CHEMICAL SAFETY REPORT - ECHA

Non-confidential version CHEMICAL SAFETY REPORT i

CHEMICAL SAFETY REPORT

Substance Name: 1,2-dichloroethane

EC Number: 203-458-1

CAS Number: 107-06-2

Applicant(s):

H&R Ölwerke Schindler GmbH,

H&R Chemisch-Pharmazeutische Spezialitäten GmbH (Co-applicant)

Use applied for:

Industrial use as a solvent and anti-solvent of the feedstock and intermediate product streams

in the combined de-waxing and de-oiling of refining of petroleum vacuum distillates for the

production of base oils and hard paraffin waxes

EC number:

203-458-1

1,2-dichloroethane CAS number:

107-06-2

Non-confidential version CHEMICAL SAFETY REPORT 21

9. EXPOSURE ASSESSMENT (and related risk

characterisation)

9.0. Introduction

9.0.1 Process description

9.0.1.1 General description

The applicants are operating two specialty refineries in Germany, one in Hamburg (H&R Ölwerke

Schindler GmbH) and one in Salzbergen (H&R Chemisch-Pharmazeutische Spezialitäten GmbH). Both

refineries are processing very similar raw material (Vacuum Gas Oil, Atmospheric Residue) with very

similar main production steps (distillation, extraction, de-waxing/de-oiling and hydrofinishing). Out of

the raw material mixture more than 800 different specialty products are generated.

Figure 1: Scheme of Base oil Production

De-waxing/De-oiling is a required production step in the couple production of these refineries. For the

production process of such a wide range of different products an effective de-waxing/de-oiling step is

necessary for achieving the required product specifications.

The purpose of solvent de-waxing is to remove waxy components from oil products out of the

extraction plants to get a base-oil with a low pour point, see Figure 1.

This first filtration stage is the so called de-waxing stage. In this step the wax is separated from the base

oil. Therefore, the raffinate has to be diluted with a selective solvent and chilled to a low temperature

(e.g. -20°C). By lowering the temperature the waxy components begin to crystallize. The solid waxy

crystals can then be removed by filtration. Important for quality aspects and product yield is the

effective washing of these crystals to remove oily components out of the filter cake.

The quality properties set by the de-waxing process include pour point of the de-waxed oil, filtration

rate and oil content of the paraffinic filter cake.

The produced wax is called slack wax. It contains some oil fraction (typically 3% to 16%). In an

additional second step, the slack wax can be warmed up a bit and then be de-oiled in a second filtration

stage to achieve a hard wax with a very low oil content and the filtrate-product of the second filtration

stage called soft wax. The process of the second filtration stage is almost similar to the de-waxing step,

it only differs in a higher temperature (typ. 0...+5°C). As quality criteria in the second filtration stage the

permeability of the filter cake and effective washing to remove oily components out of the filter cake is

elementary for this process.

The produced hard waxes have very low oil content and can then be hydrofinished or sold directly to the

Base oil

Waxes

De-waxing/Deoiling

Asphalt

PDA

Hydrofinishing

Extracts

Feed Distillates Extraction Raffinates

(ATM/AGO)Distillation

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different industries.

Picture 1: Products (left to right: Raffinate, Baseoil, Hardwax, Foots oil)

The applicants together are operating three de-waxing/de-oiling units. One of these units is located in

Salzbergen and called EP. The unit is a 2 filtration-stage process with a de-waxing stage and integrated

de-oiling stage.

Two units are located in Hamburg. The EP1 at Hamburg site is a 2 filtration-stage process with

de-waxing and integrated de-oiling stage and the process is similar to Salzbergen operation (Figure 3).

At Hamburg site there is an additional de-waxing plant called EP2, which is a 1 filtration stage process

for de-waxing only (Figure 4).

Table 10. Distribution of de-waxing and de-oiling units at the two sites

Location Unit Name De-waxing-Step De-oiling Step

Hamburg EP1 Yes Yes Figure 2

Hamburg EP2 Yes No Figure 3

Salzbergen EP Yes Yes Figure 2

Hamburg EP1 and Salzbergen EP sites have similar processes, technical equipment and risk

management measures for de-waxing and de-oiling activities. Therefore, all technical descriptions in

this section equally stand for the Hamburg and Salzbergen sites.

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Figure 2: Salzbergen, EP1 Hamburg (de-waxing with integrated de-oiling)

Figure 3: EP2 Hamburg (de-waxing without integrated de-oiling)

The advantage of an integrated configuration is, that the wax fraction has not to be processed a second

time. In the first filtration stage the waxy oil product is de-waxed, paraffinic components are removed

out of the de-waxed oil. Followed by separation of solvent the oil is a base-oil ready for sale or further

processing (e.g. hydrofinishing).

The separated paraffinic fraction is not a fully de-oiled paraffinic product, because some oily

components are still included into the wax. For a further removal of these oily fractions, a second

filtration stage is needed. The intermediate slackwax-mix from the de-waxing stage, which is stored in a

mix-vessel, is mixed with additional solvent and heated up for de-oiling. The temperature rise from

de-waxing temperature to de-oiling temperature is depending on the feed-fraction. The lower wax

fractions are melted and soft-waxes and oily occlusions in the wax crystal structure are solved. The

warm slack-wax/solvent mixture is then directed to a second filter stage. The process of filtering is the

same as in the first filtration stage. The difference is the higher filtration temperature. The liquid phase

is the occluded oil, which is called foots oil (an oily slackwax). The remaining wax is a so called

hardwax. Both products contain solvent after the filtration, which is removed in the recovery section.

Each stream has its own recovery section.

Picture 2: EP-Salzbergen

Solvent Recovery (Foots Oil) Tanks Footsoil

Solvent Recovery (Hardwax)Warm up 2. Filtration

Solvent Recovery (Base Oil)

Tanks Paraffin

Tanks Baseoil

Feed Crystallisation 1. Filtration

Solvent Recovery (Hardwax) Tanks SlackwaxFeed Crystallisation 1. Filtration

Solvent Recovery (Base Oil) Tanks Baseoil

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9.0.1.2 Description of process unit operations

The de-waxing/de-oiling process can be described in three main process unit operations:

- Crystallization in the presence of solvent

- Filtration and filter-cake washing in the presence of solvent

- Solvent Recovery section

Crystallization in the presence of solvent

The objective of the crystallization is to solidify the waxy components out of the oily components, so

that they could be removed easily by filtration. The de-waxing units are charged with warm waxy oil

(raffinate) (80-90°C) from the storage tank. Before the waxy oil begins to crystallize, it has to be diluted

with a solvent. The applicants’ plants use as solvent a specific mixture of dichloromethane (DCM) and

1,2-dichlorethane (EDC). DCM is a solvent for solving all the oily components, whereas EDC is a

solvent which is needed to precipitate waxy components out of the solution. A specified dilution is

needed to lower the viscosity of the feed and to solve all components of the feedstock components.

When it is chilled crystals of waxy compounds are built and are slowly growing. To remain it fluent, a

solvent ratio depending on the feedstock in a range from 200 %-Mass to 600%-Mass solvent-mixture

per feed needs to be maintained.

The mixture is precooled with cold filtrate from the filter section. After precooling the mixture is chilled

to the filtration temperature. The filtration temperature depends on the raffinate fraction and the

required pour point of the de-waxed oil. The chilling train consists of a special heat exchanger. Before

the solvent raffinate mixture enters the vacuum rotary filter, it’s again diluted with cold lean filtrate.

This dilution is needed to get the slurry more liquid. The mixture of DCM/EDC ensures a crystallization

performance which results in a good (fast) filtration rate with a permeable filter cake in which the oily

components can be washed through the filter cloth easily.

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Picture 3: Crystallisation Train

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Filtration and filter cake washing in the presence of solvent

The objective of the vacuum rotary filter is to separate the slurry in wax/solvent and oil /solvent.

The slurry, at filtration temperature, enters the enclosed filter from the bottom. The filter consists of a

rotating horizontal filter drum that is partially submerged (usually to about 35%) in a vat which contains

the slurry. The hood encloses the vat from the atmosphere and is blanketed with an inert gas. The inert

gas is a mixture of vaporous solvent and nitrogen. Solvent is sprayed onto the drum. The shell of the

drum is divided into small compartments. Each compartment is connected to the head of the filter by

two pipes. A grid mounted on the drum supports the filter cloth. A vacuum is used to create a pressure

differential across the filter cloth. This pressure differential is the driving force that causes the oil and

solvent system flow through the wax cake, filter cloth and piping system to the filtrate receiver. The

wax crystals are retained by the cloth and form a bulky filter cake on the cloth.

Picture 4: Rotating Vacuum Drum Filter

Solvent Recovery Section

The recovery (or distillation) sections in all units and for all the different streams are very similar. The

recovery sections consist of a multiple-effect evaporation process. The number of stages used for the

evaporation of the solvent has a significant effect on the energy demand of the recovery process.

The principle of the solvent recovery can be described as a three stage process, as seen in in a simplified

Scheme in Figure 4. Each Product stream of the filtration stages which contains solvent need its own

recovery section.

The cold wax/solvent mix respectively the rich filtrate/solvent mix is heated up by the warm stream

from the last stage (Column C-3) and by condensation of the solvent from the second stage (C-2). When

the mixture enters the first column (C-1), the liquid temperature is above the boiling point of DCM

(>75°C). The superheated solvent flashed in the first column. About 50% of the solvent evaporates in

this stage. The remaining mix is directed to the second stage (C-2). Before the mix is entering the

second stage, it is heated up to ~135°C. The heating source is superheated steam. The temperature of

approx. 135°C is above the evaporation temperature of EDC; approx. 45% of the original amount of

solvent evaporates at this stage. The evaporated solvent is used to heat up the cold mix stream in HX-1

by condensing. The condensed solvent is collected into a solvent receiver. After the second column, the

mix (which contains ~5% of the original amount of solvent) enters the last column, after the lost

temperature (from evaporation of solvent) is compensated. The heating source of heat exchanger

(HX-4) is also superheated steam.

The last columns in the recovery section are operated under vacuum conditions. The pressure in this

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column is in a range from 20 to 250 mbar abs, depending on the product stream. To match the required

product specifications of a solvent content <10 ppm, the column contains trays. Stripping steam is

injected into the bottom of the column. The product flows through the trays to the bottom of the column

and solvent is flushed out of the products by stripping steam. The finished product is cooled down by

warming up the incoming product stream and is then directed to the tank farm.

The steam/solvent mixture from the top of column C-3 is mixed with the vaporized solvent from C-1.

These streams contain some water, which has to be removed from the solvent. The streams from C-1

and C-3 therefore are condensed in HX-5. The condensate is directed to the top of column C-1. The

moist solvent is dried by the evaporated solvent. The moist solvent which enters on the top of the

column is dried on his way down leaves the column water free. This water free solvent and the

condensed solvent from C-2 are directed to a solvent collecting receiver. This solvent is used as dilution

for the waxy raffinate feed and wash solvent. For the use as wash solvent, the solvent has to be chilled to

the filtration temperature with an ammonium chiller.

The separated water phase, which contains some remaining solvent, is send to the waste water stripper.

The stripped solvent is sent for drying to C-1. The solvent free water is sent to the refinery waste water

treatment.

Due to the extensive recycling of the solvent, based on the amount replenished it has been calculated

that each EDC molecule is passing through the process more than 5000 times. This extensive recycling

is causing substantial thermal degradation of EDC during solvent recovery.

Figure 4: Simplified Recovery Scheme

Mix Receiver C-1 C-2 C-3

HX-1

HX-2 HX-3 HX-4

HX-5

Oil / Wax to tankage

Solvent Collecting Receiver

Stripping Steam

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Picture 5: Solvent recovery (Salzbergen Refinery)

9.0.1.3 Technical and organisational risk management measures - rigorous containment

Production unit

All pipes and equipment in the production unit which are containing EDC are built as enclosed system

with closed gas venting system (“Gaspendelung”, gasometer). All process transfers (storage tank,

crystallisation, filters, distillation) are monitored, automatized and under panel control and alarms.

Tanks and reactors are equipped with secure control equipment. Seals (static, dynamic) are designed for

leak tightness in accordance to German regulations (BImSchG, TA-Luft 2002).

The gas venting system is equipped with a separate solvent recovery unit. In case of emergency the unit

is connected with a secure unit tank storage and for protection of over-pressure the safety equipment is

connected to a condensing Blow-Down-System.

Trained and authorised personnel

Both companies are certified according to

EN ISO 9001 Quality Management Systems and EN ISO 14001 Environmental Management

Systems

EN ISO 18001 Occupational Health and Safety management Systems (OHSAS)

EN ISO IEC 17025 General requirements for the competence of testing and calibration

laboratories

ISO 50001 Energy Management Systems

A flyer with more information on our Integrated Management System can be provided upon request

(“IMS_Flyer_H&R_2009.pdf”).

All operators involved in plant unit production have a technical certification. General training on risks

for chemical are given each years for all operators involved in chemical handling. Specific trainings on

chemical risk handling are given regularly to all plant operators handling EDC. An important tool for

the documentation of the training is the training database. The description according to

“HUR-SU-IMS-10_01 Handout Training Database - englisch.pdf” (can be provided upon request)

indicates how to edit the training in order to ensure the monitoring and evaluation of the worker’s

training.

In Germany there are national regulations regarding the training and documentation for work with

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hazardous products according to §14 of the Ordinance of Hazardous Substances. Consequently each

worker has to be trained face to face annually on the EDC specific operating instructions. Additionally

there are operating instructions and a glove plan for each occupation of the worker. Glove plans for the

EP unit in Hamburg and similar documentation implemented in Salzbergen can be provided upon

request.

Following operational instructions have to be trained early and documented in the training database:

1) Work instruction for solvent transfer from tank trucks to dewaxing plant

2) Filling of the dewaxing unit EP I with EDC from road tankers

3) Work instruction for implementation of secondary regulations of plant section

4) Operating instruction

- acc. to BetrSichV (Ordinance of Industrial Safety), §6 & 9

- acc. to 12. BlmSchV (Federal Emission Regulation), §6

- acc. to regulation on systems dealing with substances hazardous to water (VAwS), §3

- acc. to Instructions pursuant to § 12 Employment Protection Act BGVA1, §§4 & 31

- acc. to instructions relating to dangerous substances regulation

5) Explosion protection document: according to BetrSichV (Ordinance of Industrial Safety §6) for

dewaxing unit 6)Work permission documents.

9.0.1.4 Continuous plant improvements

Since 1987, the Hamburg and Salzbergen plants are involved in a continuous improvements process

regarding use of EDC with the aim of minimising occupational exposure and environmental releases.

Both plants are in close contacts and means to realise improvements detected at one site are

communicated to the other plant for implementation. The main actions done in the past (1987 to 2014)

and future improvements planned for both sites are presented in the table 11 below.

An important technical improvement was recently (September 2014) realised in Salzbergen. Specific

measurements during sampling in EP revealed relatively high, short-term releases during this activity.

In consequence, possible technical improvements were discussed and in the following a closed

sampling device using inline sampling valves was installed with sampling bottles tightly screwed to the

outlet. Measurements confirmed that exposure during sampling was drastically reduced by the technical

change implemented (see Appendix 2). For this reason, in the exposure assessment only measurements

from 2015 onwards were used for Salzbergen. In Hamburg, inline sampling valves were installed

already in 2000.

Properties of Inline Sampling Valves are:

Sample taking without affecting product-flow

Container is fixed to the connection of the sampling valve while sample is taken. As a result it

cannot be dropped during sample taking nor can vapours and / or contingent splashes of liquid

escape the enclosed system.

There is no dead space. The sample is taken directly from current product flow. Thus it is

possible to get a representative sample without having to discard sample material which might

be present in such dead spaces.

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Picture 6: Inline Sampling Valve

The following table lists the ongoing efforts for improving safety and minimise emissions at both

plants.

Table 11. Documentation of continuous technical plant improvements

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№ Continiuous Improvement Actions

1987 to 2014

Impact on Reduction of

Solvent Loss Potentials /

Increase of safety

Plant Component Remarks

1 Fusion of 2 dewaxing plants at CPS (H&R Chemisch-

pharmazeutische Spezialitäten GmbH)

air quality protection Complete plant Reduction of equipment and consequently of

leakages

2 Renewing of 2 strippers for process and surface water

(AOX <500 µg/l)

wastewater, sewerage Wastewater treatment Wastewater strippers are components of both

plants at OWS (H&R Ölwerke Schindler

GmbH) since construction

3 Installation of dykes conform to VAwS sewerage Relevant vessels

4 Implementation of annual hazardous material training for personnel Enhancement of work

safety / plant safety

Complete plant (work

practices)

5 Monitoring of solvent loss Work safety / antipollution Complete plant

6 Implementation of new unloading station for road tankers and

optimisation of unloading procedures

air, sewerage, Plant safety /

antipollution / VAwS

Solvent unloading

station

7 Implementation of continiuous improved PPE during revision

shutdowns and for taking solvent-samples, e.g. respiratory

protection, solvent resistant gloves.

Work safety Complete plant

8 Solvent substitution feasibility study perspective to other less

hazardous solvent

Complete plant Mixture of DCM and EDC was identified to be

optimal solvent.

9 Research and development activities -

" Solvent Guide for Lube and Wax-Processing"

Mixture of DCM and EDC

was identified to be optimal

solvent in respect to

process efficiency

(separation characteristics)

and energy efficiency (at

least 10 % less carbon

dioxide emissions)

10 Regular revisions of underfloor pipes wastewater, sewerage Sewerage, VAwS

conform facilities

Ground water protection

11 Ground water protection: Installation of collecting tray coated with

foil or installation of VAwS conform floors. Partial installing of double

walled systems.

surfacewater, sewerage Washing station of

dewaxing unit

12 Installation equipment certified and conform to TA-Luft and

BImSchG such as:

- Pumps with double floating ring seals and/or magnetic clutches

- chillers, partial designed with double floating ring seals

- filters, partial with sealing gas systems

- armatures with bellows seals according to TA-Luft-regulation

air quality protection,

sewerage

Complete plant

13 Revision of process operation:

- Retrofitting of a collumn to reduce heat/cold changes

and consequently fouling and energy consumptions

air quality protection

14 Connection of tanks to ventgas system air quality protection Wastewater and slop

oil tanks

15 Filter cloth screening (optimisation of filter efficiency) in CPS as

general study

air quality protection Filtration It was checked, if process could be run with

less filters and reduced amount of circulating

solvent. Actual process conditions turned out16 Purchase of solvent resistant hose pipes for cleanout of residues.

Alternatively at OWS: Purging out of residues to the other DW-Plant

still in operation.

air quality protection,

sewerage

Complete plant

17 Installation of condensing Blow-Down-System (closed system) air (discharged gas from

relief valves)

Vessels / devices

equipped with relief

valves)

18 Use of Blow-Down-System as additional surge tank for ventgas air quality protection Filter venting system Less ventgas has to be discharged due to

larger volume of system.

19 Solvent substitution feasibility study

on occasion to increase capacity and new legal authorisation

process according to BImSchG

regulatory safety Complete plant German authority assessed mixture of DCM

and EDC as optimal solvent and state of the

art.

20 Testing of cryogenic trappig system for waste gas cleaning air quality protection Filter venting system Both refineries found out that this system was

not reliable enough.

21 Determination of room for improvement concerning filtration process air quality protection Filtration It was checked, if process could be run with


solvent. Actual process conditions turned out

to be best practice.22 Use of compressor to recover solvent. Remaining solvent vapors are

washed out (venting gas washer) with base oil and circulated to the

plant's feed. Respectively use of activated carbon adsoption facility

for waste gas cleaning.

air quality protection Filter venting system

23 Purchase of solvent detector for tracing potential minor leakages air quality protection Complete plant Minor leakages can be found more easily and

be removed.

24 MEK/TOL (methylethyl ketone/toluene) plant conversion study on

occasion of REACH-Authorisation

regulatory safety Complete plants

(CPS, OWS)

With respect to current market situation not

feasible for economical reasons. Nvertheless

we need at minimum 12 yrs for conversion

even under optimal market conditions.

25 Installation of new inline sampling stations without dead spot air quality protection,

sewerage

Solvent sampling

stations26 Individual measuring of exposition of employees (operators in the

field, truck drivers during solvent unloading, laboratory assistants).

The measuring is conducted by independant experts.

work safety Identification of individual exposition, aiming

to find options for further reduction

27 There are two options of purging of filters shutdowns for repair /

maintenance in use:

- base oil purging

- nitrogen purging

air quality protection Filters Filters are purged until they are free of

solvent before opening.

Abbr.:

Continuous improvement in the past (1987 to 2014)

VAwS = Verordnung über Anlagen zum Umgang mit wassergefährdenden Stoffen (Regulation concerning ground water protection)

TA-Luft = Technische Anleitung zur Reinhaltung der Luft (Technical Instruction to prevent air pollution)

BImSchG = Bundesimmissionsschutzgesetz (Federal Immission Protection Law)

AOX = adsorbable organic halogen compounds (in water)

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9.0.2 Combined assessment of EP1 and EP2 in Hamburg and EP in Salzbergen

This chemical safety report provides an occupational exposure assessment and risk characterisation for

both refinery sites in Hamburg and Salzbergen. This is possible because at both sites essentially the

same processes are used and the same techniques are implemented. Differences between both sites were

described above: in Hamburg a second refinery line (EP2) is realised, which does not include a

de-oiling unit (in contrast to the first line in Hamburg (EP1) and the line in Salzbergen (EP)), and,

evidently, only one line is realised in Salzbergen. But within these units, techniques installed and

exposure conditions are essentially the same: both plants are recycling EDC by a specific multi-column

distillation system, process heat is provided by steam, processes are run with the same equipment at the

same temperatures. Small differences relate to filter areas installed in columns, which are not relevant

for operators’ exposure. With the most recent changes in sampling techniques in Salzbergen, installed

in 2014, all operational conditions and risk management measures at the workplaces related to EDC use

are identical.

There are differences between to total amount of EDC used in the processes, due to the fact that two

lines are operational in Hamburg, compared to one in Salzbergen. Also, differences exist in the

treatment of waste waters. Therefore, separate assessments of exposure of humans via the environment

were performed for both sites.

9.0.3 Teams and employees involved in use of EDC

The industrial sites are producing in a continuous process, 24 hours per day, 7 days a week all year.

As described above the processes use EDC in closed systems without direct handling of EDC by

operators except for:

- EDC sampling for quality control,

- raw material unloading from a road tank (connecting/disconnecting flexible hoses),

- maintenance work,

- quality control work in the laboratory.

№ Continiuous Improvement Actions

2015 ongoing

Impact on Reduction of

Solvent Loss Potentials /

Increase of safety

Plant Component Remarks

1 Selection of suppliers using road tankers equipped with

connections for closed tank venting systems

air quality protection, work

safety

Solvent unloading

station

Enhanced unloading procudere were started

with respect continuous improvement plan

and to REACH authorisation process.

2 Selection of suppliers using road tankers equipped with ANA-

System

sewerage, air quality

protection, work safety

Solvent unloading

station

Enhanced unloading procudere were started

with respect continuous improvement plan

and to REACH authorisation process.

3 Tank truck driver provides solvent sample taken and properly

packed by supplying company.

air quality protection Solvent unloading

station

Sampling at unloading station is no longer

necessary.

4 Individual measuring of exposition of tank truck drivers, plant

operators and laboratory assistants involved in unloading

process

work safety Solvent unloading

station, laboratory

5 Installation of diffusive samplers air, quasi-continuous

sampling, improved

collection of exposition data

and atmosphere

Relevant locations in

plant and near

neighbourhood

Specific monitoring of measuring potential

EDC solvent concentration to determine air

quality in wide area

6 More intensiv Individual measuring projects of expositions

(employees)

work safety Complete plant Identification of individual exposition, aiming

to find options for further contamination /

pollution reduction7 Optimising of maintenance strategy work safety

8 Future equipment improvements according state of the art work safety Deoiling/Dewaxing

plants in the refineries

9 Additional research for improvement concerning filtration

process

air quality protection Filtration It was checked, if process could be run with


solvent. Actual process conditions turned out

to be best practice.

Abbr.:

Continuous improvements in the future (2015 ongoing)

VAwS = Verordnung über Anlagen zum Umgang mit wassergefährdenden Stoffen (Regulation concerning handling of substances hazardous to water)

TA-Luft = Technische Anleitung zur Reinhaltung der Luft (Technical Instruction to prevent air pollution)

BImSchG = Bundesimmissionsschutzgesetz (Federal Immission Protection Law)

ANA-System = Aufmerksamkeitstaster mit Not-Aus Funktion (deadman button with emergency shut-off function)

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The exposure scenario consists of the following contributing scenarios:

CS1 - Production process (de-waxing and de-oiling) (PROC 2): This CS covers the complete

operators shift (8 hours). The main activity of the operator is to supervise the production

facility. He performs visual routine controls, operates the process equipment, and takes samples

of solvent-free wax and oil products for quality control. Within this routine work the operator is

not in direct contact with EDC.

Operators also are responsible for taking solvent samples. The measured TWA exposure

concentrations for CS1 include the sampling of solvent: This activity (taking samples of

DCM/EDC mixture) was part of the activities performed during the measurement campaign

using personal sampling (see Appendix 2 for details).

At Hamburg and Salzbergen there are 4 shift teams to operate the EP lines, working in three

shifts per day (24/24): team1 = shift 1: 6:00 to 14:00; team2 = shift 2: 14:00 to 22:00; team3 =

shift3: 22:00 to 6:00 (the other teams rotating the other days). Frequency of CS1 = all year.

Hamburg: a shift team is composed of three workers: 1 operator for EP1, 1 operator for EP2, 1

supervisor (the latter one is not exposed, as he is working in the control room only). Two

workers per shift are potentially exposed in the production area. There are additional workers

entering the teams in case of sick leaves and other absences. In Hamburg, 29 workers are

regularly working at these workplaces and are expected to be exposed to EDC due to their

activities as plant operators.

Salzbergen: a shift team is composed of 4 workers: 1 operator working in the EP site, 1 pump

operator (responsible for substrate supply and product removal), 1 supervisor (not exposed, as

he is working in the control room only) and 1 operator working at the waste water treatment

plant (not exposed as this site is far from the EP site). In Salzbergen there is a pool of 22

workers constituting the work force engaged at these workplaces.

For risk characterisation it is assumed that 22 workers are sharing the workplaces in the shifts as

described above and are regularly exposed in the production area.

CS2 - Receipt of EDC from road tank (PROC 8b). This CS covers the specific operation of

EDC unloading from a road tank. This operation is done on demand, generally less than

. The duration is less than 1 hour. At both sites two persons (tank truck driver, company

operator) are doing this operation (see detailed description in section 9.1.3).The tank truck

driver is an external employee; the operator is a company employee (same as in CS1, not the

same employees as in CS3 or CS4).

CS3 – Non-routine maintenance and cleaning (PROC 8b). This CS covers the specific

operation of small repairs in case of equipment dysfunction (e.g. replacement of pumps) (see

description in section 9.1.4). This task is done only by contract maintenance operators (external

company) located at both sites. Typically, two employees from the maintenance team are

involved in such an activity (not the same employees as in CS1, CS2, or CS4). A conservative

estimate of the frequency of this activity is once per month. These non-routine maintenance

teams consist of 4 workers both in Hamburg and Salzbergen.

CS4 – General maintenance and cleaning (PROC 8b). This CS covers specific activities during

a general maintenance shutdown. For general maintenance and cleaning the plant is discharged

and purged with steam. This task is done only by special maintenance operators (external

company specialised in refinery maintenance work, not the same workers as in CS1, CS2, or

CS3). There are up to 50 workers involved in general maintenance works in each plant. General

maintenance shutdowns are performed for parts of the plant every in Salzbergen (for a

total period of approx. ). In Hamburg, the complete plant is shut down for maintenance

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every (for a period of , as the complete plant is cleaned up). The overall time

spent for general maintenance is comparable for both sites (about ).

Picture 7: Example for maintenance work (handling of heat exchanger)

CS5 – Use in laboratory (PROC 15). This CS covers the handling of EDC in the laboratory

(quality control of received EDC samples). The duration of this activity per sample is up to 1.5

hours, but actual exposure to EDC is restricted to a few minutes (time needed to prepare sample

and inject into GC, etc.). The laboratory operators are not exposed to EDC for the rest of the

shift. The laboratory operators are not the same employees as in CS1/CS2, CS3 and CS4.

Approx. 4 laboratory workers are engaged in handling EDC-containing samples at each site.

One sample is handled by one laboratory worker only. The frequency of sampling is approx. 52

per year in Salzbergen and 208 in Hamburg, where approx. 4 samples are analysed every week.

The following analyses are carried out:

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- pure EDC ( max., volume <500 ml, duration <15 minutes): density, refractive

index (both sites)

- solvent mixture, with <50% EDC (twice per week, volume <250 ml, duration 1.5 h): density,

cloud point, gas-chromatographic determination of concentration (Hamburg site only)

- sample from production process (after separation of solvent, with max. 10 ppm EDC (twice per

week, volume <250 ml, duration 1.5 h): gas-chromatographic determination of concentration,

water content, oil content (Hamburg site only)

- sample from production process, with max. 10 ppm EDC (once per week, volume <250 ml,

duration 1.5 h): gas-chromatographic determination of concentration, oil content (Salzbergen

site only).

Exemption of scientific R+D work, including laboratory work from authorisation

ECHA in its Q&A webpages for Q&A Reference number: ID 0585 regarding the scope of the

exemption from Authorisation of activities that might be considered to be falling under scientific

research and development, as per Article 56(3) laid out:

“Reference number: ID 0585 - Latest update: 4/06/2015

Question “Does the exemption for the use of Annex XIV substances in scientific research and development

under Article 56(3) REACH also apply to analytical activities such as monitoring and quality

control?”

Answer “Yes, it does. Under Article 3(23) REACH, scientific research and development means any scientific

experimentation, analysis or chemical research carried out under controlled conditions in a volume

less than one tonne per year. Thus, scientific research and development can cover analysis, and a

substance may be exempted from authorisation under Article 56(3) REACH if used, on its own or in a

mixture, in analytical activities such as monitoring and quality control. For instance, routine

quality control or release tests in laboratory scale using the substance as extraction solvent or

analytical standard fall into the definition of “scientific research and development” under Article

3(23) REACH and in the scope of the exemption foreseen in Article 56(3) REACH, as long as the

quality control or release tests are carried out under controlled conditions and in a volume not

exceeding one tonne per year and per legal entity.”

As this answer was ambiguous with regard to whether also sampling for quality control and handling in

the laboratory for quality control of process chemicals used at industrial scale is included, the applicant

by way of its consultants presented these questions to three national helpdesks (in UK, France and

Germany) and received accordant responses to the effect that activities such as sampling and handling

of substances such as EDC in laboratory for quality control are excluded, as long as the limit of 1 ton per

year is not exceeded and the substance is handled in the laboratory under “controlled conditions”. The

latter is not defined on an European scale but can be interpreted as being compliant with national

workplace legislation and performance of activities according to good practice, as, for example, in

Germany is laid down in TRGS 526 “Laboratorien” (AGS, 2008). As these conditions are fulfilled,

laboratory work is considered to be excluded from authorisation in this application. Sampling (from

process or tank trucks) is included in CS1 and 2. Nevertheless, to present a complete description of all

activities involving use of EDC, information on laboratory activities, along with available exposure

information is included (CS5), but no risks are calculated for this contributing scenario.

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9.0.4. Overview of uses and Exposure Scenarios

Identifiers Titles of exposure scenarios and the related contributing scenarios

ES1 Exposure scenario 1: Industrial use as a solvent and anti-solvent of the feedstock and intermediate

product streams in the combined de-waxing and de-oiling of refining of petroleum vacuum

distillates for the production of base oils and hard paraffin waxes

- Use as a solvent and anti-solvent in de-waxing and de-oiling (ERC 4)

- Production process including storage, transfers, sampling, and recycling of EDC (PROC 2)

- Receipt of EDC from road tank (PROC 8b)

- Non routine maintenance (PROC 8b)

- General maintenance and cleaning (PROC8b)

- Use in laboratory for quality control (PROC 15)

9.0.5. Introduction to the assessment

9.0.5.1 Exposure-risk relationship for carcinogenic effects of EDC in humans

1,2-dichloroethane has been included into Annex XIV of REACH due to its intrinsic properties

(carcinogenic substance; classification as Carc 1B). According to Regulation (EC) No 1907/2006,

Article 62 (4)(d), the CSR supporting an application for authorisation needs to cover only those risks

arising from the intrinsic properties specified in Annex XIV. Therefore only the human health risks

related to the classification of EDC as a carcinogenic substance are addressed in this CSR.

The risks of workers exposed at their workplaces as well as the potential exposure of humans via the

environment are considered.

In July 2015 ECHA published the “Reference dose response relationship for carcinogenicity of

1,2-dichloroethane” as endorsed by RAC. The following table summarises the recommendations,

which will be used for risk characterisation in this report.

Table 12. Exposure-risk relationships for 1,2-dichloroethane as recommended by RAC (ECHA,

2015)

Population Pathway Risk estimate Concentration/dose at risk level

Workers Inhalation 6.0 x 10-7 per μg/m3 16.7 µg/m3 corresp. to 1 x 10-5

Dermal 2.1 x 10-6 per μg/kg bw/day 4.8 µg/kg bw/day corresp. to 1 x 10-5

General

population

Inhalation 3.45 x 10-6 per μg/m3 0.29 µg/m3 corresp. to 1 x 10-6

oral 1.2 x 10-5 per μg/kg bw/day 0.083 µg/kg bw/day corresp. to 1 x 10-6

The risk estimate for dermal exposure of workers was derived by RAC assuming 50% percutaneous

absorption. As in this chemical safety report dermal exposure is calculated by estimating the amount

absorbed through skin by applying a model using the flux rate (see sections 5.1, 9.0.4.2 and Appendix

4) (and hence the absorbed dermal dose is obtained), a risk estimate per dose twice of that in the table

above is used: 4.2 x 10-6 per µg/kg bw/day (absorbed dose).

All other values are used for the risk characterisation in this report as given in the table.

9.0.5.2 Workers

9.0.5.2.1 Inhalation exposure assessment

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Contributing scenario 1 (CS1, general production process)

For the main contributing scenario covering the production process (CS1), the inhalation exposure

assessment for workers is based on measured data. Measurement campaigns were performed in 2014

and 2015 in Hamburg and in 2015 in Salzbergen (n=18 in total) by an external certified laboratory. In

addition, measurements (n=6, all measurements with duration >120 min) were performed by the

German BG RCI (Statutory Accident Insurance Institution, “Berufsgenossenschaft”) in Salzbergen and

in Hamburg in 2015. The data are summarised in Appendix 2.

Data measured by the companies themselves from 2013 and older are based on a non-standardised

in-house method and are not used for the assessment.

The measurement strategy employed for the measurements initiated by the company in 2014 and 2015

was based on:

CSN EN 689, BOHS NVvA sampling strategy guidance 2011 and ECHA guidance R.14, 2012

for establishing a sampling strategy.

ISO 16200 (NIOSH 1003) “Workplace air quality - Sampling and analysis of volatile organic

compounds by thermic desorption/gas chromatography” for sampling and analytical

requirements (see Appendix 1).

The sampling strategy was established based on observations made during a plant visit by a Certified

Industrial Hygienist (IOHA certification). Similar Exposure Groups (SEM) exposed to EDC have been

identified in each plant and linked with the Contributing Scenarios. Personal air sampling was

employed, with the sampling device directly attached to the employee within the worker’s breathing

zone. The certified laboratory taking the samples was obliged to give a clear description of all technical

conditions and tasks performed during sampling. Sampling and analysis was performed by a certified

laboratory in compliance with NIOSH 1003 requirements.

Contributing scenario 2 (CS2, road tank unloading)

A tank truck of an external company specially equipped with the Fort Vale system is used for

transporting EDC to the production sites in Hamburg and Salzbergen.

The Fort Vale system ensures operation of the ventilation of the tank truck from below, so the driver no

longer needs to climb the tank truck and to open the manhole cover to ventilate the boiler. Thus it is

ensured that no person involved in the unloading operation comes into contact with the product except

during connecting/disconnecting flexibles. No emissions are released to the environment either, since it

is a hermetically sealed system.

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Picture 8: Tank truck equipped with Fort Vale technique (“Closed Technology”)

The product sample is filled at the supplier company, closed and handed over to the driver of the

external company in an approved UN packaging of a good quality.

On arrival of the tank truck in the refinery, it is directed by the plant personnel to the unloading station

and the product sample is given to an operator who transports the sealed product sample to the in-house

laboratory.

After clearance is given by the testing laboratory, the product hose is connected to the tank truck and the

unloading line. The tank truck driver connects the flexible with the tank truck, whereas the company

employee operates the pump. The unloading operation is started. After about 1 hour, the unloading is

completed, the unloading hose and the remaining systems is blown free and separated by the tank truck

driver from the truck.

This activity - road tank unloading - is very infrequent and therefore it was not possible to achieve a

large number of measurements. Four measurements were obtained in 2014 (Hamburg, n=2) and 2015

(Salzbergen, n== 2) and results are included in Appendix 2. Therefore, for CS2 in addition to

measurements tier 2 modelling using Advanced Reach Tool (ART, V1.5) is used for the exposure

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assessment.

Please note:

As recommended by the model developers, for ART modelling the upper limit of the inter-quartile

confidence interval to the 75th percentile is used for risk characterisation. This value in general is similar

to the 90th percentile (which is also presented for comparison).

Contributing scenario 3 (CS3, non-routine maintenance)

No measured data exist for non-routine maintenance activities (such as pump repair or filter cleaning),

as these are infrequent and unexpected events (and therefore difficult to cover by measurements) and

expected to be associated with very low EDC exposures only. From historical records at both sites it can

be concluded that such activities occur with an average frequency of once per month (counting only

maintenance activities requiring opening of parts of the system).

Therefore, tier 2 modelling using ART is used as main approach for inhalation exposure assessment for

non-routine maintenance activities.

Contributing scenario 4 (CS4, general maintenance)

Also, for scheduled maintenance only few data, measured by BG Chemie (Statutory Accident Insurance

Institution, “Berufsgenossenschaft”) in 2009 exist, as plant shutdowns for maintenance only occur

every (see below). These available measurements are supported by tier 2 modelling using

ART for inhalation exposure assessment for routine maintenance activities.

Scheduled general maintenance is infrequent with a

- partial (about half of the plant) general maintenance procedure performed in

Salzbergen (lasting for about ) and

- a complete shutdown and maintenance every in Hamburg (lasting for about )

At these events the system is opened only after equipment and pipes are extensively flushed and purged

(either with steam or compressed air, depending on the equipment part concerned), which considerably

reduces residues of solvent present in the equipment. Therefore, exposure to EDC is expected to be

restricted to the period following opening of the system (max. first two days of the procedure).

Moreover only trained workers are authorised to perform maintenance activities and a management

system covering this activity (with documentation of all procedural steps, responsibilities and permits)

is in place and regular internal/external auditing is performed.

Contributing scenario 5 (CS5, handling in laboratory for quality control of EDC samples)

Measurements from campaigns carried out in 2014 and 2015 at both plants (14 longer-term

measurements plus 3 short-term, task-related measurements, 7 from the Hamburg site, 10 from the

Salzbergen site) are available and are used for the assessment. The results of the measurements are

summarised in Appendix 2. Laboratory activities are carried out by teams of approx. 4 laboratory

workers per site. In Hamburg approx. 4 samples are analysed every second week, whereas in

Salzbergen sampling is less frequent (approx. 12 samples analysed per year).

Duration and frequency of exposure

The dose-response relationship for EDC, as recommended by RAC, assumes continuous exposure

during 8 hours per day, 240 days per year for a working life of 40 years. For calculating the excess risk

due to EDC inhalation exposure shift average concentrations are used.

In some of the contributing scenarios described above, exposure-associated activities are regularly

followed by exposure free periods (i.e. CS2 and CS3). In order to obtain time-weighted shift average

(TWA) exposure concentrations for these activities event concentrations are averaged over 8 h. In

addition, in cases where exposure is not daily, yearly average concentrations are calculated by

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multiplying 8h-TWA with the number of exposure days divided by 240 (working days per year). This is

necessary to be able to compare with the exposure-risk relationship for carcinogenic effects, which is

based on continuous long-term exposure.

For CS1 and CS2 , as the operators are partly the same (one plant operator (CS1) and the truck driver are

performing CS2), the combined exposure will be considered in section 10. As for the truck drivers the

exposure is very infrequent and actually takes place only a few times in a work life at most, they are not

further considered in section 10.

Respiratory protection

When respiratory protection equipment is used during a specific task, an efficiency of 95% is assumed

to calculate the real exposure from the measured personal sampling concentration. The 95% efficiency

is derived from Howie et al. (2005) for the respiratory protection equipment used:

- either Dräger PAS Colt, full mask with breathing apparatus (pressured air supply) (Salzbergen)

or

- full mask (Dräger) with filter AX or full mask with breathing apparatus (pressured air supply)

(Dräger PSS 100) (Hamburg).

At both companies use of personal protection equipment (PPE) is under survey and is validated by the

companies’ EHS (Environment/Health/Safety) services. PPE is available in specified store-rooms. The

material is inspected once a year and availability of PPE is controlled by the chief operator. Audits are

done to ensure compliance with PPE instructions. The inhalation protective equipment (full masks) are

assigned to individual persons. After each use, the masks are cleaned and tested by the fire department.

Respiratory protection equipment (RPE) is worn only during specific periods/for specific activities (e.g.

sampling).

Calculation of exposure taking into account RPE:

RPE is worn partially during the shift :

C real = (C RPE * T RPE * Effic (0.05) + C noRPE * T noRPE) / (TRPE + TnoRPE)

where

C RPE and T RPE are concentration and duration when RPE used.

C noRPE and T noRPE are concentration and duration when no RPE is used.

C noRPE is calculated from long-term measurements including periods with RPE as follows:

C noRPE = (C long-term * T long-term - C RPE * T RPE)/ (T long-term - T noRPE)

where

C long-term and T long-term are shift-related concentration and duration, which includes periods with and

without RPE.

9.0.5.2.2 Dermal exposure assessment

General considerations

EDC is handled only by experienced and specifically trained workers who are also instructed in

preventing any dermal contact, e.g. through splashes of the substance. Furthermore, due to its eye and

skin irritating effect, risk management measures are in place to minimise dermal exposure. Workers

wear gloves during all tasks involving a potential release of EDC to prevent exposure due to unforeseen

events. All these measures ensure that dermal exposure is unlikely.

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Apart from these use- and site-specific considerations, EDC is a highly volatile substance with vapour

pressures of 8130 Pa at 20 °C and 10247 Pa at 25 °C (see section 1.3). This property may lead to

significant evaporation losses, which reduce the amount available for dermal absorption (see e.g. Frasch

et al., 2014; Kissel, 2011). This fact is also acknowledged in the ECHA Guidance on occupational

exposure estimation (ECHA, 2012b), which proposes considering the evaporation time in relation to

dermal absorption and refers to an equation for calculation of the evaporation (see Appendix R.14-1 in

ECHA (2012b)).

Several tools are available for modelling dermal exposure. The standard tier 1 tool under REACH

(ECETOC TRA) as well as the more advanced RISKOFDERM model (both discussed in ECHA

(2012b)) do not specifically address the high volatility of substances such as EDC. They do not include

a term accounting for evaporation from the skin (or from gloves).

Use of RISKOFDERM for dermal exposure assessment was considered, but disregarded for this

assessment, due to following reasons:

- RISKOFDERM was developed for substances and situations with significant dermal

exposures; therefore choices for input parameters available in the model are not easily related to

the exposure situations described in this report.

- Scenarios (so-called DEO (dermal exposure operation) units), available in RISKOFDERM do

not cover all activities relevant here; especially, handling of contaminated objects was excluded

from DEO unit 1 in the latest version of the model (v2.1), as explained in the spreadsheet

“Changes and validity” of the model. This missing activity is especially relevant for handling

objects during maintenance activities.

- RISKOFDERM was not made for highly volatile substances, nor are datasets including such

substances part of the empirical database used to establish the model. Actually, the draft version

of the revised ECHA Guidance on Information Requirements and CSA, R.14, Occupational

Exposure Assessment, (draft version of November 2015) states for RISKOFDERM that “Due

to a lack of data on dermal exposure to volatile substances, the model is not optimally suitable

for very volatile substances (e.g. > 500 Pa vapour pressure). Use with input values outside

those found in the measured data sets should be avoided, though results may still be

indicative.”

- Considering the high volatility of EDC, dermal exposure assessment with RISKOFDERM

would require to set the time to volatilisation equal to the exposure duration time in the model,

the justification of which is unsure; furthermore, the volatilisation times calculated for EDC for

the activities here (see below and in Appendix 4) are below the range of applicable exposure

durations of the model.

In conclusion, RISKOFDERM was not considered suitable for the exposure situations in this report and

a methodology was established, which is based on consideration of evaporation of highly volatile

substances according to ECHA (2012b).

One tool that does address evaporation from the skin and compares it with dermal absorption is the

‘Finite Dose Skin Permeation Calculator’

(http://www.cdc.gov/niosh/topics/skin/finiteSkinPermCalc.html), a model that has been developed for

the U.S. National Institute for Occupational Safety and health (NIOSH). The model is described in

detail in the literature (Fedorowicz et al., 2011; Kasting and Miller, 2006; Kasting et al., 2008; Miller

and Kasting, 2010; Wang et al., 2007). However, recent evaluations by Gajjar (Gajjar, 2010; Gajjar and

Kasting, 2014) have shown that this model may somewhat underpredict dermal absorption of EDC.

In the light of these considerations, the evaporation time of EDC was first calculated according to the

ECHA Guidance (see Appendix R.14-1 in ECHA (2012b)). Based on these data, two methods for

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estimating dermal exposure were implemented. The overall approach is described below and full details

are included in Appendix 4.

Calculation of the evaporation time

For the assessment of dermal exposure in the context of this CSR, the evaporation time was calculated

according to the equation in Appendix R.14-1 in ECHA (2012b) with the following modifications:

Use of a EDC-specific mass transfer coefficient (11.6 m/h), rather than using the default value

(8.7 m/h) in ECHA (2012b).

Calculation of the evaporation time for dermal loads (0.1-1.0 mg/cm2), rather than 1 and 5

mg/cm2 in ECHA (2012b)5. These loads reflect default dermal exposure for PROCs relevant for

the use evaluated here (i.e. PROC 2, 8b, and 15).

Full details of input parameters and results of this calculation are included in Appendix 4. The

evaporation times calculated are:

0.94 seconds for a dermal load of 0.1 mg/cm2 (applicable e.g. to PROC15 according to ECETOC

TRA (ECETOC, 2004; 2009; 2012).

1.9 seconds for a dermal load of 0.2 mg/cm2 (applicable to PROC2 according to ECETOC TRA

(ECETOC, 2004; 2009; 2012).

9.4 seconds for a dermal load of 1 mg/cm2 (applicable to PROC8b according to ECETOC TRA

(ECETOC, 2004; 2009; 2012).

These estimates are considered to represent conservative estimates, since (a) a low vapour pressure at

20 °C was applied, which represents a conservative estimate for evaporation from skin and (b) a low

value for the air velocity was applied in calculating the mass transfer coefficient that has a high impact

on the estimate. The upper end of air velocities typical for occupational settings according to the ECHA

Guidance (ECHA, 2012b) would result in lower evaporation times of 0.59 - 5.9 seconds for the dermal

loads of 0.1-1 mg/cm2.

The evaporation times calculated cover situations relevant in the context of this CSR, i.e. when splashes

or small amounts of EDC are deposited on gloves. Full immersion of the hands in EDC is not covered,

since evaporation may not be a relevant process for dermal exposure in these situations.

The evaporation times calculated were used in two different approaches: (a) approach 1 using contact

area, evaporation time and dermal flux; (b) approach 2 using contact surface area and glove permeation

rate. Both approaches are discussed in detail in Appendix 4.

Both approaches result in very similar estimates of dermal exposure per event as shown in the following

table.

Table 13. Estimation of dermal exposure: summary*

Parameter Unit

PROC

2 8b 15

Dermal dose per event (potential) – approach 1 µg/kg 0.13 1.3 0.033

Dermal dose per event (actual) – approach 1 µg/kg 0.0066 0.066 0.0017

Dermal dose per event (actual) – approach 2 µg/kg 0.0043 0.043 0.0011

* Actual exposure estimates include the protection offered by gloves (95% efficiency assumed for approach 1

estimates). All values rounded to two significant figures, but unrounded values were taken for calculation.

5 In the model calculations (Table R.14-17 of the Guidance), these values are described as amounts (1 mg and 5 mg) and no contact area is given (although required in the equation). Re-calculations for toluene, however, show that these values actually refer to loads in mg/cm2.

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The estimates are critically dependent on the skin surface area that was conservatively chosen based on

ECETOC TRA defaults for the PROCs indicated in the table. The PROCs are also related to default

dermal loads of 0.1 (PROC 15), 0.2 (PROC 2) and 1 mg/cm2 (PROC 8b) that have an impact on the

evaporation time calculated (see above). However, no modelling with ECETOC TRA was involved in

these calculations and the doses estimated would equally apply to PROCs with identical contact areas

and loads (or, in fact, to tasks for which these contact areas and loads could be verified).

Both approaches have advantages and disadvantages, as fully discussed in Appendix 4. For the purpose

of dermal exposure assessment, the higher estimates of approach 1 will be used. Both estimates already

include the protection offered by wearing suitable gloves (actual dermal exposure).

The dermal exposure estimates presented in the table above are event-based, since rapid evaporation is

assumed for each event. However, some tasks may be performed several times a day. As a consequence,

the number of events has to be taken into account. This will be addressed in each worker contributing

scenario in section 9.1 below for which dermal exposure is estimated. Similarly, exposure may not

occur on a daily basis (e.g. for maintenance tasks). Again, the exposure frequency is task-specific and

will be addressed in each worker contributing scenario in section 9.1.

The following matrix illustrates the calculation used for each relevant worker contributing scenario in

section 9.1 (where only one PROC applies).

Table 14. Matrix for calculating task-specific dermal exposures (example activity)

Parameter Unit PROC 2 PROC 8b PRO

C 15

Dermal dose per event (potential), product µg/kg 0.13 1.3 0.033

Number of events per day 1/d 10

Dermal dose per day (potential), product µg/(kg x d) 1.3

Concentration of EDC in product % 100%

Dermal EDC exposure (potential) µg/(kg x d) 1.3

Efficiency of PPE (gloves) % 95

Dermal EDC exposure (actual) µg/(kg x d) 0.066

* All values rounded to two significant figures, but unrounded values were taken for calculation.

The 95% efficiency can be justified by the use of protective gloves satisfying the specifications of EU

Directive 89/686/EEC and the standard EN 374 derived from it. The following gloves materials are

used in Salzbergen:

- Neopren, 0.9 mm, (MAPA), breakthrough time 10 min.

As only splash contact to EDC is possible at the workplaces, glove material with breakthrough times of

10 min are considered sufficient, after a careful hazard assessment carried out by the plants’ EHS

(Environment/Health/Safety) experts. Contaminated gloves are not allowed to be reused.

In Hamburg, the following material is used:

- Butyl/Viton, (Profaviton, Uvex) Level 6, breakthrough time > 480 min.

This glove consists of a butyl rubber base layer and a Viton (R) coating of 0.2 mm. The glove thickness

amounts to a total 0.6 mm.

Again, at both companies use of personal protection equipment (PPE) is continuously surveyed and is

validated by the companies’ EHS services (see “PPE Instruction OWS-AA-IMS-02_Version_0002.doc

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and similar documentation for Salzbergen, available upon request). PPE is available in specified

store-rooms. The material is inspected once a year and availability of PPE is controlled by the chief

operator. Audits are done to ensure compliance with PPE instructions Specific trainings on PPE are

given regularly to all plant operators handling EDC.

The result of this exposure assessment is compared with the exposure-risk relationship for dermal

exposure of workers derived by RAC (ECHA, 2015).

9.0.5.2.3 General information on risk management related to irritation classification

EDC is classified for its irritating properties. The applicants are downstream users of EDC. Operational

conditions and risk management measures as communicated by the supplier in the safety data sheet for

this use to avoid any detrimental effects such as irritation of skin, eyes or the respiratory tract are closely

followed.

9.0.5.3. Exposure of humans via the environment

Although the principal treatment of emissions to air and to waste water is the same at both production

sites, on-site conditions are slightly different. Therefore, two separate quantitative assessments are

performed. Both assessments are based on measured concentrations in emitted air and waste water,

which are used to calculate site-specific release factors. These release factors are used as input data for

modelling with EUSES (v.2.1.2).

In order to calculate the release factors, information on the consumed amounts of EDC at both sites are

used. Whereas detailed information on trends is given in the Analysis of Alternatives report, here the

following estimates for 2015 are used:

Hamburg:

Salzbergen:

9.0.5.3.1 Substance-specific input data

The following data were used as input in EUSES modelling. A Koc of 33 L/kg and a BCF of 2 in fish for

EDC was reported in OECD (2002; these values are also cited in section 4 of this CSR). However, the

EUSES default values for EDC (calculated from log Kow) are used in the assessment (Koc = 59.4 L/kg,

BCF fish = 3.41 L/kg w.wt.), since (a) the data reported in OECD (2002) are not well documented and

(b) the differences are small.

Table 15. Physico-chemical data, environmental properties and environmental partition

coefficients used as input values in EUSES (see section 1.3)

End points Values

Molecular weight 98.96 g/mol

Melting point -36 °C

Boiling point 83.6 °C

Vapour pressure at 25°C 10247 Pa

Octanol-water partition coefficient (log Kow) 1.45

Water solubility at 25°C 7900 mg/l

The ECHA Guidance on consumer exposure estimation (ECHA, 2012c) recommends a default body

weight of humans of 60 kg, while EUSES employs a default body weight of 70 kg. The body weight in

EUSES is used for estimating the intake of a substance from food. The underlying food consumption

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data are based on the highest country-average consumption rate for each food product. As noted by the

developers of EUSES, this “will of course lead to a total food basket, which is an unrealistic, worst-case

scenario” (RIVM, 2004). Since EUSES therefore assumes a very high intake of food, the default body

weight of EUSES was used in the assessment.

9.0.5.3.2 Releases to air

Emissions to air at both sites are regulated under the German TA Luft (First general administrative

regulation to the Federal Immission Control Act (Technical Instructions for Air Quality Control) – Erste

Allgemeine Verwaltungsvorschrift zum Bundes-Immissionsschutzgesetz (Technische Anleitung zur

Reinhaltung der Luft – TA Luft)), which allows at a maximum emissions of 2.5 g EDC/h. Compliance

with the regulation is strictly controlled by external laboratories (see below) as well as by internal

measurements (see below).

At both production sites (Hamburg and Salzbergen) all equipment of the de-waxing and de-oiling units

is connected to a general vent-gas balance vessel (gasometer tank) to ensure regular pressure in the unit

and to avoid releases.

In Salzbergen, in case of overpressure in the gasometer tank, released air is directed to an active carbon

absorber unit: waste air is purified by adsorption on active carbon before release to the environment.

Two units are operational at all times: one is connected to the gasometer, whereas the second is

regenerated. For desorbing EDC and other organic substances, steam is led into the adsorber in the

reverse direction to the adsorption. The steam drives the solvents out of the activated carbon. This

mixture of steam and solvents is then led into a condenser to be condensed and cooled. Desorbed and

condensed EDC is fed back into the production process.

Remaining emissions from the waste gas adsorber unit are regularly controlled by external and internal

measurements (see measured values below).

In Hamburg, for cleaning excess gas a treatment unit is operating, which gathers excess gas from both

EP1 and EP2. The excess gas is compressed up to 4 bar. The warm compressed excess gas (80°C) is

cooled with cooling water to 30°C. At this temperature mainly DCM and some DCE condenses. This

condensed solvent is returned into the production process. The remaining solvent in the excess gas,

mainly DCE is removed by an absorption process. To this end, the compressed excess gas is washed

counter current with solvent free filtrate (oil) in an absorption column. The remaining traces of solvent

are bound in the filtrate. The solvent free excess gas is discharged to the environment and regularly

controlled by external and internal measurements (see below). The solvent-containing filtrate is

returned to the filtrate recovery of a de-waxing unit (EP1 or EP2), where the solvent is recycled.

Hamburg – measured values

Compliance with TA Luft was controlled by measurements carried out by the external certified

laboratory Aneco Institut für Umweltschutz GmbH & Co. (report from March 2015) (see table below).

Three samples were taken on 18.2.2015 at the stack of the waste gas purification unit by sorption to

active carbon (Dräger). Samples were analysed by gas chromatography according to DIN EN 13649.

Mean off-gas volume at the stack during the measurement period was 20 m3/h. The limit of

quantification for EDC was 0.05 mg/m3.

Table 16. Results of measurements by Aneco (March 2015)

Sample mass flow (g/h) concentration (mg/m3)

1 0.01 1.1

2 0.02 1.3

3 0.01 1.0

Arithmetic mean 0.01 1.1

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The mass flow of 10 mg/h is far below the legal limit value of TA Luft (2.5 g/h) and results in a total

daily emission of 240 mg EDC (a slightly higher value of 528 mg/d results from the average

concentration of 1.1 mg/m3 multiplied by off-gas volume and 24 h).

With the yearly consumption of EDC in Hamburg as given above the emission value of 240 mg/d for

Hamburg results in a release factor of

These external measurements are supported by continuous (monthly) company-internal measurements,

carried out over the last years by GC-MS to control air emissions. The limit of quantification (LOQ) for

these measurements is 1 mg/m3 and all measured values are consistently below the LOQ.

Salzbergen – measured values

Compliance with TA Luft was controlled by measurements carried out by the external certified

laboratory TÜV Süd in August 2015 (see table below). Six samples were taken between 9:00 am and

1:00 pm on 10 August 2015 at the stack of the waste gas filter unit.

Discontinuous measurements with six sampling periods of 30 min each were performed. EDC was

measured according to DIN EN 13649 with mass spectrograph coupled gas chromatography. The limit

of quantification was 1 µg/sample. Mean off-gas volume at the stack during the measurement period

was 22.2 m3/h.

Table 17. Results of measurements by TÜV Süd (August 2015)

Sample mass flow (g/h) concentration (mg/m3)

1 0.018 0.8

2 0.007 0.3

3 0.002 0.1

4 0.002 0.1

5 0.002 0.1

6 0.002 0.1


The mass flow of 6 mg/h is far below the legal limit value of TA Luft (2.5 g/h) and results in a total daily

emission of 144 mg EDC (a similar value of 160 mg/d results from the average concentration of 0.3

mg/m3 multiplied by off-gas volume and 24 h).

With the yearly consumption of EDC in Salzbergen as given above the emission value of 144 mg/d for

Salzbergen results in a release factor of

These external measurements are supported by continuous (monthly) company-internal measurements

to control air emissions over the last years. The limit of quantification for these measurements is 5 ppm

(21 mg/m3) and all measured values are consistently below the LOQ.

9.0.5.3.3 Releases to waste water

As EDC is used in closed systems, releases to waste water are very low. Process waters (with low EDC

concentrations) and surface water are gathered and treated at both sites in stripping columns, where

EDC is extracted from the aqueous phase with steam. Extracted EDC (in a two-phase mixture) is

condensed and reintroduced into the production process.

Remaining waste water is directed to the waste water treatment plants at both refineries. The waste

water treatment plants handle all process waste waters as well as surface water from the complete

refinery. Common parts of the treatment process are mechanical screen, grit remover, oil separator

(separated hydrocarbons are reintroduced in the production process), flotation unit (where, with

addition of flotation chemicals and aeration, hydrocarbon residues are gathered in a foam phase, which

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is separated and disposed of).

At the Hamburg site the cleaned water is sent to two active carbon absorption columns (in series),

before being released to the Elbe. In Salzbergen the cleaned water is released into an advanced

treatment pond, before being released to the Ems.

Hamburg – measured values

On behalf of State authorities in Hamburg, the “Institut für Hygiene und Umwelt” regularly and without

prior notice takes samples from the effluent of the water treatment plant directed to the Elbe. Parameters

investigated include AOX (total absorbable halogen), with a detection limit of 10 µg/l and a limit value

of 100 µg/l. Notification on the results to H&R only occurs in case of violation of the limit value. No

non-compliance notices were received from the authorities (with exemption of a sample taken in May

2015). Therefore, as a general procedure parallel samples are taken and analysed in the company

laboratory (similar to DIN EN ISO 9562). Five measurements from 2013, four from 2014 and three

from 2015 are available (see table below).

Table 18. AOX- concentrations in effluent released to the Elbe

Sampling date AOX (µg/l)

22.01.2013 <10

29.05.2013 <10

24.07.2013 <10

08.10.2013 <10

03.12.2013 <10

18.02.2014 <10

03.04.2014 <10

11.06.2014 <10

06.10.2014 <10

30.01.2015 <10

19.03.2015 20

06.05.2015 170

Further, a regular monitoring programme is implemented to analyse effluent samples for EDC itself.

EDC is analysed with a quantification limit of 10 µg/L on an approx. biweekly basis. A total of 108

samples are available for the period January 2014 to January 2016, of which 80 (74%) were below the

limit of detection (see Table 1).

Total annual volume of effluent to the Elbe in 2014 was 360 000 m3.

Table 19. EDC concentrations in effluent released to the Elbe

Sampling date EDC (µg/l) Sampling date EDC (µg/l)

02.01.2014 05:00 <0.01 19.01.2015 05:00 <0.01

06.01.2014 05:00 0.1 26.01.2015 05:00 <0.01

09.01.2014 10:47 0.1 02.02.2015 05:00 <0.01

13.01.2014 05:00 <0.01 09.02.2015 05:00 <0.01

16.01.2014 05:00 <0.01 16.02.2015 05:00 <0.01

20.01.2014 05:00 <0.01 23.02.2015 05:00 <0.01

23.01.2014 05:00 0.1 02.03.2015 05:00 <0.01

27.01.2014 05:00 0.1 16.03.2015 05:00 <0.01

30.01.2014 05:00 0.1 23.03.2015 05:00 0.04

03.02.2014 05:00 <0.01 30.03.2015 05:00 <0.01

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06.02.2014 05:00 <0.01 06.04.2015 05:00 0.22

10.02.2014 05:00 <0.01 13.04.2015 05:00 0.254

13.02.2014 05:00 <0.01 20.04.2015 05:00 0.285

20.02.2014 09:14 <0.01 27.04.2015 05:00 0.27

27.02.2014 09:40 <0.01 04.05.2015 05:00 0.35

06.03.2014 07:19 <0.01 11.05.2015 05:00 0.34

28.04.2014 05:00 <0.01 18.05.2015 05:00 0.33

05.05.2014 05:00 <0.01 25.05.2015 05:00 0.35

12.05.2014 05:00 0.02 01.06.2015 05:00 0.27

19.05.2014 05:00 <0.01 08.06.2015 05:00 0.26

26.05.2014 05:00 <0.01 11.06.2015 09:57 0.06

02.06.2014 05:00 <0.01 12.06.2015 09:56 0.05

09.06.2014 05:00 <0.01 15.06.2015 05:00 0.1

16.06.2014 05:00 <0.01 15.06.2015 02:11 0.04

23.06.2014 05:00 <0.01 19.06.2015 10:23 0.04

30.06.2014 05:00 <0.01 22.06.2015 05:00 0.06

07.07.2014 05:00 0.1 29.06.2015 05:00 0.04

14.07.2014 05:00 <0.01 06.07.2015 05:00 0.05

21.07.2014 05:00 <0.01 13.07.2015 05:00 <0.01

28.07.2014 05:00 <0.01 20.07.2015 05:00 <0.01

04.08.2014 05:00 <0.01 27.07.2015 05:00 <0.01

11.08.2014 05:00 <0.01 03.08.2015 05:00 <0.01

18.08.2014 05:00 0.1 10.08.2015 05:00 <0.01

25.08.2014 05:00 <0.01 17.08.2015 05:00 <0.01

01.09.2014 05:00 <0.01 24.08.2015 05:00 <0.01

08.09.2014 05:00 <0.01 31.08.2015 05:00 <0.01

15.09.2014 05:00 <0.01 07.09.2015 05:00 <0.01

22.09.2014 05:00 <0.01 14.09.2015 05:00 <0.01

29.09.2014 05:00 <0.01 21.09.2015 05:00 <0.01

13.10.2014 05:00 <0.01 28.09.2015 05:00 <0.01

20.10.2014 05:00 <0.01 05.10.2015 05:00 <0.01

27.10.2014 05:00 <0.01 12.10.2015 05:00 <0.01

03.11.2014 05:00 <0.01 19.10.2015 05:00 <0.01

10.11.2014 05:00 <0.01 26.10.2015 05:00 <0.01

17.11.2014 05:00 0.12 02.11.2015 05:00 <0.01

18.11.2014 09:55 <0.01 09.11.2015 05:00 <0.01

24.11.2014 05:00 <0.01 16.11.2015 05:00 <0.01

01.12.2014 05:00 <0.01 23.11.2015 05:00 <0.01

08.12.2014 05:00 <0.01 30.11.2015 05:00 <0.01

15.12.2014 05:00 <0.01 07.12.2015 05:00 <0.01

22.12.2014 05:00 <0.01 14.12.2015 05:00 <0.01

29.12.2014 05:00 <0.01 21.12.2015 05:00 <0.01

05.01.2015 05:00 <0.01 28.12.2015 05:00 <0.01

12.01.2015 05:00 <0.01 04.01.2016 05:00 <0.01

Arithmetic mean (mg/L) 0.043*

* values <LOQ set at 0.5 * LOQ

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With the yearly consumption of EDC in Hamburg as given above the concentration of 43 µg/L and a

total annual effluent volume of 360 000 m3 for the release to the Elbe a total release of 15.48 kg/a (43

g/d) and a release factor of results.

While EUSES requires some adaptation of the release factors used as input data6, note that the

assessment is based on monitoring data obtained in the effluent prior to discharge into the water

compartment. Since such measurements are independent of assumptions on the behaviour of a

substance during waste water treatment (in contrast e.g. to measurements in process streams before

waste water treatment), the ultimate release estimated is considered very reliable.

Salzbergen

The effluent from the flotation pond in Salzbergen directed to the river Ems is regularly analysed by

State authorities (“Niedersächsischer Landesbetrieb für Wasserwirtschaft, Küsten- und Naturschutz”,

NLWKN) (10 measurements from January 2013 up to now; no details on methods are given in the

authority reports). Furthermore, the authority is regularly sampling the waste water stream coming from

the EP unit before entering the waste water treatment. One of the parameters measured is AOX, with a

limit of quantification of 10 µg/l. By using this parameter it is assumed in a conservative manner that all

AOX measured in the effluent belongs to EDC.

Table 20. AOX- and derived EDC concentrations in waste water from EP unit, before entering

waste water treatment

Sampling date AOX (µg/l) EDC (µg/l) **

30.01.2013 22 30.7

26.03.2013 23 32.1

30.07.2013 10* 14.0

12.11.2013 59 82.3

28.01.2014 18 25.1

25.02.2014 10* 14.0

07.04.2014 10* 14.0

07.07.2014 10* 14.0

04.11.2014 10* 14.0

04.03.2015 10* 14.0


* values <LOQ set at 0.5 * LOQ

** EDC is calculated from AOX by multiplying concentrations by 98.66/(2*35.45)

Average waste water volume from the EP unit is 4.4 m3/h or 105.6 m3/day.

Table 21. AOX- and derived EDC concentrations in effluent released to the Ems

Sampling date AOX (µg/l) EDC (µg/l) *

30.01.2013 21 29,3

26.03.2013 28 39,1

6 The release factor given refers to the release in the effluent before entering the water compartment (i.e. after waste water

treatment). EUSES requires release factors from the process, i.e. before waste water treatment. Since 47.7 % of the substance is

assumed to be released to the river in EUSES, the release factor from the process is higher than the value given in the text. For

EUSES modelling, the release factor after waste water treatment was divided by 0.477 and the resulting (higher) release factor

was used. This is entirely a technical issue for EUSES modelling. The modelled concentration in the effluent (after waste water

treatment) is identical to the monitored values that were used as the basis in deriving release factors.

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30.07.2013 24 33,5

12.11.2013 39 54,4

28.01.2014 36 50,2

25.02.2014 35 48,8

07.04.2014 34 47,5

07.07.2014 36 50,2

04.11.2014 32 44,7

04.03.2015 36 50,2

Arithmetic mean 32.1 44,8

* EDC is calculated from AOX by multiplying concentrations by 98.66/(2*35.45)

Average effluent water volume is 68.9 m3/h or 1653.6 m3/day.

The measurements show that AOX concentrations in the effluent to the Ems are higher than in the waste

water stream coming from the EP line. Obviously, other halogenated compounds contribute to the AOX

release to the Ems.

Therefore, the release factor is calculated from the AOX (EDC) concentrations in the waste water

stream of the EP line. The concentration of 25.4 µg/L and an effluent volume from the EP unit of 105.6

m3/d or 38 544 m3/a gives a total annual release of 0.98 kg/a. With the yearly consumption of EDC in

Salzbergen as given above this leads to a release factor of .

Note that the amount emitted from the EP unit of 0.98 kg/a (2.68 g/d) is diluted with waste water from

other processes (overall: 1653.6 m3/d). The modelled EDC concentration in untreated waste water is

26.8 g/d / 1653.6 m3/d = 1.62 µg/L (under the assumption that all AOX emitted from the process is

EDC).

Additional input values

The following site-specific input values were used in EUSES modelling.

Table 22. Additional site-specific input values for EUSES modelling

Parameter Value Justification

Hamburg

Discharge rate to

Elbe, point Rethe

360 000 m3/a =

986.3 m3/d

Arithmetic mean of daily measurements(N=365, 2014)

(measured by continuous flowmeter analysis)

Flow rate Rethe

(tributary to Elbe)

About -400 to 1000

(average about 300)

m3/s, average

corresponding to

2.59 x 107 m3/d

Strong tidal influence, range given representing tidal in-

and outflow; the river flow rate of the river

Flow rate Elbe 764 m3/s = 6.6 x 107

m3/d

Long-term mean (MQ) in the relevant section of the Elbe

(both Elbe streams (Norderelbe and Süderelbe)

combined)7

Salzbergen

Discharge rate to

Ems

1 653.6 m3/d Arithmetic mean of short-term measurements by authority

during sampling, N=10, 1/2013-3/2015); confirmed by

24h measurements by authority (N=7), with arithmetic

mean=1591 m3/d

7 International Commission for the Protection of the Elbe River (IKSE): "Die Elbe und ihr Einzugsgebiet" (2005), available

online: http://www.ikse-mkol.org/index.php?id=210&L=2.Accessed, Chapter 4.11, Abb. 4.11.4; accessed October 2015

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River flow rate

Ems

8.7 x 108 m3/a =

2.38 x 106 m3/d

Mean flow conditions (yearly average 2012 at Rheine

Unterschleuse) (NLWKN, 2014)

The dilution factor for discharges in surface water are calculated on the basis of these data:

- Hamburg based on less well documented data for Rethe: 26 261

- Hamburg based on more reliable data for the Elbe: 66 918

- Salzbergen: 1 442

For the Hamburg site, the dilution factor will be between the value for the Rethe (a side canal of the

Süderelbe) and the value for the Elbe (combined value for Norderelbe and Süderelbe). The resulting

dilution factors of ca. 26 000 and 67 000 are considerably higher than the value of 1 000, considered in

the ECHA Guidance (ECHA, 2012d) as the maximum value to be applied. The dilution factor applied

will – in the context of the assessment of human exposure via the environment – primarily be relevant

for exposure via drinking water, if this is abstracted from surface water. With the dilution factor set to

1 000, the corresponding concentration in drinking water abstracted from surface water would be

0.0279 µg/L (EUSES modelling, details not shown). The concentration in drinking water abstracted

from groundwater is 0.00933 µg/L, a value that is independent of the dilution factor applied.

In the city of Hamburg, drinking water is exclusively abstracted from groundwater8. As a consequence,

the dilution factor in EUSES was set to 2 000 to yield a concentration in surface water for drinking

water abstraction that is slightly below the value for groundwater (0.007 µg/L). EUSES then calculates

the intake of EDC via drinking water from the concentration in groundwater, representing the true

situation in the city of Hamburg. This modelling approach forms the basis of the assessment presented

in section 9.1.1.3.

For the Salzbergen site, the dilution was set to 1 000, a value slightly lower than the one calculated

above from waste water discharge and the river flow rate. The concentration in groundwater is then

taken by EUSES as the concentration in drinking water, since it is higher than concentration in drinking

water abstracted from surface water (factor 1.3; details not shown). This represents the true situation,

since the corresponding water work also abstracts drinking water from ground water9.

No substance is released to soil from the production units. No sludge is generated from the wastewater

treatment and the default dry sludge application rate for agricultural soil and grassland in EUSES was

set to zero.

9.0.5.4. Considerations on losses of EDC from the process

The aforementioned quantity of EDC purchased each year is effectively the tonnage of EDC used for

replenishing the following losses:

In products (base oils, slack waxes, foots oils, hard paraffin waxes), as an impurity

In the excess gas stream from the gas treatment unit

To the wastewater stream from the waste water treatment unit

From leaks from piping and equipment during normal operation (including solvent recovery)

From leaks during maintenance processes (including solvent recovery)

From solvent degradation during normal use (including solvent recovery).

8 Hamburg Wasser: Trinkwassergewinnung – ausschließlich aus Grundwasser,

http://www.hamburgwasser.de/wassergewinnung.html, accessed: October 2015 9 Trink- und Abwasserverband Bad Bentheim, Schüttorf, Salzbergen und Emsbüren (TAV),

https://www.ta-verband.de/index.php?id=136, accessed: October 2015

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With particular regard to solvent degradation, EDC hydrolyses very slowly to vinyl chloride,

2-chloroethanol and hydrochloric acid:

2CH2Cl-CH2Cl + H2O CH2=CHCl + CH2Cl-CH2OH + 2HCl

Vinyl chloride hydrolyses to acetylene, acetaldehyde and hydrochloric acid:

2CH2=CHCl + H2O C2H2 + CH3CHO + 2HCl

Meanwhile, 2-chloroethanol hydrolyses to ethylene glycol and hydrochloric acid:

CH2Cl-CH2OH + H2O CH2OH-CH2OH + HCl

These degradation products must be removed. Sodium hydroxide or ammonium derivatives are added

to neutralise the hydrochloric acid. Here the chemical reaction with sodium hydroxide is given:

HCl + NaOH NaCl + H2O

If the hydrochloric acid were allowed to accumulate, it would corrode the pipes and equipment. The

wastewater is sent to the waste water treatment unit before release to the environment.

H&R AG believes that degradation might be the most important source of losses. During normal

operations no losses should be expected from piping, etc. System flushing during maintenance may also

be a source of notable EDC losses, but this has and will be minimised in the future according to the

applicants’ continuous improvement plan.

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9.1 Exposure scenario 1: Industrial use as a solvent and anti-solvent of the

feedstock and intermediate product streams in the combined de-waxing

and de-oiling of refining of petroleum vacuum distillates for the

production of base oils and hard paraffin waxes

9.1.1. Environmental contributing scenario: Use as a solvent and anti-solvent in

de-waxing and de-oiling (ERC 4)

As EDC is listed in REACH Annex XIV due to its carcinogenic effects, no environmental exposure

assessment is performed here. However, human exposure via the environment is addressed.

9.1.1.1 Conditions of use

Table 23. Conditions of use for the Hamburg site (H&R Ölwerke Schindler GmbH)

Amount used, frequency and duration of use (or from service life)

• Daily use at site: (amount not recovered and used for exposure assessment)

• Annual use at a site: (amount not recovered and used for exposure assessment)

• Emission days: 365 d/year (maintenance not considered)

Conditions and measures related to sewage treatment plant

• Industrial STP: Yes

• Discharge rate of STP: 986 m3/d

• Application of the STP sludge on agricultural soil: no sludge, not applicable

Other conditions affecting environmental exposure

• Receiving surface water flow rate (Rethe/Elbe): 2.59-6.6 x 107 m3/d (see section 9.0.5.3)

Table 24. Conditions of use for the Salzbergen site (H&R Chemisch-Pharmazeutische

Spezialitäten GmbH)

Amount used, frequency and duration of use (or from service life)

• Daily use at site: (amount not recovered and used for exposure assessment)

• Annual use at a site: (amount not recovered and used for exposure assessment)

• Emission days: 365 d/year (maintenance not considered)

Conditions and measures related to sewage treatment plant

• Industrial STP: Yes

• Discharge rate of STP: 1 653.6 m3/d

• Application of the STP sludge on agricultural soil: no sludge, not applicable

Other conditions affecting environmental exposure

• Receiving surface water flow rate (Ems): 2.38 x 106 m3/d

9.1.1.2. Releases

The local releases to the environment are reported in the following table.

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Table 25. Local releases to the environment – site Hamburg

Release Release factor estimation method Explanation / Justification

Water Measured release (Site-specific data) Final release factor: (after on-site treatment)

Local release rate: 42.4 g/day (after on-site treatment)

Justification: see section 9.0.5.3

Air Measured release (Site-specific data) Final release factor:

Local release rate: 0.24 g/day


Soil Release factor (Site-specific data) Final release factor: 0%

Table 26. Local releases to the environment – site Salzbergen

Release Release factor estimation method Explanation / Justification

Water Measured release (Site-specific data) Final release factor: (before on-site treatment)

Local release rate: 2.68 g/day (before on-site treatment)

Justification: see section 9.0. 5.3

Air Measured release (Site-specific data) Final release factor:

Local release rate: 0.144 g/day


Soil Release factor (Site-specific data) Final release factor: 0%

9.1.1.3. Exposure and risks for human exposure via the environment

The modelled EDC concentrations for inhalation exposure and EDC doses for oral exposure are

reported in the following tables for both the regional and the local scale. The full EUSES reports are

included in Appendix 5 of this CSR.

Hamburg

Table 27. Modelled exposure for humans via the environment: inhalation

EDC concentration [µg/m3]

Regional PEC in air 7.73 x 10-06

Local PEC in air 1.28 x 10-02

Table 28. Modelled exposure for humans via the environment: oral

Scale EDC oral intake [µg/(kg x d)]

Regional assessment 1.71 x 10-06

Local assessment 6.40 x 10-04 All values rounded to three significant figures for presentation, but unrounded values were used for calculation of sums

These exposure estimates are based on release factors that were in turn calculated from measured data.

The measured data were obtained in the context of compliance with German legislation (e.g. TA Luft,

see section 9.0.5.3 for details).

The modelled values must be put into perspective. The assessment is based on the arithmetic mean that

is impacted by a few high values, with the median being almost 9-times lower (1/2 of the LoD = 5

µg/L vs. 43 µg/L, see section 9.0.5.3).

In the present case, the assumed release to water on the basis of the high arithmetic mean also has an

effect on the EDC concentration in air and in groundwater. In fact, EUSES not only models releases to

air from the unit, but also release to air from the waste water treatment process. For the Hamburg site,

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the release to air from the unit (0.24 g/d, see section 9.0.5.3) is substantially lower than the modelled

EDC release from waste water treatment (46 g/d). EUSES takes the maximum of these two values as the

basis for calculating the local PEC in air (RIVM, 2004). The local PEC in air is therefore impacted by

the release to water estimated from the high arithmetic mean EDC concentration.

If the median of 5 µg/L (1/2 of the LoD) is used in the assessment, PEC local in air is still calculated on

the basis of EDC release from the STP (5.35 g/d), since this is still higher than the release from the

process. The resulting PEC local in air is 1.49 x 10-3 µg/m3 (almost 9-times lower than the one given

above). Since the concentration in groundwater (relevant for oral exposure via drinking water) is almost

exclusively dependent on EDC deposition (because no sewage sludge is applied to soil), the lower

release to air from waste water treatment also results in a lower exposure via drinking water (the major

contributor to oral exposure in the local assessment).

Overall, the reduction of the releases to waste water by a factor of almost 9 (median instead of

arithmetic mean) result in a reduction of both inhalation exposure by about the same factor in both the

local and the regional assessment. We therefore consider the exposure estimates presented above as a

conservative assessment.

In relation to exposure via drinking water from groundwater, which dominates total oral exposure in the

local assessment (about 60% of total oral intake), it is also worth noting that the modelled EDC

concentration in groundwater is simply derived in EUSES from setting the concentration in soil

porewater as equal to the concentration in groundwater (RIVM, 2004). As these authors state, “this is a

worst-case assumption, neglecting transformation and dilution in deeper soil layers” (RIVM, 2004). In

addition, the concentration in soil porewater is driven by deposition of EDC from the air. Such

deposition is modelled in the EUSES local assessment for a circle around the source with a radius of

1000 m, which can be considered another conservative assumption (also see discussion below). Finally,

no mixing with other water is assumed in EUSES when equating the concentration in groundwater with

the concentration in drinking water. Despite these conservative assumptions, the modelled

concentration in drinking water (0.0143 µg/L) is well below the limit value of 3 µg/L according to

Council Directive 98/83/EC, implemented in the German Drinking Water Ordinance

(“Trinkwasserverordung”), which, according to WHO (2003), corresponds to a risk of 1 x 10-6 .

Drinking water in Hamburg is regularly monitored for EDC. In 2014, all EDC measurements at the

relevant waterworks were below the analytical limit of quantification (<1 µg/L)10.

The exposure estimated is multiplied with the exposure-risk relationship for carcinogenic effects of

EDC in the general population (see section 9.0.5.1). The following table shows the resulting risks for

both the regional and the local scale. The risks are presented for each of the two relevant pathways as

well as for total exposure (risks for inhalation and oral exposure added).

Table 29. Risk estimates for humans via the environment

Scale Inhalation exposure Oral exposure Total exposure

Regional assessment 2.67 x 10-11 2.05 x 10-11 4.72 x 10-11

Local assessment 4.42 x 10-08 7.68 x 10-09 5.18 x 10 -08

The calculated risks in the regional assessment are extremely low and are about five orders of

magnitude lower than the “indicative tolerable risk level” of 10-6 for the general population (ECHA,

2012a). In the local assessment, the risk from total exposure is about 20-times lower than this

“indicative tolerable risk level” and is dominated from the contribution of inhalation exposure (85% of

total exposure).

This risk estimate for local inhalation exposure has to be put into perspective. In EUSES, the local PEC

10 Hamburg Wasser: Trinkwasseranalyse Grundwasserwerk Süderelbmarsch,

http://www.hamburgwasser.de/wasseranalysen.html, accessed: October 2015

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in air is modelled for a point 100 meters from the source, a distance “assumed to be representative for

the average size of an industrial site” (RIVM, 2004).

The refinery of H&R Ölwerke Schindler GmbH in Hamburg is a large production site located within a

large industrial area. No private housings exist within a radius of 1000 m around the production site.

Please note that the concentration in air and the deposition (a key determinant for the concentration in

groundwater) are estimated in EUSES with the Operational Priority Substances (OPS) model that is

embedded in EUSES. When EUSES was developed, conservative input values were chosen (e.g. stack

height of 10 m, no excess heat of the plume emitted compared to environmental temperature and an

ideal point source). The developers of the OPS model at the Dutch RIVM more recently analysed the

impact of these conservative default settings on the estimated concentration in air and on the total

deposition. These authors concluded that ‘air concentration and total deposition used for risk

assessment purposes are likely to be overestimated due to over-conservative default settings used in the

standard scenario in EUSES’ (de Bruin et al., 2010). In the light of these findings, we conclude that the

risk estimates presented above are highly conservative.

Salzbergen

Table 30. Modelled exposure for humans via the environment: inhalation

EDC concentration [µg/m3]

Regional PEC in air 2.46 x 10-07

Local PEC in air 3.86 x 10-04

Table 31. Modelled exposure for humans via the environment: oral

Scale EDC oral intake [µg/(kg x d)]

Regional assessment 5.18 x 10-08

Local assessment 2.20 x 10-05 All values rounded to three significant figures for presentation, but unrounded values were used for calculation of sums

EDC exposure modelled for the Salzbergen site is lower than for the Hamburg site. Nonetheless, many

of the issues impacting the exposure estimate are identical. The worst case assumption of assigning all

AOX to EDC for releases to waste water was also applied. In EUSES modelling, this results in an EDC

release to air from waste water treatment (1.39 g/d) that is about 10-times higher than the release from

the process (0.144 g/d, see section 9.0.5.3). As discussed in detail for the Hamburg site above, the

release to air from waste water treatment therefore has a direct impact on the local PEC in air and on the

concentration in groundwater, which forms the basis of the calculated intake via drinking water, which

in the local assessment dominates total oral exposure (about 60 % contribution).

Similar to the situation in Hamburg, drinking water monitoring values for the relevant water work for

Salzbergen were below the analytical limit of quantification (<1 µg/L)11. The modelled value forming

the basis of the assessment is 0.000476 µg/L, is almost four orders of magnitude below the limit value

of 3 µg/L according to Council Directive 98/83/EC, implemented in the German Drinking Water

Ordinance (“Trinkwasserverordung”).

The exposure estimated is multiplied with the exposure-risk relationship for carcinogenic effects of

EDC in the general population (see section 9.0.5.1). The following table shows the resulting risks for

both the regional and the local scale. The risks are presented for each of the two relevant pathways as

well as for total exposure (risks for inhalation and oral exposure added).

11 Trink- und Abwasserverband Bad Bentheim, Schüttorf, Salzbergen und Emsbüren (TAV),

http://www.ta-verband.de/uploads/media/Trinkwasserqualitaet_01.pdf, accessed: October 2015

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Local assessment 1.33 x 10-09 2.64 x 10-10 1.60 x 10-09

The calculated risks in the regional assessment are extremely low and are about six orders of magnitude

lower than the “indicative tolerable risk level” of 10-6 for the general population (ECHA, 2012a). In the

local assessment, the risk from total exposure is about three orders of magnitude below this “indicative

tolerable risk level” and the risk from total exposure is dominated from the contribution of inhalation

exposure (85% of total exposure).

This risk estimate for local inhalation exposure has to be put into perspective. In EUSES, the local PEC

in air is modelled for a point 100 meters from the source, a distance “assumed to be representative for

the average size of an industrial site” (RIVM, 2004).

The site of H&R Chemisch-Pharmazeutische Spezialitäten GmbH in Salzbergen is also a large site,

with nobody living within a radius of 100 m of PU-F and the distillation unit. Only 3500 persons are

living within a radius of 1000 m around the production site.

In addition, we conclude that the risk estimates presented above are highly conservative due to the

conservatism built into the OPS model (see discussion above for Hamburg site).

Conclusions

In summary, the risks calculated are very low. The total risk for the local assessment is dominated at

both sites by inhalation exposure (83-85 %) and oral exposure via drinking water from groundwater

(9-10 %), together accounting for 94-95 % of the total local risk estimated. For reasons outlined above,

risk estimates for both pathways are considered very conservative. The total risk calculated for the local

assessment is therefore even more conservative.

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9.1.2 Worker contributing scenario 1: Production process including storage, transfers,

sampling, and recycling of EDC (PROC 2)

As described in the introduction of section 9.0, EDC is used in closed systems without direct handling

of EDC by operators except during sampling for quality control.

The contributing scenario 1 covers all activities associated with exposure to EDC (involving activities

related to various process stages: storage tank, crystallisation vessels, filters units, distillation reactors,

recovered EDC storage tanks).

9.1.2.1. Conditions of use

Product characteristics

• 1,2-dichloroethane – liquid

Amount used, frequency and duration of use/exposure

• The industrial sites are producing in continuous process, 24/24, all year (only interrupted for general

maintenance).

Technical and organisational conditions and measures

• All pipes and equipment in the production unit which are containing EDC are built as enclosed

system with closed gas venting system (“Gaspendelung”, gasometer). All process transfers (storage

tank, crystallisation, filters, distillation) are monitored, automatized and under panel control and

alarms.

Tanks and reactors are equipped with secure control equipment. Seals (static, dynamic) are designed

for leak tightness in accordance to German regulations (BImSchG, TA-Luft 2002).

The gas venting system is equipped with a separate solvent recovery unit. In case of emergency the unit

is connected with a secure unit tank storage and for protection of over-pressure the safety equipment is

connected to a condensing Blow-Down-System.

• Local exhaust ventilation: none

Conditions and measures related to personal protection, hygiene and health evaluation

• Dermal Protection: yes, during sampling for quality control (chemically resistant gloves conforming

to EN374 with specific activity training) (Effectiveness Dermal: 95%)

• Respiratory Protection: yes, during sampling for quality control – [Effectiveness Inhal: 95%]

Other conditions affecting workers exposure

• Place of use: Indoor – good general ventilation or outdoors

•Trained and authorized person: All operators involved in plant unit production have a technical

certification. General training on risks for chemical are given each years for all operators involved in

chemical handling. Specific trainings on chemical risks are given regularly to all plant operators

handling EDC. All tasks involving EDC are done by competent and authorized operators.

9.1.2.2. Exposure and risks for workers

Inhalation exposure assessment

Personal sampling measurements are available for operators in EP units for both Hamburg and

Salzbergen. Summary tables on the results of various measurement campaigns are presented in

Appendix 2. In total 24 long-term, personal sampling measurements are available (12 from Hamburg,

13 from Salzbergen, among them 6 measurements performed by the German BG RCI (Statutory

Accident Insurance Institution, “Berufsgenossenschaft”).

Exposure levels are similar in Hamburg and Salzbergen, confirming the similarity of exposure

situations. Short-term measurements were included in these long-term measurements and exposure

during these periods was measured separately by employing a second sampling device. During

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sampling respiratory protection was worn, which was accounted for by applying a protection factor of

0.95 for these periods only (see equations in 9.0.6.2.1).

An arithmetic mean of 0.59 mg/m3 and a 90th percentile of 1.50 mg/m3 were calculated from this

dataset. The 90th percentile is used for exposure assessment and risk characterisation. For details see

Appendix 2.

Dermal exposure assessment

Dermal exposure will only occur during sampling. This task is infrequent (up to 4 samples per week,

duration 5 to 15 min; one event per day assumed below) and related to low exposure, as sampling is

performed via a closed system, where a flask is screwed to the line. In addition, personal protection

(gloves) is worn and drops of EDC are expected to rapidly evaporate from the glove surface (see

Appendix 4).

The procedure to estimate dermal exposure to EDC and to consider evaporation of the substance is

described in 9.0.5.2.2 and Appendix 4.

Table 33. Task-specific dermal exposure assessment

Parameter Unit PROC 2

Dermal dose per event (potential), product µg/kg 0.13




Dermal EDC exposure, (potential) µg/(kg x d) 0.065




Exposure and risk estimate

Table 34. Exposure concentrations and risks for workers (CS1)

Route of

exposure

TWA 8h exposure Correction factor

for frequency

Corrected

exposure

Excess cancer risk

Inhalation 1.50 mg/m3 ** Frequency: 0.41* 0.62 mg/m3 3.7 x 10-4

Dermal 0.0033 µg/(kg x d)*** Frequency: 0.41* 0.0014 µg/(kg x d) 5.7 x 10-9

Combined

routes

3.7 x 10-4

* Frequency: activity takes place daily; 2 exposure-related workplaces per shift, 24 h/day, 365 days:

17520 hours; divided by a pool of 22 workers sharing the shifts: average exposure duration per year:

796 hours; compared to full shift exposure duration: 1920 hours: correction factor = 796/1920 = 0.41

** RPE used during sampling: 95% efficiency considered for sampling periods only

*** PPE used during sampling: 95% efficiency

With an average concentration of 0.59 mg/m3 and a 90th percentile of 1.5 mg/m3, inhalation exposure

levels to this highly volatile substance are low. Dermal exposure is not contributing to overall exposure

to a substantial extent.

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9.1.3. Worker contributing scenario 2: Receipt of EDC from road tank (PROC 8b)

This contributing scenario covers the unloading of EDC from a road tank equipped with the Fort Vale

system, which allows to operate the ventilation of the tank truck from below, The only exposure-related

activity therefore is disconnecting flexible hoses after unloading.





• Approx. EDC is unloaded from a tank truck to a storage tank. The complete duration of

this operation is less than 1 hour. 2 operators (road tank driver + plant operator) are doing the work

which consist of:

- connecting the flexible hose from road tank to storage tank (previously purged with nitrogen

gas) – duration 2 minutes

- Visual control during unloading (far-off road tank) - duration < 55 minutes

- Disconnecting the flexible (previously purged) – duration 2 minutes.


• Containment: fixed connection and hose steel connections. Bottom unloading with direct

atmospheric exchange from truck tank to storage tank – no direct emission to atmosphere.

• Assurance of leak tightness by leak test after establishing the connection and complete capture of the

residual quantities by inert gas into the flexibles



• Dermal Protection: Yes (chemically resistant gloves conforming to EN374 with specific activity

training) (Dermal: 95%)

• Respiratory Protection: No


• Place of use: Outdoors

•Trained and authorized person: Connection and transfer is done by employees competent, trained and

authorized for EDC unloading truck tank operations.



Advanced Reach Tool (ART, V1.5) model is used to estimate inhalation exposure.

o Activity 1 = connection/disconnection flexible hoses – duration 5 minutes

o Activity 2 = road tank unloading – duration 55 minutes.

No exposure is assumed during the rest of the shift, combined exposure of plant operators is

considered in section 10).

Inputs used in ART:

o Activity 1. Emission source is located in the breathing zone of the worker. During this

phase the operator connects/disconnects the flexible hoses on the plant side, whereas

the truck driver connects the hose to the tank truck.

”Handling of contaminated objects” with surface area (opening of flexible hose) is

between 0.1 and 0.3 m2; purging with nitrogen: contamination of <10% of surface is

assumed.

B

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o Activity 2. During this phase, the operator and truck driver are far away from the road

tank (> 4 m).

“Bottom loading” with a transfer rate of 100-1000 L/min ( ). As

transfer of EDC occurs via closed lines medium level containment is chosen.

An exposure estimate of 0.25 mg/m3 (upper limit of inter-quartile confidence interval to the 75th

percentile; 90th percentile amounts to 0.28 mg/m3) is obtained with ART (no respiratory protection is

used during this activity) (see Appendix 3).

As this activity occurs , few measurements are available. Exposure during

tank truck unloading was measured in Hamburg in October 2014 and in Salzbergen in April 2015. As

two workers (1 plant operator, 1 truck driver) are involved in each occasion, in total, four values from

personal sampling are available. Event concentrations (approx. 1 h) ranged from 0.18 to 1.1 mg/m3 and

shift TWA concentrations from 0.019 to 0.11 mg/m3 (see Appendix 2). These monitoring data support

the modelling results.


As described above there are 2 main phases during the unloading operation: connecting/disconnecting

flexible hoses and unloading. No dermal exposure is expected during the unloading phase as the

operator is only performing visual control. During disconnecting the hose exposure to liquid EDC is

possible.




Parameter Unit PROC 8b




Concentration of EDC in product % 100







Route of

exposure


for frequency

Corrected exposure Excess cancer

risk

Inhalation 0.25 mg/m3 0.00019* 0.05 µg/m3 2.9 x 10-8

Dermal 0.066 µg/(kg x d)** 0.00019* 0.000013 µg/(kg x d) 5.3 x 10-11

Combined

routes

2.9 x 10-8

* Frequency: activity takes place

B

B

B

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the average frequency is :

correction factor = = 0.00019

** PPE used during connecting/disconnecting hoses: 95% for dermal exposure

Due to low exposure levels and low frequency, resulting long-term average exposure is very low. As

expected, dermal exposure is not significantly contributing to overall exposure. Combined exposure

from CS1 and CS2 is considered in section 10.

9.1.4. Worker contributing scenario 3: Non-routine maintenance (PROC 8b)

This contributing scenario addresses non-routine equipment maintenance (e.g. small repairs, pump

dismantlement, filter change). These activities in general last no more than 30 minutes. They are

typically undertaken with a frequency of once per month as a maximum.





• once per month, duration 30 minutes.


Non-routine maintenance (maintenance work in case of dysfunction of equipment, e.g. pump): In case of

equipment dysfunction or equipment change, the operator from the plant unit is in charge to prepare the

equipment for repair. The operator will empty the device (e.g. a pump) and purge it with nitrogen or steam. These

actions are on/off valve actions. The unit operators are not authorized to open the system or dismantle equipment.

This task will be done by maintenance operators only after having received written consent. The description of

the maintenance work to do as well as the specific risk management measures to follow are described in a permit

procedure.



Personal protective equipment is mandatory:

• Dermal Protection: Yes (chemically resistant gloves conforming to EN374 with specific activity training)

(Dermal: 95%)

• Respiratory Protection: Yes [Effectiveness Inhal: 95%]


• Place of use: Indoor – good general ventilation or outdoors

•Trained and authorized person: All operators involved in plant unit production have a technical certification.

General training on risks for chemical are given each years for all operators involved in chemical handling.

Specific trainings on chemical risk handling are given regularly to all plant operators handling EDC. All tasks

involving EDC handling are done by competent and authorized operators.



As non-routine maintenance activities are infrequent and not planned, no measurement data exist.

Therefore, tier 2 modelling using Advanced Reach Tool (V1.5) was used for the exposure assessment

(see all details of ART inputs in Appendix 3):

Activity 1 = maintenance – duration 30 minutes (No exposure during the rest of the shift)

Justification of inputs used in ART model: the ART input “main component” (50 to 90% EDC in the

B B

B

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residual liquid) will be used as a conservative estimate for situations with a high EDC content. It is

assumed that the emission source is located in the breathing zone of the worker (ART input). The

relevant activity description from ART for maintenance is handling of contaminated objects with

surface 1 to 3 m2 (conservative estimate for surfaces after dismantling hoses and pumps) with a

contamination of <10% of the surface (due to extensive purging prior to dismantling). No localised

controls and no containment are assumed for maintenance operations. CS3 activities take place in the

production unit (large workroom or outdoors).

An exposure estimate of 26 mg/m3 (upper limit of inter-quartile confidence interval to the 75th

percentile; result without PPE efficiency; 90th percentile amounts to 22 mg/m3) is obtained with ART

(see Appendix 3). The exposure result considering PPE efficiency 95% is 1.3 mg/m3.


It is assumed that during one maintenance activity of 30 min exposure up to four splashes may occur,

where liquid contents from equipment drop on the gloves. Again, in a conservative way, it is assumed

that most of the liquid consists of EDC (assumption in agreement with ART input above: 90%).








Concentration of EDC in product % 90







Route of

exposure


for frequency


risk

Inhalation 1.3 mg/m3 ** 0.025* 0.032 mg/m3 1.9 x 10-5


Combined

routes

1.9 x 10-5

* Frequency: activity takes place once per month (12/240); the 4 non-routine maintenance workers per team (and

site) are not exposed simultaneously; with a frequency of once per month and 2 workers involved per event, every

worker is only exposed every second month: correction factor = 6/240 = 0.025

** respiratory protection (efficiency 95%) and gloves (efficiency 95%) are used during this task

Again, dermal exposure is negligible compared to inhalation exposure.

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9.1.5. Worker contributing scenario 4: General maintenance and cleaning (PROC 8b)

This contributing scenario addresses general maintenance activities with full (Hamburg )

or partial (Salzbergen, ) plant shut down.





• The annual maintenance duration is as worst case).


Before opening the system for maintenance, the equipment is purged with solvent (DCM/DCE) until all wax is

washed off. The solvent is returned to the plant‘s feed (circulated in enclosed system). Then the equipment is

purged with steam to flush out solvent completely. The description of the maintenance work to do as well as the

specific risk management measure to follow are described in a permit procedure.



Personal Protective Equipment is mandatory:


(Dermal: 95%)

• Respiratory Protection: Yes [Effectiveness Inhal: 95%]


• Place of use: Indoor – good general ventilation, or outdoors

•Trained and authorized person: All operators involved in plant unit production have a technical certification.

General training on risks for chemical are given each years for all operators involved in chemical handling.

Specific trainings on chemical risk handling are given regularly to all plant operators handling EDC. All tasks

involving EDC handling are done by competent and authorized operators.


The CS4 is covering general annual maintenance activities. CS4 is done by maintenance operators. The

maintenance duration is 1 to 6 hours maximum per day (the maximum duration of 6 h will be used in

exposure assessment as worst case). There are up to 50 employees involved in general maintenance

works in each plant. General maintenance shutdowns are performed for parts of the plant every

in Salzbergen (for a total period of approx. ). In Hamburg, the complete plant is shut down for

maintenance every (for a period of , as the complete plant is cleaned up). The overall

time spent for general maintenance ( ) is comparable for both sites. Exposure to

EDC is only expected immediately after opening the system. For the exposure assessment exposure

during the first two days of the activity is assumed.

Maintenance operators from CS4 are not the same operators working in CS1, CS2, or CS3.


As there are only few measured data, a tier 2 modelling approach using the Advanced Reach Tool

(V1.5) was applied (see all details of ART inputs in Appendix 3):

Activity 1 = maintenance – duration 360 minutes (no exposure during the remaining 120 minutes of the

shift; this is considered a conservative assumption, as exposure-related activities comprise only a small

part of the shift duration (e.g. when opening and inspecting vessels), whereas a large part of the time is

spent outdoors on preparatory work etc.).

Inputs used in ART:

A

A

A

A

A

A A

A

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As before any dismantlement, the equipment is fully flushed and purged, the potential residual EDC

concentration will be extremely small (0.1 to 0.5 % - in the equipment, residual content of EDC in the

water phase resulting from the flush and purge operation12). The emission source is assumed to be

located in the breathing zone of the worker. The relevant activity in ART for maintenance is handling of

contaminated objects with surface > 3 m2 with a contamination of 10 to 90 % of surface (e.g. opening

equipment for vessel inspection). No localised controls and no containment are assumed for

maintenance operations. “Large workrooms only” was chosen in line with the large surfaces assumed.

This scenario applies to outdoor conditions as well.

Workers are wearing respiratory protection and gloves during all exposure-related tasks.

An exposure estimate of 12 mg/m3 (upper limit of inter-quartile confidence interval to the 75th

percentile; result without PPE efficiency; 90th percentile amounts to 10 mg/m3) is obtained with ART

(see Appendix 3). The exposure result considering PPE efficiency 95% is 0.6 mg/m3.

Two measurements are available, taken by the BG Chemie (Statutory Accident Insurance Institution,

“Berufsgenossenschaft”) in 2009 in Salzbergen during a general maintenance period. Personal

sampling (2 h) during maintenance work (inspection of opened columns, exchange of parts, assembly

work, general maintenance work) resulted in exposure concentrations of 2 and 2.8 mg/m3, without

taking into consideration respiratory protection equipment. These measurements well below the

concentration estimated by ART confirm the conservativism of the modelling results.


It is assumed that during one shift of routine maintenance activity up to 20 splashes may occur, where

liquid contents from equipment drop on the gloves. Again, in agreement with ART assumptions, it is

assumed that the concentration of EDC (after purging and flushing) is ≤0.5%.








Concentration of EDC in product % 0.5







Route of

exposure


for frequency


risk

Inhalation 0.6 mg/m3 ** 0.0042* 0.0025 mg/m3 1.5 x 10-6

12 The water solubility of EDC (7.9 g/L, approximately 0.79%) supports this range, since an upper concentration

of EDC in water close to the solubility limit is assumed.

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Combined

routes

1.5 x 10-6

* Frequency: activity takes place for , equivalent to correction factor

= 0.0042

** RPE and gloves used during exposure-related activities (95% efficiency)

Again, dermal exposure is negligible compared to inhalation exposure.

9.1.6. Worker contributing scenario 5: Handling in laboratory for quality control (PROC

15)





• The EDC sampled is analysed for quality control purpose at the service laboratory. Duration < 1.5h per sample.


• Local exhaust ventilation: yes (fume cupboard)

All handling EDC samples are done under fume cupboard. This equipment is certified and controlled each year.



(Dermal: 95%)

• Respiratory Protection: No


• Place of use: Indoor – good general ventilation

• Process temperature (for liquid): <= 40 °C

•Trained and authorized person: All laboratory operators have a technical certification. General training on risks

for chemical are given each years for all operators. Specific trainings on chemical risk handling are given

regularly to all laboratory operators handling EDC. All tasks involving EDC handling are done by competent and

authorized operators.


The CS5 is covering handling of EDC in the company laboratory for quality control. CS5 is done by

laboratory operators. Laboratory operators from CS5 are not the same operators working in CS1/CS2

(general production), CS3 (unloading road tank) and CS4 (maintenance).

Details on the individual tasks are given in 9.0.3. Sampling and laboratory work is less frequent in

Salzbergen. Therefore, the following conditions from the Hamburg site are taken as a worst case

situation:

- 208 samples analysed per year

- EDC content 50%


Personal sampling measurements are available for laboratory workers for both Hamburg and

Salzbergen from campaigns carried out in 2014 and 2015. Summary tables on the results are presented

A A

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in Appendix 2. In total 17 personal sampling measurements are available (7 from Hamburg, 10 from

Salzbergen). Sampling periods lasted from 3 to 92 minutes and it was confirmed in all cases that no

EDC-related activities were carried out during the rest of shift by the laboratory worker. Therefore,

TWA values were calculated from all measurements and included in the analysis. Exposure levels are

similar in Hamburg and Salzbergen, confirming the similarity of exposure situations.

An arithmetic mean of 0.056 mg/m3 and a 90th percentile of 0.17 mg/m3 were calculated for from this

dataset. The 90th percentile is used for exposure assessment and risk characterisation.


It is assumed that during 1.5 hours of working with EDC containing samples under controlled

conditions in the laboratory up to 5 splashes may occur as a worst case, where liquid contents from

equipment drop on the gloves. A concentration of EDC of 50% is assumed.




Parameter Unit PROC 15






Efficiency of PPE (gloves) % 95%

Dermal EDC exposure (actual) µg/(kg x d) 0.0041 * All values rounded to two significant figures, but unrounded values were taken for calculation.



Route of

exposure


for frequency

Corrected

exposure

Excess cancer risk

Inhalation 0.17 mg/m3 Frequency: 0.2* 0.034 mg/m3 -

Dermal 0.0041 µg/(kg x

d)**

Frequency: 0.2* 0.00082 µg/(kg x

d)**

-

Combined

routes

exempted from

authorisation

* Frequency: 208 samples per year (4 samples per week); on average, each of 4 laboratory workers

analyses 1 sample per week: correction factor = 1/5 = 0.2

** PPE used: 95% efficiency

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10. RISK CHARACTERISATION

10.1. Workers

As described in section 9, operators (CS1) are also engaged in tank truck unloading (CS2). The latter

activity and only one operator is required per unloading event (the second

person involved is the tank truck driver). Two operators per shift are regularly exposed during CS1

activities.

The additional risk due to participating in tank truck unloading is negligible compared to the risk

pertaining to CS1. In conclusion, for the combined risks from CS1 and CS2 an excess risk value of 3.7

x 10-4 is used.

All other groups of workers are exposed only with regard to one contributing scenario.

Table 43. Calculation of combined risks for workers per contributing scenario

Contributing scenario Exposed group Associated excess

cancer risk

Associated excess

cancer risk

(combined) CS1

Plant operators (N=22

per site)

3.7 x 10-4 CS2

2.9 x 10-8

Combined risks 3.7 x 10-4 CS3 Non-routine

maintenance workers

(N=4 per site)

1.9 x 10-5 1.9 x 10-5

CS4 Routine maintenance

workers (N=50 per site)

1.5 x 10-6 1.5 x 10-6

CS5 Laboratory workers

(N=4 per site)

- exempted from

authorisation

Conclusions

As shown in the individual worker contribution scenarios, the risk from dermal exposure is at least three

orders of magnitude lower than the one associated with inhalation exposure and the risks presented

above are solely related to inhalation exposure.

As shown in the individual worker contribution scenarios, the risk from dermal exposure is generally

orders of magnitude lower than the one associated with inhalation exposure and the risks presented

above are mainly related to inhalation exposure.

The exposure estimates that are based on ART modelling are considered conservative, since it was

assumed that the emission source is within 1 m of the breathing zone of the worker for the entire

duration. For tasks during maintenance, this can certainly be considered a worst-case when applied to

all workers involved in maintenance work. In reality, one worker will be closer to the emission source,

while the other workers will be further away.

In conclusion, the highest risk for operators results from contributing scenario 1, based on measurement

values. Continuous efforts are invested at both sites to further reduce emissions and exposures, which

led to substantial improvements in the past. A high level of containment was achieved, which results in

the current, low exposure levels observed.

B

EC number:

203-458-1


107-06-2


10.2. Exposure of humans via the environment

Hamburg





Salzbergen





Conclusion for both sites

In summary, the risks calculated are very low. The total risk for the local assessment is dominated by

inhalation exposure (83-85 %) and oral exposure via drinking water from groundwater (9-10 %),

together accounting for 94-95 % of the total local risk estimated. For reasons outlined in detail in

section 9.1.1.3, risk estimates for both pathways are considered very conservative. The total risk

calculated for the local assessment is therefore even more conservative.

CHEMICAL SAFETY REPORT - ECHA

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