Complete Report Jrc84696

CERTIFICATION REPORT
The certification of the gross calorific value and

mass fractions of ash, C, H, N, S, Cl, major elements
and trace elements in three coal materials:
ERM®-EF411 (hard coal), ERM®-EF412 (brown coal)
and ERM®-EF413 (furnace coke)
EUR 26197 EN - 2013
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primary task of JRC-IRMM is to build confidence in the comparability of measurement results by the production
and dissemination of internationally accepted quality assurance tools. JRC-IRMM develops and validates testing
methods, produces reference materials, organises measurement evaluation programmes, and provides
reference measurements.
European Commission
Joint Research Centre
Institute for Reference Materials and Measurements
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JRC 84696
EUR 26197 EN
ISBN 978-92-79-33415-3
ISSN 1831-9424
doi:10.2787/80616
Luxembourg: Publications Office of the European Union
© European Union, 2013
Reproduction is authorised provided the source is acknowledged
Printed in Belgium
CERTIFICATION REPORT
The certification of the gross calorific value and

mass fractions of ash, C, H, N, S, Cl, major
elements and trace elements in three coal
materials:
ERM®-EF411 (hard coal), ERM®-EF412 (brown coal)
and ERM®-EF413 (furnace coke)
Thomas P.J. Linsinger, Barbara Raffaelli, Albert Oostra
European Commission, Joint Research Centre,

Institute for Reference Materials and Measurements (IRMM), Geel, Belgium
Disclaimer
Certain commercial equipment, instruments, and materials are identified in this paper to specify
adequately the experimental procedure. In no case does such identification imply
recommendation or endorsement by the European Commission, nor does it imply that the
material or equipment is necessarily the best available for the purpose.
Summary
This report describes the production of ERM-EF411, ERM-EF412 and ERM-EF413, three
coal materials certified for proximates and trace elements. The materials have been
produced following ISO Guide 34:2009 [1].
Industial hard coal, brown coal and furnace coke were obtained, dried, milled (ERM-EF411
and ERM-EF413) and filled into aluminium laminated sachets.
Between-unit homogeneity were quantified and stability during dispatch and storage were
assessed in accordance with ISO Guide 35:2006 [2]. Within-unit heterogeneity was
quantified to determine the minimum sample intake.
The material was characterised by an intercomparison among laboratories of demonstrated
competence and adhering to ISO/IEC 17025. Technically invalid results were removed but
no outlier was eliminated on statistical grounds only.
Uncertainties of the certified values were calculated in compliance with the Guide to the
Expression of Uncertainty in Measurement (GUM) [3] and include uncertainties related to
possible heterogeneity and instability and to characterisation.
The materials are intended for quality control and assessment of method performance. As
any reference material, they can be used for control charts or validation studies, as well. The
CRMs are available in sachets containing 50 g of dried material. The minimum amount of
sample to be used, depending on the analyte, varies from 30 mg to 1 g.
The CRM was accepted as European Reference Material (ERM®) after peer evaluation by
the partners of the European Reference Materials consortium.
The following certified values were assigned:

ERM-EF411 ERM-EF412 ERM-EF413
2 3 2 3 2 3 Unit
Value Uncert. Value Uncert. Value Uncert.
1
Gross calorific value 29.0 0.4 26.02 0.22 29.5 0.4 MJ/kg
1
Net calorific value 28.0 0.4 24.98 0.25 29.4 0.5 MJ/kg
1
Volatile matter 38.1 1.0 50.1 0.7 g/100 g
1
Ash 8.3 0.7 4.11 0.23 g/100 g
1
C 71.4 1.0 66.2 0.7 87.8 1.9 g/100 g
1
H 4.80 0.14 4.88 0.15 g/100 g
1
N 1.43 0.10 0.74 0.06 1.10 0.07 g/100 g
1
S 0.598 0.017 0.360 0.023 0.58 0.12 g/100 g
Cl 99 19 mg/kg
Ca 9.8 0.4 2.92 0.22 g/kg
Na 2.20 0.12 0.64 0.07 g/kg
K 229 18 mg/kg
Hg 0.070 0.011 mg/kg
Mn 48.6 1.9 mg/kg
Se 5.1 1.0 0.96 0.14 1.33 0.26 mg/kg
V 0.57 0.04 mg/kg
Zn 16.0 2.5 mg/kg
1) as determined by the procedures used
2) Unweighted mean value of the means of accepted sets of data, each set being obtained in a different laboratory and/or with a
different method of determination. The certified value and its uncertainty are traceable to the International System of Units (SI)."
3) The certified uncertainty is the expanded uncertainty with a coverage factor k = 2 corresponding to a level of confidence of
about 95 % estimated in accordance with ISO/IEC Guide 98-3, Guide to the Expression of Uncertainty in Measurement
(GUM:1995), ISO, 2008.
The following indicative values were assigned
Analyte ERM-EF411 ERM-EF412 ERM-EF413 Unit
1 2 1 2 1 2
Value Uncert. Value Uncert. Value Uncert.
Cl 0.35 0.13 g/kg
Cd 0.012 0.004 mg/kg
Co 3.5 0.8 mg/kg
Cu 0.68 0.22 mg/kg
Hg 0.079 0.015 mg/kg
Mg 3.73 0.16 1.23 0.19 g/kg
Pb 0.25 0.05 8.41 1.6 mg/kg
Sb 1.5 0.4 0.024 0.004 mg/kg
Tl 0.24 0.07 mg/kg
V 22 7 mg/kg
Zn 13 4 0.99 0.18 mg/kg
1) Unweighted mean value of the means of accepted sets of data, each set being obtained in a different laboratory and/or with
a different method of determination. The indicative value and its uncertainty are traceable to the International System of Units
(SI).
2) The indicative uncertainty is the expanded uncertainty with a coverage factor k = 2 corresponding to a level of confidence of
about 95 % estimated in accordance with ISO/IEC Guide 98-3, Guide to the Expression of Uncertainty in Measurement
(GUM:1995), ISO, 2008.
The following information values were assigned

Analyte ERM-EF411 ERM-EF412 ERM-EF413 Unit
Ash 10 g/100 g
S (ASTM D3177) 0.59 0.37 0.55 g/100 g
F 39 40 64 mg/kg
K 1.5 g/kg
Cu 7 mg/kg
Ni 15 mg/kg
Sn 0.1 mg/kg
Tl 0.15 mg/kg
2
1 Table of content
Summary …………………………………………………………………………………...…………2
1 Table of content ....................................................................................................... 3
2 Glossary ................................................................................................................... 5
3 Introduction .............................................................................................................. 7
3.1 Background: need for the CRM.................................................................................. 7
3.2 Choice of the material ................................................................................................ 7
3.3 Design of the project .................................................................................................. 7
4 Participants .............................................................................................................. 9
4.1 Project management and evaluation .......................................................................... 9
4.2 Processing ................................................................................................................. 9
4.3 Homogeneity study .................................................................................................... 9
4.4 Stability study ............................................................................................................ 9
4.5 Characterisation......................................................................................................... 9
5 Material processing and process control .............................................................10
5.1 ERM-EF411, hard coal .............................................................................................10
5.2 ERM-EF412, brown coal ...........................................................................................11
5.3 ERM-EF413, furnace coke ........................................................................................11
6 Assessment of homogeneity .................................................................................12
6.1 Between-unit homogeneity........................................................................................12
6.2 Within-unit homogeneity and minimum sample intake...............................................23
7 Stability....................................................................................................................23
7.1 Short-term stability study ..........................................................................................24
7.2 Long-term stability study ...........................................................................................24
7.3 Estimation of uncertainties ........................................................................................28
8 Characterisation .....................................................................................................29
8.1 Selection of participants ............................................................................................30
8.2 Study setup...............................................................................................................30
8.3 Methods used ...........................................................................................................31
8.4 Dry mass determination ............................................................................................32
8.5 Evaluation of results .................................................................................................32
9 Value Assignment ...................................................................................................44
9.1 Certified values and their uncertainties .....................................................................44
9.2 Indicative values and their uncertainties....................................................................46
9.3 Additional material information ..................................................................................47
9.4 Additional data from k0NAA ......................................................................................48
10 Metrological traceability and commutability .........................................................49
10.1 Metrological traceability ............................................................................................49
10.2 Commutability ...........................................................................................................50
11 Instructions for use ................................................................................................50
11.1 Storage conditions ....................................................................................................50
3
11.2 Safety and protection for the environment.................................................................50
11.3 Preparation and handling of the material...................................................................51
11.4 Use of the certified value ..........................................................................................51
12 Acknowledgments ..................................................................................................52
13 References ..............................................................................................................52
Annex A.1: Homogeneity data ERM-EF411 ......................................................................55
Annex B.1: Short-term stability data ERM-EF411 ............................................................64
Annex C.1 Long-term stability data ERM-EF411 ..............................................................70
Annex D.1: Methods used for determination of proximates............................................76
Annex D2: Methods used for the determination of trace elements ................................82
Annex E.1: Results obtained in the characterisation study for ERM-EF411. .................86
Annex E.2: Results obtained in the characterisation study for ERM-EF412 ................101
Annex E.3: Results obtained in the characterisation study for ERM-EF413 ................116
4
2 Glossary
AAS Atomic absorption spectrometry
AES Atomic emission spectrometry
ANOVA Analysis of variance
ASTM international ASTM international (formerly American Society for Testing and
Materials)
b Slope in the equation of linear regression y = a + bx
BCR® One of the trademarks of CRMs owned by the European
Commission; formerly Community Bureau of Reference
CI confidence interval
CRM Certified reference material
CVAAS Cold vapour atomic absorption spectrometry
CVAFS Cold vapour atomic fluorescence spectrometry
DIN Deutsches Institut fuer Normung
DMA Direct Mercury Analyzer
ERM® Trademark of European Reference Materials
EU European Union
GCV Gross calorific value
GFAAS Graphite furnace atomic absorption spectrometry
GC-TCD Gas chromatography with thermal conductivity detection
GUM Guide to the Expression of Uncertainty in Measurements
[ISO/IEC Guide 98-3:2008]
IC Ion chromatography
ICP Inductively coupled plasma
ICP-AES Inductively coupled plasma-atomic emission spectrometry
ICP-MS Inductively coupled plasma-mass spectrometry
ICP-SFMS ICP-Sectorfield mass spectrometry
ID-TIMS Isotope dilution thermal ionisation mass spectrometry
IEC International Electrotechnical Commission
INAA Instrumental neutron activation analysis
IRMM Institute for Reference Materials and Measurements of the JRC
ISE Ion selective electrode
ISO International Organization for Standardization
JRC Joint Research Centre of the European Commission
k Coverage factor
k0NAA k0-Neutron Activation Analysis
LOD Limit of detection
LOQ Limit of quantification
MS Mass spectrometry
MSbetween Mean of squares between-unit from an ANOVA
MSDS Material safety data sheet
MSwithin Mean of squares within-unit from an ANOVA
n Number of replicates per unit
N Number of samples (units) analysed
n.a. Not applicable
n.c. Not calculated
NCV Net calorific value
NIST National Institute of Standards and Technology (USA)
QC Quality control
QCM Quality control material
p Number of accepted datasets in the characterisation study
rel Index denoting relative figures (uncertainties etc.)
ret. Retained
5
RM Reference material
RSD Relative standard deviation
r2 Coefficient of determination of the linear regression
s Standard deviation
sbb Between-unit standard deviation; an additional index "rel" is added as
appropriate
sbetween Standard deviation between groups as obtained from ANOVA; an
additional index "rel" is added as appropriate
SI International System of Units
swithin Standard deviation within groups as obtained from ANOVA; an
swb Within-unit standard deviation
t Time
ti Time point for each replicate
TGA Thermogravimmetryic analysis
tα, df Critical t-value for a t-test, with a level of confidence of 1-α and df
degrees of freedom
tsl Proposed shelf life
u standard uncertainty
U expanded uncertainty
u*bb Standard uncertainty related to a maximum between-unit
homogeneity that could be hidden by method repeatability; an
ubb Standard uncertainty related to a possible between-unit
homogeneity; an additional index "rel" is added as appropriate
uc combined standard uncertainty; an additional index "rel" is added as
appropriate
ucal Standard uncertainty of calibration
uchar Standard uncertainty of the material characterisation; an additional
index "rel" is added as appropriate
uCRM Combined standard uncertainty of the certified value; an additional
index "rel" is added as appropriate
UCRM Expanded uncertainty of the certified value; an additional index "rel"
is added as appropriate
urec Standard uncertainty related to possible between-unit homogeneity
modelled as rectangular distribution; an additional index "rel" is
added as appropriate
usts Standard uncertainty of the short-term stability
XRF X-ray fluorescence spectrometry
α significance level
νsmeas Degrees of freedom for the determination of the standard deviation
smeas
ν MSwithin Degrees of freedom of MSwithin
6
3 Introduction
3.1 Background: need for the CRM
Conventional fuels are still the dominant energy source in the European Union. Moreover,
burning of coal is a substantial source of toxic trace elements like mercury and plays an
important role in the European mercury strategy. Therefore, measurement standards for
fossil fuels can contribute to more resource efficiency and to a reduced introduction of these
compounds into the environment. The measurements on the quality of fuels need to be
comparable to protect the environment and to facilitate the free movements of these goods
within the European Union, thus strengthening European competitiveness in the global
economy.
For this reason, the Community Bureau of Reference (BCR) released a suite of certified
reference materials named BCR-180, BCR-181 and BCR-182 in 1986 [4]. These materials
are exhausted and need to be replaced.
3.2 Choice of the material
While the previous coal materials all consisted of hard coal with a similar content of volatile
matter, it was decided to replace them with materials that cover a larger range of volatilie
matter. Therefore, one hard coal, one brown coal and one coke were selected as raw
materials. No particular emphasis was put on specific trace element levels, as the aim was to
certify a material as similar to natural materials as possible.
Sampling, sample preparation and grinding are important steps in coal analysis and hence
potentially important sources of error. For this purpose, the previous standards specified
minimum sample intakes for dry mass determination of 2.5 kg [5]. This, however, is not
feasible for a certified reference material. It was therefore decided to produce coarser
materials than before, but with grain sizes small enough ensure that each 50 g sample would
be representative for the whole batch.
3.3 Design of the project
After processing, homogeneity and stability testing, characterisation was based on
intercomparison of expert laboratories. No results were to be excluded on statistical reasons
alone. Such intercomparison requires clear definitions of the analytes. In coal analyses,
analytes are commonly divided into minor and trace elements and proximates. Minor and
trace elements are determined by instrumental methods or after complete digestion and are
defined by their chemical nature alone. Proximates are generally operationally defined. To
ensure comparability among laboratories, several standardisation organisations have
developed standard methods for proximate analysis. The list below gives a short description
of the methods considered for proximate analysis:
• Gross calorific value (GCV) is determined by measuring the heat produced by
combustion of a sample in a bomb calorimeter. The heat capacity of the bomb
calorimeter is tested by calibrating using the heat generated by benzoic acid.
Differences consist in the setup: GCV can be measured at constant volume or at
constant pressure. In the latter case, a part of the heat generated by combustion is
used to expand the gas. ISO 1928 [6] and ASTM D5865 [7] prescribe the
determination of GCV at constant volume. A closer look at the two standards
indicates that the results should be equivalent. This expectation is confirmed by
results in proficiency tests..
• Net calorific value (NCV) is calculated from the GCV applying a correction for the
moisture and hydrogen content of the sample. These calculations are described in
ISO 1928 and ASTM D5865, as well.
• Volatile matter is determined by heating the sample for a short time at a high
temperature in a vessel with a closed lid. The closed lid prevents exaggerated
7
oxidation of the samples. Naturally, heating conditions and the vessel (shape and
material) critically influence the result.
ISO 5071 [8] prescribes the application of two muffle furnaces. The sample is placed
in a fused silica vessel with a lid and heated first for 7 minutes at 400 °C, followed by
a second heating step of 7 minutes at 900 °C.
ISO 562 [9] prescribes the use of a fused silica vessel with lid, but restricts the
heating to 7 minutes at 900 °C in one muffle furnace. The scope of the method is
restricted to hard coal and coke, which contain less volatile matter than brown coal.
ASTM D3175 [10] prescribes the use of Pt crucibles with a lid. The sample is placed
into a vertical tube furnace heated at 950 °C. The fast evaporating volatiles are burnt
off and the total heating time is restricted to 7 minutes.
Due to the different crucible materials, different furnace setups and temperatures,
values from the ASTM method and ISO methods are not comparable.
• The ash content is defined as the mass fraction of the residue after complete
incineration of the sample.
ISO 1171 [11] prescribes ashing of the sample at a temperature of 815 °C in air until
constant mass is achieved.
ASTM D3174 [12] prescribes a final ashing temperature of 700-750 °C for coals and
950 °C for coke.
Due to this complete incineration, small deviations in the method parameters have
less influence on the result and the results of the two methods are therefore in most
cases equivalent.
• The sulfur content can be determined by various methods, each of them being
based on a different quantification principle after combustion.
ISO 351 [13], prescribes combustion in an oxygen stream at 1350 °C. The
combustion gases are absorbed in a H2O2 solution and the resulting H2SO4 and HCl
are titrated using Na2BO4. A correction for the Cl content is made.
ISO 19579 [14] and ASTM D4239 [15] work according to the same principle. The
sample is combusted in an oxygen stream at 1350 °C and the S mass fraction is
determined by infrared (IR) absorption of the formed SO2.
ASTM D3177 [16] prescribes combustion in a bomb. The combustion gases are
absorbed in water and the sulfate content is determined gravimetrically by
precipitation as BaSO4. This method was withdrawn in the meantime.
While ISO 19579 and ASTM D4239 are leading to equivalent results, the results differ
significantly from those obtained by ISO 351 and ASTM D3177.
• Carbon, hydrogen and nitrogen are quantified by analysis of the combustion gases.
ISO 29541 [17] and ASTM D5373 [18], describe the instrumental method, in which
the sample is burned in an oxygen atmosphere and the combustion products CO2,
H2O and N2 are determined by gas analysis procedures after calibration of the
apparatus with, for example ethylene diamine tetra-acetic acid (EDTA).
ISO 609 [19] describes very much the same approach: the samples are burnt at
1350 °C in a stream of oxygen and the amount of C and H are determined
gravimetrically by absorption of H2O and CO2 in solutions of Mg(ClO4)2 and NaOH.
ISO 333 [20] describes the semi-micro Kjeldahl method for the determination of N, in
which the pulverised sample is boiled with sulphuric acid and a catalyst (a mixture of
K2SO4, metallic Se and V2O5). The solution is made alkaline converting ammonium to
ammonia, which is distilled, absorbed in boric acid and the amount of ammonia is
determined by titration with sulphuric acid. These methods and their results are
equivalent.
The goal of the project was to include all methods leading to equivalent results for analytes
where several methods exist. In this way the applicability of the material to all of these
methods can be demonstrated.
8
4 Participants
4.1 Project management and evaluation
European Commission, Joint Research Centre, Institute for Reference Materials and
Measurements (IRMM), Geel, BE
(accredited to ISO Guide 34 for production of certified reference materials, BELAC No 268-RM)
4.2 Processing
European Commission, Joint Research Centre, Institute for Reference Materials and
Measurements (IRMM), Geel, BE
4.3 Homogeneity study

ALS Scandinavia AB, Luleå, SE
(measurements in the scope of ISO/IEC 17025 accreditation SWEDAC 1087)
GreenGas, Paskov, CZ
(measurements in the scope of ISO/IEC 17025 accreditation Czech Accreditation Institute 1091)
Nuon Power Generation NV, Utrecht, NL

(measurements in the scope of ISO/IEC 17025 accreditation RvA L465)
4.4 Stability study

(measurements in the scope of ISO/IEC 17025 accreditation SWEDAC 1087
GreenGas, Paskov, CZ
(measurements in the scope of ISO/IEC 17025 accreditation Czech Accreditation Institute 1091)

(measurements in the scope of ISO/IEC 17025 accreditation RvA L465)
4.5 Characterisation
(measurements in the scope of ISO/IEC 17025 accreditation SWEDAC 1087)
ArcelorMittal Ostrava a.s., Hutní a chemické laboratore, Ostrava-Kuncice, CZ

(measurements under the scope of ISO/IEC 17025 accreditation Czech Accreditation Institute 464/2008)
ASCAL ENVIRONNEMENT, Forbach, FR

(measurements under the scope of ISO/IEC 17025 accreditation COFRAC 1-1589)
Australian Nuclear Science and Technology Organisation (ANSTO), Kirrawee DC , AU

Czech Coal Services a.s., Most, CZ
(measurements under the scope of ISO/IEC 17025 accreditation Czech Accreditation Institute 624/2009)
Energie AG Oberösterreich Kraftwerke GmbH, St. Pantaleon, AT

E.ON New Build & Technology GmbH, Zentrallabor im Kraftwerk Scholven, Gelsenkirchen,
DE
(measurements under the scope of ISO/IEC 17025 accreditation DAKKS D-PL-14048-01-00)
Helsingin Energia (Helen), Helsinki, FI

(measurements under the scope of ISO/IEC 17025 accreditation INAS T250)
Incolab Services B., Oud Beijerland, NL

(measurements under the scope of ISO/IEC 17025 accreditation RvA L50)
Institut Jožef Stefan (IJS), Department of Environmental Sciences, Ljubljana, SI

(measurements under the scope of ISO/IEC 17025 accreditation Slovenska Akreditacija LP-090)
Intertek Testing Services Switzerland, Schlieren, CH

Mitteldeutsche Braunkohlengesellschaft mbH (MIBRAG), Zentrallabor, Zeitz, DE
(measurements under the scope of ISO/IEC 17025 accreditation DGA-PL1161.00)
9
measurements in the scope of ISO/IEC 17025 accreditation RvA L465
PEGOP - Energia Eléctrica, S.A., Laboratório Químico, Pego, PT

(measurements under the scope of ISO/IEC 17025 accreditation IPAC L0223)
SGS Nederland B.V., Vlissingen, NL

(measurements under the scope of ISO/IEC 17025 accreditation BELAC 005-TEST)
SGS Latvija Ltd, Riga, LV

(measurements under the scope of ISO/IEC 17025 accreditation LATAK T-320-04-2006-A)
Solvias AG, Kaiseragust, CH

Studiecentrum voor Kernenergie (SCK-CEN), Mol, BE
(measurements in the scope of ISO/IEC 17025 accreditation BELAC 015-TEST)
Technische Universiteit Delft, Reactor Institute Delft, Delft, NL

(measurements under the scope of ISO/IEC 17025 accreditation RvA L049)
Verbund Umwelttechnik GmbH, Standort FHKW Mellach, Wildon, AT

Vlaamse Instelling voor Technologisch Onderzoek (VITO), Mol, BE
Voestalpine Stahl GmbH, B4P4 - Umwelt- und Betriebsanalytik, Linz, AT
(measurements under the scope of ISO/IEC 17025 accreditation BMFWJ 20)
5 Material processing and process control

5.1 ERM-EF411, hard coal
Hard coal (120 kg) from the LaLoma open pit mine, Colombia, was provided by RWE Power
AG, Cologne, DE. The material consisted of coarse particles of up to 1 cm (see Figure 1).
Based on the content of volatile matter (42 %), the coal is classified as gas coal/flame coal.
As-delivered moisture content was 12 % (determined by oven drying at 105 °C).
Figure 1: Raw material for ERM-EF411
The material was sieved with a 2.5 mm sieve and the fraction < 2.5 mm (81 kg) was
processed further. As the lid of the original containers showed condensation, it was decided
to dry the material before the first milling step. The material was therefore dried at 50 °C for
48 h, bringing the total moisture content down to approximately 2 %. The dried material was
milled to a particle size of < 3 mm to break up agglomerates, dried again to a moisture
10
content of about 2.7 % and moved into a cone mixer. The mixer was flushed with nitrogen (5
L/min) for two days before the material was filled into aluminium-laminated sachets, each
containing 50 g dried coal.
Because of the drying at 50 °C, the material will not lose or even may take up moisture in the
first drying step at 37 °C, applied for the determination of hygroscopic moisture.
5.2 ERM-EF412, brown coal

Fluidized-bed lignite powder (120 kg) were provided by RWE Power AG, Cologne, DE. The
brown coal originates from the Hambach open pit mine in the Rhineland area. The material
was delivered as powder (see Figure 2). As-delivered moisture content was 11.5 %
(determined by oven drying at 105 °C).
At IRMM, the material was dried for 7 h at 50 °C. Subsequently, the material was transferred
into a cone mixer and was mixed for 17 days under a stream of dry nitrogen (flow 10 L/min)
at a temperature of 37 °C. After 17 days, the water content stabilised at 69 g/kg and filling
started. 2000 aluminium-laminated sachets containing 50 g each were filled while
maintaining the nitrogen flow. The sachets were put into a second plastic pouch to further
decrease potential oxygen uptake.
Because of the drying at 50 °C, the material will not lose or even may take up moisture in the
first drying step at 37 °C, applied for the determination of hygroscopic moisture.
5.3 ERM-EF413, furnace coke
Furnace coke (200 kg) were provided by the Voestalpine Stahl GmbH, Linz (AT) as lumps of
about 10 cm size ready for use in steel production (see Figure 3). After manual crushing of
the biggest pieces, smaller particles were produced using a jaw crusher. The crushed
material was further milled using a heavy duty mill with a 4 mm sieve insert. The ground
material was placed into a cone mixture and filled into aluminium laminated plastic sachets.
Mixing heated the material up to 30 °C, leading to condensation of water in the mixer.
11
6 Assessment of homogeneity
A key requirement for any reference material is the equivalence between the various units. In
this respect, it is not relevant whether the variation between units is significant compared to
the analytical variation, but whether this variation is significant to the certified uncertainty.
Consequently, ISO Guide 34 requires RM producers to quantify the between-unit variation.
This aspect is covered in between-unit homogeneity studies.
The within-unit homogeneity does not influence the uncertainty of the certified value when
the minimum sample intake is respected, but determines the minimum size of an aliquot that
is representative for the whole unit. Quantification of within-unit homogeneity is therefore
necessary to determine the minimum sample intake.
6.1 Between-unit homogeneity

The between-unit homogeneity was evaluated to ensure that - within the stated uncertainty-
the certified values of the CRM are valid for all units of the material. The number of selected
units should correspond to approximately the cubic root of the total number of the produced
units. Homogeneity of the three materials was assessed from two series of experiments: the
initial homogeneity study and the long-term study.
15 units were selected for the initial between-unit homogeneity test using a random stratified
sampling scheme covering the whole batch. For this, each batch was divided into 15 groups
(with similar number of units) and one unit was randomly selected from each group. From
each unit, three independent samples were taken and analysed.
As the repeatabilities of results for trace metals of this initial homogeneity study for ERM-
EF411 and ERM-EF413 were very poor, data from the long-term stability study were used,
as well. This was possible as no trend over time was observed, hence the samples over all
storage times are equivalent. This study comprised 20 samples from each material, also
taken using a random stratified sampling scheme. In this case, two replicate analyses were
performed on each unit. As the stability study was limited to those elements that had shown
sufficient homogeneity in the initial homogeneity study, this second assessment could not be
performed for all elements.
12
The following methods were used:
• Trace metals: Samples were digested using a mixture of HNO3 and HF. Element
concentrations in the digests were determined by ICP-SFMS or ICP-AES as described in
the literature [21]
• Proximates: ISO methods were used for GCV (ISO 1928), volatile matter (ISO 562), ash
(ISO 562), C/H/N (ISO/TS 12902) and S (ISO 351). National standard methods were used
for moisture and hygroscopic moisture (CSN 443177) and Cl (DIN 38414-S17)
The measurements were performed under repeatability conditions and in a randomised
manner to be able to separate a potential analytical drift from a trend in the filling sequence.
The results were corrected for the water content determined in each unit (see Section 6.2).
The results are shown as graphs in Annex A.
Regression analyses were performed to evaluate potential trends in the analytical sequence
as well as trends in the filling sequence. Trends in the analytical sequence that were
significant on a 99 % confidence level were visible for some analytes, pointing at an
instability of the analytical system. As the analytical sequence and the unit numbers were not
correlated, correction for these trends can improve the sensitivity of the subsequent
statistical analysis through a reduction in analytical variation without masking potential
between-unit heterogeneities. Therefore, trends in the analytical sequence were corrected if
the trend was significant on at least a 99 % confidence level as shown below.
corrected result = measured result − b ⋅ i
b = slope of the linear regression
i = position of the result in the analytical sequence
The trend-corrected dataset was tested for consistency using Grubbs outlier tests on a
confidence level of 99 % on the individual results and the unit means. Some outlying
individual results and outlying unit means were detected. Since no technical reason for the
outliers could be found, all outlier data were retained for statistical analysis.
Quantification of between-unit homogeneity was performed by an analysis of variance
(ANOVA), which separates the between-unit variation (sbb) from the within-unit variation (swb).
The latter is equivalent to the method repeatability if the individual samples are
representative for the whole unit.
Evaluation by ANOVA requires unit means which follow at least an unimodal distribution and
results for each unit that follow unimodal distributions with approximately the same standard
deviations. Distribution of the unit means was tested using histograms and normal probability
plots. Too few data are available for each unit to make a clear statement of the distribution of
individual results. Therefore, it was checked whether or not the individual data follow a
unimodal distribution using histograms and normal probability plots. Minor deviations from
unimodality of the individual values do not grossly affect the estimate of between-unit
standard deviations. The results of all statistical evaluations are given in Tables 1 through
Table 3.
13
Table 1: Results of the statistical evaluation of the homogeneity study for ERM-EF411 (hard
coal). Percentage figures in the columns "trend" give the significance level of the slope.
Trends in the filling sequence, outliers and distributions were evaluated after correcting for
trends in the analytical sequence significant on a 99 % confidence level
Method/Analyte Trends Outliers Distribution
Anal. Filling Indiv. Unit Individual Unit means
seq. sequence result means results
s
GCV no 95 % no no unimodal unimodal
Vol. matter (ISO 562/5071) no no no no normal normal
Ash (ISO 1171/ASTM D3174) no 99 % no no normal normal
C no no no no unimodal unimodal
H no no no no normal normal
N no no no yes normal normal
S (ISO 19579/ASTM D4239) 99 % no no no normal normal
Cl no no no no normal normal
Ca no no yes yes not normal skewed
Mg no no yes yes not normal skewed
Na no no yes yes not normal skewed
K 95 % no no no normal normal
As no no yes yes not normal skewed
Cd no no yes yes skewed skewed
Co no no yes no skewed skewed
Cr no no no no unimodal normal
Cu no no no no unimodal normal
Hg no no yes no unimodal normal
Hg (stability) no no no yes normal unimodal
Mn no no yes yes not normal not normal
Ni no no no no normal normal
Pb no no yes no unimodal normal
Pb (stability) no no yes yes unimodal normal
Sb no no no no unimodal normal
Sb (stability) no no yes yes unimodal skewed
Se no no no no unimodal normal
Sn no no no no normal normal
Sn (stability) no no no no normal normal
Tl no no yes no unimodal normal
V no no no no normal normal
Zn no no no no normal normal
14
Table 2: Results of the statistical evaluation of the homogeneity study for ERM-EF412
(brown coal). Percentage figures in the columns "trend" give the significance level of the
slope. Trends in the filling sequence, outliers and distributions were evaluated after
correcting for trends in the analytical sequence significant on a 99 % confidence level
Anal. Filling Indiv. Unit Individual Unit
seq. sequence results means results means
GCV no no no no normal normal
Vol. matter (ISO 562/5071) no no no no normal normal
Ash (ISO 1171/ASTM D3174) 99 % no no no normal normal
C no no no no unimodal normal
N no no no no normal normal
S (ISO 19579/ASTM D4239) no no yes no normal normal
Ca no no no no normal normal
Mg 99 % no no no normal normal
Na 99 % no no no normal normal
K 99 % no no no normal unimodal
As 95 % no no no normal normal
Cd no no yes no unimodal normal
Co no no no no normal normal
Cr no 95 % no no normal normal
Cu no no yes no unimodal normal
Hg 95 % no no no unimodal unimodal
Mn no no no no normal normal
Ni no no no no unimodal normal
Pb no no yes no unimodal unimodal
Sb 99 % no yes no normal normal
Se no no no no normal normal
Sn no no yes no normal normal
Tl no no yes yes not normal not
normal
V 95 % no no no normal normal
15
Table 3: Results of the statistical evaluation of the homogeneity study for ERM-EF413
(furnace coke). Percentage figures in the columns "trend" give the significance level of the
slope. Trends in the filling sequence, outliers and distributions were evaluated after
correcting for trends in the analytical sequence significant on a 99 % confidence level
Anal. seq. Filling Indiv. Unit Individual Unit
sequence results means results means
GCV no no no no normal normal
Vol. matter (ISO 562/5071) no no no no normal unimodal
Ash (ISO 1171/ASTM D3174) no no no no normal normal
C 95% no no no normal normal
N no no no no normal normal
S (ISO 19579/ASTM D4239) no no no no normal normal
Ca no no no no normal normal
Ca (stability) no no no no normal normal
Mg no no yes no normal normal
Mg (stability) no no no no bimodal bimodal
Na no no no no normal normal
Na (stability) 99 % no no no normal normal
K no no yes no unimodal unimodal
K (stability) no no no no normal normal
As no no yes yes unimodal unimodal
As (stability) no no no no normal normal
Cd no no no no normal normal
Cd (stability) no no no no normal normal
Co 95 % no no no unimodal normal
Co (stability) no no yes no normal normal
Cr no no yes yes not normal not normal
Cu no no no no normal normal
Cu (stability) no no no no normal normal
Hg 95 % no no no normal normal
Hg (stability) no no no no unimodal normal
Mn no no no no normal normal
Mn (stability) no no no no normal bimodal
Ni no no yes yes not normal not normal
Pb 95 % no no no normal normal
Pb (stability) no no no no normal normal
Sb 95 % no yes yes unimodal unimodal
Se no no yes no unimodal unimodal
Se (stability) no no no no normal normal
Sn no no no no normal normal
Sn (stability) no no yes yes unimodal unimodal
Tl 95 % no no no normal bimodal
Tl (stability) 99 % no yes no unimodal normal
V no no no no unimodal normal
V (stability) no no no no normal normal
Zn (stability) no no no no normal normal
An in-depth analysis of the data of the initial homogeneity study showed that the mass
fractions of Cr, Co and Ni in ERM-EF411 and ERM-EF413 are positively correlated. The
16
reason for this correlation is most likely contamination from the stainless steel equipment
used for crushing and milling of ERM-EF411 and ERM-EF413 processing. A second
correlation is visible for silicate particles. This correlation is absent for ERM-EF412, which
was delivered to IRMM as powder.
For ERM-EF411, units number 381, 521 and 1378 were outliers for Ca, Mg and Na. All three
replicate analyses of these units were consistent, demonstrating real inhomogeneity. Units
number 258 and 1310 were outliers for As. These outlying means were caused by one
outlying replicate analysis. Removal of this replicate would have brought the unit mean in line
with the other units. However, the results were retained as there was no technical reason for
exclusion.
The results of unit 787 was an outlier for Cd, as were the results for units number 1918, 521
and 381 for Mn.
Results for unit 1883 from the stability study revealed outliers for Hg, Pb and Sb, as were
the results of unit number 2 for Sb and Pb and number 593 for Sb. The consistency of the
results across the different replicates and elements indicates real inhomogeneity, most likely
due to small "nuggets" of element-rich particles.
Unit number 1995 was flagged as outlier on a 99 % confidence level for N., but the difference
of the outlier and the population mean was much smaller (5 % above the average )than it
was the case for the elements. Also here the data from the stability study were checked and
no outlier was found, demonstrating that the material is rather homogeneous for N.
ERM-EF412 was homogeneous, with only Tl having three outlying unit averages (units
number 306, 772 and 1257). All of these three outliers were caused by one replicate that was
about a factor 5 above the other results. Based on these results, the material was deemed to
heterogeneous for Tl.
For ERM-EF413, all results of unit 743 were outliers for Cr and Ni. The third replicate of unit
606 was flagged as outlier for As and Sb, causing the whole unit average to become an
outlier. The data from the stability study flagged both replicates of unit 95 as outlier for Sn
and two individual replicates of the stability study were flagged as 99 % outliers for Tl (results
about 10 % above the other results). These studies therefore show that the material is not
sufficiently homogeneous for Cr, Ni, As, Sb and Sn.
Between-unit inhomogeneity was quantified using one-way analysis of variance (ANOVA).
Relative method repeatability (swb,rel), relative between–unit standard deviation (sbb,rel) and
u*bb,rel were calculated as
MS within
s wb ,rel =
y
MS between − MS within
n
s bb ,rel =
y
MSwithin mean square within a unit from an ANOVA
MSbetween: mean squares between-unit from an ANOVA
y average of all results of the homogeneity study
n: average number of replicates per unit
ν MSwithin : degrees of freedom of MSwithin
One has to bear in mind that sbb,rel and swb,rel are estimates of the true standard deviations
and therefore subject to random fluctuations. Therefore, the mean square between groups
(MSbetween) can be smaller than the mean squares within groups (MSwithin), resulting in
negative arguments under the square root used for the estimation of the between-unit
17
variation, whereas the true variation cannot be lower than zero. In this case, u*bb, the
maximum heterogeneity that could be hidden by method repeatability, was calculated as
described in the literature. [22]. u*bb is comparable to the limit of detection of an analytical
method, yielding the maximum heterogeneity that might be undetected by the given study
setup.
MS within 2
4
n ν MSwithin
,rel =
*
u bb
y
When a trend in the filling sequence was significant at least at 99 % confidence level or in
case of the bimodal distributions for Mg and Mn for ERM-EF413, the uncertainty was
assessed in a different way. Here, an uncertainty using a rectangular distribution between
the highest and lowest unit mean was estimated (urec,rel). The uncertainty in those cases
where there was a significant trend in the filling sequence is calculated as
highest result - lowest result
u rec,rel =
2 ⋅ 3 ⋅ median y
The same approach was used for estimation of uncertainties for those parameters that
showed outlying mean values. The results of the evaluation of the between-unit variation are
summarised in Table 4 to Table 6.
18
Table 4: Results of the homogeneity study of ERM-EF411; n.c.: cannot be calculated as
MSbetween < MSwithin.
swb,rel sbb,rel u*bb,rel urec, rel
Analyte
[%] [%] [%] [%]
GCV 0.16 0.47 0.05
Vol. matter (ISO 562/5071) 0.38 1.20 0.11
Ash (ISO 1171/ASTM D3174) 0.51 filling trend 3.34
C 0.177 0.366 0.052
H 0.402 0.693 0.118
N 1.54 1.37 0.45 1.86
S(ISO 19579/ASTM D4239) 1.096 0.962 0.322
Cl 20.8 6.53 6.23
Ca 33.3 not applicable - outliers 34.8
Mg 48.2 not applicable - outliers 51.9
Na 17.0 not applicable - outliers 19.5
K 24.0 16.1 7.0
As 112 not applicable - outliers 108.1
Cd 26.3 not applicable - outliers 27.6
Co 23.5 9.6 6.9
Cr 22.1 22.6 6.5
Cu 20.5 9.6 6.0
Hg 40.6 n.c. 11.9
Hg (stability) 6.55 not applicable - outliers 6.2
Mn 45.2 not applicable - outliers 42.5
Ni 18.4 15.3 5.4
Pb 20.6 10.7 6.1
Pb (stability) 3.31 not applicable - outliers 26.4
Sb 23.3 4.3 6.8
Sb (stability) 2.60 not applicable - outliers 9.4
Se 10.7 n.c. 3.1
Sn 15.5 10.2 4.5
Sn (stability) 7.3 3.2 2.9
Tl 43.2 n.c. 12.7
V 18.3 11.6 5.4
Zn 13.9 12.4 4.1
The results of the statistical evaluations clearly show the improved repeatability of the
element analyses coming from the stability study. One potential reason for this improvement
could be that the need to grind the complete sample before taking analytical subsamples was
emphasised stronger than in the homogeneity study.
The data show allowed reliable assessment of homogeneity of ERM-EF411 for GCV, volatile
matter, ash, C, H, N, S, Cl, Co, Cu, Hg, Sb, Se, Sn, Tl, V and Zn. Uncertainties, including
those that would include the outliers detected in the studies were deemed too large for value
assignment for Ca, Mg, K, Na, As, Cd, Mn and Pb. Hg and Sb showed only one outlier in all
of the studies which, in addition did not differ too much from the main population, so
certification was envisaged.
19
MSbetween < MSwithin
Analyte
[%] [%] [%] [%]
GCV 0.137 0.357 0.040
Vol. matter (ISO 562/5071) 0.577 0.473 0.169
Ash (ISO 1171/ASTM D3174) 1.630 n.c. 0.478
C 0.194 0.132 0.057
H 0.643 0.436 0.189
N 1.96 1.21 0.57
S (ISO 19579/ASTM D4239) 4.83 n.c. 1.42
Cl 20.0 10.4 5.9
Ca 2.26 n.c. 0.66
Mg 2.45 n.c. 0.72
Na 2.37 n.c. 0.70
K 3.51 0.98 1.03
As 11.0 n.c. 3.2
Cd 21.8 3.8 6.4
Co 3.70 n.c. 1.10
Cr 4.31 filling trend 2.29
Cu 4.53 n.c. 1.33
Hg 13.3 2.7 3.9
Mn 3.27 n.c. 0.96
Ni 3.94 2.50 1.16
Pb 17.6 n.c. 5.2
Sb 7.46 2.05 2.19
Se 8.54 n.c. 2.51
Sn 4.58 1.17 1.34
Tl 77.8 not applicable - outliers 45.3
V 4.54 n.c. 1.33
Zn 17.3 2.2 5.1
The data show sufficient homogeneity of ERM-EF412 for all parameters except Tl.
20
MSbetween < MSwithin
Analyte
[%] [%] [%] [%]
GCV 0.106 0.389 0.031
Vol. matter (ISO 562/5071) 6.5 8.4 1.9
Ash (ISO 1171/ASTM D3174) 0.43 0.47 0.13
C 0.196 0.075 0.058
H 4.25 2.36 1.25
N 1.614 n.c. 0.473
S (ISO 19579/ASTM D4239) 1.565 n.c. 0.459
Cl 17.1 14.3 5.0
Ca 12.5 4.9 3.7
Ca (stability) 2.7 2.3 1.1
Mg 16.6 7.0 4.9
Mg (stability) 5.5 bimodal 6.0
Na 14.5 6.4 4.3
Na (stability) 4.6 n.c. 1.8
K 20.1 n.c. 5.9
K (stability) 6.7 n.c. 2.7
As 43.3 not applicable - outliers 33.8
As (stability) 6.2 6.7 2.8
Cd 27.4 n.c. 8.0
Cd (stability) 13.7 13.4 5.5
Co 21.5 6.7 6.3
Co (stability) 3.9 2.0 1.5
Cr 24.7 not applicable - outliers 36.7
Cu 15.6 7.8 4.6
Cu (stability) 5.4 9.7 2.1
Hg 22.1 n.c. 6.5
Hg (stability) 45.0 n.c. 17.9
Mn 19.8 7.3 5.8
Mn (stability) 4.7 bimodal 6.7
Ni 26.7 not applicable - outliers 42
Pb 29.1 n.c. 8.7
Pb (stability) 7.7 4.2 3.1
Sb 44.6 not applicable - outliers 31.4
Se 12.3 10.1 3.6
Se (stability) 4.9 3.9 1.8
Sn 18.3 5.5 5.4
Sn (stability) 11.6 not applicable - outliers 15.1
Tl 16.7 3.5 4.9
Tl (stability) 3.5 1.9 1.4
V 16.9 9.8 5.0
V (stability) 6.6 n.c. 2.6
Zn 27.4 5.1 8.1
Zn (stability) 4.7 5.5 1.9
As is the case for EF411, repeatabilities from the stability study are much better than those
from the homogeneity study for ERM-EF413.
The homogeneity assessment demonstrated that ERM-EF413 is sufficiently homogeneous
for GCV, ash, volatile matter ash C, H, N, S, Cl, Ca, Mg, Na, K, Cd, Co, Cu, Hg, Mn, Pn, Se,
21
Tl, V and Zn. Uncertainties that would include the detected outliers were deemed too large
for value assignment for As, Cr, Ni, Sb and Sn
. As for setting the uncertainties, the following approach was chosen:
• As u*bb,rel sets the limits for the detection power of the study, the larger value of sbb,rel
and u*bb,rel is adopted as uncertainty contribution to account for potential heterogeneity
hidden by the intrinsic variation of the method.
• urec, rel is used for analytes with a filling trend, outliers or bimodal distributions.
• Where results from both the initial homogeneity study and the data from the
homogeneity assessment from the long-term study are available, the data from the
study with the better repeatability are used.
The uncertainties of homogeneity (ubb,rel) assigned are listed in Table 7.
Table 7: Uncertainties of inhomogeneity assigned to the analytes of the three materials.
Analyte ubb, rel ubb, rel ubb, rel
[%] [%] [%]
GCV 0.47 0.36 0.39
Vol. matter (ISO 562/ISO 5071) 1.20 0.47 8.4
Ash (ISO 1171/ASTM D3174) 3.3 0.48 0.47
C 0.37 0.13 0.075
H 0.69 0.44 2.4
N 1.86 1.21 0.47
S ISO 19579/ASTM D4239) 0.96 1.42 0.46
Cl 6.53 10.4 14.3
Ca 34.8 0.66 2.3
Mg 51.9 0.72 6.0
Na 19.5 0.70 1.84
K 16.1 1.03 2.7
As 108.1 3.22 33.8
Cd 27.6 6.40 13.4
Co 9.6 1.10 2.0
Cr 22.6 2.3 36.7
Cu 9.6 1.33 9.7
Hg 6.2 3.9 6.5
Mn 42.5 0.96 6.7
Ni 15.3 2.5 42
Pb 26.4 5.2 4.2
Sb 9.4 2.2 31.4
Se 3.1 2.5 3.9
Sn 3.2 1.34 15.1
Tl 12.7 45.3 1.87
V 11.6 1.33 2.6
Zn 12.4 5.1 5.5
22
The high uncertainties or presence of outliers made it clear that not all parameters tested for
homogeneity could be certified. The subsequent studies (stability and characterisation) were
therefore limited to those parameters that showed sufficient homogeneity in order to
minimise cost.
6.2 Within-unit homogeneity and minimum sample intake

The within-unit homogeneity is closely correlated to the minimum sample intake. Due to the
intrinsic heterogeneity, individual aliquots of a material will not contain the same amount of
analyte. The minimum sample intake is the minimum amount of sample that is representative
for the whole unit and thus can be used in an analysis. Sample sizes equal to or above the
minimum sample intake guarantee the certified value within its stated uncertainty.
The minimum sample intake for elements was determined from the results of the
characterisation study, using the method information supplied by the participants. The
smallest sample intake that still yielded results with acceptable accuracy to be included in the
respective studies was taken as minimum sample intake. It must be borne in mind that these
amounts are only valid after the complete contents of a unit have been ground. Using the
data from Annex D, the following minimum sample intakes after grinding of a complete unit
are derived:
Hg: 30 mg
All other minor and trace elements: 200 mg
The minimum sample intake for operationally defined analytes is specified in the respective
standards as:
GCV according to ISO 1928 and ASTM D5865: 1 g
Volatile matter according to ISO 562 or ISO 5071-1: 1 g
Ash according to ISO 1171/ASTM D3174: 1 g
S according to ISO 19579/ASTM D4239: 0.2 g
C, H, N: 70 mg
7 Stability
Time, temperature and radiation were regarded as the most relevant influences on stability of
the materials. The influence of ultraviolet or visible radiation was minimised by the choice of
the containment, which eliminates most of the incoming light. In addition, materials are stored
and dispatched in the dark, thus practically eliminating the possibility of radiative
degradation. Therefore, only the influences of time and temperature needed to be
investigated.
Stability testing is necessary to establish conditions for storage (long-term stability) as well as
conditions for dispatch to the customers (short-term stability). During transport, especially in
summer time, temperatures up to 60 °C could be reached and stability against these
conditions must be demonstrated if transport at ambient temperature will be applied.
The stability studies were carried out using an isochronous design [23]. In that approach,
samples are stored for a certain time at different temperature conditions. Afterwards, the
samples are moved to conditions where further degradation can be assumed to be negligible
("reference conditions"), effectively "freezing" the degradation status of the materials. At the
end of the isochronous storage, the samples are analysed simultaneously under repeatability
conditions. Analysis of the material (after various exposure times and temperatures) under
repeatability conditions greatly improves the sensitivity of the stability tests.
Stability studies were limited to those analytes that had shown sufficient homogeneity in the
homogeneity study.
23
7.1 Short-term stability study
Samples were stored at 60 °C for 0, 1, 2 and 4 weeks for the short-term stability study. The
reference temperature was set to +18 °C. Two samples per storage time were selected using
a random stratified sampling scheme. From each unit, two subsamples were measured fpr
proximates and four subsamples for elements using the same methods as described for the
homogeneity study. The measurements were performed under repeatability conditions and in
a randomised manner to be able to separate a potential analytical drift from a trend over
storage time.
The results were screened for outliers using the single and double Grubbs test on 99 %
confidence levels. Some outlying individual results were found (see Table 8 to Table 10).
Tentative removal of the outliers confirmed that their presence or absence did not change the
statistical significance of the regression line. As no technical reason for the outliers could be
found, all data were retained for statistical analysis.
Furthermore, the data were plotted against storage time and regression lines were
calculated. The slope of the regression lines was tested for statistical significance
(loss/increase due to shipping conditions).
The results of the measurements are shown in Annex B. The results of the statistical
evaluation of the short-term stability are summarised in Table 8 to Table 10.
The material can be dispatched without further precautions under ambient conditions.
7.2 Long-term stability study
Samples were stored at 18 °C for 0, 4, 8, 12 and 20 months for the long-term stability study.
The reference temperature was set to -20 °C. Two units per storage time were selected
using a random stratified sampling scheme. From each unit, two subsamples were measured
by digestion/ICP-AES or digestion/ ICP-SFMS as described for the homogeneity study for
trace metals and by ISO 589 (moisture), ISO 1171 (ash), ISO 562 (volatile matter), ISO 1928
(calorific value), GC-TCD (C, H, N) and XRF (S, Cl). The measurements were performed
under repeatability conditions, and in a randomised manner to be able to separate a potential
analytical drift from a trend over storage time.
The obtained data were evaluated individually for each temperature. The results were
screened for outliers using the single and double Grubbs test.
Furthermore, the data were plotted against storage time and regression lines calculated. The
slope of the regression lines was then tested for statistical significance (loss/increase due to
storage conditions
The results of the measurements are shown in Annex C. The results of the statistical
evaluation of the long-term stability study are summarised in Table 8 to Table 10.
Some elements not included in the original test were tested after the characterisation study:
Two samples from reference stock and two samples from normal stock were tested in 4
replicates each and the results were compared using a t-test.
24
Table 8: Results of the statistical evaluation of the stability tests of ERM-EF411. For the
short-term study of Cu and Sn only two subsamples per unit were analysed. Data marked
with an asterisk come from the additional test after characterisation (t=44 months)
Analyte Short-term study (60 °C) Long-term study (18 °C)
Individual Significance of Individual Significance of
outlying results the trend on a outlying results the trend on a
99% confidence 99% confidence
level level
GCV no no no no
Vol. matter (ISO 562) no no no no
Ash (ISO 1171) no no no no
C no no no no
H no no 2 (retained) no
N no no no no
S no no no no
Cl result at LOD no no
Co no no no* no*
Cu yes no no data
Hg no yes no* no*
Ni no no no data
Sb no no no* no*
Se no no 2 (retained) no
Sn no no no data
Tl no yes no* no*
V no no no* no*
Zn no yes no* no*
Hg, Tl and Zn showed statistically significant trends in the short-term study. However, the
extent of the trend was small enough to ensure negligible degradation during transport to the
customer. It was therefore decided to include any potential trend from degradation in the
assessment of uncertainties.
25
Table 9: Results of the statistical evaluation of the stability tests of ERM-EF412
level level
GCV no no no no
Ash (ISO 1171) no no no no
C no no no no
H no no no no
N no no no no
S no no no no
Cl no no no no
Ca no no no no
Mg no no no no
Na 1 (retained) no 1 (retained) no
K no no no no
As no no no no
Cd no no 2 (retained) no
Co 1 (retained) no no no
Cr 1 (retained) no no no
Cu no no 1 (retained) no
Hg no no no no
Mn no no no no
Ni 1 (retained) no no no
Pb no no no no
Sb 2 no 2 (retained) no
Se 2 (retained) no 1 (retained) no
Sn no no no no
V 1 (retained) no no no
Zn 1 (retained) no no no
Several outliers were observed. For ERM-EF412, one subsample digest gave an outlier for
Na, Co, Cr, Co, Ni, Sb, V and Zn, indicating either contamination or a "nugget" of higher
metal concentration. In any case, all outliers were retained, as no technical reason for
exclusion was found. None of the regression lines was significant for ERM-412.
26
Table 10: Results of the statistical evaluation of the stability tests of ERM-EF413. For the
short-term study for Ni, only two subsamples per unit were analysed. Data marked with an
asterisk dome from the stest after the characterisation study
level level
GCV no no no no
Ash (ISO 1171) no yes no no
C no no no no
H no no no no
N no no no no
S no no no no
Cl no no no no
Ca no no no no
Mg no no no no
Na no no 2 (retained) no
K no yes no no
As no no no no
Co no no no no
Cu no no no no
Hg no no 2 (retained) no
Mn no no no no
Pb no no no no
Se no no no no
Sn no no 1 (retained) yes
Tl no no 2 (retained) no
V no no no no
Zn no no no no
For ERM-413, statistically significant trends were observed for the ash content (short-term
study), K (short-term study) and for Sn (long-term study). The trend for ash does not make
technical sense, as furnace coke is produced by calcination at temperatures much higher
than 60 °C and the ashing itself also occurs at higher temperatures. The trend is therefore
most likely a statistical artefact, which was also confirmed by the second test after
characterisation, where the same result was found for samples stored at normal conditions
and those stored at reference conditions.
It was decided to include the apparent degradation for K in the uncertainty of stability but
base the uncertainty of stability for Sn on the second test after characterisation.
27
7.3 Estimation of uncertainties
Due to the intrinsic variation of measurement results no study can rule out degradation of
materials completely, even in the absence of statistically significant trends. It is therefore
necessary to quantify the potential degradation that could be hidden by the method
repeatability, i.e. to estimate the uncertainty of stability. This means, even under ideal
conditions, the outcome of a stability study can only be "degradation is 0 ± x % per time".
Uncertainties of stability during dispatch and storage were estimated as described in the
literature [24] for each analyte. For this approach, the uncertainty of the linear regression line
with a slope of zero is calculated. The uncertainty contribution is then calculated as the
product of the chosen shelf life and the uncertainty of the regression lines as
RSD
u lts ,rel = ⋅ t sl
∑ (xi − x )2
ults,rel relative uncertainty due to potential degradation during storage
RSD relative standard deviation of all results of the stability study
xi: time point for each replicate
x: mean results for all time points
tsl: proposed shelf life (24 months at 18 ºC in this case)
The uncertainty contribution for potential degradation during transport (usts, rel) is calculated
using the same equation, using a tsl of 1 week.
In case of the uncertainty of the short term stability for ash for ERM-EF412 as well as the
uncertainty of the long term stability for Sn for ERM-EF413, the apparent degradation using
the slope b was combined with the uncertainty due to the lack of fit around the regression
line as
ults,rel , deg = (b ⋅ t sl ) 2 + ults2 ,rel
The following uncertainties were estimated:

• usts,rel, the uncertainty of degradation during dispatch. This was estimated from the
60 °C studies for a time of 0.25 months (1 week). The uncertainty therefore describes
the possible change during a dispatch at 60 °C lasting for one week.
• ults,rel, the stability during storage. This uncertainty contribution was estimated from
the 18 °C studies. The uncertainty contribution therefore describes the possible
degradation for 24 months at 18 °C.
The results of these evaluations are summarised in Table 11.
28
Table 11: Uncertainties of stability during storage and dispatch. usts,rel was calculated for a
temperature of 60 °C and 1 week; ults,rel was calculated for a storage temperature of 18 °C
and 2 years. ults for H cannot be quantified, as the results submitted by the laboratory were
below the LOQ. Data marked with an asterisk come from the second test after the
characterisation (44 months) .
Analyte ERM-EF411 ERM-EF412 ERM-EF413
usts ,rel ults,rel usts ,rel ults,rel usts ,rel ults,rel
[%] [%] [%] [%] [%] [%]
GCV 0.054 0.18 0.073 0.16 0.051 0.092
Vol. matter (ISO 562) 0.32 0.293 0.131 0.202 0.72 6.80
Ash (ISO 1171) 0.42 1.13 0.17 0.50 0.36 0.46
C 0.062 0.49 0.061 0.40 0.051 1.046
H 0.080 1.03 0.087 0.85 1.03 n.a.
N 0.17 2.62 0.26 3.36 0.35 2.94
S 0.52 0.62 0.46 0.46 0.24 9.85
Cl < LOD 1.92 2.50 0.57 2.18 10.5
Ca not tested 0.35 0.71 0.31 1.96
Mg not tested 0.22 1.02 0.60 4.01
Na not tested 0.42 1.77 0.41 3.58
K not tested 0.53 3.21 0.84 3.25
As not tested 1.13 2.73 not tested
Cd not tested 2.55 10.6 0.86 10.5
Co 0.41 1.88* 0.44 1.96 1.11 2.40
Cr not tested 1.18 1.81 not tested
Cu 3.20 0.77 1.29 1.07 5.84
Hg 1.23 3.65 2.11 3.49 2.37 23.2
Mn not tested 0.27 1.26 0.60 4.23
Ni not tested 1.61 2.51 not tested
Pb not tested 1.98 3.82 1.81 4.82
Sb 0.64 4.05 1.58 2.79 not tested
Se 0.53 8.3* 5.1 2.68 0.56 3.27
Sn 2.54 4.4 1.11 2.67 2.04 3.63*
Tl 1.84 6.7* not tested 1.37 2.65
V 0.65 6.0* 1.37 1.41 0.39 3.36
Zn 2.85 5.8* 1.68 3.73 0.98 3.96
All uncertainties will be included in the overall uncertainty budget. Therefore the material can
be transported at ambient conditions without special precautions.
After the certification campaign, the material will be subjected to IRMM's regular stability
monitoring programme to control its further stability.
8 Characterisation
The material characterisation was based on an intercomparison of expert laboratories, i.e.
the properties of the material were determined in different laboratories. This approach aims
at randomisation of laboratory bias, which reduces the combined uncertainty. Naturally, for
method-defined analytes (ash, volatile matter, S, C, H, N) all laboratories applied the same
method. For elemental analysis, different measurement procedures were applied to
demonstrate the absence of a measurement bias. GCV and NCV is an intermediate case:
while the principle is indeed method defined, the result should be independent of the
particular standard used.
29
8.1 Selection of participants
22 laboratories were selected based on criteria that comprised both technical competence
and quality management aspects. Each participant was required to operate a quality
management system and to deliver documented evidence of its laboratory proficiency in the
field by submitting results for intercomparison exercises or method validation reports. Having
a formal accreditation was not mandatory, but meeting the requirements of ISO/IEC 17025
was obligatory. In fact, all laboratories for the proximate analysis were accredited for the
measurements in question. Where measurements are covered by the scope of accreditation,
the accreditation number is stated in the list of participants (Section 4).
8.2 Study setup
Characterisation of proximates and trace element content were organised in two separate
studies, as few laboratories determine both trace elements and proximates. In addition,
sample intakes for proximates are higher than for trace elements. Therefore, laboratories
received more samples for proximate than for the trace element determination.
8.2.1 Proximates
All laboratories, with the exception of laboratory 4, which did not analyse brown coal (ERM-
EF412), submitted offers for all three materials. Samples were sent in September 2011 and
results were received within 4 months after sample dispatch.
Each laboratory received three units of the candidate CRMs for which it had submitted an
offer and was requested to provide six independent results, two per unit. The units for
material characterisation were selected using a random stratified sampling scheme and
covered the whole batch. The sample preparations and measurements had to be spread
over at least three days to ensure intermediate precision conditions. This means on each day
the complete content of one unit was ground and the ground sample was left to equilibrate
with the laboratory atmosphere to make it less hygroscopic. Dry mass in the analytical
sample was determined from this equilibrated sample and this equilibrated sample was also
used for all other proximate analysis. The moisture content in the analysis sample had to be
determined in each unit two times and results are reported on dry mass basis.
Free moisture was determined on the unground sample.
Blinded certified reference materials were sent as quality control samples together with the
candidate CRMs to allow independent assessment of method trueness and appropriateness
of the calibration. The latter was especially important, as many methods for proximate
analysis are not calibrated on a daily basis. The following certified reference materials were
used:
• BCR-180 (gas coal) for the determination of GCV, C, H, N, ash; labelled as QCM A
• BCR-331 (steam coal) for the determination of S; labelled as QCM B
• NIST SRM 39j and Fluka 33045 (benzoic acid) for checking the calibration of the
calorimeters; labelled as QCM C
• BCR-460, coal, for the determination of F; labelled as QCM D
The use of measurement uncertainties is not well-established for standardised methods. To
obtain information on the accuracy obtained in the laboratory, laboratories were asked to
indicate the standard deviation of the quality control chart for the respective analyte.
Laboratories reported deviations from the standard methods and the date of the last
calibration or operation qualification together with the results.
8.2.2 Trace elements
Each laboratory received two units of the candidate CRMs for which it had submitted an offer
and was requested to provide six independent results, three per unit. The units for material
characterisation were selected using a random stratified sampling scheme and covered the
30
whole batch. The sample preparations and measurements had to be spread over at least
three days to ensure intermediate precision conditions. This means, on each day the
complete content of one unit was ground and the ground sample was left to equilibrate with
the laboratory atmosphere to make it less hygroscopic. Dry mass in the analytical sample
was determined from this equilibrated sample and this equilibrated sample was also used for
trace metal analysis. The moisture content in the analysis sample had to be determined in
each unit two times and results are reported on dry mass basis.
NIST SRM 1632d (bitumous coal) for the determination of trace elements, labelled as QCM
E, was used as a blind quality control samples together with the candidate CRMs to allow
independent assessment of method trueness and appropriateness of the calibration. Each
laboratory received only a approximately 5 g of the material, precluding moisture
determination. All results submitted by the laboratories were corrected by the 2 % moisture
content given on the certificate. According to information from laboratory 20, actual moisture
content can vary between 2 and 9 %, depending on the conditions in the laboratory, leading
to a potential residual moisture induced bias of 7 %. This potential bias is sufficiently low to
detect serious flaws in analytical methodology.
In addition to the measurement results, laboratories were also requested to give estimations
of the expanded uncertainties of the mean value of the six results. No approach for the
estimation was prescribed, i.e. top-down and bottom-up were regarded as equally valid
procedures.
Elements for which the homogeneity studies had shown unacceptable inhomogeneity were
excluded from the general characterisation. Only neutron activation analysis (NAA)
laboratories were asked to provide data for all elements, as for these methods the additional
results come with negligible additional costs. The intention was not to certify these elements,
but to provide these results as information values.
8.3 Methods used
8.3.1 Proximates
Various methods exist for the determination of proximates (see section 3.3). To make the
material as widely applicable as possible, both ASTM and ISO methods were applied.
Information was sought from the chairman of the respective ASTM technical committee
which ASTM methods were equivalent to the respective ISO methods, so the results could
be pooled. According to this information (backed up by results from intercomparisons
provided as well), the following methods were applied:
Moisture in the analytical sample: Moisture in the analytical sample was determined by ISO
5068-2 (brown coal); ISO 11722 (hard coal); ISO 687 (coke) or ASTM D3173. The
results of this analysis was used to correct the results to dry mass.
Ash: ISO 1171 and ASTM D3174 with the intention of pooling results of both methods.
Volatile matter: ISO 562 and ASTM 3175 with no intention of pooling results of both methods.
GCV at constant volume: ISO 1928 and ASTM D5865 with the intention of pooling results of
both methods.
C, H, N: ISO 29541 and ASTM D5373 both describe the instrumental determination of CHN
and are equivalent. In addition, separate ISO methods for C, H (ISO 609) and N (ISO
333) exist. Each of these methods could be used, with the intention of pooling the
results of these methods. As it turned out, no laboratory used ISO 609.
S: ISO 19579 and ASTM D4239 deliver equivalent results, so both methods could be sued
with the intention of pooling results of both methods. Measurements by XRF were
asked to demonstrate the suitability of the materials for measurements using this
method.
31
Cl: Laboratories were free to choose either ISO 587 or ASTM D4208, with the intention of
pooling the results of these methods. In addition, data from neutron activation analysis
were sought to potentially confirm the results. Measurements by XRF were asked to
demonstrate the suitability of the materials for measurements using this method.
F: Laboratories were free to choose ISO 11724, ASTM D3761, ASTM D5987, with the
intention of pooling the results of these methods.
Laboratories could also use other methods, e.g. national standard methods. In this case,
evidence of the equivalence of these methods with the respective ISO or ASTM methods had
to be provided with the results. The information on the methods used is given in Annex D.
8.3.2 Trace elements
A variety of digestion methods (open ashing, closed microwave, high pressure digestion
using different instruments) with different quantification steps (AAS, ICP-MS, ICP-AES) as
well as methods without sample preparation (INAA, k0NAA) were used to characterise the
material. The combination of results from methods based on completely different principles
virtually should rule out undetected method bias.
All methods used during the characterisation study are summarised in Annex D. The
laboratory code (e.g. L01) is a random number and does not correspond to the order of
laboratories in Section 4.
8.4 Dry mass determination
For all measurements carried out during certification (homogeneity, stability and
characterisation studies) the protocol specified in ISO 5068 (brown coal) 11722 (hard coal);
ISO 687 (coke) or ASTM D3173 was applied:
A sample of 1 g of coal powder is dried in air or a stream of nitrogen at 105-110 °C until dry
mass is obtained. For hard coal and coke, the drying can be done in air.
8.5 Evaluation of results
The characterisation campaign resulted in up to 14 datasets per analyte. All individual results
of the participants, grouped per analyte are displayed in tabular and graphical form in Annex
E.
8.5.1 Technical evaluation
The obtained data were first checked for compliance with the requested analysis protocol
and for their validity based on technical reasons. The following criteria were considered
during the evaluation:
- compliance with the analysis protocol: sample preparations and measurements
performed on two days, and the analysis order and water content determination.
- absence of values given as below limit of detection or below limit of quantification
- method performance, i.e. agreement of the measurement results with the assigned
value of the QCM
A preliminary compilation of results was sent to the laboratories on 12 August (proximates)
and 28 August (elements) 2012 with the request for checking individual results. Deviation of
results obtained for the QCMs from their certified value were highlighted especially. The
answer and the technical investigations performed at IRMM, led to the following decisions (a
summary of all issues is given in Table 12).
Proximates
No reliable uncertainty estimates are available for many of the results from procximate
analysis. Data for the QMs were therefore deemed acceptable if they would have been in the
population of data in the characterisation studies of these QCMs. The term "values submitted
32
during characterisation" in connection with a QCM therefore refers to the characterisation
studies of BCR-180, BCR-331 and BCR-460 and not to the dataset of the current study.
Laboratory 1 reported results for Cl for QCM A significantly above the certified values. The
results were therefore not used.
Laboratory 2 failed to report results for the quality control material for most analytes, so the
results were not used for the evaluation.
Laboratory 3 reported high values for C for QCM A. It re-analysed the sample and found a
value that was in agreement with the certified value for this material. However, as this
involved a re-analysis of the material, the values were nevertheless excluded from the
evaluation.
Laboratory 4 submitted results for GCV for QCM A above all values submitted during the
characterisation, hinting at biased results. The laboratory repeated the analysis of QCM A
and obtained results in agreement with the certified value, demonstrating its general method
proficiency. Nevertheless, as there is a possibility that the results on the day of the
characterisation measurements were biased, the results were excluded.
Laboratory 5 recognised that the value for volatile matter had not been corrected for the
moisture content and that the net calorific value had been calculated on constant pressure,
not on constant volume. Corrected values were accepted, as the corrections are based on a
pure calculation without additional measurements.
The laboratory reported results for QCM A for Cl and N below all values submitted during
characterisation, hinting at biased results. The results were therefore not used.
Laboratory 6 reported results for QCM A for H above all values submitted during
Laboratory 7 submitted results for GCV and Cl for QCM A above all values submitted during
Laboratory 8 did not provide results for the QCM for volatile matter and ash. The results were
therefore not used.
The laboratory reported results for QCM A for N below all values submitted during
Laboratory 9 reported high values for H and low values for N for QCM A. In addition, the
variation of the results for hydrogen was unusually high for the candidate CRM. Based on the
results on the QCM A and the high variation for the candidate CRMs for hydrogen, these
values were rejected.
Laboratory 10 submitted results for for GCV for QCM A below, for S for QCM B above and
for F in QCM D below the values submitted during characterisation, hinting at biased results.
The results were therefore not used.
Laboratory 11 reported results for H above all values submitted during characterisation,
hinting at biased results. The results for F for QCM D were below the certified value. The
results were therefore not used.
Laboratory 12 stated that they discovered soot after the combustion of QCM C for
determination of GCV. This incomplete combustion explains the low finding for this QCM.
The laboratory argued that this low finding was caused by the nature of the sample: the
benzoic acid of QCM C was in powder form, whereas the laboratory usually uses pellets for
calibration. The absence of influence on the other samples is shown by the correct value for
QCM A. The values for GCV were retained. The laboratory did not find any explanation for
the high findings for H and C for QCM A and the values were therefore rejected.
Laboratory 13 reported that it used thermogravimmetric analysis (TGA) for determination of
ash and volatile matter in one run. This is fast, but analysis in two runs gives more reliable
results for ash. The laboratory delivered a second set of results for ash where the ash values
33
were obtained in a separate run, which are in better agreement. As these results were
received after information about the values, they are not included in the evaluation.
The results for F for QCM D were below the certified value and were therefore not used.
Triggerd by receiving the first draft of the certification report, L13 conducted made additional
investigations on the source of the deviating result. They reported that originally they had
determined volatile matter in a TGA without closing the crucible with a lid. Repeating the
analyses with a closed crucible gave significantly lower results that were in better agreement
with the certified values. However, as these tests were performed after disclosure of results
and because they were not performed by the manual method, the new results were not
included in the evaluation.
Laboratory 14 reported low results for C and high results for N and ash in QCM A as well as
high results for QCM B. One explanation for the findings could be the calibration of the CHN
analyser: the laboratory uses real samples, which might pick up moisture. However, z-scores
over the last 5 years (about 18 per analyte) are very good, which speaks against this
explanation. Based on the results on QCM A, the values for ash, C and nitrogen were
excluded from the evaluation. For S, the result is explained by a difference in the methods
used: the results from XRF differs from the ISO methods, if the samples contain FeS.
Because of this method-dependence, the values were not included in the evaluation.
Also Cl was determined by XRF. The laboratory was invited to participate with this method in
the characterisation study to demonstrate the wide applicability of the assigned value.
Because XRF requires matrix materials for calibration, traceability of the results is difficult to
ensure. Therefore the results were used as confirmatory results rather than used for value
assignment, although the results agreed with the other results submitted for Cl and although
the results for the QCM agreed with the certified value.
Ash and volatile matter: Some results obtained by TGA for ash and volatile matter differed
significantly from the results of the other methods, especially for brown coal and furnace
coke. Discussion with the laboratories using this method clarified that determination of
volatile matter by TGA is not straightforward. For each type of fuel, a correlation factor
against the manual oven measurements must be obtained. If the fuel in question behaves
differently from those with which the correlation was obtained, results will be biased. The
lower familiarity with brown coal and furnace coke may explain why TGA results were biased
especially for these two materials. TGA offers the possibility of determining volatile matter
and ash in one analytical run, correlating these two results: if results for volatile matter are
biased towards higher values, this automatically means that the results for ash are biased
towards lower values and vice versa. Therefore, it was decided to exclude all results for
volatile matter obtained by TGA, regardless of their agreement with the other oven
techniques. Ash values by TGA were included in the analysis, unless the volatile matter was
also determined by TGA in the same run. Therefore, results of laboratories 6, 10, 11 and 13
were not included in the characterisation for these parameters.
Elements
Laboratory 3: Results for Se for QCM E were significantly below the certified value.
According to the laboratory, the indication of a method bias was confirmed by another
interlaboratory comparison and the laboratory started investigation on how to improve the
method. Because of this indication of method bias, the results for Se from Laboratory 3 were
not used for value assignment.
The laboratory also checked its results V for QCM E. The laboratory re-analysed the samples
and found results approximately 20 % higher, demonstrating general method proficiency.
The results and variation is within the uncertainties reported by the laboratory and the results
were therefore retained.
Results for QCM C for Ca, Mg, Na, K do not agree with the certified values within the
respective uncertainties and were therefore not used.
Results for Tl for ERM-EF413 were partly below the LOQ and were therefore no used for
34
value assignment.
Uncertainties were taken from the reproducibility limits of the ASTM methods. These are very
high and, looking at the variation of the lab’s results, most likely overestimations of the true
uncertainty.
Laboratory 7: In the case of ERM-EF412, the Tl mass fraction was significantly below the
usual limit of detection of the laboratory. While the results are useful for comparison with the
other values, they were excluded from value assignment.
The result of the laboratory also deviated significantly from the information value for Ni for
QCM E. However, as this value is for information only, the result was retained.
The result for Mg for QCM C differs from the certified value. Therefore, the data were not
used.
The measurement uncertainty reported for Zn for ERM-EF412 is significantly above those of
the other laboratories. As the data are not comparable, the Zn results of Lab 7 for ERM-
EF412 were not used for values assignment.
Laboratory 13 casted doubts on the accuracy of the values for Pb, as the mass fractions are
at the low end of the working range. The data were not used for value assignment.
For As, the laboratory reported a low result for QCM E, which was still covered by the
reported uncertainty. A second analysis gave results in agreement with the certified values.
The laboratory stated that in its experience, hydride generation AAS frequently gives
deviating results from ICP measurements. As the result was within the uncertainty stated by
the laboratory, the results were retained.
The laboratory determined Cd with GFAAS as well as with ICP-AES. Results by GFAAS
were consistently below the results by ICP-AES for mass fractions < 0.10 mg/kg. As the
laboratory deemed the results by GFAAS more reliable, the GFAAS were used for ERM-
EF411 and ERM-EF412. Two of the 6 results of ERM-EF413 were below the LOQ and one
at the LOQ, indicating insufficient accuracy at that concentration. The values for ERM-413
were therefore not used.
The laboratory performed analyses on four days. The results of all four days (12 in total)
were used.
Results for Tl for EF413 were on one day below the limit of quantification. Using only the
results of day two would have led to biased results. The results were therefore not used for
value assignment.
Laboratory 15 reported high uncertainties for Hg, Se and Mg: Se and Hg interfere spectrally.
In these three materials, Se mass fraction is between 13 and 127 times the Hg mass fraction,
so negatively affecting the Hg determination. In line with this expectation, the laboratory
submitted results above the certified value of Hg for the QCM, which had a Se/Hg ratio of 13.
The result submitted for Se for the QCM was low, but the difference was still covered by the
respective uncertainties. Therefore, the results for Se were retained for ERM-EF411 and
ERM-EF412, but not for ERM-EF413, where only three of the six results were above the
LOQ.
At the given neutron fluxes, Al interferes with the determination of Mg, especially at high Al
mass fractions, resulting in very high uncertainties for Mg for ERM-EF411, which has an
approximate Al mass fraction of 8600 mg/kg. The same effect explains the low finding for Mg
for QCM, which has an Al mass fraction of 9100 mg/kg. Therefore, the results of L15 were
included for ERM-EF412 (low Al/Mg ratio), but were not included for ERM-EF411 and ERM-
EF413 (higher Al/Mg ratio).
The standard deviation of the results for K for ERM-EF412 and ERM-EF413 were
significantly higher than the ones of other laboratories, indicating worse method performance
for this element. Therefore, results for K from Lab 15 were not used for value assignment.
The results for V for QCM E were below the certified value, but this is a result of the very low
uncertainty reported by the laboratory and the very low uncertainty assigned to the certified
value. The value was among ll other results for this QCM.. The values were therefore
retained.
35
Laboratory 16 reported a very high Zn value for one sample preparation for ERM-EF412.
The other subsamples for this sample gave much lower results. This high result was
explained by the laboratory as being most likely caused by contamination. This individual
result was excluded, retaining the other Zn values for the material.
The laboratory determined Cd by ID-TIMS, using both the 113Cd/112Cd and the 114Cd/111Cd
ratio. These 12 results were pooled into one dataset.
Results for Ca and Sb for QCM E were below the certified values. The Ca results were
therefore not used.
Laboratory 17 reported values for Ca, Na, K, Cr, Pb and Zn that disagreed with the certified
values based on the stated uncertainties. The data were therefore not used. Also the results
for QCM E for Ni were above the information value for Ni. As this value is for information
only, the result was retained.
Laboratory 18 performed in total 12 determinations , of which two results for Mn for ERM-
EF411 were very high. The laboratory performed in total 12 determinations, two of where so
high. This was deemed to be due to sample inhomogeneity rather than due to technical
reasons and the data were therefore retained.
The laboratory stated that results for Cr in ERM-EF412 were below the effective limit of
determination. The results were therefore not used for value assignment.
The standard deviation of the results for K for ERM-EF413 were significantly higher than the
ones of other laboratories, indicating worse method performance for this element. Therefore,
results for K from Lab 18 were not used for value assignment.
The standard deviation of Zn for ERM-EF413 is unacceptably high (60 %), so the results
were not used for value assignment.
Laboratory 20 also submitted results for NIST SRM 1365, sub-bituminous coal, which was
digested and analysed together with the IRMM coals. Results for Pb and V were about 15 %
below the certified values, which is below the accepted range of ± 10 % as set by the
laboratory. Although this deviation is just covered by the uncertainty stated by the laboratory,
the fact that the results are beyond the laboratory-internal limits led to exclusion of the
results.
The laboratory also stated that the results for Hg in ERM-EF413, Cd (ERM-EF412 and ERM-
EF413), Sb, Se, Sn and Tl (ERM-EF412) are close to the limit of quantification. This was
reflected in their uncertainties and the values were therefore retained.
Results for Ca for QCM E were below the certified values. The Ca results were therefore not
used.
Laboratory 21 had measurements performed by two different analysts. Results for Cu and Zn
for ERM-EF412 and for Cr for ERM-EF413 between the two analysts differed by a factor 3
(Cu) and 2 (Zn, Cr), respectively. Because of the lack of intra-laboratory consistency, the
values were not used for value assignment.
Uncertainty for Cd for ERM-EF413 was L21 for ERM-EF413 are confirmatory only.
Results for Hg were at the LOQ and Tl were below the LOQ as stated by the laboratory. The
results were therefore rejected.
The result for QCM E for As does not agree with the certified value. However, the low
uncertainty reported by the laboratory indicates underestimation of the measurement
uncertainty. The result was therefore retained.
The results for Sb for QCM E is below the certified value. The values were therefore not used
for value assignment.
Laboratory 23 reported uncertainties for Mg that were significantly above those of the other
laboratories. As the data are not comparable, the Mg results of Lab 23 were not used for
values assignment.
36
Table 12: Datasets that showed deviations from the analysis protocol, technical
specifications or deviating values for the QCM samples, and action taken
Analyte Lab-method Description of problem Action taken
code
GCV L2 No results for the QCM A provided data not used
(ISO
L12 Results for QCM C 4 % below the certified data not used
1928/ASTM
D5865) value: the lab discovered incomplete
combustion, presumably caused by the fact
that QCM C was a powder rather than a
pellet; results for QCM A were also below the data not used
certified value.
L4, L7, L10 Result for QCM A beyond all values reported data not used
during certification
NCV L2 no results for the QCM A provided data not used
(ISO
L4, L7, L10 results for QCM A for GCV deviated (see data not used
1928/ASTM
D5865) GCV)
Volatile L2, L8 No results for the QCM A provided data not used
matter (ISO L6, L11, L13 TGA used for ash and Volatile matter data not used
562, ISO 5071)
Ash L2 No results for the QCM A provided data not used
(ISO
1171/ASTM L8 Results of the QCM A above all values data not used
D3174) reported during certification
L6, L11, L13 TGA for ash and Volatile matter; results for data not used
QCM A above the certified value
C L2 No results for the QCM A provide data not used
L3, L12, L14 Results of the QCM A 2 % above the certified data not used
values
H L2 No results for the QCM A provided data not used
L6, L9, L11, Results of the QCM A above all values data not used
L12 reported during certification
N L2 No results for the QCM A provided data not used
L5, L8, L9 Results of the QCM A below all values data not used
reported during certification
L14 Results of the QCM A above all values data not used
reported during certification
S (ISO L10, L14 Results for QCM B are 10 and 40 % above data not used
19579/ASTM the certified values
D4239)
Cl L1 Result for QCM A above certified value data not used
L5, L7 Result for QCM A below certified value data not used
L14 Measurements by XRF: Despite agreement values used for
with the certified value for QCM A, the values confirmation
were used as confirmation only.
F L10, L11, L13 Results for QCM D below certified value data not used
Ca L3, L17 Results for QCM E above the certified value data not used
37
code
L3, L7, L16, Results for QCM E below the certified value data not used
L20
L15 Interference by Al resulting in high data not used
Mg (EF411,EF413) uncertainties
L16b Uncertainty is very large (34-56 %) for results data not used
from microwave digestion
Na L3, L17 Results for QCM E above the certified value data not used
L3, L17 Results for QCM E above the certified value data not used
L15 (EF412, Standard deviation significantly higher than of data not used
K EF413) other laboratories
L18 (EF413) Standard deviation significantly higher than of data not used
other laboratories
L21 Result for QCM E below the certified value, result retained
but estimated uncertainty presumably
underestimated data retained
As
Result for QCM E low, but within uncertainty,
L13
second result gave higher values
L13 (EF411, Results from by GFAAS and ICP-AES if < 0.010 mg/kg,
EF412) provided. The results differ for mass fractions GFAAS results
< 0.10 mg/kg used
Cd L13 (EF413) Results partly below LOQ data not used
L20 (EF412, Results close to LOQ data retained
EF413)
L21 (EF413) Uncertainty larger than average data not used
L15 Significant Cr blank in the vials; resulted were data retained
blank corrected
Cr L17 Result for QCM E above the certified value
data not used
L18 (EF412) Result below LOD data not used
L21 (EF413) Results differ between two analysts data not used
L21 (EF411, Results between two analysts differ by a data not used
Cu EF412) factor of 3
L15 interference by Se data not used
Hg L20 (EF413) Results close to LOQ data retained
L21 Results partly below LOQ data not used
L18 several very high results; most likely due to data retained
Mn inhomogeneity
L7, L17 Results significantly above the information data retained
Ni value of QCM E
38
code
L13 Result on the lower end of the measurement data not used
procedure
L17 Results for QCM E above the certified value data not used
Pb
L20 Results for SRM 1635 15 % below the data not used
certified value and below the range accepted
by the laboratory.
L16, L21 Results for QCM E below the certified value data not used
Sb
L20 (EF412) Results close to LOQ data retained
L3 Apparent method bias; result for QCM E data not used
Se below the certified value
Sn L20 (EF412) Results close to LOQ data retained

L7 (EF412) Results below LOQ data not used
L13 (EF413) Results partly below LOQ data not used
Tl
L21 Results below the LOQ data not used
L15 Result for QCM E below the certified value, data retained
but uncertainty presumably underestimated
L20 Results for SRM 1635 15 % below the data not used
V certified value, and below the range accepted
by the laboratory
L21 Result for QCM E below the certified value data not used
L7 (EF412) Stated uncertainty (57 %) is significantly data not used
higher than for other labs datum deleted,
L16 (EF412) One replicate for Zn very high, most mlikely other data
caused by contamination retained
Zn Result for QCM E below the certified value data not used
L17
L18 (EF413) Large RSD (60 %) data not used
L21 (EF411, Results from 2 analysts differ by a factor of 2 data not used
EF412)
39
8.5.2 Statistical evaluation
The datasets accepted on technical grounds were tested for normality of dataset means
using kurtosis/skewness tests and normal probability plots and were tested for outlying
means using the Grubbs test and using the Cochran test for outlying standard deviations,
(both at a 99 % confidence level). Standard deviation within (swithin) and between (sbetween)
laboratories were calculated using one-way ANOVA. The results of these evaluations are
shown in Table 13 - Table 15.
Table 13: Statistical evaluation of the technically accepted datasets for ERM-EF411. p:
number of technically valid datasets. n.a.: not applicable; ret: retained. n.c.: cannot be
calculated as MSB < MSW * For results with outlying mean, the range of means rather than
the average is given.
p Outliers Dist. Statistical parameters
Means Var. Average* s sbetween swithin Unit
GCV 9 no no normal 29.005 0.170 0.167 0.088 MJ/kg
NCV 8 no no normal 28.003 0.240 0.238 0.068 MJ/kg
Vol. matter 8 no no normal 38.083 0.288 0.270 0.247 g/100 g
(ISO 562/5071)
Ash
(ISO 1171 / 10 no no normal 8.288 0.258 0.245 0.194 g/100 g
ASTM D3174)
C 10 no no normal 71.369 0.428 0.407 0.327 g/100 g
H 9 no no normal 4.798 0.111 0.108 0.059 g/100 g
N 9 no no normal 1.431 0.045 0.043 0.026 g/100 g
S (ISO
19579/ASTM 10 no no normal 0.598 0.011 0.0099 0.0130 g/100 g
D4239)
L3,
L4,
Cl 10 no normal 0.0099 0.0021 0.0020 0.0012 g/100 g
L15,
L19
F 4 no no n.a. 0.00393 0.00035 0.0003 0.00055 g/100 g
Ca 5 no no normal 1643 92 70 192 mg/kg
Mg 4 no n.a. n.a. 950 169 n.c. 682 mg/kg
Na 5 no no normal 1219 82 63 86 mg/kg
K 5 no L18 normal 1093 61 23 135 mg/kg
As 6 no no normal 4.485 0.663 0.670 0.637 mg/kg
Cd 3 n.a. 0.232 0.0028 0.028 0.037 mg/kg
Co 6 no no skewed 3.471 0.306 0.257 0.333 mg/kg
Cr 6 21 n.a. 15-28* n.a. mg/kg
Cu 2 n.a. 6.9 n.a. mg/kg
L13,
Hg 7 no normal 0.079 0.012 0.0114 0.0105 mg/kg
L16
Mn 6 no L18 normal 32.8 6.9 2.96 19.1 mg/kg
Ni 2 n.a. 14.8 mg/kg
Pb 4 no no normal 2.42 0.54 0.53 0.17 mg/kg
L15.
Sb 7 no L18. normal 1.494 0.082 0.041 0.192 mg/kg
L19
Se 9 no no normal 5.111 0.646 0.750 0.302 mg/kg
Sn 1 n.a. 0.19 n.a. 0.033 mg/kg
Tl 5 no no normal 0.236 0.019 0.0180 0.0118 mg/kg
V 5 no L18 normal 22.496 1.855 1.445 3.907 mg/kg
Zn 5 no L18 normal 13.2 1.3 1.1 2.3 mg/kg
40
Table 14: Statistical evaluation of the technically accepted datasets for ERM-EF412. . p:
Analyte p Outliers Dist. Statistical parameters
Means Var. Average s sbetween swithin Unit
GCV 8 no no normal 26.022 0.061 0.058 0.046 MJ/kg
NCV 7 no no normal 24.984 0.189 0.188 0.045 MJ/kg
Vol.
matter. 6 no no normal 50.089 0.368 0.362 0.160 g/100 g
(ISO 562/5071)
Ash
(ISO 1171/ 7 no L1 normal 4.112 0.285 0.283 0.092 g/100 g
ASTM D3174)
C 8 no L10 normal 66.229 0.407 0.392 0.270 g/100 g
H 7 no L1, L8 normal 4.875 0.152 0.150 0.064 g/100 g
N 8 no L6 normal 0.737 0.034 0.032 0.025 g/100 g
S (ISO
19579/ASTM 10 no L13 normal 0.360 0.032 0.032 0.014 g/100 g
D4239)
0.030-
Cl 9 L8 L11 n.a. n.a. 0.0012 g/100 g
0.044
F 2 n.a. 0.0040 n.a. 0.0003 g/100 g
Ca 8 no no normal 9793 374 363 230 mg/kg
Mg 5 no no normal 3732 139 140 79 mg/kg
Na 8 no no normal 2195 103 101 53 mg/kg
K 7 no L19 normal 229 11 12 10 mg/kg
0.28-
As 10 L17 L19 n.a. n.a. 0.024 mg/kg
0.42*
Cd 5 no no normal 0.0122 0.0009 0.0006 0.0016 mg/kg
0.09-
Co 10 L17 L15 n.a. n.a. 0.007 mg/kg
0.19
0.46-
Cr 7 no L15 skewed n.a. 0.075 mg/kg
0.64
Cu 5 no L7 normal 0.683 0.235 0.233 0.076 mg/kg
Hg 6 no no normal 0.0697 0.0082 0.0081 0.0036 mg/kg
L3,
Mn 11 no normal 48.583 1.764 1.718 0.995 mg/kg
L21
L17,
Ni 4 L17 n.a. 0.3-0.8* n.a. 0.051 mg/kg
L21
L18,
Sb 5 no L19, normal 0.0239 0.0028 0.0022 0.0041 mg/kg
L20
Sn 5 no L7 skewed 0.099 0.073 0.073 0.023 mg/kg
L7,
Tl 4 no normal 1.29 0.64 0.48 1.0 µg/kg
L17
V 7 no L15 normal 0.567 0.028 0.024 0.040 mg/kg
Zn 7 no L19 normal 0.988 0.153 0.135 0.208 mg/kg
41
Table 15: Statistical evaluation of the technically accepted datasets for ERM-EF413. p:
p Outliers Distr. Statistical parameters
Means Var. Average* s sbetween swithin Unit
GCV 8 no L6, L8 normal 29.52 0.45 0.45 0.13 MJ/kg
NCV 6 no L6, L8 normal 29.43 0.49 0.52 0.11 MJ/kg
Vol. matter. 7 no L3 bimodal 0.944 0.190 0.180 0.143 g/100 g
(ISO 562/5071)
Vol. matter. 1 n.a. 0.63 0.05 not applicable g/100 g
(ASTM D3175)
Ash
(ISO 1171/ 8 no L1 bimodal 9.5-10.1* not applicable 0.206 g/100 g
ASTM D3174)
C 9 no L1, L11 normal 87.83 0.65 0.63 0.35 g/100 g
H 7 L8 no n.a. 0.1-0.7* not applicable 0.019 g/100 g
N 9 no no normal 1.095 0.043 0.041 0.030 g/100 g
S (ISO
19579/ASTM 10 no L9 normal 0.578 0.025 0.024 0.018 g/100 g
D4239)
Cl 10 no no normal 0.0347 0.0032 0.0032 0.0021 g/100 g
F 3 n.a. 0.0064 0.0007 0.0007 0.0004 g/100 g
Ca 9 no L18 normal 2920 196 168 191 mg/kg
Mg 5 n.a. 1228 57 46 95 mg/ kg
L15,
Na 9 no L18, normal 642 50 50 36 mg/kg
L22
K 7 no no normal 1451 90 88 41 mg/kg
L13,
As 10 L13 L18
n.a. 1.8-6.7* not applicable 0.56 mg/kg
Cd 3 n.a. 0.033 n.a. 0.002 mg/kg
Co 10 L3 L3 na. 5.7-17* not applicable 0.64 mg/kg
Cr 5 no no normal 92 13 9 11 mg/kg
Cu 8 L3 L3, L22 n.a. 19-36* not applicable 2.6 mg/kg
Hg 4 n.a. 0.0105 0.0094 0.0101 0.0078 mg/ kg
L3,
Mn 11 L20 n.a. 78-140* not applicable 9.3 mg/kg
L18
Ni 3 n.a. 48 8 7 4 mg/ kg
Sb 4 n.a. 1.289 0.069 0.047 0.123 mg/ kg
Sn 5 no L3 normal 0.79 0.45 0.45 0.10 mg/kg
Tl 3 n.a. 0.145 0.026 0.026 0.004 mg/ kg
L16,
V 8 L18 n.a. 23-42* not applicable 1.5 mg/kg
L20
Zn 9 no L3, L19 normal 15.97 1.63 1.33 2.06 mg/kg
Most datasets showed some outlying variances. This merely reflects the fact that different
methods have different intrinsic variability. As all measurement methods were found
technically sound, all results were retained.
For ERM-EF411, the data for Cl from L13 did not agree with the tentatively assigned value
within the respective uncertainties. This was attributed to the low uncertainty and the value
42
was therefore retained.
The results submitted by Laboratory 21 for Cr were an outlier on a 99 % confidence interval
(laboratory average 28 mg/kg; other averages around 18 mg/kg). The results of the
laboratory for QCM E were in line with the certified value. The high result was therefore
deemed to reflect the inhomogeneity detected earlier, precluding assignment of any values.
The distribution of laboratory data for Co was skewed, with four results between 3.2 and
3.35 mg/kg and two results of 3.6 and 4.0 mg/kg, precluding assignment of a certified value.
Laboratory 18 submitted values between 700 and 4700 mg/kg for Mg. This resulted in a very
high within-laboratory standard deviation, which was not flagged as a Cochran outlier, as the
number of laboratories was too low. The situation was similar for K, where the laboratory
submitted results ranging from 850 to 1600 mg/kg. The results were retained, as it is
believed that this variation reflects material inhomogeneity rather than method problems.
Several more outliers of variance were found, which merely reflects the fact that different
methods have different intrinsic variability. As all measurement methods were found
technically sound, all results were retained.
For ERM-EF412, data for Cr were skewed, with three values of 0.46 and two values of 0.56
mg/kg, precluding certification.
For Sn, L7 was flagged only as 95 % but not as 99 % outlier. However, the result was a
factor 2.5 above the next highest value. Most likely the low number of datasets for Sn (5) is
responsible for this curious finding. In this case, the statistical test was overruled and the
data were treated as if L7 were an outlier.
Data from L1 and L11 for ash did not overlap with the tentatively assigned value within the
respective uncertainties. This is due to the low uncertainties rather than due to technical
inconsistency. The values were therefore retained and assignment of a value is possible.
For ERM-EF413, the result for L7 for H was about a factor 7 above the other results,
constituting a clear outlier. No reason for this deviating result was found.
Results for ash according to ISO methods followed a bimodal distribution, with one cluster of
results around 9.6 g/100 g and one around 10 g/100 g. This bimodality precluded any value
assignment.
Results for As, Co, Cu and Mn showed one outlying mean value each. No reasons for these
deviation could be identified, precluding value assignment.
Results for Hg ranged from 0.002 to 0.02, making any value assignment impossible.
For Se, skewness/kurtosis test indicated normality. This, however, might be caused by one
very low (1.0 mg/kg) and one very high (1.9 mg/kg) result each. The other five results ranged
from 1.3 to 1.5 mg/kg.
Results for Sn followed a normal distribution. However, results ranged from 0.2 to 1.5 mg/kg,
making value assignment not meaningful.
Results of L16 and L20 for V agreed very well, but were about half of the results submitted
by the other laboratories. No reason for this difference could be found.
Results for GCV from L10 and for Se (L7) did not overlap with the tentatively assigned value
within the respective uncertainties. This is due to the low uncertainties rather than due to
technical inconsistency. The values were therefore retained and assignment of a value is
possible.
43
9 Value Assignment
For these materials, certified, indicative and informative values have been assigned. No
value is assigned to any analyte where the characterisation study contained unexplained
outliers.
Certified values are values that fulfil the highest standards of accuracy. Procedures at IRMM
require generally pooling of not less than 6 datasets to assign certified values. Full
uncertainty budgets in accordance with the Guide to the expression of uncertainty in
measurement [3] must be established.
Indicative values are values where either the uncertainty is deemed too large or where too
few independent datasets were available to allow certification. Uncertainties are evaluated
according to the same rules as for certified values.
Additional material information refers to values that have been obtained in the course of the
study. For example, results reported from only one or two laboratories in cases where
individual measurement uncertainty is high, would fall under this category.
9.1 Certified values and their uncertainties
Certified values for all analytes are based on the unweighted mean of the means of the
accepted datasets as shown in Table 13 to Table 15.
The assigned uncertainty consists of uncertainties related to characterisation, uchar (see
Section 8), potential between-unit homogeneity, ubb (see Section 6) and potential
degradation during transport (usts) and long-term storage, ults (see Section 7). These different
contributions were combined to estimate the expanded, relative uncertainty of the certified
value (UCRM, rel) with a coverage factor k as
UCRM,rel = k ⋅ uchar,
2
rel + ubb,rel + usts,rel + ults,rel
2 2 2
.
• uchar,rel was estimated as described in Section 8.5.2

• ubb,rel was estimated as described in Section 6.1. The uncertainties estimated for GCV
were also assigned to NCV.
• usts,rel was estimated as described in section 7.3. The uncertainties estimated for GCV
• ults,rel was estimated as described in Section 7.3. The uncertainties estimated for GCV
Because of the sufficient numbers of the degrees of freedom of the different uncertainty
contributions, a coverage factor k of 2 was applied, to obtain the expanded uncertainties.
The certified values and their uncertainties are summarised in Table 10 to Table 18.
44
Table 16: Certified values and their uncertainties for ERM-EF411
uchar, rel ubb, rel usts, rel ults, rel UCRM,rel Certified Unit
Property UCRM
[%] [%] [%] [%] [%] valuea
GCV 0.19 0.47 0.054 0.176 1.08 29.0 0.4 MJ/kg
(ISO 1928/ASTM D5865)
NCV 0.30 0.47 0.054 0.176 1.18 28.0 0.4 MJ/kg
(ISO 1928/ASTM D5865)
Volatile matter 0.27 1.20 0.32 0.29 2.61 38.1 1.0 g/100 g
(ISO 562/ ISO 5071)
Ash 0.98 3.37 0.421 1.125 7.42 8.3 0.7 g/100 g
(ISO 1171/ASTM D3174)
C 0.19 0.37 0.062 0.489 1.29 71.4 1.0 g/100 g
(ISO 29548/ASTM D5373)
H
(ISO 609/TS12902/ASTM 0.77 0.69 0.080 1.032 2.93 4.80 0.14 g/100 g
D5373)
N
(ISO 333/TS12902/ASTM 1.05 1.86 0.17 2.62 6.77 1.43 0.10 g/100 g
D5373)
S (ISO 19579/ASTM D4239) 0.58 0.96 0.524 0.620 2.77 0.598 0.017 g/100 g
Cl 6.71 6.53 0.000 1.924 19.12 99 19 mg/kg
Se 4.21 3.10 0.53 8.30 20.16 5.1 1.0 mg/kg
a
on dry mass basis (see Section 8.4)

Property UCRM
[%] [%] [%] [%] [%] valuea
GCV 0.083 0.36 0.07 0.16 0.81 26.02 0.22 MJ/kg
(ISO 1928/ASTM D5865)
NCV
0.29 0.36 0.07 0.16 0.98 24.98 0.25 MJ/kg
(ISO 1928/ASTM D5865)
Volatile matter 0.30 0.47 0.131 0.202 1.22 50.1 0.7 g/100 g
(ISO 562 and ISO 5071)
Ash 2.62 0.48 0.167 0.496 5.43 4.11 0.23 g/100 g
(ISO 1171/ ASTM D3174)
C (ISO 29548/ASTM D5373) 0.22 0.13 0.061 0.399 0.95 66.2 0.7 g/100 g
H (ISO 609/TS12902/ 1.18 0.44 0.087 0.851 3.04 4.88 0.15 g/100 g
ASTM D5373)
N (ISO 333/TS12902/ 1.63 1.21 0.259 3.360 7.87 0.74 0.06 g/100 g
ASTM D5373)
S (ISO 19579/ASTM D4239) 2.81 1.42 0.463 0.463 6.43 0.360 0.023 g/100 g
Ca 1.49 0.66 0.350 0.710 3.62 9.8 0.4 g/kg
Na 1.66 0.70 0.420 1.770 5.12 2.20 0.12 g/kg
K 1.80 1.03 0.530 3.210 7.72 229 18 mg/kg
Hg 4.80 3.89 2.110 3.490 14.90 0.070 0.011 mg/kg
Mn 1.09 0.96 0.27 1.26 3.89 48.6 1.9 mg/kg
Se 3.01 2.51 5.100 2.680 14.37 0.96 0.14 mg/kg
V 1.87 1.33 1.370 1.410 5.75 0.57 0.04 mg/kg
a
45
Property UCRM
[%] [%] [%] [%] [%] valuea
GCV 0.54 0.39 0.051 0.092 1.35 29.5 0.4 MJ/kg
(ISO 1928/ASTM D5865)
NCV 0.68 0.39 0.051 0.092 1.58 29.4 0.5 MJ/kg
(ISO 1928/ASTM D5865)
C (ISO 29548/ASTM D5373) 0.25 0.08 0.051 1.046 2.16 87.8 1.9 g/100 g
N (ISO 333/TS12902/ 1.31 0.47 0.352 2.939 6.54 1.10 0.07 g/100 g
ASTM D5373)
S (ISO 19579/ASTM D4239) 1.37 0.46 0.241 9.854 19.92 0.58 0.12 g/100 g
Ca 2.24 2.28 3.900 1.960 10.82 2.92 0.22 g/kg
Na 2.57 1.84 0.41 3.58 9.59 0.64 0.07 g/kg
Se 8.19 3.92 1.600 3.270 19.56 1.33 0.26 mg/kg
Zn 3.40 5.50 0.980 3.960 15.29 16.0 2.5 mg/kg
a
9.2 Indicative values and their uncertainties

Indicative values were assigned for a number or trace elements, because either fewer than
six technically accepted datasets were received or because the uncertainties were deemed
too large for certified values. As all laboratories had regularly successfully participate in
proficiency tests, the results were regarded as sufficiently trustworthy to assign indicative
values. The uncertainty budgets were set up as for the certified values.
For ERM-EF411, uncertainties of stability are not available for all elements. The uncertainties
estimated for Hg were used in this case. Because of the large uncertainties, slight
underestimation should not influence the assigned uncertainty.
All values are listed together with the assigned values and the reason why an indicative
rather than a certified value was assigned in Table 19 to Table 21.
Table 19: Indicative values and their uncertainties for ERM-EF411. Codes in the column
property: u: uncertainty too high for certified values. d: too few datasets for certification.
uchar, rel ubb, rel usts, rel ults, rel UCRM,rel Indicative Unit
Property UCRM
[%] [%] [%] [%] [%] valuea
Co (u) 3.60 9.60 0.41 1.88 20.86 3.5 0.8 mg/kg
Hg (u) 5.63 6.20 1.23 3.65 18.44 0.079 0.015 mg/kg
Sb (u) 2.07 9.40 0.64 4.05 20.93 1.5 0.4 mg/kg
Tl (u, d) 3.54 12.70 1.84 6.70 29.93 0.24 0.07 mg/kg
V (u. d) 3.69 11.60 0.65 6.00 27.17 22 7 mg/kg
Zn (u, d) 4.40 12.40 2.85 5.84 29.35 13 4 mg/kg
a
: reported on dry mass basis (see Section 8.4)
46
property: u: uncertainty too high for certified values. d: too few datasets for certification
Property UCRM
[%] [%] [%] [%] [%] valuea
Mg (d) 1.67 0.72 0.22 1.02 4.33 3.73 0.16 g/kg
Cd (u, d) 3.30 6.40 2.55 10.60 26.13 0.012 0.004 mg/kg
Cu (u, d) 15.39 1.33 0.77 1.29 31.04 0.68 0.22 mg/kg
Pb (u, d) 6.75 5.20 1.98 3.82 19.09 0.25 0.05 mg/kg
Sb (d) 5.24 2.20 1.58 2.79 13.04 0.024 0.004 mg/kg
Zn (u) 5.85 5.10 1.68 3.73 17.55 0.99 0.18 mg/kg
a
property: u: uncertainty too high for certified values. d: too few datasets for certification
Property UCRM
[%] [%] [%] [%] [%] valuea
Cl (u) 2.96 14.30 2.18 10.50 35.75 0.35 0.13 g/kg
Mg (d, u) 2.32 6.00 0.60 4.01 15.21 1.23 0.19 g/kg
Pb (u) 6.79 4.20 1.81 4.82 19.00 8.41 1.6 mg/kg
a
9.3 Additional material information

The mean of laboratory means for parameters for which at least two results were obtained in
the characterisation study and where no outlying unit averages were detected in the
homogeneity studies were assigned as additional material information. As these values only
give a rough idea about the value of the, no uncertainty is estimated. The additional
information values are listed in Table 22 to Table 24
Table 22: Information values for ERM-EF411. The information values are based on the
average of p laboratory averages obtained in the characterisation study.
Information Unit
Property p
valuea
S (ASTM D3177) 3 0.59 g/100 g
F 4 39 mg/kg
Cu 2 7 mg/kg
Ni 2 15 mg/kg
a
Information Unit
Property p a
value
S (ASTM D3177) 3 0.37 g/100 g
F 2 40 mg/kg
Sn 5 0.1 mg/kg
a
47
Information Unit
Property p
valuea
Ash 8 10 g/100 g
(ISO 1171, ASTM D3174)
S (ASTM D3177) 3 0.55 g/100 g
F 3 64 mg/kg
K 7 1.5 g/kg
Tl 3 0.15 mg/kg
a
9.4 Additional data from k0NAA

Laboratories 18, 19 and 22 also provided data for elements not requested in the
characterisation study. These data are summarised in Table 25. These data list only those
data where at least two laboratories submitted data and where the range of the averages
was smaller than 30 %ofthe average.
Table 25: k0NAA results for ERM-EF411, ERM-EF412 and ERM-EF413.Only data where at
least two laboratories submitted data and where the range of the averages was smaller than
30 % are shown.All data are in mg/kg.
average range average range average range
[mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg]
Al 8842 999 695 66 13987 658
Ba 205 16 109 6 171 10
Br 0.77 0.02 15.5 0.5 8.5 0.6
Ce 6.6 1.7 0.74 0.07 18 2
Cs 0.54 0.06 0.025 0.001 1.4 0.1
Dy 0.58 0.05 1.5 0.2
Eu 0.14 0.03 0.009 0.001
Fe 4428 884 3264 240 6882 461
Ga 2.9 0.3 4.9 0.1
Hf 0.53 0.11 0.09 0.04 0.76 0.05
I 4.9 0.1 6.4 0.5
La 3.1 0.6 0.38 0.03 8.2 0.5
Mo 4.3 1.3 5.78 0.04
Nd 3.1 0.5 0.31 0.01 8.5 0.7
Rb 6.9 1.1 0.94 0.15 11 2
Sc 2.9 0.3 0.13 0.01 4.1 0.3
Sm 0.61 0.13 0.052 0.007 1.7 0.1
Sr 73 6 116 7 105 8
Ta 0.020 0.001
Tb 0.10 0.01 0.009 0.001 0.25 0.02
Th 1.05 0.13 0.159 0.001 3.1 0.2
Ti 456 65 755 30
U 0.58 0.05 1.5 0.2
W 0.51 0.13 14 2
Yb 0.035 0.001
Zr 25 6 29 6
48
10 Metrological traceability and commutability
10.1 Metrological traceability
Identity
Ca, Mg, Na, K, As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Tl, V and Cl are chemically
clearly defined substances. The participants used different methods for the sample
preparation as well as for the final determination, demonstrating absence of measurement
bias. The analyte is therefore structurally defined and independent of the measurement
method.
GCV and the amount of volatile matter, ash, S, C, H and N in this case are method-defined
analytes and can only be obtained by following the following procedure specified in ISO 1928
or ASTM D5865 (GCV, NCV), ISO 562 and ISO 5071 (volatile matter), ISO 1171 or ASTM
D3174 (ash), ISO 609 ISO TC12902 or ASTM D5373 (C ), ISO 25941 or ASTM D5373 (H)
and ISO 333, ISO 29541 or ASTM D5373 (N). Adherence to these procedures was
confirmed by agreement of the laboratories' results with the assigned value for the CRM that
was used as quality control sample. The assigned value is therefore operationally defined by
method.
49
Quantity value
Only validated methods were used for the determination of the assigned values of trace
elements. Different calibrants/calibrants of known purity and specified traceability of their
assigned values were used and all relevant input parameters were calibrated. The individual
results are therefore traceable to the SI, as it is confirmed by the agreement among the
technically accepted datasets, as well. As the assigned values are combinations of agreeing
results individually traceable to the SI, the assigned quantity values themselves are traceable
to the SI, as well.
Traceability of the obtained results of the operationally-defined measurands is based on the
traceability of all relevant input factors. Instruments in individual laboratories were verified
and calibrated with tools ensuring traceability to the SI. Consistency in the interlaboratory
comparison demonstrates that all relevant input factors were covered. As the assigned
values are combinations of agreeing results individually traceable to the SI, the assigned
quantity values themselves are traceable to the SI as well.
10.2 Commutability
Many measurement procedures include one or more steps, which are selecting specific (or
specific groups) of analytes from the sample for the subsequent steps of the whole
measurement process. Often the complete identity of these 'intermediate analytes' is not fully
known or taken into account. Therefore, it is difficult to mimic all the analytically relevant
properties of real samples within a CRM. The degree of equivalence in the analytical
behaviour of real samples and a CRM with respect to various measurement procedures
(methods) is nowadays summarised in a concept called 'commutability of a reference
material'. There are various definitions expressing this concept. For instance, the CSLI
Guideline C-53A [25] recommends the use of the following definition for the term
commutability:
"The equivalence of the mathematical relationships among the results of different
measurement procedures for an RM and for representative samples of the type intended
to be measured."
The commutability of a CRM defines its fitness for use and, thus, is a crucial characteristic in
case of the application of different measurement methods. When commutability of a CRM is
not established in such cases, the results from routinely used methods cannot be legitimately
compared with the certified value to determine whether a bias does not exist in calibration,
nor can the CRM be used as a calibrator.
ERM-EF411, EF412 and EF413 were produced from actual coals and, like other coal
samples in a laboratory, still need to be processed further for analysis. The materials are
commutable, as they are virtually identical to actual samples.
11 Instructions for use

11.1 Storage conditions
The materials shall be stored at 18 °C ± 5 ° in the dark. Care shall be taken to avoid change
of the moisture content once the units are open.
Please note that the European Commission cannot be held responsible for changes that
happen during storage of the material at the customer's premises, especially of opened
samples.
11.2 Safety and protection for the environment
The usual laboratory safety measures apply.
50
11.3 Preparation and handling of the material
Before using ERM-EF411 or ERM-EF413, the complete contents of each sachet shall be
ground to < 250 µm. All analytical samples shall be taken from this ground material, sampling
of the coarse material is not recommended and will lead to higher variation of results due to
intrinsic inhomogeneity. ERM-EF412 can be used “as is”.
The ground samples shall be left to equilibrate with the laboratory atmosphere before taking
analytical subsamples.
Note: Due to the drying process, samples of ERM-EF411 and ERM-EF412 may take up
water during this equilibration process.
11.3.1 Minimum sample intake
The minimum sample intake representative is:
Hg: 30 mg
All other minor and trace elements: 200 mg
GCV according to ISO 1928 and ASTM D5865: 1 g
Volatile matter according to ISO 562 or ISO 5071-1: 1 g
Ash according to ISO 1171/ASTM D3174: 1 g
S according to ISO 19579/ASTM D4239: 0.2 g
C, H, N: 70 mg
11.3.2 Dry mass correction
Dry mass determination shall be carried out according to ISO 5068-2 (brown coal); ISO
11722 (hard coal); ISO 687 (coke) or ASTM D3173:
A separate portion of at least 1 g of the ground and equilibrated material shall be dried in an
oven at 105 – 110 °C until constant mass (separate weighing should not differ by more than
5 mg) is attained. For ERM-EF412, this drying shall be done in an oxygen-free atmosphere.
11.4 Use of the certified value
The main purpose of these materials is to assess method performance, i.e. for checking
accuracy of analytical results/calibration. As any reference material, they can also be used
for control charts or validation studies.
Comparing an analytical result with the certified value
A result is unbiased if the combined standard uncertainty of measurement and certified value
covers the difference between the certified value and the measurement result (see also ERM
Application Note 1, www.erm-crm.org [26].
For assessing the method performance, the measured values of the CRMs are compared
with the certified values. The procedure is described here in brief:
o Calculate the absolute difference between mean measured value and the certified
value (∆m).
o Combine measurement uncertainty (um) with the uncertainty of the
certified value (uCRM): u∆ = um2 + uCRM
2
o Calculate the expanded uncertainty (U∆) from the combined uncertainty (u∆,) using an
appropriate coverage factor, corresponding to a level of confidence of approximately
95 %
o If ∆m ≤ U∆ then there is no significant difference between the measurement result and
the certified value, at a confidence level of about 95 %.
51
Use as a calibrant
It is not recommended to use this matrix material as calibrant. If used nevertheless, the
uncertainty of the certified value shall be taken into account in the estimation of the
measurement uncertainty.
Use in quality control charts
The materials can be used for quality control charts. Different CRM-units will give the same
results as heterogeneity was included in the uncertainties of the certified values.
12 Acknowledgments
The authors would like to acknowledge the support received from Jean Charoud-Got, John
Seghers, Hanne Leys and Paul de Vos (IRMM) related to the processing of this CRM and
from Maria Contreras Lopes concerning the set-up of the required isochronous studies.
Furthermore, the authors would like to thank Renata Bujak, Raquel Sanchez Romero and
Boryana Koleva (IRMM) for the reviewing of the certification report, as well as the experts of
the Certification Advisory Panel "Elements and Inorganic Ions", Steven Balsley (IAEA,
Vienna, AT), Thomas Prohaska (University of Natural Resources and Life Sciences, Vienna,
AT) and Peter Vermaercke (SCK-CEN, Mol, BE) for their constructive comments.
We furthermore acknowledge the support received from Ron Graham (SGS, Sophia WS,
USA) during the discussion of equivalence between ASTM and ISO methods.
13 References
1 ISO Guide 34, General requirements for the competence of reference materials
producers, International Organization for Standardization, Geneva, Switzerland, 2009
2 ISO Guide 35, Reference materials – General and statistical principles for certification,
International Organization for Standardization, Geneva, Switzerland, 2006
3 ISO/IEC Guide 98, Guide to the Expression of Uncertainty in Measurement, (GUM
1995), International Organization for Standardization, Geneva, Switzerland, 2009
4 Griepink B, Colinet E, Wilkinson CH (1986) The Certification of the Contents (mass
fraction) of Carbon, Hydrogen, Nitrogen, Chlorine, Arsenic, Cadmium, Manganese,
Mercury, Lead, Selenium, Vanadium and Zinc in three Coals Gas coal CRM No. 180,
Coking coal CRM No. 181, Steam coal CRM No. 182, EUR 10366EN, Commission of
the European Communities, Luxembourg
5 ISO 589 Hard coal -- Determination of total moisture, International Organization for
Standardization, Geneva, Switzerland, 2008
6 ISO 1928 Solid mineral fuels -- Determination of gross calorific value by the bomb
calorimetric method and calculation of net calorific value, International Organization for
7 ASTM D5865 Standard Test Method for Gross Calorific Value of Coal and Coke, ASTM
International, West Conshohocken 2012
8 ISO 5071-1 Brown coals and lignites -- Determination of the volatile matter in the analysis
sample -- Part 1: Two-furnace method, International Organization for Standardization,
Geneva, Switzerland, 1997
52
9 ISO 562 Hard coal and coke -- Determination of volatile matter, International Organization
for Standardization, Geneva, Switzerland, 2010
10 ASTM D3175 Standard Test Method for Volatile Matter in the Analysis Sample of Coal
and Coke, ASTM International, West Conshohocken 2011
11 ISO 1171 Solid mineral fuels -- Determination of ash, International Organization for
12 AST D3174 Standard Test Method for Ash in the Analysis Sample of Coal and Coke from
Coal, ASTM International, West Conshohocken 2012
13 ISO 351 Solid mineral fuels -- Determination of total sulfur -- High temperature
combustion method, International Organization for Standardization, Geneva,
Switzerland, 1996
14 ISO 19579 Solid mineral fuels -- Determination of sulfur by IR spectrometry, International
Organization for Standardization, Geneva, Switzerland, 2006
15 ASTM D4239 Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke
Using High Temperature Tube Furnace Combustion, ASTM International, West
Conshohocken 2012
16 ASTM D3177 Standard Test Methods for Total Sulfur in the Analysis Sample of Coal and
Coke, ASTM International, West Conshohocken 2007 (Withdrawn 2012)
17 ISO 29541 Solid mineral fuels -- Determination of total carbon, hydrogen and nitrogen
content -- Instrumental method, International Organization for Standardization, Geneva,
Switzerland, 2010
18 ASTM D5373 Standard Test Methods for Instrumental Determination of Carbon,
Hydrogen, and Nitrogen in Laboratory Samples of Coal, ASTM International, West
Conshohocken 2008
19 ISO 609 Solid mineral fuels -- Determination of carbon and hydrogen -- High temperature
combustion method, International Organization for Standardization, Geneva,
Switzerland, 1996
20 ISO 333 Coal -- Determination of nitrogen -- Semi-micro Kjeldahl method, International
Organization for Standardization, Geneva, Switzerland, 1996 (withdrawn standard)
21 Rodushkin, I., Axelsson, M.D., Burman, E. (2000), Multielement analysis of coal by ICP
techniques using solution nebulization and laser ablation, Talanta 51:743-759
22 T.P.J. Linsinger, J. Pauwels , A.M.H. van der Veen, H. Schimmel, A. Lamberty (2001)
Homogeneity and stability of reference materials, Accred. Qual. Assur. 6: 20-25
23 A. Lamberty, H. Schimmel, J. Pauwels, (1998) The study of the stability of reference
materials by isochronous measurements, Fres. J. Anal. Chem. 360: 359-361
24 T.P.J Linsinger, J. Pauwels, A. Lamberty, H. Schimmel, A.M.H. van der Veen, L.
Siekmann (2001) Estimating the Uncertainty of Stability for Matrix CRMs, Fres. J. Anal.
Chem. 370: 183-188
25 H. Vesper, H; Emons, M. Gnezda, C. P. Jain, W. G. Miller, R. Rej, G. Schumann, J. Tate,
L. Thienpont, J. E. Vaks (2010) Characterization and Qualification of Commutable
Reference Materials for Laboratory Medicine; Approved Guideline, CLSI document C53-
A, Clinical and Laboratory Standards Institute, Wayne, PA, USA
26 T.P.J. Linsinger, ERM Application Note 1: Comparison of a measurement result with the
certified value, www.erm-crm.org
53
Annexes
Annex A: Results of the homogeneity measurements
Annex B: Results of the short-term stability measurements
Annex C: Results of the long-term stability measurements
Annex D: Summary of methods used in the characterisation
Annex E: Results of the characterisation measurements
Annex A.1: Homogeneity data ERM-EF411
Shown are the average results and standard deviations of the three (initial homogeneity
study) or two (long-term stability study) replicates of each unit. Where applicable, the results
corrected for analytical trend are shown.
Homogeneity study ERM-EF411
29 38.2
28.9 38.0
28.8 37.8
Volatile matter
28.7 37.6
[g/100 g]
GCV [J/g]
28.6 37.4
28.5 37.2
28.4 37.0
28.3 36.8
28.2 36.6
28.1 36.4
28 36.2
0 200 400 600 800 1000 1200 1400 1600 1800 2000
GCV unit number

volatile matter
Homogeneity study ERM-EF411 Homogeneity study ERM-EF411

72.6 5.06 0.045
72.4 5.04 0.040

H mass fraction [g/100 g]
Cl mass fraction [g/100 g]

C mass fraction [g/100 g]
5.02 0.035
72.2
5.00
0.030
72.0 4.98
0.025
71.8 4.96
0.020
71.6 4.94
0.015
4.92
71.4
4.90 0.010
71.2 4.88 0.005
71.0 4.86 0.000
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
C H unit number Cl unit number

1.46 0.66 20 0.40
1.44 0.64 18 0.35
S mass fraction [g/100 g]
As mass fraction [mg/kg]
Cd mass fraction [mg/kg]

N mass fraction [g/100 g]
1.42 16
0.62 0.30
14
1.40
0.60 12 0.25
1.38
0.58 10 0.20
1.36
0.56 8 0.15
1.34
6
0.54 0.10
1.32 4
1.30 0.52 2 0.05
1.28 0.50 0 0.00

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
N S unit number As Cd unit number

20 25 20 0.10
18 18 0.09
Co mass fraction [mg/kg]
Cu mass fraction [mg/kg]

Cr mass fraction [mg/kg]
Hg mass fraction [mg/kg]
16 20 16 0.08
14 14 0.07
12 15 12 0.06
10 10 0.05
8 10 8 0.04
6 6 0.03
4 5 4 0.02
2 2 0.01
0 0 0 0.00
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Co Cr unit number Cu Hg unit number
55
120 30 10 2.50
9
Mn mass fraction [mg/kg]
100 25
Pb mass fraction [mg/kg]
Sb mass fraction [mg/kg]

Ni mass fraction [mg/kg]
8 2.00
7
80 20
6 1.50
60 15 5
4 1.00
40 10
3
2 0.50
20 5
1
0 0 0 0.00
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Mn Ni unit number Pb Sb unit number

8 0.40 1.0 35
0.35 0.9
7 30
Sn mass fraction [mg/kg]

Se mass fraction [mg/kg]
Tl mass fraction [mg/kg]
V mass fraction [mg/kg]

0.8
0.30
0.7 25
6
0.25 0.6
20
5 0.20 0.5
15
0.15 0.4
4
0.3 10
0.10
0.2
3 5
0.05 0.1
2 0.00 0.0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Se Sn unit number Tl V unit number

18 6000 3500
16
3000
Mg mass fraction [mg/kg]

5000
Zn mass fraction [mg/kg]
Ca mass fraction [mg/kg]
14
2500
12 4000
10 2000
3000
8 1500
6 2000
1000
4
1000 500
2
0 0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Zn unit number Ca Mg unit number
56
Homogeneity study ERM-EF411 Homogeneity from long-term stability study
2500 2000 5.0
ERM-EF411 1.8
2300 1800 4.5 1.6

Na mass fraction [mg/kg]

K mass fraction [mg/kg]
2100 1600 4.0 1.4
1900 1400 3.5
1.2
1700 1200 3.0
1.0
1500 1000 2.5
0.8
1300 800 2.0
1100 600
0.6
1.5
900 400 1.0 0.4
700 200 0.5 0.2

500 0 0.0 0.0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Na K unit number Pb Sb unit number
Homogeneity from long-term stability study

0.38
ERM-EF411 0.090
0.36 0.080

0.34 0.070
0.32 0.060
0.30 0.050
0.28 0.040
0.26 0.030
0.24 0.020
0.22 0.010
0.20 0.000
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Sn Hg unit number
57
Shown are the average results after correction for potential analytical trends and standard
deviations of the three replicates of each unit.
26 47.9 4
47.7
25.9
47.5 3.9
Volatile smatter
25.8 47.3
[g/100 g]
Ash [g/100 g]
GCV [J/g]
25.7 47.1 3.8

46.9
25.6
46.7 3.7
25.5 46.5
46.3 3.6
25.4
46.1
25.3 45.9 3.5
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
GCV vol. matter unit number ash unit number

67.0 5.14 0.81 0.32
66.5 5.09 0.79

0.31

66.0 0.77
5.04
0.30
65.5 0.75
4.99
65.0 0.73 0.29
4.94
64.5 0.71
0.28
4.89
64.0 0.69
4.84 0.27
63.5 0.67
63.0 4.79 0.65 0.26

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
C H unit number N S unit number

0.05 0.35 0.020
0.04
0.30 0.018

0.04
0.25 0.016
0.03
0.03 0.20 0.014
0.02 0.15 0.012

0.02
0.10 0.010
0.01
0.05 0.008
0.01
0.00 0.00 0.006

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Cl unit number As Cd unit number

0.12 0.60 0.6 0.10
0.11 0.55
0.09
0.10 0.55 0.5

0.08
0.09 0.45
0.08 0.50 0.4 0.07
0.07 0.35
0.06
0.06 0.45 0.3
0.05
0.05 0.25
0.04 0.40 0.2 0.04

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
58
49 0.025
0.39 0.30
48

47 0.37 0.25 0.023
46 0.35
0.20 0.021
45 0.33
44 0.15
0.31 0.019
43
0.10
0.29
42
0.017
0.27 0.05
41
40 0.25 0.00 0.015
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

0.90 0.090 0.60
0.0014
0.85
0.085

0.0012
0.80 0.55
0.080 0.0010
0.75
0.0008
0.70 0.075 0.50
0.65 0.0006
0.070
0.60 0.0004 0.45
0.065
0.55 0.0002
0.50 0.060 0.0000 0.40

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

1.6 11600 3950
1.5 3900

1.4 11100 3850

1.3 3800
1.2 10600 3750
1.1 3700
1.0 10100 3650
0.9 3600
0.8 9600 3550
0.7 3500
0.6 9100 3450
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Zn unit number Ca Mg unit number

2500 275
2300 270
265
2100
1900 260
255
1700
250
1500
245
1300
240
1100 235
900 230
700 225
500 220
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Na K unit number
59
Shown are the average results after correction for potential analytical trends and standard
deviations of the three replicates of each unit.
30.0 2.5 9.75
29.9 9.7
2.0
29.8
9.65
Ash [g/100 g]
Volatile matter
29.7
GCV [J/g]
1.5
9.6
[g/100 g]
29.6
9.55
29.5 1.0
9.5
29.4
0.5
29.3 9.45
29.2 0.0 9.4

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
GCV vol. matter unit number ash unit number

88.3 0.30 1.10 0.62
88.2 0.61

88.1 0.28 1.08

0.60
88.0
87.9 0.26 1.06 0.59
87.8 0.58
87.7 0.24 1.04 0.57
87.6
0.56
87.5 0.22 1.02
87.4 0.55
87.3 0.20 1.00 0.54

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
C H unit number N S unit number

0.060 1400
2400
1300

0.050
2200
1200
0.040 2000
1100
1800
0.030 1000
1600 900
0.020
1400 800
0.010
1200 700
0.000 1000 600

0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Cl unit number Ca Mg unit number

1000 1400 2.0
0.029
950 1.8
1200

900 1.6
850 1000 1.4 0.024
800
800
1.2
750 1.0 0.019
600 0.8
700
650 400 0.6
0.014
600 0.4
200
550 0.2
500 0 0.0 0.009
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Na K unit number As Cd unit number
60
6 10 0.04
190
9


170 8 0.04
7
4 150
6 0.03
130
3 5
110 4 0.03
2
3
90
2 0.02
1
70
1
0 50 0 0.02
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

90 100 4 1.00
80 90 3.5 0.90


70 0.80
80 3
60 0.70
70 2.5
50 0.60
60 2
40 0.50
50 1.5
30 0.40
40 1 0.30
20
10 30 0.5 0.20
0 20 0 0.10
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

0.6 0.40 0.08 12
0.38 0.07 11
0.5

0.36
0.06
0.34 10
0.4
0.32 0.05
9
0.3 0.30 0.04
8
0.28 0.03
0.2
0.26 7
0.02
0.24
0.1 6
0.22 0.01
0 0.20 0.00 5
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

10
9
8
7
6
5
4
3
2
1
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Zn unit number
61
Homogeneity from long term stability study Homogeneity from long term stability study
ERM-EF413 6
ERM-EF413
1.9 0.018 5.8


1.7 5.6
0.016
5.4
1.5
0.014 5.2
1.3
5
0.012
1.1 4.8
0.010 4.6
0.9
4.4
0.7 0.008
4.2
0.5 0.006 4
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
As Cd unit number Co unit number
ERM-EF413 140
ERM-EF413
20 0.02
18 0.02 130


16 0.01 120
14
0.01
12 110
0.01
10 100
0.01
8 90
0.01
6
0.00 80
4
2 0.00 70
0 0.00 60
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Cu Hg unit number Mn unit number
ERM-EF413 ERM-EF413
6 0.9 1.30
1.20

5.5 0.8
1.10
5 0.7
1.00
4.5 0.6 0.90
0.80
4 0.5
0.70
3.5 0.4
0.60
3 0.3 0.50
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Pb unit number Se Sn unit number
62
0.110
ERM-EF413 23 10
ERM-EF413
22 9.5


0.105
21 9
0.100 20 8.5
19 8
0.095 18 7.5
17 7
0.090
16 6.5
0.085 15 6
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Tl V unit number Zn unit number
2400
ERM-EF413 1200 540
ERM-EF413 1600
2300 1150
520

1500

1100
2200
1050 500
1400
2100 1000
480
2000 950 1300
460
1900 900
1200
850 440
1800
800
420 1100
1700 750
1600 700 400 1000
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Ca Mg unit number Na K unit number
63
Annex B.1: Short-term stability data ERM-EF411
The averages and their 95 % confidence intervals of the four replicates are shown.
Confidence intervals are based on the pooled repeatability standard deviation as obtained by
ANOVA. The data points for the different elements were separated graphically to facilitate
r e a d i ng . N o er r or ba r s c a n b e g i ve n f o r C l , a s a l l r es u l t s we r e i d e n t i c a l.
Short-term stability ERM-EF411 Short-term stability ERM-EF411
29.1 39.0 8.6 72.4

38.5
Volatile matter [g/100 g]
Ash [g/100 g]

29.0 8.4 72.2
38.0
72
28.9 37.5 8.2
GCV [MJ/gg]
37.0 71.8
28.8 8.0
36.5 71.6
28.7 36.0 7.8
71.4
35.5
28.6 7.6 71.2
35.0
28.5 34.5 7.4 71
0 1 2 3 4 5 0 1 2 3 4 5
time [weeks] time [weeks]

GCV Vol. matter Ash C
4.98 1.35 1600 1800

1400 1600

4.96 1.34
1200 1400
4.94 1.33
1200
1000
4.92 1.32 1000
800
4.9 1.31 800
600
600
4.88 1.30
400 400
4.86 1.29 200 200
4.84 1.28 0 0
0 1 2 3 4 5 0 1 2 3 4 5

H N Na K
0.58 0.021 2500 1200

0.57

0.020 2000 1000
0.56
0.019 800
0.55 1500
0.54 0.018 600
0.53 1000
0.017 400
0.52
0.016 500 200
0.51
0.5 0.015 0 0
0 1 2 3 4 5 0 1 2 3 4 5

S Cl Ca Mg
20 0.4 25
18 1.4
0.35
16 1.2 20
0.3
14 1.0
12 0.25 15
10 0.2 0.8
8 0.15 0.6 10
6 0.4
0.1
4 5
2 0.05 0.2
0 0 0.0 0
0 1 2 3 4 5 0 1 2 3 4 5

As Cd Co Cr
64
20 0.12 50 20
18 45 18


16 0.1 40 16
14 0.08 35 14
12 30 12
10 0.06 25 10
8 20 8
6 0.04 15 6
4 0.02 10 4
2 5 2
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Cu Hg Mn Ni
4 2.5 6 0.35
3.5

5 0.3
2
3
0.25
4
2.5 1.5 0.2
2 3
1 0.15
1.5
2
0.1
1
0.5 1
0.5 0.05
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Pb Sb Se Sn
0.6 40 18
35 16

0.5
30 14
0.4 12
25
10
0.3 20
8
15
0.2 6
10 4
0.1
5 2
0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Tl V Zn
65
reading.
25.9 47.8 3.8 66.4

47.6 3.78
Ash [g/100 g]

25.8 66.2
47.4 3.76
66
25.7 47.2 3.74
GCV [MJ/kg]
47 3.72 65.8
25.6
46.8 3.7 65.6
25.5 46.6 3.68
65.4
46.4 3.66
25.4 65.2
46.2 3.64
25.3 46 3.62 65
0 1 2 3 4 5 0 1 2 3 4 5

5.02 0.79 2300 250

5.00

0.78 2250 200
4.98
0.77
2200
4.96 150
0.76
4.94 2150
0.75 100
4.92
2100
0.74
4.90
2050 50
4.88 0.73
4.86 0.72 2000 0

0 1 2 3 4 5 0 1 2 3 4 5

H N Na K
0.285 0.05 10500 4000

0.045 10400 3500

0.28
0.04 10300
3000
0.275 0.035 10200
0.03 10100 2500
0.27
0.025 10000 2000
0.265 0.02 9900 1500
0.26 0.015 9800
1000
0.01 9700
0.255 500
0.005 9600
0.25 0 9500 0
0 1 2 3 4 5 0 1 2 3 4 5

S Cl Ca Mg
0.35 0.014 0.094 0.6

0.3 0.012 0.092 0.5

0.25 0.01 0.09
0.4
0.2 0.008 0.088
0.3
0.15 0.006 0.086
0.2
0.1 0.004 0.084
0.05 0.002 0.082 0.1
0 0 0.08 0
0 1 2 3 4 5 0 1 2 3 4 5

As Cd Co Cr
66
0.52 0.09 70 0.4

0.51 0.08 0.35


60
0.5 0.07 0.3
0.49 50
0.06
0.48 0.25
0.05 40
0.47 0.2
0.04 30
0.46 0.15
0.45 0.03
20
0.02 0.1
0.44
0.01 10 0.05
0.43
0.42 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Cu Hg Mn Ni
0.35 0.03 1.4 0.08

0.07

0.3 0.025 1.2
0.06
0.25 1
0.02
0.05
0.2 0.8
0.015 0.04
0.15 0.6
0.03
0.01
0.1 0.4
0.02
0.05 0.005 0.2 0.01
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Pb Sb Se Sn
0.0016 0.7 1.2

0.0014

0.6 1
0.0012
0.5
0.8
0.001
0.4
0.0008 0.6
0.3
0.0006
0.4
0.2
0.0004
0.1 0.2
0.0002
0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Tl V Zn
67
reading.
30.15 1.70 9.9 88.8

30.1 9.85 88.6
Ash [g/100 g]

1.65
9.8
30.05 88.4
1.60 9.75
30
GCV [MJ/kg]
9.7 88.2
29.95 1.55 9.65
88.0
29.9 1.50 9.6
9.55 87.8
29.85
1.45 9.5
29.8 87.6
9.45
29.75 1.40 87.4
9.4
29.7 1.35 9.35 87.2
0 1 2 3 4 5 0 1 2 3 4 5

0.3 1.12 0.565 0.06

1.11 0.56

0.25 1.1 0.05
0.555
1.09
0.2 1.08 0.55 0.04
1.07 0.545
0.15 0.03
1.06 0.54
0.1 1.05 0.535 0.02
1.04
0.53
0.05 1.03 0.01
1.02 0.525
0 1.01 0.52 0
0 1 2 3 4 5 0 1 2 3 4 5

H N S Cl
2500 1200 350 900

800

1000 300
2000 700
250
800 600
1500 200 500
600
150 400
1000
400 300
100
500 200
200 50 100
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Ca Mg Na K
1.4 0.025 4.5 90

4 80
1.2
0.02 3.5 70
1
3 60
0.8 0.015
2.5 50
0.6 2 40
0.01
1.5 30
0.4
0.005 1 20
0.2 0.5 10
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

As Cd Co Cr
68
9 0.035 120 40
8 35


0.03 100
7 30
0.025
6 80
25
5 0.02
60 20
4 0.015
15
3 40
0.01
2 10
0.005 20
1 5
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Cu Hg Mn Ni
4 0.6 0.45 0.3

3.5 0.4

0.5 0.25
3 0.35
0.4 0.3 0.2
2.5
0.25
2 0.3 0.15
0.2
1.5
0.2 0.15 0.1
1 0.1
0.1 0.05
0.5 0.05
0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5

Pb Sb Se Sn
16 0.07 10
14 9

0.06
12 8
10 0.05 7
8 0.04 6
6 5
4 0.03 4
2 0.02 3
0 2
0.01
-2 0 1 2 3 4 5 1
-4 0 0
0 1 2 3 4 5

Zn Tl V
69
Annex C.1 Long-term stability data ERM-EF411
Shown are the averages their 95 % confidence intervals of the eight replicates for each time
point. Confidence intervals are based on the pooled repeatability standard deviation as
obtained by ANOVA. The points for the different elements were separated graphically to
facilitate reading. No error bars are given for Cl as all results were identical.
Long-term stability ERM-EF411 Long-term stability ERM-EF411
29.2 39 8.6 72.4

29.15 38.5
Ash [g/100 g]

8.4 72.2
29.1 38
29.05 72
37.5 8.2
29
GCV [MJ/kg]
37 71.8
28.95 8
36.5 71.6
28.9
28.85 36 7.8
71.4
28.8 35.5
7.6 71.2
28.75 35
28.7 34.5 7.4 71
0 5 10 15 20 25 0 5 10 15 20 25
time months] time [weeks]

4.98 1.35 0.58


4.96 1.34 0.57 0.022
0.56
4.94 1.33
0.55 0.017
4.92 1.32
0.54
4.9 1.31 0.012
0.53
4.88 1.3
0.52
0.007
4.86 1.29 0.51
4.84 1.28 0.5 0.002
0 5 10 15 20 25 0 5 10 15 20 25
time [months] time [months]

H N S Cl
2500 1200 1600 2000

1800

1400
2000 1000 1600

1200
800 1400
1500 1000 1200
600 800 1000
1000 600 800
400 600
400
500 200 400
200 200
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Ca Mg Na K
20 0.4 20 25
18 18
0.35
16 16 20
0.3
14 14
12 0.25 12 15
10 0.2 10
8 0.15 8 10
6 6
0.1
4 4 5
2 0.05 2
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

As Cd Co Cr
70
20 0.12 50 20
18 45 18


16 0.1 40 16
14 0.08 35 14
12 30 12
10 0.06 25 10
8 20 8
6 0.04 15 6
4 0.02 10 4
2 5 2
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Cu Hg Mn Ni
4 2.5 6 0.35

3.5

5 0.3
2
3
0.25
4
2.5 1.5 0.2
2 3
1 0.15
1.5
2
0.1
1
0.5 1
0.5 0.05
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25
time [weeks] time [months]

Pb Sb Se Sn
0.6 40 18
16
35
0.5
30 14
0.4 12
25
10
0.3 20
8
15
0.2 6
10 4
0.1
5 2
0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Tl V Zn
71
facilitate reading.
26.2 50.5 4.04 68

GCV [MJ/kg]
Volatilematter [g/100 g]
Ash [g/100 g]

50.4 4.02 67.8
26.1
50.3 4
67.6
26.0 50.2 3.98
67.4
50.1 3.96
25.9 67.2
50 3.94
67
49.9 3.92
25.8
49.8 3.9 66.8
25.7 49.7 3.88 66.6

0 5 10 15 20 25 0 5 10 15 20 25
time [weeks] time [months]

4.86 1.18 0.53 0.06

4.84

1.16 0.525
4.82 0.05
1.14
4.8 0.52
0.04
4.78 1.12
0.515
4.76 1.1 0.03
4.74 0.51
1.08
4.72 0.02
0.505
1.06
4.7 0.01
1.04 0.5
4.68
4.66 1.02 0.495 0
0 5 10 15 20 25 0 5 10 15 20 25

H N S Cl
10100 4000 2300 2000

10000 1800

3500
2250
9900 1600
3000
9800 2200 1400
9700 2500 1200
9600 2000 2150 1000
9500 1500 800
9400 2100 600
1000
9300 2050 400
9200 500 200
9100 0 2000 0
0 5 10 15 20 25 0 5 10 15 20 25

Ca Mg Na K
0.35 0.016 0.096 0.6

0.014
0.3 0.094 0.5

0.012
0.25
0.092 0.4
0.01
0.2
0.008 0.09 0.3
0.15
0.006
0.088 0.2
0.1
0.004
0.05 0.086 0.1
0.002
0 0 0.084 0
0 5 10 15 20 25 0 5 10 15 20 25
time [months] time month]

As Cd Co Cr
72
0.53 0.08 70 0.4

0.52

0.07 0.35

60
0.51
0.06 0.3
0.5 50
0.49 0.05 0.25
40
0.48 0.04 0.2
0.47 30
0.03 0.15
0.46 20
0.02 0.1
0.45
0.01 10 0.05
0.44
0.43 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Cu Hg Mn Ni
0.35 0.025 1.4 0.08

0.07

0.3 1.2
0.02
0.06
0.25 1
0.015 0.05
0.2 0.8
0.04
0.15 0.01 0.6
0.03
0.1 0.4
0.02
0.005
0.05 0.2 0.01
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Pb Sb Se Sn
0.7 1.2
0.6 1
0.5
0.8
0.4
0.6
0.3
0.4
0.2
0.1 0.2
0 0
0 5 10 15 20 25 0 5 10 15 20 25

V Zn
73
facilitate reading.
29.95 1.2 9.8 92.5

29.9
GCV [MJ/g]
Volatilematter [g/100 g]
Ash [g/100 g]

1 9.75 92
29.85
91.5
29.8 0.8 9.7
29.75 91
0.6 9.65
29.7 90.5
29.65 0.4 9.6
90
29.6
0.2 9.55 89.5
29.55
29.5 0 9.5 89
0 5 10 15 20 25 0 5 10 15 20 25

1.2 1.5 0.8 0.06


0.7
1 1.45 0.05
0.6
0.8 0.04
1.4 0.5
0.6 0.4 0.03
1.35 0.3
0.4 0.02
0.2
0.2 1.3 0.01
0.1
0 1.25 0 0
0 5 10 15 20 25 0 5 10 15 20 25

H N S Cl
3000 1400 600 2000

1800

2500 1200 500 1600

1000 1400
2000 400
800 1200
1500 300 1000
600 800
1000 200 600
400
500 100 400
200
200
0 0 0 0
0 5 10 15 20 25 0 5 10 15 20 25

Ca Mg Na K
2.5 0.020 6 35
0.018
5.5
30
2.0 0.016
5
0.014 25
1.5 0.012 4.5
20
0.010 4
1.0 0.008 15
3.5
0.006 10
3
0.5 0.004
2.5 5
0.002
0.0 0.000 2 0
0 5 10 15 20 25 0 5 10 15 20 25

As Cd Co Cu
74
0.02 140 5.8 0.80

5.6


120 0.78
0.015 5.4
100 0.76
5.2
80 5.0 0.74
0.01
60 4.8 0.72
4.6
40 0.70
0.005 4.4
20 4.2 0.68
0 0 4.0 0.66
0 5 10 15 20 25 0 5 10 15 20 25

Hg Mn Pb Se
2.5 0.3 21.4 8.9

21.3

0.25 8.8

21.2
0.2 8.7
1.5 21.1
0.15 21.0 8.6
1
0.1 20.9 8.5
0.5 20.8
0.05 8.4
0 20.7
0 8.3
0 5 10 15 20 25 20.6
-0.5 -0.05 8.2
20.5
-1 -0.1 20.4 8.1
0 5 10 15 20 25

Sn Tl V Zn
75
Annex D.1: Methods used for determination of proximates: Grinding and
free moisture
Information given is the text as provided by the laboratories.
Grinding Free moisture
Lab
Method/equipment Checked by Method/equipment
vibratory mill VM4, 0.2 mm Air
L01 105°C (EF411, EF412)
150°C (EF413)
L02 no information given
HOLMES Pulverizer 500 DG, screen test Nitrogen/air
L03
212 µm 37 °C
Fritsch Pulverisette rotor mill, Laser diffraction Air, 22 °C
L05
210 m
L06 Laboratory ball mill, 250 µm Nitrogen 35 °C
L07 Planetary ball mill, < 212 µm air jet sieving
HOLMES Pulverizer- 350, 250 Nitrogen 40 °C
L08
µm
L09 Ball mill, < 200 µm sieving Nitrogen 30 °C
L10 Ball mill, < 212 µm sieving Oxygen 40 °C
Vibratory disc mill, 99,5 % < 200 air jet sieving Air, 40 °C
L11
µm
laboratory mill RETSCH ZM100, sieving apparatus Air, 105 °C (EF411), 200 °C
L12 212 µm "FRITSCH analysette 3 (EF413)
PRO", screen - mesh
diameter 0,212 µm
Vibratory disc mill, 99,5 % < air jet sieving Air; 4 h 38 °C
L13
200 µm
Herzog HSM 100-P grinding Air, 35 °C
L14
mill, < 200 µm
76
Annex D.1: Methods used for determination of proximates: moisture in the analytical
sample and ash
Information given is the text as provided by the laboratories. latest QC date of the latest
quality control chart test before the measurements of this study
Moisture in the analytical sample Ash
Lab
Method/equipment Latest QC. Method/equipment Latest QC.
ČSN 44 1377 19.1.2011 ISO 1171, one oven 12.5.2010
L01 drying FED 53 muffle furnace MP 05

ISO 11722/5068-2 /687 26.6.2011/ ISO 1171, two ovens OAF
Carbolite MSF/ WTW Binder 26.4.2011 Carbolite OAF and AAF 1.12.2011
L03
AAF
1.5.2011
ÖNORM G 1074/D/06-04 11/2011 ÖNORM G 1074 (eq. ISO 11/2011
L04 Leco TGA 601 1171), one oven
Leco TGA 701
ASTM D5142 28/6/2011 ASTM D5142, ISO 1171, 28.6.2011
Las Navas Instruments, TGA- one oven
L05 2000 Las Navas Insruments
TGA-2000 (ASTM D5142),
Lenton (ISO 1171)
TGA eq. to ASTM D7582-10 9/2011 ASTM D7582-10, one oven 9/2011
L06
LECO-TGA701 LECO-TGA701
ISO 11722/5068-2 /687 ISO 1171, two ovens
L07 Sartorius Balance / Heraeus Sartorius Balance / Heraeus
Drying oven Muffle Furnance
BS 1016-104.1 (eq. ISO 14.12.201 ISO 1171, 2 ovens 20.12.201
L08 11722) 1 "Carbolite" AAF 11/18 1
"Carbolite" MFS/1
ISO 5068-2 / ISO 11722 / ISO Thermoco ISO 1171, one oven Thermo
687 uple Heraeus Oven M110 couple
L09 Carbolite Oven before before
measurem measurem
ent ent
Standard M03-037 Method C daily NF 03-003 daily
L10
Mettler LP16 Carbolite CWF 1200
TGA eq. to ISO 5068-2 23.11.201 ISO 1171, one oven 23.11.201
L11
Leco TGA 501 1 Leco TGA 501 1
ČSN 44 1377, 105 °C (EF411),
26.9.2011; ISO 1171, one oven 27.9.2011
ČSN ISO 687, 135 (EF413) monthly Carbolite
L12
BMT oven internal
check
TGA eqw. to ÖNORM G 1074 18.8.2011 ÖNORM G 1074 (eq. ISO 18.8.2011
L13 Verfahren D 1171), one oven
Leco TGA 701 Leco TGA 701
ISO 11772, one oven 17-11- ISO 1171, one oven 17.11.201
Carbolite NFS1 2010; Carbolite OAF 10/1 0; latest
latest internal
L14
internal check
check 8.11.2011
8.11.2011
77
Annex D.1: Methods used for determination of proximates: Volatile matter and GCV
Information given is the text as provided by the laboratories. latest QC: date of the latest
Volatile matter GCV
Lab
Method/equipment Latest QC Method/equipment Latest QC
ISO 5071-1, 2 ovens (EF412) 12.5.2010 ISO 1928, automated 16.9.2010
ISO 562, 1 oven (EF411, LECO AC 500
L01
EF413)
muffle furnace MP 05
L01 ISO 562; no method information given
ISO 562 (EF411, EF413), 2 1.5.2011 ISO 1928, automated 17/18.10.
ovens IKA C5000 2011
L03
ISO 5071 (EF412), two ovens
Carbolite VMF
DIN 51720 (eq, ISO 562), 1 10/2011 DIN 51900-3 (2005-01) 10/2011
oven (eq. ISO 1928), semi-
L04
Muffelofen Hereus M110 automatic
IKA C5003
ISO 562, one oven 28.6.2011 ISO 1928, automated 1.11.
L05 Nabertherm IKA C5000 duo 2011
No nitrogen correction
TGA equivalent to ASTM 9/2011 ASTM D5865-10, 9/2011
L06 D7582-10, one oven automated
LECO-TGA701 LECO-AC500
ISO 562 (EF411, EF413), two ISO 1928, automated
ovens IKA Calorimeter System
L07 ISO 5071 (EF412), two ovens
Sartorius Balance / Carbolite
Muffle Oven
ISO 562, 2 ovens 14.12. ISO 1928, automated Benzoic
"Carbolite" VMF 10/6 2011 Parr 6300 acid, every
L08
7 working
days
ISO 562 / ISO 5071, one oven before ISO 1928, automated 2/12/2011
L09 Heraeus Oven M110 measurem IKA C 5003
ent
ASTM D3175_07 ISO 1928, automated daily
L10 Carbolite CWF 1200 IKA C5003 (EF413) / Parr
6300 (EF411, EF412)
TGA eq. to ISO 5071 (EF412); 23.11.201 ISO 1928, automated 12.12.2011
L11 ISO 562 (EF411, EF413) 1 IKA Kalorimeter C 5000
Leco TGA 501
ISO 562,one oven 27.9.2011; ISO 1928, automated 27.9.2011
L12 laboratory oven Martínek monthly IKA C5000
check
TGA eq. to ÖNORM G 1074 18.8.2011 DIN 51900 Teil 3 (eq. ISO 13.12.2011
Verfahren I (eq. ISO562/ISO 1928)
L13
5071), one oven IKA Kalorimeter C 5000
Leco TGA 701
ISO 562, one oven 17.11.201 ISO 1928, partially SRM 39i
Carbolite VMF 10/15 0; latest automated (benzoic
L14 internal IKA C5000 acid) on
check 23.11.2011
8.11.2011
78
Annex D.1: Methods used for determination of proximates: C and H
Lab Carbon Hydrogen
Method/equipment Latest QC Method/equipment Latest QC
L01 ISO/TS 12902 12.5.2010 ISO/TS 12902 12.5.2010
LECO TruSpec LECO TruSpec

L03 ISO 29541 22.11.201 ISO 29541 22.11.201
LECO Truspec CHN-S 1 LECO Truspec CHN-S 1
L04 DIN 51732 (eq. ISO 29541) 17.11. DIN 51732 (eq. ISO 29541) 17.11.
Flash EA 1112 2011 Flash EA 1112 2011
L05 ASTM D5373 daily with ASTM D5373 daily with
Elementar Variomax CHN phenylala Elementar Variomax CHN phenylala
nine nine
L06 ASTM D5373-08 9/2011
ASTM D5373-08 9/2011
LECO-Truspec CHN LECO-Truspec CHN
L07 ISO 29541 daily drift ISO 29541 Daily Drift
LECO TrueSpec calibration LECO TrueSpec Calibration
L08 ASTM D 5373 daily ASTM D5373 daily
ELTRA CHS-500 ; ELTRA ELTRA CHS-500 ; ELTRA
CHS-580 CHS-580
L09 ISO 29541 daily ISO 29541 daily
CE Instruments EA 1108 (now CE Instruments EA 1108
Thermo Scientific) (now Thermo Scientific)
L10 ISO/TS 12902 daily ISO TS 12902 daily
Elementar Vario EL III Elementar Vario EL III
L11 ISO 29541 23.11. ISO 29541 23.11.
Leco Truespec CHN 2011 Leco Truespec CHN 2011
L12 ASTM D 5373 – 08 26.9.2011 ASTM D5373 – 08 26.9.
LECO TruSpec CHN LECO TruSpec CHN 2011
L13 DIN 51732 (eq. ISO 29541) 14.12. DIN 51732 (eq. ISO 29541) 14.12.
Leco Truspec CHN-Analysator 2011 Leco Truspec CHN- 2011
Analysator
L14 In house method: Combustion 21.02.201 In house method: 21.02.
oven in combination with GC 1. Combustion oven in 2011.
and TCD detector Correction combination with GC and Correction
Costech ECS 4010 with a TCD detector with a
CRM Costech ECS 4010 CRM
(ASCRM- (ASCRM-
013-8) in 013-8) in
every run every run
79
Annex D.1: Methods used for determination of proximates: N and S
Lab Nitrogen Sulfur
cod Method/equipment Latest QC Method/equipment Latest QC
e
L01 ISO/TS 12902 12.5.2010 CSN 441395 (eq. ISO 12.5.2.10
LECO TruSpec 19579)
LECO SC 144DR
L03 ISO 29541 22.11.2011 ISO 19579 28.9.2011/3
LECO Truspec CHN-S LECO Truspec CHN-S 0.11.2011
L04 DIN 51732 (eq. ISO 29541) 17/11/2011 DIN 51724-3 (eq. ISO 14.12.2011
Flash EA 1112 19579)
Leco SC144 DR
L05 ASTM D5373 with ASTM D4239 (IR-detection, 25.10.11
Elementar Variomax CHN phenylalani method B) adjustment
ne each day Eltra CS 2000
of operation
L06 ASTM D5373-08 9/2011 ASTM D4239 9/2011
LECO-Truspec CHN LECO-Truspec S
L07 ISO 29541 Daily Drift ISO 19579 Daily Drift
LECO TrueSpec Calibration LECO SC632 Calibration
L08 ISO 333 Checked ASTM D4239 daily
InKjel P digestion apparatus - twice a ELTRA CHS-500 ; ELTRA
"behrotest InKjel P" ; month - CHS-580
behr S 4 fully automatic samples of
steam distillation apparatus "Round
Robin"
LQSI test
program
L09 ISO 29541 daily ISO 351 daily
CE Instruments EA 1108 Titration against BaClO4
(now Thermo Scientific)
L10 ISO TS 12902 daily M03-038 Method B
Elementar Vario EL III Sylab IRS 2000 (infrared
sulfur)
L11 ISO 29541 23.11.2011 ISO 19579 23.11.2011
Leco Truespec CHN Leco SC 144
L12 ASTM D 5373 – 08 26.9.2011 ASTM D 4239 26.9.2011
LECO TruSpec CHN LECO TruSpec S
L13 DIN 51732 (eq. ISO 29541) 14.12.2011 ÖNORM G 1071 (eq. ISO 14.12.2011
Leco Truspec CHN- 19579)
Analysator Leco Truspec Sulfur Add-
On Module
L14 In house method: 21.02.2011. XRF in-house method 18.11.2011
Combustion oven in Correction Axios Panalytical in (half-yearly)
combination with GC and with a CRM combination with Uniquant
TCD detector (ASCRM- 5 callibration software
Costech ECS 4010 013-8) in
every run
80
Annex D.1: Methods used for determination of proximates: Cl and F
Lab Chlorine Fluorine
Method/equipment Latest q.c. Method/equipment Latest q.c.
L01 Turbo Quant – pellets 8/2011 not tested
Spectro Xepos – XRF
8/2011 calibration by Spectro
L02 No information given No information given
L03 Ion - Chromatography In- 24.10.201 Eq. ISO 11724 24.10.201
house method 1 TOX-100 Metrohm IC 1
TOX-100 Metrohm IC
L04 DIN 51727 (ion 30/11/201 QI B4P-4 402: 30/11/201
chromatography) 1 porrohydrolysis – IC 1
Pyrrohydrolysis with Automatic Pyrrohydrolysis with
Quick Furnace AQF-100 , IC Automatic Quick Furnace
with Dionex ICS 3000 AQF-100 , IC with Dionex
ICS 3000
L05 Ion chromatography from 25/06/201 Ion chromatography from 25/06/201
bomb calorimeter water, ISO 1 bomb calorimeter water, 1
10304 ISO 10304
Dionex DX-120 Dionex DX-120
L07 ASTM 4208 (eq. ISO 11724) ISO 11724
IKA Calorimeter System / Prüfer - Tube combustion
DIONEX DX 600 / DIONEX furnance / DIONEX DX 600
ICS 2000 / DIONEX ICS 2000
L08 ASTM D 4208 Checked not tested
For range: 220 - 2100 ppm - twice a
48.4 + 0.13 x X, where X - month -
average result samples
Parr 6300 ; Chloride Ion of "Round
Selective Electrode - "pHoenix Robin"
Co" - "Consort". LQSI test
program
L10 M03-009 daily not tested
Mettler Titrator DL21
L11 ASTM D4208 12.12.201 ASTM D4208 12.12.201
IKA Kalorimeter C 5000, IC 1 IKA Kalorimeter C 5000, IC 1
system Dionex ICS-90; system Dionex ICS-90;
L13 Analog ÖNORM G1075 (eq. 15.12.201 Analog ÖNORM G 1075 15.12.201
ISO 10304-1) 1 (eq. ISO 10304-1) 1
DIONEX ICS-2000 DIONEX ICS-2000
L14 XRF in-house method 18.11.201 not tested
Axios Panalytical in 1 (half-
combination with Uniquant 5 yearly)
callibration software
L15, k0NAA and INAA: See Annex not tested
L18, D2
L19,
L20
L22
81
Annex D2: Methods used for the determination of trace elements
Information given is the text as provided by the laboratories.
Lab Sample preparation Analytical technique Calibration
L03 Sample intake: 200 mg ICP-MS according ASTM D6357 Multilelement standard from Inorganic
Minor elements except Hg: Open Ventures; 3 point line
destruction of the ash with 20 ml HF Hg: LECO AMA-254 mercury analyser Internal standard: Rh
/ 5 ml HNO3 / 15 ml HCl. The result (ASTM D6722 Calibration confirmed with NIST SRM 1633b
is dissolved in 50 ml water with
HNO3. Sample diluted 20x and
internal standard added. Select ICRM Coal 2008-2 // Nist SRM 1568a
Na, Mg, Na, K: ashing with

subsequent fusion with Li2B4O7
Hg: none
L07 Sample intake: 400 mg ICP-MS (trace elements): ICP-MS Multilelement standard from High Purity
Closed Microwave (Anton Paar Thermo Xseries 2; dilution 1:10 Standards;
Multiwave 3000) 4 point line
10 mL HNO3/ 2 mL HF Ca, Mg, Na, K: ICP-OES Perkin Elmer Internal standard: Rh
90 min/60 bar/200-240 °C Optima 3000XL; dilution 1:5 Calibration confirmed with NIST SRM 1633b
Subsequent addition of H3BO3
L13 Sample intake: 200 mg As, Se: HGAAS; FIAS400+AAS5100 External calibration prepared in an acid
Closed Microwave (Anton Paar Perlin Elmer mixture of the same concentration
GmbH; Multiwave 3000) Hg: CVAAS; FIMS , Perkin Elmer
8 mL HNO3 /1 mL HCl/1 mL others: ICO-OES, Varian VISTA MPX Multielement standards Merck;
30 min/60 bar/200-240 °C CCD, axial 3 points calibration curve; traceability via
NIST STM 3149
Subsequent addition of 10 mL
saturated H3BO3; 10 min/50
bar/240 °C
L15 Sample intake: 200 mg INAA Calibration: holistic single comparator method
with many calibration samples used in the
Irradiation: 10 s irradiation at 1.82*1013 past (mostly NIST certified solutions and
neutrons/cm3/s followed by 2 h at reference materials)
4.95*1012 neutrons/cm3/s
Decay time: 10 min, 5 d and 21 d

Detector 10 min and 5 d: HPGe 2 x
planar
Detector 21 d: HPGe well-type
Quantification via all γ-lines; blank from

empty HDPE capsule
L16a Sample intake: 500 mg Na, K, Ca, Mg: ICP-AES Perkin-elmer As, Cr, Cu, Ni, Pb, Se, V, Zn: multielement
High Pressure Asher (Anton Paar) 3000 DV standard Spex; traceability via NIST SRM
90 min /100 bar/240 °C (twice) 3149a;
Step1 : 3 mL HNO3 +1 mL HCl Step Others: SF-ICP-MS (high resolution) Mn,
2 : 1 mL HNO3
L16b Sample intake: 250 mg Ca, Mg, Na, K, Mn: ICP-AES ICP-AES Spex Certiprep monoelement standards
Closed Microwave (Milstone mls Perkin-Elmer Optima 3000 DV; verified against NIST SRMs 3109a (Ca),
1200 Mega) Ca; Mg; Na and K measured radial, Mn 3131a (Mg), 3152a (Na), 3141a (K)
Step 1: 2 mL HF + 3 mL HNO3 + 1 axial Multielement standard CPI verified against
ml HCL; left overnight; then 19 min NIST SRM3100 series (Mn)
in the microwave Hg: cold vapor-atomic fluorescence
Step 2: addition of 1 mL HNO3; 19 spectrometry (CVAFS)
min in the microwave
Step 3: addition of 22 mL HBO3 and
3 min in the microwave
Dilution gravimetrically to 50 mL
83
L17 Sample intake 200 mg As, Cd, Cr, Co, Cu, Hg, Mn, Ni, Pb, Tl, V, As, Cd, Cr, Cu., Mn, Ni, Pb, Tl, V, Zn,
Digestion : Closed microwave (Anton Zn, Ca, Mg, Na, K: ICP-MS Multielement standards from Teknolab AB
Paar Multiwave 300) verified against NIST SRMs
8 mL HNO3/2 mL HF/1 mL H2O2 Hg: CV-AAS with NaBH4/HCl
200 °C/60 bar/70 min Hg, Ca, Mg, Na, K: Multielement standards
dilution to 50 mL from Teknolab AB verified against NIST
SRMs
L18 Sample intake: 100-150 mg k0NAA Mn, V, Mg, Cl: Flux monitor: NIST 3121
Mn, V, Mg, Cl: irradiation for 1.5 min with
about 2 *1013 neutrons/cm3/s As, Co, Cr, Sb, Se, Zn, Ca, Na, K: Flux
monitor: IRMM 530-RC
As, Co, Cr, Sb, Se, Zn, Ca, Na, K: Blank via empty capsule
irradiation for 720 min at about 6*1012
neutrons/cm3/s Detector: Ortec GEM
25% P-type high purity germanium
Quantification using single γ-lines
L19 Sample intake: 30 mg (Hg); 250 mg Hg: DMA (Milestone Sr): controlled Hg: Single element standard HACH LANGE
(NAA) combustion at 650-750 °C; quantification GmbH verified against NIST SRM
by AAS
Flux monitor: Al-Au0.1% alloy (IRMM-530R)
As, Co, Cr, Sb, Se, V, Zn, Ca, Na, K:
k0NAA Blank: SPRONK system (pure polyethylene
Irradiation for 1080 min at 1.1*1012 ampoule)
neutrons/cm3/s
HPGe coaxial detector (40 and 45%)
Mn, V, Mg, Cl: k0NAA

Irradiation for 5 min at 1.1*1012
neutrons/cm3/s
HPGe coaxial detector (40 and 45%)
84
L20 Sample intake: 200 mg ICP-SFMS with mass resolutions of 300 Multielement standards Ultra Scientific
Digestion: closed microwave (CEM (Cd, Hg, Pb, Sb, Sn, Tl), 3400 (Cr, Cu, traceable via NIST SRM 31xx series
MARS 5) Ni, V, Zn, Ca, Mg, Na) and 12000 (As, Internal standard: In
5ml HNO3+0.5 ml H2O2+0.1 ml HF Se, K)
> 140 bar
Dilution with 1.4 M HNO3
L21 Sample intake: 200 mg ICP-MS Multielement standards Perkin Elmer
Digestion: Closed microwave Mass resolution for all elements: 300 traceable via NIST 31xx series
(Milestone ultraClave IV) 1 isotope per element Internal standards: Li, Sc, Y, In, Tb, Lu, Bi
4 mL HNO3 + 0.1 mL HCl
250 °C/160 bar/60 min
Dilution to 10 mL
L22 Sample intake: 200-500 mg k0NAA Flux monitor: IRMM 530-R
Mn, V, Mg, Cl: irradiation for 10 min with Blank via empty capsule
about 2 *1011 neutrons/cm3/s – decay of
5 and 30 min. QC via several IRMM CRM’s
As, Co, Cr, Sb, Se, Zn, Ca, Na, K:

irradiation for 7 h at about 3*1011
neutrons/cm3/s - decay of 1-2 days and
21 days
85
Annex E.1: Results obtained in the characterisation study for ERM-EF411. The graphs give the average results and the expanded
uncertainties estimated as two times the standard deviation from the control chart (proximates) or as stated by the laboratories (elements). An asterisk after the method means
that two times the standard deviation of the results from the characterisation exercise was used as measurement uncertainty. The solid red lines give the certified range, the
dashed red lines the indicative range. Shaded results are results not accepted on technical grounds.
ERM-EF411-GCV (ISO 1928/ASTM D5865) in MJ/kg (certified value)

Lab Results
L1 28.599 28.635 28.855 28.789 28.959 28.972 ERM-EF411-GCV (ISO 1928/ASTM D5865)
L3 29.145 29.142 29.327 29.256 29.316 29.226 29.6
L5 29.018 28.979 29.082 29.132 29.158 29.146 29.4
29.2
L6 29.01 29 28.809 28.952 28.776 28.834
GCV [MJ/kg]
29.0
L8 29.34 29.32 29.26 29.3 29.25 29.3 28.8
L9 28.83 28.72 28.78 28.87 28.84 28.94 28.6
L11 28.98 28.95 28.92 28.9 28.96 28.99 28.4
L13 28.84 28.84 29.01 28.98 29.07 29.09 28.2
L14 28.911 28.93 28.99 28.991 29.036 29.023 28.0
L9-ISO 1928*
L11-ISO 1928*
L7-ISO 1928*
L10-NF ISO 1928*
L1-ISO 1928
L5-ISO 1928
L6-ASTM D5865-10
L8-ISO 1928
L13-Eq. ISO 1928

L14-ISO 1928
L12-ČSN ISO 1928

L4-eq. ISO 1928*
L3-ISO 1928
Results not accepted on technical grounds
L4 29.17 29.139 29.063 29.075 29.278 29.297
L7 29.24 29.23 29.259 29.147 29.298 29.239
L10 28.809 28.849 28.927 28.941 28.891 29.009
L12 28.88 28.88 28.88 28.81 28.8 28.74
ERM-EF411- NCV (ISO 1928/ASTM D5865) in MJ/kg (certified value)

Lab Results ERM-EF411 - Net calorific value
L3 28.161 28.157 28.319 28.248 28.304 28.213 28.6
L5 28.056 28.017 28.11 28.16 28.185 28.173 28.4
28.2
L6 27.761 27.72 27.56 27.693 27.522 27.572
NCV [MJ/kg]
28.0
L8 28.436 28.424 28.366 28.398 28.353 28.39 27.8
L9 27.83 27.82 27.88 27.93 27.78 27.88 27.6
L11 27.87 27.84 27.82 27.81 27.86 27.88 27.4
27.2
L13 27.82 27.83 27.98 27.94 28.04 28.06 27.0
L14 27.927 27.944 28.01 27.996 28.052 28.026
L6-ASTM D5865-10*
L4-DIN 51900-3eq.
L3-ISO 1928*
L5-ISO 1928*
L8-ISO 1928*
L9-ISO 1928*
L11-ISO 1928*
L13-ISO 1928*
L14-ISO 1928*
L7-ISO 1928*
L10-ISO 1928*
ISO 1928*
L4 28.155 28.147 28.034 28.044 28.258 28.272
L7 28.248 28.238 28.275 28.162 28.308 28.249
L10 27.974 27.955 28.03 28.044 27.995 28.052
86
ERM-EF411-Volatile matter (ISO 562) in g/100 g (certified value )
Lab Results ERM-EF411-Volatile matter (ISO 562)
L1 37.47 37.62 37.52 37.47 37.75 37.74 42.0
L3 38.649 38.076 38.126 38.261 39.069 38.809 41.0
L4 38.72 38.55 38.46 38.6 38.07 37.97
Mass fraction [g/100 g]

40.0
L5 37.636 37.604 38.084 38.047 38.153 38.17 39.0
L7 38.08 38.04 37.66 37.77 37.85 37.86 38.0
L9 37.95 37.972 38.311 38.168 38.402 38.254
37.0
L12 38.01 38.15 38.33 37.96 37.9 37.94
36.0
L14 38.102 37.848 37.918 38.241 38.103 38.538
35.0
L1- ISO 562
L3-ISO 562*
L4-eq. ISO 562*
L7-ISO 562*
L9-ISO 562*
L2-ISO 562*
L11-ISO 562*
L13-eq ISO 562*

L5-ISO 562
L12-ISO 562
L14-ISO 562
L8-ISO 562
L2 38.84 39.08 39.23 39.27
L8 38.316 38.11 37.983 37.804 37.752 37.811
L11 38.9 39 39.1 39.3 36.5 39.6
L13 40.3 40.2 40.3 40.2 39.9 40.2
ERM-EF411 - Ash (ISO 1171/ASTM D3174/ASTM D5142) in g/100 g (certified value)

L1 9.15 9.17 8.55 8.58 8.43 8.44 42.0
L3 8.005 8.036 7.541 7.564 7.711 7.753
41.0
L4 8.284 8.318 8.378 8.376 8.029 8.06

L5-ISO 8.693 8.539 8.32 8.313 8.176 8.164 40.0
L5- 39.0
ASTM 8.505 8.622 8.297 8.332 8.163 8.163 38.0
L7 8.39 8.34 8.38 8.38 8.24 8.27
37.0
L9 8.8 8.756 8.354 8.398 8.419 8.056
36.0
L10 8.3 8.4 8.4 8.4 8.4 8.4
L12 7.96 7.9 7.95 7.87 8.13 8.15 35.0
L13-eq ISO 562*

L1- ISO 562
L5-ISO 562
L12-ISO 562
L14-ISO 562
L8-ISO 562
L3-ISO 562*
L4-eq. ISO 562*
L7-ISO 562*
L9-ISO 562*
L2-ISO 562*
L11-ISO 562*
L14 8.4 8.392 8.243 8.261 8.144 8.141

L2 8.11 8.19 8.3 7.95 8.03 8.12
L6 8.19 8.31 8.53 8.57 8.47 8.58
L8 8.766 8.682 8.697 8.716 8.653 8.701
L11 8.22 8.15 8.35 8.25 8.21 8.16
L13 8.57 8.6 8.27 8.26 8 8.07
87
ERM-EF411 - Carbon (C) (ISO 29541, ISO/TS12902 ASTM D5373) in g/100 g (certified value)
Lab Results
ERM-EF411 - Carbon (C) (ISO 29541, ISO/TS12902 ASTM
L1 71.23 70.79 72.08 71.82 72.11 72.17 D5373)
L4 71.43 71.39 70.84 70.81 71.56 71.47 74.0
L5 71.573 71.407 71.683 71.621 71.781 71.75 73.0
L6 71.72 71.6 71.87 71.83 71.75 71.98

72.0
L7 71.5 71.53 71.55 71.67 71.57 71.55 71.0
L8 71.182 71.177 70.709 70.962 70.372 70.207
70.0
L9 71.201 71.206 71.576 71.033 72.089 72.136
69.0
L10 71.2 70.9 71.1 71.3 71.1 71.2
L11 70.72 71.01 70.41 70.12 70.71 70.41 68.0
L12-ASTM D 5373 - 08
L2-not given*
L14-GC-TCD
L4-DIN 51732 (eq.ISO
L13-DIN 51732 (eq. ISO

L1-ISO/TS 12902
L5-ASTM D5373
L6-ASTM D5373-08
L8-ASTM D5373
L3-ISO 29541
L7-ISO 29541*
L9-ISO 29541*
L10-ISO/TS 12902*
L11-ISO 29541*
L13 71.3 71.5 71.8 71.9 71.9 72.1
29541)
25941)*
L2 69.28 69.52 68.77 69.19 69.13
L3 73.014 72.784 72.841 72.988 72.651 72.672
L12 72.67 72.95 72.94 73.04 72.54 72.74
L14 71.96 71.82 71.64 72.19 72.67 72.3
Hydrogen (H) (ISO 609, ISO/TS12902, ASTM D5373) in g/100 g (certified value)
Lab Results
L1 4.92 4.98 4.88 4.84 4.97 4.95 ERM-EF411 - Hydrogen (H) (ISO 609, ISO/TS12902,
L3 4.789 4.768 4.872 4.914 4.913 4.913 5.8
ASTM D5373)
L4 4.65 4.55 4.71 4.73 4.68 4.7 5.6
L5 4.654 4.681 4.736 4.701 4.738 4.708 5.4
Mass fraction [g/100 g

5.2
L7 4.81 4.82 4.78 4.76 4.78 4.81 5.0
L8 4.988 4.953 4.93 4.911 4.963 4.973 4.8
L10 4.76 4.78 5 4.86 4.83 4.84 4.6
L13 4.66 4.63 4.75 4.72 4.52 4.53 4.4
L14 4.78 4.79 4.76 4.83 4.77 4.84 4.2
4.0
L14-GC-TCD
L7-ISO 29541*
L10-ISO TS 12902*
L11-ISO 29541*
L1-ISO/TS 12902
L3-ISO 29541
L5-ASTM D5373
L8-ASTM D5373
L6-ASTM D5373-08
L9-ISO 29541
L12-ASTM D 5373 -
L4-DIN 51732 (eq.
L13-DIN 51732 (eq.
L2-n.a.
ISO 29541)
ISO 25941)*
L2 4.76 4.77 4.75 4.75
08
L6 5.24 5.24 5.29 5.33 5.29 5.32
L9 4.673 4.672 4.375 4.586 5.142 5.116
L11 5.03 5.09 5.04 5.02 5.08 5.05
L12 4.96 4.94 4.92 4.95 4.96 4.94
88
Nitrogen (N) (ISO 333, ISO/TS12902, ASTM D5373) in g/100 g (certified value)
Lab Results ERM-EF411 - Nitrogen (N) (ISO 333, ISO/TS12902,
L1 1.41 1.42 1.44 1.4 1.41 1.43 ASTM D5373)
1.7
L3 1.464 1.475 1.456 1.477 1.494 1.441
1.6
L4 1.36 1.36 1.36 1.38 1.44 1.45
1.5

L6 1.35 1.36 1.42 1.41 1.34 1.35
1.4
L7 1.45 1.42 1.38 1.4 1.46 1.5
1.3
L10 1.43 1.44 1.44 1.44 1.42 1.43
1.2
L11 1.48 1.46 1.48 1.46 1.47 1.48 1.1
L12 1.52 1.5 1.53 1.49 1.5 1.48
L1-ISO/TS 12902
L6-ASTM D5373-08
L12-ASTM D 5373 - 08
L8-ISO 333
L13-DIN 51732 (eq.
L14-GC-TCD
L10-ISO TS 12902*
L11-ISO 29541*
L3-ISO 29541
L7-ISO 29541
L5-ASTM D5373
L9-ISO 29541
L13 1.4 1.37 1.38 1.38 1.38 1.38
ISO 25941)*
25941)
L5 1.317 1.329 1.324 1.325 1.374 1.324
L8 1.442 1.444 1.448 1.435 1.449 1.463
L9 1.335 1.335 1.335 1.335 1.335 1.335
L14 1.65 1.61 1.57 1.61 1.55 1.59
ERM-EF411 - Sulfur (S) (ISO 19579, ASTM D4239) in g/100 g (certified value) ERM-EF411 - Sulfur (S) (ISO 19579, ASTM D4239)
Lab Results
L1 0.602 0.602 0.605 0.597 0.593 0.6 0.70
0.68
L3 0.595 0.589 0.611 0.585 0.589 0.593 0.66
L4 0.602 0.606 0.608 0.602 0.581 0.576

0.64
0.62
L5 0.601 0.6 0.587 0.585 0.59 0.582 0.60
L6 0.606 0.598 0.593 0.582 0.59 0.588 0.58
L7 0.595 0.613 0.616 0.632 0.588 0.595 0.56
0.54
L8 0.606 0.607 0.598 0.599 0.592 0.595 0.52
L11 0.63 0.647 0.623 0.608 0.599 0.586 0.50
G1071 (eq. ISO…

L1-ČSN 44 1395
L12-ASTM D4239
L3-ISO 19579
L5-ASTM D 4239
L6-ASTM D4239
L7-ISO 19579
L8-ASTM D4239
L11-ISO 19579
L10-NF M03-038
L14-XRF in house
L4-DIN 51724-3 (eq.
L13-OENORM
L12 0.58 0.57 0.58 0.58 0.57 0.58
(ISO 19579)
Method B
L13 0.611 0.594 0.641 0.634 0.6 0.592
ISO 19579)
method
L10 0.67 0.68 0.67 0.68 0.67 0.68
L14 0.67 0.669 0.668 0.664 0.661 0.66
89
Sulphur (S) (ASTM D3177) in g/100 g (additional material information value)
Lab Results ERM-EF411 - Sulfur (ASTM D3177)
0.62
L6 0.606 0.598 0.593 0.582 0.59 0.588
L8 0.606 0.607 0.598 0.599 0.592 0.595 0.60

L12 0.58 0.57 0.58 0.58 0.57 0.58
0.58
0.56
0.54
0.52
0.50
L6*
L8*
L12*
Chlorine (Cl) in mg/kg (certified value)
Lab Results
L3 89 88 90 105 87 100 ERM-EF411 - Chlorine (Cl)
L4 130 90 90 90 100 100 200
L8 161 160 149 148 123 124 180
L10 100 100 100 100 100 100 160
Mass fraction [mg/kg]

140
L11 100 80 100 90 90 110
120
L13 119 119 127 135 140 121 100
L15 78 83 79 79 88 87 80
L18 89 82 84 87 148 72 60
L15-INAA
L18-k0NAA*
L4-IC (DIN 51727)
L10-NF M03-009
L11-IC (ASTM D4208)
L13-IC (ÖNORM G
L5-IC (ASTM D4208)

L7-IC (ASTM D4208)
L14-ASTM D4208
L1-Turbo Quant
L3-IC
L19-k0NAA
L22-k0NAA
L8-ISE (ISO 10304)
84 95 91 93 92 75
L19 82 83 81 77 76 78
1075)*
L22 70 80 76 86

L1 90 100 110 100 100 110
L5 80 70 80 80 80 80
L7 100 80 90 110 90 100
L14 100 110 100 100 100 110
90
Fluorine (F) in g/100 g (additional material information value)
Lab Results ERM-EF411 - Fluorine (F)
L3 0.004 0.004 0.005 0.004 0.004 0.004 0.016
L4 0.005 0.004 0.004 0.004 0.004 0.004 0.014
L5 0.003 0.003 0.004 0.004 0.004 0.004 0.012

0.010
L7 0.004 0.005 0.003 0.003 0.003 0.004
0.008
0.006
Results not accepted on technical grounds 0.004
L10 0.005 0.009 0.007 0.008 0.007 0.014 0.002
L11 0.005 0.004 0.005 0.004 0.005 0.004 0.000
L3-ISO 11724
L5- ISO 10304
L11-ASTM D3761
L13-ÖNORM G107
L7-ISO 11724*
L10-not given*
L4-combustion-IC IC
L13 0.004 0.004 0.004 0.003 0.004 0.003
ERM-EF411 – Calcium (Ca) in g/kg (no value assigned)

ERM-EF411 - Calcium (Ca)
Lab Results
2.5
L13 1.729 1.686 1.643 1.892 1.724 1.68
1.912 1.947 1.881 1.749 1.773 1.827
2.0
Mass fraction [g/kg]

L15 1.639 1.936 1.163 1.783 1.581 1.657
L18 1.28 1.45 1.49 2.07 1.33 1.71
1.5
2.15 1.54 1.74 1.71 1.78 1.77
L19 1.577 1.655 1.522 1.617 1.471 1.449
1.0
L22 1.62 1.64 1.37 1.71 1.7 1.49
0.5
0.0
L15-INAA
k0NAA
k0NAA
k0NAA*
L13-MW-
ICP-AES
L19-
L22-
L18-
91
ERM-EF411 – Magnesium (Mg) in g/kg (no value assigned)
Lab Results ERM-EF411 - Magnesium (Mg)
L13 0.954 0.995 0.874 1.084 0.975 0.917 3.0
1.095 1.087 1.069 0.942 0.937 1.052
L18 1.264 0.748 0.654 0.623 4.718 0.606 2.5

0.761 0.766 1.535 1.148 0.572 0.631 2.0
L19 0.875 0.753 0.854 0.867 0.743 0.854
L22 0.835 0.76 0.72 0.88 0.8 0.86 1.5
1.0
L15 0.622 0.811 0.697 0.639 0.683 0.732 0.5
0.0
L19-k0NAA
L22-k0NAA
L15-INAA
L18-k0NAA*
L13-MW-ICP-
AES
ERM-EF411 – Sodium (Na) in mg/kg (no value assigned)
Lab Results ERM-EF411 - Sodium (Na)
L13 1221 1226 1192 1286 1216 1240 1500
1249 1255 1248 1185 1188 1202 1400
L15 1195 1219 1225 1149 1100 1134

1300
L18 1080 1230 1160 1230 1170 1170
1200
1540 1190 1210 1100 1310 1300
1100
L19 1170 1171 1091 1197 1074 1079
1000
L22 1280 1560 1400 1210 1280 1350
900
800
L15-INAA
L18-k0NAA*
L13-MW-ICP-
L19-k0NAA
L22-k0NAA
AES
92
ERM-EF411 - Potassium (K) in mg/kg (no value assigned)
Lab Results ERM-EF411 - Potassium (K)
1700
L13 1036 1042 1007 1115 1094 1102
1100 1127 1115 1085 1111 1082 1500

L15 1101 1250 1023 1015 1078 1042 1300
L18 850 1140 910 990 940 848 1100
1580 1090 990 1100 1460 1180 900
L19 1092 1102 955 1085 929 945 700
L22 1190 1140 1180 1150 1240 1230 500
300
L15-INAA
L18-k0NAA*
L13-MW-ICP-
L19-k0NAA
L22-k0NAA
AES
ERM-EF411 – Arsenic (As) in mg/kg (no value assigned)
Lab Results ERM-EF411 - Arsenic (As)
L13 5.16 5.28 5.1 5.27 5.41 5.34 6.0
6.04 5.44 5.46 5.28 5.64 5.21
L15 4.353 4.142 4.812 6.153 3.787 4.21 5.0

L18 3.58 3.46 3.23 4.53 3.28 3.00
4.0
4.67 2.86 5.43 4.05 5.12 4.41
L19 4.81 4.99 4.1 4.99 3.85 4.06 3.0
L21 3.13 3.13 3.13 3.97 3.86 4.07
L22 4.53 5.56 4.9 4.66 4.16 5.98 2.0
1.0
0.0
L15-INAA
L13-MW-
k0NAA
k0NAA
k0NAA*
ICP-MS*
HPMW-
HGAAS
L19-
L22-
L18-
L21-
93
ERM-EF411 – Cadmium (Cd) in mg/kg (no value assigned)
Lab Results ERM-EF411 - Cadmium (Cd)
L13 – 0.26 0.28 0.27 0.27 0.29 0.21 0.40
ICP-AES 0.22 0.37 0.25 0.24 0.27 0.25
L13 - 0.35

GFAAS 0.16 0.23 0.24 0.23 0.19 0.27 0.30
Results excluded on technical grounds 0.25

L21 0.188 0.188 0.188 0.23 0.24 0.24 0.20
0.15
0.10
0.05
GFAAS
ICP-SFMS
L13-MW-
ICP-AES
L21-MW-
L13-
ERM-EF411-Cobalt (Co) in mg/kg (indicative value)
Lab Results ERM-EF411-Cobalt (Co)
L13 3.49 3.53 3.56 3 3.24 3.26 5.0
3.26 3.54 3.2 3.27 2.72 3.32 4.5

L15 3.153 3.015 3.533 3.027 3.345 3.307

L18 3.81 3.08 3.15 4.22 3.52 3.01 4.0
3.74 3.47 3.34 4.36 3.5 3.97 3.5

L19 3.47 3.52 3.21 3.48 3.18 3.22
L21 2.93 2.93 2.93 3.76 3.66 3.76 3.0
L22 3.71 4.38 4.27 3.49 4.25 4.14
2.5
L13 3.47 3.52 3.21 3.48 3.18 3.22
2.0
L15-INAA
k0NAA
k0NAA
k0NAA
L13-MW-
L21-MW-
ICP-AES
L18-
L19-
L22-
SFMS
ICP-
94
ERM-EF411 – Chromium (Cr) in mg/kg (no value assigned)
Lab Results
ERM-EF411 - Chromium (Cr)
L13 16.2 16.9 19 15.5 19 18.8
40
16.9 18 16.1 19.3 19.1 19.3
L18 12.6 18.1 14.2 20.5 19.7 19 35

24.8 19.8 20.9 13.3 18.5 25.5 30
L19 16.9 18.1 16.4 17.1 16.3 16.2
L22 13 17.4 17.8 12.4 14.1 16.4 25
20
15
L15 15.41 18.43 20.48 14.53 18.46 19.97
L21 25.1 25.1 25.1 31.3 30.3 31.3 10
ICP-SFMS*
L15-INAA
k0NAA*
L13-MW-
L19-k0NAA
L22-k0NAA
ICP-AES
L21-MW-
L18-
ERM-EF411 – Copper (Cu) in mg/kg (no value assigned)
ERM-EF411 - Copper (Cu)
Lab Results
11
L13 5.8 5.6 6.3 9.4 7.8 9.6 10
6.8 6.7 6.7 6.6 6.6 6.6 9

8
Results not accepted on technical grounds 7
L21 5.33 5.33 5.33 8.04 7.94 8.04 6
5
4
3
2
L21-MW-ICP-
L13-MW-ICP-AES
SFMS*
95
ERM-EF411 – Mercury (Hg) in mg/kg (indicative value)
Lab Results
L3 0.073 0.074 0.066 0.07 0.068 0.07 ERM-EF411 - Mercury (Hg)
L7 0.0618 0.0652 0.0621 0.07 0.0705 0.0713 0.16
L13 0.099 0.088 0.087 0.117 0.085 0.107 0.14

0.09 0.094 0.091 0.079 0.094 0.08

0.12
L16 0.094 0.066 0.078 0.076 0.126 0.116 0.10
L17 0.091 0.088 0.087 0.091 0.092 0.085 0.08
L19 0.0624 0.0644 0.0747 0.0639 0.0675 0.0764 0.06
L20 0.076 0.075 0.076 0.075 0.073 0.074 0.04
0.02
L21 0.053 0.051 0.052 0.037 0.035 0.034
L20-MW-ICP-
L21-MW-ICP-
L3-DMA
L7-MW-ICP-MS
L13-MW-CVAAS
L16-MW-CVAFS
L17-MW-CVAAS
L19-DMA
SFMS*
SFMS
ERM-EF411 - Manganese (Mn) in mg/kg (no value assigned) ERM-EF411 - Manganese (Mn)
Lab Results 130
L13 36.9 35.3 33.1 38.8 39.2 36.1
38.1 38.8 37.4 40.5 35.4 37 110

L15 25.14 36.35 27.79 21.91 26.08 26.22 90
30.8 23.1 22.2 20.3 117.9 22.1
70
L18 27.3 47.4 121.9 52.5 21.1 26.3
L19 31.6 32.1 33.1 30.7 32.4 32.5 50
L21 24 24 24 34.5 33.4 34.5
30
L22 26.3 22.2 20.9 26.6 31.5 32.3
10
L15-INAA
L18-k0NAA*
L13-MW-ICP-
L21-HPMW-
L19-k0NAA
L22-k0NAA
ICP-MS*
AES
96
ERM-EF411 Nickel (Ni) in mg/kg (no value assigned) ERM-EF411 - Nickel (Ni)
Lab Results 23
L13 14.5 14.4 16.8 14.1 16.2 16.4 21
14.7 16.4 14.9 17.1 17 17.5

19
L21 10.44 11.49 10.44 16.71 16.71 16.71
17
15
13
11
9
7
5
ICP-MS*
L13-MW-
ICP-AES
HPMW-
L21-
ERM-EF411 Lead (Pb) in mg/kg (no value assigned)
Lab Results ERM-EF411 - Lead (Pb)
L7 3.003 3.023 2.968 3.366 3.306 3.264 4.5
L16 2.565 2.406 2.397 2.34 2.339 2.425 4.0
L20 1.92 1.88 1.89 1.98 1.9 1.87 3.5

3.0
L21 1.95 1.96 1.93 2.49 2.35 2.43
2.5
2.0
1.5
L3 2.2 2.1 2.2 2.1 2 2.1 1.0
L13 <1 <1 <1 <1 1 1.3 0.5
L17 3.512 3.561 3.448 3.537 3.875 3.863
L16-HPA-SF-ICPMS
L21-HPMW-ICP-MS
L3-a-ICP-MS
L7-MW-ICP-MS
L20-MW-ICP-SFMS
L13-MW-ICP-AES
L17-MW-ICP-MS
97
ERM-EF411 – Antimony (Sb) in mg/kg (indicative value)
ERM-EF411 - Antimony (Sb)
Lab Results 2.3
L3a 1.4 1.4 1.4 1.4 1.4 1.4 2.1
L7 1.611 1.612 1.637 1.578 1.548 1.575 1.9

L15 1.587 1.306 1.713 1.537 1.477 1.271 1.7
L18 1.016 1.55 1.38 1.8 1.22 0.996 1.5
1.32 1.38 1.48 1.52 1.47 1.66 1.3
L19 1.67 1.67 1.54 1.65 1.53 1.51 1.1
L20 1.47 1.48 1.48 1.47 1.45 1.39 0.9
L22 2.17 1.32 1.33 1.37 1.79 1.19 0.7
0.5
L16-HPA-ICP-
L21-HPMW-ICP-
L3-a-ICP-MS
L7-MW-ICP-MS
L15-INAA*
L18-k0NAA*
L20-MW-ICP-
L19-k0NAA
L22-k0NAA
SFMS
SFMS
L16 0.804 0.778 0.857 0.844 0.727 0.773
MS
L21 0.057 0.058 0.065 0.018 0.021 0.024
ERM-EF411 - Selenium (Se) in mg/kg (certified value)

Lab Results ERM-EF411 - Selenium (Se)
8
L7 5.517 5.634 5.609 5.652 5.512 5.75
L13 4.47 4.06 3.75 3.91 3.89 3.87 7

3.72 3.85 3.63 3.58 3.73 3.79 6
L15 4.648 4.859 5.584 5.561 5.013 5.001
5
L16 5.456 5.352 4.907 4.682 5.29 4.725
L18 6 7.09 5.22 5.73 5.86 6.19 4
5.57 5.3 6.22 5.79 5.97 6.01 3

L19 5.72 5.65 5.47 5.74 5.5 5.77 2
L20 4.66 4.69 4.65 4.49 4.54 4.55
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L21-HPMW-ICP-MS
L15-INAA*
L18-k0NAA*
L13-HGAAS
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L21 4.31 4.48 4.5 4.93 4.91 5.08
L22 5.46 5.4 5.46 5.58 5.4 5.7
ERM-EF411 Tin (Sn) in mg/kg (no value assigned)

Lab Results
L21 0.178 0.157 0.157 0.23 0.219 0.219
98
ERM-EF411 - Thallium (Tl) in mg/kg (indicative value)
Lab Results ERM-EF411 - Thallium (Tl)
L3 0.2 0.2 0.2 0.22 0.22 0.22 0.35
L7 0.234 0.232 0.231 0.264 0.259 0.248 0.30
L16 0.229 0.259 0.252 0.219 0.218 0.238

0.25
L17 0.265 0.267 0.26 0.261 0.25 0.258
0.20
L20 0.223 0.221 0.23 0.235 0.232 0.228
0.15
0.10
L21 0.193 0.266 0.26 0.105 0.13 0.135 0.05
0.00
L21-HPMW-ICP-MS
L3-a-ICP-MS*
L16-HPA-ICP-
-
L7-MW-ICP-MS
L17-MW-ICP-MS
L20-MW-ICP-SFMS
SFMS
ERM-EF411 - Vanadium (V) in mg/kg (indicative value)
Lab ERM-EF411 - Vanadium (V)
L13 22.1 21.6 20.3 22.8 21.2 20.9 45
22.5 22.5 21.1 21 21 22.5 40

L15 21.17 22.94 18.11 21.22 19.16 19.28 35
L18 28.6 24.4 21.1 18.8 36.7 26.8 30

25
18.4 20.6 26.6 38.3 23.8 18.7
20
L19 23.8 23.4 21.4 22.2 20.5 21
15
L22 18.3 25.2 21.5 26.4 24.3 23.8
10
5
0
L21 16.7 16.7 16.7 20.9 19.9 20.9
L15-INAA*
L13-ICP-
-
L19-k0NAA
L22-k0NAA
k0NAA*
ICP-MS*
HPMW-
L18-
L21-
AES
99
ERM-EF411 - Zinc (Zn) in mg/kg (indicative value)
Lab ERM-EF411 - Zinc (Zn)
L13 10.6 11.4 14.7 11.1 14.2 10.6 25.00
11.8 12.2 11.5 11.2 12.5 11.4

20.00

L15 13.67 12.84 12.39 11.65 12.91 13.67
L18 11.1 15.5 11.5 11.2 10.8 11.1
17 22.6 12.5 10.8 14.8 17.4 15.00
L19 13.4 13.1 11.3 12.6 10.7 10.5
L22 14.7 14.6 13.7 15.6 15.8 14.7 10.00

L21 7.83 7.94 8.04 14.6 7.83
0.00
L15-INAA
L13-ICP-
k0NAA
k0NAA
k0NAA*
ICP-MS*
HPMW-
L19-
L22-
L18-
L21-
100 AES
ERM-E F412-Gross calorific value (GCV) (ISO 1928/ASTM D5865) in MJ/kg (certified value)
Lab ERM-EF412-GCV
L1 25.908 25.998 26.044 26.127 26.018 25.931 27.0
L3 26.103 26.171 26.178 26.175 26.038 26.084 26.8
26.6
L6 25.987 25.971 25.962 25.987 26.046 25.992
GCV [MJ/kg]]
26.4
L8 26.04 26.074 26.14 26.087 26.089 26.108 26.2
L9 25.99 25.96 26.03 26.01 26.04 26 26.0
L11 25.97 25.96 26.07 26.09 26 26.04 25.8
25.6
L13 25.92 25.89 25.92 25.94 25.95 25.94 25.4
L14 26.009 26.007 26.061 26.043 25.969 25.978 25.2
25.0
L13-Eq. ISO 1928*
L12- ISO 1928*

L1-ISO 1928
L6-ASTM D5865-10
L8-ISO 1928
L9-ISO 1928
L14-ISO 1928
L7-DIN 51900-3
L11-ISO 1928*
L2-ISO 1928*
L10-ISO 1928*
(eq. ISO 1928)*
L3-ISO 1928
L2 26.19 26.23
L7 26.118 26.09 26.275 26.213 26.284 26.215
L10 25.792 25.398 25.922 25.917 25.723 25.812
L12 25.76 25.7 25.77 25.67 25.81 25.73
ERM-EF411 – Net calorific value (NVV) in MJ/kg (certified value)

Lab Results
ERM-EF412 - Net calorific value
L3 25.116 25.184 25.181 25.177 25.04 25.086
26.0
L6 24.65 24.644 24.603 24.629 24.685 24.634
L8 25.185 25.226 25.167 25.203 25.285 25.298 25.5
NCV [MJ/kg]]
L9 25.05 24.99 25.09 25.08 25.05 24.95 25.0
L11 24.89 24.88 24.99 25 24.9 24.94
L13 24.89 24.86 24.88 24.9 24.92 24.9 24.5
L14 25.022 25.018 25.078 25.051 24.983 25.002 24.0
L3-ISO 1928 *
L6-ASTM D5865-10*
L8-ISO 1928*
L9-ISO 1928*
L11-ISO 1928*
L13-ISO 1928*
L14-ISO 1928*
L2-ISO 1928*
L7-ISO 1928*
L10-ISO 1928*
L2 25.21 25.24
L7 25.129 25.102 25.285 25.222 25.295 25.225
L10 24.012 23.976 23.952 23.921 24 24
101
ERM-EF412-Volatile matter (ISO 562, ISO 5071) in g/100 g (certified value)
L1 49.36 49.51 49.3 49.33 49.51 49.47 52
L3 49.99 49.978 50.301 50.13 50.297 50.199 52
L7 50.27 50.33 49.98 49.85 50.01 49.88 51

L9 50.593 50.601 50.432 50.338 50.598 50.521 51
L12 50.36 50.46 50.26 50.19 50.06 50.29 50
L14 50.235 50.035 50.156 49.736 50.244 50.404 50
49
L2 46.33 46.24 48
L8 50.289 50.574 50.53 50.925 50.613 50.477
L3-ISO 562*
L7-ISO 562*
L9-ISO 562*
L2-ISO 562*
L11-eq ISO 562*
L13-eq ISO 562*

L1-ISO 562
L12-ISO 562
L14-ISO 562
L8-ISO 562
L11 55.3 55.6 55.8 55.0 54.7 54.7
L13 55.1 55.1 55.4 54.6 54.7 51.1
ERM-EF412 - Ash (ISO 1171/ASTM D3174) in g/100 g (certified value)

Lab Results ERM-EF412 - Ash (ISO 1171/ASTM D3174)
L1 4.33 4.34 4.42 4.47 4.73 4.71 5.0
L3 3.99 3.975 3.955 3.989 3.973 3.964 4.8
4.6
L7 4.22 4.26 4.15 4.21 4.14 4.22

4.4
L9 4.134 4.091 4.118 4.11 4.169 4.085 4.2
L10 4.3 4.3 4.5 4.4 4.4 4.2 4.0
3.8
L12 3.67 3.55 3.6 3.64 3.58 3.65 3.6
L14 4.079 4.126 4.128 4.017 3.895 3.899 3.4
3.2
3.0
L1-ISO 1171
L7-ASTM D7582-10
L12-ISO 1171
L14-ISO 1171
L8-ISO 1171
L11-ISO 1171
L13-ISO 1171
L3-ISO 1171*
L9-ISO 1171*
L10-NF 03-003*
L2-ISO 1171*
L2 3.97 4.10
L8 4.139 4.109 4.131 4.304 4.087 4.242
L11 3.63 3.61 3.62 3.6 3.61 3.62
L13 3.61 3.59 3.61 3.62 3.6 3.6
102
ERM-EF412 - Carbon (C) (ISO 29548, ASTM D5373) in g/100 g (certified value)
Lab Results ERM-EF412 - Carbon (C) (ISO 29548, ASTM
L1 66.41 66.48 66.69 67.03 66.65 66.97 69
D5373)
L6 66.43 66.55 67.09 66.88 66.98 66.92 68
L7 66.29 66.15 66.27 66.25 66.13 66.39 68

67
L8 66.135 66.42 66.089 66.197 66.626 66.244 67
L9 66.266 66.21 66.012 65.933 66.435 66.331 66
L10 66 65 66.6 66.1 65.4 65.9 66
65
L11 65.5 65.31 65.5 65.44 65.77 65.89 65
L13 66.1 66.1 66.2 66.3 66.2 66.2 64
L1-ISO/TS 12902
L8-ASTM D5373-08
L12-ASTM D 5373 - 08
L6-DIN 51732 (eq.ISO
L9-ISO 29541*
L13-ISO 29541*
L2-n.a.*
L14-GC-TCD
L7-ASTM D5373
L10-ASTM D 5373
L11-ISO 29541
L3-ISO 29541
L2 61.15 61.06
29541)
L3 67.526 67.526 67.05 67.05 66.989 66.967
L12 66.9 66.78 67.15 66.79 66.89 66.9
Hydrogen (H) (ISO 609, ISO/TS12902, ASTM D5373) in g/100 g (certified value)
Lab Results ERM-EF412-Hydrogen (H) (ISO 609,
L1 5.01 5.09 4.88 4.93 4.95 4.96 5.8
ISO/TS12902, ASTM D5373)
L3 4.761 4.815 4.837 4.848 4.856 4.834 5.6
L7 4.79 4.81 4.8 4.77 4.76 4.78 5.4
5.2

L8 5.229 5.201 5.303 5.301 4.992 5.02 5.0
L10 4.83 4.93 4.82 4.83 4.88 4.86 4.8
4.6
L13 4.71 4.72 4.74 4.76 4.75 4.7 4.4
L14 4.79 4.8 4.77 4.82 4.79 4.74 4.2
4.0
L14-GC-TCD
L1-ISO/TS 12902
L3-ISO 29541
L8-ISO 333
L6-ASTM D5373-08
L9-ISO 29541
L12-ASTM D 5373 - 08
L7-ISO 29541*
L10-ISO TS 12902*
L2-ISO 29541*
L11-ISO 29541*
L2 4.43 4.47
25941)*
L6 5.3 5.25 5.43 5.41 5.41 5.39
L9 4.599 4.687 4.547 4.512 4.798 5.098
L11 4.95 4.96 4.96 4.99 5.03 5.05
L12 4.91 4.92 4.92 4.94 4.95 4.96
103
Nitrogen (N) (ISO 333, ISO/TS12902, ASTM D5373) in g/100 g (certified value)
Lab Results ERM-EF412 - Nitrogen (N) (ISO 333, ISO/TS12902,
L1 0.775 0.769 0.758 0.825 0.742 0.761 ASTM D5373)
1.0
L3 0.714 0.729 0.709 0.7 0.716 0.712
0.9
L6 0.65 0.64 0.78 0.72 0.66 0.67
0.8

L7 0.699 0.728 0.732 0.75 0.717 0.714
0.7
L10 0.76 0.74 0.76 0.75 0.75 0.75
L11 0.801 0.797 0.789 0.764 0.792 0.776 0.6
L12 0.77 0.79 0.73 0.72 0.73 0.76 0.5

L13 0.696 0.719 0.709 0.704 0.712 0.72 0.4
L14-GC-TCD
L1-ISO/TS 12902
L3-ISO 29541
L6-ASTM D5373-08
L12-ASTM D 5373 - 08
L2-not given
L9-ISO 29541
L7-ISO 29541*
L10-ISO TS 12902*
L11-ISO 29541*
L8-ISO 333*
25941)*
L2 0.62 63
L8 0.657 0.716 0.719 0.708 0.748 0.736
L9 0.566 0.586 0.566 0.587 0.566 0.587
L14 1.15 1.21 1 1.05 1.07 1.06
ERM-EF412 - Sulfur (S) (ISO 19579/ASTM D4239) g/100 g (certified value)

Lab Results ERM-EF412 - Sulfur (S) (ISO 19579/ASTM D4239)
L1 0.367 0.37 0.343 0.366 0.329 0.332 0.50
L3 0.394 0.384 0.358 0.351 0.358 0.362 0.45
L4 0.365 0.345 0.374 0.356 0.368 0.349

0.40
L6 0.361 0.353 0.358 0.347 0.356 0.355
L7 0.365 0.345 0.374 0.356 0.368 0.349 0.35
L8 0.393 0.385 0.383 0.387 0.386 0.385 0.30
L9 0.42 0.392 0.424 0.426 0.422 0.422
0.25
L11 0.285 0.275 0.301 0.288 0.287 0.308
L12 0.36 0.36 0.38 0.38 0.36 0.36 0.20
L1-ČSN 44 1395
L3-ISO 19579
L4-ASTM D4239
L6-ASTM D4239
L8-ASTM D4239
L9-ISO 351
L12-ASTM D4239
L13-DIN 51724-3
L10-NF M03-038
L14-XRF in house
L7-ISO 19579*
L11-ISO 19579*
(eq. ISO 19579)

L13 0.322 0.336 0.376 0.384 0.326 0.337
(ISO 19579)
Method B*
method
L10 0.41 0.4 0.41 0.41 0.41 0.41
L14 0.511 0.505 0.502 0.504 0.499 0.499
104
ERM-EF412 - Sulfur (S) (ASTM D3177) g/100 g (no value assigned )
Lab Results ERM-EF412 - Sulfur (ASTM D3177)
L6* 0.361 0.353 0.358 0.347 0.356 L6* 0.40
L8* 0.393 0.385 0.383 0.387 0.386 L8* 0.39
L12* 0.36 0.36 0.38 0.38 0.36 L12* 0.38

0.37
0.36
0.35
0.34
0.33
0.32
0.31
0.30
L6*
L8*
L12*
ERM-EF412 – Chlorine (Cl) in mg/kg (no value assigned)
Lab Results
L3 320 310 340 330 320 320 ERM-EF412 - Chlorine (Cl)
L8 450 450 440 450 430 450 500
L10 300 300 300 300 300 300 450

L11 300 280 320 340 310 270 400
L13 340 330 350 350 340 350
350
L15 320 320 340 330 340 350
L18 340 320 320 340 330 350 300
330 360 250
L3-IC
L1-Turbo Quant*
L5-ISE (ASTM D4208)
L14-ASTM D4208
L11-ISE (ASTM
L10-NF M03-009*
L15-INAA*
L18-k0NAA*
L7-IC (ASTM D4208)*

L19-k0NAA
L22-k0NAA
L8-ISE (ISO 10304)
L13-ÖNORM G 1075-
L19 330 340 340 360 330 330
L22 310 320 320 320 320 310
D4208)*
IC*
L1 350 340 330 340 330 360
L5 350 340 330 340 330 360
L7 290 290 280 280 270 270
L14 470 460 460 460 460 450
105
ERM-EF412 - Fluorine (F)
ERM-EF412 – Fluorine (F) in mg/kg (additional material information value)
140.0000
Lab Results
L3 50 47 51 49 46 44 120.0000
Mass fraction [mg/ kg]

L7 40 30 30 30 30 30
100.0000

L10 50 70 100 110 80 70 60.0000
L11 40 30 30 40 30 30
L13 30 30 30 30 30 30 40.0000
20.0000
0.0000
L11-ASTM
ÖNORM
L3-ISO
L10-not
11724*
L7-ISO
11724
given*
G107
D3761
L13-
ERM-EF412 - Calcium (Ca) in g/kg (certified value)
Lab Results ERM-EF412 - Calcium (Ca)
L7 9.311 9.305 9.283 9.364 9.229 9.317 12.0
L15 10.28 9.658 9.543 9.698 9.89 9.728 11.5

11.0
L16 10.09847 10.2619 10.327 9.8407 9.7113 10.32089

10.5
L16b-MW 10.49426 9.93516 10.688 9.9269 10.629 10.10659
10.0
L18 9.99 10.28 10.17 10.28 10.34 10.13
9.5
9.78 10.2
9.0
L19 9.262 9.329 9.114 9.458 9.517 9.369
8.5
L20 9.9 9.9 9.7 10 9.8 9.7
8.0
L22 9 9.3 9.8 9.8 9.7 9.6
L7-MW-ICP-AES
L15-INAA
L16-HPA-IPAES
L16b-MW-ICP-AES
L18-k0NAA*
L19-k0NAA
L22-k0NAA
L3-ICP-MS
L17-MW-ICP-MS
L20-MW-ICP-
SFMS
L3 10.45 10.32 10.33 11.32 11.19 11.31
L17 10.199 10.01 10.03 9.93 9.96 9.94
106
ERM-EF412 - Magnesium (Mg) in g/kg (indicative value)
L15 3.536 3.633 3.709 3.493 3.502 3.671 5.0
4.8
L17 3.730 3.829 3.736 3.725 3.737 3.789
4.6
L18 3.925 3.81 3.789 3.834 3.893 3.988

4.4
3.917 4.1 4.2
L19 3.842 3.748 3.722 3.884 3.834 3.84 4.0
L22 3.45 3.64 3.61 3.63 3.61 3.61 3.8
3.6
3.4
L3 4.01 4.06 3.95 4.39 4.46 4.41 3.0
L15-INAA
L16-HPA-IPAES
L17-MW-ICP-MS
L18-k0NAA*
L19-k0NAA
L22-k0NAA
L3-ICP-MS
L7-MW-ICP-AES
L16b-MW-ICP-
L20-MW-ICP-
L7 3.602 3.583 3.608 3.622 3.566 3.606
SFMS
L16 3.960 3.987 4.045 3.833 3.799 4.006
AES
L16b 4.054 3.825 4.056 3.841 4.083 3.659
L20 3.94 3.96 3.95 4.15 4.08 4.09
ERM-EF412 - Sodium (Na) in g/kg (certified value)

L7 2.084 2.055 2.071 2.054 2.07 2.054 2.7
L15 2.174 2.17 2.207 2.168 2.185 2.202
2.5
L16 2.36 2.33 2.36 2.29 2.24 2.367

L16b- 2.3
MW 2.35 2.24 2.37 2.28 2.37 2.22 2.1
L18 2.34 2.19 2.43 2.21 2.22 2.38 1.9
2.32 2.2
1.7
L19 2.157 2.13 2.116 2.156 2.151 2.166
1.5
L20 2.11 2.02 2.13 2.01 2 2.1
L7-MW-ICP-AES
L15-INAA
L16-HPA-ICP-AES
L18-k0NAA*
L20-MW-ICP-SFMS
L3-ICP-MS
L17-MW-ICP-MS
L16b-MW-ICP-AES
L19-k0NAA
L22-k0NAA
L22 2.19 2.18 2.15 2.22 2.18 2.18

L3 1.62 1.61 1.58 1.71 1.71 1.76
L17 2.418 2.555 2.516 2.422 2.588 2.544
107
ERM-EF412 - Potassium (K) in mg/kg (certified value)
Lab Results ERM-EF412 - Potassium (K)
L7 209.5 211.7 212.9 211.4 207.4 203.5 400
L16 253.099 240.139 222.55 202.525 200.86 214.511 350
L16b 231.238 253.239 222.33 232.703 250.007 232.085

300
L18 228 233 220 237 219 239
250
L19 230 239 272 220 217 234
L20 237 249 241 246 239 243 200
L22 226 222 225 232 227 223 150
100
L18-k0NAA*
L7-MW-ICP-AES
L16-HPA-IPAES
L16b-MW-ICP-AES
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L3-ICP-MS
L15-INAA
L17-MW-ICP-MS
L3 150 140 150 180 170 170
L15 246 394 255 237 149 295
L17 327 346 357 348 327 320

L3 0.26 0.3 0.29 0.29 0.3 0.27
L7 0.314 0.322 0.318 0.313 0.282 0.271 0.4
L15 0.318 0.343 0.351 0.313 0.329 0.373

L16 0.317 0.309 0.317 0.29 0.291 0.313 0.2
L17 0.418 0.387 0.425 0.426 0.405 0.472
L18 0.297 0.3 0.309 0.302 0.314 0.313
0.0
L19 0.27 0.33 0.24 0.36 0.4 0.32
L15-INAA
L21-HPMW-ICP-MS
L18-k0NAA*
L3-ICP-MS
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L17--MW-ICP-MS
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L20 0.287 0.277 0.264 0.278 0.279 0.276
L21 0.289 0.29 0.289 0.286 0.296 0.283
L22 0.311 0.3 0.305 0.31 0.28 0.3
108
ERM-EF412 - Cadmium (Cd) in mg/kg (indicative value)
ERM-EF412 - Cadmium (Cd)
Lab
0.020
L7 0.014 0.014 0.017 0.011 0.01 0.012
0.018
L16 0.013 0.012 0.015 0.01 0.015 0.015

0.016
0.012 0.011 0.013 0.01 0.012 0.012
0.014
L17 0.011 0.012 0.01 0.011 0.01 0.01
0.012
L20 0.011 0.011 0.013 0.011 0.014 0.012
0.010
L21 0.013 0.013 0.013 0.013 0.011 0.013
0.008
0.006
0.004
0.002
0.000
L16-HPA-
ICP-SFMS
ICP-MS
L7-MW-
L17-MW-
HPMW-
ICP-MS
ICP-MS
L20-MW-
IDTIMS
L21-
ERM-EF412 – Cobalt (Co) in mg/kg (no value assigned)
Lab Results ERM-EF412-Cobalt (Co)
0.21
L3 0.12 0.13 0.13 0.12 0.11 0.12
0.19
L7 0.095 0.094 0.094 0.094 0.098 0.091
0.17
L15 0.119 0.11 0.079 0.088 0.102 0.122

0.15
L16 0.101 0.1 0.103 0.096 0.102 0.102
0.13
L17 0.189 0.189 0.189 0.189 0.199 0.194 0.11
L18 0.103 0.106 0.106 0.099 0.094 0.107 0.09
L19 0.094 0.093 0.092 0.096 0.09 0.096 0.07
L20 0.091 0.09 0.09 0.094 0.089 0.086 0.05
L3-ICP-MS*
L20-MW-ICP-SFMS*
L21-HPMW-ICP-
L15-INAA
L16-HPA-ICP-SFMS
L19-k0NAA
L22-k0NAA
L7-MW-ICP-MS*
L17-MW-ICP-MS*
L18-k0NAA*
L21 0.122 0.127 0.127 0.123 0.12 0.118
L22 0.103 0.098 0.102 0.115 0.105 0.105
MS*
109
ERM-EF412 - Chromium (Cr) in mg/kg (no value assigned)
Lab Results
L3 <0.42 0.46 0.45 0.48 0.45 0.44 0.8
L7 0.545 0.594 0.595 0.55 0.526 0.555
0.7
L15 0.76 0.3 0.593 0.8 0.767 0.589

L16 0.538 0.502 0.526 0.506 0.513 0.561 0.6
L19 0.435 0.423 0.439 0.512 0.492 0.475 0.5
L20 0.473 0.477 0.474 0.467 0.488 0.479 0.4
L21 0.466 0.487 0.482 0.454 0.468 0.439 0.3
0.2
L15-INAA
L21-HPMW-ICP-MS
L3-ICP-MS
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L19-k0NAA
L20-MW-ICP-SFMS
L17-MW-ICP-MS
L17 1.16 1.31 1.1 1.27 1.16 1.21
ERM-EF412 - Copper (Cu) in mg/kg (indicative value)

Lab Results ERM-EF412 - Copper (Cu)
L3 0.59 0.64 0.62 0.51 0.53 0.65 1.40
L7 0.933 0.941 0.985 1.199 0.917 1.247 1.20

L16 0.529 0.482 0.526 0.481 0.542 0.508

1.00
L17 0.802 0.762 0.855 0.889 0.763 0.751
0.80
L20 0.469 0.472 0.473 0.475 0.486 0.471
0.60

L21 0.51 0.519 0.515 1.65 1.75 1.83 0.20
L3-ICP-MS
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L17-MW-ICP-MS
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
110
ERM-EF412 - Mercury (Hg) in mg/kg (certified value)
Lab Results
ERM-EF412 - Mercury (Hg)
L3 0.065 0.066 0.068 0.064 0.075 0.073 0.11
L7 0.067 0.068 0.064 0.063 0.067 0.063
0.10
L16b 0.064 0.067 0.056 0.062 0.056 0.057

L17 0.08 0.082 0.085 0.085 0.08 0.088 0.09
L19 0.068 0.062 0.064 0.07 0.06 0.07
0.08
L20 0.076 0.075 0.076 0.075 0.073 0.074
0.07
0.06
L15 0.044 0.078 0.088 0.099 0.072 0.094
L21 0.062 0.059 0.093 0.051 0.039 0.044 0.05
0.04
L16b-MW-
L17-MW-
L21-HPMW-
L3-DMA
ICP-SFMS
L15-INAA
L19-Hg
L7-MW-ICP-
L20-MW-
CVAAS
CVAFS
ICP-MS
MS
ERM-EF412 - Manganese (Mn) in mg/kg (certified value)
Lab Results ERM-EF412 - Manganese (Mn)
L3 44 49 49 46 46 46 65
L7 46.99 45.9 46.2 46.18 47.13 47.44 60
L15 47.57 47.13 46.99 46.71 47.03 46.62

55
L16 50.353 49.966 52.025 50.753 51.176 50.538 50
L16c 51.221 49.124 51.722 50.649 50.048 50.119 45
L17 47.94 48.33 47.75 47.43 48.14 47.98 40
L18 50.3 48.8 49.4 50.6 50.3 50.9 35
50.3 51.6 30
L18-k0NAA*
L3-ICP-MS
L7-MW-ICP-MS
L15-INAA
L16-MW-ICP-AES
L16c-HPA-IPAES
L17-MW-ICP-MS
L19-k0NAA
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
L22-k0NAA
L19 49 49 48.6 49.1 49.2 47.6
L20 50.5 51.9 51.6 50.4 51.8 49.8
L21 48 49.5 50.6 46.9 47 46.5
L22 47.4 46.6 47.9 46.5 45.7 46.6
111
ERM-EF412 – Nickel (Ni) in mg/kg ((no value assigned)
Lab Results
L16 0.299 0.324 0.304 0.287 0.292 0.306 ERM-EF412 - Nickel (Ni)
1.0
L17 0.702 0.793 0.889 0.856 0.738 0.935
0.9
L20 0.315 0.308 0.311 0.316 0.328 0.309 0.8

L21 0.437 0.404 0.419 0.487 0.386 0.363 0.7
0.6
0.5
0.4
0.3
0.2
0.1
L16-HPA-ICP-SFMS
L21-HPMW-ICP-MS
L17-MW-ICP-MS
L20-MW-ICP-SFMS
ERM-EF412 - Lead (Pb) in mg/kg (indicative value)
Lab Results ERM-EF412 - Lead (Pb)
0.3134 0.3361 0.3097 0.2538 0.2631 0.2695 0.40
L7
L16 0.235518 0.24567 0.232 0.22668 0.21417 0.22106 0.35
0.226 0.22 0.212 0.218 0.219 0.223

L20 0.30
L21 0.25 0.241 0.243 0.292 0.296 0.299
0.25
L3 0.14 0.21 0.16 0.11 0.17 0.15 0.15

L17 1.146 1.088 1.233 1.033 1.1 1.44 0.10
L16-HPA-SF-
L21-HPMW-ICP-
L7-MW-ICP-MS
L3-ICP-MS
L17-MW-ICP-MS
L20-MW-ICP-
ICPMS
SFMS
MS
112
ERM-EF412 - Antimony (Sb) in mg/kg (indicative value)
Lab Results ERM-EF412 - Antimony (Sb)
L3 0.02 0.02 0.02 0.02 0.02 0.02 0.050
L18 0.026 0.026 0.03 0.025 0.025 0.027 0.045
0.032 0.009 0.040

L19 0.024 0.023 0.022 0.02 0.025 0.02 0.035
L20 0.028 0.026 0.028 0.028 0.027 0.025 0.030
L22 0.032 0.027 0.02 0.024 0.022 0.027 0.025
0.020
L16 0.028 0.026 0.026 0.024 0.024 0.025 0.010
L18-k0NAA*
L20-MW-ICP-
L16-HPA-ICP-
L21-HPMW-ICP-
L3-ICP-MS
L19-k0NAA
L22-k0NAA
L21 0.027 0.143 0.037 0.013 0.038 0.014
SFMS
SFMS
MS
Lab Results ERM-EF412 - Selenium (Se)
L7 1.064 1.071 1.07 1.006 1.061 1.09 1.5
L15 0.94 0.903 1.004 0.918 0.851 1.024 1.4
1.3
L16 0.964 0.94 0.925 0.936 0.896 0.916 1.2

L18 0.976 1.121 1.026 1.036 1.049 0.994 1.1
1.066 1.033 1.0
0.9
L19 1.03 1 0.97 0.97 0.97 1.01 0.8
L20 0.803 0.809 0.795 0.845 0.811 0.815 0.7
0.6
L21 0.822 0.822 0.858 0.941 0.926 1 0.5
L22 1.01 0.96 0.97 1.13 1 1.08
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
L3-ICP-MS
L15-INAA*
L18-k0NAA*
L19-k0NAA
L22-k0NAA
L3 0.49 0.48 0.59 0.59 0.62 0.59
113
ERM-EF412 – Tin (Sn) in mg/kg(additional material information va lue)
ERM-EF412 - Tin (Sn)
Lab Results
0.45
L3 0.07 0.08 0.07 0.08 0.1 0.12 0.40
L7 0.27 0.248 0.273 0.196 0.172 0.202 0.35

L16 0.072 0.068 0.066 0.085 0.067 0.06 0.30
L21 0.006 0.055 0.029 0.058 0.055 0.044 0.25
0.20
0.15
L20 0.068 0.068 0.067 0.07 0.071 0.071 0.05
0.00
L3-ICP-MS
L7-MW-ICP-MS
L16-HPA-ICP-SFMS
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
ERM-EF412 – Thallium (Tl) in mg/kg (no value assigned)
L7 0.001 0.002 -0.001 0.005 0.003 0.002 0.0070
L16 0.001 0.001 0.001 0.001 0.001 0.001
0.0060
L17 0.001 0.001 0.002 0.002 0.002 0.001

L20 0.001 0.001 0.001 0.001 0.001 0.001 0.0050
0.0040
L21 0 0 0.005 0 0 0 0.0030
0.0020
0.0010
0.0000
L17-MW-
HPMW-
ICP-SFMS
ICP-SFMS
ICP-MS
ICP-MS*
L7-MW-
L16-HPA-
ICP-MS
L20-MW-
L21-
114
ERM-EF412 - Vanadium (V) in mg/kg (certified value )
Lab Results ERM-EF412 - Vanadium (V)
L7 0.522 0.529 0.523 0.524 0.536 0.518 0.80
L15 0.455 0.579 0.58 0.567 0.655 0.653
0.75
L16 0.586 0.566 0.581 0.552 0.52 0.599

L17 0.582 0.586 0.597 0.606 0.605 0.584 0.70
L18 0.61 0.543 0.618 0.676 0.631 0.553 0.65

0.591 0.568 0.60
L19 0.6 0.53 0.59 0.53 0.64 0.54
0.55
L20 0.548 0.553 0.555 0.563 0.578 0.559
L22 0.51 0.53 0.52 0.54 0.58 0.52 0.50
0.45
HPMW-…
L3 0.5 0.56 0.56 0.51 0.5 0.48
L15-INAA*
L7-MW-
L17-MW-
ICP-SFMS
L19-k0NAA
L22-k0NAA
L3-ICP-MS
ICP-SFMS
k0NAA*
ICP-MS
L16-HPA-
ICP-MS
L20-MW-
L18-
L21-
L21 0.51 0.525 0.523 0.514 0.506 0.506
ERM-EF412 - Zinc (Zn) in mg/kg (indicative value)

Lab Results
ERM-EF412 - Zinc (Zn)
L3 0.86 1 0.92 0.71 0.73 0.71
2.0
L15 1.17 1.41 1.11 1.12 1.21 0.65
1.8
L16 1.031 1.045 0.992 0.906 0.933 1.6

L19 1.19 1.83 0.86 0.73 0.76 0.84 1.4
L20 0.759 0.781 0.788 0.767 0.749 0.749 1.2
L22 0.87 0.97 1.02 1 0.97 1.14 1.0
0.8
L7 2.135 1.667 1.834 1.357 1.106 1.018 0.4
L18-k0NAA*
L3-ICP-MS
L15-INAA
L16-HPA-ICP-SFMS
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L7-MW-ICP-AES
L17-MW-ICP-MS
L21-HPMW-ICP-MS
L17 1.411 1.554 1.482 1.553 1.662 1.695
L18 1.21 1.27 1.58 1.1 1.21 1.07
1.19 0.99
L21 0.8 0.789 0.759 1.318 1.516 1.285
115
ERM-EF413-Gross calorific value (GCV) (ISO 1928/ASTM D5865) in MJ/kg (certified value)
Lab Results ERM-EF413-Gross calorific value (GCV) (ISO
L1 29.77 29.846 29.328 29.432 29.807 29.831 1928/ASTM D5865)
L3 29.911 29.972 30.013 29.92 30.014 29.932 30.3
30.1
L6 28.512 28.298 28.42 28.759 28.7 28.818 29.9
L8 29.37 29.34 29.2 29.114 29.005 29.049
GCV [MJ/kg]]
29.7
L9 29.87 29.9 29.94 29.86 30 30 29.5
29.3
L11 29.53 29.46 29.45 29.48 29.47 29.48 29.1
L13 29.73 29.67 29.61 29.61 29.64 29.67 28.9
28.7
L14 29.638 29.623 29.751 29.744 29.826 29.798 28.5
L1-ISO 1928
L6-ASTM D5865-10
L8-ISO 1928
L13-Eq. ISO 1928

L9-ISO 1928*
L11-ISO 1928*
L14-ISO 1928*
L4-ISO 1928*
L7-ISO 1928*
L10-NF ISO 1928*
L12-ČSN ISO 1928
L3-ISO 1928
L4 30.095 30.08 30.02 30.072 30.166 30.155
L7 29.993 29.963 30.023 29.935 30.064 30.042
L10 29.942 29.915 29.966 30.009 29.981 29.917
L12 28.91 28.93 28.21 28.11 28.77 28.8
ERM-EF413 – Net calorific value (NCV) in MJ/kg (certified value)

Lab Results
L3 29.87 29.93 29.963 29.871 29.962 29.879 ERM-EF413 - Net calorific value
30.5
L6 28.512 28.299 28.421 28.76 28.702 28.816
L8 29.257 29.227 29.079 28.992 28.885 28.928 30.0
NCV [MJ/kg]
L9 29.83 29.88 29.9 29.83 29.97 29.97
29.5
L11 29.47 29.4 29.39 29.42 29.42 29.43
L13 29.7 29.65 29.59 29.59 29.62 29.65 29.0
28.5
L4 30.066 30.052 29.987 30.039 30.142 30.128 28.0
L3-ISO 1928 *
L6-ASTM D5865-10*
L8-ISO 1928*
L9-ISO 1928*
L11-ISO 1928*
L13-ISO 1928*
L4-ISO 1928*
L7-ISO 1928*
L10-ISO 1928*
L7 29.941 29.911 29.969 29.88 30.009 29.987
L10 29.822 29.795 29.846 29.859 29.861 29.827
116
ERM-EF413 – Volatile matter (ISO 562) in g/100 g (no value assigned)
Lab Results
ERM-EF413-Volatile matter (ISO 562)
L1 1.04 1.02 1.22 1.25 0.99 1.17
L3 1.093 0.865 1.282 1.374 1.512 1.538 1.9
L4 0.78 0.86 0.92 1.02 0.64 0.68 1.7

1.5
L7 0.866 0.947 0.968 0.807 0.943 0.853
1.3
L9 0.932 0.822 0.922 0.953 0.845 1.01
1.1
L12 0.67 0.65 0.55 0.66 0.9 0.89
0.9
L14 0.887 0.91 1.06 0.831 0.794 0.731
0.7
0.5
L1-ISO 562
L12-ISO 562
L14-ISO 562
L6-eq. ISO 562
L8-ISO 562
L11-ISO 562
L13-eq ISO 562

L3-ISO 562*
L4-eq. ISO 562*
L7-ISO 562*
L9-ISO 562*
L6 0.8 0.84 1.02 1.08 1 1.02
L8 2.002 2.074 2.222 2.201 2.258 2.208
L11 5.01 5.08 5.06 5.09 4.74 4.34
L13 4.22 4.54 4.12 4.2 3.66 3.89
ERM-EF413 - Ash (ISO 1171/ASTM D3174) in g/100 g (no value assigned)

Lab Results ERM-EF413 - Ash (ISO 1171/ASTM D3174)
L1 9.7 9.7 10.78 10.79 9.92 9.93 10.6
L3 10.007 10.022 10.045 10.003 9.924 9.956 10.4
L4 9.674 9.699 9.656 9.64 9.62 9.621 10.2

L7 9.55 9.52 9.68 9.69 9.59 9.61 10.0
L9 9.634 9.665 9.743 9.656 9.415 9.419 9.8
L10 9.9 9.8 10.2 10.1 9.9 9.7 9.6
L12 9.49 9.44 9.5 9.59 9.51 9.53
9.4
L14 9.746 9.743 9.604 9.652 9.492 9.517
9.2
9.0
L1-ISO 1171
L12-ISO 1171
L14-ISO 1171
L8-ISO 1171
L11-ISO 1171
L3-ISO 1171*
1074/G/06-04*
L7-ISO 1171*
L9-ISO 1171*
L10-NF 03-003*
L6-ASTM D7582
L4-ÖNORM G
L13-eq. ISO
L6 9.39 9.35 9.59 9.57 9.52 9.53
1171*
L8 10.437 10.434 10.385 10.34 10.351 10.402
L11 9.59 9.65 9.53 9.56 9.41 9.43
L13 9.54 9.56 9.47 9.48 9.35 9.35
117
ERM-EF413 - Carbon (C) in g/100 g (certified value)
Lab Results ERM-EF413 - Carbon (C) (ISO 29548, ASTM D5373)
L1 89.53 89.4 87.95 88.14 88.74 88.38 92
L4 86.72 86.93 86.53 86.55 86.76 87.01 91
L6 88.07 87.98 87.91 88.03 88.25 88.16 90

L7 87.76 87.74 87.85 87.57 87.56 87.66 89
L8 88.077 88.337 88.427 88.341 88.233 88.158 88
L9 88.29 87.975 88.296 88.455 87.816 88.136 87
L10 88.1 88.4 88 88.1 88 87.9 86
L11 86.78 86.5 86.31 86.17 87.57 87.68 85
L13 88.2 88.1 87.7 87.6 88.1 87.8 84
(eq.ISO 29541)
L13-DIN 51732 (eq.
L12-ASTM D 5373 -
L14-GC-TCD
L1-ISO/TS 12902
L6-ASTM D5373-08
L8-ASTM D 5373
L9-ISO 29541
L2-not given
L3-ISO 29541
L7-ISO 29541*
L10-ISO TS 12902*
L11-ISO 29541*
L4-DIN 51732
ISO 25941)
08
L2 69.28 69.52 68.77 69.19 69.13
L3 88.56 88.58 87.998 88.099 88.051 88.082
L12 88.55 88.34 88.59 88.72 88.63 88.46
L14 89.29 91.6 89.08 88.64 89.75 89.14
ERM-EF413 - Hydrogen (H) in g/100 g (no value assigned)

EF413-Hydrogen (H) (ISO 609, ISO/TS12902, ASTM
Lab Results D5373)
L1 0.283 0.279 0.317 0.293 0.314 0.327 1.0
0.9
L3 0.198 0.209 0.211 0.27 0.256 0.255 0.8
L4 0.13 0.13 0.15 0.15 0.11 0.12 0.7

0.6
L7 0.241 0.261 0.252 0.268 0.264 0.27 0.5
L8 0.66 0.658 0.673 0.674 0.673 0.676 0.4
0.3
L10 0.2 0.2 0.2 0.2 0.21 0.22 0.2
L13 0.107 0.124 0.066 0.112 0.065 0.122 0.1
0.0
L1-ISO/TS 12902
L9-ASTM D5373-08
L7-ISO 29541*
L10-ISO TS 12902*
L13-DIN 51732 (eq.

L3-ISO 29541
L8-ISO 333
L11-ISO 29541
L12-ISO 29541*
ISO 25941)*
L9 0.202 0.13 0.201 0.161 0.13 0.13
29541)
L11 0.267 0.277 0.283 0.289 0.265 0.245
L12 0.42 0.42 0.4 0.42 0.41 0.43
118
ERM-EF413 - Nitrogen (N) in g/100 g (certified value) ERM-EF413 - Nitrogen (N) (: ISO 333, ISO/TS12902,
Lab Results ASTM D5373)
L1 1.15 1.12 1.03 1.09 1.06 1.1 1.4
L3 1.225 1.205 1.187 1.146 1.174 1.204 1.3
L4 0.98 0.99 1.03 1.05 1.09 1.1 1.2

1.1
L6 1.09 1.09 1.08 1.15 1.06 1.07
1.0
L7 1.04 1.07 1.03 1.05 1.04 1.07
0.9
L10 1.11 1.13 1.08 1.09 1.07 1.07
0.8
L11 1.16 1.13 1.09 1.11 1.12 1.1
0.7
L12 1.12 1.11 1.07 1.08 1.1 1.11
0.6
L13 1.08 1.08 1.09 1.1 1.09 1.07
L14-GC-TCD
L1-ISO/TS 12902
L3-ISO 29541
L6-ASTM D5373-08
L7-ISO 29541
L10-ISO TS 12902
L11-ISO 29541
L8-ISO 333
L9-ISO 29541
L4-DIN 51732 (eq.
L12-ASTM D 5373 -
L13-DIN 51732 (eq.
ISO 25941)
ISO 25941)
08
L8 0.458 0.463 0.462 0.455 0.509 0.561
L9 0.945 0.9 1.026 0.872 1.026 0.872
L14 1.43 1.32 1.44 1.31 1.29 1.28
ERM-EF413 - Sulfur (S) (ISO 19579/ASTM D4239) in g/100 g (certified value) ERM-EF413 - Sulfur (S) (ISO 19579/ASTM D4239)
Lab Results
0.9
L1 0.585 0.585 0.556 0.583 0.594 0.588
L3 0.576 0.587 0.56 0.563 0.566 0.569 0.8

L4 0.587 0.586 0.587 0.584 0.572 0.572 0.7
L6 0.493 0.53 0.548 0.561 0.552 0.559
0.6
L7 0.615 0.595 0.596 0.615 0.583 0.589
L8 0.606 0.597 0.577 0.574 0.577 0.572 0.5
L9 0.564 0.593 0.639 0.655 0.585 0.589 0.4

L11 0.572 0.626 0.618 0.585 0.605 0.566 0.3
L12 0.52 0.53 0.53 0.53 0.53 0.53
L1-ČSN 44 1395
L6-ASTM D4239*
L8-ASTM D4239*
L11-ASTM D4239*
L12-ASTM D4239*
L3-ISO 19579
L13-DIN 51724-3
L10-NF M03-038
L14-XRF in house
L7-ISO 19579*
L9-ISO 19579*
L4-DIN 51724-3 (eq.
(eq. ISO 19579)

(ISO 19579)
Method B*
L13 0.614 0.587 0.606 0.59 0.601 0.592
ISO 19579)
method
L10 0.69 0.65 0.67 0.68 0.66 0.67
L14 0.699 0.695 0.679 0.684 0.67 0.673
119
ERM-EF413 - Sulfur (S) (ASTM D3177) in g/100 g (no value assigned)
ERM-EF413 - Sulfur (ASTM D3177)
Lab Results
0.80
L6* 0.493 0.53 0.548 0.561 0.552 0.559
L8* 0.606 0.597 0.577 0.574 0.577 0.572 0.70

L12* 0.52 0.53 0.53 0.53 0.53 0.53
0.60
0.50
0.40
0.30
0.20
L6*
L8*
L12*
ERM-EF413 - Chlorine (Cl) in g/kg (indicative value)
Lab Results
L3 0.32 0.33 0.35 0.37 0.35 0.38 ERM-EF413 - Chlorine (Cl)
0.8
L4 0.37 0.39 0.4 0.39 0.37 0.38
0.7
L8 0.32 0.32 0.34 0.34 0.35 0.32 0.6

L10 0.3 0.3 0.3 0.3 0.3 0.3 0.5
L11 0.32 0.29 0.32 0.28 0.28 0.3 0.4
L13 0.32 0.33 0.32 0.34 0.33 0.34 0.3
L15 0.39 0.37 0.34 0.35 0.4 0.37 0.2
L18 0.4 0.36 0.43 0.35 0.36 0.36 0.1
L14-ASTM D4208
L10-NF M03-009*
L11-ISE (ASTM D4208)*
L18-k0NAA*
L1-Turbo Quant*
L4-IC (DIN 51727)
L8-IS (ISO 10304)
L7-IC (ASTM D4208)

L3-IC
L15-INAA
L19-koNAA
L22-k0NAA
L13-ÖNORM G 1075-IC*
0.36 0.44 0.34 0.4 0.4 0.35
L19 0.383 0.372 0.391 0.37 0.386 0.415
L22 0.33 0.33 0.31 0.34 0.34 0.39

L1 0.57 0.6 0.57 0.57 0.57 0.62
L7 0.33 0.33 0.3 0.32 0.29 0.29
L14 0.46 0.44 0.44 0.45 0.44 0.44
120
ERM-EF413 – Fluorine (F) in mg/kg (additional material information value)
Lab Results ERM-EF413 - Fluorine (F)
L3 61 65 66 66 57 64 80.000
L4 70 70 70 70 70 80
70.000
L7 60 60 60 60 50 60

60.000
L10 80 90 90 60 50 260 40.000
L11 50 50 50 50 50 50
30.000
L13 40 50 40 40 40 50
20.000
L11-ASTM D3761*
L13-ÖNORM G107*
L3-ISO 11724*
L4-combustion-IC*
L7-ISO 11724*
L10-not given*
ERM-EF413 - Calcium (Ca) in g/kg (certified value)
Lab Results ERM-EF413 - Calcium (Ca)
L7 3.074 3.172 3.149 3.127 3.014 3.026 4.0
L13 2.786 2.793 2.749 2.837 2.78 2.739 3.8
2.943 2.917 2.889 2.877 2.953 2.9 3.6

L15 3.251 3.071 3.325 3.322 3.136 3.062 3.4
3.2
L16 2.892 2.693 3.039 2.830 2.801 2.928 3.0
L16b 2.935 2.767 2.766 2.836 2.689 2.834 2.8
L18 2.78 2.66 2.76 3.25 3.42 3.77 2.6
2.4
3.33 2.98 2.58 2.93 2.72 2.97
2.2
L19 3.005 3.012 3.267 2.934 3.399 3.151 2.0
L20 2.65 2.68 2.72 2.65 2.73 2.64
L15-INAA
L16-HPA-IPAES
L18-k0NAA*
L7-MW-ICP-
L16b-MW-ICP-
L20-MW-ICP-
L13-ICP-AES
L19-k0NAA
L22-k0NAA
L3-ICP-MS
L22 2.7 2.33 2.89 2.8 2.49 2.74
SFMS
AES
AES
L3 2.9 2.9 2.89 2.54 2.5 2.53
121
ERM-EF413 - Magnesium (Mg) in g/kg (indicative value)
L13 1.23 1.236 1.232 1.264 1.248 1.222 1.8
1.284 1.271 1.278 1.261 1.274 1.276 1.6
1.4
L16 1.164 1.137 1.247 1.190 1.153 1.200

1.2
L18 1.206 1.076 1.027 1.063 1.151 1.032
1.0
1.331 1.344 1.06 1.406 1.222 1.134
0.8
L19 1.282 1.341 1.297 1.264 1.3 1.328 0.6
L22 1.3 1.2 1.1 1.2 1.1 1.3 0.4
0.2
L13-ICP-AES
L16-HPA-IPAES
L15-INAA
L18-k0NAA*
L19-k0NAA
L22-k0NAA
L3-ICP-MS
L7-MW-ICP-AES
L16b-MW-ICP-AES
L20-MW-ICP-SFMS
L3 1.36 1.34 1.33 1.22 1.18 1.22
L7 1.264 1.271 1.309 1.227 1.246 1.249
L15 1.422 1.174 1.21 0.873 1.193 1.324
L16b 0.814 1.088 1.146 0.943 0.960 0.826
L20 0.844 0.835 0.865 0.888 0.859 0.871
ERM-EF413 - Sodium (Na) in g/kg (certified value)

L7 0.6299 0.6285 0.6602 0.641 0.6467 0.6465 0.90
L13 0.664 0.67 0.649 0.678 0.683 0.661
0.80
0.656 0.648 0.643 0.641 0.649 0.645

L15 0.66 0.613 0.629 0.652 0.693 0.745 0.70
0.651 0.60
L16 0.666 0.6366 0.686 0.670 0.647 0.658
0.50
L16b 0.650 0.604 0.600 0.625 0.589 0.617
L18 0.672 0.778 0.601 0.719 0.716 0.779 0.40
0.635 0.805 0.702 0.727 0.72 0.651 0.30
L7-MW-ICP-AES
L13-ICP-AES
L15-INAA
L16-HPA-IPAES
L3-ICP-MS
L18-k0NAA*
L20-MW-ICP-
L16b-MW-ICP-AES
L19-k0NAA
L22-k0NAA
L19 0.671 0.66 0.667 0.673 0.674 0.672
SFMS
L20 0.543 0.534 0.55 0.517 0.543 0.532
L22 0.654 0.604 0.553 0.626 0.612 0.62

L3 0.62 0.61 0.61 0.64 0.66 0.63
122
ERM-EF413 – Potassium (K) in g/kg (additional material information value)
Lab Results
ERM-EF413 - Potassium (K)
L7 1.517 1.579 1.583 1.574 1.518 1.514
1.9
L13 1.509 1.512 1.492 1.546 1.532 1.504 1.8
1.549 1.539 1.531 1.523 1.525 1.525 1.7

L16 1.400 1.357 1.473 1.362 1.366 1.383 1.6
L16b 1.564 1.536 1.552 1.539 1.578 1.553 1.5
1.4
L19 1.360 1.400 1.350 1.400 1.410 1.420
1.3
L20 1.510 1.390 1.310 1.510 1.430 1.410 1.2
L22 1.283 1.396 1.392 1.309 1.297 1.277 1.1
L13-ICP-AES
L16-HPA-IPAES
L15-INAA
L18-k0NAA*
L7-MW-ICP-AES
L16b-MW-ICP-AES
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L3-ICP-MS
L3 1.53 1.51 1.53 1.52 1.57 1.51
L15 1.767 1.356 1.512 1.593 1.523 2.105
L18 1.46 2.54 1.35 1.63 1.63 1.57
1.49 1.38 1.52 2.74 1.38 1.2

L3 2.7 3.3 3.2 3.1 3.2 3.1 10
L7 3.44 3.505 3.383 3.827 3.632 3.747 9
L13 5.42 5.26 5.16 6.48 6.42 5.44 8

7
7.64 7.66 7.93 7.64 8.16 7.68 6
L15 3.317 3.34 3.37 3.465 3.293 3.545 5
L16 2.344 2.061 2.478 2.193 2.34 2.416 4
L18 3.75 3.06 3.75 3.04 4.55 3.38 3
2
3.69 2.91 2.68 3.38 2.95 3
1
L19 3.48 3.46 3.5 3.71 3.48 3.51
L15-INAA
L21-HPMW-ICP-MS
L3-ICP-MS
L7-MW-ICP-MS
L13-MW-HGAAS
L16-HPA-ICP-SFMS
L18-k0NAA
L19-k0NAA
L20-MW-ICP-SFMS
L22-k0NAA
L20 1.78 1.79 1.79 1.87 1.83 1.85
L21 3.17 3.1 3.16 3.21 3.57 2.95
L22 3.31 3.09 2.86 3.47 3.36 3.2
123
ERM-EF413 Cadmium (Cd) in mg/kg (no value assigned)
ERM-EF413 - Cadmium (Cd)
Lab Results
0.14
L7 0.056 0.057 0.051 0.053 0.048 0.051
L16 0.029 0.027 0.029 0.031 0.031 0.031 0.12

0.031 0.027 0.029 0.033 0.033 0.034 0.10
L20 3.17 3.1 3.16 3.21 3.57 2.95 0.08
0.06
L13 (ICP- 0.13 0.15 0.12 0.11 0.08 0.06
0.02
AES) 0.07 0.08 0.05 0.02 0.08 0.05
0.00
L13 (GFAAS) 0.02 0.11 0.03 <0.01 <0.01 0.01
L21-HPMW-ICP-
L7-MW-ICP-MS
L16-HPA-ID-TIMS
L13-ICP-AES
L13-GFAAS
L20-MW-ICP-
L21 0.045 0.044 0.042 0.053 0.059 0.046
SFMS
MS
ERM-EF413-Cobalt (Co) in mg/kg (no value assigned)
Lab Results
L3 17 18 19 16 16 16 ERM-EF413-Cobalt (Co)
L7 9.14 9.067 8.961 9.351 9.095 9.062 15
L13 9 10.1 9.6 8.1 8.6 9 14
13
9.4 8.7 8.7 9.2 9 8.6 12

L15 9.197 9.79 9.871 9.64 9.893 9.197 11
10
L16 7.682 6.922 8.314 7.667 8.241 7.682 9
L18 9.56 9.42 9.22 10 8.8 9.56 8
10 9.32 8.15 9.46 9.3 7.9 7
6
L19 10.2 10 10.1 10 10.3 10.1 5
L15-INAA
L16-HPA-ICP-SFMS
L3-ICP-MS*
L7-MW-ICP-MS*
L18-k0NAA*
L20-MW-ICP-SFMS*
L21-HPMW-ICP-MS*
L13-MW-ICP-AES
L19-k0NAA
L22-k0NAA
L20 5.65 5.71 5.62 5.87 5.77 5.83
L21 9.01 9.11 9.01 9.51 8.08 9.01
L22 9.9 10.1 8.5 10.5 10.1 9.9
124
ERM-EF413 - Chromium (Cr) in mg/kg (no value assigned)
Lab Results
310
L13 84 94 86 90 81 89
82 85 86 96 91 95 260

L15 94.94 103.5 110.2 132.9 99.4 111.4 210
L18 84.2 71.7 76.6 81.8 81.8 88.3 160
115.6 81.3 67.3 100 92 67.9 110
L19 99.9 87.9 104 85.5 106 104
60
L22 90 80.3 75.2 100 103 89
10
L15-INAA
L21-HPMW-ICP-MS
L18-k0NAA*
L13-MW-ICP-AES
L19-k0NAA
L22-k0NAA
L21 131.7 128.6 131.7 212.4 232 195
ERM-EF413 - Copper (Cu) in mg/kg (no value assigned)

Lab Results
L3 35 42 47 32 31 34 ERM-EF413 - Copper (Cu)
50
L7 22.35 23.06 23.16 23.04 23.43 23.34
45
L13 22.9 25.8 23.2 24.2 24.7 23.1
40

21.3 23.2 22.6 24.8 21.8 22.5 35
L15 23.2 26.7 23.6 30
L16 18.236 16.661 20.027 19.162 19.597 19.24 25
L20 19.4 19.5 19.3 20.1 19.7 20.2 20
L21 24.6 24.7 24.4 25.5 27.4 23.3 15
L22 26 23.4 20 19.2 17 19 10
L3-a-ICP-MS
L7-MW-ICP-MS
L13-MW-ICP-AES
L15-INAA
L16-HPA-ICP-SFMS
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
L22-k0NAA
125
ERM-EF413 - Mercury (Hg) in mg/kg (no value assigned)
Lab Results
ERM-EF413 - Mercury (Hg)
L3 0.004 0.003 0.004 0.002 0.003 0.003
0.040
L13 0.024 0.016 0.018 0.053 0.02 0.015
0.026 0.031 0.017 0.034 0.02 0.006 0.035

L16 0.0011 0.0013 0.0027 0.003 0.0006 0.0023 0.030
0.025
L19 0.004 0.003 0.005 0.003 0.004 0.004
0.020
L15 0.12 0.010
L20 0.014 0.012 0.013 0.009 0.011 0.01
0.005
L21 0.003 0.004 0.001 0 0 0
0.000
L15-INAA
L19-Hg
L13-MW-
L16-MW-
HPMW-
L3-DMA
ICP-SFMS
ICP-MS
L20-MW-
CVAAS
CVAFS
L21-
ERM-EF413 - Manganese (Mn) in mg/kg (no value assigned)
Lab Results ERM-EF413 - Manganese (Mn)
L3 120 132 132 110 109 113 180
L7 88.12 92.41 90.89 93.69 94.79 94.09 160
L13 93.6 87.1 89 97.2 98.9 86.6

140
97.6 97.3 97.6 88.9 90.1 89.9
120
L15 77.37 89.41 74.75 82.42 77.72 90.51
100
L16 76.323 71.862 82.653 83.966 81.323 79.088
L18 85.2 79.4 88.4 75.4 65.7 77.1 80
83.4 117.7 83.6 105.4 85.1 82.6 60
L18-k0NAA*
L3-ICP-MS
L7-MW-ICP-MS
L13-MW-ICP-AES
L15-INAA
L16-HPA-ICP-AES
L19-k0NAA
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
L22-k0NAA
L23-MW-ICP-AES
L19 91.7 90.6 93.3 101 90.2 96.5
L20 138 139 133 147 143 143
L21 85.8 86.2 85.4 77.8 83.4 69.8
L22 74.1 80.6 81.9 75 73.4 86
L23 84.839 81.371 79.612 84.202 81.062 86.04
126
ERM-EF413 - Nickel (Ni) in mg/kg (no value assigned)
Lab Results ERM-EF413 - Nickel (Ni)
L13 48.5 54.6 51.6 48.9 44.9 51.2 55
48 49.7 48 56.5 54.3 55.8
L15 53.81 46.85 54.45 60.02 59.25 47.21 50

L21 41.2 41.2 41.2 38.3 41.3 34.2
45
40
35
30
L15-INAA
ICP-MS*
L13-MW-
ICP-AES
HPMW-
L21-
ERM-EF413 - Lead (Pb) in mg/kg (indicative value)
Lab Results
ERM-EF413 - Lead (Pb)
L3 7 8.5 9.1 7.3 7.3 7.2 12.0
L7 9.295 9.232 9.292 9.475 9.49 9.436
11.0
L16 8.682 7.758 10.277 8.863 9.502 8.682

L20 6.45 6.39 6.51 6.65 6.54 6.45 10.0
L21 9.55 9.32 9.23 10.4 8.86 9.55 9.0
8.0
7.0
L13 6.6 7 7.4 6.9 6.9 6.6
7.5 8 7.7 7.9 8.5 8.4 6.0
5.0
4.0
L7-MW-
L13-MW-
L3-ICP-MS
SF-ICPMS
ICP-SFMS
ICP-MS
HPMW-
ICP-MS
ICP-AES
L16-HPA-
L20-MW-
L21-
127
ERM-EF413 - Antimony (Sb) in mg/kg (no value assigned)
Lab Results ERM-EF413 - Antimony (Sb)
1.8
L15 1.38 1.381 1.401 1.369 1.324 1.325
1.6
L18 1.28 1.41 1.73 1.22 1.28 1.1 1.4

1.26 1.16 1.028 1.3 1.13 1.16 1.2
L19 1.33 1.33 1.36 1.31 1.31 1.33 1.0
L22 1.31 1.22 1.11 1.18 1.24 1.2 0.8
0.6
0.4
L21 0.07 0.06 0.06 0.04 0.05 0.04 0.0
L15-INAA
L18-k0NAA*
L21-HPMW-ICP-MS*
L19-k0NAA
L22-k0NAA
Lab Results
L7 1.895 1.858 1.955 1.995 1.877 1.895 ERM-EF413 - Selenium (Se)
2.5
L13 1.32 1.34 1.26 1.3 1.24 1.32
1.27 1.39 1.29 1.39 1.42 1.34 2.0
L16 1.096 0.924 1.067 1.095 1.131 1.096

1.5
L18 1.46 1.15 1.54 1.43 1.19 1.46
1.23 1.49 1.33 1.65 1.23 1.41 1.0
L19 1.15 1.42 1.32 1.37 1.34 1.15
0.5
L20 0.875 0.86 0.866 0.848 0.878 0.875
L21 1.49 1.48 1.44 1.75 1.45 1.49 0.0
L7-MW-ICP-MS
L13-MW-ICP-AES
L16-HPA-ICP-SFMS
L19-k0NAA
L20-MW-ICP-SFMS
L21-HPMW-ICP-MS
L22-k0NAA
L15-INAA
L18-k0NAA*
L22 1.24 1.3 1.29 1.32 1.53 1.24

L15 < LOQ < LOQ 1.13 0.76 0.81 < LOQ
128
ERM-EF413 - Tin (Sn) in mg/kg (no value assigned)
Lab Results
ERM-EF413 - Tin (Sn)
L3 1.2 1.3 1.6 1.3 1.7 1.6
2.6
L7 0.934 0.97 0.991 0.914 0.873 0.884
L16 0.59 0.476 0.623 0.613 0.586 0.564
2.1

L21 0.165 0.205 0.227 0.248 0.269 0.295
1.6
L20 0.776 0.753 0.747 0.752 0.767 0.756
1.1
0.6
0.1
L7-MW-
HPMW-
L3-ICP-MS
ICP-SFMS
ICP-SFMS
ICP-MS
ICP-MS
L16-HPA-
L20-MW-
L21-
ERM-EF413 - Thallium (Tl) in mg/kg (additional material information value)
0.20
L7 0.169 0.172 0.173 0.176 0.177 0.177
0.18
L16 0.142 0.13 0.144 0.139 0.142 0.139 0.16

L20 0.119 0.121 0.123 0.128 0.123 0.122 0.14
0.12
L3 < LOQ < LOQ < LOQ 0.12 0.12 0.13 0.08
0.06
L21 0.068 0.079 0.075 0.007 0.036 0
0.04
0.02
L7-MW-ICP-MS
L21-HPMW-ICP-MS
L3-ICP-MS*
L16-HPA-ICP-
L20-MW-ICP-SFMS
SFMS
129
ERM-EF413 - Vanadium (V) in mg/kg (no value assigned)
Lab Results ERM-EF413 - Vanadium (V)
L3 25 29 31 25 23 23 50
L7 38.26 39.32 38.62 39.51 39.73 39.23
45
L13 36.8 36.2 36.1 36.3 35.5 36

38.1 37.9 36.7 37.4 37.9 37.6 40
L15 39.46 39.46 44.1 40.49 40.1 40.71
L16 23.508 23.187 23.959 22.2 24.391 23.06 35
L18 41.9 41.8 45.1 40.5 42.2 44.2
43.3 42.2 36 42.1 37.9 39.1 30
L19 42.2 41 41.9 41.5 41.6 43.8 25

L22 40.1 38.6 41.6 38.4 37 38.6
20
HPMW-…
L15-INAA*
L7-MW-
L13-MW-
L3-ICP-MS
ICP-SFMS
L19-k0NAA
L22-k0NAA
ICP-SFMS
k0NAA*
ICP-MS
ICP-AES
L16-HPA-
L20-MW-
L18-
L21-
L20 24.3 24.1 23.5 24.9 23.8 25.3
L21 32.2 32 32.8 32.5 35.3 30.3
ERM-EF413 - Zinc (Zn) in mg/kg (certified value)

Lab Results
L3 16 18 23 13 14 13
L7 17.14 16.83 16.54 16.72 15.8 16.82 ERM-EF413 - Zinc (Zn)
L13 13.4 15.8 14.7 15.2 16.1 16.2 25
14.7 15.6 14.4 15.9 16.1 14.6 23
L15 17.82 14.22 18.29 15.95 19.51 15.82 21
Mass fraction [gg/kg]

L16 13.762 12.059 14.466 13.912 15.001 15.317 19
L19 16.6 16.5 19.6 17.3 28 18.7 17
L20 13.9 13.7 13.7 14.5 14.3 14.8 15
L21 14.7 15.1 15.9 15.7 17.2 14.2 13
L22 15.9 16.1 14.7 16.5 16.8 16.6 11
9
L18 19.6 14.1 19 14.8 26.1 14.4 5
HPMW-…
16.2 19.5 31.3 14.1 59.5 11.8
L3-ICP-
L13-MW-
ICP-AES
L15-INAA
ICP-SFMS
k0NAA
ICP-SFMS
k0NAA
k0NAA*
ICP-AES
L16-HPA-
L7-MW-
L20-MW-
L19-
L22-
L21-
L18-
MS
130
European Commission
EUR 26197 EN – Joint Research Centre – Institute for Reference Materials and Measurements
Title: The certification of the gross calorific value and mass fractions of ash, C, H, N, S, Cl, major elements and
trace elements in three coal materials: ERM®-EF411 (hard coal), ERM®-EF412 (brown coal) and
ERM®-EF413 (furnace coke)
Author(s): Thomas P.J. Linsinger, Barbara Raffaelli, Albert Oostra
European Commission, Joint Research Centre,Institute for Reference Materials and Measurements
(IRMM), Geel, Belgium
Luxembourg: Publications Office of the European Union

2013 – 130 pp. – 21.0 x 29.7 cm
EUR – Scientific and Technical Research series – ISSN 1831-9424
ISBN 978-92-79-33415-3
doi:10.2787/80616
Abstract
This report describes the production of ERM-EF411, ERM-EF412 and ERM-EF413, three coal materials certified for
proximates and trace elements. The materials have been produced following ISO Guide 34:2009.
Industrial hard coal, brown coal and furnace coke were obtained, dried, milled (ERM-EF411 and ERM-EF413) and
filled into aluminium laminated sachets.
Between-unit homogeneity was quantified and stability during dispatch and storage were assessed in accordance
with ISO Guide 35:2006. Within-unit heterogeneity was quantified to determine the minimum sample intake.
The material was characterised by an intercomparison among laboratories of demonstrated competence and
adhering to ISO/IEC 17025. Technically invalid results were removed but no outlier was eliminated on statistical
grounds only.
Uncertainties of the certified values were calculated in compliance with the Guide to the Expression of Uncertainty in
Measurement (GUM) and include uncertainties related to possible heterogeneity and instability and to
characterisation.
The materials are intended for quality control and assessment of method performance. As any reference material,
they can be used for control charts or validation studies, as well. The CRMs are available in sachets containing 50 g
of dried material. The minimum amount of sample to be used, depending on the analyse, varies from 30 mg to 1 g.
The CRM was accepted as European Reference Material (ERM®) after peer evaluation by the partners of the
European Reference Materials consortium.
.
LA-NA-26197-EN-N
As the Commission's in-house science service, the Joint Research Centre's mission is to provide EU
policies with independent, evidence-based scientific and technical support throughout the whole
policy cycle.
Working in close cooperation with policy Directorates-General, the JRC addresses key societal
challenges while stimulating innovation through developing new methods, tools and standards, and
sharing its know-how with the Member States, the scientific community and international partners.
Key policy areas include: environment and climate change; energy and transport; agriculture and food
security; health and consumer protection; information society and digital agenda; safety and security,
including nuclear; all supported through a cross-cutting and multi-disciplinary approach.

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CERTIFICATION REPORT

The certification of the gross calorific value and

Luxembourg: Publications Office of the European Union

© European Union, 2013

Reproduction is authorised provided the source is acknowledged

The certification of the gross calorific value and

Thomas P.J. Linsinger, Barbara Raffaelli, Albert Oostra

European Commission, Joint Research Centre,

The following certified values were assigned:

The following information values were assigned

4.3 Homogeneity study

Nuon Power Generation NV, Utrecht, NL

4.4 Stability study

Nuon Power Generation NV, Utrecht, NL

ArcelorMittal Ostrava a.s., Hutní a chemické laboratore, Ostrava-Kuncice, CZ

ASCAL ENVIRONNEMENT, Forbach, FR

Australian Nuclear Science and Technology Organisation (ANSTO), Kirrawee DC , AU

Energie AG Oberösterreich Kraftwerke GmbH, St. Pantaleon, AT

Helsingin Energia (Helen), Helsinki, FI

Incolab Services B., Oud Beijerland, NL

Institut Jožef Stefan (IJS), Department of Environmental Sciences, Ljubljana, SI

Intertek Testing Services Switzerland, Schlieren, CH

PEGOP - Energia Eléctrica, S.A., Laboratório Químico, Pego, PT

SGS Nederland B.V., Vlissingen, NL

SGS Latvija Ltd, Riga, LV

Solvias AG, Kaiseragust, CH

Technische Universiteit Delft, Reactor Institute Delft, Delft, NL

Verbund Umwelttechnik GmbH, Standort FHKW Mellach, Wildon, AT

5 Material processing and process control

Figure 1: Raw material for ERM-EF411

5.2 ERM-EF412, brown coal

Figure 2: Raw material for ERM-EF412

6.1 Between-unit homogeneity

6.2 Within-unit homogeneity and minimum sample intake

ults,rel , deg = (b ⋅ t sl ) 2 + ults2 ,rel

The following uncertainties were estimated:

Sn L20 (EF412) Results close to LOQ data retained

• uchar,rel was estimated as described in Section 8.5.2

Table 17: Certified values and their uncertainties for ERM-EF412

9.2 Indicative values and their uncertainties

9.3 Additional material information

9.4 Additional data from k0NAA

11 Instructions for use

GCV unit number

Homogeneity study ERM-EF411 Homogeneity study ERM-EF411

72.4 5.04 0.040

Cl mass fraction [g/100 g]

C H unit number Cl unit number

Homogeneity study ERM-EF411 Homogeneity study ERM-EF411

As mass fraction [mg/kg]

Cd mass fraction [mg/kg]

1.28 0.50 0 0.00

N S unit number As Cd unit number

Homogeneity study ERM-EF411 Homogeneity study ERM-EF411

Cu mass fraction [mg/kg]

Hg mass fraction [mg/kg]

Co Cr unit number Cu Hg unit number

Pb mass fraction [mg/kg]

Sb mass fraction [mg/kg]

Mn Ni unit number Pb Sb unit number