 2.1, November 2012.


Michel K, Scheel J, Karsten S, Stelter N, and Wind T, 2013. Risk assessment of

amorphous silicon dioxide nanoparticles in a glass cleaner formulation. Nanotoxicology,

7(5-8), 974-988.



421

Nørgaard, A.W., Jensen, K.A., Janfelt, C., Lauritsen, F.R., Clausen, P.A., and Wolkoff, P.,

2009, Release of VOCs and Particles During Use of Nanofilm Spray Products.

Environmental Science and Technology, 43. 7824-7830, doi: 10.1021/es9019468.

Roberts WO, 2006. Chapter 12 Manufacturing and applications of water-borne colloidal

silica. In HE Bergna and WO Roberts (Eds.) Colloidal Silica: Fundamentals and

Applications. Surfactant Science Series, 131. CRC Press Taylor & Francis Group, FL, USA.

ISBN 0-8247-0967-5. page. 131-176.

Schneider T, Brouwer D, Koponen IK, Fransman W, Jensen KA, van Duuren-Stuurman B,

van Tongeren M & Tielemans E., 2011. Conceptual model for assessment of inhalation

exposure to Manufactured Nanoparticles. Journal of Exposure Science and

Environmental Epidemiology 21, 450–463.

422

Scenario 13 - Product: Air conditioner and air purifier device 8.14

containing nano-silver


Is an air filtering device working as an air condition device in a room.

Step 1 Charactherisation and relevant exposure parameters

From the data collected and the conclusions in chapter 4, information regarding the parameters

listed below is filled in.

Parameter Specified

data*


Product

category

Air cleaner

Type of

Product

filterbased

ID of

nanomaterial

Silver As the system is called a nano-health system the silver in the

filter is considered to be on nanoform.

http://www.samsung.com/ph/consumer/learningresources/wa

shingmachine/silver_nano/site.html

Physical

matrix/form of

product

Surface-bound

Package

design, volume

-

Application/us

e/ handling

Air filtering

device that

circulates and

filters air

Location of

nanomaterial

eg. free/

matrix-bound

Filtermatrix

with

embedded of

surface-

bound nano-

silver.

Direct/ indirect

exposure

Indirect

Indoor/

outdoor use

Indoor

Generation of

nanomaterial

during use

no

Specific target

group

(children,

teenagers etc.)

All

Forseeable

misuse

-

Site of contact/

exposure

airborne

423

Primary

exposure

route(s)

inhalation Dermal exposure is theoretically possible in relation to changing

filter or repair work.

Concentratio

n of

nanomaterial

in product

-

Volume of

product used,

exposed to

-

Body area

exposed to

-

Retention

rate on body

surface

-

Migration/lib

eration rate

of

nanomaterial

from matrix

-

Ingested

amount

-

Volume of

product

released to

air /

concentratio

n in air

-

Duration of

exposure

- Up to 24

h/day

Frequency of

exposure

- daily

* “ - “ if not given or not relevant

Step 2 Algorithms for exposure estimation + specific data



section 4.2) :


References

Inhalation exposure

Concentration in indoor air (mg/m3) of nano-

silver has to be estimated, based on data/ estimates on

release of nano-Ag during the filtering process, see

data below.

Dinhal (mg(kg bw/d) =

Conc air (mg /m3) x Inhalation volume (m3/

bw (kg)/d )

424

Very few data on this scenario is available.

Quadros et al. (2013) investigated the emission from two air humidifiers; a nano-technology based

manual humidifier and one with a conventional silver accessory for the water tank, respectively. The

use-situations were investigated in a 36 m3 room, with carpets and furniture to simulate a bedroom,

and test conditions at less than 25C and 40%RH. ICP-MS analysis of 5 and 17 days old tank water

resulted in 0.8 ppb Ag at 5 days, but not detectable concentrations in 17 days old tank water.

Condensates (300 ml water of atomized over 90 minutes) generated by the table-top humidifier

with the conventional Ag accessory, contained 2.30.4 ppb of Ag (measured as total Ag and most

probably related to dissolved Ag-ions), suggesting a very low exposure level during regular use.

(This corresponds to total liberation into air of 0.69 µg Ag over 90 minutes). No silver was detected

from in the reservoir from the nanotechnology based humidifier. Also the simulated use did not

result in any detectable amounts of particles emitted.

Based on these study results it was concluded that there seem to be a very low –if any- release

potential for silver particles from the air humidifiers.

Step 3 Target groups

Target groups: all ages


Negligible inhalational exposure is assumed as liberation of silver nanoparticles from the filter is

not expected.

Dermal exposure is considered to be too hypothetical to be further quantitatively estimated.


According to the product information the filter liberates Ag ions and thus the silver is either surface

bound or embedded in the filter-matrix. There is not specific knowledge whether the silver actually

exist on nanoform. The release of the silver pertains to silver ions from the filter surface.

So overall, no great uncertainties exist that may compromise the assessment of zero to negligible

exposure to nano-silver particles from use of the air conditioner/purifier.

However, this assessment may only pertain to this type of air purification technologies and other

air-purification technologies may exist that may not be covered.


Perspectivation of the exposure scenario with respect to:

Air filtering devices containing silver nano-tehcnology for liberating silver ions seems to have little

–if any - potential for release of silver nano-particles into the air.

References

http://www.samsung.com/ph/consumer/learningresources/washingmachine/silver_nano/site.ht

ml

http://www.samsung.com/ph/consumer/learningresources/washingmachine/silver_nano/site.html

http://www.samsung.com/ph/consumer/learningresources/washingmachine/silver_nano/site.html

425

Quadros et al. (2013). Release of silver from nanothechnology-based consumer products for

children. Env Sci Tech 47, 8894-8901.

426

Scenario 14 - Product: Disinfectant pump spray containing nano-8.15

Ag

Description of exposure scenario: Spraying an article or surface with a pump spray

Step 1




Estimated*


Product category

dis-infectant spray

http://nanodb.dk/en/products/?keyword=sanitizer http://www.nanotec.pl/en/index.php?go=produkty&id=nanotec_sanitizer http://nanodb.dk/en/products/antibacterial-shoe-deodorizer-with-silver-ions/ http://www.nanotol.de/textilien/123/textol-pro-nanoversiegelung-fuer-schuhe

Type of Product

Antibacterial cleaning agent for fabric and materials

A specific product is described: “Sanitizer NPS 200 is a professional surface disinfector. Sanitizer NPS 200 strongly differs from the traditional products, simply by containing nano-particles of silver. These particles in the process of decontamination of disinfected surfaces penetrate hardly reachable surfaces such the fabric, leather, sponge, crack, micro seasons, cracks, fugue, dilatation, scratches and kill bactericides and fungicides on contaminated surfaces….” http://www.nanotec.pl/en/index.php?go=produkty&id=nanotec_sanitizer

ID of nanomaterial

Ag The products in this product group may sometimes contain ionic silver instead of nano-Ag. The products may, in addition to Ag (either nano-Ag or Ag ions), also in some cases contain other or more than one nano-ingredient (nano-TiO2, nano-silica, nano-ZnO). http://web.archive.org/web/20061004150907/http://www.aircleanermedium.com/Nano-Silver-Photocatalyst.html http://web.archive.org/web/20061029034709/http://www.root-cn.com/pdf/Super-Hydrophile-Self-cleaning-Instruction.pdf


NA NA NA

Nano-Ag Sizes of nano-Ag were not found specifically reported for any of these products. Nano-Ag can be purchased in many different sizes covering the entire nanoscale and beyond.


nano-Ag dispersion in pump spray

Nanoparticles assumed considering the nanoparticle focus of the assessment


50 mL Larger product volumes are available from different venders

http://www.nanotol.de/textilien/123/textol-pro-nanoversiegelung-fuer-schuhe http://www.nanotec.pl/en/index.php?go=produkty&id=nanotec_sanitizer

Application/u pump

http://nanodb.dk/en/products/?keyword=sanitizer



http://nanodb.dk/en/products/antibacterial-shoe-deodorizer-with-silver-ions/

http://nanodb.dk/en/products/antibacterial-shoe-deodorizer-with-silver-ions/

http://www.nanotol.de/textilien/123/textol-pro-nanoversiegelung-fuer-schuhe




http://web.archive.org/web/20061004150907/http:/www.aircleanermedium.com/Nano-Silver-Photocatalyst.html


http://web.archive.org/web/20061029034709/http:/www.root-cn.com/pdf/Super-Hydrophile-Self-cleaning-Instruction.pdf






427

se/ handling spray Location of nanomaterial eg. free/ matrix-bound

in liquid suspension


Direct exposure

Indoor/ outdoor use

Indoor/Outdoor


Yes Both alcohol and water-based “nano-pump-spray” have been shown to generate nanoparticles during use; both with and without presence of solid nanomaterials in dispersion (Nørgaard et al., 2009). – Hence, if the product contains ionic Ag alone, it can be assumed that the dissolved ions will condensate during evaporation of aerosolized solvent droplets during use.


Teenagers and Adults

Forseeable misuse

Yes 1) Spraying indoors in room with low ventilation and no personal protection. 2) Not spraying at the correct distance to the object


palms Touching and carrying the treated objects. In addition deposition of overspray is possible.



Inhalation and dermal exposure is considered due to overspray and aerosolization during use. Additional dermal exposure could arise from direct spraying on hands while holding an object to be treated as well as from dermal contact with freshly treated objects. General dermal exposure due to overspray and aerosolized product is possible, but not considered further.


NA 1% Scientific literature data have shown that two specific disinfectant pump sprays had nano-Ag concentrations of 12.5 and 27.5 ppm Ag (Quadros and Marr, 2011). In another case, a commercially available water-based nano-Ag spray contained 1 wt% nano-Ag (Hagendorfer et al., 2010). Hence, assuming 1 wt% appears to be a reasonable worst case concentration estimate.


NA typically 100 mL

The volume product required depends entirely on the size of the objects treated.

Body area exposed to

Hands Dermal area Men 40<50

Women 40<50 Teen 16-21y

Hands cm2 1118.0 906.2 828.0

Head cm2 1419.0 1170.6 754.4

Total cm2 21500 18880 18400

Nordic Council of Ministers (2011) Retention rate on body surface (1)

Assumed 1

R.15 v. 2.1 (ECHA, 2012)

Migration/liberation rate of nanomateri

None

428

al from matrix Ingested amount

Possible Inadvertent ingestion may occur, but the doses are considered very low due to the low frequency consumer use.


25 µg Ag/min or 1 µg/ml < 3.4 x 103 particles/cm3

There is no immediate information of the volume required to treat a product. It is assumed that the amount of product required to treat and disinfect is comparable to the amount required to produce a surface coating using this type of product. 10-25 ml/m2 is required of comparable products (not silver based; http://www.nanocover.dk) Assuming a maximum of 25 ml/m2 and that 4 m2 will be treated, 100 ml of product would be required. We assume 1 ml per pump for this product and a total dispensing time of 4 minutes. The average use-rate is then 25 mL/min (equal to 25 g/min). Assuming that the solvent is water and the nano-Ag content is 1 wt%, the total use rate nano-Ag is 250 mg/min (2.75 mg per minute if the Ag-concentration in the surface disinfectant spray in Quadros and Marr (2011) is used). Using the air-concentration for silane and siloxane in Nørgaard et al. (2009) and neglecting that a fraction of these compounds are semivolatile, a total of up to 0.01 wt% was released to air during use of pump sprays. This results in an upper aerosol release rate of concentration of (250 mg Ag/min x 0.01 wt% / 100) 25 µg/min. Nørgaard et al. (2009) determined a respirable aerosol generation of 3.1 x 108 particles/g for a water-based pump spray with ca. 1 wt% TiO2. However, this is the entire concentration of aerosolized droplets with nano-TiO2 and not the nano-TiO2 particle concentration. Use of a different product with comparable release rate in an un-ventilated 17. 4 m3 room was estimated to give a peak concentration 6 x 103 particles/cm3 (authors’ correction) by treating 7 m2 surface. Direct scaling to 4 m2 would result in 3.4 x 103 particles/cm3.


10 min 5 min

inhalation dermal (hand exposure)


once per week

There appears to be no information on recommended use and frequency on the internet. We assume application for general cleaning with a weekly use rate.




http://www.nanocover.dk/

429

Step 2



section 4.2) :


References

Inhalation

exposure

Use of a different product with comparable release rate in

an un-ventilated 17. 4 m3 room was estimated to give a peak

concentration 6 x 103 particles/cm3 by treating 7 m2 surface.

Direct scaling to 4 m2 would result in 3.4 x 10

3 particles/cm

3

(Authors’ correction to Nørgaard et al., 2009).

A mass-based assessment of the inhalation exposure is

made using the traditional Tier 1 estimation of inhaled dose

in R.15 (ECHA, 2011):

nBW

TIHCFD

contactairinhresp

inh

Input



[mg/m3]


[-]


[m³/d]


[d]

BW Body weight [kg]


[/d]

Output parameter

Description


[mg/kg BW d]


10/6 min4,,

inh

iaveinh C

V

tRC , for it = 1, 2,

3, 4

where R = emission rate [ 25 µg/min], Cinh,4min = peak

concentration reached after 4 min spraying; t = time [min],

and


Using the above-mentioned estimated release rate of 1

µg/ml and a total exposure time of 10 min (effective

spraying for 4 minutes in a 20 m3 un-ventilated room

Nørgaard et

al. (2009)

ECHA (2011)

430

(according to R.15 version 2.1; 2012)) adding 6 minutes for

wiping, aveinhC , reaches:

4.25 µg Ag/m3 (peak value = 5 µg/m3 from 4 to 10 min) for a

total of 10 min exposure.

Dermal

overspray

exposure

No applicable model

Dermal contact

exposure

The external dermal load (Lder) and dose (Dder) at direct contact the

procedure by ECETOC TRA Equation R.15-5, 15-6 and 15.7 (ECHA,

2012):

D

CCTHCcmmgL

prod

derderderder

1000/

BW

nALkgmgD skinder

BWder /










ECHA (2012)

Oral exposure

Not assessed directly, but the inhaled exposure dose is the

upper limit for gastro-intestinal exposure dose.

Eye exposure


Step 3







431


Anatomical

/Physiological

parameters



60 kg (female)

71.6 (16-<21

years)


Retention rate 1

Skin surface (hand,

head):

(male and female 41

- <51 years old;

teenager 16 - <21

years old)



Dermal area

Men 40<50

Women 40<50

Teen 16-21y

Hands; cm2 1118.0 906.2 828.0

Total; cm2 21500 18880 18400

Density 1 g/cm3 For the spray product

Daily amount NA

Application per year 52 Once every week

Amount which may

get in contact with

skin through

splashes or direct

contact.

Assessed from the

area of the hands

Concentration of

nanomaterial in

product

<1% For assessment, a concentration of 1 wt% was used.

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

0.1 mm

100%


Other relevant parameters, which are not used in the exposure assessment.


References

Inhalation exposure

Ventilation rate


Surface deposition


Schneider et al.

(2011)

Dermal exposure Physico-chemical form of the nanomaterial if the

product contains ionic Ag instead of nano-Ag

Oral Physico-chemical form of the nanomaterial if the


Eye Physico-chemical form of the nanomaterial if the


432

Step 4




2012)

daykgµgkg

daymm

µg

nBW

TIHCFD maleBW

contactairinhresp

inh ,

3

3

/017.0170

24

6

1

32.4025.41

Annual inhaled dose for one treatment per week: 52 x 0.017 µg/KgBW,maleday =

0.881

µg/KgBW,maleYear

Considering the particle number concentrations (17.4m3 /20 m3) x 6 x 103 particles/cm3) from

Nørgaard et al. (2009) the annual inhaled dose would be on the order of:

2.71 x 105

n//KgBW,maleYear


23

2 /25001.01

1000251000/ cmµgcm

µg

D

CCTHCcmmgL

prod

derderderder

maleBWskinder

BWder kgµgkg

cmcm

µg

BW

nALkgmgD ,

2

2

/6.19970

11185.025

/

(per case)

Considering weekly use the annual dermal dose is 52 x 199.6 µg/kgBW,male = 10.38 mg/kgBW,maleYear



2012)

daykgµgkg

daymm

µg

nBW

TIHCFD femaleBW

contactairinhresp

inh ,

3

3

/0198.0160

24

6

1

32.4025.41

433

Annual inhaled dose for one treatment per week: 52 x 0.0198 µg/KgBW,femaleday =

1.03

µg/KgBW,female,yea

r



2.71 x 105

n//KgBW,femaleYear


23

2 /25001.01

1000251000/ cmµgm

µg

D

CCTHCcmmgL

prod

derderderder

BWskinder

BWder kgµgkg

cmcm

µg

BW

nALkgmgD /8.188

60

2.9065.025

/

2

2

(per case)

Considering weekly use the annual dermal dose is 52 x 188.8 µg/kgBW,male = 9.817

mg/kgBW,femaleYear




daykgµgkg

daymm

µg

nBW

TIHCFD teenBW

contactairinhresp

inh ,

3

3

/0154.016.71

24

6

1

44.3725.41

Annual inhaled dose for one treatment per week: 52 x 0.0154 µg/KgBW,teenday =

0.803

µg/KgBW,female,yea

r



2.71 x 105

n//KgBW,teenYear

434


23

2 /25001.01

1000251000/ cmµgcm

µg

D

CCTHCcmmgL

prod

derderderder

teenBWskinder

BWder kgµgkg

cmcm

µg

BW

nALkgmgD ,

2

2

/6.1446.71

8285.025

/

(per case)

Considering weekly use the annual dermal dose is 52 x 144.6 µg/kgBW,male = 7.52 mg/kgBW,teenYear

Summary Table: Estimated inhalation and dermal dose for females, males and teenagers during use

of a nano-Ag disinfectant spray.

Ag

disinfecta

nt spray

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

(1621 years)

Inhalatio

n

[µg/kgDa

y]

Dermal

overspray

[mg/kgDa

y]

Dermal

contact

[mg/kgDa

y]

Inhalatio

n

[µg/kgDa

y]

Dermal

overspray

[mg/kgDa

y]

Dermal

contact

[mg/kgDa

y]

f 0.0198

m 0.0170 NA

0.189

0.200 0.0154 NA 0.145

Ag

disinfecta

nt spray

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

(1621 years)

Inhalation

[mg/kgYe

ar]

Dermal

overspray

[mg/kgYe

ar]

Dermal

contact

[mg/kgYe

ar]

Inhalatio

n

[µg/kgYe

ar]

Dermal

overspray

[mg/kgYe

ar]

Dermal

contact

[mg/kgYe

ar]

f 1.030

m 0.881 NA

9.82

10.38 0.803 NA 7.52

Step 5



Little information is available on the Ag actually used in this type of product. However, it is known

that nano-Ag is used is some of the products and it might be generated during spraying. No data are

available on the characteristics on the nano-Ag in the specific case and still limited high-quality

information exist on the exposure characteristics and source strengts from consumer products. In

435

this case, we assume a content of 1 wt% nano-Ag in the pump spray, which is considered reasonably

worst case.

The assessment of inhalation exposure levels should be considered with some care as it arise from

read-across from different pump spray products. There is a high need to establish data on products

with specific relevance for this product group. In the inhalation scenarios, the airborne exposure

concentrations are set based on assumptions of use, concentrations in the product and information

from published experimental results on typical nano-Ag concentrations, relevant and partially

analogues emission and exposure data. Overall, combined the assumptions on the product and

exposure characteristics are assumed reasonable to worst case.

On relative scale, the exposure doses can, however, be considered worst case. The exposure was

assessed without taking into consideration that the user should wear gloves and mask and work in a

ventilated area. Real exposure measurement data on this product group do not exist at this point in

time. In the exposure assessment, we assume no mask is used by the consumer and a 100% air-way

deposition efficiency, because the published data suggest that the entire airborne fraction is

respirable.

The dermal contact exposure was assessed for a case where the inner side of the hands touched a

newly treated surface (0.1 mm) with 100% transfer from the exposed area to the hand. This

assumption appears to be a worst case estimate. In addition to direct contact, dermal exposure may

also arise from overspray. The level of overspray was not assessed as no model is yet appropriate for

assessment of this type of product.



respiratory tract and finally by accidental uptake via inadvertent hand-to-mouth transfer.


The current scenario is considered relevant and realistic for this type of product.

Consumers may also be exposed from nano-Ag from many other types of products.




References:









Quadros ME, and Marr LC. 2011. Silver Nanoparticles and Total Aerosols Emitted by

Nanotechnology-Related Consumer Spray Products. Environ. Sci. Technol 45,10713-10719.



436




450–463.

437

Scenario 15 - Product: Disinfectant multipurpose sanitizer with 8.16

Nano-Ag (Propellant spray)

Description of exposure scenario: Case 15: Spraying a 4 m2 textile with pressurized spray

can

Step 1




Estimated*


Product category

deoderizer / dis-infectant spray

http://www.nanotechproject.org/cpi/products/air-sanitizer-nano-silver-

photocatalyst/ http://web.archive.org/web/20061004150907/http://www.aircleanermedium.c

om/Nano-Silver-Photocatalyst.html

Type of Product

Antibacterial cleaning agent and cleaning for fabric and materials

The products in this product group may sometimes contain ionic silver instead of nano-Ag. The products may, in addition to Ag (either nano-Ag or Ag ions), also in some cases contain other or more than one nano-ingredient (nano-TiO2, nano-silica, nano-ZnO). http://web.archive.org/web/20061004150907/http://www.aircleanermedium.com/Nano-Silver-Photocatalyst.html http://web.archive.org/web/20061029034709/http://www.root-cn.com/pdf/Super-Hydrophile-Self-cleaning-Instruction.pdf A website describes the uses as primarily textiles, but also, purifying accessible indoor office and household goods, such as telephone, computer keyboard, mouse, table, cabinet, chair, armrest, doorknob, lamps and lanterns and button of elevator, etc. http://web.archive.org/web/20061004150907/http://www.aircleanermedium.com/Nano-Silver-Photocatalyst.html

ID of nanomaterial

Ag Sizes of nano-Ag were not found specifically reported for any of these products. Nano-Ag can be purchased in many different sizes covering the entire nanoscale and beyond.


NA NA NA

Nano-Ag Nanoparticles assumed considering the nanoparticle focus of the assessment


nano-Ag pressurized spray can

http://web.archive.org/web/20061029034709/http://www.root-cn.com/pdf/Super-Hydrophile-Self-cleaning-Instruction.pdf


100-1000 mL

http://web.archive.org/web/20061004150907/http://www.aircleanermedium.com/Nano-Silver-Photocatalyst.html


Spray


in liquid suspension


Direct exposure















438

Indoor/ outdoor use

Indoor


yes Spray cans have been shown to generate nanoparticles during use (Nørgaard et al., 2009). – Hence, if the product contains ionic Ag alone, it is assumed that the dissolved ions will condensate during evaporation of aerosolized solvent droplets during use.



Forseeable misuse

Yes 1) Spraying indoors in room with low ventilation and no personal protection. 2) Not spraying at the correct distance to the object


Direct surface contact by unprotected hands,

Touching or carrying treated objects



Inhalation and dermal exposure is considered due to overspray and aerosolization during use. Additional dermal exposure could arise from direct spraying on hands while holding an object to be treated as well as from dermal contact with freshly treated objects. General dermal exposure due to overspray and aerosolized product is possible, but not considered further due to lack of suitable model for this type of product.


NA 1% No specific information was found. Scientific literature data have shown that two specific disinfectant pump sprays had nano-Ag concentrations of 12.5 and 27.5 ppm Ag (Quadros and Marr, 2011). In another case, a commercially available water-based nano-Ag spray contained 1 wt% nano-Ag (Hagendorfer et al., 2010). Hence, assuming 1 wt% appears to be a reasonable concentration estimate. Higher concentrations may be possible, but have not been observed in this survey. Consequently 1 wt% may be assumed a worst case.


NA typically 100 mL

The volume product required depends entirely on the size of the objects treated.


Hands Dermal area Men 40<50

Women 40<50 Teen 16-21y

Hands cm2 1118.0 906.2 828.0

Head cm2 1419.0 1170.6 754.4

Total cm2 21500 18880 18400 Nordic Council of Ministers (2011)


Assumed 1

R.15 v. 2.1 (ECHA, 2012)


None

Ingested Possible Inadvertent ingestion may occur, but the doses are considered

439

amount very low for rare consumer use. Concentration in air/ Volume of product released into air

NA (1 g/min nanoAg is assumed dispensed from spray can towards the surface)

There is no immediate information of the volume required to treat a product. It is assumed that the amount of product required to treat and disinfect is comparable to the amount required to produce a surface coating using this type of product. 10-25 ml/m2 is required of comparable products (not silver based; http://www.nanocover.dk) Assuming a maximum of 25 ml/m2 and that 4 m2 will be treated, 100 ml of product would be required. It is assumed that the spray can will deliver the product four times faster as compared to pump sprays resulting in a total dispensing time of 1 minute (see scenario 14). Hence, the spray can deliver 100 mL/min (equal to 100 g/min). Assuming that the solvent is water and the nano-Ag content is 1 wt%, the total use rate nano-Ag is then 1 g/min


10 min 1 times

inhalation dermal (hand exposure)


once every year

A specific nanoproduct claims that the treated textile may be washed 50 times and still retaining more then 95% efficiency. http://web.archive.org/web/20061004150907/http://www.aircleanermedium.com/Nano-Silver-Photocatalyst.html




Step 2



section 4.2) :

Exposure

route

Algorithms used Comments/

References

Inhalation

exposure

Spray cans have been shown to generate nanoparticles during

use (Nørgaard et al., 2009). Without any quantitative

comparison use of a pressurized spray resulted in 100 times

higher particle concentrations and much smaller nano-size

particles than three pump sprays with different compounds

(Nørgaard et al., 2009) – Hence, if the product contains ionic

Ag alone, it is assumed that the dissolved ions will condensate

during evaporation of aerosolized solvent droplets during use.

Hagendorfer et al. (2010) also observed testing water-based

nano-Ag spray can and pump sprays that the emission

increased from not measurable using pump spray to high

using pressurized spray cans with nanoAg. Care should be

taken in analysing just the number of particles as this study

showed a high fraction of condensates in the test of a

reference spray-can without nano-Ag. The specific nanoAg

particles were emitted as nano-size free and agglomerated

particles. 14,000 particles/cm3 with a peak size around 25 nm

was measured shortly after spraying into a 300 L glove box

with a very high air-exchange rate and background aerosol

concentrations of ca. 500 particles/cm3.

Nørgaard et al.

(2009)

Hagendorfer et

al. (2010)

http://www.nanocover.dk/



440

Dermal

overspray

exposure

No applicable model

Dermal contact

exposure

The external dermal load (Lder) and dose (Dder) at direct

contact the procedure by ECETOC TRA Equation R.15-5, 15-6

and 15.7 (ECHA, 2012):

D

CCTHCcmmgL

prod

derderderder

1000/

BW

nALkgmgD skinder

BWder /





Cprod: Concentration of substance in product before dilution

(g/cm3)





ECHA (2011)

Oral exposure

Not assessed directly, but the inhaled exposure dose is the

upper limit for gastro-intestinal exposure dose.

Eye exposure


Step 3








Anatomical

/Physiological

parameters



60 kg (female)

71.6 (16-<21

years)


441

Retention rate 1

Skin surface (hand,

head):

(male and female 41

- <51 years old;

teenager 16 - <21

years old)



Dermal area

Men 40<50

Women 40<50

Teen 16-21y

Hands; cm2 1118.0 906.2 828.0

Total; cm2 21500 18880 18400

Density 10.5 g/cm3 webmineral.com

Daily amount NA

Application per year 1 Once every year

Amount which may

get in contact with

skin through

splashes or direct

contact.

Assessed from the

area of the hands

Concentration of

nanomaterial in

product

<1% For assessment, a concentration of 1 wt% was used.

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

0.1 mm

100%


Other relevant parameters not considered in the exposure assessment models.


References

Inhalation exposure

Ventilation rate


Surface deposition


Schneider et al.

(2011)

Dermal exposure Physico-chemical form of the nanomaterial if not a

chemical

Oral Relevant, but not assessed

Eye Relevant, but not assessed

Step 4



No inhalation exposure estimations have been made due to high uncertainty in the emission

characteristics. The emission rate from using a spray can is very specific to the product and vary

with, among others, the type of propellant, nozzle-configuration, pressure in the spray an, presence

of condensable matter etc.

442


23

2 /25001.01

1000/251000/ cmµg

cmµg

D

CCTHCcmmgL

prod

derderderder

maleBWskinder

BWder kgµgkg

cmcmµg

BW

nALkgmgD ,

22

/6.19970

11185.0/25/

(per case)

The product type is normally applied to stay on the product or surface for longer durations of time

and treatment will be repeated when needed. Product indications suggest that treatment is needed

once per year. Consequently, the daily dose per case is also the annual dose.


No inhalation exposure estimations have been made due to high uncertainty in the emission characteristics. The emission rate from using a spray can is very specific to the product and vary with a.o. the type of propellant, nozzle-configuration, pressure in the spray an, presence of condensable matter etc.


23

2 /25001.01

1000/251000/ cmµg

cmµg

D

CCTHCcmmgL

prod

derderderder

femaleBWskinder

BWder kgµgkg

cmcm

µg

BW

nALkgmgD ,

2

3

/8.18860

2.9065.025

/

(per case)





No inhalation exposure estimations have been made due to high uncertainty in the emission characteristics. The emission rate from using a spray can is very specific to the product and varies with a.o. the type of propellant, nozzle-configuration, pressure in the spray can, presence of condensable matter etc.


23

2 /25001.01

1000/251000/ cmµg

cmµg

D

CCTHCcmmgL

prod

derderderder

teenBWskinder

BWder kgµgkg

cmcmµg

BW

nALkgmgD ,

22

/6.1446.71

8285.0/25/

(per case)




443

Summary Table: Estimated inhalation and dermal dose for females, males and teenagers during use

of a nano-Ag disinfectant pressurized spray-can.

Ag

disinfectan

t spray

Adult,

female (60 kg)

male (70 kg)

Teen (56.8 kg)

(1621 years)

Inhalation

[µg/kgYear

]

Dermal

overspray

[mg/kgYear

]

Dermal

contact

[mg/kgYear

]

Inhalation

[µg/kgYear

]

Dermal

overspray

[mg/kgYear

]

Dermal

contact

[mg/kgYear

]

NA NA

f 0.189

m 0.200 NA NA 0.145

Step 5



Little information is available on the form of the Ag actually used in this type of product. However,

it is known that nano-Ag is used is some of the products and it might be generated during spraying

if present at ionic Ag. No data are available on the characteristics on the nano-Ag in the specific case

and still limited high-quality information exist on the exposure characteristics and source strengts

from consumer products.

It was decided not to estimate the airborne exposure due to lack of appropriate data. There are

some indications from previous studies, but the variability between emissions from pump sprays to

pressurized spray cans are great and also expected to be some in between pressurized spray cans.

Based on pump-spray data and experience from other types spray cans, nano-size particles will be

released or formed during use of a spray can and result in relatively high exposure levels. However,

the fraction and behaviour of the nano-Ag or ionic Ag during spraying is not described and the

emission rate from the product is not known. This is considered a significant information gap in

relation to a potentially very high consumer exposure situation. There is a high need to establish

data on products with specific relevance for this product group.

The dermal exposure was assessed without taking into consideration that the user should wear

gloves. The dermal contact exposure was assessed for a case where the inner side of the hands

touched a newly treated surface (0.1 mm) with 100% transfer from the exposed area to the hand.

This assumption appears to be a worst case estimate.

Again, overspray exposure is possible, but it is not possible to assess the dose due to this effect

without a proper model or data.



respiratory tract and finally by accidental uptake via inadvertent hand-to-mouth transfer.

444


In general, limited information is available for assessing exposures and thereby risks from

application of nanomaterial containing propellant sprays. This is considered a significant

information gap to be addressed in WP5.

Consumers may also be exposed from nano-Ag from many other types of products.




References:












450–463.



445

Scenario 16 - Product: T-shirt containing nano-Ag 8.17


Wearing a T-shirt with nano-Ag in a textile fiber matrix.

Step 1

From chapter 5.6 the most relevant data for this scenario is considered the data by Goetz et al.

(2013) supported by the data from the Danish EPA (2012) as these exposure scenarios are based on

the measured migration of Ag into artificial sweat.

Parameter Specified data* Estimated* Comments/ References

Product category Textile, clothing

Type of Product T-Shirt e.g.:

http://www.alibaba.com/produc

t-detail/Silberschutz-Nano-

Silver-Top-Short-

sleeve_100281477.html

ID of nanomaterial Ag Ag as nanoparticles according to

manufacturer (Goetz et al. 2013)

Characterisation e.g. size distr. - - No specific information given by

Goetz et al. (2013).Often textiles

claimed as nano-enabled do not

contain nanoparticles**

Physical matrix/form of product Textile matrix According to Danish EPA

(2012). Metallic silver or silver

salts (in the form of particles or

threads) may either be

embedded in the textile fiber or

surface coat the fiber. The

particles may be up to 10,000

nm in diameter.

Package design, volume T-shirt

Application/use/ handling Wearing of aT-shirt

Location of nanomaterial eg. free/

matrix-bound

Surface

attached or

embedded in

textile fiber

Direct/ indirect exposure Indirect by

migration or

detachment of

particles

Indoor/ outdoor use both

Generation of nanomaterial during

use

Migration of

nano-Ag or

formation of

nanoparticle

s from

precipitation

of soluble

Ag-ions

cannot be

About 50 % of the amount of

migrated Ag was as particulates

< 450 µm mainly as AgCl (Goetz

et al. 2013).

(Scanning transmission electron

microscopy for size and Energy-

dispersive X-ray spectroscopy

for chemical ID)

446

excluded.


teenagers etc.)

Children and adults

Forseeable misuse - - -

Site of contact/ exposure Dermal Mouthing of part of T-shirt may

occur e.g. by children.

The potential for inhalational

exposure is considered more

speculative and is judged to be

negligible.

Primary exposure route(s) Dermal

Concentration of nanomaterial

in product

183 µg Ag/ g

(Goetz et al. 2013)


exposed to (1)

64 g/89 g Weight of female/ male T-shirt

(Goetz et al. 2013)

Body area exposed to 6900 cm2/ 9800cm2 Surface area exposed by T-shirt

(females/males) (Goetz et al.

2013)

Retention rate on body surface 1



43 µg dissolved Ag/

g textile/ L artificial

sweat

and

31 µg particulate

Ag/ g textile/ L

artificial sweat

(particulates <

450 nm)

(added value of 74

µg Ag/ g textile/ L

artificial sweat)

(120 ml artificial sweat used per

g textile for an incubation

duration of 30 minutes) (Goetz

et al. 2013)

Ingested amount - Not determined by Goetz et al.

(2013)



into air

-

Duration of exposure 1 hr

Soaked T-shirt with maximum

migration potential. Is not

considered to be worn more

than 1 hour by Goetz et al.

(2013).

Frequency of exposure 1/d

May be used on a daily basis,

however the migration may be

lowered after the first time use

as washing may wash out the

silver.

447


Step 2 Algorithms



section 4.2) :


References

Inhalation exposure

Inhalation exposure is in theory possible in connection

with inhalation of dust liberated from the textile,

however, exposure from this route is considered

marginal.

Danish EPA

(2012)

Dermal exposure

E (µg/kg) = mtextile x asubst x rsweat x texpo x Aexpo x

fcontact / mbw

Where

E = ….

mtextile = weight of the textile (g)

asubst = released amount of substance from

fabric into sweat (µg/g/ml)

rsweat = released volume of sweat per time and

body weight (mL/min/m2; 1.8 and 1.25

mL/min/m2 used for males and females)

texpo = duration of exposure (min)

Aexpo = body surface area covered by the fabric

(m2)

fcontact = fraction of fabric in close contact with

sweat and skin (a value of 1 is used)

mbw = body weight (kg; 77 kg and 62 kg used

for men and women)

Dermal load = E (µg/kg) x mbw / Aexpo

(Goetz et al.

2013)

Oral exposure

Oral exp = Ag migration textile / bw

Oral exp: µg/kg

Ag migration textile: total Ag migration from sucked

textile (µg)

bw: bodyweight

Eye exposure

-

448

Step 3 Target groups







Target population: adult and children


parameters


References

Body weight 62 kg / 77 kg

(female/male)

18.6 kg (average

for 3-6 year-

old- children)

(Goetz et al. 2013)

Nordic Council of

Ministers, (2011)

Inhalation rate

Skin surface (site of contact) 6900 cm2/

9800cm2

(female/male)



Children:

Sucking a textile

surface area of

10 cm x 10 cm

No scenario for mouthing

was performed by Goetz

et al. 2013)

assumed

Others


Dermal exposure

E (µg/kg) = mtextile x asubst x rsweat x texpo x Aexpo x fcontact / mbw

Females:

449

E (µg/kg) = 64 g x 74x10-3 µg Ag/g/ml x 1.25 ml/min/m2 x 60 min x 0.69 m2 x 1 / 62 kg = 4.0 µg

Ag/kg

Males:

E (µg/kg) = 89 g x 74x10-3 µg Ag/g/ml x 1.8 ml/min/m2 x 60 min x 0.98 m2 x 1 / 77 kg = 9.0 µg

Ag/kg

Dermal load

Dermal load = E (µg/kg) x mbw / Aexpo

Females:

Dermal load = 4.0 µg Ag/kg x 62 kg/ 6900 cm2 = 0.036 µg Ag/cm2

Males:

Dermal load = 9.0 µg Ag/kg x 77 kg/ 9800 cm2 = 0.071 µg Ag/cm2

It may be noticed that male exposure is about twice the female exposure. This is due to the

increased rate of sweating and the considerable higher body surface area in contact with the T-shirt.

Thus the male exposure may be considered as a worst case exposure.

Children:

Most probably dermal exposure to children would be lower than females as children have lower

sweat rates than adults (Yeargin 2012).

Oral Exposure

Oral exp = Ag migration textile / bw

Although not considered by (Goetz et al. 2013) a scenario for sucking the upper part of the T-shirt

by children may be derived.

Target population:

Assuming a child weighing 18.6 kg (average for 3-6 year-old- children).

Scenario:

Assuming a child sucking a total area of 100 cm2 (10 x 10 cm2) and assuming the same

migration rate of 74 µg Ag/ g textile/ L as found by Goetz et al. (2013).

Weight of 100 cm2 T-shirt:

6900 cm2 of a female T-shirt weighs 64 g

i.e. 1 cm2 textile weighs 9.3 mg

i.e.

100 cm2 of a T-shirt weigh 930 mg = 0.93 g

450

Migration of Ag from 100 cm2 (930 mg):

A migration rate of 74 µg Ag/ g textile/ L artificial sweat was found after incubation in 120

ml of migration liquid contained

Thus a total amount of 0.120 L x 74 ug Ag/ g textile/ L = 8.88 µg Ag/ g textile was

migrated

From 100 cm2 (0.93 g) this correspond to a migration of 0.93 g x 8.88 ug Ag/ g textile =

8.3 µg Ag

Oral exposure estimate:

Oral exp = 8.3 µg Ag/ 18.6 kg = 0.45 µg Ag/kg


In general there is a great uncertainty whether textile claimed to contain nano-Ag actually contain

silver in nanoform either as metallic silver or silver salts Thus the Danish EPA (2012) found that

only 1 out of 12 textile products actually contained Ag in nanoform. Also migration of silver from the

textile may be greatly affected by the ID of the silver (metallic silver og silver salts) or to which

extent the silver (or silver salts) are embedded in or surface coated to the textile fibers.

The above estimates are based on migration from a new T-shirt. When using on a daily basis after

washing the exposure is assumed to be significantly lower as migration typically decrease over time

as the silver content is gradually washed out. Thus, when using the calculated vales for continuous

exposure this should clearly be considered as worst case estimates.

Furthermore most publication do not discriminate between the form of silver and measure the

migration of silver from textile as total silver content (i.e dissolved + particulate silver) which makes

it difficult to estimate the actual nano-Ag exposure.

The above calculation is based on total silver and will therefor to a great extent overestimate the

exposure to nano-Ag particles liberated from the textile. The derived estimates may therefore be

considered as an upper bond and a very conservative estimate for the nano-Ag exposure both in

relation to the dermal as well as the oral exposure.

This specific exposure estimate derived from Goetz et al. (2013) with specific data on migration

from on T-shirt may not necessarily represent a worst case as other T-shits on the market may have

a higher potential for migration. However, the present estimate is considered to be supported by

previous estimates:

It should be noted that the estimates for T-shirt exposure of 4.0 and 9.0 µg Ag/kg for female and

males are very comparable to the exposure estimation made by the Danish EPA (2012) of 12.7 µg

Ag/kg for a young girl wearing a tank-top (containing 12 µg Ag/ g textile). This estimation was also

based on migration data in artificial sweat.

Modelling by using ECETOC TRA and Consexpo resulted in exposure of 10.5 and 34.6 µg Ag/kg for

adults from a T-shirt containing 10 µg Ag/g textile. In this estimate an overall Ag migration rate of

45% from the textile was assumed as a worst case (NANEX 2010).

Step 6 (information for WP5)

Goetz et al. (2013) also evaluated exposure to sport trousers and found additional dermal exposure

of around 6 and 9 µg Ag/kg for females and males, respectively. This corresponds to a T-shirt +

trousers combined exposure of around 10 and 18 µg Ag/kg.

451

Goetz et al. (2013) stated, however, that nano-Ag exposure from hand cream containing up to 0.1%

silver may lead to a much higher dermal exposure of up to 4.8 mg Ag/day (i.e around 70 µg Ag/kg).

Dermal exposure to nano-Ag may also occur in connection to the use of specific wound dressing

primarily for treating burns.

Further dermal exposure to nano-Ag may occur in connection with using indoor paint containing

nano-Ag or using air cleaner spray contaning nano-Ag.

Oral exposure to silver includiong nano-silver may occur from the use of food supplement

containing colloid silver or from migration of silver from food packing material into the food items.

References

Danish EPA 2012. Assessment of nanosilver on textiles on the Danish market. Environmental

Project No 1432. 77 pp + appendices.

Goetz NV, Lorenz C, Windler L, Nowack B, Heuberger M, and Hungerbühler K. 2013. Migration of

Ag- and TiO2-(Nano)particles from Textiles into Artificial Sweat under Physical Stress:

Experiments and Exposure Modeling. . Environ. Sci. Technol. 47, 9979-9987

Nanex 2010. Development of Exposure Scenarios for Manufactured Nanomaterials). Work package

4 report on consumer exposure. http://www.nanex-project.eu/mainpages/public-

documents/doc_download/101-nanex-project-final-report-.pdf

+ FP7 Nanex project (http://nanex-project.eu/) surveying literature and existing exposure models

to identify knowledge about consumer exposure scenarios and assessment of nanomaterials

Yergin 2012. Do Children Handle Heat As Well As Adults? http://www.momsteam.com/health-

safety/children-handle-heat-as-well-as-adults-studies-say



452

Scenario 17 - Product: Cement containing nano-TiO2 8.18

Description of exposure scenario :

Do It Yourself (DIY) application of cement, e.g. for repairing private house, driveway, etc.

Step 1



Parameter Specifie

d data*

Estimate

d*


Product

category

Construc

tion

material

Type of Product Cement

ID of

nanomaterial

Nano-

TiO2

E.g. HeidelbergCement as referred to by: BG Bau

(http://www.bgbau.de/praev/fachinformationen/gef

ahrstoffe/nano/pdf-files/nano-liste.pdf)

Characterisation

e.g. size distr.

Size

Crystal form

Size

Distribut

ion not

indicated

, but see

commen

t column

Anatase

http://www.bgbau.de/praev/fachinformationen/gef

ahrstoffe/nano/pdf-files/nano-liste.pdf

notes the following:"Die photokatalytische

Eigenschaft wird durch

die Ausbildung von Nanostrukturen erzielt.

Diese Strukturen werden durch Titandioxid

(TiO2)-Nanopartikel erzeugt, die als

Aggregate vorliegen. Die Aggregate weisen

eine stark vergrößerte Oberfläche auf.";

I.e. the product has photocatalytic properties

provided by nano-TiO2 particles. These are highly

aggregated, but still have a high specific surface area.

Given that the photocatalystic properties of this type

of cement, it is assumed that a high percentage of the

TiO2 is in the anatase form.

Physical

matrix/form of

product

Powder

Package design,

volume

>10 kg Per bag

Application/use/

handling

Pouring/m

ixing

Location of

nanomaterial eg.

free/ matrix-

bound

Not bound

in matrix,

but part of

powder

mixture

Direct/ indirect

exposure

Direct But unintended

Indoor/ outdoor

use

Mainly

outdoor

Generation of

nanomaterial

No

http://www.bgbau.de/praev/fachinformationen/gefahrstoffe/nano/pdf-files/nano-liste.pdf




453

during use

Specific target

group (children,

teenagers etc.)

Mainly

adults

Forseeable

misuse

No

Site of contact/

exposure

Hands

when

handling

Primary

exposure

route(s)

Dermal

and

inhalatio

n (eye)

Concentration

of

nanomaterial

in product

5% in

cement

water-

slurry

2%

cement

replacem

ent

5% is

considered

worst case

for

consumer

application

s

Shen et al. (2011) in relation to photocatalytic

surfaces.

Nazari et al. (2010), but in relation to strength

considerations

Volume of

product used,

exposed to (1)

> 10 kg

Body area

exposed to (1)

Arms, but

potentially

also other

areas of the

body

Retention rate

on body

surface (1)

Assumed 1

Migration/libe

ration rate of

nanomaterial

from matrix

It must

assumed

that there

can be

exposure

to the

entire nano

content in

powders

and

454

slurries

Ingested

amount

NA

Concentration

in air/

Volume of

product

released into

air

To be

estimated

Duration of

exposure

8 hours per

days

Frequency of

exposure

Every day

for a

period




Step 2



section 4.2) :

Expos

ure

route

Algorithms used Comme

nts/

Referen

ces

Inhalati

on

exposur

e

Estimate will be based on measurements cement worker exposure and by

assuming a worst case nano-TiO2 content of 5%.

Dermal

exposur

e

No literature has been identified estimating the dermal exposure level of

cement, although a considerable amount of literature address that dermal

cement exposure might lead to skin disorders. It is generally recommended

to avoid skin contact via the use of gloves/protective equipment.

We will estimate dermal exposure via use of ECETOC TRA consumer v 3.1

with the following input parameters:

Product subcategory: Plasters and floor equalizers

Production Ingredient Fraction: 0.05 (i.e. 5% nano-TiO2)

Skin Contact Area:

o Whole body: 21500 cm2

o Arms and hands: 20.4% of whole body adult: 4386 cm2

455

Produc

t

Ingredi

ent

(g/g)

Cont

act

Area

(cm2)

Transf

er

Factor

(unitle

ss)

FreQue

ncy of

use

(events

/ day)

Thickn

ess of

Layer

(cm)

Dens

ity

(g/c

m3)

Convers

ion

Factor

(mg/g)

Body

Weig

ht

(kg)

(PI

x

CA

x

TF x FQ x TL

x

D

x

1000) /

BW

Oral

exposur

e

NA

Eye

exposur

e

Qualitative considerations

Step 3







456

Target population: Adults


parameters


References

Body weight 60kg Nordic Council of

Ministers (2011)

Inhalation rate 10 m³/8 hours

light activity

ECHA (2012b)

Skin surface (site of contact) Arms and

hands:

4386 cm2

Whole body:

2.15 m²

(=21 500 cm2)

Nordic Council of

Ministers (2011)



Others




References

Inhalation exposure

Room volume




Dustiness

Etc.


Viscosity

Etc

Oral

Eye

Step 4

Inhalation

Peters et al. (2009) performed personal measurements of cement worker exposure to inhalable dust

and inhalable cement dust. 180 measurements were performed among cement plant and

construction workers with average sampling times of 7 hours and 43 minutes.

Highest cement exposures among construction workers were found for the following workers:

457

Operation Number of

measurement

days

Number

of

workers

Number

of

samples

Aritetic/Geometric

means (mg/m³)

Range

(mg/m³)

Concrete

repair

4 2 8 1.5/1.2 0.44-3.3

Tile setting 8 5 16 1.7/0.75 0.36-17*

Floor screed

laying

8 5 20 2.3/1.9 0.58-7.5

* It is noted that the values above 10 mg/m³ were associated with grinding machines

It is mention in the paper that these estimates are in line with other findings in the literature. It is

not noted to which extend these workers wear personal protective equipment to reduce those

exposure values.

These operations could be performed by consumers fixing their houses, driveways, etc.

However, it must be assumed that performing such operations at home would often involve less

amounts of handled cement. However, the conditions for the work may be less appropriate and it

cannot be assumed that consumers consistently apply personal protective equipment for reducing

exposure.

Overall, it seems that a reasonable worst case 8-hour average exposure estimate would be around 5

mg/m³ and around 15 mg/m³ for cement grinding operations.

Assuming as a worst case that cement could contain up to 5% nano-TiO2 and assuming that nano-

TiO2 contributes proportionally to the inhalation exposure, this would give around 0.25 mg nano-

TiO2/m³ as a worst case for cement handling and 0.75 mg/m³ for cement grinding

operations.

As a daily dose assuming 8 hour work and an inhalation volume 10m3 during 8 hours light activity

(ECHA, 2012b) this would give a daily dose of:

Cement handling: 0.25 mg/m³ * 10 m³ /60kg = 2.5 mg/day / 60 kg = 0.042 mg nano-TiO2/kg

bw/day

Grinding operations: 0.75 mg/m³ * 10 m³ /60kg = 7.5 mg/day / 60 kg = 0.13 mg nano-TiO2/kg

bw/day

Dermal

ECETOC TRA:

PC9b: Fillers, putties, plasters, modelling clay

Sub group: Plasters and floor equalizers

458

Equation:

Product

Ingredien

t

(g/g)

Contact

Area

(cm2)

Transfer

Factor

(unitless)

FreQuenc

y of use

(events /

day)

Thickness

of Layer

(cm)

Density

(g/cm3)

Conversio

n Factor

(mg/g)

Body

Weight

(kg)

(PI x CA

x

TF x FQ x TL x D x 1000) /

BW

0.05 4386

cm2

1

(default

)

1 /day

(default)

0.01 cm

(default

)

1 g/cm3

(default

)

1000 60 kg

(default

)

0.05 21

500

cm2

1

(default

)

1 /day

(default)

0.01 cm

(default

)

1 g/cm3

(default

)

1000 60 kg

(default

)

Arms and hands exposure: 36.6 mg nano-TiO2/kg bw/day

Whole body exposure: 179 mg nano-TiO2/kg bw/day

Eye:

The eye could be exposed to concentration similar to those estimated for inhalation exposure.

Further assessment of eye exposure will await eye hazard assessment of nano-TiO2 in WP3.

Step 5



There are great uncertainties associated with the concentration of nano-TiO2 in cement, but the

applied 5% is considered worst case. Further, it appears that the market penetration of nano-TiO2

cement is rather low and it might be that photocatlytic cement has not yet reached the consumer

segment.

The derived estimates for inhalation are based on reasonable worst case for workers and must

therefore be considered worst case for consumer, generally applying lower volumes of the product

and with less intensity during a work day. Consumer would also generally apply cement for a

shorter period.

In the estimation, it has generally been assumed that nano-TiO2 added to cement would

proportionally contribute to cement inhalable exposure. No data have been identified to validate

this assumption. In line with this, no data have been identified investigating to which extent nano-

TiO2 is agglomerated or bound to other particles, or could appear as free primary particles.

In relation to dermal exposure, the estimate is based on ECETOC TRA, which is a low tier and

therefore conservative exposure estimation tool. The dermal exposure estimate is of course also

affected by the nano-TiO2 content.

Overall, consumer exposure to nano-TiO2 in cement might due to market development be a

potential future exposure situation and the estimated dermal and inhalation concentrations must be

considered worst case for consumers.

459


Especially, the combination between the corrosive cement dust or slurry splashes and nanoTiO2

should be given special attention in the risk assessment.

In relation to dermal exposure, it should be considered that exposure to cement can lead to several

skin disorders such as5:

Dry skin or irritation (mild ICD)

Irritant contact dermatitis (ICD)

Allergic contact dermatitis (ACD)

Caustic burns (alkaline burns)

Which might enhance the dermal penetration/absorption of nano-TiO2.


References:

Burton M. 2011. Previous concrete with titanium dioxide as a photocatalyst compound for a greener

urban environment. M.Sc. thesis. Washington university. December 2011.

ECHA. 2012b. Guidance on information requirements and chemical safety assessment. Chapter

R.8: Characterisation of dose [concentration]-response for human health. ECHA-2010-G-19-EN.

European Chemicals Bureau, Finland.

Nazari A, Riahi Sha, Riahi Shi, Shamekhi SF, Khademno A. 2010. Assessment of the effects of the

cement paste composite in presence TiO2 Nanoparticles. Journal of American Science. 2010, 6(4),

43-46.

Peters S, Thomassen Y, Fechter-Rink E, Kromhout H. 2009. Personal Exposure to Inhalable

Cement Dust among Construction Workers. Journal of Physics:ConferenceSeries 151 (2009)

012054, 1-5.

5 See e.g.

http://www.elcosh.org/document/60/d000458/A%2BSafety%2B%2526%2BHealth%2BPractitioner%2527s%2BGuide%2Bto%

2BSkin%2BProtection.html?show_text=1#4

460

Scenario 18 - Product: Wound dressing containing nano-Ag 8.19

Description of product:

Several nano-silver wound dressings exist and are generally intended for professional treatment of

wounds, especially burns.

The wound dressing is an absorbent post-operative dressing which may consist of e.g.:

A Nanocrystalline silver-coated polyurethane layer

A white polyurethane foam pad

An adhesive coated waterproof polyurethane film layer

The dressing may be left in place over a wound for up to 7 days.

Description of exposure scenario

For use by private consumers it is anticipated that only small patches are used as healing of larger

wounds and uses of larger patches would call for professional treatment.

(Also small everyday wound-patches containing nano-Ag for small scratches are increasingly found

on the market, however this scenario cover larger patches that may be used on larger surfaces).

Step 1



Parameter Specified

data*


Product category Medical

device

Type of Product Wound

dressing

http://www.smith-

nephew.com/professional/products/all-

products/acticoat-surgical/

ID of nanomaterial Nano-Ag Particle diameter of silver crystals

(primary particle size) measured to

200-450 nm using scanning electron

microscopy (Rigo et al. 2012)


product

Textile

matrix

Package design, volume Skin patch,

4” x 43/4”

http://www.smith-

nephew.com/professional/products/all-

products/acticoat-surgical/

Application/use/

handling

Skin

application

Location of nanomaterial

eg. free/ matrix-bound

Semi-

bound

(sustained

release)

Direct/ indirect exposure Direct

exposure


Generation of

nanomaterial during use

Perhaps Nano-silver particles may be released or

dissolved silver may precipitate as

nanosize silvercompounds.

http://www.smith-nephew.com/professional/products/all-products/acticoat-surgical/






461

Specific target group

(children, teenagers etc.)

All/ child Children chosen as target group as their

lower body weight would result in a

higher weight based exposure compared

to adults.

Forseeable misuse -

Site of contact/ exposure wound

surface

Primary exposure

route(s)

Dermal

Concentration of

nanomaterial in

product

- 1.64 mg/cm2 Rigo et al. (2012); Roman et al. (2013).

Volume of product

used, exposed to

1 skin patch Area:

4" x 43/4" or

10 x 12 cm

(120 cm2)

Body area exposed to 10 x 12 cm

(120 cm2)

Considered as worst case consumer use,

as use of larger patches would call for

professional treatment.

Retention rate on

body surface

1 100% of the dose remain at the

application site

Migration/liberation

rate of nanomaterial

from matrix

Up to 60% Roman et al. (2012)

Ingested amount -

Volume of product

released to air /

concentration in air

-

Duration of exposure 1 day Conservative as a new silver load is

considered every day. According to the

recommendations the patch may rest

for up to 7 days on the skin.

Frequency of

exposure

daily 21 days is assumed as longest treatment

period

* “ - “ if not given or not relevant

Step 2 Algorithms



section 4.2) :

462

Exposure route Algorithms used Comments

/

References

Dermal exposure

Surface exposure (mg/cm2) = Dermal load (mg/cm2) x Migration rate

Dose (mg /kg bw d) =

Skin Area (cm2) x Dermal load (mg/cm2) / bodyweight x Migration

rate x Events/ day

That the external dermal exposure to wound dressings may lead to silver migration, absorption and

increased serum levels of silver has been verified by Vlachou et a. (2007), see section 5.8.2.

Step 3 Target group







Target population: Child 2 years


parameters


References

Body weight 13 kg Danish EPA (2006)/

Nordic Council of

Ministers (2011)

Skin surface (site of contact) on

damaged skin/ wound

10 x 12 cm

(120 cm2)

Assumed


The wound dressing (skin patch) may contain up to 1.64 mg of nano-Ag per cm2 of dressing. The

dressings are used for their aseptic properties and for the healing of wounds especially in

connection with skin burns.

For consumer scenario a worst case scenario with a 2 year-old child (body weight of 13 kg) is

assumed using 1 dressing (10cm x 12 cm) per day in 21 days. It is not assumed realistic that parents

would treat larger wounds themselves as larges wounds would call for professional treatment.

Although not recommended, the patch is as a worst case assumed to be changed each day during

the treatment period. I.e. the treatment is considered to end after 3 weeks either because of healing

of the wound or because of change to other type of treatment in case no healing occurs.

Measured data on release indicate a release rate of up to 60% (Roman et al. 2013).

From this the external dermal dose can be calculated as:

463

Child:

Surface exposure (mg/cm2) = Dermal load (mg/cm2) x Migration rate

Surface exposure (mg/cm2) = 1.64 mg nano-Ag/cm2 x 0.6 = 0.98 mg Ag/cm2

Dermal Dose (mg /kg bw d) =

Skin Area (cm2) x Dermal load (mg/cm2) / bw x migration rate x events/ day

Dermal Dose (mg /kg bw d) =

120 cm2 x 1.64 mg nano-Ag/cm2 / 13 kg x 0.6 x 1/ day = 9.08 mg nano-Ag/ kg bw d

Step 5 Uncertainties of the described exposure scenario

Description of the validity and robustness of the exposure estimates Also larger particles sizes of

200-450 nm has been measured and reported for such products. Several data indicate that the

concentration of nano-Ag is up to 1.64 mg Ag/cm2, which is used as a worst case.

It is not considered realistic that parents would treat larger body areas than an area of 120 cm2 of a

child with the wound dressing as larger wounds would call for professional treatment.

Measured data indicate release of up to 60% from the patch to the skin and this is considered as a

worst case assumption for 24 h exposure.

Also the use of 21 patches during a 21 days period is a worst case.

All in all a daily dermal exposure of 9.08 mg nano-Ag/ kg bw d is considered as a realistic worst

case consumer scenario for the product.

Step 6 (for WP5)

This type of dermal scenario with nano-Ag used in wound dressing may be seen in context with

other textile dermal exposure scenarios for nano-Ag e.g. the use of nano-AG in sports socks, T-shirt

underwear etc. Also aggregated exposure may be seen in context with other uses for nano-Ag e.g.

cleaning sprays air fresheners etc.

Medical treatment of larger burns in clinics and hospitals might lead to considerably higher

exposures.

References


Rigo, C., Roman M., Munivrana, I., Vindigni, V., Azzena, B., Barbante, C., Cairns, W.R.L.

2012.Characterization and evaluation of silver release from four different dressings used in burns

care. Burns.38, 1131–1142.

Roman M., Rigo, C., Munivrana, I., Vindigni, V., Azzena, B., Barbante, C., Fenzi, F., Guerriero, P.,

Cairns, W.R.L. 2013. Development and application of methods for the determination of silver in

polymeric dressings used for the care of burns. Talanta 115, 94-103.


464

Vlachou, E., Chipp, E., Shale, E., Wilson, Y.T., Papini, E., Moiemen, N.S. 2007.The safety of

nanocrystalline silver dressings on burns: A study of systemic silver absorption. Burns 33, 979-985.

465

Scenario 19 - Product: Nanocomposite product for dental 8.20

replacement and restoration containing nano-Zirconia and nano-

silica

Description of exposure scenario: Casting and fitting with dentist tools

Step 1




Estimated*


Product category

dental product

http://solutions.3m.co.uk/wps/portal/3M/en_GB/3M_ESPE/Dental-Manufacturers/Products/Dental-Restorative-Materials/Dental-Composites/Dental-Nanocomposites/

Type of Product

ceramic tooth for dental replacement

ID of nanomaterial

nano-ZrO2 and nano-Silica

Van Landyot et al. (2012). The material safety data sheet (MSDS) contains no specific information on the nanomaterials: http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YteMx2Zlv70kDVFNvu9lxtD7SSSSSS--

http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YtUlYt15v70kDVFNvu9lxtD7SSSSSS-- However, the first MSDS informs that in one case the silica is a silane-treated silica with a concentration of 5-10 % and that the material consists of 65-75% silane-treated ceramic http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YteMx2Zlv70kDVFNvu9lxtD7SSSSSS--


20 nm nanosilica 5-20 nm nano-Zirconia NA

Van Landyot et al. (2012).


Nanocomposite


1 g Estimated mass of replacement/repeared tooth


Dental replacement


In viscous paste during applicatio




http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YteMx2Zlv70kDVFNvu9lxtD7SSSSSS--


http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YtUlYt15v70kDVFNvu9lxtD7SSSSSS--

http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YtUlYt15v70kDVFNvu9lxtD7SSSSSS--



466

n matrix bound during use


Direct exposure

Indoor/ outdoor use

NA


yes Yes

Wear test show high resistance to wear. Following a specific test the product wore of 5 µm/200.000 cycles and were among the best in the test panel. “The wear rate of Filtek™ Supreme XTE Universal Restorative DEB shades and T shades is comparable to the 3-body wear of Filtek™ Supreme XT

Universal Restorative. In addition our tests have also proven that the 3-body wear of Filtek Supreme XTE universal is lower than a wide range other competitive microfills and universal restoratives on the market” http://solutions.3m.co.uk/wps/portal/3M/en_GB/3M_ESPE/Dental-Manufacturers/Products/Dental-Restorative-Materials/Dental-Composites/Dental-Nanocomposites/#tab4 Van Landyot et al. (2012) showed release of debris particles during reshaping the replacement tooth.


Adults, teenagers, and children

Forseeable misuse

No


oral exposure

The replacement tooth involves risk of long-term exposure to wear-debris


Inhalation and oral

Inhalation during installation of the tooth and re-shaping (fitting) Oral during installation of the tooth and re-shaping (fitting) as well as long-term use.


5-10 wt% nanosilica

65-75 wt% nanoZrO2

The MSDS informs in one case that the replacement tooth consists of 5-10% silane-treated silica and 65-75% silane-treated ceramic http://multimedia.3m.com/mws/mediawebserver?mwsId=SSSSSuUn_zu8lzNv4YteMx2Zlv70kDVFNvu9lxtD7SSSSSS--

The total silica and ceramic (ZrO2) content is assumed to be ascribed as nanomaterials.


NA 1 g The replacement tooth is assumed to weigh 1 g


oral cavity


Assumed 1

R.15 v. 2.1 (ECHA, 2012)


Yes, but low

The rate of degradation is low according to the wear test. http://solutions.3m.co.uk/wps/portal/3M/en_GB/3M_ESPE/Dental-Manufacturers/Products/Dental-Restorative-

http://solutions.3m.co.uk/wps/portal/3M/en_GB/3M_ESPE/Dental-Manufacturers/Products/Dental-Restorative-Materials/Dental-Composites/Dental-Nanocomposites/#tab4







467


Materials/Dental-Composites/Dental-Nanocomposites/#tab4. See discussion under oral exposure below.

Ingested amount

Possible Acute relatively high ingestion rate during instillation and shaping of replacement tooth. Slow ingestion rate from debris.


1 mg/m3 Concentrations of Particulate Matter (PM10) smaller than 1 µm in size have been shown to exceed 60 µg/m3 in a workplace measurement in a dental clinique. The total suspended dust concentrations reached 10 mg/m3 (Van Landyot et al., 2012). Since respirable dust is ca. PM4.5, and the consumer is at the source, it is estimated that the average respirable dust concentration could be on the order of 1 mg/m3 during processing the tooth.


30 min 30 min 10 years

inhalation (estimate) Acute oral exposure (estimate) Chronic oral exposure (estimate)


Acute (once every 10 year) Chronic

during establishment of the replacement tooth during long-term wear and degradation of the tooth




Step 2



section 4.2) :


References

Inhalation

exposure

Concentrations of Particulate Matter (PM10) smaller than 1 µm in size have been shown to exceed 60 µg/m3 in a workplace measurement in a dental clinique. The total suspended dust concentrations reached 10 mg/m3 (Van Landyot et al., 2012).

Since respirable dust is ca. PM4.5, it is estimated the that

average respirable dust concentration could be on the

order of 1 mg/m3 during the 30 min processing the

tooth. The exact composition of the dust was not

characterized, so it is conservatively assumed that all

dust was due to the nanocomposite debris.

A mass-based assessment of the inhalation exposure is

made using the traditional Tier 1 estimation of inhaled

dose in R.15 (ECHA, 2011):

nBW

TIHCFD

contactairinhresp

inh

Input


Cinh Concentration of [mg/m3]

Van Landyot et

al. (2012)

ECHA (2011)


468

substance in air of room


[-]


[m³/d]


[d]

BW Body weight [kg]


[/d]

Output parameter

Description


[mg/kg BW d]

Oral exposure It is evident that there is acute oral exposure in

connection with instillation and shaping the replacement

tooth/filling. Wear tests also show that some wear occurs

even-though it is small. However, no relevant data was

found on the amount of debris produced during finishing

that could be used for human exposure assessment.

Similar, no measurement data were found for assessment

of the chronic exposure during use.

Wear tests by one of the producers

http://solutions.3m.co.uk/

wps/portal/3M/en_GB/3M_ESPE/Dental-

Manufacturers/ Products/Dental-Restorative-

Materials/Dental-Composites/ Dental-

Nanocomposites/#tab4 reveal that ca. 5 µm were worn

of after 200.000 standard test cycles. Assuming a 0.75

cm2 chewing area of a tooth repair and similar wear

during 1 years of use this gives an annual release of (0.75

cm2 x 0.0005 cm) 3.75x10-4 mg assuming density is 1

g/cm3). However, this purely a speculative value. More

documentation is needed to complete a trustworthy

assessment.

It should, be noted that the inhaled exposure dose

calculated below also contribute to the gastro-intestinal

exposure dose.

Dermal contact

exposure

Oral cavity exposure is relevant, but no useable data were

found for this assessment.

Eye exposure


http://solutions.3m.co.uk/%20wps/portal/3M/en_GB/3M_ESPE/Dental-Manufacturers/%20Products/Dental-Restorative-Materials/Dental-Composites/%20Dental-Nanocomposites/#tab4





469

Step 3








Anatomical

/Physiological

parameters



60 kg (female)

71.6 (16-<21

years)

18.6 kg (3-<6

years)


Retention rate 1

Skin surface (hand,

head):

NA

Density NA

Daily amount NA

Application per year 1/10 One tooth replacement and repair every 10 years

Amount which may

get in contact with

skin through

splashes or direct

contact.

NA Oral cavity contact with saliver and tongue. Area not

assessed.

Concentration of

nanomaterial in

product

<85 wt% The combined concentration of nano-Silica and nano-

Zirconia

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

NA

Other relevant parameters not used in the algorithms for exposure assessment.


References

Inhalation exposure

Ventilation rate


Surface deposition


Schneider et al.

(2011)

470

Dermal exposure Relevant, but not assessed

Oral Relevant, but not assessed

Eye Not assessed

Step 4




2012)

daykgmg

dayday

m

m

mg

nBW

TIHCFD maleBW

contactairinhresp

inh ,

3

3

/012.0170

24

2

1

32.4011

First year inhaled dose for one treatment: 1 x 0.012 mg/KgBW,maleday =

0.012

mg/KgBW,maleYear

If life-time of replacement is 10 years the average annual dose is: 0.0012 mg/KgBW,maleYear



2012)

daykgmgkg

daymm

mg

nBW

TIHCFD femaleBW

contactairinhresp

inh ,

3

3

/014.0160

24

2

1

32.4011

First year inhaled dose for one treatment: 1 x 0.014 mg/KgBW,femaleday =

0.014

mg/KgBW,femaleYear

If life-time of replacement is 10 years the average annual dose is: 0.0014 mg/KgBW,femaleYear

471

Child (18.6 kg):

Inhaled Dose: Respiration rate 0.00576 m3/min (8.3 m3/day) for moderate intensity; body-weight

= 18.6 kg (Nordic Minister Council report; 2012):

daykgmgkg

dayday

m

m

mg

nBW

TIHCFD childBW

contactairinhresp

inh ,

3

3

/0093.016.18

24

2

1

3.811

First year inhaled dose for one treatment: 1 x 0.0093 mg/KgBW,childday =

0.0093

mg/KgBW,shildYear

If life-time of replacement is 10 years the average annual dose is: 0.00109 mg/KgBW,childYear

Nanocomposite dental

replacement (1 g)

Male (70 kg), [µg/kg] Female (60 kg),

[µg/kg]

Children (18.6 kg)

µg/kg

Acute inhalation dose 12 14 9.3

Average annual

inhalation dose

1.2 1.4 1.1

Step 5



The composition of different ceramic tooth repair and replacements can vary considerably. In this

specific composition with a relatively high total ceramic content was used for the assessment. Other

products may have different compositions and from the reported standardized wear-data a higher

potential release rate during both finishing and use leading to acute and long-term (chronic)

exposure.

In the inhalation scenarios, the airborne exposure is assessed assuming that the measured room

concentration values at the dentistry found in a scientific publication is indicative of the consumer

exposure during treatment. It was observed that the concentrations of Particulate Matter

(PM10) exceeded 60 µg/m3 in a dental clinique and the total suspended dust

concentrations reached 10 mg/m3 (Van Landyot et al., 2012). It was assumed that the

average concentration of respirable dust (PM4.5; particles up to 4.5 µm size) at the

consumer was 1 mg/m3 and therefore higher than the room concentration of PM10

(particles up to 10 µm in size). This is a highly uncertain estimate, but assuming that the

entire estimated respirable dust was consisted of nanomaterial and that the duration of the

treatment was 30 min, the scenario is considered to be reasonable precuationary. However,

experimental evidence is highly warrented to clarify this type of exposure.

Dermal and gastric exposure (oral cavity) was not assessed specifically due to lack of enough

material detail or exposure data. Oral uptake would also come from the inhalation dose where

transport from nose and mouth as well as the mucusiliary escalator from the respiratory tract

472

contribute to the oral exposure. So the inhaled dose is also the worst case oral dose. Considering,

the theoretical consideration above, an annual wear of one tooth would result in 3.75x10-4 mg

release from the tooth every year. Using the body weight of the small child (18.6 kg) this

amounts to 2.02x10-5 mg/KgBWchild per year. This is ca. 461 times less than the inhalation

exposure assessed for the clinical exposure.


The application of nanoceramic dental products is said to be increasing fats and is already widely

used.

There are rarely other sources for nano-zirconia inhalation and oral exposure whereas exposure to

nanosilica can arise from different sources.




References:









450–463.

Van Landuyt KL, Yoshihara K, Geebelen B, Peumans M, Godderis L, Hoet P, van Meerbeek B. 2012.

Should web e concerned about composute (nano-)dust?. Dental Materials 28, 1162-1170.



473

Scenario 20 - Product: Golf club with CNT re-enforced shaft 8.21

Description of exposure scenarios: Fitting of shaft and wear and tear during use

Step 1


with additional information when necessary. Parameter Specified

data* Estimated*


Product category

Sports equipment

http://www.nanocyl.com/en/Products-

Solutions/Sectors/Recreational

http://www.yonex.com/i-ezone/technology/ http://www.shaftdeals.com/productdetail.cfm?InventoryID=659 http://www.harrison.com/custom-fitting

Type of Product golf club ID of nanomaterial

SWCNT and CSWCNT

Nanocyl produces Multi-walled carbon nanotubes (MWCNT) for

sports equipment http://www.nanocyl.com/en/Products-


Several of Yonex golf clubs have been known to contain Cup-Stack

Carbon Nanotubes; CSCNT (e.g., Yonex Rexis Premium Golf Shaft,

Nanopreme™, Nanospeed, and i-EZONE). http://www.yonex.com/i-

ezone/technology/. However, single-walled (SW) CNT may also be

applied by this company. Muggen series shafts: “Strategically positioned Single Walled Carbon Nanotubes (SWNTs) are embedded in the tip section of the shaft to further strengthen and enhance the Muggen Blues performance and durability.” http://www.shaftdeals.com/productdetail.cfm?InventoryID=659 Similar technology is described by others: http://www.harrison.com/staticpages/carbon-nanotubes; http://www.harrison.com/custom-fitting


"Generic" CNTs

No specific details on the dimensions and functionalizations are given for any of the CNT mentioned in specific products.


nanocomposite / layer nanocomposite


NA NA Amount is unknown.


Leisure sports equipment


matrix bound or layered nanocomposite

Nanocyl’s EPOCYL™ products. These products offer sporting goods

designers and manufacturers an integrated, innovative technology for

improving the strength, fracture toughness, shelf life, and antistatic

properties in composite parts. Common applications include bike

frames, hockey sticks, tennis rackets, golf shafts, and skis.



Yonex: Nanopreme™, the carbon nanotube (CNT) enhanced epoxy

resin results in improved performance of golf clubs and racquets. This

application has been found in e.g., the Yonex Nanospeed 3i AW Iron

http://www.nanocyl.com/en/Products-Solutions/Sectors/Recreational


http://www.yonex.com/i-ezone/technology/

http://www.shaftdeals.com/productdetail.cfm?InventoryID=659

http://www.harrison.com/custom-fitting





http://www.shaftdeals.com/productdetail.cfm?InventoryID=659

http://www.harrison.com/staticpages/carbon-nanotubes




474

and i-EZONE technology. http://www.yonex.com/i-ezone/technology/

”SWNTs are known as one of the lightest and strongest materials

available today. …….When embedded in the tip section, the weakest

part of a golf shaft, SWNTs enhance its strength and stability with

negligible weight increase.”

http://www.harrison.com/staticpages/carbon-nanotubes;

http://www.harrison.com/custom-fitting Direct/ indirect exposure

Directexposure Indirect

During fitting During wear/tear of the product

Indoor/ outdoor use

Indoor Outdoor

Indoor use is possible and chosen for the reworking scenario Outdoor use is typical intended application


yes

It is assumed possible that small amounts of CNT may be liberated during intended use and accidents such as breaking the club. Release is especially possible if the product is aged or breaks after extensive use and UV-degradation of the matrix (see review by Jensen et al., submitted). Fitting/repair of the club via sanding/drilling is assumed to liberate CNT. It has been demonstrated that CNT may be partially liberated from layer composites and also matrix nanocomposites. Especially, if the product is aged by UV-degradation.


Adults

Forseeable misuse

Yes The consumer may break the golf club to investigate its structure or accidentally (?) grind into the layer with CNT.


NA




NA


NA


hands


Assumed 1

R.15 v. 2.1 (ECHA, 2012)


NA

Ingested amount

Possible Inadvertent oral exposure (finger to mouth contact) is possible, but the possible dose for consumer use is considered low.


NA Discussed below

Normal use: There are no data available on the CNT exposure or release during use of consumer products. The risk of exposure during normal use is considered low (Kingston et al., 2014; Jensen et al., submitted). There are no specific case-studies on the CNT release from golf clubs. However, qualitative assessments suggest risk of exposure during breaking and mechanical reworking on sports equipment (Jensen et al., 2014). This is supported by results from release studies of emissions during sanding, grinding and cutting CNT-based matrix




475

nanocomposites. Duration of exposure

30 min 1½ hour

Inhalation (estimate in case of fitting and breaking the shaft) Dermal contact exposure (estimate for weekly normal use)


2 per year Weekly

Cutting, sanding or breaking the shaft Normal use




Step 2



section 4.2) :


References

Inhalation

exposure

There are no data available on the exposure during use of

CNT-re-enforced golf clubs. However, relevant studies on

the dust- and CNT-release characteristics and rates during

mechanical processes and weathering of CNT products

have been published.

Producers and distributers describe that the CNT in golf-

clubs are embedded in an epoxy resin.


Solutions/Sectors/Recreational,

http://www.yonex.com/i-ezone/technology/,

http://www.harrison.com/staticpages/carbon-nanotubes;


Products based on epoxy resins are hard and brittle, the

matrix degrades by UV-irradiation (CNT can stabilize

this), they are susceptible to oxidation and hydrolysis, but

have overall low rate of mechanical degradation resulting

in a low release potential.

Jensen et al. (in press) and this report (see Chapter 5)

conclude that mechanical reworking of weathered

products will increase the likelihood of CNT exposure

considerably. Jensen et al. (submitted) states that there,

especially for CNT-layer nano-composites, is potential for

exposure during use of UV-degraded products, and

products with mechanical failure and their mechanical

reworking. However, at the percentages normally used in

consumer products, it appears unlikely to reach critical

exposure levels during normal consumer use.

Release studies on polyurethane with and without 3 wt%

MWCNT showed particle release during treatment with

both taber abrasion (normal use), sanding, and

weathering. Protruding MWCNT was found in debris

particles from mechanical treatment and at least 97 wt%

of the CNT was determined to remain associated with the

Kingston et al.

(2014)

Jensen et al. (in

press)

Wohlleben et al.

(2013)






476

polyurethane. Weathering caused formation of a MWCNT

rich crust (723 wt% CNT) at the surface of the product

after 9 and 18 months weathering.

Abrasion of epoxy nanocomposite with 0, 0.1 and 1 wt%

CNT resulted in a release of ca. 8,000 – 20,000 fine sub-

µm size particles/cm2 and 1,000 – 3,000 particles/cm2 in

the 0.6 to 2.5 µm range. Free CNT and agglomerates were

observed in the abrasion dust, but the fraction of CNT was

not quantified.

Cutting, grinding, and sanding of a carbon nanofiber-

doped plastic composite in an occupational setting showed

personal exposure levels reaching 1,934 particles/cm3

during wet-sawing without ventilation and observation of

free carbon nanofibers in air-samples. Higher, but

comparable concentrations were observed for sanding,

which also liberated carbon nanofibers.

Gomez et al. (2014) investigated the release rate and

characteristics of sanding EPOCYL NC R128-04 Resin

with 20 wt% NC7000 MWCNT (given as CNT with 9.5 nm

diameter and 1.5 µm length). This product may be similar

to the type of resin used on sports products with

EPOCYLTM as mentioned above. No significant difference

was observed in the size-distributions of released dust (2

or one broad mode from ca. 100 nm to 10 µm with at least

a peak mode around 1 µm). The release rate during

sanding was highest (ca. 4-6 x 103 particles/cm3sec in a

0.66 m3 chamber) for particles in the 300 nm to 1 µm

range. Abrasion particles with protruding CNT were

observed, but free CNT was not observed.

Schlagenhauf et

al. (2012)

Methner et al.

(2012)

Gomez et al.

(2014)

Dermal contact

exposure

There are no data available on the dermal exposure during

use of golf clubs with CNT.

The dermal consumer exposure risk and exposure levels

are generally evaluated negligible to very low for the

product types currently identified on the market.

However, there is potential for exposure during use of UV-

degraded products, especially layer nano-composites, and

products with mechanical failure and their mechanical

reworking. (Jensen et al., submitted).

Jensen et al.

(submitted)

Oral exposure

Inadvertent oral exposure is possible, but the possible

dose for consumer use is considered low.

Eye exposure

Considered possible, but negligible

477

Step 3








Anatomical

/Physiological

parameters



60 kg (female)

71.6 (16-<21

years)


Retention rate 1

Skin surface (hand,

head):

NA

Density NA

Daily amount NA NA

Application per year 2

52

Cutting, sanding or breaking the shaft

Using the golf club

Amount which may

get in contact with

skin through

splashes or direct

contact.

NA

Concentration of

nanomaterial in

product

NA

Specific behaviour

(duration for e.g.

mouthing of

children)

NA

Layer thickness

Transfer efficiency

NA

Step 4


No exposure estimations are made. According to the description in section 3, exposure to free CNT

is possible. This is especially true during shaft fitting and if the product has been subjected to wear

and tear. There is no precise information on the abundances of CNT in the products. Due to the

many unknown factors, exposure estimations have not been completed at this stage. However,

qualitatively, exposure is possible:

478

Products based on epoxy resins are hard and brittle, the matrix degrades by UV-irradiation (CNT

can stabilize this), they are susceptible to oxidation and hydrolysis, but have overall low rate of

mechanical degradation resulting in a low release potential.

Jensen et al. (in press) and this report (see Chapter 5) states that there, especially for CNT-layer

nano-composites, is potential for exposure during use of UV-degraded products, and products with

mechanical failure and their mechanical reworking. However, at the percentages normally used in

consumer products, it appears unlikely to reach critical exposure levels during normal consumer

use.

Abrasion of epoxy nanocomposite with 0, 0.1 and 1 wt% CNT resulted in a release of ca. 8,000 –

20,000 fine sub-µm size particles/cm2 and 1,000 – 3,000 particles/cm2 in the 0.6 to 2.5 µm range.

Free CNT and agglomerates were observed in the abrasion dust, but the fraction of CNT was not

quantified.

Cutting, grinding, and sanding of a carbon nanofiber-doped plastic composite in an occupational

setting showed personal exposure levels reaching 1,934 particles/cm3 during wet-sawing without

ventilation and observation of free carbon nanofibers in air-samples (Methner et al., 2012). Higher,

but comparable concentrations were observed for sanding, which also liberated carbon nanofibers.

Gomez et al. (2014) investigated the release rate and characteristics of sanding EPOCYL NC R128-

04 Resin with 20 wt% NC7000 MWCNT (given as CNT with 9.5 nm diameter and 1.5 µm length).

This product may be similar to the type of resin used on sports products with EPOCYLTM as

mentioned above. No significant difference was observed in the size-distributions of released dust

(2 or one broad mode from ca. 100 nm to 10 µm with at least a peak mode around 1 µm). The

release rate during sanding was highest (ca. 4-6 x 103 particles/cm3sec in a 0.66 m3 chamber) for

particles in the 300 nm to 1 µm range. Abrasion particles with protruding CNT were observed, but

free CNT was not observed.

The dermal consumer exposure risk and exposure levels are generally evaluated negligible to very

low for the product types currently identified on the market. However, there is potential for

exposure during use of UV-degraded products, especially layer nano-composites, and products with

mechanical failure and their mechanical reworking. (see Chapter 5; Jensen et al., submitted).

All in all, the published data suggest that exposure to free CNT may occur in some cases. The

highest risk of exposure is associated with abrasion (shaft fitting) and if the golf-club is aged or

weathered. Due to the amount of CNT in each golf club, it is considered that the actual exposure

level to free CNT is very low to moderate. However, the final assessment strongly depends on the

hazard.

Step 5



Absolute exposure estimates could not be completed due to lack of relevant emission and exposure

data. There is great uncertainty in which amounts CNT is used in golf clubs and at what structural

location. Relevant data for this product group is highly needed.


479

There is a possibility for CNT exposure during fitting and use of the golf club. However, the

expected exposure levels are low. Most of the exposure will be to composite fragments with

embedded or protruding CNT. Consult the exposure characterization in Step 2.

This scenario is assessed to be generally relevant for CNT in sports equipment such as rackets, skis

etc.


References:






Gomez V, Levin M, Saber AT, Irusta S, Dal Maso M, Hanoi R, Santamaria J, Jensen KA, Wallin H,

Koponen IK, 2014. Comparison of dust release from epoxy and paint nanocomposites and

conventional products during sanding and sawing. Annals of Occupational Hygiene, e-pub ahead of

print. doi:10.1093/annhyg/meu046

Jensen KA, Bøgelund J, Jackson P, Jacobsen NR, Birkedal R, Clausen PA, Saber AT, Wallin H,

Vogel UB, submitted. Carbon nanotubes - Types, products, market, and provisional assessment of

the associated risks to man and the environment. Environmental Report. Danish Ministry of the

Environment, Environmental Protection Agency. 143 pp.

Kingston C, Zepp R, Andrady A, Boverhof D, Fehir R, Hawkins D, Roberts J, Sayre P, Shelton B,

Sultan Y, Vejins V, and Wohlleben W. 2014. Release characteristics of selected carbon nanotube

polymer composites. Carbon 68, 33-57.

Methner M, Crawford C and Geraci C. 2012. Evaluation of the potential airborne release of carbon

nanofibers during the preperation, grinding, and cutting of epoxy-based nanocomposite material.

Journal of Occupational and Environmental Hygiene 9, 308-318.

Schlagenhauf L, Chu BTT, Buha J, Nüesch F, and Wang J. 2012. Release of Carbon Nanotubes from

an Epoxy-Based Nanocomposite during an Abrasion Process., 7366-7372. Environ. Sci. Technol.

Wohlleben W, Meier MW, Vogel S, Landsiedel R, Cox G, Hirth S, and Tomovic Z. 2013. Elastic

CNT-polyurethane nanocomposite: synthesis, performance and assessment of fragment release

during use. Nanoscale 5, 369-380.



Strandgade 29

1401 Copenhagen K, Denmark

Tel.: (+45) 72 54 40 00

www.mst.dk

Appendix report

Appendix for environmental project No. 1636: Exposure assessment of nanomaterials in consumer

products.