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CCQM-K102 E-mail: [email protected]
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EUROPEAN COMMISSION JOINT RESEARCH CENTRE Directorate F- Health, Consumers & Reference Materials (Geel) Reference Materials Unit
CCQM-K102
Polybrominated diphenyl ethers in sediment
"Track A" - Low polarity analytes in abiotic matrix
Final Report
Coordinating laboratory:
Marina Ricci*, Penka Shegunova, Patrick Conneely
European Commission, Joint Research Centre (JRC)
Directorate F- Health, Consumers & Reference Materials
Retieseweg 111, 2440 Geel, Belgium
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With contributions from:
Roland Becker
Bundesanstalt für Materialforschung (BAM), Germany
Mauricio Maldonado Torres, Mariana Arce Osuna
Centro Nacional de Metrologia (CENAM), Mexico
Tang Po On, Lee Ho Man
Government Laboratory Hong Kong (GLHK), Hong Kong S.A.R.
Song-Yee Baek and Byungjoo Kim
Korea Research Institute of Standards and Science (KRISS), Republic of Korea
Christopher Hopley, Camilla Liscio, John Warren
LGC Limited (LGC), United Kingdom
Véronique Le Diouron, Sophie Lardy-Fontan, Béatrice Lalere
Laboratoire National de Métrologie et d'Essais (LNE), France
Shao Mingwu
National Institute of Metrology (NIM), China
John Kucklick
National Institute of Standards and Technology (NIST), United States
Veronica Vamathevan
National Measurement Institute Australia (NMIA), Australia
Shigetomo Matsuyama, Masahiko Numata
National Metrology Institute of Japan (NMIJ), Japan
Martin Brits, Laura Quinn, Maria Fernandes-Whaley
National Metrology Institute of South Africa (NMISA), South Africa
Ahmet Ceyhan Gören, Burcu Binici
National Metrology Institute of Turkey (UME), Turkey
Leonid Konopelko, Anatoli Krylov, Alena Mikheeva
D.I. Mendeleyev Institute for Metrology (VNIIM), Russia
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TABLE OF CONTENTS
1. INTRODUCTION ....................................................................................................... 4
2. STUDY ANALYTES .................................................................................................. 5
3. STUDY MATERIAL .................................................................................................. 6
3.1 Material preparation and initial characterisation ................................................... 6
3.2 Homogeneity study ................................................................................................ 7
3.3 Stability study ........................................................................................................ 7
4. SAMPLES DISTRIBUTION AND STUDY GUIDELINES ..................................... 9
5. CALIBRANTS' TRACEABILITY ........................................................................... 10
6. ANALYTICAL METHODS EMPLOYED .............................................................. 12
6.1 Dry mass determination ....................................................................................... 15
7. RESULTS .................................................................................................................. 15
8. APPROACHES TO UNCERTAINTY BUDGET ESTIMATION ........................... 17
9. KEY COMPARISON REFERENCE VALUES CALCULATION ......................... 21
10. DEGREES OF EQUIVALENCE (DOE) CALCULATION .................................... 24
11. CORE COMPETENCIES AND HOW FAR DOES THE LIGHT SHINE? ............ 30
12. CONCLUSIONS ....................................................................................................... 31
13. ACKNOWLEDGEMENTS ...................................................................................... 31
14. REFERENCES .......................................................................................................... 31
ANNEX A ......................................................................................................................... 32
ANNEX B ......................................................................................................................... 48
ANNEX C ......................................................................................................................... 52
ANNEX D ......................................................................................................................... 66
ANNEX E .......................................................................................................................... 68
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1. INTRODUCTION
Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants (i.e., to
reduce the inflammability) in many combustible commercial and household products,
such as polymers, electrical and electronic equipment, textiles, furniture, building and
packaging materials, since the last few decades. PBDEs are additives type brominated
flame retardants, meaning that they are not chemically bound but only physically
mixed/dissolved in the material. Due to the lack of covalent bonds between PBDEs and
the material, the release of these compounds into the environment can occur not only
when they are manufactured but also when products that contain them are used and
disposed of [1-2].
Environmental contamination by PBDEs has attracted public attention and concern in
recent years due to their large use, ubiquity (linked to the potential for long-range
atmospheric transport [3]) and high persistence, bioaccumulation and toxicity, thus
presenting a potential threat to wildlife and human health. Presence of PBDEs has been
reported in a range of environmental media and biota including fish, sediment, treated
sewage sludge and household dust [4-6]. PBDEs #28, 47, 99, 100, 153 and 154 are listed
as Priority Substances under the EU Water Framework Directive (WFD) and they are
also considered of primary interest for the environment in US and Canada (e.g., EPA
Method 1614).
Three technical mixtures namely pentabromodiphenyl ether (Penta-BDE),
octabromodiphenyl ether (Octa-BDE) and decabromodiphenyl ether (Deca-BDE) were
the most used brominated flame retardants until early 2000s, when the production and
usage of Penta– and Octa-BDE began to be regulated worldwide. The European Union
banned Penta-BDE and Octa-BDE in 2004 [7a] and prohibited the use of PBDEs (and
polybrominated biphenyls) in electric and electronic devices as of 1st July 2006 [7b].
The three commercial mixtures are composed of a mixture of congeners, and are named
according to their average bromine content, see Table 1.
Table 1. Composition of technical PBDEs products (% m/m) [8]
Technical
product tetraBDEs pentaBDEs hexaBDEs heptaBDEs octaBDEs nonaBDEs decaBDE
Penta-BDE 24-38 50-60 4-8
Octa-BDE 10-12 44 31-35 10-11 <1
Deca-BDE <3 97-98
The Track A suite of Key Comparisons was set by the CCQM OAWG to provide
objective evidences of core competencies needed to underpin the CMCs of an NMI for
the delivery of measurement services to customers. At the CCQM OAWG meeting held
in April 2011, it was agreed to have a comparison on brominated flame retardants in
sediment (fitting the category "low polarity analytes in abiotic matrix") as Track A study
for 2012 (service categories 5-10). This Key Comparison K102 was accompanied by the
parallel Pilot Study P138 (where the same study material was used).
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JRC-IRMM (renamed in 2016 as JRC, Directorate F - Health, Consumers & Reference
Materials) provided the sediment study material and coordinated the study, including
preparation and distribution of samples, data analysis and evaluation, drafting of reports.
NMIs/DIs with current published CMC claims in Appendix C of the Key Comparison
Database (KCDB) under the Mutual Recognition Arrangement of the International
Committee for Weights and Measures (CIPM MRA) or anticipating to propose CMC
claims in the selected measurement field (see Section 11) were expected to participate in
K102, so to avoid delays in the review, approval and acceptance of existing or future
CMC claims.
2. STUDY ANALYTES
Minimum reporting requirements for participants to CCQM-K102 were the mass
fractions (on a dry mass basis) of BDE 47, 99 and 153 in the freshwater sediment study
material. Possibility of reporting also the mass fraction of BDE 209 was left open to the
participants.
Among all PBDEs congeners, BDE 47, 99 and 153 were chosen considering the
following issues:
- analytical properties: different molar masses, different polarity and volatility, different
bromine substitutions (from tetra- to hexa-) (see Table 2)
Table 2. PBDEs selected as study analytes for CCQM K102
Congener Structural formula Chemical formula
(MW g/mol) Log Kow [9]
BDE-47
2,2',4,4'-tetraBDE
C12H6Br4O (485.8) 6.81 ± 0.08
BDE-99
2,2',4,4',5-pentaBDE
C12H5Br5O (564.7) 7.32 ± 0.14
BDE-153
2,2',4,4',5,5'-hexaBDE
C12H4Br6O (643.6) 7.90 ± 0.14
- analytical challenges: e.g. discrimination, likelihood of interferences. More specifically:
BDE 47: possible issues with discrimination in the GC injector
BDE 47, 99 and 153: possibility of co-elution with other environmental contaminants
O
Br Br
BrBr
O
Br Br
BrBr
Br
O
Br Br
BrBr
BrBr
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e.g., PCBs and/or other classes of flame retardants/halogenated compounds
- legislative and environmental relevance (see Section 1): BDE 47 and 99 are the most
abundant compounds present in the Penta-BDE commercial technical mixture
- attributes of the study material, with regard to the presence, mass fraction levels as well
as homogeneity and stability evaluation (see Section 3)
- connection to the previous pilot study CCQM-P114, Brominated flame retardants in
polypropylene, in which BDE 47 was measured.
The approximate mass fraction range on a dry mass basis of the selected PBDEs (47, 99
and 153) was anticipated to be between 1 and 50 μg/kg.
3. STUDY MATERIAL
3.1 Material preparation and initial characterisation
The sediment study material was prepared at JRC-IRMM. It originated from a river in
Belgium and contained PBDEs at levels typically found in environmental monitoring.
The material underwent a first series of processing steps: air-drying, sieving (1 mm), jet-
milling, homogenisation and γ-irradiation. The final powdered sediment was dispensed in
portions of about 40 g into 60 mL amber glass bottles with aluminium coated screw caps
sealed with a shrink film.
Water determination by volumetric Karl-Fischer titration was carried out in duplicate on
15 bottles randomly selected over the whole production batch and yielded a value of 0.45
± 0.06 g/100g (mean ± U, k = 2) (preliminary result with the drying-oven method: ≈ 0.5
g/100g). Total organic carbon measurements (in accordance to ISO 10694:1995) were
carried out in duplicate on 3 bottles, leading to a value of 0.641 ± 0.071 % C (mean ± U,
k = 2, dry mass basis).
The homogeneity data on this first batch prepared were unfortunately not satisfactory,
thus some bottles of the original batch were opened, re-sieved (125 µm), mixed, re-
bottled (see first batch) and subjected again to γ-irradiation. This re-processed second
batch of 92 units was further characterised with respect to the particle size. Particle size
analysis (laser light diffraction) was carried out in triplicate on one bottle randomly
chosen and revealed an average top particle size X90 = 55.64 ± 11.57 µm (mean ± U,
k=2). The study material was stored at + 4 °C ± 3 °C in the dark.
Fig. 1 Example of bottles of study material
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3.2 Homogeneity study
LNE kindly volunteered to analyse the newly prepared batch of study material by GC-
ID-MS/MS for assessing the homogeneity and stability of BDEs 28, 47, 99, 100, 153,
154, 183 and 209.
Homogeneity was assessed by triplicate analysis on 8 units (1 g sample intake) measured
in random order and under “quasi” repeatability conditions. Regression analyses did not
detect trends either in the analytical sequence or in the filling sequence. Estimation of
potential between-unit inhomogeneity (ubb) was accomplished by ANOVA. When the
mean square between groups (MSbetween) is smaller than the mean square within groups
(MSwithin), the between-unit variation sbb cannot be calculated and ubb*, maximum
inhomogeneity that could be hidden by method repeatability [10], is calculated instead.
The largest among sbb and ubb* is adopted as ubb, uncertainty contribution to account for
potential material inhomogeneity. The uncertainty contributions due to potential material
inhomogeneity were estimated as 2.7, 1.8 and 2.2 % for BDE 47, 99 and 153,
respectively, confirming the suitability of these analytes as study measurands for the
CCQM-K102 (Table 3).
Table 3. Homogeneity results (study analytes are green shaded)
% ubb
BDE 28 2.9 (ubb*)
BDE 47 2.7 (sbb)
BDE 99 1.8 (ubb*)
BDE 100 2.4 (ubb*)
BDE 153 2.2 (sbb)
BDE 154 2.9 (ubb*)
BDE 183 4.2 (sbb)
BDE 209 4.0 (sbb)
3.3 Stability study
An isochronous short-term stability study was performed at 18 °C with time points 0, 1, 2
and 4 weeks. One unit per time point was selected using a random stratified sampling
scheme and analysed in triplicate by GC-ID-MS/MS in random order and under “quasi”
repeatability conditions (1 g sample intake). For all PBDEs, the slopes of the regression
lines were not significantly different from zero (both at 95 % and 99 % confidence
levels), with the sole exception of BDE 209. For BDE 209, the slope of the linear
regression was significantly different from zero at 95 % (but not at 99 % confidence
level), possibly indicating degradation, and one outlier was detected (Grubbs single test
both at 99 and 95 % confidence level).
The stability study confirmed that the study measurands were stable at 18 °C for at least
4 weeks (Figure 2a, 2b and 2c). As a conservative mean, the dispatch and storage
temperature was set at 4 °C.
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Fig.2a Stability study at 18 ° C for BDE47
Fig.2b Stability study at 18 ° C for BDE99
Fig.2c Stability study at 18 ° C for BDE153
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4. SAMPLES DISTRIBUTION AND STUDY GUIDELINES
Fourteen NMIs/DI and one associate member subscribed for participation to the CCQM-
K102. Three bottles of the study material, each bottle containing 40 g of dried river
sediment, were dispatched with cooling elements by courier to the participants.
Additional bottles were sent to two laboratories upon request. The dispatch took place on
several dates during July and August 2014. Participants were asked to check the physical
conditions of the samples upon receipt, put it for storage at + 4 °C and report back to the
study coordinator. All laboratories received the samples in good conditions in 2-3 days,
except few laboratories for which delivery took longer due to customs problems (see
Table 4 for more details).
The study protocol, the registration form, the sample receipt form and the reporting sheet
for the results were sent to all laboratories by e-mail before or at the same time of the
dispatch of the samples. The Core Competency table was sent by e-mail in October 2014,
after revision by the CCQM OAWG at the fall meeting 2014.
Table 4. Samples dispatch schedule
Dispatch date Receipt date
Participants were requested to report the mass fractions (µg/kg) of BDEs 47, 99 and 153
on a dry mass basis in the study material applying their own analytical methodology, but
following some additional recommendations given by the study coordinator:
- upon receipt and until analysis, the samples should be stored at + 4 °C in the dark.
Equilibration to room temperature should be ensured before commencing the analytical
procedure. Before opening, the bottle should be shaken by turning upside down for 2
minutes for allowing material re-homogenisation.
The minimum sample intake had to be at least 1 g and the dry mass determination had to
be performed according the following protocol:
- a correction for dry mass shall be performed at the same time of the analysis by taking
2 separate portions of at least 1 g from each bottle analysed, drying them in an oven at
(105 ± 2) °C until constant mass is attained (subsequent weightings should not differ
more than 0.5 mg).
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The participants were requested to report the following data in the provided reporting
sheet to [email protected] (together with the Core Competency table) before the
deadline for submission (extended to 15th
April 2015):
Participant's details
Mass fractions (µg/kg) of each individual measurand (see Table 2) in the study
sample on a dry mass basis
Standard and expanded measurement uncertainties, with a detailed
description/breakdown of the full uncertainty budget
Description of the analytical procedure employed (extraction, clean-up,
separation/detection and quantification) as well as details concerning the
calibration and internal standards used (purity statement or verifications done at
the laboratory's premises etc…), especially if not mentioned in the Core
Competency table.
5. CALIBRANTS' TRACEABILITY
The information on the calibration standards used by the participants in CCQM-K102 are
given in Table 5.
CRM PBDEs solutions are available from NIST and NIM China. Pure PBDEs are also
commercially available from different suppliers as neat reagents (Chiron) and as
solutions (e.g., Chiron, Accustandard, Wellington Laboratories, CIL).
Almost half of the participating laboratories (6 out of 14) used NIST 2257 (PBDE
Congeners in 2,2,4-Trimethylpentane) as direct source of traceability. Other five
laboratories (NMISA, NMIA, LNE, CENAM and KRISS) used NIST 2257 in a transfer
value assignment process on commercially available standards (CIL, Wellington Lab.
and Accustandard); in particular, KRISS assessed the purity of the calibrants employed
by GC-FID, with cross-confirmation with SRM 2257; NMIA cross-checked the transfer
value assignment process by also using GBW(E)081124 and GBW(E)081125.
NIM used their own CRM, GBW(E)081124, Industrial penta-BDE in iso-octane. Two
laboratories, LGE and TUBITAK UME, assessed in-house the purity of the purchased
standards by means of qNMR, either on the neat substances or on solutions thereof.
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Table 5. Calibrants used in CCQM-K102
Participant
laboratory
Calibrants'
source
Purity % or
certified value
Purity assessment
JRC-IRMM NIST 2257
BDE47: 2.09±0.16 µg/g
BDE99: 2.127 ± 0.090 µg/g
BDE153: 2.048 ± 0.068 µg/g
N/A
LGC Chiron neat
substances > 98 %
qNMR to value assign BDE
solutions (+ verification on
neat BDE47 and 99)
NMISA CIL
BDE47: 68.28±5.77 µg/g
BDE99: 68.21±3.87 µg/g
BDE153: 68.59 ± 3.87 µg/g
values assigned using
SRM 2257
NIM GBW(E)081124
BDE47: 20.0 µg/mL U=4 %
BDE99: 20.5 µg/mL U=4 %
BDE153: 1.43 µg/mL U=4 %
N/A
VNIIM NIST 2257 see above N/A
KRISS AccuStandard
BDE 47, 99, and 153 were
98.75%, 95.50 %, and 95.83 %,
respectively
GC-FID assigned values
confirmed with SRM2257
TÜBITAK
UME
Chiron neat
substances
BDE47: 99.2±0.03 %
BDE99: 98.7±0.02 %
BDE153: 99.5±0.05 %
determined by qNMR
(SRM 1944 used for
confirmation, but BDEs
values are not certified)
GLHK NIST 2257
BDE47: 2.09±0.16 µg/g
BDE99: 2.127 ± 0.090 µg/g
BDE153: 2.048 ± 0.068 µg/g
N/A
NMIA Wellington Lab.
BDE47: 50 ± 2.5 µg/mL
BDE99: 50 ± 2.5 µg/mL
BDE153: 50 ± 2.5 µg/mL
10 % toluene in nonane
values assigned by
comparison to SRM 2257,
GBW(E)081124 and
GBW(E)081125
BAM NIST 2257 see above N/A
NIST NIST 2257 see above N/A
LNE AccuStandard
BDE47: U = 2 %
BDE99: U = 2 %
BDE153: U = 2.5 %
values assigned using
SRM 2257
NMIJ NIST 2257 see above N/A
CENAM CIL
BDE47: 49.8±2.5 µg/mL
BDE99: 50.0±2.5 µg/mL
BDE153: 50.0±2.5 µg/mL
values assigned against
SRM 2257
INMETRO Results not submitted
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6. ANALYTICAL METHODS EMPLOYED
The participating laboratories were encouraged to apply analytical methods of their own
choice. The methods for sample preparation, the analytical techniques for instrumental
analysis, the internal standards as well as the calibration type used in CCQM-K102 are
summarised in Table 6. The full details on the analytical methods, as reported by each
participant, are given in ANNEX A.
For the extraction step, most participants (9 out of 14) applied pressurised liquid
extraction (PLE), while 2 participants choose Soxhlet. NMIJ was the only one using
ultrasonic extraction. Solvents employed were hexane, acetone, CH2Cl2, toluene and
various mixtures thereof.
Clean-up of the sample was achieved mostly using solid phase extraction (SPE) and/or
multi-layer silica and Al2O3 columns.
Regarding the instrumental analysis, the splitting among different detection modes was
almost equal: 5 laboratories used GC-MS/MS, 5 laboratories used GC-MS (among which
NMISA using a TOF instrument), 4 laboratories used GC-HRMS. The ionisation mode
was electron impact for all laboratories, except JRC-IRMM which opted for negative
chemical ionisation.
All laboratories quantified with IDMS using the corresponding 13
C labelled PBDEs,
except JRC-IRMM which used internal standard quantification with BDE 77. Most
laboratories applied single-point calibration, while the rest choose for bracketing or 3 to 6
point calibration or a combination thereof.
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Table 6. Summary of analytical methodologies used in CCQM-K102
participant
sample
intake /
unit(s) #
(pre-treatment)
extraction clean-up
instrumental
technique internal standard(s) calibration
JRC-IRMM 2 g / 56 (Cu) ASE hexane/acetone
3:1 SPE, elution with hexane GC-MS (NCI) BDE 77
5 point internal
standard calibration
LGC 2 g / 48
(wetting overnight with
900 μL of ultrapure H2O)
Soxhlet, hexane/acetone
1:1
Step 1: SPE Acid silica/Florisil/Basic
silica/ Florisil
Step 2: LC Hypercarb fractionation
GC-MS 13
C BDEs 47, 99, 153
Bracketed Double
Exact Matching
IDMS
NMISA 1 g / 7, 50 ASE,
CH2Cl2: hexane 3:1
clean-up with Cu and neutral Al2O3
directly in the ASE cell GC-TOF MS
Wellington
Laboratories 13
C BDEs
solutions
IDMS followed by
bracketing double
IDMS
NIM 2 g / 17, 34,
67
ASE,
CH2Cl2: hexane 1:1
SPE combination of Alumina and
HLB, elution CH2Cl2 : hexane 2:1 GC-MS/MS
CIL 13
C BDEs
solutions IDMS single point
VNIIM 2.5 g / 35,
65, 19
ASE, hexane/acetone 9:1,
SoxTherm, toluene
silica multilayer column, Al2O3,
neutral Cu GC-MS
CIL EPA Method 1614 13
C BDEs solution EO-
5277
IDMS short range
KRISS 2 g / 45 PLE
CH2Cl2
SPE cartridge (silica gel), elution
with hexane GC-MS
CIL 13
C BDEs 47, 99,
153
IDMS Single-point
exact matching
double ID
TÜBITAK
UME 2 g / 41
(Cu/Na2SO4 3:1 + inert
dispersing agent)
PLE, n-hexane: acetone 7:3
multilayer column: deactiv. alumina,
deactiv. silica, acidified sílica,
elution CH2Cl2 : n-hexane 1:1
GC-MS/MS
Wellington
Laboratories 13
C BDEs
47, 99, 153
IDMS single-point
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Table 6 cont.
participant
sample
intake /
unit(s) #
(pre-treatment)
extraction clean-up
instrumental
technique internal standard(s) calibration
GLHK 2.5 g / 27,
52, 83 Soxhlet, CH2Cl2
Multi-layer silica gel and alumina
columns in sequence GC-HRMS
CIL 13
C BDEs
solutions
Exact matching
IDMS
NMIA 2 g / 21,
37, 53, 81
ASE, Toluene (other
conditions and Soxhlet used
for confirmation)
H2SO4 and H2O wash, automated SPE
with multi-layer silica (neutral, acidic,
basic) and Al2O3
GC-HRMS
Wellington
Laboratories 13
C
BDEs 47, 99, 153
Exact-matching
single-point double
IDMS with
bracketing
BAM 1.5 g / 15,
42 PLE
Al2O3 and multilayer silica (neutral,
acidic, basic) columns GC-MS
CIL 13
C BDEs 47, 99,
153
IDMS, 6 point
calibration
NIST 3 g / 57
(mix with granular
precombusted Na2SO4)
PLE, CH2Cl2
deactivated Al2O3 column, elution with
CH2Cl2:hexane 35:65 GC-MS/MS
13C BDEs 47, 99, 153
5 point calibration
curve followed by
bracketing
LNE 1 g / 8, 44,
77 ASE, CH2Cl2 pretreated silica and Al2O3 column GC-MS/MS
CIL 13
C BDEs 47, 99,
153
IDMS multipoint
calibration curve
NMIJ
14.8 –
16.3 g /
11, 39, 73
ultrasonic extraction CH2Cl2
Cu and Na2SO4; acidic silica column,
elution CH2Cl2/hexane 2/8; SPE,
elution acetone/hexane 1/9
GC-HRMS
CIL EPA Method
1614 13
C BDEs
solution EO-5277
IDMS, 3 point
calibration
CENAM 2 g / 16 Soxhlet, CH2Cl2 SPE silica GC-MS/MS CIL
13C BDEs 47, 99,
153 IDMS single-point
INMETRO Results not submitted
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6.1 Dry mass determination
All participants followed the prescribed protocol for dry mass determination (see section
4), entailing a drying oven procedure, except TÜBITAK UME which used Karl Fischer
titration and performed the analysis using a sample intake of 0.2 g (instead of 1 g).
Correction factors calculated by the participants and applied to report the results on a dry
mass basis corresponded to an amount of volatiles between 0.23 and 1.01 % (m/m), with
the large majority of laboratories finding a % m/m value between 0.4 and 0.8. The details
on the dry mass determinations are reported in ANNEX A.
7. RESULTS
The measurement results officially submitted for BDE 47, 99 and 153 in CCQM-K102
are reported in Table 7, 8 and 9, respectively.
LNE, NIM and NIST provided results also for BDE 209 (optional measurand of the
study). These results are presented in ANNEX B, Table 1-B.
Table 7. BDE 47 results in CCQM-K102
Participant
Mass
fraction
(µg/kg)
Combined
standard
uncertainty
u (µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Volatiles
content
(% m/m)
JRC-IRMM 16.3 0.70 2 1.4 0.65
LGC 15.81 0.41 2 0.82 0.69
NMISA 14.04 0.94 2.025 1.90 0.40
NIM 14.65 0.35 2 0.70 0.70
VNIIM 14.8 0.58 2 1.2 0.63
KRISS 16.63 0.23 2.45 0.56 0.63
TÜBITAK UME 16.91 0.76 2 1.52 0.59
GLHK 14.8 0.7 2 1.4 0.23
NMIA 16.2 1.0 2.12 2.1 0.50
BAM 14.364 0.9114 2 1.823 1.01
NIST 15.6 0.65 4.3 2.8 0.75
LNE 15.77 2.99 2 5.98 0.63
NMIJ 13.8 0.55 2 1.1 0.77
CENAM 16.43 0.91 2.18 1.98 0.48
INMETRO Result not submitted
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Table 8. BDE 99 results in CCQM-K102
Participant
Mass
fraction
(µg/kg)
Combined
standard
uncertainty
u (µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Volatiles
content
(% m/m)
JRC-IRMM 34.1 3.33 2 6.7 0.65
LGC 33.69 0.61 2 1.22 0.69
NMISA 48.12 4.01 2.025 8.13 0.40
NIM 35.00 0.78 2 1.56 0.70
VNIIM 32.8 0.89 2 1.8 0.63
KRISS 36.0 1.1 2.78 3.1 0.63
TÜBITAK UME 39.50 2.04 2 4.07 0.59
GLHK 31.21 1.35 2 2.70 0.23
NMIA 34.4 2.3 2.03 4.7 0.50
BAM 31.299 1.174 2 2.349 1.01
NIST 41.1 0.85 4.3 3.7 0.75
LNE 30.93 3.83 2 7.66 0.63
NMIJ 31.2 0.77 2 1.55 0.77
CENAM 35.14 1.43 2.57 3.69 0.48
INMETRO Result not submitted
Upon discussion at the OAWG meeting in spring 2015, when the results were presented
for the first time, some of the laboratories deemed necessary a thorough review of their
submitted results, in relation to the influence of a proper chromatographic separation on
the measured mass fraction values, especially for BDE 153.
The further review of the results resulted in revised datasets, both for mass fraction
values and/or uncertainty values for some of the laboratories, which caused the
withdrawing of some results for BDE 99 and 153 from consideration in the calculation of
the KCRV. The data re-submitted by some laboratories are reported in ANNEX B,
Tables 2-B, 3-B and 4-B with the explanation substantiating the applied revision. Figures
2-B, 3-B and 4-B in ANNEX B report the graphs showing both officially submitted and
revised results with their standard uncertainties.
The calculations of the KCRV and DoE were carried out only taking into account valid
officially submitted results and uncertainties, see below Section 9.
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Table 9. BDE 153 results in CCQM-K102
Participant
Mass
fraction
(µg/kg)
Combined
standard
uncertainty
u (µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Volatiles
content
(% m/m)
JRC-IRMM 5.9 0.74 2 1.5 0.65
LGC 6.38 0.21 2 0.42 0.69
NMISA 7.12 0.52 2.013 1.05 0.40
NIM 7.177 0.19 2 0.38 0.70
VNIIM 6.11 0.16 2 0.32 0.63
KRISS 5.78 0.20 2.57 0.51 0.63
TÜBITAK UME 11.03 0.72 2 1.45 0.59
GLHK 5.757 0.308 2 0.617 0.23
NMIA 6.24 0.36 2.02 0.73 0.50
BAM 7.489 0.2338 2 0.457 1.01
NIST 8.97 0.2 4.3 0.87 0.75
LNE 7.03 1.75 2 3.50 0.63
NMIJ 6.28 0.31 2 0.62 0.77
CENAM 7.72 0.86 2.20 1.88 0.48
INMETRO Result not submitted
8. APPROACHES TO UNCERTAINTY BUDGET ESTIMATION
The (main) contributions to the uncertainty budgets declared by the participating
laboratories are summarised in Table 10. The full details of the uncertainty evaluation
reported by the laboratories are given in ANNEX C.
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Table 10. Overview of participants' uncertainty budget estimation in CCQM-K102
Participant Sources of main uncertainty contributions
BAM
ratio native/internal standard (rsample)
intercept of calibration line (ic)
analyte remaining in the sample (corlod)
contribution from all weighings
extraction variability (Fex)
integration variability (Fch)
concentration of native standards (Fpurity)
CENAM
m0 Standard mass
mI0 Standard isotope mass
mx Sample mass
mIx Standard isotope mass in sample
R0 Response ratio of standards
Rx Response ratio of sample
w0 Mass fraction of standard
CFh Humidity correction factor
wx Mass fraction of measurand in sample
GLHK
The systematic uncertainty included:
uncertainty of calibration standard solution (ucal): preparation of
standard solution (weighing) and uncertainty of NIST BDE
standard solutions uncertainty due to preparation of sample blend and calibration blend
(uweighing)
the uncertainty due to moisture correction (umoisture)
The random uncertainty was calculated from the precision (standard
deviation) of multiple measurement results from three bottles.
10
)(
ilod
losspuritychex
samplealiquot
issolventislod
sample
sample
Fandcorwith
FFFFmm
cmmcor
sl
icrc
CFhwmRm
mRmw
Ix
xIx
x *0
00
0
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Table 10 cont.
JRC-IRMM
repeatability (n1=7)
intermediate precision (n2=1)
trueness (based on recovery)
preparation of calibration standards
22
2
2
1
2
* caltrue
iprepuu
n
RSD
n
RSDkU
Values inferred from method validation data
KRISS
Combination of systematic and random uncertainties as shown below:
Main contributions to the systematic term:
Uncertainty of gravimetric preparation for standard solutions
Uncertainty of gravimetric mixing for calibration isotope standard
mixtures
Area ratio native/labelled PBDE for the calibration mixture, observed by
GC/MS
LGC
LNE
Preparation of sample blends (weighings)
Calibration model
Preparation of calibration blend (weighings)
Precision
NIM Method precision
Calibration solution
n
suCu
22
systematics.p.,mean )(
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Table 10 cont.
NIST
measurement repeatability
water content determination
calibration (including uncertainty of the certified value of the calibration
solution)
The 95 % expanded uncertainties were estimated using the two-tailed Student’s t
value for two degrees of freedom, t(95,2) = 4.3
NMIA
Method Precision
Method Trueness
Standard
Moisture Content
Gravimetry
Isotope Amount Ratio
Blend Isotope Amount Ratio
NMIJ concentration of primary standard
repeatability from GC/MS analysis for sample
calibration curve
NMISA
Native solution added to calibration blend
Ratio of peaks areas of native/labelled in the samples
Measurement repeatability
Dry mass correction factor repeatability
TÜBITAK
UME
Bottom up approach considering the following sources:
Mass of sample intake
Labelled stock solution
Spiking of labelled stock solution
Recovery
Repeatability
Karl-Fisher water determination
Mass of final sample
VNIIM
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9. KEY COMPARISON REFERENCE VALUES CALCULATION
The OAWG has established criteria for the inclusion of results in the calculation of
the KCRV e.g., use of a properly validated method, calibration standards with a
metrologically traceable assigned purity value (CRM or material which purity has
been suitably assessed by the participant). The KCRVs established for the CCQM-
K102 will be the reference values for the CCQM-P138.
Discussion at the CCQM meeting in April 2015 in Sèvres pointed to the possibility
of chromatographic interferences for BDE153 leading to some results being biased
high. Several laboratories deemed it necessary to perform a follow-up study during
2015 to investigate this issue. As a result, several laboratories submitted revised data
and/or uncertainties and three of them decided to withdraw some of the officially
submitted results. The revised results were not considered for the calculation of the
KCRVs.
LNE and VNIIM reviewed uncertainty contributions to their measurement
uncertainty budgets and re-submitted lower and slightly higher estimates,
respectively. NMISA discovered a calculation error for the BDE 99 and 153 values
and withdrew these results.
NIST also withdrew the submitted results for BDE 99 and 153, after a follow-up
study using a chromatographic column of 30 m (instead of 10 m, see ANNEX B).
TÜBITAK UME withdrew the result for BDE 153, also as a consequence of the
employment of a longer column for analysis (60 m instead of 15 m). In both cases
the use of longer columns removed interferences that had biased the originally
reported results.
At the OAWG meeting in October 2015, D. Duewer (NIST) presented an analysis
of different KCRV estimators: mean, median and Der-Simonian Laird (weighted
based on uncertainties). As no significant difference existed among these estimators,
the final suggestion was to use a robust and simple estimator like the median that
was considered as fit-for-purpose for this dataset. The OAWG also made a thorough
examination of the data and discussed a possible inclusion of a heterogeneity factor
to enlarge the KCRV uncertainty due to concerns from some participants about the
potential effect of sample heterogeneity. Regarding the introduction of such a
heterogeneity factor to enlarge the KCRV uncertainty, it was deemed not necessary
in the view of 1) median and MADe are reasonable approximations to the
homogeneity values, 2) 8 out of 13 (for BDE 47) and 7 out of 11 (for BDE 99 and
153) laboratories submitted results based on 2 to 4 bottles and 3) the number of
participants was large enough to capture possible effects of heterogeneity (see also
[11]). Nevertheless, a vote on inclusion of a heterogeneity factor was carried out and
the majority voted against (two in favour out of eleven participants present).
Furthermore, the OAWG took the final decision to use the median as the estimate
for the KCRV.
In the final calculation of the KCRVs, the data from TÜBITAK UME were not
included due to the fact that the laboratory did not follow the prescribed method for
the dry mass determination, using Karl-Fischer instead of the oven-drying that was
provided in the study protocol. This creates a traceability issue, because the amount
CCQM-K102_Final report.doc E-mail: [email protected]
Page 22 of 82
of volatiles determined with the oven-drying is method–dependant, while with the
Karl-Fischer method only water is determined.
The assessment of the traceability of the purity values used by the participants was
considered with regard to the results' inclusion in the KCRV calculation. KRISS
results were initially excluded from the KCRVs’ calculation because the purity of
the commercial calibrants employed was reported as only being assessed by GC-
FID. An in-depth discussion revealed that SRM2257 was used to confirm the purity
assigned by GC-FID thereby performing a transfer-value assignment similarly to
other laboratories (see Table 5). Their results were therefore included in the final
calculation of the KCRVs.
As a result of the overall above-mentioned evaluation, the KCRVs were calculated
as the median of thirteen valid results for BDE 47 and eleven results for BDE99 and
BDE 153, respectively (see Table 11a, b, c and Figures 3a, b, c).
The KCRV, its associated standard uncertainty and the results of the participants
(with their standard uncertainties) in CCQM-K102 are reported in Table 11a, b, c
and Figures 3a, b, c for BDE 47, 99 and 153, respectively. Graphs reporting the
KCRV, its expanded uncertainty and the laboratories' expanded uncertainties are
given in ANNEX D.
Table 11a. BDE 47 in CCQM-K102
KCRV and associated uncertainty (µg/kg dry mass basis)
KCRV (median) 15.60
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 1.19
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=13) 0.41
U95 % (k*u) k = 2 0.82
Figure 3a. CCQM-K102: KCRV and its standard uncertainty for BDE 47.
Participants' results are also displayed with their standard uncertainties.
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Table 11b. BDE 99 in CCQM-K102
KCRV and associated uncertainty (µg/kg dry mass basis)
KCRV (median) 33.69
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 2.15
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=11) 0.81
U95 % (k*u) k = 2 1.62
Figure 3b. CCQM-K102: KCRV and its standard uncertainty for BDE 99.
Participants' results are also displayed with their standard uncertainties.
CCQM-K102_Final report.doc E-mail: [email protected]
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Table 11c. BDE 153 in CCQM-K102
KCRV and associated uncertainty for (µg/kg dry mass basis)
KCRV (median) 6.28
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 0.74
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=11) 0.28
U95 % (k*u) k = 2 0.56
Figure 3c. CCQM-K102: KCRV and its standard uncertainty for BDE 153.
Participants' results are also displayed with their standard uncertainties.
10. DEGREES OF EQUIVALENCE (DOE) CALCULATION
The Degrees of Equivalence (DoE) of each result with the KCRV is expressed
quantitatively by two components: a value component and an uncertainty
component. The DoE and its uncertainty between an NMI result and the KCRV is
calculated within CCQM according to the following equations:
- the value component is di = xi - xref
Where, di is the degree of equivalence between the participant's result xi and the
KCRV = xref.
- the uncertainty component is U(di) = k * u(di)
Where, the expanded uncertainty U(di) is calculated by combining the standard
uncertainties ui of xi and uref of xref and multiplying by the coverage factor k=2 as
follows: U(di) = 2 ∗ √ui2 + uref
2 .
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Tables 12a, b and c list the absolute and relative [% di = 100·di/KCRV and U (% di)
= 100·U(di)/KCRV] DoE and their associated expanded uncertainty; the last column
shows the ABS (di)/U(di).
A reported result xi is consistent with the KCRV in CCQM-K102 within its stated
uncertainty at the 95 % confidence level when ABS (di)/U(di) < 1 (visually: when
the uncertainty bars in Figures 4a-e cross the red line).
Figures 4a-e display the absolute di ± U (di) and the relative % di ± U (% di) for
BDE 47, BDE 99 and BDE 153, respectively, in CCQM-K102.
Table 12a. BDE 47 in CCQM-K102
Degrees of equivalence [di] and expanded uncertainties [U(di)]
BDE 47
participant µg/kg %
di U(di) % di % U(di) di /U(di)
NMIJ -1.80 1.374 -11.5 8.8 1.31
NMISA -1.56 2.052 -10.0 13.2 0.76
BAM -1.24 2.000 -7.9 12.8 0.62
NIM -0.95 1.080 -6.1 6.9 0.88
GLHK -0.80 1.624 -5.1 10.4 0.49
VNIIM -0.80 1.422 -5.1 9.1 0.56
NIST 0.00 1.538 0.0 9.9 0.00
LNE 0.17 6.036 1.1 38.7 0.03
LGC 0.21 1.162 1.3 7.4 0.18
NMIA 0.60 2.163 3.8 13.9 0.28
JRC-IRMM 0.70 1.624 4.5 10.4 0.43
CENAM 0.83 1.997 5.3 12.8 0.42
KRISS 1.03 0.942 6.6 6.0 1.09
TÜBITAK UME 1.31 1.728 8.4 11.1 0.76
The entries in italic are results not included in the KCRV calculation
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Figure 4a. Absolute degrees of equivalence for BDE 47 in CCQM-K102.
The vertical bars correspond to ±U(di).
The horizontal red line marks the zero deviation from the KCRV.
Figure 4b. Relative degrees of equivalence for BDE 47 in CCQM-K102.
The vertical bars correspond to ±U(%di).
The horizontal red line marks the zero deviation from the KCRV.
-6.0
-4.0
-2.0
0.0
2.0
4.0
6.0
De
gre
e o
f e
qu
ival
en
ce µ
g/kg
BDE 47
-40.0
-30.0
-20.0
-10.0
0.0
10.0
20.0
30.0
40.0
De
gre
e o
f e
qu
ival
en
ce %
BDE 47
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Table 12b. BDE 99 in CCQM-K102
Degrees of equivalence [di] and expanded uncertainties [U(di)]
BDE 99
participant µg/kg %
di U(di) % di % U(di) di /U(di)
LNE -2.76 7.830 -8.2 23.2 0.35
NMIJ -2.49 2.236 -7.4 6.6 1.11
GLHK -2.48 3.149 -7.4 9.3 0.79
BAM -2.39 2.853 -7.1 8.5 0.84
VNIIM -0.89 2.407 -2.6 7.1 0.37
LGC 0.00 2.029 0.0 6.0 0.00
JRC-IRMM 0.41 6.854 1.2 20.3 0.06
NMIA 0.71 4.877 2.1 14.5 0.15
NIM 1.31 2.250 3.9 6.7 0.58
CENAM 1.45 3.287 4.3 9.8 0.44
KRISS 2.31 2.733 6.9 8.1 0.85
TÜBITAK UME 5.81 4.390 17.2 13.0 1.32
NIST 7.41 2.349 22.0 7.0 3.15
NMISA 14.43 8.182 42.8 24.3 1.76
The entries in italic are results not included in the KCRV calculation
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Figure 4c. Absolute degrees of equivalence for BDE 99 in CCQM-K102.
The vertical bars correspond to ±U(di).
The horizontal red line marks the zero deviation from the KCRV.
Figure 4d. Relative degrees of equivalence for BDE 99 in CCQM-K102.
The vertical bars correspond to ±U(%di).
The horizontal red line marks the zero deviation from the KCRV.
-10.0
-6.0
-2.0
2.0
6.0
10.0
14.0
18.0
De
gre
e o
f e
qu
ival
en
ce µ
g/kg
BDE 99
-40.0
-20.0
0.0
20.0
40.0
60.0
80.0
De
gre
e o
f e
qu
ival
en
ce %
BDE 99
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Table 12c. BDE 153 in CCQM-K102
Degrees of equivalence [di] and expanded uncertainties [U(di)]
BDE 153
participant µg/kg %
di U(di) % di % U(di) di /U(di)
GLHK -0.52 0.832 -8.3 13.2 0.63
KRISS -0.50 0.687 -8.0 10.9 0.73
JRC-IRMM -0.38 1.582 -6.1 25.2 0.24
VNIIM -0.17 0.644 -2.7 10.3 0.26
NMIA -0.04 0.911 -0.6 14.5 0.04
NMIJ 0.00 0.835 0.0 13.3 0.00
LGC 0.10 0.699 1.6 11.1 0.14
LNE 0.75 3.544 11.9 56.4 0.21
NMISA 0.84 1.181 13.4 18.8 0.71
NIM 0.90 0.676 14.3 10.8 1.33
BAM 1.21 0.729 19.3 11.6 1.66
CENAM 1.44 1.809 22.9 28.8 0.80
NIST 2.69 0.687 42.8 10.9 3.91
TÜBITAK UME 4.75 1.545 75.6 24.6 3.08
The entries in italic are results not included in the KCRV calculation
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Figure 4d. Absolute degrees of equivalence for BDE 153 in CCQM-K102.
The vertical bars correspond to ±U(di).
The horizontal red line marks the zero deviation from the KCRV.
Figure 4e. Relative degrees of equivalence for BDE 153 in CCQM-K102.
The vertical bars correspond to ±U(%di).
The horizontal red line marks the zero deviation from the KCRV.
11. CORE COMPETENCIES AND HOW FAR DOES THE LIGHT SHINE?
The participation to the Track A "Low polarity analytes in abiotic matrix" CCQM-
K102 study, polybrominated diphenyl ethers in sediment, was intended to
demonstrate the capability of NMIs/DIs of analysing non-polar organic molecules in
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
6.0
De
gre
e o
f e
qu
ival
en
ce µ
g/kg
BDE 153
-40.0
-20.0
0.0
20.0
40.0
60.0
80.0
100.0
De
gre
e o
f e
qu
ival
en
ce %
BDE 153
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abiotic dried matrices using procedures requiring extraction from the matrix, clean-
up from interfering substances, analytical separation, selective detection and final
quantification. The details of the specific approaches/techniques used by each
participant underpinning their competencies are reported in the Core Competency
Tables given in ANNEX E.
More specifically, the comparison was designed to demonstrate the laboratory's
competence in the quantification of organic molecules in the approximate range of
molecular weights from 100 to 800 g/mol, having polarity corresponding to pKow <
-2 and for the range of mass fraction 1-1000 μg/kg in abiotic dried matrices.
12. CONCLUSIONS
Most of the participants to CCQM-K102 were able to demonstrate or confirm their
capabilities in the analysis of non-polar organic molecules in abiotic dried matrices.
Throughout the study, it became clear that matrix interferences can influence the
accurate quantification of the PBDEs, if the analytical methodology applied is not
appropriately adapted and optimised. This comparison shows that quantification of
PBDEs at the µg/kg low-middle range in a challenging environmental abiotic dried
matrix can be achieved with relative expanded uncertainties below 15 % (more than 70
% of participating laboratories), well in line with the best measurement
performances in the environmental analysis field.
13. ACKNOWLEDGEMENTS
The study coordinator wishes to thank the JRC-Geel Reference Materials Processing
Team and Giovani Kerckhove of the Engineering Materials Laboratory for the
electron microscopy work in the assessment of the study material homogeneity. A
particular thank goes to D. Duewer for precious statistical and pragmatic advice and
to L. Mackay, chair of the OAWG, for her advice.
14. REFERENCES
[1] J. Xu, Z. Gao, Q. Xian, H. Yu, J. Feng (2009) Environ. Pollut. 157: 1911-16.
[2] M. Osako, Y.J. Kim, S. Sakai (2004) Chemosphere. 57: 1571-79.
[3] A.Hassanin et al. (2004) Environ. Sci. Technol. 38:738-745.
[4] J. de Boer, P.G. Wester, A. van der Horst, P.E.G. Leonards (2003) Environ.
Pollut. 122: 63-74.
[5] R.A. Hites (2004) Environ Sci Technol. 38(4): 945–956.
[6] R.J. Law et al. (2008) Chemosphere 73(2): 223–241.
[7] (a) Directive 2003/11/EC (24th
Amendment to Directive 76/769/EEC), (b)
Directive 2002/95/EC.
[8] Scientific opinion on PBDEs in food, EFSA Panel on contaminants in the Food
chain (CONTAM), EFSA Journal (2011) 9(5): 2156.
[9] Braekevelt, E., Tittlemier, S.A., Tomy, G.T. (2003) Chemosphere 51: 563–567.
[10] T.P.J Linsinger, J. Pauwels, A.M.H. van der Veen, H. Schimmel, A. Lamberty
(2001) Accred. Qual. Assur. 6: 20-25.
[11] CCQM Guidance note: Estimation of consensus KCRV and associated Degrees
of Equivalence" version 10, 2013-04-12.
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ANNEX A
Full details of the analytical methods employed by the participants in CCQM-
K102
BAM
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable)
Extraction method/conditions PLE
T=100 °C
p=140 bar
static-time: 10 min
cycles 3
Clean-up procedure Al2O3 column chromatography (1 cm of sodium sulfate; 25 g of
(e.g., SPE, GPC) alumia oxide; 1 cm of sodium sulfate)
Multilayer column chromatography (1,0 g of sodium sulfat / 0,5 g silica
gel/silver nitrate; 0,2 g of silica gel; 1,0 g of silica gel/sulfuric acid; 0,2 g
of silica gel; 0,5 g of silica gel/sodium hydroxid
Analytical instrumentation used GC-MS (Agilent 7890A with 5975C MSD)
(e.g., GC-MS ) Cold injektion system (CIS): 90°C for 0.01 min then 10°C/sec to 360°CGC settings for 15 min; injection volume 2µl splitless
(e.g., injection mode, T and volume; carrier gas ZB-5 HT Inferno 15 m x 250 µm x 0.1 µm; flow 1 ml/min (He)
and flow; column type, oven temperature program) Oven programm: 80 °C for 1 min then 20 °C/min to 340 °C for 5 min
MS settingsMS settings EI-mode; gain factor 10 (Em voltage 2388) source 300°C / quad 150 °C
(e.g., MS mode, monitored ions, T, electron Ions for BDE47/MBDE47: 325.9; 337.9; 483.7; 485.7; 495.8; 497.8; 499.8
multiplier voltage, gas) Ions for BDE99/MBDE99: 405.7; 415.8; 417.8; 563.6; 565.6; 575.7; 577.7
Ions for BDE153/MBDE153: 485.7; 495.8; 497.8; 641.5; 643.5; 655.6; 657.7
Water content determination(please describe the procedure, if deviating intake: 1,2 - 1,4 g
from the one prescribed in the protocol drying temperature: 105 °C
and the calculation of dry mass correction factor)
Calibration type / details IDMS
(e.g., single-point, bracketing / BDE47: 18.8; 37.6; 97.3; 196.1; 301.2; 362.8 ng/ml
external calibration, internal standard calibration, IDMS) BDE99: 19.1; 38.3; 99.0; 199.6; 306.5; 369.2 ng/ml
BDE153: 18.4; 36.9; 95.3; 192.2; 295.1; 355.2 ng/ml
Calibration standards NIST 2257
(e.g., source, purity, uncertainty) BDE 47: 2.09 ± 0.16 µg/g
BDE 99: 2.127 ± 0.090 µg/g
BDE 153: 2.048 ± 0.068 µg/g
Internal standards used 13C12, 99% BDE-47 (CIL) about 239 ng/ml(Please specify the compounds, and at which stage 13C12, 99% BDE-99 (CIL) about 497 ng/ml
13C12, 99% BDE-153 (CIL) about 110 ng/ml
1.5
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
Page 33 of 82
CENAM
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) none
Extraction method/conditions Automated Soxhlet Extraction (Soxhlet Standard)
Solvent used dichloromethane
Lower heating level 7
Time 4 h
Clean-up procedure SPE Silica
(e.g., SPE, GPC)
Analytical instrumentation used GC-MS/MS Injection volume 2 µL
(e.g., GC-MS ) Injection mode: Splitless MSD transfer line:300 °CGC settings Injector temperature: 280 °C Carrier gas: Helium
(e.g., injection mode, T and volume; carrier gas Column: HP-5MS 15m x 250 µm x 0.25µm Flow:0.9 mL/min
and flow; column type, oven temperature program) Oven: 60 °C (1 min); 40°C/min. to 170 °C (0 min); 10 °C/min. to 310 °C(3 min)
MS mode: MRM Source temperature: 230 °C Quad MS1 temp: 200 °CMS settings Monitored ions EMV: 1194.9; 1263.9 and 1306.1 CID Gas: Helium
(e.g., MS mode, monitored ions, T, electron 485.7 - 325.7 325.8-218.8 497.7 - 337.7 337.8 - 228.8
multiplier voltage, gas) 565.6 - 405.6 563.6 - 403.7 577.6 - 417.6 575.6 - 415.7
483.7 - 323.6 643.6 - 483.6 655.6 - 495.6 495.7 - 335.6
Water content determination Protocol method: Two 1 g subsamples were measured from bottle 0016
(please describe the procedure, if deviating by oven method described in the protocol.
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Dry mass correction factor: CF = 100 + % humidity / 100
Calibration type / details IDMS
(e.g., single-point, bracketing / Single point, verified with 3 independent preparations
external calibration, internal standard calibration, IDMS)
Calibration standards Source (µg/mL) U (µg/mL)
(e.g., source, purity, uncertainty) BDE-47 CIL 49.8 2.5
BDE-99 CIL 50.0 2.5
BDE-153 CIL 50.0 2.5
Internal standards used BDE-47 (13C12) CIL 50 1.3
(Please specify the compounds, and at which stage BDE-99 (13C12) CIL 50.2 4.2
BDE-153 (13C12) CIL 47.2 2.3
Purity assessment of the calibrant (if applicable)
(e.g. methods used for value assignment/verification) The uncertainty of the calibration solutions were estimated at CENAM
since the pure calibrants were not possible to procurement them.
The calibration solutions were verified using SRM2257
2
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
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GLHK
Informat ion about the analy t ical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analys is g
Sample pre-t reatment (i f applicable) NA
Extract ion method/condit ions Soxhlet extraction with dichloromethane for 16 hours
Clean-up procedure Clean-up in sequence by:-
(e.g., SPE, GPC) 1) Multi-layer silica gel column
Pack a glass chromatographic column from bottom to top with activated silica gel,
basic silica gel, acidic silica gel, activated silica gel, anhydrous Na2SO4
2) Alumina column
Analy t ical ins t rumentat ion used HRGC-HRMS
(e.g., GC-MS ) Splitless Injection at 290 °C; UHP He carrier gas at 1.2 ml/min (Constant flow);
GC settings Separation by Agilent DB-XLB column (30m x 0.25mm, 0.1µm)
(e.g., injection mode, T and volume; carrier gas Injection volume 3uL;
and flow; column type, oven temperature program) Oven program:100°C (hold for 3 min), 5°C/min ramped to 320 °C (hold for 5 min)
MS settings SIR mode:
(e.g., MS mode, monitored ions, T, electron BDE-99 m/z 563.6216 and 565.6196; 13C-BDE-99 m/z 575.6619 and 577.6598
multiplier voltage, gas) BDE-153 m/z 641.5322 and 643.5302 ; 13C-BDE-153 m/z 655.5704 and 657.5683
BDE-47 m/z 485.7111 and 483.7132 ; 13C-BDE-47 m/z 497.7514 and 499.7493
Water content determinat ion NA
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibrat ion type / details Exact matching IDMS
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibrat ion s tandards NIST SRM 2257
(e.g., source, purity, uncertainty) BDE-47 2.09 ± 0.16 µg/g
BDE-99 2.127 ± 0.090 µg/g
BDE-153 2.048 ± 0.068 µg/g
Internal s tandards used Standard solutions from Cambridge Isotope Laboratories Inc.
(Please specify the compounds, and at which stage were 13C12-BDE-47, 50 µg/mL;13C12-BDE-99, 50 µg/mL;13C12-BDE-153, 50 µg/mL
2.5
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
Page 35 of 82
JRC-IRMM
Sample pre-treatment (if applicable) N/A
Extraction method/conditions ASE
Pressure: 1500 psi; Temperature: 120 °C; Preheat time: 5 min;
Static time: 6 min; Flush volume: 150 %; Purge time: 120 sec;
Static cycles: 3; Solvents: hexane/acetone 3:1
Clean-up procedure SPE
(e.g., SPE, GPC) Conditioning: 3 mL; Load: 1 mL sample; elution: 4 mL;
Flow speed: 1 mL/min; Cartridge: Bond-Elute PCB (1g, 3 mL)
Solvent: Hexane
Analytical instrumentation used GC-MS
(e.g., GC-MS )GC settings Pulsed splitless; Initial temp: 90 °C; Pressure: 2.69 psi; Carrier gas: He
(e.g., injection mode, T and volume; carrier gas Total flow: 103.3 mL/min; column: DB-5MS, 15 m * 0.25 mm * 0.25 µm
and flow; column type, oven temperature program) T Progr.: 90 °C (1.5 min), 20 °C/min to 270 °C (0 min), 10 °C/min to 285 °C
(0 min), 35 °C/min to 300 °C (7 min), 50 °C/min to 320 °C (5 min)
MS settings NCI; monitored ions: 79, 81; AUX 250 °C, Methane, 25 eV
(e.g., MS mode, monitored ions, T, electron
multiplier voltage, gas)
Water content determination According to the CCQM-K102/P138 protocol
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details internal standard 5 points calibration
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards NIST SRM 2257
(e.g., source, purity, uncertainty) Certified concentrations of compounds:
PBDE 47 - 2.09 ± 0.16 ug/g
PBDE 99 - 2.127 ± 0.090 ug/g
PBDE 153 - 2.048 ± 0.068 ug/g
Internal standards used PBDE 77 (Accustandard), Purity (GC/MS) - 100%±5% (U )
(Please specify the compounds, and at which stage
were added) Added after weighing of the sample
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
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KRISS
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) N/A
Extraction method/conditions Pressurized Liquid Extraction (PLE) method was used for sample extraction.
Extraction conditions were with temperature 100 °C , pressure 1500 psi, extraction time 5 min,
and number of extraction cycle 2 with dichoro methane as a solvent.
Clean-up procedure
(e.g., SPE, GPC) Cleaned up by using SPE cartridge (silica gel) with hexane as eluant
Analytical instrumentation used GC/MS (JMS-800D, Jeol)
(e.g., GC-MS ) GC condition
GC settings Injection mode: on-column injection (confirmatory: splitless injection)
(e.g., injection mode, T and volume; carrier gas Injection volume: 1 uL of sample
and flow; column type, oven temperature program) Carrier gas : He, 1.5 mL/min
MS condition
MS settings Ion source: EI mode
(e.g., MS mode, monitored ions, T, electron Resolution : 1000 (with confirmatory check by high resolution measurement at 10,000)
multiplier voltage, gas) primary monitoring channel: m/z 485.7 for BDE-47, m/z 403.8 for BDE-99, and m/z 483.7 for BDE-153
confirmatory channel: m/z 325.9 for BDE-47, m/z 563.6 for BDE-99, and m/z 643.5 for BDE-153
Water content determination We took more than 1 g of three subsamples from the bottle(No. 45),
(please describe the procedure, if deviating and then dried in the oven at 105 °C until constant mass is attained. It took 1~2 hrs.
from the one prescribed in the protocol The mean water content of each subsamples was 0.63%
and the calculation of dry mass correction factor) Dry mass correction factor is calculated as follows
X= water contents
Calibration type / details
(e.g., single-point, bracketing / Single-point with exact matching double ID for IDMS
external calibration, internal standard calibration, IDMS)
Calibration standards Neat commercial calibrants for BDE-47, 99, 153 were from Accustandard.
(e.g., source, purity, uncertainty)
Internal standards used
(Please specify the compounds, and at which stage
Purity assessment of the calibrant (if applicable) For the determination of the purities of the primary reference materials of BDE-47, BDE-99, and BDE-153,
(e.g. methods used for value assignment/verification) Purities of the materials were assessed only with GC/FID analysis for structurally related impurities.
As the amounts of BDE-47, 99, and153 primary reference materials were limited
Karl-Fischer Coulometry for water content, thermogravimetric analysis for non-volatile inorganic residues,
and headspace-GC/MS for residual solvents could not be carried out.
The purities assessed by KRISS was indirectly confirmed by comparing the standard solution prepared
with the materials to NIST SRM 2257
Estimation of impurities (if applicable)
(e.g. type of impurity, mass fraction, uncertainty) GC/FID result Content unc DOF
BDE47 98.75% 0.002% 2
BDE99 95.50% 0.105% 2
BDE153 95.83% 0.006% 2
2
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
13C12-BDE-47, 13C12-BDE-99, and 13C12-BDE-153, purchased from CIL, were used
as the internal standards of BDE-47, BDE-99, and BDE-153, respectively.
The purities were assessed by KRISS with GC-FID, but water content and non-volatile impurities were
not tested due to the limited amounts of the materials. Purities: BDE 47, 99, and 153 were 98.75%,
95.50%, and 95.83%, respectively. The purities assessed by KRISS was indirectly confirmed by comparing
the standard solution prepared with the materials to NIST SRM 2257
)1/(1 xf
CCQM-K102_Final report.doc E-mail: [email protected]
Page 37 of 82
LGC
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) Wetting overnight adding 900 μL of ultrapure water
Extraction method/conditions Soxhlet extraction
Extraction time 24 hours
Extraction Solvent200 mL Hexane/Acetone 1:1
Clean-up procedure Step 1: SPE Acid silica/Florisil/Basic silica/ Florisil
(e.g., SPE, GPC) Step 2: LC Hypercarb fractionation
Analytical instrumentation used GC-EI-MS, equipped with Dean switch used as divert valve, single quadrupole Agilent 7890GC and 5975C MS
(e.g., GC-MS ) Splitless mode, Splitless time= 2 minGC settings Injector temperature 250 °C, 1 μL injection volume, He carrier gas F=1 mL/min
(e.g., injection mode, T and volume; carrier gas Colum DB-XLB 30 m x 0.25 mm x0.25 μm
and flow; column type, oven temperature program) Oven program: 90C held for 2 min; 40C/min to 290C, held for 0.5; 3C/min to 330C,
held for 5 min; 40C/min to 340C, held for 14 min MS settings SIM mode. BDE 47 Quan Ions: 485.6 Labelled 497.6, Qual ions 325.8, 337.8, 563.5
(e.g., MS mode, monitored ions, T, electron BDE 99 Quan Ions: 563.5 Labelled 575.6, Qual ions 403.7, 415.7, 643.4
multiplier voltage, gas) BDE 153 Quan Ions: 481.6/483.6/485.6 Labelled 493.6, 495.6, 497.6, Qual ions 643.4, 655.4, 721.0
Source 300C, Quadrupole 150C, EMV 1765 Gain 15.0
Water content determination As protocol, 2 aliquots, average value used for dry mass correction
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details Bracketed Double Exact Matching IDMS
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards
(e.g., source, purity, uncertainty)
Internal standards used BDE 47 13C
(Please specify the compounds, and at which stage BDE 99 13C
BDE 153 13C
Purity assessment of the calibrant (if applicable) Stock Concentration and Purity assessed by qNMR
(e.g. methods used for value assignment/verification)
Estimation of impurities (if applicable) N/A
(e.g. type of impurity, mass fraction, uncertainty)
2
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
All IS spiked at beginning of soxhlet extraction to enable extraction/equilibration
with the samples. Degredation of IS checked and not found to be an issue
Chiron neat materials >98% pure, 47 and 99
solids checked by qNMR, made into solutions to
be value assigned by qNMR for
concentration/purity
CCQM-K102_Final report.doc E-mail: [email protected]
Page 38 of 82
LNE
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) rehomogeneisation by shaking the flask about 2min
Extraction method/conditions extraction by ASE200 : 2 static phases of 6min , 100°C, 140 bars ,
100 % DCM
Clean-up procedure purification on a column of pretreated silica and alumina
(e.g., SPE, GPC)
Analytical instrumentation used GC/MS²
(e.g., GC-MS ) injection: 10 µl injected by solvent ventGC settings carrier gas: helium 1.2ml/mn
(e.g., injection mode, T and volume; carrier gas column: non polar type 5MS , length: 15m, di:0.25 mm, film:0.1 µm
and flow; column type, oven temperature program) temperature program: 50°C during 3.30 min , then 20°C/min until 150°C
during 0min, then 10°C/min until 260°C during 0 min then 40°C/min MS settings until 320°C during 7min.
(e.g., MS mode, monitored ions, T, electron electronic impact with 70eV, source temperature:180°C, transfert line
multiplier voltage, gas) température:290°C, MS/MS mode,
Water content determination drying 1g of sediment at 105°C +/- 2°C until 2 subsequent weightings
(please describe the procedure, if deviating do not differ more than 1 mg
from the one prescribed in the protocol dry mass correction factor= final mass/ initial mass of sediment
and the calculation of dry mass correction factor)
Calibration type / details IDMS with calibration curve
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards certified solutions from AccuStandard with 2% combined standard
(e.g., source, purity, uncertainty) uncertainty for PBDE 47 and 99 and 2.5 % for PBDE 153
Internal standards used C13 labeled compounds from Cambridge Isotope Laboratories
(Please specify the compounds, and at which stage
Purity assessment of the calibrant (if applicable) verified with SRM2257 from NIST
(e.g. methods used for value assignment/verification)
1
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
Page 39 of 82
NIM
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable)
Extraction method/conditions
Clean-up procedure
(e.g., SPE, GPC)
Analytical instrumentation used
(e.g., GC-MS )GC settings
(e.g., injection mode, T and volume; carrier gas
and flow; column type, oven temperature program)
MS/MS:
MS settings
(e.g., MS mode, monitored ions, T, electron
multiplier voltage, gas)
Water content determination
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details 1) Calibration method: Single point.
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards
(e.g., source, purity, uncertainty)
Internal standards used
(Please specify the compounds, and at which stage
were added)
Purity assessment of the calibrant (if applicable)
(e.g. methods used for value assignment/verification)
Estimation of impurities (if applicable) No.
(e.g. type of impurity, mass fraction, uncertainty)
2
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
2) quantification mode:BDE-47,99,153: GC-IDMS, BDE-
209:internal standard calibration.
GBW(E)081124 , GBW08709 are all from NIM,China.
Each bottle were shaken by turning upside down for 30 minutes
before analysis
ASE / 100°C, 1500 psi, 4 cycles, dichloromethane : hexane =1:1 (v : v)
SPE/combination of Alumina and HLB,preconditioned with 15 mL
hexane, eluted with 3 * 3 mL mixed solvents (dichloromethane:hexane
=2:1)
GC-MS/MS
GC: splitless injection, 300 °C, 2 μL;He at 1.5 mL/min; DB-5 15 m
* 0.25 mm * 0.10 μm, 90 °C increased to 300 °C at 20 °C/min
Their uncertainty are 4% ,1.4% respectively (K=2 ).
The solution of BDE-47,99,153 (13C labled) and internal
standard(BDE-207) is from Cambridge Isotope Laboratories.
They are added to sample before extraction.
The purity of neat BDE-47,99,153 is determined by HPLC-DAD
and qNMR. The purity of BDE- 209 is determined by HPLC-DAD
and HPLC-ICP-MS.
MRM, monitored ions were summarized in table 1 at the bottom of
this part, ion source tempeature: 280 °C, gas: He;
2 separate portions of 1.0 g sediment from bottle No.0017 and 0034
were drying in an oven at (105 ± 2) °C until constant mass is attained
(for 4 hours).
CCQM-K102_Final report.doc E-mail: [email protected]
Page 40 of 82
Table 1 Monitored ions in MRM mode
Compound Precusor Product
47 485.7 325.8
47 483.7 325.8
47 325.8 244.9
47L 337.6 256.9
47L 337.6 228
99 405.7 296.9
99 403.7 296.9
99L 417.7 307.8
99L 417.7 257.8
153 643.5 483.6
153 483.6 376.7
153 483.6 323.8
153L 655.5 495.6
153L 495.6 335.8
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Page 41 of 82
NIST
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis 1 g for 209 determination
Sample pre-treatment (if applicable)
Extraction method/conditions Samples were mixed with granular precombusted sodium sulfate (650oC for 18 hours) and then transferred to a pressurized fluid extract. cell.
Internal standard was added and then samples were extracted with
dichloromethane (100 oC, equilibration 5 min, static time 5 min, cell
pressure 13.8 MPa, with three cycles using 1/3 of the solvent each time
Clean-up procedure Samples were cleaned up using 1.8 g deactivated alumina columns
(e.g., SPE, GPC) (5 % water mass fraction) by adding sample in hexane and eluting with
9 mL 35:65 dichloromethane:hexane (mass fraction)
Analytical instrumentation used GC-MS/MS; on column injection (2 uL); 60 oC initial temperature and then
(e.g., GC-MS ) in oven track mode. Carrier gas was helium at 1.4 mL/min for 10 min thenGC settings 3 mL for min. The column was a 10 m x 0.18 mm x 0.18 um film thickness
(e.g., injection mode, T and volume; carrier gas thickness 5 % methyl polysiloxane column coupled to a 1 m retention gap.
and flow; column type, oven temperature program) Oven program: 70 oC for 1 min, 40 oC/min to 175 oC and then 10 oC to 305 oC
(10 min hold) followed by 40 oC to 325 oC. Data acquired in MRM mode.MS settings Electron ionization was used (70 eV).
(e.g., MS mode, monitored ions, T, electron
multiplier voltage, gas)
Water content determination 2 g to 3 g of the samples (n-5) were placed in glass culture tubes, dried
(please describe the procedure, if deviating 24 hours at 120 oC then cooled in a desiccator for 1 hour and re-weighed.
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details Five point calibrat. curve that bracketed the expected sample response.
(e.g., single-point, bracketing / This was achieved for all compounds except BDE 209 in the K103/P138
external calibration, internal standard calibration, IDMS) which was 30% higher than the highest calibration point.
Carbon labeled PBDE 47, 99, 153 and 209 were used as internal
standards.
Calibration standards Calibration standards were prepared from SRMs 2257 and 2258.
(e.g., source, purity, uncertainty)
Internal standards used Internal standards added before extraction and included(Please specify the compounds, and at which stage Carbon labeled PBDEs 47, 99, 153, and 209.
3 g for BDE 47, 99, and 153
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
Page 42 of 82
NMIA
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) Sediment sub-samples were spiked with solutions of carbon 13-labelled BDE47, 99 and 153
and then mixed by rotation overnight (at least 12 hours) prior to solvent extraction.
Extraction method/conditions Method 1: Accelerated Solvent Extraction (ASE) with 100% toluene: samples were extracted three times.
Extraction conditions: 2 static cycles of 8 minutes each at 150 oC and 1700 psi
Method 2: Hot Soxhlet Extraction with 100% toluene; 10 hours cycle time with constant reflux (for confirmation)
Method 3: ASE with ethanol/toluene (68:32) and then 100% toluene; samples were extracted
three times with each solvent (for confirmation)
Method 4: ASE with acetone/hexane (50:50): samples were extracted three times (for confirmation)
Clean-up procedure 1. Concentrated sulphuric acid wash (3 x 20 mL)
(e.g., SPE, GPC) 2. Ultra-high purity water wash (3 x 20 mL)
3. Gel permeation chromatography using dichloromethane (this clean-up step was found to be unnecessary for
the CCQM study sample; however, GPC clean-up was used for samples of NIST SRM1944, a reference material
used in this study)
4. Automated solid phase extraction with multi-layer silica (neutral, acidic, basic) and alumina
columns
Analytical instrumentation used 1. Gas chromatography with high resolution mass spectrometry (GC-HRMS) (Thermo Scientific DFS)
(e.g., GC-MS ) GC SettingsGC settings Injection mode: PTV Large Volume at 140 oC, injection volume: 1 uL
(e.g., injection mode, T and volume; carrier gas Carrier gas: Helium
and flow; column type, oven temperature program) Column: Agilent DB-5 (0.1 mm x 10 m, 0.1 um film thickness)
Carrier flow rate: 0.4 mL/minMS settings Temperature program: 80 oC hold for 6 minutes, ramp at 20 oC/min to 245 oC, ramp at 5 oC/min
(e.g., MS mode, monitored ions, T, electron to 290 oC, ramp at 10 oC/min to 325 oC, hold for 5 minutes
multiplier voltage, gas)
MS Settings
MS mode: EI, 45 eV, resolution ~10,000 (5% valley definition)
Source temperature: 285 oC
Electron multiplier voltage: 1520 V
Reference gas: PFK
Monitored ions: BDE 47 & 13C12-BDE 47 (483.71262, 485.71057, 487.70853, 497.75080, 499.74880)
BDE 99 & 13C12-BDE 99 (563.62109, 565.61904, 575.66130, 577.65930)
BDE 153 & 13C12-BDE 153 (481.69697, 483.69492, 493.73723, 495.73518)
2. Gas chromatography tandem mass spectrometry (GC-MS/MS) (Agilent 7000B GC-QQQ)
GC Settings
Injection mode: PTV Solvent Vent at 140 oC, injection volume: 5 uL
Carrier gas: Helium
Column: Phenomenex Zebron ZB-SemiVolatiles (0.18 mm x 10 m, 0.18 um film thickness)
Carrier flow rate: 0.4 mL/min
Temperature program: 80 oC hold for 4 minutes, ramp at 20 oC/min to 245 oC, ramp at 5 oC/min
to 290 oC, ramp at 10 oC/min to 325 oC, hold for 10 minutes
MS Settings
MS mode: EI, 50 eV
Source temperature: 300 oC
Electron multiplier voltage: 1639 V
Reference gas: FC-43
Monitored SRMs:
BDE 47: 487.7 > 327.9, 485.7 > 325.9, 483.7 > 325.9
13C12-BDE 47: 499.8 > 339.9, 497.8 > 337.9, 495.8 > 335.9
BDE 99: 565.6 > 405.8, 565.6 > 403.8, 563.6 > 403.8, 561.6 > 401.8
13C12-BDE 99: 577.7 > 417.8, 577.7 > 415.8, 575.7 > 415.8, 573.7 > 415.8
BDE 153: 643.5 > 483.6, 485.6 > 325.9, 483.6 > 323.9, 481.6 > 323.9
13C12-BDE 153: 657.6 > 497.7, 655.6 > 495.7, 653.6 > 493.7, 495.8 > 335.9
Water content determination Procedure: oven drying at 105 oC until constant mass achieved (<0.5 mg difference between
(please describe the procedure, if deviating consecutive readings) as per study protocol, sample size ~1 g
from the one prescribed in the protocol Dry mass correction factor: The dry mass correction factor was calculated as (1/(1-MC)) where MC is the average
and the calculation of dry mass correction factor) measured moisture content of the study sample.
The average measured moisture content in 6 sub-samples of the study material were 0.50%, 0.52%, 0.51%,
0.51%, 0.48% and 0.48%.
The dry mass correction factor determined was: 1.00502 with a standard u of 0.00093 (degrees of freedom = 5).
2
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102_Final report.doc E-mail: [email protected]
Page 43 of 82
NMIA cont.
Calibration type / details Exact-matching single-point double IDMS with bracketing
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards 1. Wellington Laboratories
(e.g., source, purity, uncertainty) BDE47: 50 ± 2.5 ug/mL in toluene (10%)/nonane
BDE99: 50 ± 2.5 ug/mL in toluene (10%)/nonane
BDE153: 50 ± 2.5 ug/mL in toluene (10%)/nonane
2. NIST SRM 2257
PBDE Congeners in 2,2,4-Trimethylpentane
BDE47: 2.09 ± 0.16 ug/g
BDE99: 2.127 ± 0.090 ug/g
BDE153: 2.048 ± 0.068 ug/g
3. NIM China Certified Reference Material GBW (E) 081124
Calibration Solution of Industrial Penta-BDE in Iso-octane
BDE47: 20.0 ug/mL (expanded relative uncertainty 6%, k = 2)
BDE99: 20.5 ug/mL (expanded relative uncertainty 6%, k = 2)
BDE153: 1.43 ug/mL (expanded relative uncertainty 6%, k = 2)
4. NIM China Certified Reference Material GBW (E) 081125
Calibration Solution of Industrial Octa-BDE in Iso-octane
BDE153: 3.60 ug/mL (expanded relative uncertainty 6%, k = 2)
Internal standards used Wellington Laboratories; Carbon 13-labelled BDE 47, 99 and 153 (13C12-BDE47,
(Please specify the compounds, and at which stage
were added)13C12-BDE99, 13C12-BDE153).
Sediment sub-samples were spiked with solutions of carbon 13-labelled BDE47, 99 and 153
and then mixed by rotation overnight (at least 12 hours) prior to solvent extraction.
Purity assessment of the calibrant (if applicable) Not applicable.
(e.g. methods used for value assignment/verification) Calibration standards prepared from the materials purchased from Wellington Laboratories
were assigned values by performing a comparison of standards with the NIST SRM2257 and
NIM China Penta and Octa Mix solutions.
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Page 44 of 82
NMIJ
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable)
Extraction method/conditions The sediment was weighed and EO-5277 (CIL: 13C-labeled BDEs) 0.21 g-0.23 g
was spiked CH2Cl2 (30 mL) was added and extracted by ultrasonic (10 min)
The mixture was centrifuged to recover the supernatant (which was kept in
a brown bottle) CH2Cl2 (30 mL) was added to the precipitate, and extracted
again by ultrasonic (10 min). The mixture was centrifuged to recover the
supernatant (combine the supernatant in the brown bottle)
Clean-up procedure Solvent of the supernatant was replaced with hexane and concentr. to 1 mL
(e.g., SPE, GPC) Cu powder was added and shaken for 3 min to remove elemental sulfur
Anhydrous Na2SO4 was added and shaken for 3 min to remove moisture
The solution was passed through to a column packed with 3 g of silica
impregnated with concentrated sulfuric acid (44 %), then eluted with 25 mL
of CH2Cl2/hexane (20/80, v/v)
Solvent of the eluate was replaced with hexane and concentrated to 1 mL
The solution was loaded onto a SPE column (Supelclean Sulfoxide, 3 g/6 mL
SUPELCO), and washed with 4 mL of hexane and the eluate was discarded;
then BDEs were recovered with 10 mL of acetone/hexane (10/90, v/v)
Solvent of the eluate was replaced to hexane and concentrated to 0.2 mL
Analytical instrumentation used GC Agilent GC6890
(e.g., GC-MS ) Injection Splitless 280 deg. 1 uLGC settings Carrier gas He 1.0 mL/min constant flow
(e.g., injection mode, T and volume; carrier gas Column type Frontier Lab. UltraALLOY-PBDE
15 m * 0.25 mmI.D. * 0.05 um Thickness
and flow; column type, oven temperature program) Oven temperature 60 deg. (2 min) - (10 deg./min) - 160deg. (0 min)
(5 deg./min) - 250 deg. (0 min) - (10 deg./min)
- 300 deg. (7 min)MS settings MS Micromass Autospec NT R=10000
(e.g., MS mode, monitored ions, T, electron Mode EI 50 eV SIM
multiplier voltage, gas) Monitor ion 4Br Native: 325.8763, 323.8783, 13C: 337.9171, 335.9191;
5Br Native: 403.7868, 405.7848, 13C: 415.8276, 417.7341;
6Br: 483.6953, 481.6973, 13C: 495.7361, 493.7381
Electron multiplier voltage 350 kV
Water content determination Dried in the oven (105 deg.) for 5 and 7 days.
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details IDMS (3-point calibration)
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards NIST SRM 2257: PBDE Congeners in 2,2,4-Trimethylpentane
(e.g., source, purity, uncertainty)
Internal standards used EO-5277, CIL ( U.S. EPA Method 1614 Standard Mixtures: including eight
(Please specify the compounds, and at which stage were added) 13C-labeled BDE congeners)
Added to the sample before extraction
14.8 - 16.3
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
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Page 45 of 82
NMISA
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) N/A
Extraction method/conditions
Clean-up procedure
(e.g., SPE, GPC)
Analytical instrumentation used(e.g., GC-MS )GC settings
(e.g., injection mode, T and volume; carrier gas
and flow; column type, oven temperature program)
MS settings
(e.g., MS mode, monitored ions, T, electron
multiplier voltage, gas)
Water content determination Procedure as described in protocol
(please describe the procedure, if deviating
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards
(e.g., source, purity, uncertainty)
Internal standards used
(Please specify the compounds, and at which stage
BFR-LCS labelled compound solution from Wellington Laboratories was added before extraction. This solution
contain twenty C13 labelled compounds including MBDE-47 (2,2',4,4'-Tetrabromo[13C12]diphenyl ether),
MBDE-99 (2,2',4,4',5-Pentabromo[13C12]diphenyl ether) and MBDE-153 (2,2',4,4',5,5'-
Hexabromo[13C12]diphenyl ether)
Preliminary isotope dilution mass spectrometry followed by bracketing double isotope mass spectrometry
calibration
Calibration solution were used during quantification.
The primary standard, NIST Standard reference material 2257 was used to assign the values to the secondary
standards:
Cambridge Isotope Laboratory, BDE-47-CS-0
Cambridge Isotope Laboratory, BDE-99-CS-0
Cambridge Isotope Laboratory, BDE-153-CS-0
The NIST 2257 concentrations are expressed as the certified value ± the expanded uncertainty.
PBDE 47 (2,2',4,4'-Tetrabromodiphenyl ether) - 2.09 ± 0.16 μg/g
PBDE 99 (2,2',4,4',5-Pentabromodiphenyl ether) - 2.127 ± 0.090 μg/g
PBDE 153 (2,2',4,4',5,5'-Hexabromodiphenyl ether) - 2.048 ± 0.068 μg/g
1
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
GC settings:
The GC-TOFMS system was used for the analysis operating in 1D mode. The injector was set at 300 °C using helium as
the carrier gas at a constant flow of 2.0 ml/min. Samples were injected using a splitless 1µl injection. The GC column
combination consisted of a 5 m x 0.25 mm id Rtx®guard column and a 15 m x 0.25 mm id x 0.1 µm df Rti®5Sil MS
column, connected using a deactivated universal press-tight connector. The GC oven program is provided in table 1.
TOFMS settings:
The transfer line was set at 300°C and the ion source at 250°C. The detector was set at 1800 V to collect a full scan
mass range from 100 – 1000 m/z at a data acquisition rate of 10 spectra/second.
Quantitation and qualification settings:
The quantitation and ions, qualifying ions as well as the and ratios used during the quantification process is listed in
Table 2.
Pressurised Liquid extraction (PLE) settings:
Selective PLE (SPLE) was carried out using a fully automated Accelerated Solvent Extraction (ASE) system. In short,
extraction cells were loaded by inserting two pre-cleaned cellulose filters followed by 5 g of activated neutral
Alumina. The sediment samples were mixed with activated neutral alumina and activated copper powder (1:2:2)
and loaded on the Alumina followed by a celluloses filter. The extraction cell was heated to 100°C and extracted
using two cycles with 3:1 DCM/Hexane as solvent. The total extraction duration was approximately 30 minutes.
The Selective PLE (SPLE) method incorporates in-cell Solid Phase Extraction (SPE) clean-up using activated copper
powder and activated neutral Alumina
CCQM-K102_Final report.doc E-mail: [email protected]
Page 46 of 82
TÜBITAK UME
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) 2 g of sample was mixed with 5 g of Cu/Na2SO4 (3:1 w/w) mixture and 6 g of
inert dispersing agent and loaded to extraction cell. In order to establish IDMS technique
isotopic labelled standards for all compound were added into the sample at this stage.
Extraction method/conditions Pressurized Solvent Extraction was used. T: 120 C, P:130 bar, Cycle:3
Solvent: n -hexane: acetone (70:30 %), static time 10 min
Clean-up procedure Multilayer column was prepared. From bottom to top 3 g of 3% deactivated
(e.g., SPE, GPC) alumina, 1.5 g of 3% deactivated silica gel, 1.5 g of 44% acidified silica gel and
1 g of Na2SO4 was placed into the glass column. First, the column was washed with
10 mL of n-hexane. Then, 5 mL of extract was loaded. Elution was performed by 50
mL of dichloromethane:n -hexane (1:1) mixture. Final amount was gravimetrically adjusted
to 200 mg by evaporating solvent under gentle stream of nitrogen.
Analytical instrumentation used Triple Quadrupole GC-MS/MS was used. Temperature program was initiated at
(e.g., GC-MS ) 130 ˚C and held for two minutes, increased to 230 ˚C with 5 ˚C/min rate andGC settings increased to 300 ˚C with 5 ˚C/min rate and held for 5 minutes.
(e.g., injection mode, T and volume; carrier gas 15mx0.25mmx0.1µm DB-5MS capillary column was used. PTV injector operating
and flow; column type, oven temperature program) in splitless mode was used. Injection temperature was 150 ˚C (held 0.8 min),
transfer rate, temperature and holding time was 13 ˚C/s, 300 ˚C and 5 min, respectively.
Helium was used as carrier gas at constant flow and 1 mL/min flow rate.MS settings
(e.g., MS mode, monitored ions, T, electron
multiplier voltage, gas) 4712C 485.56 325.84 16
4713C 497.69 337.80 17
9912C 563.72 403.84 15
9913C 575.71 415.94 16
15312C 643.65 483.66 15
15313C 655.64 495.64 15
Water content determination Water determination was carried out by coulometric Karl Fischer titration at 105 ˚C
(please describe the procedure, if deviating in triplicate. Sample intake was 200 mg. Karl Fischer method is treacable to NIST 2890
from the one prescribed in the protocol Water Saturated Octanol standard reference material.
and the calculation of dry mass correction factor)
Calibration type / details IDMS single-point calibration was used.
(e.g., single-point, bracketing /
external calibration, internal standard calibration, IDMS)
Calibration standards BDE-47, BDE-99, BDE-153 neat crystals were obtained from CHIRON. 13C BDE-47, 13C BDE-99,
(e.g., source, purity, uncertainty) 13C BDE-153 were obtained Wellington Laboratories.
The purity of BD47, BDE-99 and BDE-153 were determined by qNMR and NIST SRM-1944 was
used for further check.
The sample NMR spectrum was given below for BDE-47 in section 7.
Internal standards used 13C BDE-47 13C BDE-99 13C BDE-153
(Please specify the compounds, and at which stage Isotopic labelled compounds were added into the sample at the begining of extraction.
Purity assessment of the calibrant (if applicable) The purity of BDE-47, BDE-99, BDE-153 neat crystals were determined by Q-NMR
(e.g. methods used for value assignment/verification)
Estimation of impurities (if applicable) BDE-47 (99,2±0,03) %
(e.g. type of impurity, mass fraction, uncertainty) BDE-99 (98,7±0,02) %
BDE-153 (99,5±0,05) %
1.12
1.00
1.08
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
Congener Product Ion (m/z ) Parent Ion (m/z ) CID voltaj Isotope Ratio
2
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Page 47 of 82
VNIIM
Information about the analytical procedure (N.B. especially for details not mentioned in the Core Competency Table)
Sample intake used for analysis g
Sample pre-treatment (if applicable) No
Extraction method/conditions ASE: Hexane/Acetone=90/10, 20 min, 8 cycles; T=120C; P=1700psi
SoxTherm: Toluene, 16 h, 12 cycles/h
Clean-up procedure As in the Method EPA 1614:
(e.g., SPE, GPC) Silica gel multilayer column
Aluminum oxide, neutral
Copper
Analytical instrumentation used Agilent 6890/5973N
(e.g., GC-MS )GC settings As in the Method EPA 1614:
(e.g., injection mode, T and volume; carrier gas T inj = 300 C, T interface = 320 C
and flow; column type, oven temperature program) Splitless, He, 1 ml/min, Constant Flow
100 C (3 min) - 5 C/min - 320 C (20 min)
MS settings SIM&windows: PBDE#47 - 483,7/485,7 495,7/497,7
(e.g., MS mode, monitored ions, T, electron PBDE#99 - 563,6/565,6 575,7/577,7 PBDE#153 - 641,5/643,5 653,5/655,5
multiplier voltage, gas) DB-5HT 30m*0.25mm*0.10um
Water content determination Mass of samples were about 2 g
(please describe the procedure, if deviating T = 105 C
from the one prescribed in the protocol
and the calculation of dry mass correction factor)
Calibration type / details IDMS
(e.g., single-point, bracketing / Short range calibration
external calibration, internal standard calibration, IDMS)
Calibration standards PBDE Congeners in i-Octane NIST SRM 2257
(e.g., source, purity, uncertainty)
Internal standards used Method EPA 1614 Labeled Surrogate Stock Solution
(Please specify the compounds, and at which stage EO-5277
2.5
(e.g., PLE, Soxhlet / T, P, duration and cycles, solvents)
CCQM-K102 E-mail: [email protected]
Page 48 of 82
ANNEX B
Results for BDE 209, optional analyte in CCQM-K102, for which no KCRV
was to be determined.
Table 1-B. BDE209 results
Participant Mass fraction
(µg/kg)
Combined standard
uncertainty u (µg/kg)
Coverage
factor
Expanded
uncertainty U
(µg/kg)
LNE 8751 481 2 962
NIST 7980 220 4.3 944
NIM (GC-MS, NCI) 8776 380 2 760
NIM (HPLC-PAD) 8440 270 2 540
Figure 1-B. BDE209 results, displaying participants' standard uncertainty
7000
7500
8000
8500
9000
9500
NIM (HPLC-PAD) LNE NIM (GC-MS,NCI)
NIST
µg/kg BDE209
CCQM-K102_Final report.doc E-mail: [email protected]
Page 49 of 82
Revised results submitted by some participants in CCQM-K102.
Table 2-B. BDE 47: officially submitted and revised (in yellow) results in CCQM-K102
Participant
Mass
fraction
(µg/kg)
Combined
standard
uncertainty u
(µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Reason for revision
VNIIM 14.8 0.58 (0.65) 2 1.2 (1.3) Slight correction of
uncertainty estimation
LNE 15.77 2.99 (0.87) 2 5.98 (1.74)
mistake in uweighing +
introducing
measurements'
independency
(dividing SD by √n)
TÜBITAK
UME 16.91 (17.72) 0.76 2 1.52 (1.59)
use of 60 m column
(instead of 15 m)
Figure 2-B. BDE 47: KCRV and its standard uncertainty, officially submitted (blue diamonds) and
revised results (yellow squares), displaying participants' standard uncertainty. In red the value
excluded from the KCRV calculation.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 50 of 82
Table 3-B. BDE 99: officially submitted and revised (in yellow) results in CCQM-K102
Participant Mass fraction
(µg/kg)
Combined
standard
uncertainty
u (µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Reason for revision
NMISA 48.12 (32.21) 4.01 (2.69) 2.025 8.13 (5.44) calculation error
NIST 41.1
(35.0, DB- XLB
34.6, DB-5MS)
0.85 4.35
3.7
(2.90, DB- XLB
2.14, DB-5MS)
using DB-XLB and
DB-5MS 30 m
columns (instead of
10 m) to improve
separation of potential
interferences
LNE 30.93 3.83 (1.095) 2 7.66 (2.19)
mistake in uweighing +
introducing
measurements'
independency
(dividing SD by √n)
TÜBITAK
UME 39.50 (35.24) 2.04 2 4.07 (3.63)
Use of 60 m column
(instead of a 15 m) to
improve separation of
potential interferences
VNIIM 32.8 0.89 (1.05) 2 1.8 (2.1) Slight correction of
uncertainty estimation
Figure 3-B. BDE 99 KCRV and its standard uncertainty, officially submitted (blue diamonds) and
revised results (yellow squares), displaying participants' standard uncertainty. In red the value(s)
excluded from the KCRV calculation.
N.B. The revised NIST results displayed are the ones obtained using the 30 m DB-5MS column.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 51 of 82
Table 4-B. BDE 153: officially submitted and revised (in yellow) results in CCQM-K102
Participant Mass fraction
(µg/kg)
Combined
standard
uncertainty
u (µg/kg)
Coverage
factor
Expanded
uncertainty
U(µg/kg)
Reason for revision
NMISA 7.12 (7.29) 0.52 (0.54) 2.013 1.05 (1.09) calculation error
TÜBITAK
UME 11.03 (6.86) 0.72 2 1.45 (0.90)
Use of 60 m column
(instead of 15 m) to
improve separation of
potential interferences
NIST 8.97
(6.10, DB-XLB
6.50, DB-5MS)
0.2 4.35
0.87
(0.55, DB-XLB
0.65, DB-5MS)
using DB-XLB and
DB-5MS 30 m
columns (instead of
10 m) to improve
separation of potential
interferences
LNE 7.03 1.75 (0.46) 2 3.50 (0.92)
mistake in uweighing and
introducing
measurements'
independency by
dividing SD by √n
VNIIM 6.11 0.16 (0.21) 2 0.32 (0.42) Slight correction of
uncertainty estimation
Figure 4-B. BDE 153 KCRV and its standard uncertainty, officially submitted (blue diamonds) and
revised results (yellow squares), displaying participants' standard uncertainty. In red the value(s)
excluded from the KCRV calculation.
N.B. The revised NIST results displayed are the ones obtained using the 30 m DB-5MS column.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 52 of 82
ANNEX C
Full details of the uncertainty budgets estimated by the participants in CCQM-K102
BAM
Contributions to the uncertainty budget and worst case estimation
ucom=SQRT(Ʃui2). The individual contributions ui are as follows:
-------------------------------------------------------------------------------------------------------------------------------
CENAM
m0 Standard mass
mI0 Standard isotope mass
mx Sample mass
mIx Standard isotope mass in sample
R0 Response ratio of standards
Rx Response ratio of sample
w0 Mass fraction of standard
CFh Humidity correction factor
wx Mass fraction of measurand in sample
10
)(
ilod
losspuritychex
samplealiquot
issolventislod
sample
sample
Fandcorwith
FFFFmm
cmmcor
sl
icrc
CFhwmRm
mRmw
Ix
xIx
x *0
00
0
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Page 53 of 82
GLHK
Each standard uncertainty of PBDE- 47, 99 and 153 was obtained by combining the systematic
uncertainty and random uncertainty as shown below equation.
The systematic uncertainty included the followings:
1) the uncertainty of calibration standard solution (Ucal) by combining the uncertainty of preparation of
standard solution (weighing) and uncertainty of NIST BDE standard solutions obtained from the
certificate;
2) the uncertainty due to preparation of sample blend and calibration blend (Uweighing);
3) the uncertainty due to moisture correction (Umoisture)
The random uncertainty was calculated from the precision (standard deviation) of multiple measurement
results from three bottles.
-------------------------------------------------------------------------------------------------------------------------------
JRC-IRMM
k coverage factor (k=2) resulting in a confidence level of approx. 95 %
u cal relative uncertainty related to the preparation of the calibration standards
including contribution arising from purity and gravimetric steps
RSD rep relative standard deviation of repeatability (from ANOVA) - from validation data
n1 number of independent samples used for analysis (n1=7)
RSD ip relative standard deviation of intermediate precision (from ANOVA) – from validation data
n2 number of days (n2=1)
u true relative uncertainty of trueness, estimated from the recovery - from validation data
------------------------------------------------------------------------------------------------------------------------
22
2
2
1
2
* caltrue
iprepuu
n
RSD
n
RSDkU
u rep, % uip, % u trueness, % ustds, % u, % U, %
BDE47 3.3 1.3 0.9 3.8 4.3 8.6
BDE99 7.4 8.5 3.3 2.1 9.8 19.5
BDE153 6.7 11.9 2.8 1.7 12.6 25.2
MoistureR
R
M
M
M
MCC
Bc
B
Yc
Zc
X
YZX
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Page 54 of 82
KRISS
f: dry-mass correction factor;
Csample: is the concentration of analytes in the sample;
Cs-sol: is the concentration of the analytes standard solution;
Msample: is the mass of the sample taken for analysis;
Mis-sol, spiked: is the mass of the isotope standard solution added to the sample aliquot;
Mis-sol, std. mix.: is the mass of the isotope standard solution added to the isotope ratio standard solution;
Ms-sol, std. mix.: is the mass of the standard solution added to the isotope ratio standard solution;
ARsample: is the area ratio of analyte/isotope for sample extract, observed by GC/MS;
ARstd. mix.: is the area ratio of analyte/isotope for the isotope ratio standard solution, observed by GC/MS.
Random : Standard deviations of multiple measurement results from five subsamplings
Combined standard uncertainties were obtained by combining systematic uncertainties and random uncertainties as shown below equation
------------------------------------------------------------------------------------------------------------------------
n
suCu
22
systematics.p.,mean )(
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Page 55 of 82
LGC
LNE
Csed: mass fraction of PBDE in the sediment in µg/kg Clab: mass fraction of labeled PBDE solution in µg/kg mlab: mass of labeled solution in the sediment
msed: mass of sediment sample Rsed: unlabeled/labeled ion peak area ratio in the sediment sample
a: gradient of the slope for linear regression plot b: intercept on y axis for the linear regression plot
f standard: correction factor due to the standard solutions uncertainty
f F: correction factor due to measurement precision
Fdards
sed
ffbRsedam
mlabClabCsed
tan)(
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Page 56 of 82
PBDE 47
Type (A or B) relative Uncertainty (%)
vial 8 vial 44 vial 77
preparationof sample blends (weighings) B 60.10% 14.64% 73.65%
Calibration model B 0.11% 0.03% 0.15%
Preparation of calibration blend (weighings)
B 15.15% 3.75% 21.26%
Precision B 24.65% 81.57% 4.95%
PBDE 99
Type (A or B) relative Uncertainty (%)
vial 8 vial 44 vial 77
preparationof sample blends (weighings) B 43.56% 39.53% 46.51%
Calibration model B 0.05% 0.05% 0.06%
Preparation of calibration blend (weighings)
B 47.69% 42.18% 51.76%
Precision B 8.69% 18.25% 1.67%
PBDE 153
Type (A or B) relative Uncertainty (%)
vial 8 vial 44 vial 77
preparationof sample blends (weighings) B 84.98% 6.93% 78.43%
Calibration model B 1.38% 0.19% 1.23%
Preparation of calibration blend (weighings)
B 8.17% 0.50% 7.98%
Precision B 5.48% 92.38% 12.37%
------------------------------------------------------------------------------------------------------------------------
NIM
Measurement uncertainty mainly come from measurement precision and calibration solution.
Uncertainty source BDE-47 BDE-99 BDE-153 BDE-209
(HPLC)
BDE-209
(GCMS)
Mesurement
result(µg/kg) 14.65 35.00 7.177 8.440 8.776
Method precision 0.18 0.33 0.11 0.26 0.37
Calibration solution 0.29 0.70 0.14 0.059 0.061
Combined standard
uncertainty 0.35 0.78 0.19 0.27 0.38
Coverage factor 2 2 2 2 2
Combined expanded
uncertainty 0.70 1.56 0.38 0.54 0.76
------------------------------------------------------------------------------------------------------------------------
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Page 57 of 82
NIST
The combined uncertainty was estimated as the mean value times the square root of the sum of
squares of the relative uncertainties (CVs) for: triplicate measurements, water content
determination, calibration and the uncertainty in the certified value of the calibration solution. The
95 % expanded uncertainties were estimated as the two-tailed Student’s t value for two degrees of
freedom, t(95,2) = 4.3, times the combined uncertainty
------------------------------------------------------------------------------------------------------------------------
NMIA
where;
ωx = mass fraction of analyte in sample
ωz = mass fraction of analyte in the calibration standard solution used to prepare calibration blend
My = mass of internal standard solution added to sample blend
Myc = mass of internal standard solution added to calibration blend
Mx = mass of sample added to sample blend
Mzc = mass of calibration standard solution added to calibration blend
Rb = ratio of measured peak areas corresponding to the analyte and internal standard in the sample blend
Rbc = ratio of measured peak areas corresponding to the analyte and internal standard in the calibration blend
Rx = ratio of measured peak areas corresponding to the analyte and internal standard in the sample
Rz = ratio of measured peak areas corresponding to the analyte and internal standard in the calibration standard
Ry = ratio of measured peak areas corresponding to the analyte and internal standard in the internal standard
MCCF = moisture content correction factor
F(MP) = method precision term
F(MT) = method trueness factor
All masses and mass fractions used to calculate ωx were determined using balances calibrated
with metrological traceability to the SI unit of the kilogram through Australian national standards for mass.
Peak areas were determined from chromatographic traces generated for characteristic ions corresponding to analytes and
internal standards. 32 sub-samples taken from Bottles 21, 37, 53 and 81 of the study material were analysed in
seven batches between November 2014 - March 2015. Moisture content was determined according to the study protocol.
Tables showing the measurement uncertainty budgets for BDEs 47, 99 and 153 are provided on the Tabs named,
Uncertainty BDE47, "Uncertainty BDE99", and "Uncertainty BDE153".
A standard uncertainty was estimated for all components in the measurement equation. These were combined using
derived sensitivity coefficients to estimate a combined standard uncertainty in the reported result for each analyte
in the study sample. The total effective degrees of freedom was determined using the Welch-Satterthwaite
equation to calculate the appropriate coverage (k) factor to expand the combined standard uncertainty to a 95% confidence
interval for reporting. The method precision term was calculated as the standard deviation of all the measurements used in the
calculation of the reference value.
To ensure that all likely sources of bias would be accounted for in the final uncertainty budget a trueness factor was also included.
This factor was assigned a nominal value of one with an uncertainty representing the potential magnitude of undetected bias due to
factors affecting the measured peak area ratios such as matrix interferences and matrix effects and bias due to the incomplete
recovery of native BDE analytes from the sediment matrix. The magnitude of the standard uncertainty in the trueness factor was
estimated as the standard deviation of the various average analyte mass fractions determined in multiple sediment samples
analysed by the primary method of analysis and the different confirmatory methods of analysis used to assess bias due to matrix
interferences/effects and the recovery of analytes from the sample matrix.
MTMP
BcY
ZcB
XB
BY
Yc
Zc
X
YZX FFMCCF
RR
RR
RR
RR
M
M
M
M
CCQM-K102_Final report.doc E-mail: [email protected]
Page 58 of 82
BDE 47
BDE 99
Summary of Contributions to Total Combined Measurement Uncertainty
Number Name of Component Symbol Units Value
Standard
Uncertainty
Relative
Standard
Uncertainty
Degrees of
Freedom
i Xi xi u(xi) u(xi)/xi (%) vi
1 Method Precision F(MP) dimensionless 1.000 0.031 3.1% 40.0
2 Method Trueness F(MT) dimensionless 1.000 0.018 1.8% 7.0
3 Standard Wz ng/g 328 14 4.4% 6.0
4 Moisture Content MC n/a 1.00502 0.00093 0.092% 5.0
5 Gravimetry Mx g 2.0126 0.00026 0.013% 100.0
6 Gravimetry My(SB) g 0.0869 0.00026 0.30% 100.0
7 Gravimetry Mz g 0.0944 0.00026 0.28% 100.0
8 Gravimetry My(CB) g 0.0852 0.00026 0.31% 100.0
9 Isotope Amount Ratio Rx,Rz mol/mol 6.1E+05 5.3E+05 87% 4.0
10 Isotope Amount Ratio Ry mol/mol 0.000012 0.000021 186% 4.0
11Blend Isotope Amount
RatioR(SB) mol/mol 0.7878 25.0
12Blend Isotope Amount
RatioR(CB) mol/mol 0.7614 25.0
Summary of Contributions to Total Combined Measurement Uncertainty
Number
Name of
Component Symbol Units Value
Standard
Uncertainty
Relative Standard
Uncertainty
Degrees of
Freedom
i Xi xi u(xi) u(xi)/xi (%) vi
1Method
PrecisionF(MP) dimensionless 1.000 0.049 4.9% 40.0
2Method
TruenessF(MT) dimensionless 1.000 0.017 1.7% 7.0
3 Standard Wz ng/g 792 31 3.9% 6.0
4Moisture
ContentMC n/a 1.00502 0.00093 0.092% 5.0
5 Gravimetry Mx g 2.0126 0.00026 0.013% 100.0
6 Gravimetry My(SB) g 0.0778 0.00026 0.33% 100.0
7 Gravimetry Mz g 0.0883 0.00026 0.29% 100.0
8 Gravimetry My(CB) g 0.0764 0.00026 0.34% 100.0
9Isotope Amount
RatioRx,Rz mol/mol 3.2E+06 1.6E+06 49% 4.0
10Isotope Amount
RatioRy mol/mol 0.0000087 0.0000032 37% 4.0
11Blend Isotope
Amount RatioR(SB) mol/mol 1.1672 25.0
12Blend Isotope
Amount RatioR(CB) mol/mol 1.1886 25.0
CCQM-K102_Final report.doc E-mail: [email protected]
Page 59 of 82
BDE 153
---------------------------------------------------------------------------------------------------------------------------------
NMIJ
Summary of Contributions to Total Combined Measurement Uncertainty
Number Name of Component Symbol Units Value
Standard
Uncertainty
Relative
Standard
Uncertainty
Degrees of
Freedom
i Xi xi u(xi) u(xi)/xi (%) vi
1 Method Precision F(MP) dimensionless 1.000 0.044 4.4% 36.0
2 Method Trueness F(MT) dimensionless 1.000 0.021 2.1% 6.0
3 Standard Wz ng/g 126.5 3.4 2.7% 6.0
4 Moisture Content MC n/a 1.00502 0.00093 0.092% 5.0
5 Gravimetry Mx g 2.0130 0.00026 0.013% 100.0
6 Gravimetry My(SB) g 0.0776 0.00026 0.34% 100.0
7 Gravimetry Mz g 0.0911 0.00026 0.29% 100.0
8 Gravimetry My(CB) g 0.0773 0.00026 0.34% 100.0
9 Isotope Amount Ratio Rx,Rz mol/mol 5.8E+06 1.4E+06 24% 1.0
10 Isotope Amount Ratio Ry mol/mol 0.000000163 0.000000037 22% 4.0
11Blend Isotope Amount
RatioR(SB) mol/mol 1.0950 22.0
12Blend Isotope Amount
RatioR(CB) mol/mol 0.9936 22.0
CCQM-K102_Final report.doc E-mail: [email protected]
Page 60 of 82
BDE47 total No.11 No.39 No.73
concentration of primary standard
0.038 0.038 0.038 0.038
mass ratio of standards solutions
0.00022 0.00022 0.00022 0.00022
mass ratio of sediment and 13C-BDE
0.00011 0.00011 0.00011 0.00011
Water content 0.000088 0.000088 0.000088 0.000088
repeatability from GC/MS analysis for sample
0.0048 0.0046 0.0033 0.004
calibration curve 0.0095 0.0094 0.01 0.0092
total 0.04 0.04 0.04 0.04
N.B. total uncertainty of "repeatability from GC/MS" was calculated from ANOVA
BDE99 total No.11 No.39 No.73
concentration of primary standard
0.021 0.021 0.021 0.021
mass ratio of standards solutions
0.00022 0.00022 0.00022 0.00022
mass ratio of sediment and 13C-BDE
0.00011 0.00011 0.00011 0.00011
Water content 0.000088 0.000088 0.000088 0.000088
repeatability from GC/MS analysis for sample
0.0021 0.0038 0.0085 0.0095
calibration curve 0.013 0.013 0.013 0.013
total 0.024 0.025 0.026 0.026
CCQM-K102_Final report.doc E-mail: [email protected]
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------------------------------------------------------------------------------------------------------------------------
NMISA
BDE 47
CCQM-K102_Final report.doc E-mail: [email protected]
Page 62 of 82
BDE 99
BDE 153
------------------------------------------------------------------------------------------------------------------------
TÜBITAK UME
Bottom up approach was used considering the following sources:
x u u/x u/x2 v
W z
[native] solution added to calibration blend
(ug/ g)68208.45 1936.70 0.03 8.06E-04 2
m z
weight native solution added to calibration
blend (g)0.155 1.00E-04 6.44E-04 4.15E-07 5
m y
weight of Isotope solution added to sample
(g)0.099 1.00E-04 1.01E-03 1.01E-06 5
m yc
weight of Isotope solution added to
calibration blend (g)0.099 1.00E-04 1.01E-03 1.02E-06 3
m x weight of sample analysed 1.000 1.00E-04 1.00E-04 9.99E-09 5
R' B /R' BC
ratio of peaks areas of native/ labelled in the
samples1.088 4.19E-02 3.85E-02 1.48E-03 5
Precision Repeat measurements 32.334 2.06E+00 6.37E-02 4.06E-03 5
FRepeat
dry mass correction factor1.004 2.36E-02 2.35E-02 5.55E-04 7
2.69 u
5.44 U (k = 2.013)
16.83 Urel
Factors in uncertainty
x u u/x u/x2 v
W z
[native] solution added to calibration blend
(ug/ g)66454.14 1875.79 0.03 7.97E-04 2
m z
weight native solution added to calibration
blend (g)0.155 1.00E-04 6.44E-04 4.15E-07 5
m y
weight of Isotope solution added to sample
(g)0.099 1.00E-04 1.01E-03 1.01E-06 5
m yc
weight of Isotope solution added to
calibration blend (g)0.099 1.00E-04 1.01E-03 1.02E-06 3
m x weight of sample analysed 1.000 1.00E-04 1.00E-04 9.99E-09 5
R' B /R' BC
ratio of peaks areas of native/ labelled in the
samples1.032 4.22E-02 4.09E-02 1.67E-03 5
Precision Repeat measurements 7.080 3.49E-01 4.93E-02 2.43E-03 5
FRepeat
dry mass correction factor1.004 2.36E-02 2.35E-02 5.55E-04 7
0.52 u
1.05 U (k = 2.013)
14.87 Urel
Factors in uncertainty
CCQM-K102_Final report.doc E-mail: [email protected]
Page 63 of 82
1-Mass of sample intake
Value Standard Uncertainty
Mass of sediment sample
Calibration msediment umcalibrationsample
Mass of Tare
Calibration mtare umcalibrationtare
Since same balance was used umcalibrationsample and umcalibrationtare is equal to same value
2-Isotopic Labelled Compounds Stock Solution
Value Standard Uncertainty
Purity of Compound
PCompound13C12 uPCompound13C12
Mass
Mass of first compound
Calibration m1st compound umCalibration
Mass of second compound
Calibration m2nd compound umCalibration
Mass of third compound
Calibration m3rd compound umCalibration
Mass of Solvent
Calibration msolvent umCalibration
Mass of Tare
Calibration mtare umCalibration
Since same balance was used all umcalibration are equal to same value
Combined Standard Measurement Uncertainty
3-Spiking of Isotopic Labelled Stock Solution by Gas Tight Syringe
Value Standard Uncertainty
Calibration
uVC
Temperature
uVT
CCQM-K102_Final report.doc E-mail: [email protected]
Page 64 of 82
4-Uncertainty of Recovery
uCobs standard measurement uncertainty of observed concentration of analyte
Cobs observed concentration of analyte
uCcert standard measurement uncertainty of certified concentration of analyte
Ccert certified concentration of analyte
5-Uncertainty of Repeatability
6-Karl-Fisher Water Determination - Mass of Sample
- Repeatability of Karl Fisher measurement
7-Mass of final sample
Value Standard Uncertainty
Mass of sediment final sample
Calibration mfinal sample umcalibrationsample
Mass of solvent
Calibration mtare umcalibrationsolvent
Mass of Tare
Calibration mtare umcalibrationtare
Since same balance was used all umcalibration are equal to same value
------------------------------------------------------------------------------------------------------------------------------
CCQM-K102_Final report.doc E-mail: [email protected]
Page 65 of 82
VNIIM
-----------------------------------------------------------------------------------------------------------------------------
uA – standard uncertainty of results of 9 measurements, % ;
uB – standard uncertainty consisting of
standard uncertainty of calibration – ucal, %,
standard uncertainty of weighing of sample – usample, %,
standard uncertainty of blank – ublank, %;
and standard uncertainty of dry mass determnation – udry, %.
In turn ucal consists of
standard uncertainty of SRM – usrm, %,
standard uncertainty of weighing of solution – usolution, %,
standard uncertainty of spiking of IS – uis, %,
and of standard uncertainty of RR (relative response) – uRR, %.
The meanings of u sample, u blank, u dry are negligible so the equation is
CCQM-K102_Final report.doc E-mail: [email protected]
Page 66 of 82
ANNEX D
KCRVs, associated expanded uncertainty and the participants' results
displaying expanded uncertainties for BDE 47, BDE 99 and BDE 153 in
CCQM-K102.
Figure 1-D. CCQM-K102: KCRV and its expanded uncertainty for BDE 47.
Participants' results are also displayed with their expanded uncertainties.
KCRV (median) 15.60
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 1.19
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=13) 0.41
U95 % (k*u) k = 2 0.82
CCQM-K102_Final report.doc E-mail: [email protected]
Page 67 of 82
Figure 2-D. CCQM-K102: KCRV and its expanded uncertainty for BDE 99.
Participants' results are also displayed with their expanded uncertainties.
KCRV (median) 33.69
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 2.15
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=11) 0.81
U95 % (k*u) k = 2 1.62
Figure 3-D. CCQM-K102: KCRV and its expanded uncertainty for BDE 153.
Participants' results are also displayed with their expanded uncertainties.
KCRV (median) 6.28
𝑀𝐴𝐷𝑒 = 𝑚𝑎𝑑 ∗ 1.483 0.74
𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 (𝑢) = 1.25 ∗ 𝑀𝐴𝐷𝑒/√𝑛 (n=11) 0.28
U95 % (k*u) k = 2 0.56
CCQM-K102_Final report.doc E-mail: [email protected]
Page 68 of 82
ANNEX E
CCQM-K102: Core Competency Tables [Analyte(s) in Matrix]
Instructions:
In the middle column place a tick, cross or say the entry is not applicable for each of the
competencies listed (the first row does not require a response)
Fill in the right hand column with the information requested in blue in each row
Enter the details of the calibrant in the top row, then for materials which would not meet the CIPM
traceability requirements the three rows with a # require entries
BAM
CCQM-K102 BAM PBDE in sediment Scope of Measurement: quantification of organic molecules in the approximate range of molecular weights
from 100 to 800 g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000
μg/kg in abiotic dried matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
N/A
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time, mass spec ion ratios, (GC/MS)
Extraction of analyte(s) of interest from
matrix √ ASE, toluene, 3 cycles, 100°C, 140 bar
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ Clean-up
1) Al2O3 column chromatography
(1 cm of sodium sulfate; 25 g of Al2O3; 1 cm of
sodium sulfate)
2) Multilayer column chromatography
(1,0 g of sodium sulfate / 0.5 g silica gel/silver
nitrate; 0.2 g of silica gel;
1.0 g of silica gel/sulfuric acid; 0.2 g of silica gel;
0.5 g of silica gel/sodium hydroxide)
Transformation - conversion of analyte(s)
of interest to detectable/measurable form (if
used)
N/A none
Analytical system √ GC-MS, quadrupole
Calibration approach for value-assignment
of analyte(s) in matrix √ a) IDMS, internal standards labelled BDE 47,99,153
b) 6-point calibration curve
Verification method(s) for value-
assignment of analyte(s) in sample (if used)
N/A
Other N/A
BDE 153 degree of equivalence expanded uncertainty does not cross zero, value not consistent
with the KCRV: no specific competency identified as reason.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 69 of 82
CENAM
CCQM-K102 NMI PBDEs in sediment Scope of Measurement: quantification of organic molecules in the approximate range of molecular weights
from 100 to 800 g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000
μg/kg in abiotic dried matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Calibration solution from Cambridge Isotope
Laboratories (CIL) verified by SRM2257
Identity verification of analyte(s) in
calibration material.#
√ GC-MS/MS
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
For calibrants which are a calibration
solution: Value-assignment method(s).#
√ We use SRM-2257from NIST to verify calibrants RF,
CIL calibration curve were verified with SRM2257
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time and MRM ion pairs
Extraction of analyte(s) of interest from
matrix √ Automated Soxhlet Extraction
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ SPE silica
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used)
N/A
Analytical system √ GC-MS/MS
Calibration approach for value-assignment
of analyte(s) in matrix √ IDMS single-point calibration
Verification method(s) for value-assignment
of analyte(s) in sample (if used)
N/A SRM 2257 was used as control RM which were treated
under the same sample prep as the test sample
Other N/A Indicate any other competencies demonstrated.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 70 of 82
GLHK
CCQM-K102 GLHK Track „A“- low polarity analytes in abiotic matrix
Polybrominated diphenyl ethers in sediment
Scope of Measurement: Quantification of organic molecules in the approximate range of MW from 100 to 800
g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1 – 1000 µg/kg in abiotic
dried matrices.
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Certified reference material SRM 2257 (PBDE
congeners in 2,2,4-trimethylpentane) obtained from the
NIST.
Identity verification of analyte(s) in
calibration material.#
N/A
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
N/A
Sample Analysis Competencies Identification of analyte(s) in sample √ Relative retention time, ion ratios
Extraction of analyte(s) of interest from
matrix √ Soxhlet extraction
Cleanup - separation of analyte(s) of interest
from other interfering matrix components (if
used)
√ Multi-silica gel column and alumina column clean-up
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used)
N/A
Analytical system √ GC-HRMS (Double focusing HRMS)
Calibration approach for value-assignment of
analyte(s) in matrix √ a) IDMS
b) exact matching
Verification method(s) for value-assignment
of analyte(s) in sample (if used)
N/A
Other
CCQM-K102_Final report.doc E-mail: [email protected]
Page 71 of 82
JRC-IRMM
CCQM-K102
JRC-
IRMM
Polybrominated diphenyl ethers in
sediment Scope of Measurement: quantification of organic molecules in the approximate range of MW from 100 to 800
g/mol, having low polarity (pKow < -2) and for the range of mass fraction 1 – 1000 µg/kg in abiotic dried
matrices
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Calibration solution NIST SRM 2257
Identity verification of analyte(s) in
calibration material.#
Cross-checked by GC-MS with in-house prepared
standards from neat crystals
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
N/A
Sample Analysis Competencies Identification of analyte(s) in sample
Retention time, mass spec ion ratios by GC-MS
Extraction of analyte(s) of interest from
matrix
ASE
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
SPE
Transformation - conversion of analyte(s)
of interest to detectable/measurable form (if
used)
N/A
Analytical system
GC-ECNI-MS
Calibration approach for value-assignment
of analyte(s) in matrix
a) internal standard (PBDE 77)
b) 5-point calibration curve
Verification method(s) for value-
assignment of analyte(s) in sample (if used)
Value assignment cross checked with in-house
prepared standards and quality control samples
(spiked study sediment and SRM 1944, with reference
mass fraction values)
Other Method was in-house validated previously
CCQM-K102_Final report.doc E-mail: [email protected]
Page 72 of 82
KRISS
CCQM-K102 KRISS
Polybrominated diphenyl ethers in
sediment Scope of Measurement: quantification of organic molecules in the approximate range of molecular weights
from 100 to 800 g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000
μg/kg in abiotic dried matrices
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Neat commercial calibrants for BDE-47, 99, 153 were
from Accustandard.
Identity verification of analyte(s) in
calibration material.#
√ GC/MS
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
√ The purities were assessed by KRISS with GC-FID, but
water content and non-volatile impurities were not
tested due to the limited amounts of the materials.
Purities: BDE 47, 99, and 153 were 98.75%, 95.50%,
and 95.83%, respectively. The purities assessed by
KRISS was indirectly confirmed by comparing the
calibration solution prepared with the materials to NIST
SRM 2257
For calibrants which are a calibration
solution: Value-assignment method(s).#
√ Calibration solutions were gravimetrically prepared in
KRISS and verified by cross-checking of multiple
calibration solutions. Secondary confirmation by
comparison with NIST SRM 2257
Sample Analysis Competencies Identification of analyte(s) in sample √ GC Retention time, mass spec ion ratios, comparison of
GC/MS measurement results by low resolution SIM,
high resolution SIM at two different channels for each
analytes
Extraction of analyte(s) of interest from
matrix √ Pressurized Liquid Extraction (PLE) with
dichloromethane
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ SPE cartridge (silica gel)
Transformation - conversion of analyte(s)
of interest to detectable/measurable form (if
used)
N/A
Analytical system √ On-column GC/MS (low resolution) in SIM mode at a
primary channel and a secondary (confirmatory)
channel for each analytes
Calibration approach for value-assignment
of analyte(s) in matrix √ IDMS with exact matching single-point calibration
Verification method(s) for value-
assignment of analyte(s) in sample (if used) √ On-column GC-HRMS (R=10000) for confirmatory
measurement
Other N/A
CCQM-K102_Final report.doc E-mail: [email protected]
Page 73 of 82
LGC
CCQM-K102 LGC
Polybrominated diphenyl ethers in
sediment Scope of Measurement: Demonstration of the lab's competency in quantification of organic
molecules in the approximate range of MW from 100 to 800 g/mol, having polarity
corresponding to pKow < -2 and for the range of mass fraction 1 – 1000 µg/kg in abiotic dried
matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Pure solid materials of PDBEs 47, 99 and 153 were
obtained from Chiron. Their identity was confirmed
within LGC by 1H NMR and MS.
Identity verification of analyte(s) in
calibration material.#
The calibration solutions of the three calibrants in
2,2,4-Trimethylpentane were prepared in house from
pure materials above
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A PDBEs 47 and 99 ‘pure materials’ were value assigned
by qNMR using maleic acid as an internal standard (
maleic acid purity assigned in house by LGC)
For calibrants which are a calibration
solution: Value-assignment method(s).#
√ 2,2,4-trimethylpentane stock solutions of the three
PDBEs were prepared from ‘pure’ solid materials and
then assayed by qNMR using dimethyl sulphone
(DMSO2) as an internal standard in deuterated
acetonitrile. Purity of DMSO2 reference material
assigned by LGC and NMIJ.
Sample Analysis Competencies Identification of analyte(s) in sample √ Comparison with standards in terms of Retention Time
and full scan spectra, as well as ion ratios between SIM
quantifier and qualifier ions
Extraction of analyte(s) of interest from
matrix √ Exhaustive soxhlet extraction, with acetone/hexane
solvent composition
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ Initial clean-up of the extracts was with SPE(acid/basic
florisil columns) followed by normal phase LC
fractionation, using hypercarb columns with a
toluene/hexane mobile phase and temperature gradient
Transformation - conversion of analyte(s)
of interest to detectable/measurable form (if
used)
N/A N/A
Analytical system √ GC-MS with EI source, equipped with Dean switch used
as divert valve
Calibration approach for value-assignment
of analyte(s) in matrix √ Bracketing double exact matching IDMS was used for
all three analytes with 13C internal standards
Verification method(s) for value-
assignment of analyte(s) in sample (if used)
N/A
Other N/A
CCQM-K102_Final report.doc E-mail: [email protected]
Page 74 of 82
LNE
CCQM-K102 LNE Polybrominated diphenyl ethers in
sediment Scope of Measurement: demonstrate the laboratories competence in the quantification of organic
molecules in the approximate range of molecular weights from 100 to 800 g/mol , having polarity
corresponding to pKow < -2 and for the range of mass fraction 1-1000 µg/kg in abiotic dried matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
SRM2257
Identity verification of analyte(s) in
calibration material.# √
Identification by comparison with the pure analyte , (
mass spectrum ,retention time, abundance of
characteristics ions) and with the NIST library
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
N/A
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time and specific transitions
Extraction of analyte(s) of interest from
matrix √ ASE
Cleanup - separation of analyte(s) of interest
from other interfering matrix components (if
used)
√ Purification of the ASE extract on a pretreated silica
and alumina column
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used)
N/A Indicate chemical transformation method(s), if any, (i.e.,
hydrolysis, derivatization, other)
Analytical system √ GC/MS²
Calibration approach for value-assignment
of analyte(s) in matrix √ a) quantification mode used : IDMS
b) calibration mode used: 11 points calibration curve
Verification method(s) for value-assignment
of analyte(s) in sample (if used)
N/A Indicate any confirmative method(s) used, if any.
Other N/A Indicate any other competencies demonstrated.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 75 of 82
NIM
CCQM-K102 NIM
Polybrominated diphenyl ethers in
sediment Scope of Measurement: quantification of organic molecules in the approximate range of MW from 100
to 800 g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1 – 1000
µg/kg in abiotic dried matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution? GBW(E)081124 , GBW08709, from NIM,China.
Identity verification of analyte(s) in
calibration material.#
√ GC-MS
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
√
The purity of neat BDE-47,99,153 is determined by
HPLC-DAD and qNMR. The purity of BDE- 209 is
determined by HPLC-DAD and HPLC-ICP-MS
For calibrants which are a calibration
solution: Value-assignment method(s).#
√ The calibration solution is prepared by the weight
capacity method.
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time and mass spec ion ratios
Extraction of analyte(s) of interest from
matrix √
ASE
Cleanup - separation of analyte(s) of interest
from other interfering matrix components (if
used) √ SPE
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used) N/A No
Analytical system √ 1) BDE-47,99,153: GC-MS/MS
2) BDE-209: HPLC-PDA
Calibration approach for value-assignment
of analyte(s) in matrix √
a) BDE-47,99,153: IDMS
b) BDE-209: internal standard.
c) single-point calibration,
Verification method(s) for value-assignment
of analyte(s) in sample (if used) √
Recovery is determined by adding standard solution to
blank sediment.
Other “N/A”
BDE 153 degree of equivalence expanded uncertainty does not cross zero, value not consistent
with the KCRV: no specific competency identified as reason.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 76 of 82
NIST
CCQM-K102/P138 NIST Polybrominated Diphenyl Ethers in Sediment Scope of Measurement: quantification of organic molecules in the approximate range of MW from 100 to 800
g/mol, having polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000 µg /kg in abiotic
dried matrices
Competency Specific Information as Provided by NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
NIST Standard Reference Materials 2257 and 2258
Identity verification of analyte(s) in
calibration material. √ Preparation from commercially obtained materials,
confirmed by GC-MS
For highly-pure substance: Value-
Assignment / Purity Assessment method(s). NA
For calibration solution: value-assignment
methods. √ Gravimetric preparation and analytical results
determined using gas chromatography.
Sample Analysis Competencies Identification of analyte(s) in sample √ Identification in samples based on retention time and
MRM transitions obtained with SRM 2257 and 2258
Extraction of analyte(s) of interest from
matrix √
Pressurized Fluid Extraction
Cleanup - separation of analyte(s) of interest
from other interfering matrix components (if
used)
√ Elution through 1.8 g SPE cartridge of deactivated
alumina.
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used)
NA
Analytical system X GC-MS/MS
For BDE 99 and 153 results biased high, interferences
not separated during chromatography
Calibration approach for value-assignment
of analyte(s) in matrix √
Isotope dilution with calibration curve.
Verification method(s) for value-assignment
of analyte(s) in sample (if used) √ Concurrent analysis of PBDE congeners in SRM 1944
New York New Jersey Waterway Sediment.
BDE 99 and 153 degree of equivalence expanded uncertainties do not cross zero (see Analytical
system box above), values not consistent with the KCRV.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 77 of 82
NMIA
CCQM-K102 NMIA
Low Polarity Analytes in an Abiotic
Matrix: Polybrominated Diphenyl
Ethers in Sediment Scope of Measurement:
Quantification of organic molecules in the approximate range of molecular weights from 100 to 800 g/mol,
having polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000 µg /kg in abiotic
dried matrices.
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Calibration solutions of BDEs 47, 99 and 153
Source: Wellington Laboratories, Ontario, Canada
Product numbers: BDE-47, BDE-99 and BDE-153
Identity verification of analyte(s) in
calibration material.#
- Chromatographic retention time
- GCHRMS – a minimum of 2 ions monitored
- GCMSMS – a minimum of 2 SRM
transitions monitored
- LCMSMS – a minimum of 2 SRM
transitions monitored
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
Multiple standards comparison against solution
matrix certified reference materials, NIST SRM 2257
and NIM China GBW (E) 081124 and GBW (E)
081125
Sample Analysis Competencies Identification of analyte(s) in sample
- Chromatographic retention time
- GCHRMS – a minimum of 2 ions monitored
- GCMSMS – a minimum of 2 SRM
transitions monitored
- LCMSMS – a minimum of 2 SRM
transitions monitored
Extraction of analyte(s) of interest from
matrix Method 1: Accelerated Solvent Extraction (ASE)
with toluene
Method 2: Hot Soxhlet extraction with toluene
Method 3: ASE with ethanol/toluene (68:32) and
toluene
Method 4: ASE with acetone/hexane (50:50)
Cleanup - separation of analyte(s) of interest
from other interfering matrix components (if
used)
1. Concentrated sulphuric acid wash
2. Ultra-high purity water wash
3. Solid phase extraction with multi-layer (acidic,
neutral and basic) silica and alumina columns
Note: Gel permeation chromatography (GPC) with
dichloromethane was used as an additional clean-up
step for SRM1944, a matrix reference material for
PBDEs in sediment. GPC clean-up was found to be
unnecessary for the CCQM study sample.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 78 of 82
Transformation - conversion of analyte(s) of
interest to detectable/measurable form (if
used)
N/A N/A
Analytical system GC-HRMS (EI)
GC-MS/MS (EI) (for confirmation)
LC-MS/MS (APCI/APPI) (for confirmation)
Calibration approach for value-assignment of
analyte(s) in matrix Exact-matching (single-point calibration) double
isotope dilution mass spectrometry with
bracketing
Verification method(s) for value-assignment
of analyte(s) in sample (if used) Comparison of results using independent extraction
and detection techniques
1. ASE with ethanol/toluene and toluene
2. ASE with acetone/hexane
3. Hot Soxhlet extraction with toluene
4. GC-MS/MS (EI) analysis
4. LC-MS/MS (APCI/APPI) analysis with high
performance liquid chromatography (HPLC) clean-up
of sediment extracts
5. GCHRMS analysis using chromatography columns
with stationary phases of differing polarity (J&W
DB5 and Agilent VF-17MS)
Other 1. Investigation of complete analyte/internal standard
equilibration
- comparison of experimental procedures involving
addition of internal standard directly to sediment
samples packed in ASE cells versus addition of
internal standard to sediment samples weighed into
glass vials and then mixed by rotation for a minimum
of 12 hours
- exhaustive extraction of sediment samples
(optimisation of the number of static cycles and the
static/hold time used for ASE)
- comparison of Hot Soxhlet extraction of sediment
samples for 10 hours versus ASE
- comparison of different extraction solvents for ASE
2. Investigation of possible background
contamination: analysis of method blank samples,
using pre-cleaned hydromatrix as the blank matrix
CCQM-K102_Final report.doc E-mail: [email protected]
Page 79 of 82
NMIJ
CCQM-K102 NMIJ PBDEs in sediment Scope of Measurement: Organic molecules in the approximate range of molecular weights from 100 to 800
g/mol, having low polarity corresponding to pKow < -2 and for the range of mass fraction 1-1000 µg /kg in
abiotic dried matrices.
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
Calibration solution (NIST SRM 2257)
Identity verification of analyte(s) in
calibration material.#
GC/MS (The BDE-47, 99, and 153 was identified
from the information on retention order of BDE
isomers from used GC column (IEC 62321, 2008),
and comparison to another standard solution, EO-
5277 (CIL).)
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A -
For calibrants which are a calibration
solution: Value-assignment method(s).#
NIST certificate (Purity assessment by GC and
Gravimetric preparation)
Sample Analysis Competencies Identification of analyte(s) in sample GC/MS (Retention time and mass spec ion ratios)
Extraction of analyte(s) of interest from
matrix
Ultrasonic extraction (CH2Cl2)
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
Sulfur cleanup with activated Cu
Sulfuric acid treatment (column packed with silica
impregnated with concentrated sulfuric acid, 44 %)
SPE (Supelclean Sulfoxide, 3 g/6 mL; SUPELCO)
Transformation - conversion of analyte(s)
of interest to detectable/measurable form
(if used)
N/A -
Analytical system GC-HRMS (EI, R=10000) equipped with GC
column, UltraALLOY-PBDE (15 m x 0.25 mmI.D. x
0.05 um Thickness)
Calibration approach for value-assignment
of analyte(s) in matrix
a) IDMS
b) 3-point calibration curve
Verification method(s) for value-
assignment of analyte(s) in sample (if
used)
x (The extraction and cleanup conditions have been
optimized using NIST SRM 1944. However, obtained
analytical results for tetra- to hexa-BDEs have not
been verified.)
Other N/A
BDE 47 degree of equivalence expanded uncertainty does not cross zero, value not consistent
with the KCRV: no specific competency identified as reason.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 80 of 82
NMISA
CCQM-K102 NMISA Polybrominated diphenyl ethers in
sediment Scope of Measurement: Demonstration of the competency in quantification of organic molecules in the
approximate range of Mw from 100 to 800 g/mol, having polarity corresponding to pKow < -2 and for the
range of mass fraction 1 – 1000 µg/kg in abiotic dried matrices.
Competency
Tick,
cross,
or
“N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution? Calibration solution.
Identity verification of analyte(s) in
calibration material.#
√ Verification against NIST SRM 2257 through mass
spectral ion ratios and retention times using Gas
Chromatography – Time-of-flight mass spectrometry
(GC-TOFMS)
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
√ The primary standard, NIST Standard reference
material 2257 was used to assign the values to the
secondary standards:
Cambridge Isotope Laboratory, BDE-47-CS-0, BDE-
99-CS-0 and BDE-153-CS-0. Value assignment was
performed using external and isotope dilution mass
spectrometry (IDMS) calibration
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time
Mass spectrometric ion ratios
Full range mass spectra
Extraction of analyte(s) of interest from
matrix √ Pressurized liquid Extraction (PLE)
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ Solid phase extraction (SPE)
Sulphuric acid digestion and activated copper cleanup
Transformation - conversion of analyte(s)
of interest to detectable/measurable form
(if used)
N/A
Analytical system √ Gas Chromatography – Time-of-flight mass
spectrometry (GC-TOFMS)
Calibration approach for value-assignment
of analyte(s) in matrix √ Preliminary IDMS followed by bracketing double
IDMS calibration
Verification method(s) for value-
assignment of analyte(s) in sample (if
used)
N/A
Other √ Water content determination by gravimetric loss on
drying as specified in protocol
BDE 99 degree of equivalence expanded uncertainty does not cross zero, value not consistent
with the KCRV: calculation error.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 81 of 82
TÜBITAK UME
CCQM-K102 NMI:TÜBİTAK UME PBDEs in sediment Scope of Measurement: Demonstration of the lab's competency in quantification of organic molecules in the
approximate range of MW from 100 to 800 g/mol, having polarity corresponding to pKow < -2 and for the
range of mass fraction 1 – 1000 µg/kg in abiotic dried matrices.
Competency Tick, cross,
or “N/A”
Specific Information as Provided by
NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
BDE-47, BDE-99, BDE-153 neat crystals were
obtained from CHIRON. (1962.125MG, 1967.12-
5MG, 1971.12-5MG) 13
C BDE-47, 13
C BDE-99, 13
C BDE-153 were
obtained from Wellington Laboratories.
(MBDE471009, MBDE0990611, MBDE1530710)
The purity of BD47, BDE-99 and BDE-153 were
determined by qNMR and NIST SRM-1944 was used
for further check, Newyork/New Jersey Waterway
Sediment
Identity verification of analyte(s) in
calibration material.#
Triple quadrupole GC-MS/MS
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
qNMR
For calibrants which are a calibration
solution: Value-assignment
method(s).#
N/A -
Sample Analysis Competencies
Identification of analyte(s) in sample
IDMS, GC-MS/MS
Extraction of analyte(s) of interest
from matrix
Pressurized Solvent Extraction was used. T: 120 ˚C,
P:130 bar, Cycle:3, Solvent: n-hexane: acetone
(70:30 %), static time 10 min
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
Multilayer column was prepared. From bottom to top
3 g of 3% deactivated alumina, 1.5 g of 3%
deactivated silica gel, 1.5 g of 44% acidified silica
gel and 1 g of Na2SO4 was placed into the glass
column. First, the column was washed with 10 mL of
n-hexane. Then, 5 mL of extract was loaded. Elution
was performed by 50 mL of dichloromethane:
n-hexane (1:1) mixture. Final amount was
gravimetrically adjusted to 200 mg by evaporating
solvent under gentle stream of nitrogen
Transformation - conversion of
analyte(s) of interest to
detectable/measurable form (if used)
N/A -
Analytical system X Triple Quadrupole GC-MS/MS
For BDE 99 and 153 results biased high,
interferences not separated during chromatography
Calibration approach for value-
assignment of analyte(s) in matrix
IDMS single-point calibration
Verification method(s) for value-
assignment of analyte(s) in sample (if
used)
Recovery were examined by using NIST SRM-1944,
Newyork/New Jersey Waterway Sediment and spiking
of pure compounds to matrices for double check.
Other N/A -
BDE 99 and 153 degree of equivalence expanded uncertainties do not cross zero (see
Analytical system box above), values not consistent with the KCRV.
CCQM-K102_Final report.doc E-mail: [email protected]
Page 82 of 82
VNIIM
CCQM-K102 VNIIM
Polybrominated diphenyl ethers in
sediment Scope of Measurement: Quantification of organic molecules in the approximate range of MW from 100 to 800 g/mol, having low
polarity (pKow < -2) and for the range of mass fraction 1 - 1000 µg/kg in abiotic dried matrices
Competency
Tick,
cross, or
“N/A”
Specific Information as Provided
by NMI/DI
Competencies for Value-Assignment of Calibrant
Calibrant: Did you use a “highly-pure
substance” or calibration solution?
PBDE Congeners in i-Octane NIST SRM 2257
Identity verification of analyte(s) in
calibration material.#
N/A
For calibrants which are a highly-pure
substance: Value-Assignment / Purity
Assessment method(s).#
N/A
For calibrants which are a calibration
solution: Value-assignment method(s).#
N/A
Sample Analysis Competencies Identification of analyte(s) in sample √ Retention time
Ion ratios of the two molecular m/z
Extraction of analyte(s) of interest from
matrix √ SoxTherm (Toluene, 16 h, 12 cycles/h)
ASE (Hexane/Acetone=90/10, 20 min, 8 cycles;
T=120 ºC; P=1700 psi)
Cleanup - separation of analyte(s) of
interest from other interfering matrix
components (if used)
√ Silica gel clean-up (multilayer column with Sil,
Sil/H2SO4, Sil/KOH)
Al2O3 fractionation
Copper clean-up
Transformation - conversion of analyte(s)
of interest to detectable/measurable form
(if used)
N/A
Analytical system √ GC-LRMS
Calibration approach for value-assignment
of analyte(s) in matrix √ a) IDMS (mass of IS – about 40 ng)
b) Calibration into short range (in accordance with
analytes mass in the sample – from 16ng to
74ng)
Verification method(s) for value-
assignment of analyte(s) in sample (if
used)
N/A As the reference meaning was taken average result
of long-time (48h) Soxhlet extractions
Other N/A