Report of the interlaboratory comparison organised by the …publications.jrc.ec.europa.eu/repository/bitstream... · 2014. 5. 14. · This publication is a Reference Report by the

Report EUR 25685 EN

2 0 1 2

Giorgia Beldì, Natalia Jakubowska, Emma Bradley and Catherine Simoneau

ILC02 2012- Primary Aromatic Amines in 3% acetic acid migration solution

Report of the interlaboratory comparison organised by the European Reference Laboratory for Food Contact Materials

European Commission Joint Research Centre Institute for Health and Consumer Protection Contact information Catherine Simoneau Address: Joint Research Centre, Via Enrico Fermi 2749, TP 260, 21027 Ispra (VA), Italy E-mail: [email protected] Tel.: +39 0332 78 5889 Fax: +39 0332 78 5707 http://ihcp.jrc.ec.europa.eu/ http://www.jrc.ec.europa.eu/ This publication is a Reference Report by the Joint Research Centre of the European Commission. Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication. Europe Direct is a service to help you find answers to your questions about the European Union Freephone number (*): 00 800 6 7 8 9 10 11 (*) Certain mobile telephone operators do not allow access to 00 800 numbers or these calls may be billed.

A great deal of additional information on the European Union is available on the Internet. It can be accessed through the Europa server http://europa.eu/. JRC77620 EUR 25685 EN ISBN 978-92-79-28084-9 ISSN 1831-9424 doi:10.2788/77260 Luxembourg: Publications Office of the European Union, 2012 © European Union, 2012 Reproduction is authorised provided the source is acknowledged. Printed in Italy

EURL – FCM ILC02 2012- Primary Aromatic amines in 3% acetic acid migration solution

Report of the interlaboratory comparison

ILC02 2012- Primary Aromatic Amines in 3% acetic acid

migration solution

EC-JRC-IHCP, CAT Unit action 15014

2012

No SANCO/2011/FOOD SAFETY070-Food Contact Materials

Giorgia Beldì, Natalia Jakubowska, Emma Bradley and Catherine Simoneau

EURL – FCM ILC02 2012- Primary Aromatic Amines in 3% acetic acid migration solution

4

Table of content 1. Summary...................................................................................................................... 5

2. Introduction ................................................................................................................. 6

3. Scope ........................................................................................................................... 7

4. Time frame................................................................................................................... 7

5. Test materials.............................................................................................................. 7

5.1 Preparation........................................................................................................... 7

5.2 Homogeneity assessment .................................................................................... 7

5.3 Stability test .......................................................................................................... 8

5.4 Distribution ........................................................................................................... 8

6. Instructions to participants........................................................................................ 8

7. Assigned values.......................................................................................................... 8

8. Target standard deviation .......................................................................................... 9

9. Evaluation of results................................................................................................... 9

9.1 General observations ........................................................................................... 9

9.2 Statistical evaluation of results ............................................................................. 9

9.2.1. Determination of the consensus value .......................................................... 9 9.2.2. Scores and evaluation criteria....................................................................... 9

9.3 Laboratory results and scores ............................................................................ 10

10. Conclusion .............................................................................................................. 22

11. Acknowledgements ................................................................................................ 23

12. References............................................................................................................... 24

13. Annexes ................................................................................................................... 24


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1. Summary The Institute for Health and Consumer Protection (IHCP) of the European Commission’s Directorate-General Joint Research Centre hosts the EU Reference Laboratory for Food Contact Materials (EURL-FCM). One of its core tasks is to organise interlaboratory comparisons (ILCs) amongst appointed National Reference Laboratories (NRLs).

This report presents the results of the ILC of the EURL-FCM which focused on the quantification of Primary Aromatic Amines (PAAs) in migration solutions of 3% acetic acid from food contact materials. In particular the exercise focused on the determination of the amines reported in table1.

Table 1. Primary Aromatic Amines quantified in the ILC02 2012 PAAs. Name

(Abbreviation) CAS No. Structure MW

Aniline

(ANL) 62-53-3

93.1

4,4’-Methylenedianiline

(4,4’-MDA) 101-77-9

198.3

2,4-Toluenediamine

(2,4-TDA) 95-80-7

122.1

2,6-Toluenediamine

(2,6-TDA) 823-40-5

122.1

The test material used for preparation of the migration solutions were polyamide kitchenware containing PAAs kindly provided by the NRL-UK. Two concentration levels of migration solutions were distributed to the NRLs. The general aim of the exercise was to assess the performance of the Official Control Laboratories (OCLs) and consequently the participants were free to use any analytical method of their choice.

This ILC targeted the correct implementation of Regulation 284/2011 on China and Hong Kong imports of kitchenware which requires the analysis of 10% of the consignments. The proficiency test aimed at the application of the technical guidelines EUR 24815 EN, 2011 that were developed specifically in support of this regulation by the EURL-FCM and NRLs. The laboratories were expected to take part in the exercise.

The homogeneity and stability studies were performed by the NRL UK laboratory and statistically elaborated from the EURL-FCM. Participants were invited to report 4 results for each concentration level. Laboratory results were processed using several algorithms: ISO 13528 [1], Harmonized protocol [2], DIN 38402 A45 (Q-Hampel) [3]. The assigned values were obtained after applying the robust statistics to the results of the participants. Standard deviations for proficiency assessment (also called target standard deviations) were set based on Horwitz equation [4].

There were 29 participants to whom samples were dispatched (EURL, 27 NRLs + 1 guest from Belgium) and 27 of which submitted results. 24 laboratories submitted results obtained using the chromatographic methods stipulated in the technical guidelines towards the implementation of the Regulation EU 284/2011 on imports. 3

NH2

H2N NH2

NH2

NH2

NH2H2 N


6

laboratories reported their results as equivalent of aniline/kg using a spectrophotometric method, i.e. with a method which was not fit for purpose of the exercise, so those results could not be taken into consideration. The level of participation in this ILC was 93% overall.

The results of the proficiency were as follows:

For the first concentration level PAAs, cocktail 1:

ANL : 87.5% of the results were satisfactory; 8.3% were questionable and 4.2% were unsatisfactory;

4,4-MDA: 91.3% of the results were satisfactory; 8.7% were questionable and none was unsatisfactory;

2,4-TDA: 90.5% of the results were satisfactory; 9.5% were questionable and none was unsatisfactory.

For the second concentration level PAAs, cocktail 2:

ANL : 100 % of the results were satisfactory;

4,4-MDA: 91.3 % of the results were satisfactory; none was questionable and 8.7 % were unsatisfactory;

2,4-TDA: 95.2 % of the results were satisfactory; 4.8 % were questionable and none was unsatisfactory;

2,6-TDA: 88.2 % of the results were satisfactory; 5.9 % were questionable and 5.9 % were unsatisfactory.

This exercise showed that there were no particular issues regarding the analysis (identification and quantification) of the most common PAAs and for the effective enforcement of the Regulation EU 284/2011 at least for the 24 laboratories using the suggested chromatographic method.

2. Introduction ILC studies are an essential element of laboratory quality assurance which allow individual laboratories to compare their analytical results with those from other laboratories while providing them objective standards to perform against.

It is one of the core duties of the EU Reference Laboratories to organize interlaboratory comparisons, as is stated in Regulation (EC) No 882/2004 of the European Parliament and of the Council [5].

In accordance with the above requirements the European Reference Laboratory for Food Contact Materials (EURL-FCM) organised in 2011-2012 interlaboratory comparison tests for the network of appointed National Reference Laboratories (NRLs).


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3. Scope

The scope of this ILC was to test the competence of the appointed NRLs to analyse PAAs in migration solutions of 3% acetic acid from polyamide kitchenware. The 3% acetic acid simulant used represented the worst case for the articles in question. The different concentration levels were obtained from real polyamide kitchenware migration solutions. The assessment of the measurement results was undertaken on the basis of requirements laid down in international standards and guidelines [1-4, 6].

4. Time frame

The ILC02 2012 was launched in July 2012. Invitation letters were sent to the laboratories on 26th July 2012 (Annex 1). Laboratories were invited to fill in a letter of confirmation of their participation (Annex 2). Homogeneity tests were run in July 2012. The results from homogeneity test were accepted as time zero for stability test.

The samples were dispatched to participants by the NRL UK in the end of July 2012, together with the letters accompanying the samples (Annex 3) and a format for the compilation of results (Annex 5). Electronic ProLab files where the results should be inserted were sent to the participants by e-mail. The participants were asked to compile a letter of confirmation of the receipt of the samples (Annex 4). The deadline for reporting was set to 17th September 2012.

5. Test materials

5.1 Preparation

The preparation of the test materials was done by the NRL-UK laboratory. The migration solutions were obtained after migration experiment from polyamide kitchenware. The two samples were obtained from an original migration solution. The concentration range for all four compounds was chosen in order to obtain a reliable overview of the precision and reproducibility for the concentration range where the decision should be made by the Competent Authorities.

Table 2. Test materials

5.2 Homogeneity assessment

The homogeneity assessment was conducted by the NRL-UK. Ten randomly selected test specimens for each sample (PAAS1 and PAAs2) were analysed for Aniline, 4,4’-Methylenedianiline, 2,4-Toluenediamine and 2,6-Toluenediamine by LC-MS. The EURL-FCM evaluated the homogeneity results using the ProLab Software [7] according to IUPAC International Harmonized Protocol [2], F-test and to the method proposed in

Exercise Name Sample

PAAs1 1 bottle of 3% acetic acid migration solution at level 1 ILC 02 2012 PAAs PAAs2 1 bottle of 3% acetic acid migration solution at level 2


8

the ISO 13528 [1]. The results together with their statistical evaluation are given in Annex 6. All solutions showed sufficient homogeneity for the target standard deviation.

5.3 Stability test

The test samples were monitored for stability from the date of preparation and homogeneity assessment to the closing of the ILC02 2012. The evaluation of data was carried out by performing a linear regression on the determined concentration of aniline, 4,4-MDA, 2,4-TDA and 2,6-TDA versus time. For all compounds and concentration levels the intercepts were (within uncertainty) equal to the assigned value whereas the slope did not differ significantly from zero. All the samples were therefore stable along the ILC 02 2012 PAAs exercise.

5.4 Distribution

The sample kits were dispatched to the participants by the NRL-UK in the end of July. Each participant received:

a) The box containing the test materials;

b) The accompanying letters with instructions on samples handling, analysis and reporting of results by e-mail (Annex 3);

c) The receipt form to confirm the samples arrival by e-mail (Annex 4);

d) The form for reporting the result in non-electronic format by e-mail (Annex 5);

The sample codes, the laboratory codes and the PROLAB files were dispatched to participants by the EURL-FCM by e-mail.

6. Instructions to participants

Detailed instructions were given to all participants in the letters that accompanied the samples (Annex 3). Laboratories were asked to report 4 results for each analyte for each concentration level. Participants were asked to follow their own procedures within the ones stipulated in the Guidelines EUR 24815 EN 2011 and to indicate sample preparation method and the instrumental method of analysis, HPLC-DAD, LC-MS or other. The results had to be reported using the unit of measure indicated in the instruction letter. The results were reported in a specific form sent to the participants by e-mail.

7. Assigned values The test materials used for this exercise were migration solutions of polyamide kitchenware in 3% acetic acid. The assigned values were established as the robust mean values (for each level of concentrations) which came from the participants test results and obtained from robust statistics using the ProLab software [7].


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8. Target standard deviation

The value of target standard deviation (σp) determines the limits of satisfactory performance in ILC test. It should be set as a value that reflects best practice for the analysis in question. The standard deviation of the reproducibility found in the collaborative trials is generally considered as an appropriate indicator of the best agreement that can be obtained between laboratories. However, it is not applicable to all cases. In the absence of appropriate collaborative trial data, σp could be derived from the appropriate form of the Horwitz equation [4]. For all samples of this ILC02 2012 exercise the target standard deviation was set to the calculated by Horwitz formula.

9. Evaluation of results

9.1 General observations

Samples were dispatched to 29 participants (EURL, 27 NRLs + 1 official control laboratory from Belgium), 27 of which submitted results. Two laboratories do not submit results. The ILC was closed permanently on 17th of September 2012 for statistical interpretation.

9.2 Statistical evaluation of results

9.2.1. Determination of the consensus value

The statistical evaluation of the results was performed using the ProLab software [7] according to Q/Hampel estimator (DIN 38402 A45) [3]

9.2.2. Scores and evaluation criteria

Individual laboratory performance was expressed in terms of z-scores (z) in accordance with ISO 13528 [1] and the International Harmonised Protocol [2]:

p

assignedlab Xxz

σ)( −

= ,

where:

x lab is the measurement result reported by a participant;

X assigned is the assigned value;

σ p is the target standard deviation for proficiency assessment .

The z- scores can be interpreted as follow:

|z|≤2 satisfactory result;

2<|z|≤3 questionable result;

|z|>3 unsatisfactory result.


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9.3 Laboratory results and scores

The summary of the laboratory’s results for PAAs with their robust repeatability standard deviations and robust reproducibility standard deviations calculated according to Q/Hampel algorithm (ISO 20612:2007 [8] and DIN 38402 A45 [3] ) by ProLab software as well as assigned values, target standard deviation and z-score of the ILC, are given in Table 3-7 and Figures 1-7. The results obtained using the spectrophotometric method are reported in Table 8 since they could not be part of the statistical evaluation.

Table 3. Summary of results for PAAs calculated according to DIN 38402 A45

Method DIN 38402 A45 PAAs 1 PAAs 2 ANL

Robust Mean = Assigned value , μg/kg 16.56 19.70 Robust Repeatability s.d., μg/kg 0.59 0.58 Robust Reproducibility s.d., μg/kg 4.39 2.05 Rel. target s.d., % 29.65 28.89 Rel. Reproducibility s.d., % 26.53 10.39 Rel. Repeatability s.d., % 3.58 2.95 Lower limit of tolerance, μg/kg 6.64 8.32 Upper limit of tolerance, μg/kg 26.38 31.08 No. of results 24 24

4,4-MDA Robust Mean = Assigned value , μg/kg 22.73 65.56 Robust Repeatability s.d., μg/kg 0.49 1.06 Robust Reproducibility s.d., μg/kg 4.04 7.98 Rel. target s.d., % 28.27 24.11 Rel. Reproducibility s.d., % 17.76 12.18 Rel. Repeatability s.d., % 2.14 1.62 Lower limit of tolerance, μg/kg 9.88 33.95 Upper limit of tolerance, μg/kg 35.59 97.17 No. of results 23 23

2,4-TDA Robust Mean = Assigned value , μg/kg 16.69 27.06 Robust Repeatability s.d., μg/kg 0.71 0.64 Robust Reproducibility s.d., μg/kg 6.66 5.53 Rel. target s.d., % 29.62 27.54 Rel. Reproducibility s.d., % 39.90 20.44 Rel. Repeatability s.d., % 4.27 2.38 Lower limit of tolerance, μg/kg 6.80 12.16 Upper limit of tolerance, μg/kg 26.58 41.96 No. of results 21 21

2,6-TDA Robust Mean = Assigned value , μg/kg - 24.67 Robust Repeatability s.d., μg/kg - 0.84 Robust Reproducibility s.d., μg/kg - 5.90 Rel. target s.d., % - 27.93 Rel. Reproducibility s.d., % - 23.92 Rel. Repeatability s.d., % - 3.40 Lower limit of tolerance, μg/kg - 10.89 Upper limit of tolerance, μg/kg - 38.45 No. of results - 17


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Figure 1. Summary graph of the laboratory’s test results and the laboratory’s z-scores for aniline (PAAs1).


12

Figure 2. Summary graph of the laboratory’s test results and the laboratory’s z-scores for 4,4-MDA (PAAs1).


13

Figure 3. Summary graph of the laboratory’s test results and the laboratory’s z-scores for 2,4-TDA (PAAs1).


14

Figure 4. Summary graph of the laboratory’s test results and the laboratory’s z-scores for aniline (PAAs2).


15

Figure 5. Summary graph of the laboratory’s test results and the laboratory’s z-scores for 4,4-MDA (PAAs2).


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17



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Table 4. Laboratories’ z-scores for ANL

Laboratory Code

PAAs1 PAAs2

LC0003 -0.643 -0.289 LC0004 - - LC0005 0.027 -0.183 LC0006 - - LC0007 - - LC0010 -0.017 -0.021 LC0011 - - LC0013 0.187 -0.035 LC0016 1.618 -0.196 LC0017 1.013 0.786 LC0018 -0.588 -0.541 LC0020 0.717 0.739 LC0025 -0.281 -0.070 LC0028 0.146 -0.111 LC0029 - - LC0031 -0.197 0.029 LC0037 -0.017 -0.068 LC0038 0.077 0.162 LC0040 -0.724 -0.720 LC0041 -2.405 0.207 LC0043 0.433 0.301 LC0044 0.549 -0.013 LC0048 0.562 0.000 LC0049 -3.161 0.139 LC0050 0.046 -0.190 LC0055 0.513 0.343 LC0056 -2.714 -0.115 LC0065 -0.711 -0.392 LC0112 1.085 1.115


19

Table 5. Laboratories’ z-scores for 4,4-MDA

Laboratory Code

PAAs1 PAAs2

LC0003 0.524 0.429 LC0004 - - LC0005 0.314 0.379 LC0006 - - LC0007 - - LC0010 -0.102 -0.312 LC0011 - - LC0013 0.718 -0.124 LC0016 -0.822 -3.180 LC0017 -2.717 -3.209 LC0018 -0.805 -1.187 LC0020 0.193 0.208 LC0025 -1.055 -0.061 LC0028 0.410 0.130 LC0029 - - LC0031 0.109 0.180 LC0037 0.362 0.416 LC0038 0.370 0.437 LC0040 -0.274 -0.192 LC0041 -0.258 -0.175 LC0043 - - LC0044 0.835 0.403 LC0048 0.225 0.047 LC0049 -2.146 -1.553 LC0050 0.221 0.137 LC0055 -0.134 0.086 LC0056 -0.161 -0.511 LC0065 0.161 0.260 LC0112 -0.153 -0.259


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Table 6. Laboratories’ z-scores for 2,4-TDA

Laboratory Code

PAAs1 PAAs2

LC0003 1.326 0.327 LC0004 - - LC0005 0.834 -0.951 LC0006 - - LC0007 - - LC0010 0.052 -0.219 LC0011 - - LC0013 0.522 -0.236 LC0016 -2.632 -2.732 LC0017 0.353 0.746 LC0018 -1.191 -0.297 LC0020 1.483 0.317 LC0025 0.123 0.358 LC0028 0.261 0.075 LC0029 - - LC0031 -0.886 0.265 LC0037 -1.019 -0.142 LC0038 -0.419 1.153 LC0040 -1.000 -0.401 LC0041 0.047 -0.437 LC0043 - - LC0044 1.569 0.592 LC0048 1.048 0.163 LC0049 - - LC0050 - - LC0055 0.113 0.673 LC0056 1.808 0.248 LC0065 -0.983 -0.473 LC0112 -2.809 -1.716


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Table 7. Laboratories’ z-scores for 2,6-TDA

Laboratory Code

PAAs2

LC0003 - LC0004 - LC0005 -2.530 LC0006 - LC0007 - LC0010 0.832 LC0011 - LC0013 0.153 LC0016 - LC0017 0.774 LC0018 -0.777 LC0020 0.756 LC0025 0.429 LC0028 0.371 LC0029 - LC0031 -0.139 LC0037 -1.019 LC0038 0.574 LC0040 -0.431 LC0041 - LC0043 -0.577 LC0044 0.607 LC0048 - LC0049 - LC0050 - LC0055 -3.171 LC0056 0.754 LC0065 -0.339 LC0112 -


22

Table 8. Laboratories’ results for total Primary Aromatic Amines using spectrophotometric method [μg aniline equiv./Kg]

Laboratory code Sample Test result

1 Test result

2 Test result

3 Test result

4

Total PAAs chromatographic

[μg/Kg] LC0004 350 350 - - LC0006 68.9 67.6 65.8 68.2 LC0007

PAA1

68 59 65 63

55.98

LC0004 130 130 - - LC0006 42.2 41.5 40.6 41.0 LC0007

PAA2

115 122 103 110

136.99

10. Conclusion An overview of the ILC02 2012 outcome shows that the participation of the laboratories in the ILC02 2012 could be regarded as satisfactory. 27 participants (93.1%) reported results out of 29 sent sample kits. 24 laboratories submitted results obtained using the chromatographic methods stipulated in the technical guidelines towards the implementation of the Regulation EU 284/2011 on imports. 3 laboratories reported their results as equivalent of aniline/kg using a spectrophotometric method which was not fit for purpose for the objective of the exercise, so those results could not be evaluated. The evaluation was carried out of the 24 laboratories using chromatographic methods on the individual substances.

As a conclusion of the ILC exercise on the quantification of PAAs in the migration solutions of polyamide kitchenware in 3% acetic acid, the results of the proficiency were as follows:

For the first concentration level PAAs, cocktail 1:

ANL : 87.5 % of the results were satisfactory; 8.3 % were questionable and 4.2 % were unsatisfactory;

4,4-MDA: 91.3 % of the results were satisfactory; 8.7 % were questionable and none was unsatisfactory;

2,4-TDA: 90.5 % of the results were satisfactory; 9.5 % were questionable and none was unsatisfactory.

For the second concentration level PAAs, cocktail 2:

ANL : 100 % of the results were satisfactory;

4,4-MDA: 91.3 % of the results were satisfactory; none was questionable and 8.7 % were unsatisfactory;

2,4-TDA: 95.2 % of the results were satisfactory; 4.8 % were questionable and none was unsatisfactory;

2,6-TDA: 88.2 % of the results were satisfactory; 5.9 % were questionable and 5.9 % were unsatisfactory.


23

This exercise showed that there are no particular issues regarding the analysis (identification and quantification) of the most common PAAs and for the effective enforcement of the Regulation EU 284/2011. However it should be also noted that the 2,6 TDA was not reported by all laboratories and therefore the reasons why need be investigated.

11. Acknowledgements The NRLs participating in this exercise - listed below - are kindly acknowledged. NRLs AUSTRIA Austrian Agency for Health and Food Safety (AGES), Wien

BELGIUM Institute of Public Health, ISSP-LP, Bruxelles

BULGARIA National Centre for Public Health Protection, Sofia

CYPRUS Laboratory for Control of Food Contact Materials and Control of Toys

Ministry of Health, State General Laboratory (SGL), Nicosia

CZECH NIPH- NRL for Food Contact Materials and for Articles for children under 3 years old, National

Institute of Public Health (SZU’), Praha

DENMARK Department of Food Chemistry, Danish Veterinary and Food Administration, Lystrup

ESTONIA Health Protection Inspectorate - Central Laboratory of Chemistry, Tallinn

FINLAND Finnish Customs Laboratory, Espoo

FRANCE Centre for Energy Material and Packaging - Laboratoire National d'Essais, Trappes Cedex

FRANCE SCL Laboratoire de Bordeaux-Pessac, Pessac

GERMANY Bundesinstitut für Risikobewertung (BFR) (Federal Institute for Risk Assessment), Berlin

GREECE General Chemical State Laboratory, D’ Chemical Service of Athens, Section Laboratory of Articles

and Materials in Contact with Foodstuffs, Athens

HUNGARY Central Agricultural Office, Food and Feed Safety Directorate, Food Toxicology National Reference

Laboratory, Budapest

IRELAND Public Analyst Laboratory - Sir Patrick Duns Hospital, Dublin

ITALY Istituto Superiore di Sanità, Laboratorio Esposizione e rischio da materiali, c/o Dipartimento

ambiente e connessa prevenzione primaria, Roma

LUXEMBOURG Laboratoire National de Santé, Division du Controle des Denrées Alimentaires, Luxembourg

POLAND Laboratory of Department of Food and Consumer Articles Research, National Institute of Hygene,

Warsaw

PORTUGAL ESB-SE (Portuguese Catholic University - Biotechnology College – Packaging Department), Porto

SLOVAKIA National Reference Centre and Laboratory for material and articles intended to come into contact

with food, Regional Public Health Authority In Poprad (RUVZ), Poprad

SLOVENIA National Institute of Public Health of Republic of Slovenia, Department of Sanitary Chemistry,

Ljubijana

SPAIN Centro Nacional de Alimentación, Agencia Espanola de Seguridad Alimentaria y Nutrición (AESAN),

Madrid

SWEDEN National Food Administration, Food Standards Devision, Uppsala

THE NETHERLANDS Food and Consumer Product Safety Authority (VWA), Ministry of Economic Affairs, Agriculture and

Innovation, Groningen

UNITED KINGDOM Central Science Laboratory, York

BELGIUM (GUEST) Agence Federale Pour la Securite Alimentaire, Liege

SWITZERLAND Official Food Control Authority of the Canton of Zurich


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12. References

13. Annexes

Annex 1: Invitation letter to laboratories ILC02 2012

Annex 2: Format for confirmation of participation to ILC02 2012

Annex 3: Letters accompanying the sample ILC02 2012

Annex 4: Letter of confirmation of receipt of ILC02 2012

Annex 5: Form for the compilation of the results in non-electronic format

Annex 6: Results of the homogeneity study

[1] ISO 13528:2005; Statistical Methods for Use in Proficiency Testing by Interlaboratory Comparisons

[2] The International Harmonised Protocol for the Proficiency Testing of Analytical Chemistry Laboratories by M. Thompson et al., Pure and Applied Chemistry (2006), 78, 145–196

[3] DIN 38402 A45 Ringversuche zur externen Qualitätskontrolle von Laboratorien

[4] M. Thompson, Analyst, (2000), 125, 385-386

[5] Regulation (EC) No 882/2004 of the European Parliament and of the Council of 29 April 2004 on official controls performed to ensure the verification of compliance with feed and food law, animal health and animal welfare rules

[6] T. Linsinger et al., Accreditation and Quality Assurance in Analytical Chemistry (2001), 6, 20-25

[7] ProLab Software – QuoData, Drezden – www.quodata.de

[8] ISO/TS 20612 Water quality – Interlaboratory comparison for proficiency testing of analytical chemistry laboratories


25

Annex 1. Invitation letter to laboratories ILC02 2012


26

Annex 2. Format for confirmation of participation to ILC02 2012


27

Annex 3. Letters accompanying the sample ILC02 2012


28


29


30

Annex 4. Letter of confirmation of receipt of ILC02 2012


31

Annex 5. Form for the compilation of the results in non-electronic format


32

Annex 6. Results of the homogeneity study

Sample Measurand Unit Mean s(analytical) % Mode s(target) HORRAT s(target) %

F-test Check for significant

heterogeneity

ISO 13528 Check for sufficient homogeneity

Harmonized Protocol - test on

significant heterogeneity

ANL μg/kg 19.20 5.53 1 29.00 OK OK OK

4,4-MDA μg/kg 27.74 1.78 1 27.44 OK OK OK

2,4-TDA μg/kg 25.43 2.22 1 27.80 OK OK OK PAAs1

2,6-TDA μg/kg - - - - - - -

ANL μg/kg 19.72 3.07 1 28.88 OK OK OK

4,4-MDA μg/kg 72.46 1.75 1 23.75 OK OK OK

2,4-TDA μg/kg 31.84 1.29 1 26.88 OK OK OK PAAs2

2,6-TDA μg/kg 29.10 1.45

Horwitz

1 27.24 OK OK OK


European Commission EUR 25685 – Joint Research Centre – Institute for Health and Consumer Protection Title: Report of the interlaboratory comparison organised by the European Reference Laboratory for Food Contact Material, ILC02 2012- Primary Aromatic Amines in 3% acetic acid migration solution. Author(s): Giorgia Beldì, Natalia Jakubowska and Catherine Simoneau Luxembourg: Publications Office of the European Union 2012 – 32 pp. – 21.0 x 29.7 cm EUR – Scientific and Technical Research series – ISSN 1831-9424 ISBN 978-92-79-28084-9 doi:10.2788/77260 Abstract This report presents the results of the ILC of the EURL-FCM, which focused on the quantification of Primary Aromatic Amines (PAAs) in migration solutions of 3% acetic acid from food contact materials. In particular the exercise was focused on the determination of the aniline, 4,4 MDA, 2,4 TDA and 2,6 TDA. The test material used for preparation of the migration solutions were polyamide kitchenware containing PAAs. The homogeneity and stability studies were performed by the NRL UK laboratory and statistically elaborated from the EURL-FCM. Two concentration levels of migration solutions were distributed to the NRLs. The general aim of the exercise was to assess the performance of the official control laboratories and consequently the participants were free to use any analytical method of their choice. Participants were invited to report 4 results for each concentration level. There were 29 participants to whom samples were dispatched (EURL, 27 NRLs + 1 guest from Belgium) and 27 of which submitted results. 24 laboratories submitted results obtained using the chromatographic methods, 3 laboratories reported their results only as equivalent of aniline/kg using the spectrophotometric method. The assigned values were obtained after applying the robust statistics to the results of the participants. Standard deviations for proficiency assessment (also called target standard deviations) were set based on Horwitz equation. The ILC showed that the participation in the ILC was satisfactory regarding the number of the participating laboratories.For the first concentration level PAAs1 for aniline 87.5 % of the results were satisfactory, 8.3 % were questionable and 4.2 % were unsatisfactory; for 4,4-MDA 91.3 % of the results were satisfactory and 8.7 % were questionable; for 2,4-TDA 90.5 % of the results were satisfactory and 9.5 % were questionable. For the second concentration level PAAs2 for aniline 100 % of the results were satisfactory; for 4,4-MDA 91.3 % of the results were satisfactory and 8.7 % were unsatisfactory; for 2,4-TDA 95.2 % of the results were satisfactory and 4.8 % were questionable; for 2,6-TDA 88.2 % of the results were satisfactory, 5.9 % were questionable and 5.9 % were unsatisfactory.

EURL – FCM ILC02 2012- Primary Aromatic Amines in 3% acetic acid migration solution z

As the Commission’s in-house science service, the Joint Research Centre’s mission is to provide EU policies with independent, evidence-based scientific and technical support throughout the whole policy cycle. Working in close cooperation with policy Directorates-General, the JRC addresses key societal challenges while stimulating innovation through developing new standards, methods and tools, and sharing and transferring its know-how to the Member States and international community. Key policy areas include: environment and climate change; energy and transport; agriculture and food security; health and consumer protection; information society and digital agenda; safety and security including nuclear; all supported through a cross-cutting and multi-disciplinary approach.

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Report of the interlaboratory comparison organised by the …publications.jrc.ec.europa.eu/repository/bitstream... · 2014. 5. 14. · This publication is a Reference Report by the