First European Meeting on Metrology of Biofuels, 06.

Microsoft Word - editorial_1_ biofuels_Engl_korrigiert.doc6-7 November 2008 Strasbourg, Francebiofuels and metrology
First European Meeting on Metrology of Biofuels 6-7 November 2008 in Strasbourg
Philippe Charlet (LNE), Klaus-Dieter Sommer (PTB),
Jean-Remy Filtz (LNE), Harro Bauer (PTB)
Biofuels are considered as a relevant alternative source of energy complementary to the fossil fuels used today. Directive 2003/30/EC of the European Parliament and of the Council of 8 May 2003 promotes the use of biofuels and other renewable fuels for transport. Within the Directive, the European Union establishes recommendations for partially replacing fossil fuels by biofuels. It is recognized that due to existing technological limits as well as with the view to avoid a significant influence on the feedstock prices, biofuel production will never be capable of replacing fossil fuels completely. This first workshop “BioFuels Met 2008 - biofuels and metrology” was organized in Strasbourg, France, by the Laboratoire National de Métrologie et d'Essais (LNE) and the Physikalisch-Technische Bundesanstalt (PTB) in cooperation with the Collège Français de Métrologie (CFM). It aimed at exchanging ideas and feedback between scientists involved in this area to allow a better understanding of the metrological needs to support production and use of energy from biomaterials, with respect to technical and socio-economic issues, and to take on challenges to be solved in the near future. The workshop dealt with metrology on all types of biomaterials used for energy production: biogas, liquid biofuel and solid materials. These biofuels should also be considered along with fossil fuels because they are often used in parallel or in combination. The workshop was organized in different sessions with oral presentations and poster sessions: Traceability, Environmental Sustainability, Legal Metrology and Standardization, Energy and Thermo-physical Properties, Health and Safety, and Engineering. The meeting ended with a panel discussion on the definition of the prospective needs of metrology on the issue of biofuels. 70 people from around the world attended the meeting. Many National Metrology Institutes (NMIs) were represented at this workshop. Following the presentations and the debate during the panel discussion with the invited experts, it is possible to draw some conclusions and to propose recommendations for “Biofuel Metrology”. The metrological field of biofuels is a wide area that is comprised of both metrology in chemistry for traceably determining the composition of the fuels, and the determination of thermo-physical and transport properties. It furthermore requires the development of new measurement techniques.
6-7 November 2008 Strasbourg, Francebiofuels and metrology
The most challenging point is the necessary consideration and measurability of the social sustainability of all the measures taken. Therefore, it needs an intrinsically interdisciplinary collaboration of all relevant metrology and standardization partners. A good example is the Tripartite Task Force (Brazil, the European Union and the United States of America) and the “White Paper on Internationally Compatible Biofuels Standards” they published on 31 December 2007, aiming at the harmonization of standards, which is obviously essential for international trade. It has been stated that the NMIs worldwide do not need to mount parallel structures, but rather must activate the existing structures at an international level. The experts are of the opinion that NMIs should take leadership on the issue of biofuels. It is essential to have harmonization across borders and this can be done by bringing together the views: of regulatory and standardization organizations of metrology organizations at regional and international (CIPM) level of stake-holders such as trade organizations and car manufacturers of specialized research organizations. Therefore, the metrology community should take clear actions to support standardization, regulation and accreditation bodies in order to achieve comparable, “standardized” measuring methods. The issues to be resolved are complex and of different kinds, for instance related to engine parameters, sustainability, or health aspects. Therefore, these groups alone, but also the NMIs, cannot solve all the issues by themselves. On the specific scientific role of metrology organizations and NMIs From a general point of view, improving knowledge on biofuels requires competencies in very different fields, in physical and chemical areas, and, therefore, NMIs have to set up transverse activities. The priority for NMIs and related international institutes is to produce reference materials to be used as tools for method validation and instrument calibration. The most difficult task is the dissemination of these reference materials, because all field laboratories use them or should use them. Another important role for NMIs is also related to training, since there is a clear need for field testing laboratories to estimate their measurement uncertainty and to maintain traceability. It has been stated that the priority for the NMIs is to focus on the measurement traceability of important components of biofuels, and to acquire knowledge about the relevance of the so-called “sum-parameters” like pHe and conductivity and their reliability as “quality indicators” for biofuels. There is a need for practical methods establishing the “trackability of biofuels”, that is to say for tracing the geographical origin of biomaterials, for evident reasons of sustainability. It is one of the basic tasks of NMIs to establish metrological traceability of energy-content measurements of biofuels. This starts with the development of new physical standards for determining the calorific, thermal and transport properties of the relevant fuels related to their chemical composition and stretches to reliable field measurements and the standardization of
the methods used. The composition of the exhaust gases needs particular attention with respect to the effects on the environment and human health. The Proficiency Testing (PT) providers should have an important role in supporting testing laboratories to improve their analytical competencies. NMIs can be part of this improvement process and provide necessary metrological assistance to PT providers. This could be done through the “supply” of a traceable reference value by the NMI to the PT scheme. Regarding the documentary standards, opinions among experts are divided: some believe that the parameters and techniques are already well known, and there is simply a need to harmonize. Some others, on the other hand, consider that NMIs have to work on the relevance of methods and parameters currently used by field laboratories. Clear concepts are to be developed. This might be seen as a coordinating task of international metrological organizations. The environmental and societal aspects are deemed very important by all experts. In particular, the uncertainty about the outputs of life cycle assessments have to be evaluated. Metrology can build upon these approaches by simplifying the language and highlighting the lack of confidence in this type of analysis. European politics understands these environmental and societal aspects as the most important duty of NMIs and their international organizations. There should be greater participation of NMIs in societal issues debates to provide appropriate responses to current issues such as “food against biofuels”, and “biofuels and rain forest deforestation”. It was reported, at the end of the meeting that, among all the meetings held on biofuels in the world, this one had one of the most excellent scientific levels. It was also organized at the right time to bring together all the parties to gain a clear view of the relevant issues and to activate harmonization across borders. Based on the presentations during the workshop, the organizers have asked the authors to prepare a manuscript that fits the scope and purpose of the journal “ACQUAL”. Selected papers from this workshop will be published in a special issue of this journal.
Opening lecture Metrology to enable the worldwide use of biofuels J. A. H. Jornada (INMETRO - National Institute of Metrology, Standardization and Industrial Quality of Brazil)
6-7 November 2008 Strasbourg, Francebiofuels and metrology 6-7 November 2008 Strasbourg, Francebiofuels and metrology
BioFuels Met 2008- Biofuels and Metrology Strasbourg, November 6-7th, 2008
João Alziro Herz da Jornada Presidente of Inmetro- Brazil
Metrology to Enable the Worldwide Use of Biofuels
The importance of Biofuels- central to major world concerns today:
Energy, Environment and Security
• Sustainability- global warming and the emergence of developing countries
• Economics- growth of the world economy and shortage of oil- high fuel prices
• Security of supply- oil supply is concentrated in few places
ScarcityScarcity andand FossilFossil FuelFuel CostCost
Graph of Oil Production Source: Colin Campbell of the Association for the Study of Peak Oil and Gas (ASPO) Newsletter as
in Wikapedia http://en.wikipedia.org/wiki/Peak_oil
The concern with environment and the need for reliable Life Cycle Analysis-LCA
In response to this challenge, several countries and international
organisations launched profound and far reaching programs
Targets for 2020: • 20-30% GHG reduction • 20% energy efficiency improvement • 20% renewable energy including 10% biofuels
EU Policy (Thomsen Report of September 2007- binding, 2008):
Source- USA EPA- 2008- Hecht
World Production of Biofuels, in Billions of Litters
Source: Dileep K. Birur, Thomas W. Hertel, Wallace E. Tyner, 2007
Ethanol in Brazil: 83 years of experience
Source: Brazilian Ministry of Mines and Energy
Brasil E-20-25 e para VFF qualquer mistura EUA E-10 e para VFF E-85 Canadá E-10 e para VFF E-85 Suécia E-5 e para VFF E-85 Índia E-5 Austrália E-10 Tailândia E-10 China E-10 - E-15 Colômbia E-10 Peru E-10 Paraguai E-7 Japão 3% (autorizado) UE E-5 em 2011 e E-10 em 2020
*VFF: veículo flex fuel
Source: Petrobrás Idéias Elaboração: Consultoria
“The fuel of the future is going to come from fruit like that sumach out by the road, or from apples, weeds,
awdust – almost anything.
There's enough alcohol in one year's yield of an acre of potatoes to drive
the machinery necessary to cultivate the fields for a hundred years.”1
Henry Ford - 1925
1- “Ford predicts fuel from vegetation”, New York Times, sept.
20, 1925, p.24
First Results for a 100% Ethanol-Powered Vehicle: 1979
Source: Brazilian Ministry of Mines and Energy
FFV sells in Brazil (Mar. 2003 to Sept. De 2006)
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Source: Institute for Research in Worlsd-Systems
A difficult problem: rapid change in a very complex network of interdependent economical and technical players working coherently
Tools in need to reprogram rapidly this network: “Infrastructure Technologies”
Standardization and Technical Regulations- Clear description of the technical issues
Conformity Assessment- Demonstration of compliance
Metrology- Confidence in measurements; wide acceptance of the results; basis for standards, regulations and CA
A
TP
B
C
KEY ENABLERS- INFRASTRUCTURE TECHNOLOGIES
Some distinguished features of the biofuel issue:
1- Very large economic, social and environmental impact. 2- Rapid paradigm shift: need fast implementation to a whole new set of commodities, for worldwide use; change in production and commerce networks. 3- Imply new international and national frameworks strongly tied by formal constrains and regulations. 4- Politically sensitive subject- conflicting interests and disputed “truths”
5- Demand for uniformity and quality for measurements in a whole new set of situations, to underpin this paradigm shift. Confidence in measurements must arise from formal and well structured systems.
6- Deep knowledge of measurement science to support regulations and standardization needs, as well as new production processes.
7- Disputed opinions: importance, how quick, in what extent, for how long
Basic needs for Metrology: 1- Production- traditional and “new generations”
2- Storage, transportation and distribution
3- End-use- effects on engines environment an health
4- Regulation and Standardization
Biofuels and Metrology/NMIs
scientific knowledge about measurements; infrastructure; institutional recognition
• Weaknesses- low social/political visibility- the severe message from the last CGPM;
• Opportunities- to be an important player in the biofuels world effort- engagement in a very important, visible and technically challenging activity.
• Treats- other players supplying the high-level metrological needs for biofuels- weakening
Biofuels and Metrology/NMIs
A thought from strategic planning: We are in the business of providing confidence to measurements.
General needs: 1- International fora for articulation uniformity and world wide acceptance: K.C. , CIPM-MRA,...
2- CRM development and validation. Stability is a big issue, especially for biodiesel.
3- P.T. and training.
5- Deeper scientific and technological understanding to support: better instruments, standards, regulations and CA.
6- Measurements related to side effect of biofuels use: corrosion of engine parts, environmental and health effects.
Some specific needs: 1- Net energy content; e.g. Water content in ethanol...
2- Harmful impurities; e.g. Cu, S, Na, Glycerol...
3- Other physico-chemical characteristics; e.g. different esthers content and jellification temperature for biodiesel.
4- Information about the origin, both geographical and related to raw materials; fundamental do comply with
certain regulations.
WHITE PAPER
especificações para biocombustíveis)
Classification ofClassification of BioethanolBioethanol SpecificationsSpecifications Category A
Category C fundamental differences
appearance acidity
copper content chloride content
* This topic is under discussion. While the
differences in water level allowed does not prevent ethanol trade, there are costs associated with
additional drying
Classification ofClassification of BiodieselBiodiesel SpecificationsSpecifications Category A
Category C fundamental differences
sulfated ash total glycerol content sulfur content alkali and alkaline earth metal content
phosphorus content cold climate operability
free glycerol content carbon residue cetane number copper strip corrosion ester content oxidation stability methanol and ethanol content
distillation temperature mono, di-, tri- acylglycerides
acid number flash point density total contamination kinematic viscosity water content and sediment
iodine number
INMETRO BIOFUELS PROGRAM- AIMING AT PRODUCTS,
PRODUCTION, USES AND IMPACTS:
• Proficiency Testings and Training
• Analytical methods and Procedures
• Support to regulation
• International cooperation
Parameters for Bioethanol to be included in MRC
Density Sulfate content Sulfur content
Copper content Iron content
Sodium content Ethanol content
As presented in the
Development of CRM : Ethanol Fuel (cooperation with NIST-USA)
HYDRATED ANHYDROUS
Inmetro and NIST- exchange CRMs- ethanol (Inmetro) e soy biodiesel(NIST)for validation
Project BIOREMA- CRMs with UE
Production of high-quality measurement standards
CCQM-K27, Ethanol in Aqueous Matrix, Original and Both Subsequent Studies - Relative Results
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Parameters for biodiesel to be included in CRM
Alkali and alkaline earth metals
Free glycerol contente
Methanol & ethanol content
“White Paper”
Cetane number
Oxidation satability
Biodiesel with guaranteed origin
Program to identify the composition of Biodiesel and to produce samples with guaranteed origin.
An ESI-MS (electrospray ionization mass spectrometry) technique is used giving a fingerprint for each biodiesel.
Conclusions 1- Biofuels are really important, at least in the short term
2- Metrology is a key enabling technology for the worldwide use of biofuels.
3- Excellent opportunity for NMIs, and the metrology community
4- Wide range of demands- from very technical details to cutting edge scientific problems.
5- Some relevant short term needs: CRM, PT, awareness, work with regulators and SDOs, biology metrology, origin determination, new methods (esp. in field),… 6- Exiting time!
Thank you for your attention www.inmetro.gov.br
Session 1: Traceability Reference materials for biofuel measurements - demands and challenges H. Emons (IRMM - Institute for Reference Materials and Measurements) The role of metrology in proficiency testing schemes on bioethanol, a cooperation between LNE and BIPEA P. Charlet (LNE - French National Metrology Institute), G. Mathiaud (BIPEAE - Bureau InterProfessionnel d'Etudes Analytiques) Needs for reference materials for biofuel specifications A. Baldan, A. M. H. van der Veen, M. van Son (NMi - National Metrology Institute of the Netherlands) Reference materials for biofuel specifications (poster) A. Baldan, M. van Son, A. M. H. van der Veen, (NMi - National Metrology Institute of the Netherlands) Japanese standards for chemical compositions of biofuels, and preliminary studies on development of biofuel CRMs by the National Metrology Institute of Japan (NMIJ) (poster) M. Numata, M. Matsuo, T. Yarita (NMIJ - National Metrology Institute of Japan) Development of certified reference material on electrolytic conductivity in bioethanol (poster) V. S. da Cunha, P. P. Borges, I. C. S. Fraga, B. S. R. Marques, C. M. Ribeiro, J. C. Lopes, W. B. da Silva Jr., J. C. Dias, S. P. Sobral (INMETRO - National Institute of Metrology, Standardization and Industrial Quality of Brazil) Biodiesel: Can comprehensive two dimensional gas chromatography and time-of-3flight mass spectrometry (GCXGC-TOFMS) using novel column combinations add a new dimension? (poster) B.J. de Vos, S. Prins (NMISA - National Metrology Institute of South Africa) Determination of Na, K, Mg, Ca and P in biodiesel of different origins by ICP OES (poster) L. C. C. de Oliveira, V. de Souza, V. S. da Cunha, P. R. G. Couto, F. A. Á. Rodrigues (INMETRO - National Institute of Metrology, Standardization and Industrial Quality of Brazil, University of Rio de Janeiro), R. C. de Campos (PUC-Rio – Catholic University of Rio de Janeiro), Towards a need for traceable measurements of pesticides in cereals (poster) B. Lalère, K. El Mrabet, V. Le Diouron, S. Vaslin-Reimann (LNE - French National Metrology Institute) Traceability of pH measurements for bioethanol (poster) P. Fisicaro, P. Charlet, R. Champion, J. Lachenal, S. Vaslin-Reimann (LNE - French National Metrology Institute)
1RM Unit / HE / 06-11-2008
Institute for Reference Materials and Measurements (IRMM) Joint Research Centre, European Commission, Geel, Belgium
[email protected]
3RM Unit / HE / 06-11-2008
real sample
5RM Unit / HE / 06-11-2008
additional investigations
• stated meas. uncertainty • stated homogeneity & stability • intended use
• statements on homogeneity & stability
main applications
Validated analytical methods
7RM Unit / HE / 06-11-2008
Different situation at different markets
“Bioethanol”Biodiesel
Brazil & USA only as blending component used in heavy duty vehicles
standards applicable for FAME & FAEE
EU stand-alone diesel fuel or
blending component many diesel passenger cars
standards applicable for FAME
8RM Unit / HE / 06-11-2008
Specifications of EU, USA, Brazilian classified into: Cat. A: already similar Cat. B: significant differences between parameters & methods,
but might be aligned Cat. C: fundamental differences, not bridgeable in the foreseeable future
"Bioethanol"
Cu; Fe; Na EtOH
9RM Unit / HE / 06-11-2008
Biodiesel Category A Category B Category C
Na; K P S Mg; Ca ester content monoglycerides MeOH / EtOH water (& sediments) diglycerides free glycerine total glycerine triglycerides sulfated ash carbon residue linoleric acid
methylester acid value total contamination polyunsat. ME Cu corrosion flashpoint iodine value
cetane number oxidation stability density viscosity cold filter plugging point
European specifications in EN 14214
10RM Unit / HE / 06-11-2008
be measured’) measurable target/property establishment & dissemination of measurement units/scales (e.g., also pH, …)
Measurement Uncertainty - requires:
sound approach(es) for its estimation harmonized inclusion of all relevant sources for MU adequate reporting of MU & its use in decisions
11RM Unit / HE / 06-11-2008
only partially possible in the “classic” meaning for biodiesel
Na, K, Mg, Ca, P, S, Cu, Fe, Cl-, SO4 2-
CRM
CRM
primary reference measurement procedure
definition of (SI) unit
secondary reference measurement procedure
13RM Unit / HE / 06-11-2008
X
extraction
clean-up
quantification (e.g., GC-FID)
15RM Unit / HE / 06-11-2008
Existing RMs: no problem for matrix-matching of ethanol fuels, but for biodiesel materials
Open issues: • Long-term stability? • Commutability? • Operationally defined parameters according
to EN & ISO standards
RMs for biofuel analysis
NIST with Inmetro:
2 candidate RMs “biodiesel” - based on soy - based on animal fat
Real “Biofuel RMs” in the pipe:
16RM Unit / HE / 06-11-2008
Related IRMM CRMs IRMM’s liquid fuel CRMs Diesel: ERM-EF104; ERM-EF671;
ERM-EF672; BCR-106; BCR-107 all certified for sulfur content
BCR-395 certified for CFPP
Petrol: ERM-EF211 for sulfur
BCR-162R (soya-maize oil blend) BCR-163 (beef-pork fat blend)
Ongoing feasibility studies for rapeseed-based biodiesel RMs
17RM Unit / HE / 06-11-2008
RME as candidate RM
EN 14214 defines biodiesel as FAME in general no restrictions for raw material in Europe most experiences with rapeseed oil methylester limits are based on properties of RME
GC-FID method: Sample concentration 10 mg/ml; sample amount injected 1 µl
18RM Unit / HE / 06-11-2008
- Stability - Short-term stability (transport) - Long-term stability (storage)
- Establishing commutability: equivalent behaviour of RM & test sample in the analytical process
- Traceability: relating & scaling of measurement data to a common reference system (avoid too many method-specific steps)
for RM / CRM characterisation:
19RM Unit / HE / 06-11-2008
Uses of Biofuel RMs
Method development Method validation
– lab-internal quality control (‘charting’)
– operator or equipment qualification
(external benchmarking)
Why:
Roadmap for Standards
US-EU Biofuels Cooperation
Mandates to CEN
Task Force “Biofuels”
Lead: IE Petten
JRC Reference Report “Biofuels in the European context: Facts and uncertainties”
http://ec.europa.eu/dgs/jrc/ downloads/jrc_biofuels_ report.pdf
Partner in EU Project BIOREMA
IRMM
21RM Unit / HE / 06-11-2008
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NMi - the Art of Measurement
Needs for Reference Materials for Biofuel Specifications
A. Baldan, A.M.H. van der Veen, M. van Son NMi Van Swinden Laboratorium
BioFuels Met 2008, 6-7 November 2008, Strasbourg, France
Roadmap of presentation
• EU Regulation • Role of CRMs for biofuels • International cooperation • Biorema project • Project approach • Project components
Regulation
• Examples of EU regulation on renewable energy – EU directive 2003/30/EC (Biofuels
Guideline)
– EC Proposal for new Renewable Energy Directive, Jan 2008 • Biofuel target 10% in 2020 • Sustainability criteria
Policy & Standards
• Come into force of EU regulation on the addition of biological products to petrol and diesel – Importance of quality of these products
and need for motor fuel specifications
• CEN TCs develop specification standards
• NMIs develop certified reference materials
Role of Certified Reference Materials for Biofuels
International cooperation
• Tripartite Task Force (BR, EU, USA) – Proposal for compatible international
documentary standards (“White Paper on International compatible Biofuel Standards”, December 2007)
– Recommendations on specification levels
Classification of bioethanol specifications
Color Ethanol content Water content
Appearance Acidity
Classification of biodiesel specifications
Sulfated ash Total glycerol content
Sulfur content
Free glycerol Carbon residue Cetane number
Copper strip corrosion
Total contamination Kinematic viscosity
BIOREMA project
Theme 5 – Energy – Coordination and Support Action (support
type)
Project objectives
• Development of biofuel test samples with well characterized reference values
• Information on current quality of measurement results by carrying out interlaboratory comparisons with these materials
• Guidance report to the production of reference materials
Consortium
• National Physical Laboratory, NPL, UK • National Institute of Metrology,
Standardization and Industrial Quality, INMETRO, BR
• National Institute of Standards and Technology, NIST, USA
Consortium experience
• Application of high quality measurement techniques; results linked to SI
• Scrutinized measurement data evaluation including uncertainty calculations
• Characterization of biofuels
• Organization of interlaboratory comparisons
Project components
reference materials • Characterization and stability
measurements of reference materials • Interlaboratory comparisons • Dissemination
Project components
Identification of parameters for which no suitable RMs are available
Specifications of biogas and advanced biofuels
Measurement methods and performance characteristics for biogas and advanced biofuels
Availability of RMs for traditional as well as advanced biofuels
Project components
Feasibility study
Close to specification levels
To detect unexpected problems
Project components
Characterization and stability measurements
Stability tested for each selected parameter
Specialised laboratories for method defined parameters
•Primary methods applied •Complete uncertainty budget
Project components
Interlaboratory comparisons
Input for the development of: • reference materials • documentary standards
Project components
Dissemination
Workshop, Strasbourg, 6-7 November
…..
…..
Thank you for your attention!
NMi Van Swinden Laboratorium B.V. T (+31) 15 269 15 00 P.O. Box 654 F (+31) 15 261 29 71 2600 AR Delft E [email protected] The Netherlands I www.nmi.nl
For information on this poster please contact: Michel van Son
E [email protected]
T (+31) 15 269 1672 NMi Van Swinden Laboratorium B.V. T (+31) 15 269 1500 P.O. Box 654 F (+31) 15 261 2971 2600 AR Delft E [email protected] The Netherlands I www.NMi.nl
Reference Materials for Biofuel Specifications Adriaan van der Veen, Annarita Baldan, Michel van Son
Abstract: In the framework of an EC funded project with the acronym BIOREMA, REference MAterials for BIOfuel specifications, a number of reference materials for Bioethanol and Biodiesel will be investigated. The aim of this investigation is to demonstrate the feasibility of preparing and characterizing reference materials for biofuels. Further, the project will establish the current quality of measurement practice by means of interlaboratory comparisons using these test materials.
Introduction With the increased addition of biological products to gasoline and
diesel, e.g. ethanol and FAME, the quality of these products
becomes more important. There is however up to now no
international consensus on the technical specifications of biofuel.
Neither is it clear what measurement standards, reference materials
and measurement techniques are needed.
Needs
values are essential for pre-normative research and standardization
(EN 153761 and EN 142142), i.e., in the development and validation
of measurement methods. They are also fundamental during testing
to proof reliability and quality of the measurement data.
BIOREMA project A two-year project funded by the European Commission under the
7th Framework Programme has started in November 2008 to deal
with the issue of reference materials for biofuel specifications
(BIOREMA).
IRMM (European Commission)
NPL (United Kingdom)
Objectives
Survey on the available reference materials Feasibility study for preparation of reference materials for
the identified gaps Characterization and stability measurements of reference
materials Establishing current quality of measurement practice by
means of interlaboratory comparisons 1EN 15376 “Automotive fuels - Ethanol as a blending component for petrol - Requirements and test methods” 2EN 14214 “Automotive fuels - Fatty acid methyl esters (FAME) for diesel engines - Requirements and test methods”
Figure 1. Harvest of rapeseed for Biodiesel production
Feasibility study
Feasibility study
Close to specification levels
To detect unexpected problems
Stability tested for each selected parameter
Specialised laboratories for method defined parameters
•Primary methods applied •Complete uncertainty budget
Input for the development of: • reference materials • documentary standards
Japanese Standards for Chemical Compositions of Biofuels, and
Preliminary Studies on Development of Biofuel CRMs
by the National Metrology Institute of Japan (NMIJ)
Masahiko Numata, Mayumi Matsuo, Takashi Yarita
National Metrology Institute of Japan (NMIJ), AIST
BioFuel Met 2008, Nov. 6, 2008, Strasbourg
Trends and Policies for Biofuels in Japan
1997 2010 2020 2030
Bio -ethanol
NFV, AIST (2008)
ETBE 7%
Kyoto Protocol
(106 kL)
BTL, DME
Hydrotreated BDF
Biofuel Issues in Japan Humid climate
Ethanol vs. ETBE
No biofuel CRM
No FFV (Flexible Fuel Vehicle)
Various raw materials Increasing moisture
in FAME, ethanol Waste cooking (Tempura) oil is the main source of FAME in Japan
Low quality analytical data
Low upper limit of Biofuel blending rate
Quality control is not prescribed in the biofuel standards Are CRMs (and [SI] traceability) required by testing labs?
Ministry of the Environment Ethanol (high vapor pressure,
hygroscopicity, corrosion) Petroleum companies ETBE (environmental risk?)
USA (ASTM D6751-07a)EU (EN 14214) Japan (JIS K 2390)
Item LevelTest method
JIS K 2501, K 0070
Total acid number
47 51 Cetane number
15 mg/kg 10 mg/kgSulfur
1.9 - 6.0 mm2/s3.5 - 5.0 mm2/sKinematic Viscosity
--- 96.5 mass%Ester content
--- 24 mg/kg Total contamination
---0.86 - 0.90 g/mLDensity
(for Blending with Diesel Fuel)
10 mg/kg 10 mg/kg 10 mg/kg EN 14107Phosphorous
5 mg/kg 5 mg/kg 5 mg/kg EN 14538Metals (Ca+Mg)
USA (ASTM D6751-07a)EU (EN 14214) Japan (JIS K 2390)
Item LevelTest method
--- 0.20 mass% Triglyceride
--- 0.20 mass% Diglyceride
5 mg/kg 5 mg/kg Metals (Na+K)
--- 0.80 mass% Monoglyceride
Single chemical species, Chemical group, Indirect index
Standards for Neat-FAME (2) (for Blending with Diesel Fuel)
JIS K 2541-6/7
ASTM D 6423
USA (ASTM D4806-04a)Brazil (Portaria ANP no 2)
30 mg/kg 4 mg/kg (sulfate) 10 mg/kgSulfur
6.5 - 9.0 (pHe)(6.0 - 8.0)7.0±1.0 (pHe)pH
0.007 mass% 30 mg/L 0.0070 mass% Acidity As acetic acid
--- 500 S/m 500 S/mElectric conductivity
------ 10 g/L Organic impurity except Methanol
1 vol%--- 0.70 mass%Water
--- 99.3 (92.6-93.8) mass % 99.5 vol%Alcohol
Transparent, No-turbidity
---( 5 mg/100mL) 5.0 mg/100mLEvaporated residue
0.5 vol%--- 4.0 g/LMethanol
NMIJ CRMs and Calibration System
Matrix CRM
Standard gas CRM
Standard gas
Accredited bodies
Impurity analysis
Biofuel CRM development (plan) by NMIJ Pure material, standard solution CRMs
Pure Ethanol: Supplied as NMIJ CRM 4001-a Standard solutions of element: Supplied for the JCSS Pure ETBE: Considered as a CRM candidate Sulfur in toluene: Supplied as NMIJ CRM 4215-a
Blank-toluene is under development Pure FAMEs (or std. solution): Not yet considered
Matrix CRMs BDF (Neat FAME): Considered as a CRM
candidate (Preliminary investigations on actual samples, left)
(Bio-)Ethanol: Considered as a CRM candidate FAME/ethanol blended fuel: Not yet consideredBDF samples (Neat FAME)
NMIJ CRM 4001-a
Water Measurement: Karl-Fischer titration (Coulometric, Volumetric)
Is KF the primary method? (External reference needed)
Traceability: BiofuelWater std. solution? Pure water ? SI
Error factors: Sulfur compounds, Unsaturated FAME?, Moisture in atmosphere
How can such interferences be cancelled?
Current status: Preliminary investigations on BDFs (Comparison between direct injection and vaporization, Coulometric KF)
Reaction of FAME (direct injection) is slower than water/alcohol. Results of vaporization method is temperature dependent.
Methanol, Ethanol (Alcohol content) Measurement:
Methanol (Ethanol), GC-FID, (ID-)GC/MS (Headspace, Water extraction, Direct injection)
Alcohol content, Alcoholometer (density)
(Biofuel NMIJ CRM 4001-aSI)
Error factor: Hydrolysis of FAMEs (methanol) Loss by evaporation, Hygroscopicity
Current status: Preliminary investigations on BDFs (Methanol: Comparison between above methods)
FAMEs, Glycerides Measurement: GC-FID, (ID-)GC/MS
(FAMEs, Direct injection; glycerides, silylation with MSTFA)
Traceability: No pure material/standard solution CRM It is impossible to keep traceability for all compounds. (NMIJ CRMs for PCB: PCB homologue concentrations
were given as reference values by assuming GC/MS response factors of homologue members are same.)
Error factor: Difference of response factors among compounds (among methods)
Hydrolysis/oxidation of FAMEs
1
Elements (Na, K, Mg, Ca, Cu, P, S) Pretreatment: Acid digestion,
Direct injection (dilution with solvent)
Measurement: (ID-)ICP-MS, ICP-AES, AAS etc.
Traceability: Biofuel JCSS standard solution NMIJ CRMs SI
Error factor : Precipitation during storage (?) (If necessary) How are these elements added?
Current status: Preliminary investigations on BDFs (Acid digestion / ICP-MS etc.;
Sulfur: UV-fluorescence analyzer)
Images of NMIJ Matrix Biofuel CRMs BDF (Neat FAME)
Concentration: regulation levels or 1/10 of them Certified values: Elements (Na,K,Mg,Ca,P,S)
Water, Methanol (SI-traceable) (Reference values: FAMEs, Glycerides,
other items [obtained by official methods]?)
(Bio-)Ethanol Concentration: regulation levels or 1/10 of them Certified values: Elements (Cu,S), Methanol,
Water, Ethanol? (SI-traceable) (Reference values: Alcohol content,
other items [obtained by official methods]?)
1
The principal aim of this work is to present the
results of the studies of certification of reference material
of electrolytic conductivity measurements in AFEA in
order to developing CRM for this parameter.
Introduction
Conclusions
References
It is relevant to emphasize that these studies of certification of reference material on electrolytic conductivity in bioethanol will contribute to the improvement of the quality of the results of the measurements of this kind of fuel that is very important to the national clients and to the international competitiveness of this product to external trade.
Purpose
Experimental
DEVELOPMENT OF CERTIFIED REFERENCE MATERIAL ON ELECTROLYTIC CONDUCTIVITY IN BIOETHANOL
Paulo P. Borges, Isabel Cristina S. Fraga, Bianca S. R. Marques, Carla M. Ribeiro, Jéssica C. Lopes, Wiler B. da Silva Junior, Júlio Cesar Dias, Sidney P. Sobral, Valnei S. da Cunha
Instituto Nacional de Metrologia, Normalização e Qualidade Industrial-Inmetro Diretoria de Metrologia Científica e Industrial-Dimci/Divisão de Metrologia Química-Dquim
Laboratório de Eletroquímica-Label/Tel.: +55 21 2679 9134 Fax: +55 21 2679 9069, [email protected] Av. Nossa Senhora das Graças, 50, CEP 25250-020-Xerém, Duque de Caxias, Rio de Janeiro, Brasil
[email protected]
Bioethanol’s origin in renewable sugar cane very used as
biofuels contributes to the reduction of the CO2 in the
atmosphere and helps to reduce the global warming. The
National Agency of Petroleum, Natural Gas and Biofuels
(ANP) is responsible for the control of several parameters
for the quality of biofuels in Brazil.
Electrolytic conductivity is one of the parameters
specified in the Brazilian Standard for anhydrous fuel
ethyl alcohol (AFEA). The value higher than 500 S.m-1
can contribute to the corrosive effect on vehicle engines.
Because of the difficulty in measuring the low electrolytic
conductivity value in alcoholic solutions, the
Electrochemistry Laboratory of the Chemical Metrology
Division – Dquim at the National Institute of Metrology,
Standardization and Industrial Quality – Inmetro has
focused its attention on the need for accurate and reliable
measurements through the work for developing and
producing Certified Reference Material (CRM) for AFEA.
Acknowledgments
The authors would like to thank Inmetro, CNPQ and FINEP for the financial support.
Results and Discussion
cell with constant value of 0.090 cm-1 (Metrohm);
CRM 25.00 µS.cm-1 (Radiometer);
The representative AFEA samples were taken from a
Brazilian producer.
carried out by using the procedure described in the
Brazilian Standard.
material (RM) is notable for being one of the most
important factors to assure the maintenance of the
physico-chemical properties of the studied material.
The study of stability is carried out in order to control
the capacity of RM to maintain the value of this specific
property studied in the course of time, simulating
transport (short-term study) and storage conditions
(long-term study).
value of the property of the studied RM.
The studies of the certification of the RM for
bioethanol were based on ISO Guide 35 related to the
studies the homogeneity, the stability (short-term and
long-term) and the characterization.
[1] NBR 10547: Álcool etílico – Determinação da condutividade elétrica, 2006. [2] ISO GUIDE 35: Reference materials - General and statistical principles for certification, 2006. [3] Guia para a Expressão da Incerteza de Medição, Terceira Edição Brasileira, Edição Revisada, ABNT/Inmetro, Rio de Janeiro, 2003.
CRM of electrolytic conductivity on bioethanol
CRM on Eletrolytic Conductivity in Bioethanol
-2
-1
0
1
2
Expanded uncertainty (k = 2; 95%) 0.686
Results of Electrolytic Conductivity Measurements in Bioethanol
The results of these studies carried out in twelve months on electrolytic conductivity measurements at 25.0 °C were (1.352 0.686) µS.cm-1 (k = 2; confidence level of approximately 95%).
1J de Vos, 2P Gorst-Allman and 3S Prins 1,3NMISA, Private Bag X34, Lynnwood Ridge, 0040, South Africa
2LECO Africa (Pty) Ltd., PO Box 1439, Kempton Park, 1620, South Africa E-mail: [email protected]
Introduction Biodiesel is becoming increasingly important as an alternative source of
fuel, especially as the price of petroleum products continues to skyrocket.
However, for this fuel source to be effective and accepted it is necessary
that reliable analytical methodology is developed to identify and quantify
the components in the final product. This is a complex analysis, as regularly
many FAME isomers are present in the biodiesel and separation becomes
a major difficulty.
choice for maximum chromatographic resolution of all the components
present in FAME and biodiesel samples. When coupled to time-of-flight
mass spectrometer, a wealth of information is available about sample
components.
Objective Comprehensive two-dimensional gas chromatographic methods were
developed for the analysis of FAME mixtures and local and international
biodiesel samples. An FID detector was used initially and this detector
provided excellent quantitative results for the components present in the
standard samples.
was also investigated, and this methodology provided structural
information about the sample components.
Tentative quantification was made using the NLEA standard.
Experimental GCxGC-FID
GC Parameters: Agilent 6890N GC modified for GCxGC by LECO Corporation
Injection parameters 0.05 μl, splitless at 250 °C Primary column DB-23 (20 m x 0.18 mm id x
0.20 μm film) Secondary column Rtx-5 (1.1 m x 0.18 mm id x
0.2 μm film) Carrier gas Helium, 1 ml/min, corrected
constant flow Oven programme 80 °C for 2 min, 3 °C/min to
250 °C, hold 2 min Secondary oven 100 °C for 2 min, 3 °C/min to
270 °C, hold 2 min Modulator offset 30 °C Modulation time 8 seconds Analysis time 60.667 min
FID conditions:
Temperature 250 °C Hydrogen flow 50 ml/min Air flow 450 ml/min Make up gas Nitrogen Make up flow 40 ml/min Data collection rate 50 Hz Acquisition delay 120 sec
Experimental GC-TOFMS GC Parameters: Agilent 6890N GC
Injection parameters 0.1 μl, split (20:1) at 225 °C GC column ZB-Wax (30 m x 0.25 mm id x
0.25 μm film) Carrier gas Helium, 1,2 ml/ min, constant flow Oven programme 50 °C for 1 min, 5 °C/min to 250
°C, hold 10 min Transferline temp 250 °C Analysis time 51 min
MS parameters: LECO Pegasus III GC-TOFMS
Ionisation Electron ionisation at -70 eV Source temp 200 °C Acquisition rate 10 spectra/second Mass range 50 - 450 amu Acquisition delay 180 sec
NLEA FAME Standard & Samples An NLEA FAME Standard Mix, Cat No 35078, and sold by Restek, was
used to evaluate the GCxGC method, and to assist with identification of
the components present in subsequent samples.
This standard mixture contained the following components: 4:0, 6:0, 8:0, 10:0, 11:0, 12:0, 13:0, 14:0, 14:1 (cis-9), 15:0, 16:0, 16:1 (cis-9),
17:0, 18:0, 18:1 (cis-9), 18:1 (trans-9), 18:2 (cis-9,12), 18:2 (trans-9,12), 18:3
(cis-9,12,15), 20:0, 20:1 (cis-11), 22:0, 22:1 (cis-13), 23:0, 24:0, 20:5 (cis- 5,8,11,14,17), 24:1 (cis-15), and 22:6 (cis-4,7,10,13,16,19).
Biodiesel samples:
Local Biodiesel Chromatogram GCxGC-FID
Imported Biodiesel Chromatogram GCxGC-FID
NLEA FAME Standard & Samples (ZB-Wax combo) using the LECO Pegasus III GC-TOFMS
FAME Compounds found in Biodiesel Samples
GCxGC-FID Results Imported Biodiesel
2nd Dim RT"
2 Pentadecanoic acid ME
15:0 1488 4.04 2.6 -
3 Hexadecanoic acid ME
4 Hexadecanoic acid ME
16:1 1672 3.41 1.7 -
5 Octadecanoic acid ME
Local Biodiesel
Imported Biodiesel
Local Biodiesel
Conc = μg/ml
Conc = μg/ml
Hexanoic acid ME 371.45 183 2 1 Octanoic acid ME 652.35 241 43 15 Decanoic acid ME 947.35 236 - 1
Dodecanoic acid ME 1224.45 356 - 1 Tetradecanoic acid ME 1478.45 110 2 4 Pentadecanoic acid ME 1597.55 67 - - Hexadecanoic acid ME 1712.25 390 515 172
9-Hexadecenoic acid ME 1741.35 164 17 2 Heptadecanoic acid ME 1821.55 85 2 1 Octadecanoic acid ME 1927.15 174 144 72
9-Octadecenoic acid ME 1948.45 596 1138 462 9,12-Octadecadienoic
acid ME 1996.25 403 344 1202
9,12,15-Octadecatrienoic acid ME
2062.05 179 1 5
Eicosanoic acid ME 2125.85 98 7 5 11-Eicosenoic acid ME 2145.85 56 2 3 Docosanoic acid ME 2310.95 113 7 6
13-Docosenoic acid ME 2330.85 65 - 2 Tetracosanoic acid ME 2484.05 129 1 1
Discussion & Conclusion GCxGC-FID offers exciting possibilities for the analysis of fatty acid methyl
esters (FAMES) and biodiesel samples. Using the column combination employed in the poster, all the components of the standard mixture are
well resolved, with the exception of the cis and trans isomers of 18:1 and 18:2. For biodiesel work it is not necessary to separate these isomers as
it is only the overall percentage of the compound which is important.
In the analysis of FAMEs in the food industry this becomes more important
as the different isomers have different dietary considerations. However, it has been shown that increasing the length of the DB-23 column permits
the separation of the cis and trans isomers.
GC-TOFMS offers an alternative approach. Using a wax column the
components of the FAME standard are well separated (again excluding cis and trans isomers). An advantage of this approach is the ability to identify
components which are not present in the FAME standard, and may occur
in the biodiesel samples. The considerable power of the ChromaTOF software package, including the peak find and spectral de-convolution
software, is an added bonus when using this approach.
K-6928 [www.kashangroup.com]
What’s the Buzz about Biodiesel? Can Comprehensive Two Dimentional Gas Chromatography with FID or Time-of-Flight Mass Spectometry add a new dimansion?
National Metrology Institute of South Africa
10:0
8:0
6:0
4:0
4:0
Determination of Na, K, Mg, Ca and P in biodiesel of different Determination of Na, K, Mg, Ca and P in biodiesel of different origins by ICP OESorigins by ICP OES Lígia Claudia Castro de Oliveiraa,b*, Reinaldo Calixto de Camposb, Vanderléa de Souzaa, Valnei Smarçaro Cunhaa,
Paulo Roberto Guimarães Coutoa and Francisco Alixandre Ávila Rodrigues [email protected]
aInstituto Nacional de Metrologia, Normalização e Qualidade Industrial Xerém – Duque de Caxias, RJ, Brazil
bPontifícia Universidade Católica do Rio de Janeiro (PUC-Rio), Departamento de Química, Rio de Janeiro, RJ, Brazil
Introduction
*Alternative to diesel for internal combustions engines
*Reduction of the amount of emitted gaseous pollutants
*Decreease emission of greenhouse gases
Determination of trace elements in biodiesel quality control
Brazilian Fuel Agency (ANP) current specifications for BiodieselBrazilian Fuel Agency (ANP) current specifications for Biodiesel ::
RESOLUTION ANP NRESOLUTION ANP Nºº 7 (March, 19, 2008)7 (March, 19, 2008)
Specifications for biodiesel (permitted levels)Specifications for biodiesel (permitted levels)
Na + K= 5 mg/kgNa + K= 5 mg/kg
Ca + Mg= 5 mg/kgCa + Mg= 5 mg/kg
P= 10 mg/kgP= 10 mg/kg
Objective
Optimize the determination of Na, K, Ca, Mg and P by ICP OES, with special consideration to:
Take into account biodiesel samples of different origins;
Determine the four elements in the same sample solution.
Material and MethodsMaterial and Methods
Liberty – series II Inductively Coupled Plasma-Optical Emission Spectrometry with radial viewed configuration;
System to the introduction of organic solvents (nebulizer, spray chamber, injector and tubes) and peristaltic pump capable to supply flows between 0,5 mL/min and 3 mL/min;
S-23 (100 µg g-1) Multielementar Oil Standard (Conostan, USA);
Kerosene, boiling range included between 150º and 325° (Sigma – Aldrich);
Paraffin Oil, low viscosity (Vetec and Isofar, Rio de Janeiro, Brazil);
Argon, with minimum purity w (Ar)=99,99% (v/v)
Investigated parameters: dilution factor, matrix composition, observation height, RF and aspiration rate.
Results
ICP OES: Curves of analyte addition in different biodiesel samples Curves of calibration of Ca and Mg: 0,0; 0,1; 0,5; 1,0 e 5,0
Curves of calibration Na: 0,0; 0,5; 1,0; 2,0 e 10,0
Curves of calibration K: 0,0; 5,0; 10,0; 15,0 e 20,0
Curves of calibration P: 0,0; 0,5; 1,0; 2,0 e 4,0
RSD(%)= 1,96 RSD(%)= 1,71 RSD(%)= 1,16
RSD(%)= 1,08 RSD(%)= 4,87
Conclusions
The considered method although not yet to be completely validated already one reveals sufficiently efficient.
Low aspiration rates and 1:10 sample dilution with kerosene for the determination of Na,Ca, Mg, P and 1:2 for K permitted external calibration using organic standards diluted in kerosene and adjusted with mineral oil for viscosity.
Samples and standards must be diluted just previously to the analysis, due to stability problems of the diluted solutions. Thus, large autosampler batches are not recommended.
The present work gave support to the NBR 15553 Brazilian norm for biodiesel analysis.
ACKNOWLEDGEMENTSACKNOWLEDGEMENTS
INMETRO/Lamoc
CNPq, Finep, Puc-Rio, Petrobras/Reduc and Nutec-Ce
Bovine tallow Biodiesel Mamona Biodiesel Maize seed Biodiesel Soy seed Biodiesel Kerosene diluted calibration solutions
RSD(%)= 2,19
TOWARDS A NEED FOR TRACEABLE MEASUREMENTS
OF PESTICIDES IN CEREALS Béatrice LALERE, Khadija EL MRABET, Véronique LE DIOURON, Sophie VASLIN-REIMANN
Laboratoire national de métrologie et d’essai, LNE, 1 rue Gaston Boissier 75724 Paris Cedex 15
INTRODUCTION
CONCLUSION

A reference method, that is reliable and robust has been developed for the determination of pesticides in cereals. Now, LNE, involved in ensuring traceability of
chemical analyses, will begin the evaluation of different candidates materials in order to provide CRMs for this type of analytical procedures, and will assign reference
values for proficiency testing schemes for pesticides in cereals.
RESULTS

ion (m/z)
M son
ion (m/z)
Acétochlor/ Acétochlor D11 Herbicide Chloroacétanilide 270/281 224/235
Aldicarbe/ Aldicarb D3 Insecticide Carbamate 197/216 114/89
Azoxystrobine Fongicide Strobilurine/ methoxyacrylate 404 372
Bentazone/ Bentazone D6 Herbicide Thiadiazinone 239/245 132/132
Bromoxynil Herbicide Hydroxy-benzonitriles 276 81
Carbofuran / Carbofuran D3 Insecticide Carbamate 222/225 77/165
Carfentrazone éthyle Herbicide Triazolinone 412 346
Chlorpyriphos/ Chlorpyriphos D10 Insecticide Organophosphate 350/360 198/199
Chlorpyriphos méthyle/ CM D6 Insecticide Organophosphoré 321/330 97/289
Chlortoluron/ Chlortoluron D6 Herbicide Urée 213/219 72/78
Cyproconazole Fongicide Triazole 292 70
Cyprodinil Fongicide Phénylaminopyrimidine 226 93
Dichlorvos/ Dichlorvos D6 Insecticide Organophosphoré 221/227 109/115
Diflufénicanil Herbicide Phenoxynicotinanilide 395 266
Diméthenamide Herbicide Chloroacetamide 276 244
Dimethoate/ Dimethoate D6 Insecticide Organophosphate 230/236 125/131
Fenpropidine Fongicide Pipéridine 274 147
Fipronil Insecticide Pyrazole 435 330
Florasulam Herbicide Sulfonamide 358 167
Fludioxonil Fongicide Phénylpyrrole 247 180
Fluroxypyr Herbicide Acide picolinique 253 195
Flutriafol Fongicide Triazole 302 123
Hexaconazole Fongicide Triazole 314 70
Imazaquine Herbicide Imidazolinone 312 267
Imidaclopride/ Imidacloprid D4 Insecticide Nitromethylene 256/258 209/155
Ioxynil Herbicide Benzonitrile 370 127
Isoxaben Herbicide Amide 333 165
Malathion/ Malathion D6 Insecticide Organophosphoré 331/337 127/127
Mécoprop/ Mecoprop D 3
Herbicide Aryloxyacide 213/216 141/144
Métalochlor/ Métolachlor D6 Herbicide Chloroacétanilide 284/290 252/258
Métosulam Herbicide Triazolopyrimidine 418 175
parathion éthyl Insecticide Organophosphate 292 94
Pirimiphos méthyl (PM)/ PM D6 Insecticide Organophosphate 306/312 164/164
Prochloraze Fongicide Imidazole 376 308
Quinoxyfène Fongicide Quinoléine 308 197
Spiroxamine Fongicide Spiracétalamine 298 144
Triallate Herbicide Carbamate 304 143
Tridémorphe Fongicide Morpholine 298 130
System : Surveyor LC pump/ TSQ Quantum Discovery Max (Thermo Fisher Scientific)
Column : Symmetry Shield RP18 150 *2.1 mm d.i, 3.5 µm (Waters)
Phase mobile : H2O with 0.005% acetic acid / Acetonitril with 0.005% acetic acid
Injection volume : 10 µl
Detection : MRM mode
Accreditation according ISO 17025
Mutual Recognition Arrangement

B e n ta zo n e
C h lo rto lu ro n
D ime th o a te
M e c o p ro p
2,4 D
R e c o
Labelled compound
For the whole analytical process, good recovery rates were obtained (between 80 and 100%) as well as good reproductibility (< 10 %).
Labelled compounds behave like non labelled ones, during the extraction and purification steps. So, as there is no change of the ratio, the quantification can be
correctly processed. We estimate that this method is efficient and robust.
The increasing use of biofuels will require more and more cereals, as
actually they represent 4% of the raw product of this carburant. In order to
reach the highest possible rate of production and as the intended use is
not for feeding or for food production, producers will use more phyto
pharmaceutical products ; especially there is no regulation on the
pesticides concentrations in this type of cereals.
But as the becoming of these phytopharmaceutical products during the
crop combustion is not well known and documented, it will be safer to
evaluate if the cereals contain compounds that could be spread in the
environment or degraded into more toxic ones.
A lot of laboratories propose analytical procedures to determine the
concentration of pesticides in cereals. But their results are not yet
metrologically traceable. That is why LNE has developed a reference
method in order to offer the necessary tools for assuring traceability of this
type of chemical analyses.
Paola Fisicaro, Philippe Charlet, Rachel Champion, Jacques Lachenal, Sophie Vaslin-Reimann

! " #"!$

%
&

'()

Session 2: Environmental sustainability Metrology with respect to sustainability requirements H. Brandi (INMETRO - National Institute of Metrology, Standardization and Industrial Quality of Brazil) Key factors and uncertainties for assessing carbon balances and environmental impacts of biofuels R. Zah (EMPA - Swiss Federal Institute for Materials Testing and Research) Estimation of climate relevant gas emissions released from biogas facilities J. Daniel, J. Liebetrau (DBFZ - German Biomass Research Centre)
BioFuels Met 2008 November, 6-7 2008,
Strasbourg, France
Humberto S. Brandi President of SIM (Sistema Interamericano de Metrologia)
Director of Scientific and Industrial Metrology Inmetro
Strasbourg, France
Strasbourg, France
Sustainability means
to meet the needs of the present without compromising the ability of future generations to meet their own needs
(“Our Common Future” –Gro Harlem Brundtland - Brundtland Report 1987)
Strasbourg, France
Strasbourg, France
and Development
Clear understanding of what is wanted: Standardization
Garanty that “what one has is what is wanted”: Conformity Assessment
Trust in measurements: Metrology
Strasbourg, France
Transport Energy Demand and CO2 Emissions
The world economy is highly dependent on liquid fuels mainly derived from petroleum
Strasbourg, France
The use petroleum has given rise to energy security concerns, contributions to climate change and other economical, social and environmental challenges.
Strasbourg, France
Biofuels are a petroleum alternative which address to these growing concerns and has significant impact on the three axis of sustainability.
Strasbourg, France
Strasbourg, France
aw Material
Energy output-demand relation in the ethanol agro-industry Macedo, 2005 and AIE/EET, 2005.
ECONOMY
Strasbourg, France
Flex cars
Strasbourg, France SOCIETY
Strasbourg, France
Deforestation and BiodiversityControversy
Brazil substitute 50% of petrol consumption with less than 1% of the total agriculturable land used for sugar cane
The Amazon does nor have the required conditions for growing sugar cane
IPCC 2004-Deforestation in Brazil cannot be blamed to ethanol
New legislations require sustainability
Cerrado agriculture capacity: 90 Mha
Strasbourg, France
2007
3%
50,7
1654
2006
2%
36,9
1583
2005
2%
31,3
1599
2004
2%
25,8
1642
Biofuels account for 1% of the world total agriculture land
Biofuels account for 2%-3% of worls cereal consumption in 2004-2007
US is the sole major cereal to ethanol producer. In 2007 the increase in the US maize production outstripped the US demand
Prices driven by increasing demand in developing countries, dietary changes, commodity funds, energy prices, poor harvest...
Fact Biofuels can hardly be blamed for the recent increase in food prices
Cereal production was expected in 2008 to increase to a 1.7 billion tons record
Strasbourg, France
sustainability requirements
Strasbourg, France
1st visit of President Bush to Brazil. Was the launch of biofuel seed
Meeting “US-Brazil Comercial Dialogue” between Secretary Gutierrez and Minister Furlan.
Nov. 2005
Jun. 2006
.”US-Brazil Ministerial Joint Comission Meeting”. In this event Inmetro and Nist established a Cooperation Agreement in Metrology and Standards in Biofuels
Jun. 2006
The U.S.-Brazil JCM acknowledged the long history of cooperation between the United States and Brazil in the area of the measurement sciences. The JCM confirmed the importance of cooperation in the fields of metrology and standards and welcomed the report on the activities agreed to by the National Institute for Standards and Technology (NIST) and the National Institute of Metrology, Standardization and Industrial Quality (INMETRO) under the Science and Technology Agreement between the Government of Brazil and the Government of the United States and under the U.S.-Brazil Commercial Dialogue in measurement standards. It noted the mutually agreed desire for future collaboration in the areas of nanoscale science, postdoctoral exchanges, and measurement standards in high-priority areas such as biofuels and nano-materials.
The JCM recognized and encouraged expanded cooperation in standards and metrology activities that impact innovation and competitiveness and support economic growth and development, including in nanotechnology and biofuels
Sept. 2006
Strasbourg, France
2nd visit of President Bush to Brazil. Signed the Memorandum of Understanding about Cooperation in the biofuel area
Mar. 2007
Jul. 2007
In the Washington Symposium was organized the Tripartite Task Force involving Brazil, USA and EU regarding harmonization of fuel quality specifications for bioethanol and biodiesel
Jul. 2007
Oct. 2007
In Brasilia, in the second Commercial Dialogue meeting between Secretary Gutierrez and Minister Miguel Jorge, INMETRO and NIST defined the cooperation agenda involving:
Strasbourg, France
1) Joint development and production of Certified Reference Materials – CRM´s with the main quality parameters of Regional ethanol and biodiesel specifications. 2) Development and validation of a method for the biodiesel source identification (eg. Soy, animal fat, palm oil, castor oil etc.) based on chemical fingerprint. 3) Development of a method based on isotope ratio analysis by mass spectrometry to identify the geographical origin of biodiesel as a tool for the certification process.
Oct. 2007
g i r a s s o l
Oct. 2007
Strasbourg, France
Jan. 2008
Jan. 2008
On January 23-24, 2008, representatives from NIST and INMETRO met to discuss the joint development of three biofuelCRMs in 2008. NIST was represented by Dr. Willie E. May, Director of the NIST Chemical Science and Technology Laboratory (CSTL) and Dr. Stephen A. Wise, Chief of the Analytical Chemistry Division within CSTL. INMETRO was represented by Prof. João Jornada, President INMETRO; Prof. Humberto S. Brandi, INMETRO Director of Scient ific and Industrial Metrology; Prof. Romeu Jose Daroda, Biofuels Project Coordinator; and Dr. Vanderlea Souza, Headof the Chemical Metrology Division.
Based on discussions/agreements from the January meeting, NIST and INMETRO will work collaboratively to produce CRMs for both bioethanol and biodiesel. INMETRO will take the lead in producing a bioethanol CRM, and NIST will take the lead in producingthe biodiesel CRMs. INMETRO is currently preparing two candidate CRMs for bioethanol, anhydrous ethanol and hydrated ethanol. NIST has prepared two candidate biodiesel CRMs, one material is soy-based and the other material is animal fat-based.
WHITE PAPER ON
TRIPARTITE TASK FORCE BRAZIL, EUROPEAN UNION & UNITED STATES OF AMERICA
DECEMBER 31 2007
Strasbourg, France
Jan. 2008
Strasbourg, France
May 2008
Oct. 2008
Feb. 2009
Strasbourg, France
Strasbourg, France
Legislation guarantee
through a certification program internationally recognized, that demonstrates not only the quality aspects of the product, such as its energetic and impurities, but mainly aspects of social and environmental sustainability related to its production;
Strasbourg, France
Life-cycle assessment (LCA) The legislation seeks to incorporate social and environmental sustainability criteria through LCA.
LCA is a tool which aims to account for all the resources used and waste produced during the life cycle of a given product, process or service. The analysis of LCA is a challenge because it requires an enormous amount of information to compare different quantities which implies difficult interpretation leading sometimes to conflicting results, particularly when it tries to incorporate in the calculation indirect parameters, such indirect use of land. •The use of this type parameters should be avoided in any reliable LCA.
Strasbourg, France
Strasbourg, France
Strasbourg, France
Conclusions •Parameters for the harmonization of bioethanol and biodiesel standards concluded, •MRCs and test methods for bioethanol and biodiesel, in process of validation, • Most biofuels bring environmental benefits … • … but a science based system is needed to tackle social and enviromental aspects
Strasbourg, France
Key Factors and Uncertainties for Assessing Carbon Balances and Environmental Impacts of Biofuels
Rainer Zah & Mireille Faist Life Cycle Assessment & Modelling
Ma ter ials Sci ence & Technolog y
Zuckerrohrfeld auf Hawaii
CultivationSewing TransportHarvestingHarvesting
Seed Production
Fertilizer Production
Tractor Production
Auxiliaries Production
Truck Production
Car Production
Environmental Impacts of Biofuels ,
Environmental impacts of Biofuels?
Biofuels Production: LCA for Greenhouse Gas
Emissions
for Greenhouse Gas Emissions; best practice for
other emissions
for GHG emissions and total environmental
impact
THE FULL VALUE CHAIN
EnvironmentalEnvironmental Standards Standards forfor BiofuelsBiofuels
basedbased on Life on Life CycleCycle AssessmentAssessment (LCA)(LCA)
triggerstriggers thethe largestlargest
UBP [P t/pkm]
Aggregated Environmental Impact
-0.05 0.00 0.05 0.10 0.15 0.20 0.25
100% Rape ME CH
100% Rape ME RER
100% Palmoil ME MY
100% Soy ME US
100% Soy ME BR
Methanol fixed bed CH
Methanol fluidized bed CH
Biodiesel: Greenhouse gas emissions
N2O-emissions up to 50%
Speiseöl-ME CH
Speiseöl-ME FR
Raps-ME CH
Raps-ME RER
Soja-ME US
Soja-ME BR
Palm-ME MY
Large differences among paths
-0.03 -0.02 -0.01 0.00 0.01 0.02 0.03 0.04 0.05 0.06
Cosubstrat
Gülle
environmentalenvironmental impactimpact of of
Sensitivity Magnitude of flows
and 200% and analysing the
impact on the overall result
Uncertainty Reliability (measured, estimated)
(U1-U6):
95 exp bUUUUUUU
UBP [P t/pkm]
Aggregated Environmental Impact
-0.05 0.00 0.05 0.10 0.15 0.20 0.25
100% Rape ME CH
100% Rape ME RER
100% Palmoil ME MY
100% Soy ME US
100% Soy ME BR
Methanol fixed bed CH
Methanol fluidized bed CH
Global Warming Potential
fertilizerland use machinery to wateremissions to air emissions to soil
Ecoindicator
S e n
80%
90%
100%
110%
120%
130%
Key factors for the environmental impacts of biofuels
are agricultural processes
of mineral fertilizer
nutrient leaching, heavy metal emissions
Most key factors also exhibit a high uncertainty,
because direct measurements are strongly dependant
on local / temporal conditions
Deutsches BiomasseForschungsZentrum gemeinnützige GmbH, Torgauer Str. 116, D-04347 Leipzig, www.dbfz.de
Deutsches BiomasseForschungsZentrum German Biomass Research Centre
Estimation of climate relevant gas emissions released from biogas facilities
BioFuel Met 2008 – biofuels and metrology 6. November 2008, Strasbourg
Jaqueline Daniel-Gromke, Dr. Jan Liebetrau (DBFZ)
with the support of Dr. Achim Clemens, Carsten Hafermann (Gewitra)
Departments
DBFZ
Brennstofflabor und Feuerungs-
The German Biomass Research Centre is an application-orientated research institute on the field of biomass/bioenergy including solid, liquid and gaseous biofuels
owner: Federal Ministry of Food, Agriculture and Customer Protection
Sources of emissions within the process chain
Energy crops
Distribution/Application digestate
Humus balance?
Nutrition balance?
Leakages?
Coverage?
Emissiones not investigated yet
dependend on substrates, moisture content of the soil, climate, time and period of application
Large variations in N2O emissions u.a. Methane emissions from open storage tanks; Dependend on processing + substrates
Methane losses – Biogas upgrading?
Emissions influenced by distribution techniques
State of Art
Biogas facilities based on energy crops do not reduced greenhouse gas emissions compared to conventional manure handling if biogas are emitted from open storage tanks
Ammonia emissions are critical (mainly during storage and land application)
no data available regarding the emissions during the process
Renewable Energy Act (EEG) makes it obligatory to cover the storage tanks for plant of a size above 1000 kW (overall capacity) in order to become eligible for energy crop bonus
State of Art
Digestion reduces methane potential, increases the ammonium content and pH in comparison to untreated manure
Emissions during storage and application have been evaluated Storage:
• Negligible nitrous oxide emissions - Open storage tank: methane and ammonia emissions - Covered with straw
Reduced ammonia emissions Increased methane emissions
- Covered with gas collection system Optimal solution for emission reduction
Application • Digestion does not reduce emission significantly • application close to ground and directly! leads to the lowest lost
of ammonia emissions • Injection leads to increased nitrous oxide emissions but
reduced ammonia emissions
Results greenhouse gas emissions under variation of emissions from storage tank
GL = storage tank Greenhouse gas emissions (kg CO2Äq./kWhel) Standard biogas plant in comparison to german overall electricity production
-0,6
-0,4
-0,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
Güllegutschrift Strommix DE Summe
Credit – manure Total emissionsElectricity mix
Energy crops / Manure (100 % / 0%)
Energy crops / Manure (70 % / 30%)
Energy crops / Manure (40 % /60%)
Electricity Mix
Objectives of a recent project
Analysis and Quantification of the emissions during the biogas production and utilization process
data base for LCA and evaluation of ecological effects of biogas plant operation
• Focus on typical Gases (CH4, N2O, NH3, H2S, and co-generation unit exhaust gas (NOx and SO2) in order to determine greenhouses gas emissions as well as potential of acidification
Evaluation and update of existing LCA
Method development for emission measurements, comparison laboratory/ field tests
In Combination with the evaluation of the applied technology the emission of all plants will be estimated (based on a comprehensive data basis of all biogas plants in Germany)
Project Partners of a recent project
Project partners
• German Biomass Research Centre (Coordination, LCA) Dr. Jan Liebetrau, Jaqueline Daniel-Gromke e-mail: [email protected]
• VtI - Johann Heinrich von Thünen-Institut (Lab. tests) Prof. Dr.-Ing. Peter Weiland, Jörg Friehe e-mail: [email protected]
• Gewitra (Emission measurement, Field tests) Dr. Achim Clemens, Carsten Hafermann e-mail: [email protected]
With the support of Agency for Renewable Resources (FNR e.V. ) Project term: 2008 - 2010
Methodology
10 plants will be evaluated during two periods of a week each Plant components will be tested:
• Silage storage facilities • Hopper/ preliminary tank
- Hopper used for mixing of substrate with digestate - Solid material feed in device
• Digester - Permeability of rubber membrane, leakages - Pressure relief valves
• Storage tank (digestate) • Gas utilization
- Co generation unit - Upgrading facilities (Feed in with natural gas quality)
• Application of digestate on the field
Methodology
Two principal methods: Aerated and not aerated chambers • Aeration is necessary for gases which are in an equilibrium with a
dissolved phase in the liquid (e.g. NH3) in order to create an open system Defined flow rates, emission rates are calculated based on the flow and the load detected
• Not aerated chambers for gases which do not form ions in the liquid (e.g. CH4 and N2O) Emission rates are calculated based on the change of concentration in the chamber
used methods for measurements: • Ammonia (scrubber and electro-chemical sensor, QRAE Plus) • N2O (sample analysed with GC-ECD) • H2S (electro-chemical sensor, QRAE Plus) • NMVOC, VOC: HORIBA-FID
Field test - measurement
The following slides shows the emission measurements and first results of the field tests of the project partner GEWITRA
Contact: Dr. Achim Clemens, Carsten Hafermann e-mail: [email protected]
Field test: silage storage
NH3: 0 g H2S: n.n g
Minuten
m g
C /(m
no methane and ammonia emissions expected
Field test: leakage detection
m g/
(m in
Methane emissions can be expected
Leakage detection: mobile CH

First European Meeting on Metrology of Biofuels, 06.

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