Results of Proficiency Test Phthalates in Plastics May 2015

Transcription

1 Results of Proficiency Test Phthalates in Plastics May 2015 Organised by: Author: Corrector: Report: Institute for Interlaboratory Studies Spijkenisse, the Netherlands ing. C.M. Nijssen-Wester dr. R.G. Visser & ing. N. Boelhouwer iis15p03 July 2015

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3 Spijkenisse, July 2015 Institute for Interlaboratory Studies CONTENTS 1 INTRODUCTION SET UP ACCREDITATION PROTOCOL CONFIDENTIALITY STATEMENT SAMPLES ANALYSIS RESULTS STATISTICS GRAPHICS Z-SCORES EVALUATION EVALUATION PER PHTHALATE/SAMPLE PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES COMPARISON OF THE PROFICIENCY TEST OF MAY 2015 WITH PREVIOUS PTS Appendices: 1. Data, statistical results and graphic results Method information Number of participating laboratories per country Abbreviations and literature Phthalates in Plastics: iis15p03 page 3 of 52

4 Institute for Interlaboratory Studies Spijkenisse, July INTRODUCTION Phthalates act as softeners and are commonly used as plasticizers in PVC. Phthalates may migrate fairly easily from PVC into the environment. Because phthalates appeared to have negative effects on health and the environment, regulations have been set up. The manufacture and import of toys into the EC is regulated by the European Union s Toy Directive 88/378, with in addition the general product safety, which is covered by EU directive 2001/95 and Council Directive + amendments 76/769/EEC. These regulations govern conditions related to toys intended for children under 36 months of age (this group often suck or chew on toys and phthalates migrate easily). Therefore plastic toys are not allowed to contain either more than 0.1 %M/M of DEHP, DBP and BBP combined or more than 0.1%M/M of DINP (3 mixtures, ref. 21), DIDP (2 mixtures, ref 22) and DNOP combined. The following phthalates are banned or suspect. benzylbutylphthalate (BBP) CASno EINECS no bis(2-ethylhexyl)phthalate (DEHP) 1) CASno EINECS no di-ethylphthalate (DEP) CASno EINECS no di-butylphthalate (DBP) CASno EINECS no di-isobutylphtalate (DiBP) CASno EINECS no di-n-pentylphthalate (DnPP) CASno EINECS no di-cyclohexylphthalate (DCHP) CASno EINECS no di-n-octylphthalate (DNOP) CASno EINECS no di-isononylphthalate (DINP-1) CASno EINECS no di-isononylphthalate (DINP-2) CASno EINECS no di-isononylphthalate (DINP-3) CASno EINECS no di-isodecylphthalate (DIDP-1) CASno EINECS no di-isodecylphthalate (DIDP-2) CASno EINECS no ) DEHP is also known as di-(iso)-octylphthalate (DOP). The determination of phthalates in plastics is known to give problems with the comparability of laboratory results. The fact that phthalates, used in the plastic industry are not pure components, but complex (and overlapping) mixtures is one of the causes for these problems. However, no appropriate Plastic reference materials are yet available (ref. 20). As an alternative, participation in a proficiency test may enable laboratories to check their performance. Therefore, a proficiency test (laboratory-evaluating interlaboratory study) for the determination of phthalates in plastics was again organized by the Institute for Interlaboratory Studies in May In the 2015 iis interlaboratory study iis15p01, 188 laboratories in 41 different countries did participate. See appendix 3 for the number of participating laboratories per country. In this report the results of the proficiency test are presented and discussed. This report is also electronically available through the iis internet site page 4 of 52 Phthalates in Plastics: iis15p03

5 Spijkenisse, July 2015 Institute for Interlaboratory Studies 2 SET UP The Institute for Interlaboratory Studies in Spijkenisse was the organiser of this proficiency test. It was decided to send two different PVC samples. Both batches were a PVC granulate, especially prepared by a Chinese factory by addition of technical mixtures of phthalates to PVC and subsequent homogenization. Analyses were subcontracted to an ISO17025 accredited laboratory. 2.1 ACCREDITATION The Institute for Interlaboratory Studies in Spijkenisse, the Netherlands, is accredited in accordance with ISO/IEC 17043:2010, (R007), since January 2000, by the Dutch Accreditation Council (Raad voor Accreditatie, see also This PT falls under the accredited scope. This ensures strict adherence to protocols for sample preparation and statistical evaluation and 100% confidentially of participant s data. Feedback from the participants on the reported data is encouraged and customer s satisfaction is measured on regular basis by sending out questionnaires. 2.2 PROTOCOL The protocol followed in the organisation was the one as described for proficiency testing in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of April 2014 (iis-protocol, version 3.3). This protocol can be downloaded via the FAQ page of the iis website CONFIDENTIALITY STATEMENT All data presented in this report must be regarded as confidential and for use by the participating companies only. Disclosure of the information in this report is only allowed by means of the entire report. Use of the contents of this report for third parties is only allowed by written permission of the Institute for Interlaboratory Studies. Disclosure of the identity of one or more of the participating companies will be done only after receipt of a written agreement of the companies involved. 2.4 SAMPLES Two samples were prepared from two different bulk materials. The first sample was a purple coloured PVC, to which small, known amounts of DEP, DiBP, DEHP and DIDP were added, as well as tributyl acetyl citrate (TBAC). The batch of PVC was granulated after thoroughly mixing. From this batch, 200 plastic bags with 3 grams of granulate sample each were prepared and labelled # The homogeneity of the subsamples #15065 was checked by determination of all added phthalates on 8 stratified, randomly selected subsamples. Phthalates in Plastics: iis15p03 page 5 of 52

6 Institute for Interlaboratory Studies Spijkenisse, July 2015 DEP in %M/M DiBP in %M/M DEHP in %M/M DIDP in %M/M Sample # Sample # Sample # Sample # Sample # Sample # Sample # Sample # Table 1: homogeneity test results of the subsamples #15065 From the above test results the repeatabilities were calculated and compared with the repeatability of EN14372 in agreement with the procedure of ISO 13528, Annex B2 in the next table; DEP in %M/M DiBP in %M/M DEHP in %M/M DIDP in %M/M r (observed) # reference method EN14372:04 EN14372:04 EN14372:04 EN14372:04 r (ref. method) Table 2: evaluation of repeatabilities of phthalate contents of the subsamples #15065 The second sample was a green/blue coloured PVC, to which small, known amounts of DBP, DNOP, DCHP and DnPP were added as well as DEHT. The batch of PVC was granulated after thoroughly mixing. From this batch, 200 plastic bags of 3 gram of granulated sample each were prepared and labelled # The homogeneity of the subsamples #15066 was checked by determination of all added phthalates on seven (or six) stratified, randomly selected subsamples. DBP in %M/M DNOP in %M/M DCHP in %M/M DnPP in %M/M Sample # Sample # Sample # Sample # Sample # Sample # Sample # Table 3: homogeneity test results of the subsamples #15066 From the above test results the repeatabilities were calculated and compared with the repeatibility of EN14372 in agreement with the procedure of ISO 13528, Annex B2 in the next table; DBP in %M/M DNOP in %M/M DCHP in %M/M DnPP in %M/M r (observed) # reference method EN14372:04 EN14372:04 EN14372:04 EN14372: x R (ref. method) Table 4: evaluation of repeatabilities of phthalate contents of the subsamples #15066 page 6 of 52 Phthalates in Plastics: iis15p03

7 Spijkenisse, July 2015 Institute for Interlaboratory Studies As the observed repeatabilities of the results of the homogeneity tests were all in agreement with the respective target precision data, the homogeneity of subsamples #15065 and #15066 was assumed. To each of the participating laboratories, one sample of approx. 3 grams granulate, labelled #15065 and one sample of approx. 3 grams granulate, labelled #15066 were sent on April 22, ANALYSIS The participants were requested to determine and report eight individual phthalates (DINP, DBP, BBP, DHP, DIDP, DNOP, DEHP and DiBP) and other phthalates on both samples #15065 and # The participants were explicitly asked to treat the samples as if they were routine samples and to report the analytical results using the indicated units on the report form and not to round the test results, but report as much significant figures as possible. The participants were also asked not to report less than results which are above the detection limit, because such results can not be used for meaningful statistical calculations. To get comparable results a detailed report form, on which the units were prescribed, was sent together with each set of samples. Also a letter of instructions was added to the package. The laboratories were asked to complete the report form with the requested details of the methods used. 3 RESULTS During four weeks after sample despatch, the results of the individual laboratories were gathered. The original data are tabulated in the appendices of this report. The laboratories are presented by their code numbers. Directly after the deadline, a reminder fax was sent to those laboratories that had not yet reported. Shortly after the deadline, the available results were screened for suspect data. A result was called suspect in case the Huber Elimination Rule (a robust outlier test, see lit.5) found it to be an outlier. The laboratories that produced these suspect data were asked to check the results. Additional or corrected data are placed under 'Remarks' in the result tables in appendix 1. A list of abbreviations used in the tables can be found in appendix STATISTICS Statistical calculations were performed as described in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of April 2014 (iis-protocol, version 3.3) For the statistical evaluation the unrounded (when available) figures were used instead of the rounded results. Results reported as < or > were not used in the statistical evaluation. First, the normality of the distribution of the various data sets per determination was checked by means of the Lilliefors-test a variant of the Kolmogorov-Smirnov test and by the calculation of Phthalates in Plastics: iis15p03 page 7 of 52

8 Institute for Interlaboratory Studies Spijkenisse, July 2015 skewness and kurtosis. Evaluation of the three normality indicators in combination with the visual evaluation of the graphic Kernel density plot, lead to judgement of the normality being either unknown, OK, suspect or not OK. After removal of outliers, this check was repeated. Not all data sets proved to have a normal distribution, in which cases the statistical evaluation of the results should be used with due care. According to ISO 5725 (1986 and 1994, lit.8 and 9) the original results per determination were submitted subsequently to Dixon s, Grubbs' and Rosner outlier tests. Outliers are marked by D(0.01) for the Dixon s test, by G(0.01) or DG(0.01) for the Grubbs test and by R(0.01) for the Rosner General ESD test (ref. 15). Stragglers are marked by D(0.05) for the Dixon s test, by G(0.05) or DG(0.05) for the Grubbs test and by R(0.05) for the Rosner General ESD test (ref. 27). Both outliers and stragglers were not included in the calculations of averages and standard deviations. For each assigned value the uncertainty was determined in accordance with ISO Subsequently the calculated uncertainty was evaluated against the respective requirement based on the target reproducibility in accordance with ISO When the uncertainty passed the evaluation no remarks are made in the report. However, when the uncertainty failed the evaluation it is mentioned in the report and it will have consequences for the evaluation of the test results. Finally, the reproducibilities were calculated from the standard deviations by multiplying them with a factor of GRAPHICS In order to visualise the data against the reproducibilities from literature, Gauss plots were made, using the sorted data for one determination (see appendix 1). On the Y-axis the reported analysis results are plotted. The corresponding laboratory numbers are under the X-axis. The straight horizontal line presents the consensus value (a trimmed mean). The four striped lines, parallel to the consensus value line, are the +3s, +2s, -2s and -3s target reproducibility limits of the selected standard. Outliers and other data, which were excluded from the calculations, are represented as a cross. Accepted data are represented as a triangle. Furthermore, Kernel Density Graphs were made. This is a method for producing a smooth density approximation to a set of data that avoids some problems associated with histograms (see appendix 4, nos.17-18). Also a normal Gauss curve was projected over the Kernel Density Graph for reference. 3.3 Z-SCORES To evaluate the performance of the participating laboratories the z-scores were calculated. As it was decided to evaluate the performance of the participants in this proficiency test (PT) against the literature requirements, e.g. ASTM reproducibilities, the z-scores were calculated using a target standard deviation. This results in an evaluation independent of the spread of this page 8 of 52 Phthalates in Plastics: iis15p03

9 Spijkenisse, July 2015 Institute for Interlaboratory Studies interlaboratory study. The target standard deviation was calculated from the literature reproducibility by division with 2.8. When a laboratory did use a test method with a reproducibility that is significantly different from the reproducibility of the reference test method used in this report, it is strongly advised to recalculate the z-score, while using the reproducibility of the actual test method used this in order to evaluate whether the reported test result is fit-for-use. In case no literature reproducibility was available, other target values were used. In some cases literature repeatability is available; in other cases a reproducibility of a former iis proficiency test could be used and also the Horwitz equation can be used to estimate target reproducibility. The z-scores were calculated according to: z (target) = (result - average of PT) / target standard deviation Absolute values for z<2 are very common and absolute values for z>3 are very rare. The usual interpretation of z-scores is as follows: z < 1 good 1 < z < 2 satisfactory 2 < z < 3 questionable 3 < z unsatisfactory 4 EVALUATION In this interlaboratory study no problems were encountered with the dispatch of the samples. Four participants did not report any test results and twenty-nine participants reported after the final reporting date. Finally, 184 laboratories reported 1014 numerical results. Observed were 43 statistically outlying test results, which is 4.2% of all results. In proficiency studies outlier percentages of 3% - 7.5% are quite normal. 4.1 EVALUATION PER PHTHALATE AND PER SAMPLE In this section the results are discussed per component. A test method was mentioned on the report form by 112 laboratories. Of this group, 81 laboratories performed CPSC-CH-C , a test method based on THF extraction. From the test details of all 184 reporting laboratories, it is clear that no less than 135 laboratories used THF as extraction solvent. Some other standard test methods were also used: EN14372 (Soxhlet extraction with diethyl ether) and in-house methods. Regretfully, the CPSC method does not contain any precision statements. Therefore, the requirements from the standardised method EN14372, Child use and care articles, Cutlery and feeding utensils, Safety requirements and tests were used for evaluation of the results of this interlaboratory study. Phthalates in Plastics: iis15p03 page 9 of 52

10 Institute for Interlaboratory Studies Spijkenisse, July 2015 In EN14372, only a relative within-laboratory standard deviation RSDr is given. Multiplication of RSDr by 2.8 gives the repeatability. Multiplication of the repeatability by 3 gives a good estimate of the target reproducibility. General: Almost all laboratories did identify the materials of #15065 and #15066 correctly as PVC (see appendix 2). The majority of the group identified all added banned phthalates correctly: #15065 contained DIDP, DEHP, DiBP and DEP and sample #15066 contained DBP, DNOP, DnPP and DCHP. Sample #15065 DIDP: The determination of DIDP may be problematic at the level of %M/M. Fourteen statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. DEHP: DiBP: DEP: The determination of DEHP may be problematic at the level of %M/M. Eight statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. The determination of DiBP may be problematic at the level of %M/M. Three statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. The determination of DEP may be problematic at the level of %M/M. Two statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. For DINP, DBP, BBP, DNOP, and DHP the group of participants agreed on a concentration below <0.05 or <0.02 %M/M. Therefore no significant conclusions were drawn. Sample #15066 DBP: The determination of DBP may be problematic at the level of %M/M. Five statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. DNOP: The determination of DNOP may be very problematic at the level of %M/M. Seven statistical outliers were observed. The calculated reproducibility after rejection of the statistical outliers is not at all in agreement with the estimated reproducibility of EN14372:04. Eight laboratories reported a possibly false negative test result. page 10 of 52 Phthalates in Plastics: iis15p03

11 Spijkenisse, July 2015 Institute for Interlaboratory Studies DnPP: DCHP: The determination of DnPP may be problematic at the level of %M/M. Two statistical outliers were detected. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. The determination of DCHP may be problematic at the level of %M/M. Two statistical outliers were observed. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the estimated reproducibility of EN14372:04. For DINP, BBP, DIDP, DEHP, DiBP and DHP the group of participants agreed on a concentration below <0.02 %M/M. Therefore no significant conclusions were drawn. 4.2 PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES A comparison has been made between the reproducibilities as found for the group of participating laboratories and the estimated reproducibilities of EN14372:2004 (R target ) in the next tables: Parameter Unit n Average 2.8 * sd R (target) DIDP %M/M DEHP %M/M DiBP %M/M DEP %M/M Table 5: overview of results for sample #15065 Parameter Unit n Average 2.8 * sd R (target) DBP %M/M DNOP %M/M DnPP %M/M DCHP %M/M Table 6: overview of results for sample # COMPARISON OF THE PROFICIENCY TEST OF MAY 2015 WITH PREVIOUS PTS May 2015 May 2014 April 2013 February 2012 Number of reporting labs Number of results reported Statistical outliers Percentage outliers 4.2% 7.9% 4.3% 5.5% Table 7: comparison with previous proficiency tests In proficiency tests, outlier percentages of 3% - 7.5% are quite normal. Phthalates in Plastics: iis15p03 page 11 of 52

12 Institute for Interlaboratory Studies Spijkenisse, July 2015 In table 8 the observed uncertainties in this PT are compared with the uncertainties as observed in previous PTs. May 2014 May 2014 April 2013 February 2012 February 2011 February 2010 February 2009 RSDR (EN14372) DINP 1) T 60 E -- 9 DBP ) T 22 E 9 DEHP T 55 E 16 E 19 T 9 BBP E 45 T 9 DIDP ) DNOP DHP DiBP DEP DnPP DCHP Table 8: Comparison of uncertainties (relative in %) of phthalates in this PT and previous PTs (E=EN14372; T=THF dissolution) 1) Mix of DINP-1 and DINP-2 isomers 2) sample with 37% DINP present From significant differences between the EN14372 results and the results from THF dissolution were observed. In the PTs of this was no longer the case. In the proficiency test of 2015, the majority of laboratories used THF as extraction solvent. The uncertainty appears to stabilise at 13-17% for all phthalates except DNOP. The estimated target (RSDR) of 9%, derived from the repeatability coefficient of variation of EN14372 (RSDr = 3%) may be too strict to be met. A new precision statement in EN14372, containing a reproducibility value, is therefore needed. Perhaps the repeatability coefficient of variation of EN14372 is underestimated. From the observed RSDR range 13-17%, a repeatability coefficient of variation of 4-5% would be more realistic. page 12 of 52 Phthalates in Plastics: iis15p03

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14 Institute for Interlaboratory Studies Spijkenisse, July 2015 APPENDIX 1 Determination of DIDP on sample #15065; results in %M/M lab method value mark z(targ) lab method value mark z(targ) ISO14389: ISO R(0.05) CPSC-CH-C R(0.05) CPSC-CH-C GB/T R(0.05) CPSC-CH-C C,R(0.05) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C R(0.01) CPSC-CH-C C ISO CPSC-CH-C ISO14389Mod CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C INH in house CPSC-CH-C CPSC-CH-C CPSC-CH-C ISO CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house JTSS-ST CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house CPSC-CH-C CPSC-CH-C C CPSC-CH-C EN14372: CPSC-CH-C C,R(0.05) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C in house CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C R(0.05) CPSC-CH-C CPSC-CH-C CPSC-CH-C EN CPSC-CH-C CPSC-CH-C C,R(0.05) R(0.05) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C C,R(0.05) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C R(0.05) CPSC-CH-C EN CPSC-CH-C EN14372: C,R(0.05) GB/T in house C CPSC-CH-C CPSC-CH-C page 14 of 52 Phthalates in Plastics: iis15p03

15 Spijkenisse, July 2015 Institute for Interlaboratory Studies SN/T KS M CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C in house R(0.05) in house INH C,R(0.05) CPSC-CH-C ISO14389: CPSC-CH-C CPSC-CH-C JTSS-ST CPSC-CH-C CPSC-CH-C ST CPSC-CH-C CPSC-CH-C normality suspect n 166 outliers 14 mean (n) st.dev. (n) R(calc.) R(EN14372:04) Compare R(Horwitz): Lab 622 first reported: n.d. Lab 2138 also reported: (LC-MS) Lab 2228 first reported: Lab 2264 first reported: Lab 2320 first reported: Lab 2415 first reported: Lab 2497 first reported: Lab 2504 first reported: Lab 2581 first reported: Lab 2595 first reported: Lab 2670 first reported: Lab 2672 first reported: Lab 3239 first reported: Kernel Density Phthalates in Plastics: iis15p03 page 15 of 52

16 Institute for Interlaboratory Studies Spijkenisse, July 2015 Determination of DEHP on sample #15065; results in %M/M lab method value mark z(targ) lab method value mark z(targ) ISO14389: ISO CPSC-CH-C R(0.05) CPSC-CH-C C R(0.05) GB/T CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C ISO KS M R(0.05) CPSC-CH-C ISO14389Mod CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C INH in house C CPSC-CH-C CPSC-CH-C CPSC-CH-C ISO CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house JTSS-ST CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C in house CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C C,R(0.01) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C in house CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C C CPSC-CH-C C CPSC-CH-C CPSC-CH-C C,R(0.01) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C R(0.01) CPSC-CH-C EN CPSC-CH-C EN14372: C,R(0.01) GB/T in house CPSC-CH-C CPSC-CH-C page 16 of 52 Phthalates in Plastics: iis15p03

17 Spijkenisse, July 2015 Institute for Interlaboratory Studies SN/T KS M CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C C in house in house in house INH C,R(0.05) CPSC-CH-C ISO14389: CPSC-CH-C C ASTM F CPSC-CH-C JTSS-ST CPSC-CH-C CPSC-CH-C ST CPSC-CH-C CPSC-CH-C normality not OK n 176 outliers 8 mean (n) st.dev. (n) R(calc.) R(EN14372:04) Compare R(Horwitz): Lab 1051 first reported: Lab 2213 first reported: 0.42 Lab 2264 first reported: Lab 2295 first reported: Lab 2296 first reported: Lab 2390 first reported: Lab 2415 first reported: Lab 2442 first reported: 0.23 Lab 2497 first reported: Lab 2504 first reported: Lab 2581 first reported: Lab 2595 first reported: < Lab 2670 first reported: Lab 3182 first reported: Lab 3237 first reported: Lab 3239 first reported: Kernel Density Phthalates in Plastics: iis15p03 page 17 of 52

18 Institute for Interlaboratory Studies Spijkenisse, July 2015 Determination of DiBP on sample #15065; results in %M/M lab method value mark z(targ) lab method value mark z(targ) ISO14389: ISO CPSC-CH-C CPSC-CH-C GB/T CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C C ISO R(0.05) CPSC-CH-C ISO14389Mod CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C INH in house CPSC-CH-C CPSC-CH-C CPSC-CH-C ISO CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house JTSS-ST CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house CPSC-CH-C C CPSC-CH-C EN14372: CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C in house CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN CPSC-CH-C detected CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C R(0.01) CPSC-CH-C EN CPSC-CH-C GB/T in house CPSC-CH-C CPSC-CH-C page 18 of 52 Phthalates in Plastics: iis15p03

19 Spijkenisse, July 2015 Institute for Interlaboratory Studies SN/T KS M CPSC-CH-C CPSC-CH-C C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN14372: CPSC-CH-C in house in house in house INH C,R(0.01) CPSC-CH-C ISO14389: CPSC-CH-C CPSC-CH-C CPSC-CH-C ST CPSC-CH-C CPSC-CH-C normality suspect n 162 outliers 3 mean (n) st.dev. (n) R(calc.) R(EN14372:04) Compare R(Horwitz): Lab 2228 first reported: Lab 2295 first reported as DHP Lab 2296 first reported: Lab 2301 first reported as DHP Lab 2406 first reported: <0.010 Lab 2415 first reported: Lab 2504 first reported: Lab 3212 first reported: Lab 3239 first reported: Kernel Density Phthalates in Plastics: iis15p03 page 19 of 52

20 Institute for Interlaboratory Studies Spijkenisse, July 2015 Determination of DEP on sample #15065; results in %M/M lab method value mark z(targ) lab method value mark z(targ) ISO14389: ISO CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C ISO CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C in house in house CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C C CPSC-CH-C R(0.01) CPSC-CH-C CPSC-CH-C CPSC-CH-C CPSC-CH-C EN CPSC-CH-C EN14372: C,R(0.01) in house CPSC-CH-C page 20 of 52 Phthalates in Plastics: iis15p03

21 Spijkenisse, July 2015 Institute for Interlaboratory Studies CPSC-CH-C EN14372: in house in house INH ISO14389: CPSC-CH-C normality OK n 56 outliers 2 mean (n) st.dev. (n) R(calc.) R(EN14372:04) Compare R(Horwitz): Lab 2581 first reported: Lab 2670 first reported: Kernel Density Phthalates in Plastics: iis15p03 page 21 of 52

22 Institute for Interlaboratory Studies Spijkenisse, July 2015 Determination of DINP, DBP and BBP on sample #15065; results in %M/M Lab method DINP mark DBP mark BBP mark remark < < n.d. 622 n.d. n.d. n.d CPSC-CH-C <0.01 <0.01 < CPSC-CH-C < < ISO n.d. n.d n.d. n.d ISO14389Mod. <0.02 <0.02 < CPSC-CH-C n.d. n.d. n.d CPSC-CH-C <0.001 <0.001 < INH n.d. n.d. n.d CPSC-CH-C <0.010 <0.010 < CPSC-CH-C n.d. n.d. n.d CPSC-CH-C <0.010 <0.010 < <0.005 <0.005 < CPSC-CH-C n.d. n.d. n.d JTSS-ST2012 n.d. n.d. n.d <0.01 < CPSC-CH-C <0.010 <0.010 < CPSC-CH-C n.d. n.d. n.d CPSC-CH-C EN14372:2004 <0.02 <0.01 < n.d. n.d. n.d <0.01 < CPSC-CH-C <0.010 < n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d n.d. n.d. n.d <0.010 <0.004 < EN14372 n.d. n.d. n.d CPSC-CH-C <0.005 <0.005 < CPSC-CH-C <0.01 < CPSC-CH-C n.d. n.d CPSC-CH-C <0.01 <0.01 < CPSC-CH-C CPSC-CH-C n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d n.d. n.d. n.d C n.d. n.d. n.d CPSC-CH-C <0.005 <0.005 < EN n.d. n.d CPSC-CH-C n.d. n.d GB/T22048 n.d. n.d. n.d n.d. n.d. n.d CPSC-CH-C n.d. n.d. page 22 of 52 Phthalates in Plastics: iis15p03

23 Spijkenisse, July 2015 Institute for Interlaboratory Studies 2374 <0.005 <0.005 < ISO n.d. n.d. n.d CPSC-CH-C <0.010 < GB/T22048 n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d <0.010 <0.005 < CPSC-CH-C <0.010 < CPSC-CH-C <0.01 <0.01 < CPSC-CH-C n.d. n.d. n.d n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d CPSC-CH-C n.d. n.d CPSC-CH-C <0.01 < CPSC-CH-C <0.005 <0.005 < n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d CPSC-CH-C in house <0.01 < CPSC-CH-C CPSC-CH-C n.d. n.d. n.d CPSC-CH-C <0.100 <0.100 < CPSC-CH-C n.d. n.d. n.d <0.005 <0.005 < CPSC-CH-C <0.01 <0.01 < CPSC-CH-C <0.01 <0.01 < CPSC-CH-C n.d. n.d. n.d <0.4 <0.01 < n.d. n.d. n.d n.d. n.d. n.d CPSC n.d. n.d. n.d <0.01 <0.01 < n.d. n.d. n.d CPSC-CH-C <0.01 < n.d. n.d. n.d < < < n.d. n.d. n.d n.d. n.d. n.d CPSC-CH-C n.d. n.d. n.d CPSC-CH-C <0.03 <0.03 < CPSC-CH-C n.d. n.d. n.d n.d. n.d. n.d EN14372:2004 n.d. n.d. C n.d n.d. n.d. n.d in house <0.01 <0.01 < CPSC-CH-C n.d. n.d. n.d. Phthalates in Plastics: iis15p03 page 23 of 52