Report of the interlaboratory comparison organised by the...

Report EUR 25686 EN

2 0 1 2

Giorgia Beldì, Natalia Jakubowska, Oguzhan Yavuz and Catherine Simoneau

ILC01 2012- Formaldehyde and Melamine 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/. JRC77619 EUR 25686 EN ISBN 978-92-79-28085-6 ISSN 1831-9424 doi:10.2788/77358 Luxembourg: Publications Office of the European Union, 2012 © European Union, 2012 Reproduction is authorised provided the source is acknowledged. Printed in Italy

EURL – FCM ILC01 2012- Formaldehyde and melamine in food contact migration solution

Report of the interlaboratory comparison

ILC01 2012- Formaldehyde and Melamine 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, Oguzhan Yavuz and Catherine Simoneau


4

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

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

3. Scope ........................................................................................................................... 6

4. Time frame................................................................................................................... 6

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. Migration exercise................................................................................................... 25

11. Conclusion .............................................................................................................. 31

12. Acknowledgements ................................................................................................ 33

12. References............................................................................................................... 35

13. Annexes ................................................................................................................... 35


5

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) among appointed National Reference Laboratories (NRLs).

This report presents the results of the ILC of the EURL-FCM which focused on the quantification of formaldehyde and melamine in migration solutions of 3% acetic acid from food contact materials. The test material used for preparation of the migration solutions were melamine kitchenware (spoons). The migration was done in 3% acetic acid (w/v) which is the simulant for acidic foods and represents the worst case scenario for melamine plastics. The EURL prepared and distributed three concentration levels of migration solutions and three spoon samples (only for 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.

The homogeneity and stability studies were performed by the EURL-FCM laboratory. Participants were invited to report 4 results for each concentration level and 2 results for each spoon. Laboratory results were processed using several algorithms: ISO 13528 [1], Harmonized protocol [2], DIN 38402 A45 (Q-Hampel) [3] and ISO GUIDE 35:2006 [4]. 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 [5].

There were 70 participants to whom samples were dispatched (EURL, 27 NRLs + 42 Official Control Laboratories (OCLs) from Belgium, France, Germany, Italy, Poland, Slovenia, Spain and United Kingdom) and 66 of which submitted results, as follows: 4 for melamine only, 27 for formaldehyde only, and 35 for both formaldehyde and melamine. In the context of the physical check of formaldehyde the total results submitted were thus 62.

As a conclusion of the ILC exercise on the quantification of formaldehyde and melamine in the migration solutions of kitchenware in 3% acetic acid, this ILC showed that:

The level of participation was 94%, of which 88.5% for formaldehyde,56% for melamine and 50% for both substances under test. As this ILC targeted the correct implementation of Regulation 284/2011 on China and Hong Kong imports which requires the analysis of 10% of the consignments, all reporting laboratories were expected to report at least results for formaldehyde.

The level of success in the exercise was of 80% of correctly estimated results for formaldehyde and 89% for melamine (for all three concentration levels) when considering all 66 laboratories comprising of NRLs and OCLs. With regards to the performance of NRLs only, 79 % of all reported results were correctly estimated for formaldehyde, and 88% for melamine.

Therefore for this exercise and the enforcement of the physical tests for consignment of imports under Regulation 284/2011, the OCLs and NRLs performance was the same as can be considered as one unique population in terms of reliability of results.


6

2. Introduction

ILC studies are an essential element of laboratory quality assurance and 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 [6].

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).

3. Scope

The scope of this ILC was to test the competence of the appointed NRLs to analyse formaldehyde and melamine from melamine kitchenware into migration solutions of 3% acetic acid as acidic simulant according to Regulation 10/2011. The different concentration levels were obtained by dilution/ spiking from real melamine kitchenware migration solutions.

The purpose of the exercise was 2-fold

Demonstration of the continued capacity of NRLs and guests to perform adequately the measurement of formaldehyde from a migration solution in the context of support to Regulation (EU) No 284/2011 for melamine kitchenware.

Demonstration and provision to the accreditation body of the third line control for the accreditation of NRLs and OCLs for the method for formaldehyde.

An additional optional scope for this ILC only for volunteer NRLs was to quantify concentration of formaldehyde migrated from kitchen utensils (spoons) into 3% acetic acid food simulant. Melamine spoon samples were used to carry out the migration exercise.

The assessment of the measurement results was undertaken on the basis of requirements laid down in international standards and guidelines [1-5, 7].

4. Time frame

The ILC01 2012 was launched in January 2012. Invitation letters were sent to the laboratories on 20th January 2012 (Annex 1). Laboratories were invited to fill in a letter of confirmation of their participation (Annex 2).


7

The samples were prepared in December 2011. Homogeneity tests were also run in December 2011. The results from homogeneity test were accepted as time zero for stability test.

The samples were dispatched to participants on 8th February 2012, together with the letters accompanying the samples (Annex 3) and a format for the compilation of results to be eventually sent in non-electronic format (Annex 5). Electronic ProLab files, where the result should be inserted, were sent to the participants by e-mail on 8th February 2012.The participants were asked to compile a letter of confirmation of the receipt of the samples (Annex 4).

The deadline for reporting has been set to 16th March 2012.

5. Test materials 5.1 Preparation

The preparation of the test materials was done by the EURL-FCM laboratory.

The migration solutions were obtained after migration experiment immersing melamine kitchenware (e.g. a batch of spoons) in 3% acetic acid for 2 hours at 70 °C. The three levels of concentrations were obtained by dilution/spiking of the original migration solution in order to obtain more reliable data of the precision and reproducibility for the concentration range under, around and above the permitted limit for formaldehyde (15 mg/kg) and melamine (2.5 mg/kg), where the decision should be made by the Competent Authorities.

Additionally, 3 spoon samples were dispatched to volunteer NRLs for a formaldehyde migration exercise (Table 1).

Table 1. Test materials

5.2 Homogeneity assessment

The samples were tested for homogeneity by the EURL laboratory. Ten randomly selected test specimens for each sample (F&M01, F&M02 and F&M03) were analysed in duplicate for formaldehyde and melamine using the CEN 13130-23 chromotropic acid method [8] and CEN 13130-27 [9] respectively. The homogeneity of the migration solutions matrices was evaluated by the ProLab Software [10] according to IUPAC International Harmonized Protocol [2], F-test and to the method proposed in 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. The batch of

Exercise Name Sample

F&M01 1 bottle of 3% acetic acid migration solution at level 1



ILC

01

2012

F&M04 3 spoon samples for formaldehyde migration exercise (NRLs ONLY)


8

spoons used for migration exercise was also analysed for homogeneity. The results showed that the batch of spoons did not pass the homogeneity to allow EURL-FCM to allocate the z-scores to laboratories. This confirms that for articles that are grossly non-compliant, the intrinsic homogeneity of objects within a batch is already very low.

5.3 Stability test

Randomly selected specimens for each sample (F&M01, F&M02, and F&M03) were stored at 3 different temperature conditions (5 ºC, 20 °C and 40 ºC). The test samples were monitored for stability by the EURL laboratory from the date of preparation (December 2011) and homogeneity assessment to the closing of the ILC01 2012 (March 2012). Stability was evaluated as described in ISO GUIDE 35:2006 [4]. No significant trend was observed for the test samples at all temperature conditions i.e. 5 ºC, 20 °C and 40 ºC (Annex 7).

5.4 Distribution

The sample kits were dispatched to the participants by the EURL-FCM on 8th February 2012. Each participant received:

a) The box containing the test materials;

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

c) The receipt form to confirm the samples arrival (Annex 4);

d) The form for reporting the result in non-electronic format (Annex 5).

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 concentration level and 2 results for each spoon. Participants were asked to follow their own procedures and to indicate sample preparation method – CR-chromotropic acid, AA-acetyl acetone, 2,4DNPH-2,4 dinitrophenylhydrazine or other, and instrumental method of analysis – UV-VIS, 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 in hard copy and electronic format (Annex 5).

7. Assigned values

The assigned values from the migration solutions 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 [10].


9

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 modified Horwitz equation [5]. For all samples of this ILC01 2012 exercise the target standard deviation was set to the calculated by Horwitz formula.

9. Evaluation of results 9.1 General observations

There were 70 participants to whom samples were dispatched (EURL, 27 NRLs + 42 national control laboratories from Belgium, France, Germany, Italy, Poland, Slovenia, Spain and United Kingdom), 66 of which submitted results. Out of the submitted results 62 submitted for formaldehyde, 27 had reported only formaldehyde (not both formaldehyde and melamine as requested), and 4 laboratories reported only for melamine and gave no results for formaldehyde. 35 laboratories submitted as requested results both for formaldehyde and melamine. The overall level of participation in the exercise was therefore 94% in total, of which 88.5% for formaldehyde, 56% for melamine and 50% for both substances under test.

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 [10] 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:


10

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.

9.3 Laboratory results and scores

The summary of the laboratories’ results for formaldehyde and melamine with their robust repeatability standard deviations and robust reproducibility standard deviations was calculated according to Q/Hampel algorithm (ISO 20612:2007 [11] and DIN 38402 A45 [3] ). This was done by the ProLab software as well as assigned values and target standard deviation of the ILC and are reported in Tables 2-3 and Figures 1-6. The summary of the calculated z-scores are reported in Tables 4 and 5, while Figures 7-12 present graphs of the calculated by ProLab z-scores with the tolerance limit z = 2.

Table 2. Summary of results for formaldehyde calculated according to DIN 38402 A45 F&M01 F&M02 F&M03

Method DIN 38402 A45 Robust Mean = Assigned value , mg/kg 9.12 18.85 229.45 Robust Repeatability s.d., mg/kg 0.11 0.21 2.48 Robust Reproducibility s.d., mg/kg 1.10 2.18 38.06 Rel. target s.d., % 11.47 10.28 7.06 Rel. Reproducibility s.d., % 12.02 11.54 16.59 Rel. Repeatability s.d., % 1.23 1.11 1.08 Lower limit of tolerance, mg/kg 7.03 14.97 197.05 Upper limit of tolerance, mg/kg 11.22 22.73 261.84 No. of results 62 62 62

Table 3. Summary of results for melamine calculated according to DIN 38402 A45 F&M01 F&M02 F&M03

Method DIN 38402 A45 Robust Mean = Assigned value , mg/kg 0.25 2.39 3.96 Robust Repeatability s.d., mg/kg 0.01 0.06 0.09 Robust Reproducibility s.d., mg/kg 0.05 0.33 0.77 Rel. target s.d., % 19.68 14.03 13.01 Rel. Reproducibility s.d., % 18.93 13.69 19.43 Rel. Repeatability s.d., % 3.53 2.37 2.28 Lower limit of tolerance, mg/kg 0.15 1.72 2.93 Upper limit of tolerance, mg/kg 0.35 3.06 4.99 No. of results 36 39 39


11

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Labo

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ry

LC0032

LC0004

LC0108

LC0060

LC0048

LC0043

LC0018

LC0101

LC0103

LC0006

LC0034

LC0020

LC0029

LC0105

LC0027

LC0066

LC0041

LC0011

LC0095

LC0075

LC0039

LC0003

LC0067

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LC0106

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LC0098

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LC0076

LC0082

LC0005

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LC0078

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LC0093

LC0100

LC0109

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mg/kg18 17 16 15 14 13 12 11 10 9 8 7 6

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Assign

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Mean

Lim

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Lim

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Figure 1. Summary graph of the laboratory’s test results for formaldehyde (F&M01)


12

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LC0060

LC0018

LC0043

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LC0103

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LC0077

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LC0108

LC0075

LC0067

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LC0101

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LC0041

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LC0061

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LC0082

LC0100

LC0013

LC0109

LC0093

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mg/kg30 28 26 24 22 20 18 16 14 12

E

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No.

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Ass

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18.8

499

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kg (E

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10.2

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its o

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7265

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kg

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13

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LC0041

LC0011

LC0102

LC0107

LC0089

LC0035

LC0073

LC0013

LC0109

LC0032

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LC0076

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LC0060

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LC0010

LC0105

LC0110

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LC0029

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LC0082

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LC0031

LC0103

LC0038

LC0003

LC0101

LC0056

LC0043

LC0050

LC0093

LC0034

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LC0044

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LC0005

LC0080

LC0095

LC0025

LC0020

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300

250

200

150

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Figure 4. Summary graph of the laboratory’s test results for melamine (F&M01)


15

ProL

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LC0034

LC0035

LC0027

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LC0094

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LC0002

LC0039

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LC0073

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LC0029

LC0090

LC0032

LC0074

mg/kg

8

7.5 7

6.5 6

5.5 5

4.5 4

3.5 3

2.5 2

1.5 1

E

EE

E

Sam

ple:

F&M

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elam

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DIN

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02 A

45N

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s:39

Ass

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d va

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2.38

66 m

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(Em

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t s.d

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.03%

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witz

func

tion)

Rel

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bilit

y s.

d.:

2.37

%Li

mits

of t

oler

ance

:1.

7167

- 3.

0564

mg/

kg

(|Z s

core

| < 2

.00)

Assign

ed va

lue

Mean

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



16

ProL

ab 2

010

Labo

rato

ry

LC0034

LC0035

LC0044

LC0111

LC0027

LC0006

LC0002

LC0094

LC0104

LC0020

LC0007

LC0082

LC0040

LC0018

LC0093

LC0039

LC0061

LC0067

LC0075

LC0050

LC0078

LC0041

LC0033

LC0073

LC0029

LC0016

LC0032

LC0099

LC0013

LC0066

LC0110

LC0077

LC0017

LC0038

LC0060

LC0098

LC0090

LC0107

LC0074

mg/kg10 9.5 9

8.5 8

7.5 7

6.5 6

5.5 5

4.5 4

3.5 3

2.5 2

E

E

E

E

Sam

ple:

F&M

03M

easu

rand

:M

elam

ine

Met

hod:

DIN

384

02 A

45N

o. o

f lab

orat

orie

s:39

Ass

igne

d va

lue:

3.95

79 m

g/kg

(Em

piric

al v

alue

)R

el. t

arge

t s.d

.:13

.01%

(Hor

witz

func

tion)

Rel

. rep

eata

bilit

y s.

d.:

2.28

%Li

mits

of t

oler

ance

:2.

9284

- 4.

9874

mg/

kg

(|Z s

core

| < 2

.00)

Assign

ed va

lue

Mean

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



17

Table 4. Laboratories’ z-scores for formaldehyde

Laboratory Code

F&M01 F&M02 F&M03 Laborator

y Code F&M01 F&M02 F&M03

LC0003 -0.380 -0.129 1.161 LC0056 0.334 -0.753 1.204 LC0004 -1.814 -2.154 -8.997 LC0060 -1.477 -1.804 0.013 LC0005 0.838 0.929 2.812 LC0061 0.133 0.123 -6.622 LC0006 -1.026 -0.696 2.596 LC0064 1.041 1.056 -2.359 LC0007 -0.304 -0.142 -12.408 LC0066 -0.562 -0.494 -9.507 LC0010 0.336 -0.168 0.210 LC0067 -0.342 -0.431 -2.215 LC0011 -0.548 -0.658 -1.875 LC0073 0.050 -0.052 -1.046 LC0013 2.193 2.257 -0.708 LC0074 0.468 0.847 0.446 LC0016 -0.194 -0.338 -2.117 LC0075 -0.500 -0.439 -0.583 LC0017 1.108 1.102 -1.945 LC0076 0.645 0.660 -0.431 LC0018 -1.315 -1.715 -0.364 LC0077 0.250 -0.593 0.061 LC0020 -0.858 -1.122 6.563 LC0078 1.842 1.264 -4.303 LC0025 0.599 0.322 4.004 LC0080 0.635 0.626 2.884 LC0027 -0.586 -1.025 0.946 LC0082 0.709 1.566 0.821 LC0029 -0.660 -0.944 0.488 LC0089 0.104 0.172 -1.281 LC0031 0.623 0.903 0.990 LC0090 0.520 0.868 2.648 LC0032 -2.516 -2.848 -0.617 LC0093 2.417 2.947 2.124 LC0033 0.609 0.507 -2.047 LC0095 -0.502 -0.329 3.695 LC0034 -0.971 -1.447 2.152 LC0098 0.456 0.568 -1.923 LC0035 0.186 0.034 -1.100 LC0100 2.998 2.142 0.785 LC0037 0.286 -0.383 -0.386 LC0101 -1.080 -0.178 1.193 LC0038 0.286 -0.035 1.140 LC0102 8.218 4.793 -1.686 LC0039 -0.457 -0.488 0.425 LC0103 -1.067 -1.359 0.994 LC0040 0.002 -0.206 -3.346 LC0104 2.033 1.109 2.195 LC0041 -0.551 -0.151 -1.898 LC0105 -0.619 -0.542 0.219 LC0043 -1.339 -1.512 1.231 LC0106 -0.304 -0.673 -2.129 LC0044 0.121 0.129 2.442 LC0107 0.910 0.838 -1.585 LC0048 -1.408 -1.109 0.899 LC0108 -1.695 -0.451 0.775 LC0049 0.243 0.357 -1.935 LC0109 3.550 2.323 -0.679 LC0050 0.026 1.058 1.518 LC0110 0.456 0.477 0.420 LC0052 0.260 0.613 -0.352 LC0111 0.508 0.459 -2.065


18

Table 5. Laboratories’ z-scores for melamine

Laboratory Code

F&M01 F&M02 F&M03

LC0002 0.152 -0.370 -1.366 LC0006 -0.955 -1.378 -1.424 LC0007 -0.452 -0.624 -0.652 LC0013 -0.699 0.903 1.106 LC0016 0.403 0.480 0.349 LC0017 - 0.801 1.544 LC0018 -0.170 0.053 -0.580 LC0020 -0.236 -0.647 -1.035 LC0027 -2.867 -1.400 -1.623 LC0029 0.313 1.331 0.286 LC0032 1.153 2.317 1.024 LC0033 -0.075 0.406 0.092 LC0034 -2.616 -2.490 -2.988 LC0035 -1.222 -1.500 -1.940 LC0038 0.504 -0.318 1.631 LC0039 -0.402 -0.326 -0.462 LC0040 -0.518 -0.318 -0.588 LC0041 2.224 0.464 0.052 LC0044 -1.308 -0.378 -1.866 LC0050 7.700 0.898 -0.064 LC0060 0.182 -0.232 1.734 LC0061 0.001 0.077 -0.404 LC0066 1.359 0.645 1.349 LC0067 0.051 0.010 -0.176 LC0073 0.303 0.488 0.179 LC0074 67.982 13.909 10.306 LC0075 - 0.339 -0.112 LC0077 0.051 0.070 1.485 LC0078 0.605 0.592 -0.015 LC0082 -0.301 -0.579 -0.627 LC0090 1.973 2.261 2.175 LC0093 1.269 -0.655 -0.504 LC0094 -0.050 -0.751 -1.307 LC0098 -0.200 -0.102 1.981 LC0099 1.812 0.495 1.024 LC0104 -0.804 -1.236 -1.060 LC0107 -0.146 0.143 2.680 LC0110 - 1.234 1.442 LC0111 -0.251 -0.117 -1.647


19

ProL

ab 2

010

Labo

rato

ry

LC0032

LC0004

LC0108

LC0060

LC0048

LC0043

LC0018

LC0101

LC0103

LC0006

LC0034

LC0020

LC0029

LC0105

LC0027

LC0066

LC0041

LC0011

LC0095

LC0075

LC0039

LC0003

LC0067

LC0007

LC0106

LC0016

LC0040

LC0050

LC0073

LC0089

LC0044

LC0061

LC0035

LC0049

LC0077

LC0052

LC0037

LC0038

LC0056

LC0010

LC0098

LC0110

LC0074

LC0111

LC0090

LC0025

LC0033

LC0031

LC0080

LC0076

LC0082

LC0005

LC0107

LC0064

LC0017

LC0078

LC0104

LC0013

LC0093

LC0100

LC0109

LC0102

Z score

8 6 4 2 0 -2

E

EE

E

E

E

E

Sam

ple:

F&M

01M

easu

rand

:Fo

rmal

dehy

deM

etho

d:D

IN 3

8402

A45

No.

of l

abor

ator

ies:

62

Ass

igne

d va

lue:

9.12

31 m

g/kg

(Em

piric

al v

alue

)R

el. t

arge

t s.d

.:11

.47%

(Hor

witz

func

tion)

Rel

. rep

eata

bilit

y s.

d.:

1.23

%Li

mits

of t

oler

ance

:7.

0304

- 11

.215

8 m

g/kg

(|Z

sco

re| <

2.0

0)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e

Figure 7. Summary graph of the laboratory’s z-scores for formaldehyde (F&M01)


20

ProL

ab 2

010

Labo

rato

ry

LC0032

LC0004

LC0060

LC0018

LC0043

LC0034

LC0103

LC0020

LC0048

LC0027

LC0029

LC0056

LC0006

LC0106

LC0011

LC0077

LC0105

LC0066

LC0039

LC0108

LC0075

LC0067

LC0037

LC0016

LC0095

LC0040

LC0101

LC0010

LC0041

LC0007

LC0003

LC0073

LC0038

LC0035

LC0061

LC0044

LC0089

LC0025

LC0049

LC0111

LC0110

LC0033

LC0098

LC0052

LC0080

LC0076

LC0107

LC0074

LC0090

LC0031

LC0005

LC0064

LC0050

LC0017

LC0104

LC0078

LC0082

LC0100

LC0013

LC0109

LC0093

LC0102

Z score6 4 2 0 -2

EE

EE

E

E

E

Sam

ple:

F&M

02M

easu

rand

:Fo

rmal

dehy

deM

etho

d:D

IN 3

8402

A45

No.

of l

abor

ator

ies:

62

Ass

igne

d va

lue:

18.8

499

mg/

kg (E

mpi

rical

val

ue)

Rel

. tar

get s

.d.:

10.2

8% (H

orw

itz fu

nctio

n)R

el. r

epea

tabi

lity

s.d.

:1.

11%

Lim

its o

f tol

eran

ce:

14.9

734

- 22.

7265

mg/

kg

(|Z s

core

| < 2

.00)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



21

ProL

ab 2

010

Labo

rato

ry

LC0007

LC0066

LC0004

LC0061

LC0078

LC0040

LC0064

LC0067

LC0106

LC0016

LC0111

LC0033

LC0017

LC0049

LC0098

LC0041

LC0011

LC0102

LC0107

LC0089

LC0035

LC0073

LC0013

LC0109

LC0032

LC0075

LC0076

LC0037

LC0018

LC0052

LC0060

LC0077

LC0010

LC0105

LC0110

LC0039

LC0074

LC0029

LC0108

LC0100

LC0082

LC0048

LC0027

LC0031

LC0103

LC0038

LC0003

LC0101

LC0056

LC0043

LC0050

LC0093

LC0034

LC0104

LC0044

LC0006

LC0090

LC0005

LC0080

LC0095

LC0025

LC0020

Z score

6 4 2 0 -2 -4 -6 -8 -10

-12

EE

EE

EE

EE

EE

EE

EE

EE

EE

EE

EE

E

Sam

ple:

F&M

03M

easu

rand

:Fo

rmal

dehy

deM

etho

d:D

IN 3

8402

A45

No.

of l

abor

ator

ies:

62

Ass

igne

d va

lue:

229.

4457

mg/

kg (E

mpi

rical

val

ue)

Rel

. tar

get s

.d.:

7.06

% (H

orw

itz fu

nctio

n)R

el. r

epea

tabi

lity

s.d.

:1.

08%

Lim

its o

f tol

eran

ce:

197.

0515

- 26

1.83

99 m

g/kg

(|Z

sco

re| <

2.0

0)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



22

ProL

ab 2

010

Labo

rato

ry

LC0027

LC0034

LC0044

LC0035

LC0006

LC0104

LC0013

LC0040

LC0007

LC0039

LC0082

LC0111

LC0020

LC0098

LC0018

LC0107

LC0033

LC0094

LC0061

LC0067

LC0077

LC0002

LC0060

LC0073

LC0029

LC0016

LC0038

LC0078

LC0032

LC0093

LC0066

LC0099

LC0090

LC0041

LC0050

LC0074

Z score10 8 6 4 2 0 -2 -4

EE

E

E

Sam

ple:

F&M

01M

easu

rand

:M

elam

ine

Met

hod:

DIN

384

02 A

45N

o. o

f lab

orat

orie

s:36

Ass

igne

d va

lue:

0.25

25 m

g/kg

(Em

piric

al v

alue

)R

el. t

arge

t s.d

.:19

.68%

(Hor

witz

func

tion)

Rel

. rep

eata

bilit

y s.

d.:

3.53

%Li

mits

of t

oler

ance

:0.

1531

- 0.

3518

mg/

kg

(|Z s

core

| < 2

.00)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e

Figure 10. Summary graph of the laboratory’s z-scores for melamine (F&M01)


23

ProL

ab 2

010

Labo

rato

ry

LC0034

LC0035

LC0027

LC0006

LC0104

LC0094

LC0093

LC0020

LC0007

LC0082

LC0044

LC0002

LC0039

LC0038

LC0040

LC0060

LC0111

LC0098

LC0067

LC0018

LC0077

LC0061

LC0107

LC0075

LC0033

LC0041

LC0016

LC0073

LC0099

LC0078

LC0066

LC0017

LC0050

LC0013

LC0110

LC0029

LC0090

LC0032

LC0074

Z score10 8 6 4 2 0 -2 -4

E

EE

Sam

ple:

F&M

02M

easu

rand

:M

elam

ine

Met

hod:

DIN

384

02 A

45N

o. o

f lab

orat

orie

s:39

Ass

igne

d va

lue:

2.38

66 m

g/kg

(Em

piric

al v

alue

)R

el. t

arge

t s.d

.:14

.03%

(Hor

witz

func

tion)

Rel

. rep

eata

bilit

y s.

d.:

2.37

%Li

mits

of t

oler

ance

:1.

7167

- 3.

0564

mg/

kg

(|Z s

core

| < 2

.00)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



24

ProL

ab 2

010

Labo

rato

ry

LC0034

LC0035

LC0044

LC0111

LC0027

LC0006

LC0002

LC0094

LC0104

LC0020

LC0007

LC0082

LC0040

LC0018

LC0093

LC0039

LC0061

LC0067

LC0075

LC0050

LC0078

LC0041

LC0033

LC0073

LC0029

LC0016

LC0032

LC0099

LC0013

LC0066

LC0110

LC0077

LC0017

LC0038

LC0060

LC0098

LC0090

LC0107

LC0074

Z score10 8 6 4 2 0 -2 -4

E

E

E

ES

ampl

e:F&

M03

Mea

sura

nd:

Mel

amin

eM

etho

d:D

IN 3

8402

A45

No.

of l

abor

ator

ies:

39

Ass

igne

d va

lue:

3.95

79 m

g/kg

(Em

piric

al v

alue

)R

el. t

arge

t s.d

.:13

.01%

(Hor

witz

func

tion)

Rel

. rep

eata

bilit

y s.

d.:

2.28

%Li

mits

of t

oler

ance

:2.

9284

- 4.

9874

mg/

kg

(|Z s

core

| < 2

.00)

Lim

it of

tole

ranc

e

Lim

it of

tole

ranc

e



25

10. Migration exercise

In addition to migration solution samples, 19 volunteer NRLs received three melamine spoons which they tested for migration of formaldehyde into 3% acetic acid.

Participants received the corresponding standard operation procedure to carry out the test on the articles (Annex 3).

Participating laboratories were informed that the batch of the articles came from the market and released non compliant levels of formaldehyde.

EURL-FCM performed the homogeneity test on three consecutive migrations from the spoons. All solutions showed different level of heterogeneity in particular the second and the third migrations. For this reason the EURL-FCM asked to participants to quantify formaldehyde in the first migration solution and left them free to quantify the concentrations of formaldehyde also in the second and third migration solutions.

NRLs were asked to report two results of the resulting concentration of formaldehyde from the migration solution for each spoon, and to also report the volume of simulant used1 to perform the test and an estimation of the contact surface area.

The data were analysed statistically using ProLab and the robust mean was calculated by Q/Hampel algorithm (DIN 38402 A45) [3] and reported in Figure13. Due to insufficient homogeneity of the spoons themselves, the z-scores for this part of exercise were not allocated.

The data compared are reported in Table 6. In Figure 14 the concentration of formaldehyde from first, second and third migration solution obtained from migration are presented to evaluate possible trend in the release of formaldehyde along the migration exposure. Any significant trend was observed.

1 Excerpt of Regulation EU 10/2011[12]: “for materials and articles for which it is impracticable to estimate the relationship between the surface area and the quantity of food in contact therewith, for example due to their shape or use, the migration is calculated using the conventional surface area/volume conversion factor of 6 dm2/kg.”.

26

Table 6. Summary results from migration exercise

FIRST MIGRATION

Laboratory code Sample

Formaldehyde in migration

solution [mg/L]

Volume of migration

solution [L]

Formaldehyde in migration solution [mg]

Contact surface [dm2]

Formaldehyde (based on individual surface estimation)

[mg/dm2]

Formaldehyde (based on

surface robust mean)

[mg/dm2]


individual surface estimation) by using S/V* 6

dm2/kg [mg/kg]

Formaldehyde (based on surface robust mean, 1.52)

by using S/V* 6 dm2/kg [mg/kg]

1st Spoon A 181.52 0.590 107.10 77.61 70.23 465.63 421.40 1st Spoon B 187.51 0.590 110.63 80.17 72.55 480.99 435.30 2nd Spoon A 188.59 0.590 111.27 80.63 72.97 483.77 437.82 2nd Spoon B 188.53 0.590 111.23 80.60 72.95 483.63 437.68 3rd Spoon A 122.71 0.590 72.40 52.46 47.48 314.77 284.87

LC0013

3rd Spoon B 123.73 0.590 73.00

1.38

52.90 47.88 317.40 287.25 1st Spoon A 64.07 0.600 38.44 - 25.21 - 151.26 1st Spoon B 64.02 0.600 38.41 - 25.19 - 151.14 2nd Spoon A 70.34 0.600 42.20 - 27.68 - 166.06 2nd Spoon B 70.59 0.600 42.35 - 27.78 - 166.65 3rd Spoon A 78.54 0.600 47.12 - 30.90 - 185.42

LC0017

3rd Spoon B 78.85 0.600 47.31

-

- 31.03 - 186.16 1st Spoon A 64.05 0.891 57.06 40.02 37.42 240.10 224.53 1st Spoon B 63.24 0.891 56.34 39.51 36.95 237.05 221.67 2nd Spoon A 54.84 0.868 47.61 33.39 31.22 200.34 187.34 2nd Spoon B 55.65 0.868 48.32 33.89 31.69 203.32 190.13 3rd Spoon A 68.72 0.896 61.56 43.17 40.37 259.02 242.22

LC0018

3rd Spoon B 65.20 0.896 58.40

1.43

40.95 38.30 245.73 229.79 1st Spoon A 187.25 0.452 84.64 47.55 55.50 285.29 333.03 1st Spoon B 174.22 0.452 78.75 44.24 51.64 265.44 309.86 2nd Spoon A 245.37 0.450 110.42 62.03 72.41 372.19 434.47 2nd Spoon B 238.80 0.450 107.46 60.37 70.47 362.22 422.83 3rd Spoon A 181.93 0.460 83.69 47.02 54.88 282.10 329.30

LC0027

3rd Spoon B 181.01 0.460 83.27

1.78


LC0033

3rd Spoon B 16.57 0.650 10.77

1.74

6.19 7.06 37.14 42.38

27

FIRST MIGRATION



solution [mg/L]

Volume of migration

solution [L]




[mg/dm2]



[mg/dm2]



dm2/kg [mg/kg]




LC0035

3rd Spoon B 212.70 0.470 99.97

1.61


LC0037

3rd Spoon B 118.20 0.492 58.15

1.50


LC0038

3rd Spoon B 212.93 0.500 106.46

1.66

64.13 69.82 384.81 418.91 1st Spoon A 61.06 0.600 36.64 29.55 24.03 177.27 144.16 1st Spoon B - - - - - - - 2nd Spoon A 42.65 0.600 25.59 20.64 16.78 123.82 100.69 2nd Spoon B - - - - - - - 3rd Spoon A 20.94 0.600 12.56 10.13 8.24 60.79 49.44

LC0039

3rd Spoon B - - -

1.24

- - - - 1st Spoon A 115.46 0.530 61.19 30.75 40.13 184.50 240.79 1st Spoon B 115.58 0.530 61.26 30.78 40.17 184.70 241.04 2nd Spoon A 153.77 0.530 81.50 40.95 53.45 245.72 320.68 2nd Spoon B 152.35 0.530 80.75 40.58 52.95 243.45 317.72 3rd Spoon A 149.89 0.530 79.44 39.92 52.10 239.52 312.59

LC0040

3rd Spoon B 150.44 0.530 79.73

1.99

40.07 52.29 240.40 313.73

28

FIRST MIGRATION



solution [mg/L]

Volume of migration

solution [L]




[mg/dm2]



[mg/dm2]



dm2/kg [mg/kg]




LC0060

3rd Spoon B 91.54 0.800 73.23

1.60


LC0066

3rd Spoon B 73.15 0.580 42.43

-

- 27.82 - 166.94 1st Spoon A 233.70 0.500 116.85 - 76.63 - 459.78 1st Spoon B 233.40 0.500 116.70 - 76.53 - 459.19 2nd Spoon A 193.20 0.500 96.60 - 63.35 - 380.10 2nd Spoon B 195.00 0.500 97.50 - 63.94 - 383.64 3rd Spoon A 123.40 0.500 61.70 - 40.46 - 242.78

LC0067

3rd Spoon B 123.10 0.500 61.55

-


LC0073

3rd Spoon B 183.47 0.500 91.74

1.72


LC0077

3rd Spoon B 137.20 0.495 67.91

-

- 44.54 - 267.23

29

FIRST MIGRATION



solution [mg/L]

Volume of migration

solution [L]




[mg/dm2]



[mg/dm2]



dm2/kg [mg/kg]



1st Spoon A 112.50 0.510 57.38 - 37.63 - 225.76 1st Spoon B 116.30 0.510 59.31 - 38.90 - 233.39 2nd Spoon A 90.10 0.495 44.60 - 29.25 - 175.49 2nd Spoon B 91.70 0.495 45.39 - 29.77 - 178.61 3rd Spoon A 107.70 0.485 52.23 - 34.26 - 205.53

LC0093

3rd Spoon B 110.90 0.485 53.79

-


LC0098

3rd Spoon B 161.40 0.490 79.09

1.57


LC0107

3rd Spoon B 115.60 0.600 69.36

1.40


LC0111

3rd Spoon B 84.48 0.630 53.22

0.73

72.91 34.90 437.44 209.42


30

ProL

ab 2

010

Labo

rato

ry

LC0033

LC0039

LC0066

LC0017

LC0093

LC0111

LC0107

LC0018

LC0098

LC0077

LC0037

LC0040

LC0060

LC0073

LC0035

LC0027

LC0067

LC0013

LC0038

mg/kg500

450

400

350

300

250

200

150

100 50 0

E

EE

E

EE

E

E

E

E

E

E

EE

E

Sam

ple:

F&M

04M

easu

rand

:Fo

rmal

dehy

deM

etho

d:D

IN 3

8402

A45

No.

of l

abor

ator

ies:

19M

ean:

260.

8407

mg/

kg

Mean



31

Figure 14. Comparison of the formaldehyde concentration from first, second and third migration ( 1st spoon)

11. Conclusion

An overview of the ILC01 2012 outcome shows that the participation of the laboratories in the ILC01 2012 could be regarded as satisfactory. Sixty six participants (94.3%) reported results out of 70 sent sample kits. Four participants do not report results. Out of the laboratories who reported results, 88.5% reported for formaldehyde, 56% for melamine and 50% for both substances under test.

As this ILC targeted the correct implementation of Regulation 284/2011 on imports which requires the analysis of 10% of the consignments, all reporting laboratories were expected to report at least results for formaldehyde.

Regarding the quantification of formaldehyde and melamine in the migration solutions of kitchenware in 3% acetic acid, this ILC showed that:

For all 66 laboratories comprising of NRLs and OCLs

o For formaldehyde 80 % of all reported results (for all three concentration levels) were properly estimated;


32

o For melamine 89 % of all reported results were properly estimated;

For the NRLs-FCM:

o for formaldehyde 79 % of all reported results were correctly calculated;

o for melamine 88 % of all reported results were properly estimated.

Therefore for this exercise and the enforcement of the physical tests for consignment of imports under Regulation 284/2011, the OCLs and NRLs performance was the same as can be considered as one unique population in terms of reliability of results.

The results and z-scores for NRLs were investigated further specifically on formaldehyde for the 62 laboratories who submitted results. The results for F&M01 and F&M02 had 7 of the 62 laboratories (ca. 11%) returning questionable or unsatisfactory results. For the third solution, F&M03, 23 of the 62 laboratories (ca. 37%) returned questionable or unsatisfactory (i.e. z-score higher than 2). The third sample required dilution step before analysis, which could have caused the highest robust reproducibility standard deviation value, so possible reasons were investigated.

The EURL-FCM will therefore follow up with a questionnaire in order to identify the potential processes that led to the questionable or unsatisfactory performance (including how and when diluted, what was the measured concentration and what was the calibration range). This will constitute the first measure (root cause analysis) as prescribed by Eurachem for underperformance. The second measure will be the production of a new blind solution that will be sent to underperforming NRLs and give the opportunity to improve performance.

For melamine, F&M01, F&M02 and F&M03 88% of the laboratories reported satisfactory results.

With regards to the migration experiments, the data highlighted that the release of formaldehyde does not follow a diffusion-led migration as the results between 1st, 2nd and 3rd migration do not decrease steadily and remain somewhat unpredictable. The results confirmed a great variability between kitchen items for the high migrating non compliant articles, indicating a lack of good manufacturing practice in their production.


33

12. Acknowledgements The NRLs and guests signed up for this exercise are listed below. 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

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

LATVIA Institute of food Safety, animal Health and Environment (BIOR), Riga

LITHUANIA National Public Health Investigation Centre, Laboratory of Chemistry, Vilnius

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 SWEDEN National Food Agency, Science Department, Uppsala

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

UNITED KINGDOM Central Science Laboratory, York GUESTs BELGIUM Agence Federale Pour la Securite Alimentaire, Liege

FRANCE SCL, Oullins Cedex

GERMANY Chemisches und Veterinäruntersuchungsamt Stuttgart, Fellbach

GERMANY CVUA-OWL, Detmold

GERMANY CVUA-RRW, Krefeld

GERMANY Hessisches Landeslabor, Wiesbaden

GERMANY Landesamt für Gesundheit und Verbraucherschutz (LGV), Saarbrücken


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GERMANY Landeshauptstadt Düsseldorf, Der Oberbürgermeister Amt für Verbraucherschutz – Chemische und

Lebensmitteluntersuchung, Düsseldorf

GERMANY Landesuntersuchungsamt, Institut für Lebensmittelchemie Koblenz, Koblenz

GERMANY LAV Sachsen-Anhalt, Fachbereich Lebensmittelsicherheit, Halle

GERMANY Niedersächsisches Landesamt für Verbraucherschutz und Lebensmittelsicherheit,

Institut für Bedaefsgegenstände Lüneburg, Lüneburg

ITALY ASL Varese

ITALY ARPA Calabria, Cosenza

ITALY ARPA Lazio, Roma

ITALY ARPA Liguria, Genova

ITALY ARPA Marche, Pesaro

ITALY ARPA Piemonte – Polo Alimenti, La Loggia

ITALY ARPA Trento, Trento

ITALY ARPA Umbria, Terni

ITALY ARPA Veneto, Verona

ITALY Istituto Zooprofilattico Sperimentale, Lombardia Emilia Romagna, Bologna

ITALY Istituto Zooprofilattico Sperimentale dell'Umbria e delle Marche, Perugia

ITALY Laboratorio di Prevenzione di Milano

ITALY Laboratorio di Sanità Pubblica, Azienda Sanitaria di Firenze

POLAND WSSE, Białystok

POLAND WSSE, Kielce

POLAND WSSE, Lublin

POLAND WSSE, Łódź

POLAND WSSE, Olsztyn

POLAND WSSE, Poznań

POLAND WSSE, Szczecin

POLAND WSSE, Warszawa

SLOVENIA Zavod za Zdravstveno Varstvo Maribor, Maribor

SPAIN Centro Analitico de Inspeccion y Control de Calidad de Comercio Exterior, Madrit

SPAIN CNTA-Laboratorio del Ebro, San Adrian

SPAIN Laboratorio de Salud Publica Alicante

SPAIN Laboratorio de Salud Publica de Telavera de la Reina, Toledo

SWITZERLAND Kantonales Labor Zürich, Zürich

UNITED KINGDOM Worcestershire Scientific Services, Worcester

UNITED KINGDOM Kent Scientific Services, Kent

UNITED KINGDOM West Yorkshire Analytical Services, Leeds

UNITED KINGDOM Public Analyst Scientific Services Ltd., Norwich


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12. References

13. Annexes

Annex 1: Invitation letter to laboratories ILC01 2012

Annex 2: Format for confirmation of participation to ILC01 2012

Annex 3: Letters accompanying the sample ILC01 2012

Annex 4: Letter of confirmation of receipt of ILC01 2012

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

Annex 6: Results of the homogeneity study

Annex 7: Results of the stability 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] ISO GUIDE 35:2006; Reference materials–General and statistical principles for certification

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

[6] 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

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

[8] CEN 13130-23:2005, Determination of formaldehyde and hexamethylenete-tramine in food simulants

[9] CEN 13130-27:2005, Determination of 2,4,6-triamino-1,3,5-triazine in food simulants

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

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

[12] Regulation (EC) No 10/2011 of the European Parliament and the Council of 14 January 2011 on plastic materials and articles intended to come into contact with food


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Annex 1. Invitation letter to laboratories ILC01 2012


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Annex 2. Format for confirmation of participation to ILC01 2012


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Annex 3. Letters accompanying the sample ILC01 2012


39


40


41


42


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Annex 4. Letter of confirmation of receipt of ILC01 2012


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


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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

Formaldehyde mg/kg 9.53 5.77 1 11.39 OK OK OK F&M01

Melamine mg/kg 0.27 2.77 1 19.51 OK OK OK


Melamine mg/kg 2.41 1.90 1 14.01 OK OK OK


Melamine mg/kg 4.86 8.79

Horwitz

1 12.61 OK OK OK


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Annex 7. Results of the stability study A)

B) C)

Figure 15. Results of the stability for formaldehyde A) F&M01, B) F&M02 and C)

F&M03


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A)

B)

C)

Figure 16. Results of the stability for melamine A) F&M01, B) F&M02 and C) F&M03


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European Commission EUR 25686 – 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, ILC01 2012- Formaldehyde and Melamine in 3% acetic acid migration solution. Author(s): Giorgia Beldì, Natalia Jakubowska, Oguzhan Yavuz and Catherine Simoneau Luxembourg: Publications Office of the European Union 2012 – 49 pp. – 21.0 x 29.7 cm EUR – Scientific and Technical Research series – ISSN 1831-9424 ISBN 978-92-79-28085-6 doi:10.2788/77358 Abstract This report presents the results of the Inter-laboratory comparison (ILC) organised by the EURL-FCM, Ispra (Italy), which focused on the quantification of formaldehyde and melamine in migration solutions of 3% acetic acid from food contact materials. The test materials used for preparation of the migration solutions were melamine kitchenware (spoons) containing formaldehyde and melamine. The EURL prepared and distributed three concentration levels of migration solution and in addition three melamine kitchen articles (spoons). 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. There were 70 participants to whom samples were dispatched (EURL, 27 NRLs + 42 national control laboratories from Belgium, France, Germany, Italy, Poland, Slovenia, Spain and United Kingdom) and 66 of which submitted results. The assigned values were obtained after applying the robust statistics to the results of the participants. Participants were invited to report 4 results for each concentration level and 2 results for each spoon. The ILC showed that the participation in the ILC was satisfactory regarding the number of the participating laboratories. For formaldehyde 80 % of all reported results were properly estimated, for melamine 89 % of all reported results were properly estimated.

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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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A-25686-E

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