Report of an Interlaboratory Comparison from the European ......2013 Report EUR 26468 EN Juliana...
Transcript of Report of an Interlaboratory Comparison from the European ......2013 Report EUR 26468 EN Juliana...
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Report EUR 26468 EN
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Juliana Silva Félix, Giorgia Beldì
and Catherine Simoneau
ILC001-2013 – Proficiency Testing on Food Simulant E containing a cocktail of potential migrant substances
Report of an Interlaboratory Comparison
from the European Reference Laboratory
for Food Contact Materials
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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.
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JRC87459
EUR 26468 EN
ISBN 978-92-79-35268-3 (pdf)
ISSN 1831-9424 (online)
doi:10.2788/6263
Luxembourg: Publications Office of the European Union, 2013
© European Union, 2013
Reproduction is authorised provided the source is acknowledged.
Printed in Italy
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EURL – FCM ILC001-2013 on food simulant E containing unknown substances
EC-JRC-IHCP, CAT Unit
Action Programme 15014
2013
EURL Food Contact Materials
No SANCO/2013/FOOD SAFETY076-Food Contact Materials
Juliana Silva Félix, Giorgia Beldì and Catherine Simoneau
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Table of content
1. Executive Summary .................................................................................................................. 5
2. Introduction ............................................................................................................................... 6
3. Scope ....................................................................................................................................... 7
4. Time frame................................................................................................................................ 7
5. Test material ............................................................................................................................. 7
5.1. Sample preparation ............................................................................................................ 8
5.2. Homogeneity assessment .................................................................................................. 8
5.3. Stability test........................................................................................................................ 8
5.4. Distribution of the sample kits ............................................................................................ 9
6. Instructions to the participants .................................................................................................. 9
7. Evaluation of the results ............................................................................................................ 9
7.1. General observations ......................................................................................................... 9
7.2. Statistical evaluation of results ......................................................................................... 10
7.2.1. Assigned value .............................................................................................................. 10
7.2.2. Target standard deviation .............................................................................................. 10
7.2.3. Kernel density ............................................................................................................... 10
7.2.4. z-score .......................................................................................................................... 10
8. Results .................................................................................................................................... 11
8.1. Preliminary considerations ............................................................................................... 11
8.2. Laboratories performance and z-scores ........................................................................... 11
9. Final conclusion ...................................................................................................................... 29
Acknowledgements ..................................................................................................................... 30
10. References ........................................................................................................................... 31
11. Annexes ................................................................................................................................ 32
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1. Executive Summary
Food simulant E, also commercially named Tenax®, was established in Regulation (EU) No 10/2011 for testing specific migration into dry foodstuffs [1]. The first Interlaboratory Comparison (ILC) on Food Simulant E was carried out in 2011-2012. The general aim was to establish precision criteria of an optimised method for the analysis a number of migrants representing different physicochemical characteristics (n=5) in Tenax® and from a migration test from a fortified plastic film into Tenax® and subsequent quantification. Volunteer laboratories with some experience in simulant E participated using a Standard Operating Procedure (SOP) prepared by the European Reference Laboratory for Food Contact Material (EURL-FCM) [2]. The 2013 Interlaboratory Comparison (ILC001-2013) was taken as a further step since it was planned to 1) expand the range of polarity and volatility of the substances under investigation; 2) test the ability of laboratories i.e. take it to the next level being a proficiency testing (PT) with choice of any analytical method and 3) include unknown substances to test the screening ability (identification and quantification) of the laboratories. The test material used in this exercise was the spiked food simulant E prepared by the EURL-FCM. Before sending the sample to the participants, a list containing the name of 10 chemical substances was distributed, from which five would be present in the simulant. Other two unknown substances not included in the list were also added to the simulant. The choice of the substances was based on the relevant scientific literature related to migration from food contact materials (plastic and paperboard) into simulant E [2-6]. The concentration of each substance in the simulant was the closest as possible to its own specific migration limit (SML), when available in Regulation (EU) 10/2011 or tailored for the exercise. The substances chosen for the exercise 2013 were acetophenone (ACPH), benzophenone (BP), caprolactam (CAP), diethylhexyladipate (DEHA), 2,4-di-tert-butylphenol (DTBP), 2-ethyl-1-hexanol (ETHX) and 1-octene (OCT). The homogeneity and stability studies were performed by the EURL-FCM laboratory. There were 35 participants from 26 countries to whom samples were dispatched. 30 laboratories submitted results, of which 24 were NRLs, 5 were OCLs and one was the EURL-FCM itself. The participants were invited to report four replicate measurements under repeatability conditions. This was done by most of the participants. The participants were free to use their own analytical methods or use the SOP [2] that the EURL provided as a guide. The assigned values were obtained as consensus values after applying robust statistics to the results obtained from the participants. Laboratory results were rated with z-scores in accordance with ISO 13528 [7]. Reproducibility standard deviations (%) calculated by DIN 38402 A45 for the different substances in food simulant E are summarised below.
Substance SML mg/kg Assigned value mg/kg Reprod. SD % at the assigned value
ACPH - 11.03 18.12
BP 0.6 0.7 30.02
CAP 15 11.89 37.63
DEHA 18 8.37 32.52
DTBP - 6.98 12.29
ETHX 30 9.24 23.54
OCT 15 12.13 32.20
The participation of the laboratories on this PT on the identification and quantification of ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT in the simulant E was satisfactory regarding the number of received results as well as overall performance.
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2. Introduction ILC studies are an essential and very important element of laboratory quality assurance, which allows 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 European Reference Laboratories to organise interlaboratory comparisons, as stipulated in Regulation (EC) No 882/2004 of the European Parliament and of the Council [8]. In accordance with the above requirements the EURL-FCM organised in 2013 interlaboratory comparison tests for the network of appointed NRLs. The scopes of the ILC tests for 2013 were discussed and established on the plenaries with all NRLs. It was agreed that the aim of one of the ILCs would be the evaluation of the laboratory performance on the identification and the quantification of 7 substances in food simulant E (e.g. Tenax®), of which 5 would be out of a list containing several substance names and 2 would remain undisclosed. Tenax® is a trademark of poly(2,6-diphenyl-p-phenylene oxide), which in Regulation (EU) No 10/2011 [1] is established as food simulant E for testing specific migration into dry foodstuffs. It is a porous polymer, which has extremely high adsorption capacity. Table 1 shows the list that the EURL established as potential choices or range for the 5 substances potentially fortified in simulant E. Table 1. List of the potential substances potentially added to the food simulant E
List of Substances CAS number
Benzophenone 119-61-9
1-Octene 111-66-0
Laurolactam 947-04-6
Chimassorb 81 1843-05-6
Diethylhexyl adipate 103-23-1
Diphenylbutadiene 538-81-8
Caprolactam 105-60-2
2-Ethyl-1-hexanol 104-76-7
Irganox 1076 2082-79-3
Benzyl butyl phthatale 85-68-7
They were chosen as model substances because they were reported in the literature as migrants from plastic packaging materials and/or from paperboard into food simulant E, and also due to their adequate stability in that particular simulant. Of those, 5 were chosen for spiking as follows: benzophenone (BP) which is a light stabilizer (UV absorber), diethylhexyladipate (DEHA) which is used as plasticizer in plastic food packaging, 2-ethyl-1-hexanol (ETHX) and 1-octene (OCT) which are monomers or starting substances. In addition, simulant E was fortified with two "unknown" substances, i.e. substances which remained undisclosed until the completion of the exercise. These substances were Acetophenone (ACPH) which can be used for production of coatings, inks and adhesives, and 2,4-di-tert-butylphenol (DTBP) which is a degradation product of antioxidants as Irgafos 168. The laboratories participating in the ILC001-2013 exercise were asked to identify and to quantify the model substances in the simulant at one concentration level. The participants
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were free to use their own analytical methods, since this exercise was a PT. They were invited to report four replicate measurements in repeatability conditions. 3. Scope The scope of this ILC was a PT with two objectives:
to test the laboratory performance of the appointed NRLs and OCLs to identify the substances BP, CAP, DEHA, ETHX and OCT added to food simulant E for dry foods;
to test the laboratory performance of the NRLs and OCLs to identify undisclosed substances (e.g. ACPH , DTBP)
to quantify all the substances described above that were added to food simulant E. The assessment of the measurement results was undertaken on the basis of requirements laid down in international standards and guidelines [7, 9-11]. 4. Time frame During the plenary meeting (EURL – Food Contact Materials and its Network of NRLs) held on the 26th of June 2013, the EURL disclosed the list containing the names of 10 chemical substances (Table 1). Only five substances from that list had been added to the food simulant E. Other two unknown substances not included in the list were added to the same batch of the simulant E. The NRLs had the task identify and quantify all substances. The ILC001-2013 was officially launched on the 9th of July 2013. Invitation letters and instructions were sent to the participants (Annexes 1 and 5). The laboratories were invited to fill in a letter of confirmation of their participation (Annex 2). The final batch of food simulant E, spiked with the seven substances at one concentration level was prepared by the EURL-FCM from 09 to 11 September 2013. The sample was dispatched to the participants on the 12th of September 2013, together with the shipping kit (Annex 3). The participants were asked to fill in a letter of confirmation of the receipt of the samples (Annex 4). The deadline for reporting was set to the 30th of October 2013. 5. Test material The sample kit sent to the participants is shown in Table 2. The non-spiked food simulant E, from the same batch as the spiked one, was sent to the participants for control purposes. Additionally, virgin Tenax® was provided to NRLs for calibration purposes. Table 2. Sample kit for the ILC001-2013 Name Sample
TNX1 One bottle with 20 g of the spiked food simulant E
Blank TNX1 One vial with 5 g of the not spiked food simulant E
Virgin TNX One box with 10 g of virgin Tenax® TA 60/80 (Supelco) – NRLs only
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5.1. Sample preparation Preparation and homogenization of the test materials were done by the EURL-FCM laboratory according to the procedure described in Annex 6. After spiking and homogenization, 20 g portions of the spiked simulant E were filled into glass amber bottles. 5.2. Homogeneity assessment The samples were tested for homogeneity by the EURL Laboratory. Ten randomly selected test specimens for the sample TNX1 were analysed in duplicate to quantify ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT. Homogeneity was evaluated according to ISO 13528 [7], F-test and IUPAC International Harmonized Protocol [11] using the ProLab Software [12]. The homogeneity results and their statistical evaluation were obtained using Horwitz as target standard deviation (Annex 8). All test materials showed sufficient homogeneity. 5.3. Stability test Randomly selected specimens for sample TNX1 were stored at 3 different temperature conditions (4ºC, 20°C and 40ºC). The test samples were monitored for stability by the EURL laboratory for all substances from the date of preparation (homogeneity assessment) to the closing of the ILC001-2013. The stability was evaluated as described in ISO GUIDE 35:2006 [13]. The evaluation of data was carried out by performing a linear regression on the experimentally determined concentrations of ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT (mean values) versus time (days). For a stable material, it is expected that the intercept is (within uncertainty) equal to the assigned value, whereas the slope does not differ significantly from zero. Using the linear regression equation: Y(ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT mg/kg) = b0 +b1 X (time, days) the slope is not significantly different from zero if the following requirement is respected;
where b1 is the slope obtained from the linear regression, t0.95,n-2 is the Student’s t-factor for n-2 degrees of freedom and p = 0.95 (95% level of
confidence) and s(b1) is the uncertainty associated with the slope. This can be calculated as follows:
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The value of s (standard deviation of the time-points) can be obtained from:
where n is the number of points of the linear regression. The stability results and their statistical evaluation are given in Annex 9. It should be pointed out that no significant trend was observed for the test sample at all temperature conditions (4ºC, 20°C and 40ºC) for the time span of the ILC001-2013. It was concluded that the substances were stable for at least two months following their preparation. 5.4. Distribution of the sample kits
The sample kits were dispatched to the participants by the EURL-FCM on the 12th of September 2013. Each participant received a box containing the test materials as follows:
One amber glass bottle with 20 g of the spiked food simulant E (TNX1)
One glass vial with 5 g of the food simulant E not spiked, from the same batch of the spiked one (Blank TNX1)
One plastic box containing virgin Tenax® TA 60/80 (10 g) – (NRLs only). and accompanying letters:
Instructions on sample handling and on compilation of the results (Annex 5);
Confirmation of receipt (Annex 4);
Electronic excel file for reporting the results (Annex 7). 6. Instructions to the participants Instructions were given to all participants in the letters that accompanied the sample (Annex 5). Laboratories were asked to report 4 results for each substance using the unit of measure indicated in the electronic excel file for reporting the results (Annex 7). Participants were free to use their own analytical methods. However, the SOP [2] validated in the previous exercise on Food Simulant E was also distributed as a guide if needed. 7. Evaluation of the results
7.1. General observations There were 35 participants to whom samples were dispatched (EURL, 29 NRLs + 5 national control laboratories from Germany and Spain) and 30 of which submitted results. The ILC was closed permanently at the beginning of November for statistical interpretation.
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7.2. Statistical evaluation of results The statistical evaluation of the results was performed using the ProLab software [12]. 7.2.1. Assigned value As the “true” values for the concentration of each evaluated substance could not be known due to the complexity of sample preparation and possible loss of substances during the evaporation step, the assigned value was evaluated according to Q-method/Hampel estimator (DIN 38402 A45) [14]. A robust mean of the results reported by the participants was chosen as a consensus for the assigned value in the ILC001-2013. The results reported as "smaller than" (
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Xassigned is the assigned value; σp is the target standard deviation for proficiency assessment. The z-score can be interpreted as follow: |z|≤2 satisfactory result; 23 unsatisfactory result.
In this exercise the z-scores calculated with the reproducibility SD as p were used to assess
the performance of the laboratories. Nevertheless, the z-scores with Horwitz SD as p were also calculated. 8. Results 8.1. Preliminary considerations Thirty laboratories submitted results, of which 24 were from NRL network, 5 were OCLs (4 from Germany and 1 from Spain) and one was the EURL-FCM itself. As requested, most of the laboratories reported four replicate results under repeatability conditions. The participation of the laboratories was regarded as satisfactory concerning the number of received results (86% of participation). 8.2. Laboratories performance and z-scores The EURL-FCM collected information about the different procedures used by the participants in the exercise (Annex 10). The reported methodologies refer to the different stages of the analysis, such as: cleaning of the simulant, extraction of substances from the simulant, calibration and quantification, analytical technique and chromatographic column. The procedure for cleaning described in the SOP [2] of 6 hours of Soxhlet with acetone was used by 80% of the laboratories. Hexane, acetone and acetonitrile were the solvents most commonly used for the extraction. Most of the laboratories performed the calibration spiking the matrix and the quantification using internal standard. Gas chromatography coupled to mass spectrometer was chosen by 80% of the participants with the capillary columns HP-5MS and DB-17HT. The overall performance for individual substance was evaluated taking into account the results submitted (Figure 1). The blue bars represent the number of laboratories able to identify the substance. The yellow bars denote to the number of laboratories that quantified the substance and the green bars mean the number of laboratories that quantified the substance within the tolerance limits. The overall performance of the laboratories regarding all the 7 evaluated substances is shown in Table 3. Concerning the identification, 83% of the participants were able to identify at least 5 substances (25 results out of 30). It is important to note that 15 laboratories could identify all the 7 substances. In relation to the quantification, 61% of the participants were able to quantify all the 7 substances within the tolerance limit (17 results out of 28 quantitative results).
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Table 3. Overall performance of the laboratories in the identification and quantification of the substances Lab. code
Identified substances
Total n. substances
Percentage (%)
Successful Quantified substances
Total n. substances
Percentage (%)
Successful Quant. subst.
within tolerance limit
Total n. substances
Percentage (%)
Overall Successful
LC0002 7 7 100 Yes 7 7 100 Yes 6 7 86 Yes
LC0003 2 7 29 No 2 7 29 No 2 7 29 No
LC0004 7 7 100 Yes 7 7 100 Yes 6 7 86 Yes
LC0004B 7 7 100 Yes 7 7 100 Yes 6 7 86 Yes
LC0005 4 7 57 No 4 7 57 No 3 7 43 No
LC0006 3 7 43 No 3 7 43 No 1 7 14 No
LC0007 6 7 86 Yes 3 7 43 No 0 7 0 No
LC0008 1 7 14 No 1 7 14 No 1 7 14 No
LC0010 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0011 0 7 0 No 0 7 0 No 0 7 0 No
LC0013 6 7 86 Yes 6 7 86 Yes 6 7 86 Yes
LC0016 6 7 86 Yes 4 7 57 No 4 7 57 No
LC0017 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0018 6 7 86 Yes 6 7 86 Yes 6 7 86 Yes
LC0020 7 7 100 Yes 5 7 71 Yes 3 7 43 No
LC0024 5 7 71 Yes 3 7 43 No 3 7 43 No
LC0025 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0028 6 7 86 Yes 6 7 86 Yes 6 7 86 Yes
LC0029 0 7 0 No 0 7 0 No 0 7 0 No
LC0031 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0034 0 7 0 No 0 7 0 No 0 7 0 No
LC0037 6 7 86 Yes 6 7 86 Yes 5 7 71 Yes
LC0038 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0040 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0041 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0043 0 7 0 No 0 7 0 No 0 7 0 No
LC0044 0 7 0 No 0 7 0 No 0 7 0 No
LC0047 7 7 100 Yes 7 7 100 Yes 7 7 100 Yes
LC0048 7 7 100 Yes 7 7 100 Yes 6 7 86 Yes
LC0049 6 7 86 Yes 0 7 0 No 0 7 0 No
LC0050 6 7 86 Yes 6 7 86 Yes 4 7 57 No
LC0055 4 7 57 No 4 7 57 No 3 7 43 No
LC0056 7 7 100 Yes 6 7 86 Yes 0 7 0 No
LC0059 6 7 86 Yes 0 7 0 No 0 7 0 No
LC0064 7 7 100 Yes 6 7 86 Yes 5 7 71 Yes
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0
5
10
15
20
25
30
35
ACPH BP CAP DEHA DTBP ETHX OCT
Nu
mb
er
of
La
bo
rato
rie
sIdentification and quantification of the substances
Identified Quantified Quantified within tolerance limit
Figure 1. General overview of the results obtained for each substance BP and DEHA had been already the subject of a quantification exercise in simulant E in the previous ILC exercise. The repeatability SD and reproducibility SD from both exercises are shown in Table 4. In the ILC002-2012 the participants had to follow strictly a single method (SOP) to quantify these substances in simulant E. In the ILC001-2013, BP and DEHA were quantified using different analytical methods chosen by the participants. This approach could explain higher values obtained for the reproducibility SD in the ILC001-2013. The repeatability SDs achieved in both ILC exercises are similar, although in the present ILC the participants applied different analytical methods. These findings indicate that the approaches do not differ regarding their repeatability. Table 4. Repeatability SD and reproducibility SD for BP and DEHA in Simulant E
Substance
ILC02-2011 ILC001-2013
Assigned value (mg/kg)
Reprod. SD
Repeat.SD
Assigned value (mg/kg)
Reprod. SD
Repeat.SD
BP 0.49 20 8 0.70 30 7
DEHA 17.49 21 7 8.37 33 6
Summaries of the results obtained for ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT with their robust repeatability SD and robust reproducibility SD calculated by ProLab software according to Q-method/Hampel estimator (DIN 38402 A45) [14] as well as assigned values, target standard deviations and z-scores, are given in Tables 5-12 and Figures 2-8. In Tables 6-12 z-scores calculated against two different target SDs are presented.
30 participants
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Table 5. Summary of results for ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT calculated according to DIN 38402 A45
ProLab Results SUBSTANCES
ACPH BP CAP DEHA DTBP ETHX OCT
Assigned value = Robust Mean, mg/kg 11.03 0.70 11.89 8.37 6.98 9.24 12.13
Robust Repeatability SD, mg/kg 0.81 0.05 1.05 0.49 0.42 0.62 1.13
Robust Reproducibility SD, mg/kg 2.00 0.21 4.47 2.72 0.86 2.17 3.90
Target SD (Reproducibility SD), mg/kg 2.00 0.21 4.47 2.72 0.86 2.17 3.90
Target SD (Horwitz), mg/kg 1.23 0.12 1.31 0.97 0.83 1.06 1.33
Rel. target SD (Reproducibility SD), % 18.12 30.02 37.63 32.52 12.29 23.54 32.20
Rel. target SD (Horwitz), % 11.15 16.88 11.02 11.62 11.94 11.45 10.99
Rel. Repeatability SD, % 7.37 6.99 8.82 5.83 5.95 6.66 9.29
Lower limit of tolerance, mg/kg 7.03 0.28 2.94 2.93 5.27 4.89 4.32
Upper limit of tolerance, mg/kg 15.02 1.12 20.83 13.82 8.70 13.59 19.93
Laboratories 18 25 21 28 17 23 23
Test results 71 99 81 111 67 91 91
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Table 6. Summary of the z-scores against different target SD for ACPH
z-scores for ACPH
Laboratory classical Horwitz Reproducibility SD
LC0002 -1.567 -0.964
LC0004 2.607 1.604
LC0004B 2.107 1.296
LC0010 0.077 0.047
LC0017 -0.255 -0.157
LC0018 1.841 1.132
LC0025 -0.781 -0.481
LC0028 0.596 0.366
LC0031 1.281 0.788
LC0037 -1.099 -0.676
LC0038 -0.324 -0.199
LC0040 -0.102 -0.063
LC0041 0.435 0.268
LC0047 -1.587 -0.976
LC0048 -0.061 -0.038
LC0050 -2.238 -1.376
LC0056 41.903 25.773
LC0064 -0.761 -0.468
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Table 7. Summary of the z-scores against different target SD for BP
z-scores for BP
Laboratory classical Horwitz Reproducibility SD
LC0002 -0.962 -0.541
LC0004 8.436 4.743
LC0004B 6.278 3.530
LC0005 -1.505 -0.846
LC0006 4.417 2.484
LC0010 0.060 0.034
LC0013 -1.695 -0.953
LC0016 -0.320 -0.180
LC0017 0.949 0.533
LC0018 2.746 1.544
LC0020 0.289 0.162
LC0024 -1.822 -1.024
LC0025 -1.145 -0.644
LC0028 0.378 0.212
LC0031 -0.489 -0.275
LC0037 -1.039 -0.584
LC0038 -0.722 -0.406
LC0040 -0.595 -0.335
LC0041 -1.420 -0.798
LC0047 -0.320 -0.180
LC0048 5.284 2.971
LC0050 -0.849 -0.477
LC0055 3.339 1.877
LC0056 30.664 17.241
LC0064 -1.187 -0.668
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Table 8. Summary of the z-scores against different target SD for CAP
z-scores for CAP
Laboratory classical Horwitz Reproducibility SD
LC0002 3.673 1.076
LC0003 -1.155 -0.338
LC0004 -0.824 -0.242
LC0004B 1.263 0.370
LC0010 -0.170 -0.050
LC0013 1.620 0.474
LC0016 1.927 0.564
LC0017 2.351 0.689
LC0018 1.994 0.584
LC0020 -8.296 -2.430
LC0024 -5.366 -1.572
LC0025 0.038 0.011
LC0028 -3.898 -1.142
LC0031 2.013 0.590
LC0038 0.277 0.081
LC0040 2.314 0.678
LC0041 -2.374 -0.695
LC0047 1.536 0.450
LC0048 -0.342 -0.100
LC0050 -7.585 -2.222
LC0056 8.729 2.557
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Table 9. Summary of the z-scores against different target SD for DEHA
z-scores for DEHA
Laboratory classical Horwitz Reproducibility SD
LC0002 1.880 0.672
LC0003 -4.880 -1.744
LC0004 2.368 0.846
LC0004B 2.803 1.001
LC0005 0.510 0.182
LC0006 12.282 4.388
LC0007 -7.009 -2.504
LC0008 -0.017 -0.006
LC0010 0.186 0.066
LC0013 -0.320 -0.114
LC0016 -1.089 -0.389
LC0017 0.854 0.305
LC0018 0.543 0.194
LC0020 -3.270 -1.168
LC0024 -3.119 -1.114
LC0025 1.811 0.647
LC0028 2.044 0.730
LC0031 1.494 0.534
LC0037 21.183 7.568
LC0038 1.063 0.380
LC0040 -1.554 -0.555
LC0041 1.510 0.539
LC0047 1.057 0.378
LC0048 1.371 0.490
LC0050 -3.158 -1.128
LC0055 11.716 4.186
LC0056 75.184 26.863
LC0064 0.238 0.085
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Table 10. Summary of the z-scores against different target SD for DTBP
z-scores for DTBP
Laboratory classical Horwitz Reproducibility SD
LC0002 2.378 2.311
LC0004 0.490 0.476
LC0004B -1.288 -1.251
LC0010 0.230 0.223
LC0013 -0.409 -0.398
LC0017 -0.430 -0.418
LC0025 0.610 0.593
LC0028 1.069 1.039
LC0031 0.259 0.252
LC0037 0.379 0.369
LC0038 -0.604 -0.587
LC0040 0.068 0.066
LC0041 0.829 0.806
LC0047 -0.370 -0.360
LC0048 -0.460 -0.447
LC0055 -0.412 -0.400
LC0064 -3.125 -3.037
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Table 11. Summary of the z-scores against different target SD for ETHX
z-scores for ETHX
Laboratory classical Horwitz Reproducibility SD
LC0002 1.225 0.596
LC0004 1.861 0.905
LC0004B 1.485 0.722
LC0005 -7.303 -3.551
LC0007 -6.972 -3.391
LC0010 -3.234 -1.573
LC0013 0.409 0.199
LC0016 0.390 0.190
LC0017 1.343 0.653
LC0018 1.336 0.650
LC0020 -1.904 -0.926
LC0025 -0.809 -0.393
LC0028 1.305 0.635
LC0031 2.187 1.063
LC0037 0.981 0.477
LC0038 0.132 0.064
LC0040 -0.073 -0.036
LC0041 -0.227 -0.110
LC0047 -0.366 -0.178
LC0048 0.478 0.232
LC0050 -6.537 -3.179
LC0056 75.970 36.946
LC0064 0.281 0.137
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Table 12. Summary of the z-scores against different target SD for OCT Seven sets of figures for TNX1 sample are presented below. Each set included: individual laboratories values and their mean and standard deviation (first graphic), Kernel density plot (second graphic) and z- scores (third graphic).
z-scores for OCT
Laboratory classical Horwitz Reproducibility SD
LC0002 -0.794 -0.271
LC0004 0.974 0.332
LC0004B 0.974 0.332
LC0005 -0.640 -0.218
LC0006 -1.347 -0.460
LC0007 -9.045 -3.087
LC0010 -0.038 -0.013
LC0013 4.216 1.439
LC0017 1.077 0.368
LC0018 3.396 1.159
LC0020 -7.179 -2.450
LC0025 1.525 0.521
LC0031 2.327 0.794
LC0037 1.126 0.384
LC0038 0.672 0.229
LC0040 -2.556 -0.872
LC0041 -0.893 -0.305
LC0047 2.158 0.736
LC0048 1.826 0.623
LC0050 -4.653 -1.588
LC0055 -2.132 -0.728
LC0056 74.959 25.583
LC0064 1.062 0.362
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PROLab Plus
Laboratory
LC
00
50
LC
00
47
LC
00
02
LC
00
37
LC
00
25
LC
00
64
LC
00
38
LC
00
17
LC
00
40
LC
00
48
LC
00
10
LC
00
41
LC
00
28
LC
00
31
LC
00
18
LC
00
04
B
LC
00
04
LC
00
56
mg
/kg
70
60
50
40
30
20
10
00
Sample: Spiked TenaxMeasurand: AcetophenoneMethod: DIN 38402 A45No. of laboratories: 18
Assigned value: 11.025 mg/kg (Empirical value)Rel. target s.d.: 18.12% (Empirical value)Rel. repeatability s.d.: 7.37%Range of tolerance: 7.029 - 15.022 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
24
LC
00
13
LC
00
05
LC
00
41
LC
00
64
LC
00
25
LC
00
37
LC
00
02
LC
00
50
LC
00
38
LC
00
40
LC
00
31
LC
00
16
LC
00
47
LC
00
10
LC
00
20
LC
00
28
LC
00
17
LC
00
18
LC
00
55
LC
00
06
LC
00
48
LC
00
04
B
LC
00
04
LC
00
56
mg
/kg
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
-1.0
Sample: Spiked TenaxMeasurand: benzophenoneMethod: DIN 38402 A45No. of laboratories: 25
Assigned value: 0.700 mg/kg (Empirical value)Rel. target s.d.: 30.02% (Empirical value)Rel. repeatability s.d.: 6.99%Range of tolerance: 0.280 - 1.121 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
20
LC
00
50
LC
00
24
LC
00
28
LC
00
41
LC
00
03
LC
00
04
LC
00
48
LC
00
10
LC
00
25
LC
00
38
LC
00
04
B
LC
00
47
LC
00
13
LC
00
16
LC
00
18
LC
00
31
LC
00
40
LC
00
17
LC
00
02
LC
00
56
mg
/kg
30
28
25
23
20
18
15
13
10
08
05
03
00
-03
-05
Sample: Spiked TenaxMeasurand: CaprolactamMethod: DIN 38402 A45No. of laboratories: 21
Assigned value: 11.888 mg/kg (Empirical value)Rel. target s.d.: 37.63% (Empirical value)Rel. repeatability s.d.: 8.82%Range of tolerance: 2.942 - 20.834 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
07
LC
00
03
LC
00
20
LC
00
50
LC
00
24
LC
00
40
LC
00
16
LC
00
13
LC
00
08
LC
00
10
LC
00
64
LC
00
05
LC
00
18
LC
00
17
LC
00
47
LC
00
38
LC
00
48
LC
00
31
LC
00
41
LC
00
25
LC
00
02
LC
00
28
LC
00
04
LC
00
04
B
LC
00
55
LC
00
06
LC
00
37
LC
00
56
mg
/kg
100
90
80
70
60
50
40
30
20
10
00
-10
Sample: Spiked TenaxMeasurand: diethylhexyladipateMethod: DIN 38402 A45No. of laboratories: 28
Assigned value: 8.371 mg/kg (Empirical value)Rel. target s.d.: 32.52% (Empirical value)Rel. repeatability s.d.: 5.83%Range of tolerance: 2.927 - 13.816 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
64
LC
00
04
B
LC
00
38
LC
00
48
LC
00
17
LC
00
55
LC
00
13
LC
00
47
LC
00
40
LC
00
10
LC
00
31
LC
00
37
LC
00
04
LC
00
25
LC
00
41
LC
00
28
LC
00
02
mg
/kg
11
10
09
08
07
06
05
04
03
02
Sample: Spiked TenaxMeasurand: 2,4-di-tert-butylphenolMethod: DIN 38402 A45No. of laboratories: 17
Assigned value: 6.984 mg/kg (Empirical value)Rel. target s.d.: 12.29% (Empirical value)Rel. repeatability s.d.: 5.95%Range of tolerance: 5.267 - 8.700 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
05
LC
00
07
LC
00
50
LC
00
10
LC
00
20
LC
00
25
LC
00
47
LC
00
41
LC
00
40
LC
00
38
LC
00
64
LC
00
16
LC
00
13
LC
00
48
LC
00
37
LC
00
02
LC
00
28
LC
00
18
LC
00
17
LC
00
04
B
LC
00
04
LC
00
31
LC
00
56
mg
/kg
110
100
90
80
70
60
50
40
30
20
10
00
-10
Sample: Spiked TenaxMeasurand: 2-Ethyl 1-HexanolMethod: DIN 38402 A45No. of laboratories: 23
Assigned value: 9.238 mg/kg (Empirical value)Rel. target s.d.: 23.54% (Empirical value)Rel. repeatability s.d.: 6.66%Range of tolerance: 4.889 - 13.586 mg/kg (|Z Score|
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PROLab Plus
Laboratory
LC
00
07
LC
00
20
LC
00
50
LC
00
40
LC
00
55
LC
00
06
LC
00
41
LC
00
02
LC
00
05
LC
00
10
LC
00
38
LC
00
04
LC
00
04
B
LC
00
64
LC
00
17
LC
00
37
LC
00
25
LC
00
48
LC
00
47
LC
00
31
LC
00
18
LC
00
13
LC
00
56
mg
/kg
140
120
100
80
60
40
20
00
Sample: Spiked TenaxMeasurand: 1-OcteneMethod: DIN 38402 A45No. of laboratories: 23
Assigned value: 12.125 mg/kg (Empirical value)Rel. target s.d.: 32.20% (Empirical value)Rel. repeatability s.d.: 9.29%Range of tolerance: 4.317 - 19.933 mg/kg (|Z Score|
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9. Final conclusion The participation of NRLs and OCLs in the ILC001-2013 was satisfactory particiation with thirty laboratories out of 35 which reported results (86% of participation). The laboratories' performance concerning the identification of the unknown substances was satisfactory, with 25 correct results out of 30 (83%), even taking into account the complexity of the exercise. Regarding the quantification within tolerance limits, 17 results out of 28 were satisfactory, which represented a success rate of 61%. This was however for all substances, therefore for a very challenging exercise that included undisclosed substances (unknowns). Considering the individual substances, more than 80% of satisfactory quantification within tolerance limits was achieved (ACPH 94%, BP 80%, CAP 86%, DEHA 82%, DTBP 88%, ETHX 83% and OCT 87%). This exercise was the first Proficiency Testing carried out at EU level on food simulant E with the aim to evaluate the performance of the National Reference Laboratories across the Member States. It was therefore a very positive first-time result. In addition, this ILC001-2013 provided the first successful attempt to derive data at EU level for identification and quantification of potential unknown migrants, at the SML levels in food simulant E. These migrants are commonly found in food contact materials such as plastic packaging and paperboard.
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Acknowledgements The NRLs and OCLs 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
DENMARK Danish Veterinary and Food Administration Laboratory Århus, 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
SLOVAKIA National Reference Centre and Laboratory for material and articles intended to come into
contact with food, Regional Public Health Authority In Poprad (RUVZ)
SLOVENIA National Institute of Public Health of Republic of Slovenia, Department of Sanitary Chemistry,
Ljubijana
SPAIN Centro Nacional de Alimentación, Agencia Española de Seguridad Alimentaria y Nutrición
(AESAN), Madrid
THE NETHERLANDS Food and Consumer Product Safety Authority (VWA), Ministry of Economic Affairs, Agriculture
and Innovation, Groningen
OCLs
GERMANY Landesamt für Verbraucherschutz Sachsen-Anhalt, Halle
GERMANY Landesuntersuchungsanstalt für das Gesundheits- und Veterinärwesen Sachsen, Dresden
GERMANY Chemisches und Veterinäruntersuchungsamt, Fellbach
GERMANY Niedersächsisches Amt für Verbraucherschutz und Lebensmittelsicherheit (LAVES), Lüneburg
SPAIN Laboratorio de Salud Pública, Alicante
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10. References
[1] Regulation EC10/2011 of the European Parliament and the Council of 14 January 2011 on plastic materials and articles intended to come into contact with food
[2] Beldì et al. 2012. Development of a harmonised method for specific migration into the new simulant for dry foods established in Regulation 10/2011; Establishment of precision criteria from an EU interlaboratory comparison organised by the EURL Food Contact Materials for the quantification from and migration into poly(2,6-diphenyl phenylene oxide). European Commission - Joint Research Centre - Institute for Health and Consumer Protection - EUR 25680. doi:10.2788/76804
[3] Félix et al. 2012. Analytical Bioanalytical Chemistry 403:2869-2882. doi: 10.1007/s00216-012-5965-z
[4] Canellas et al. 2012. Journal of Chromatography A 1235: 141-148. doi: 10.1016/j.chroma.2012.02.039
[5] Poças et al. 2011. Food Control 22: 303-312. doi:10.2788/76804
[6] Nerín et al. 2002. Journal of Agricultural and Food Chemistry 50: 7488-7492. doi: 10.1021/jf0257143
[7] ISO 13528:2005; Statistical Methods for Use in Proficiency Testing by Interlaboratory Comparisons
[8] 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
[9] M. Thompson, Analyst, (2000), 125, 385-386
[10] T. Linsinger et al., Accreditation and Quality Assurance in Analytical Chemistry (2001), 6, 20-25
[11] 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
[12] ProLab Software – QuoData, Drezden – www.quodata.de
[13] ISO GUIDE 35:2006; Reference materials–General and statistical principles for
certification.
[14] DIN 38402 A45 Ringversuche zur externen Qualitätskontrolle von Laboratorien.
[15] AMC, Representing data distributions with kernel density estimates. AMC Technical Brief, 2006, http://www.rsc.org/images/brief4_tcm18-25925.pdf
[16] P.J. Lowthian and M. Thompson, Bump-Hunting for the proficiency tester - searching for multimodality. The Analyst, 2002. 127: p. 1359, https://www.swetswise.com/eAccess/viewAbstract.do?articleID=14625081
http://www.quodata.de/
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11. Annexes
Annex 1. Invitation letter to the laboratories to ILC001-2013
Annex 2. Letter for confirmation of participation to ILC001-2013
Annex 3. Shipping kit letter accompanying the sample TNX1 to ILC001-2013
Annex 4. Letter of confirmation of receipt of the sample to ILC001-2013
Annex 5. Letter Instructions for the compilation of the results from ILC001-2013
Annex 6. Procedure for the preparation of the spiked food simulant E
Annex 7. Form for the compilation of the results in non-electronic format
Annex 8. Results of the homogeneity study
Annex 9. Results of the stability study and the statistical evaluation
Annex 10. Methodologies used by the participants
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Annex 1. Invitation letter to the laboratories to ILC001-2013
EUROPEAN COMMISSION GENERAL DIRECTORATE JRC JOINT RESEARCH CENTRE Institute for Health and Consumer Protection – IHCP Unit Chemical Assessment and Testing
Ispra July 9th
, 2013
Dear Madam, Sir Interlaboratory Comparison (ILC) exercise on food simulant E
On behalf of the EURL for food contact materials, I would like to invite you to participate in an Interlaboratory comparison (ILC) exercise for the determination of known and unknown substances in food simulant E which is due to start by the beginning of September. As agreed in the last EURL-NRL FCM plenary, the scope of this ILC exercise is a Proficiency testing, laboratories are free to use their own methods. This ILC aims at the extraction and identification/quantification of substances from food simulant E. There is no migration experiment in this exercise. You will receive a list of ten substances. Only five substances from that list have been spiked into the food simulant E. You need to identify and quantify them. Additionally you should be able to identify and quantify other two unknown substances, also spiked in the same simulant E but not included in the list described above. I would like to remind you that it is a duty for you as an NRL-FCM to participate in the ILCs organised by the EURL-FCM since the work programme is decided with your agreement. For this reason we require all of you to actively participate in this exercise. There is no charge for participation. We have pre-registered everyone, which means we will send test kits to all of you. We however need to receive the proformat of your participation for our own administrative purposes. Kindly send back the proformat by 19
th
July to: Juliana Silva Félix ([email protected]).
The samples will be sent to you in the beginning of September. You will find additional information on the form “Shipping kit ILC001 2013” that you will receive by e-mail. You will also receive more detailed instructions for the compilation of the results on the form "Instructions Excel ILC001 2013". The deadline for submission of results is 30
th October 2013.
If you have any question, please contact Juliana Silva Félix ([email protected]). Sincerely yours,
Catherine Simoneau
Dr. Catherine Simoneau Operating Manager, European Reference Laboratory for Food Contact Materials European Commission, DG-Joint Research Centre Institute for Health and Consumer Protection Unit Chemical Assessment and Testing, T.P. 260 Ispra Va 21020 Italy
Cc: P. Aguar (JRC), D. Rembges (JRC)
A. Schaefer, B. Schupp (SANCO)
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Annex 2. Letter for confirmation of participation to ILC001-2013
EUROPEAN COMMISSION GENERAL DIRECTORATE JRC JOINT RESEARCH CENTRE Institute for Health and Consumer Protection – IHCP Unit Chemical Assessment and Testing
Ispra July 9th 2013
Participation to EURL-FCM ILC001 2013 Interlaboratory comparison (ILC) exercise
on food simulant E
CONFIRMATION OF PARTICIPATION
Your Name:
Organization:
Address:
E-mail:
Phone:
item YES NO
I have already the package with the files for filling the results and especially RingDat3.exe file from last year and I need only lab files for this year’s ILC
I don’t have the package with the files for filling the results from last year
Kindly send back this proformat to: Juliana Silva Félix ([email protected]) by the 19th of July 2013. The samples will be sent to you in the beginning of September. You will find additional information in the kit sent. The deadline for submission of results is 30th October 2013. Sincerely yours,
Catherine Simoneau
mailto:[email protected]
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Annex 3. Shipping kit letter accompanying the sample TNX1 to ILC001 2013
EUROPEAN COMMISSION GENERAL DIRECTORATE JRC JOINT RESEARCH CENTRE Institute for Health and Consumer Protection – IHCP Unit Chemical Assessment and Testing
Ispra 9th July 2013
Shipping kit for Interlaboratory comparison (ILC) exercise on food simulant E - EURL-FCM ILC001 2013
Shipping kit - samples
- TNX1 – One glass bottle containing food simulant E spiked with the unknown substances1
- Blank TNX1 – For control purposes: one glass vial containing the food simulant E not spiked, from the same batch of the spiked one
- One plastic box containing virgin Tenax® TA 60/80 (10 g)* – (NRLs only) Shipping kit – documentation (send by email)
Letter of confirmation of receipt (Sample Receipt ILC001 2013) ; Letter with instructions for the compilation of the results for interlaboratory
comparative testing (Instructions Excel ILC001 2013); Electronic excel file” ILC001 2013 test result TNX.xls”.
Storage
- Sample TNX1 – should be kept in the fridge at + 4°C. Instructions Use the excel form “ILC001 2013 test result TNX.xls” to provide your results. 1 Phthalates eventually present in the food simulant E could come from contamination source and were not intentionally spiked.
* Remember that the Tenax® must be cleaned before the first use.
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Annex 4. Letter of confirmation of receipt of the sample to ILC001 2013
EUROPEAN COMMISSION GENERAL DIRECTORATE JRC JOINT RESEARCH CENTRE Institute for Health and Consumer Protection – IHCP Unit Chemical Assessment and Testing
Ispra July 9th 2013
Participation to Interlaboratory comparison (ILC) exercise on food simulant E - EURL-FCM ILC001 2013
CONFIRMATION OF RECEIPT OF THE SAMPLES
Please return this form to confirm that the sample package has arrived. In case the package
is damaged, please state this on the form and contact us immediately.
Your Name:
Organization:
E-mail:
Phone:
Any remarks …………………….
Date arrival package …………………….
Signature …………………….
Kindly send back this form to: Juliana Silva Félix ([email protected]) Sincerely yours,
Dr. Catherine Simoneau Operating Manager, ЕU Laboratory for Food Contact Materials European Commission, DG-Joint Research Centre Institute for Health and Consumer Protection Unit CAT, T.P. 260 Ispra Va 21020 Italy
mailto:[email protected]
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Annex 5. Letter Instructions for the compilation of the results from ILC001 2013
EUROPEAN COMMISSION GENERAL DIRECTORATE JRC JOINT RESEARCH CENTRE Institute for Health and Consumer Protection – IHCP Unit Chemical Assessment and Testing
Ispra July 9
th 2013
Instructions for the compilation of the results for Interlaboratory comparison
(ILC) exercise on food simulant E - EURL-FCM ILC001 2013
DEADLINE: Monday, October 30th
2013
You can find in the table below a list of ten substances. Only five substances from that list are spiked
in the food simulant E. You need to identify and quantify them. Additionally you should be able to
identify and quantify other two unknown substances, also spiked in the same simulant E but not
included in the list.
LIST OF 10 SUBSTANCES
1-Octene
DEHA
Diphenylbutadiene
Benzophenone
Laurolactam
Irganox 1076
2-Ethyl-1-hexanol
Benzyl butyl phthalate
Chimasorb 81
Caprolactam
UNKNOWN SUBSTANCES
XXX
XXX
Perform four replicates for the sample TNX1 and report the name of the substances and their
concentration using the unit of measure specified in the Excel form “ILC001 2013 test result TNX.xls”.
Please fill your results and send it back by e-mail to Juliana Silva Félix (juliana.silva-
[email protected]) by October 30th
2013. If you have any question, please contact Juliana Silva
Félix ([email protected]), ph. +39.0332.789782
Sincerely yours,
Dr. Catherine Simoneau Operating Manager, ЕU Laboratory for Food Contact Materials European Commission, DG-Joint Research Centre Institute for Health and Consumer Protection Unit CAT, T.P. 260 Ispra Va 21020 Italy
mailto:[email protected]:[email protected]:[email protected]
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Annex 6. Procedure for the preparation of the spiked food simulant E 1. Washing of the 10 L round bottom flask:
10 L mixing round bottom flask was washed in a dish washer, then filled with the deionised water (resistivity 18 MΩ.cm @ 25 °C) and mixed;
The water was removed;
The mixing bottle was filled with 0.5 L of pentane (Aldrich, HPLC grade + 99%) and shaked;
Pentane was removed. 2. Preparation of the spiking solutions: a) Stock solution of ACPH, BP, DEHA, DTBP, ETHX and OCT in hexane (approx. 1000 mg/L)
50 mg of each compound was weighted separately into a 50 mL class A volumetric flask and dissolved in hexane;
the flask was filled up to the mark with hexane. b) Stock solution of CAP in ethanol (approx. 1000 mg/L)
50 mg of caprolactam was weighted into a 50 mL class A volumetric flask and dissolved in ethanol;
the flask was filled up to the mark with ethanol. c) Spiking solution of ACPH, BP, CAP, DEHA, DTBP, ETHX and OCT in pentane
10 mL of ACPH, 0.6 mL of BP, 15 mL of CAP, 9 mL of DEHA, 7.5 mL of DTBP, 10 mL of ETHX and 15 mL of OCT (from the stock solutions) were pipetting into the 2 L volumetric flask;
the flask was filled up to the mark with pentane; 3. Preparation of the spiking food simulant E:
1 kg of the cleaned simulant was weighted and transferred into the 10 L round bottom flask;
2 L of the spiking solution in pentane was add to the simulant;
The volumetric flask was rinsed by other 2 liters of pentane and all the solvent was collected into the round bottom flask;
The flask was closed and the simulant was mixed continuously for 2.5 hours;
The flask was opened and the simulant was mixed till the complete evaporation of the pentane (approximately 2 days).
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Annex 7. Form for the compilation of the results in non-electronic format
I. Determination of the subtances from the list reported in the form "Instructions Excel ILC001 2013.doc"
No. Substance name Replicate 1 (mg/kg) Replicate 2 (mg/kg) Replicate 3 (mg/kg) Replicate 4 (mg/kg) remark
1
2
3
4
5
II. Determination of the unknown substances
1
2
Place and date
.................. ........................
Laboratory Manager Signature
FCM EURL-NRL ILC 2013_001 Food Simulant E
TEST RESULTS
Lab Code - LC00......
TNX 1
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Annex 8. Results of the homogeneity study
Measurand Mean
(mg/kg) Mode
s(target) s(target)
[%]
F-test Check for significant
heterogeneity
ISO 13528 Check for sufficient
homogeneity
Harmonized Protocol Test on significant
heterogeneity
1-OCT 14.502 HORWITZ 10.697 OK OK OK
ETHX 9.470 HORWITZ 11.405 OK OK OK
ACPH 10.549 HORWITZ 11.221 OK OK OK
CAP 11.944 HORWITZ 11.014 OK OK OK
DTBP 6.364 HORWITZ 12.108 OK OK OK
BP 0.645 HORWITZ 17.090 OK OK OK
DEHA 9.348 HORWITZ 11.427 OK OK OK
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Annex 9. Results of the stability study and the statistical evaluation
Compound Test
condition Intercept
(b0) Slope (b1)
s(b1) t(α=0.95,n-
2)·s(b1) |b1|< t(α=0.95,n-
2)·s(b1)
ACPH
40ºC 10.6176 -0.0016 0.0029 0.0092 OK
20ºC 10.5903 -0.0004 0.0034 0.0107 OK
4ºC 10.5829 -0.0001 0.0013 0.0043 OK
BP
40ºC 0.6227 -0.0003 0.0004 0.0013 OK
20ºC 0.6235 -0.0003 0.0004 0.0011 OK
4ºC 0.6236 -0.0002 0.0004 0.0012 OK
CAP
40ºC 11.7981 0.0148 0.0080 0.0254 OK
20ºC 12.1394 0.0075 0.0095 0.0301 OK
4ºC 12.2614 0.0054 0.0093 0.0297 OK
DEHA
40ºC 9.1618 -0.0033 0.0127 0.0404 OK
20ºC 9.2355 0.0110 0.0105 0.0334 OK
4ºC 9.2017 0.0127 0.0138 0.0439 OK
DTBP
40ºC 6.0009 -0.0147 0.0066 0.0209 OK
20ºC 6.3496 0.0031 0.0031 0.0100 OK
4ºC 6.2302 -0.0042 0.0036 0.0116 OK
ETHX
40ºC 9.4671 -0.0041 0.0042 0.0132 OK
20ºC 9.4132 -0.0004 0.0041 0.0130 OK
4ºC 9.4102 0.0007 0.0027 0.0085 OK
1-OCT
40ºC 13.4768 -0.0080 0.0459 0.1460 OK
20ºC 13.6078 -0.0107 0.0299 0.0951 OK
4ºC 13.9415 -0.0142 0.0434 0.1382 OK
A) 1-Octene
y = -0.0142x + 13.9415
y = -0.0107x + 13.6078
y = -0.0080x + 13.4768
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
0 10 20 30 40 50 60
1-OCTENE
4°C
20°C
40°C
mg
/kg
Time [days]
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B) 2-Ethyl-1-hexanol
y = 0.0007x + 9.4102
y = -0.0004x + 9.4132
y = -0.0041x + 9.4671
6.00
7.00
8.00
9.00
10.00
11.00
12.00
0 10 20 30 40 50 60
2-ETHYL-1-HEXANOL
4°C
20°C
40°C
mg
/kg
Time [days]
C) Acetophenone
y = -0.0001x + 10.5829
y = -0.0004x + 10.5903
y = -0.0016x + 10.6176
9.00
9.50
10.00
10.50
11.00
11.50
12.00
0 10 20 30 40 50 60
ACETOPHENONE
4°C
20°C
40°C
mg
/kg
Time [days]
D) Caprolactam
y = 0.0054x + 12.2614
y = 0.0075x + 12.1394
y = 0.0148x + 11.7981
10.00
10.50
11.00
11.50
12.00
12.50
13.00
13.50
14.00
0 10 20 30 40 50 60
CAPROLACTAM
4°C
20
40°C
mg
/kg
Time [days]
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E) 2,4-Di-tert-butylphenol
y = -0.0042x + 6.2302
y = 0.0031x + 6.3496
y = -0.0147x + 6.0009
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
0 10 20 30 40 50 60
2,4-DI-TERT-BUTYLPHENOL
4°C
20°C
40°C
mg
/kg
Time [days]
F) Benzophenone
y = -0.0002x + 0.6236
y = -0.0003x + 0.6235
y = -0.0003x + 0.6227
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0 10 20 30 40 50 60
BENZOPHENONE
4°C
20°C
40°C
mg
/kg
Time [days]
G) DEHA
y = 0.0127x + 9.2017
y = 0.0110x + 9.2355
y = -0.0033x + 9.1618
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
0 10 20 30 40 50 60
BIS(2-ETHYLHEXYL) ADIPATE
4°C
20°C
40°C
mg
/kg
Time [days]
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Annex 10. Methodologies used by the participants
6h Soxhlet ACTN80%
ACTN4%
Reflux diethylether
4%
Soxhlet ≠ solvents
4%
MEOH (5X)4%
ASE ACTN4%
Cleaning Tenax
HX60%
ACTN10%
ACN12%
Headspace5%
MEOH5%
Diethylether2%
HX-DCM2%
ETOH2%
THF2%
Extraction
Spiking Tenax75%
Solvents18%
Solvents/ Tenax
7%
Calibration
Internal Standard
69%
External Standard
31%
Quantification
GC-MS80%
GC-FID8%
HPLC-DAD6%
LC-MS3%
NMR3%
Analytical Technique
HP-5MS58%
DB-17HT16%
SBP-6245%BP-20/ODS2
2%
DB-12%
C182%
RTX-5 amine3%
TG-17Sil MS3%
RTX-35MS3%
HT-8PCB3%
CPWAX3%
Chromatographic Column
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European Commission
EUR 26468 EN – Joint Research Centre – Institute for Health and Consumer Protection
Title: Report of an Interlaboratory Comparison from the European Reference Laboratory for Food Contact Materials:
ILC001-2013 – Proficiency Testing on Food Simulant E containing a cocktail of potential migrant substances
Author(s): Juliana Silva Félix, Giorgia Beldì and Catherine Simoneau
Luxembourg: Publications Office of the European Union
2013 – 45 pp. – 21.0 x 29.7 cm
EUR – Scientific and Technical Research series –ISSN 1831-9424 (online)
ISBN 978-92-79-35268-3 (pdf)
doi:10.2788/6263
Abstract This report presents the results of the EU Interlaboratory comparison (ILC) of the EURL-FCM, which were obtained in the identification and the quantification of unknown substances in the food simulant E. Regulation (EU) No 10/2011 establishes poly(2,6-diphenyl-p-phenylene oxide) (e.g. Tenax®) as food simulant E for testing migration compliance of plastics in contact with dry foodstuffs. The choice of the substances was based on the recent scientific literature related to migration from food contact materials (plastic and paperboard) into simulant E. The simulant E was spiked with 7 substances at given concentrations the closest as possible to its own specific migration limit (SML), when available in Regulation (EU) 10/2011 or tailored for the exercise. A list containing 10 substances in which 5 were effectively present in the simulant was distributed to the participants. The other 2 unknown substances were not reported in the list. Homogeneity and stability studies were conducted. As this ILC was a proficiency testing, the National Reference Laboratories (NRLs) and the Official Control Laboratories (OCLs) had to identify and quantify the unknown substances using analytical methods of their choice. The laboratories performance was successful with more than 61% satisfactory results over the entire exercise which was quite complex and extensive. Considering the individual substances, more than 80% of satisfactory quantification within tolerance limits was achieved (ACPH 94%, BP 80%, CAP 86%, DEHA 82%, DTBP 88%, ETHX 83% and OCT 87%). The laboratories performance concerning the identification of the unknown substances was successful, with 25 correct results out of 30 (83%), even taking into account the complexity of the exercise. This exercise was the first Proficiency Testing carried out at EU level on Food Simulant E with the aim to evaluate the performance of the National Reference Laboratories among the Member States. The ILC001-2013 provided the first successful attempt to derive data at EU level for identification and quantification of potential migrants including unknowns coming from food contact material, as plastic packaging and paperboard, in food simulant E.
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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.
LB
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46
8-E
N-N
doi:10.2788/6263 ISBN 978-92-79-35268-3 (pdf)