Validation of analysis of phthalates in wines (OIV-OENO 477-2013)
RESOLUTION OIV-OENO 596-2019
VALIDATION OF ANALYSIS OF PHTHALATES IN WINES (OIV OENO 477-2013)
|
WARNING: this resolution amends the following resolution: OIV-OENO 477-2013 |
THE GENERAL ASSEMBLY,
IN VIEW of article 2, paragraph 2 iv of the Agreement of 3 April 2001 establishing the International Organisation of Vine and Wine,
CONSIDERING the proposal of the “Methods of Analysis” Sub-commission,
CONSIDERING the resolution OIV-OENO 477-2013 “detection and assay of phthalates in wines”, adopted in 2013,
DECIDES to complete the field of application of the resolution OIV-OENO 477-2013 through a footnote by listing the phthalates adopted as type II (DCHP BBP DBP DIBP DEP) and those remaining adopted as type IV (DIDP DINP DNOP DEHP DMP).
The classification of analytical methods is described in the OIV-MA-AS1-03 sheet of the Compendium of International Methods of Analysis of Wines and Musts,
DECIDES to amend the method of analysis OIV-MA-AS323-10 by adding the following document as annexe:
VALIDATION OF ANALYSIS OF PHTHALATES IN WINES
1. Executive Summary
The Institute for Reference Materials and Measurements (IRMM) organised in close collaboration with the International Organisation of Vine and Wine (OIV) this collaborative study to validate Compendium method OIV-MA-AS323-10:2013 for the determination of ten phthalates in wine by gas chromatography - mass spectrometry (GC-MS).
The design of the method performance study complied with provisions given in ISO 5725-2 and those established by the OIV. The test samples consisted of red wine, white wine, and sweet wine presented as blind duplicates (see Table 1).
The wines were spiked at IRMM, bottled into ampoules, and dispatched to the participants of the validation study.
In addition to the test samples, participants received a deuterated phthalate solution, in order to be able to prepare the internal standard solutions.
The participants of the study were identified by the OIV following a pre-validation study for the method. They comprised laboratories from Europe, Asia, South America and Australia (see Table 2).
The evaluation of the reported results was performed according to ISO 5725-2 and ISO 5725-4, as well as the provisions established by the OIV. Relative standard deviations for reproducibility were mostly within the range of 9% to 71%.
Table 1
|
Sample |
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
|
Nature |
White wine |
Red wine |
Sweet wine |
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2. Participants in the study
Table 2: Participants in the study
|
Analab Chile S.A. |
Chile |
|
Animal & Plant & Food Inspection Centre, Tianjin Exit- Entry Inspection and Quarantine Bureau |
People's Republic of China |
|
Bureau Interprofessionnel du Cognac |
France |
|
Central National de Verificare a Calitatii Productiei Alcoolice |
Republic of Moldova |
|
Chemisches und Veterinaeruntersuchungsamt Stuttgart |
Germany |
|
Escola Superior de Biotecnologia Universidade Católica Portuguesa |
Portugal |
|
Instituto Nacional de Vitivinicultura Departamento de Normas Analiticas Especiales |
Argentina |
|
Laboratorio Arbitral Agroalimentario |
Spain |
|
Laboratoire DUBERNET |
France |
|
Miguel Torres S.A. |
Spain |
|
SAILab |
Spain |
|
SCL Laboratoire de Bordeaux |
France |
|
SCL Laboratoire de Montpellier |
France |
|
The Australian Wine Research Institute |
Australia |
3. Evaluation of submitted results
The fitness-for-purpose of the calculated reproducibility standard deviation was evaluated. For this purpose, the calculated reproducibility relative standard deviation (RSDR) was compared to the relative standard deviation derived from the modified Horwitz equation (RSDmH), as proposed by Thompson (Thompson 2000). The latter provides a concentration dependant guidance level for reproducibility.
The agreement with the guidance level of precision was expressed as HORRAT values for reproducibility (HORRATR).
4. Evaluation of systematic effects
Laboratories reporting results that, for one or more analytes, exceeded the 1% threshold level of either the Mandel's h or Mandel's k tests were contacted by the organisers and requested to check their reported data and to confirm them if appropriate. Results were excluded from data evaluations if the laboratory did not confirm the correctness of the reported analytical results.
5. Evaluation of reported results by analyte
Based on the results of the separate analysis of each analyte and according to the reproducibility results, the method should be considered as either type II (DCHP BBP DBP DIBP DEP) or type IV (DIDP DINP DNOP DEHP DMP).
Table 3: Dimethyl phthalate (DMP)[1] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
11 |
10 |
11 |
10 |
10 |
11 |
|
|
Mean |
mg/l |
0.020 |
0.073 |
0.018 |
0.031 |
0.053 |
0.027 |
|
Median |
mg/l |
0.020 |
0.060 |
0.018 |
0.030 |
0.056 |
0.028 |
|
Assigned value |
mg/l |
0.030 |
0.097 |
0.030 |
0.049 |
0.104 |
0.046 |
|
Rel. dev. assign. value |
-33.3% |
-38.1% |
-40.0% |
-38.8% |
-46.2% |
-39.1% |
|
|
Repeatability s.d. |
mg/l |
0.003 |
0.007 |
0.002 |
0.006 |
0.011 |
0.003 |
|
Reproducibility s.d. |
mg/l |
0.006 |
0.041 |
0.007 |
0.011 |
0.022 |
0.009 |
|
Rel. repeatability s.d. |
9.42% |
7.33% |
8.04% |
13.00% |
10.25% |
7.09% |
|
|
Rel. reproducibility s.d. |
20.10% |
42.40% |
23.12% |
22.54% |
21.10% |
19.07% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
0.91 |
1.93 |
1.05 |
1.02 |
0.96 |
0.87 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.008 |
0.020 |
0.007 |
0.018 |
0.030 |
0.009 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.017 |
0.114 |
0.019 |
0.031 |
0.061 |
0.024 |
|
Rel. limit of repeatability |
26.09% |
20.32% |
22.28% |
36.00% |
28.38% |
19.64% |
|
|
Rel. limit of reproducibility |
55.67% |
117.45% |
64.05% |
62.44% |
58.45% |
52.84% |
|
|
No. of laboratories after elimination of outliers |
9 |
9 |
8 |
8 |
9 |
10 |
|
|
No. of measurement values without outliers |
18 |
18 |
15 |
16 |
18 |
20 |
Table 4: Diethyl phthalate (DEP)[2] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
12 |
11 |
11 |
11 |
10 |
12 |
|
|
Mean |
mg/l |
0.048 |
0.065 |
0.030 |
0.039 |
0.021 |
0.059 |
|
Median |
mg/l |
0.044 |
0.076 |
0.029 |
0.041 |
0.023 |
0.061 |
|
Assigned value |
mg/l |
0.057 |
0.092 |
0.031 |
0.056 |
0.030 |
0.089 |
|
Rel. dev. assign. value |
-22.8% |
-17.4% |
-6.5% |
-26.8% |
-23.3% |
-31.5% |
|
|
Repeatability s.d. |
mg/l |
0.006 |
0.010 |
0.005 |
0.004 |
0.003 |
0.002 |
|
Reproducibility s.d. |
mg/l |
0.026 |
0.026 |
0.015 |
0.017 |
0.008 |
0.019 |
|
Rel. repeatability s.d. |
10.49% |
11.32% |
15.28% |
7.00% |
11.41% |
2.53% |
|
|
Rel. reproducibility s.d. |
45.36% |
28.49% |
47.95% |
29.71% |
25.74% |
20.98% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
2.06 |
1.30 |
2.18 |
1.35 |
1.17 |
0.95 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.017 |
0.029 |
0.013 |
0.011 |
0.009 |
0.006 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.072 |
0.073 |
0.041 |
0.046 |
0.021 |
0.052 |
|
Rel. limit of repeatability |
29.05% |
31.35% |
42.32% |
19.40% |
31.60% |
7.01% |
|
|
Rel. limit of reproducibility |
125.66% |
78.91% |
132.81% |
82.29% |
71.30% |
58.12% |
|
|
No. of laboratories after elimination of outliers |
11 |
10 |
11 |
9 |
10 |
11 |
|
|
No. of measurement values without outliers |
21 |
20 |
21 |
17 |
20 |
22 |
Table 5: Diisobutyl phthalate (DIBP)[3] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
11 |
10 |
11 |
10 |
10 |
11 |
|
|
Mean |
mg/l |
0.049 |
0.087 |
0.076 |
0.119 |
0.054 |
0.046 |
|
Median |
mg/l |
0.049 |
0.085 |
0.076 |
0.123 |
0.055 |
0.045 |
|
Assigned value |
mg/l |
0.035 |
0.076 |
0.058 |
0.107 |
0.061 |
0.045 |
|
Rel. dev. assign. value |
40.0% |
11.8% |
31.0% |
15.0% |
-9.8% |
0.0% |
|
|
Repeatability s.d. |
mg/l |
0.003 |
0.006 |
0.007 |
0.009 |
0.002 |
0.004 |
|
Reproducibility s.d. |
mg/l |
0.011 |
0.019 |
0.014 |
0.023 |
0.012 |
0.013 |
|
Rel. repeatability s.d. |
7.43% |
7.71% |
11.55% |
8.81% |
4.04% |
9.54% |
|
|
Rel. reproducibility s.d. |
32.18% |
25.23% |
24.48% |
21.95% |
19.98% |
28.37% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
1.46 |
1.15 |
1.11 |
1.00 |
0.91 |
1.29 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.007 |
0.016 |
0.019 |
0.026 |
0.007 |
0.012 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.031 |
0.053 |
0.039 |
0.065 |
0.034 |
0.035 |
|
Rel. limit of repeatability |
20.58% |
21.35% |
31.98% |
24.42% |
11.19% |
26.44% |
|
|
Rel. limit of reproducibility |
89.15% |
69.88% |
67.80% |
60.81% |
55.35% |
78.58% |
|
|
No. of laboratories after elimination of outliers |
11 |
10 |
11 |
10 |
10 |
11 |
|
|
No. of measurement values without outliers |
21 |
20 |
21 |
20 |
20 |
22 |
Table 6: Dibutyl phthalate (DBP)[4] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
12 |
11 |
12 |
11 |
11 |
12 |
|
|
Mean |
mg/l |
0.103 |
0.264 |
0.078 |
0.728 |
0.090 |
0.178 |
|
Median |
mg/l |
0.103 |
0.266 |
0.074 |
0.666 |
0.089 |
0.174 |
|
Assigned value |
mg/l |
0.107 |
0.281 |
0.057 |
1.039 |
0.032 |
0.153 |
|
Rel. dev. assign. value |
-3.7% |
-5.3% |
29.8% |
-35.9% |
|||
|
Repeatability s.d. |
mg/l |
0.009 |
0.014 |
0.011 |
0.033 |
0.004 |
0.012 |
|
Reproducibility s.d. |
mg/l |
0.022 |
0.048 |
0.021 |
0.314 |
0.018 |
0.022 |
|
Rel. repeatability s.d. |
8.24% |
5.03% |
19.11% |
3.21% |
13.79% |
7.87% |
|
|
Rel. reproducibility s.d. |
20.73% |
17.01% |
36.78% |
30.25% |
57.05% |
14.66% |
|
|
Modified Horwitz s.d. ** |
22.00% |
19.36% |
22.00% |
15.91% |
22.00% |
21.22% |
|
|
HORRATR |
0.94 |
0.88 |
1.67 |
1.90 |
2.59 |
0.69 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.024 |
0.039 |
0.030 |
0.092 |
0.012 |
0.033 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.061 |
0.132 |
0.058 |
0.871 |
0.051 |
0.062 |
|
Rel. limit of repeatability |
22.81% |
13.92% |
52.94% |
8.89% |
38.21% |
21.80% |
|
|
Rel. limit of reproducibility |
57.43% |
47.12% |
101.88% |
83.79% |
158.03% |
40.60% |
|
|
No. of laboratories after elimination of outliers |
12 |
11 |
12 |
10 |
11 |
11 |
|
|
No. of measurement values without outliers |
23 |
22 |
23 |
20 |
22 |
22 |
Table 7: Benzyl butyl phthalate (BBP)[5] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
11 |
10 |
11 |
10 |
10 |
11 |
|
|
Mean |
mg/l |
0.049 |
0.026 |
0.033 |
0.074 |
0.075 |
0.050 |
|
Median |
mg/l |
0.050 |
0.027 |
0.034 |
0.075 |
0.078 |
0.051 |
|
Assigned value |
mg/l |
0.057 |
0.029 |
0.037 |
0.088 |
0.087 |
0.053 |
|
Rel. dev. assign. value |
-12.3% |
-6.9% |
-8.1% |
-14.8% |
-10.3% |
-3.8% |
|
|
Repeatability s.d. |
mg/l |
0.002 |
0.001 |
0.003 |
0.004 |
0.003 |
0.003 |
|
Reproducibility s.d. |
mg/l |
0.008 |
0.004 |
0.005 |
0.011 |
0.015 |
0.007 |
|
Rel. repeatability s.d. |
4.30% |
4.96% |
8.08% |
5.10% |
3.31% |
4.78% |
|
|
Rel. reproducibility s.d. |
13.71% |
13.82% |
13.93% |
12.72% |
17.00% |
14.00% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
0.62 |
0.63 |
0.63 |
0.58 |
0.77 |
0.64 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.007 |
0.004 |
0.008 |
0.012 |
0.008 |
0.007 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.022 |
0.011 |
0.014 |
0.031 |
0.041 |
0.021 |
|
Rel. limit of repeatability |
11.90% |
13.75% |
22.38% |
14.14% |
9.16% |
13.23% |
|
|
Rel. limit of reproducibility |
37.98% |
38.27% |
38.58% |
35.23% |
47.09% |
38.77% |
|
|
No. of laboratories after elimination of outliers |
9 |
8 |
10 |
9 |
9 |
10 |
|
|
No. of measurement values without outliers |
17 |
15 |
19 |
18 |
18 |
20 |
Table 8: Dicyclohexyl phthalate (DCHP)[6] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
9 |
8 |
9 |
8 |
8 |
9 |
|
|
Mean |
mg/l |
0.079 |
0.042 |
0.030 |
0.088 |
0.046 |
0.031 |
|
Median |
mg/l |
0.076 |
0.044 |
0.033 |
0.091 |
0.050 |
0.033 |
|
Assigned value |
mg/l |
0.084 |
0.048 |
0.038 |
0.105 |
0.057 |
0.036 |
|
Rel. dev. assign. value |
-9.5% |
-8.3% |
-13.2% |
-13.3% |
-12.3% |
-8.3% |
|
|
Repeatability s.d. |
mg/l |
0.005 |
0.006 |
0.003 |
0.005 |
0.002 |
0.001 |
|
Reproducibility s.d. |
mg/l |
0.024 |
0.008 |
0.005 |
0.011 |
0.011 |
0.006 |
|
Rel. repeatability s.d. |
5.60% |
13.13% |
6.75% |
4.84% |
3.25% |
3.67% |
|
|
Rel. reproducibility s.d. |
28.46% |
16.05% |
12.93% |
10.20% |
18.83% |
16.37% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
1.29 |
0.73 |
0.59 |
0.46 |
0.86 |
0.74 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.013 |
0.017 |
0.007 |
0.014 |
0.005 |
0.004 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.066 |
0.021 |
0.014 |
0.030 |
0.030 |
0.016 |
|
Rel. limit of repeatability |
15.53% |
36.37% |
18.69% |
13.40% |
9.00% |
10.18% |
|
|
Rel. limit of reproducibility |
78.83% |
44.46% |
35.82% |
28.24% |
52.15% |
45.35% |
|
|
No. of laboratories after elimination of outliers |
9 |
7 |
8 |
7 |
7 |
8 |
|
|
No. of measurement values without outliers |
18 |
14 |
15 |
14 |
14 |
16 |
Table 9: Bis (2-ethylhexyl) phthalate (DEHP)[7] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
12 |
11 |
12 |
11 |
11 |
12 |
|
|
Mean |
mg/l |
0.101 |
0.028 |
0.602 |
0.150 |
0.741 |
1.032 |
|
Median |
mg/l |
0.099 |
0.026 |
0.654 |
0.180 |
0.709 |
1.115 |
|
Assigned value |
mg/l |
0.217 |
0.046 |
1.049 |
0.328 |
1.569 |
2.013 |
|
Rel. dev. assign. value |
-54.4% |
-43.5% |
-37.7% |
-45.1% |
-54.8% |
-44.6% |
|
|
Repeatability s.d. |
mg/l |
0.017 |
0.005 |
0.206 |
0.016 |
0.122 |
0.266 |
|
Reproducibility s.d. |
mg/l |
0.019 |
0.011 |
0.238 |
0.063 |
0.465 |
0.563 |
|
Rel. repeatability s.d. |
7.72% |
11.54% |
19.66% |
4.82% |
7.78% |
13.20% |
|
|
Rel. reproducibility s.d. |
8.92% |
24.15% |
22.70% |
19.11% |
29.61% |
27.96% |
|
|
Modified Horwitz s.d. ** |
20.13% |
22.00% |
15.88% |
18.92% |
14.95% |
14.40% |
|
|
HORRATR |
0.44 |
1.10 |
1.43 |
1.01 |
1.98 |
1.94 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.046 |
0.015 |
0.571 |
0.044 |
0.338 |
0.736 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.054 |
0.031 |
0.660 |
0.174 |
1.287 |
1.559 |
|
Rel. limit of repeatability |
21.39% |
31.98% |
54.45% |
13.36% |
21.54% |
36.55% |
|
|
Rel. limit of reproducibility |
24.70% |
66.91% |
62.87% |
52.93% |
82.03% |
77.46% |
|
|
No. of laboratories after elimination of outliers |
10 |
10 |
12 |
9 |
11 |
12 |
|
|
No. of measurement values without outliers |
20 |
20 |
23 |
18 |
22 |
24 |
Table 10: Di-n-octyl phthalate (DNOP)[8] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
11 |
10 |
11 |
10 |
9 |
10 |
|
|
Mean |
mg/l |
0.031 |
0.015 |
0.051 |
0.073 |
0.016 |
0.026 |
|
Median |
mg/l |
0.035 |
0.015 |
0.049 |
0.061 |
0.019 |
0.028 |
|
Assigned value |
mg/l |
0.086 |
0.031 |
0.059 |
0.114 |
0.036 |
0.054 |
|
Rel. dev. assign. value |
-59.3% |
-51.6% |
-16.9% |
-46.5% |
-47.2% |
-48.1% |
|
|
Repeatability s.d. |
mg/l |
0.007 |
0.003 |
0.021 |
0.005 |
0.004 |
0.005 |
|
Reproducibility s.d. |
mg/l |
0.010 |
0.003 |
0.023 |
0.038 |
0.008 |
0.011 |
|
Rel. repeatability s.d. |
7.84% |
9.25% |
36.33% |
4.51% |
11.18% |
9.23% |
|
|
Rel. reproducibility s.d. |
11.50% |
9.33% |
38.90% |
33.40% |
23.32% |
20.10% |
|
|
Modified Horwitz s.d. ** |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
22.00% |
|
|
HORRATR |
0.52 |
0.42 |
1.77 |
1.52 |
1.06 |
0.91 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.019 |
0.008 |
0.059 |
0.014 |
0.011 |
0.014 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.027 |
0.008 |
0.064 |
0.105 |
0.023 |
0.030 |
|
Rel. limit of repeatability |
21.73% |
25.61% |
100.62% |
12.50% |
30.97% |
25.56% |
|
|
Rel. limit of reproducibility |
31.85% |
25.85% |
107.76% |
92.52% |
64.60% |
55.66% |
|
|
No. of laboratories after elimination of outliers |
9 |
8 |
10 |
9 |
7 |
8 |
|
|
No. of measurement values without outliers |
18 |
15 |
18 |
16 |
14 |
16 |
Table 11: Diisononyl phthalate (DINP)[9] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
9 |
8 |
10 |
8 |
8 |
9 |
|
|
Mean |
mg/l |
0.027 |
0.108 |
1.820 |
0.059 |
0.115 |
0.064 |
|
Median |
mg/l |
0.028 |
0.116 |
1.497 |
0.058 |
0.136 |
0.051 |
|
Assigned value |
mg/l |
0.054 |
0.242 |
3.134 |
0.104 |
0.271 |
0.057 |
|
Rel. dev. assign. value |
-48.1% |
-52.1% |
-52.2% |
-44.2% |
-49.8% |
-10.5% |
|
|
Repeatability s.d. |
mg/l |
0.004 |
0.019 |
0.520 |
0.005 |
0.010 |
0.003 |
|
Reproducibility s.d. |
mg/l |
0.006 |
0.027 |
1.067 |
0.019 |
0.072 |
0.040 |
|
Rel. repeatability s.d. |
8.14% |
7.84% |
16.60% |
5.17% |
3.83% |
5.51% |
|
|
Rel. reproducibility s.d. |
10.27% |
11.18% |
34.06% |
18.41% |
26.60% |
70.59% |
|
|
Modified Horwitz s.d. ** |
20.00% |
20.00% |
20.00% |
20.00% |
20.00% |
20.00% |
|
|
HORRATR |
0.51 |
0.56 |
1.70 |
0.92 |
1.33 |
3.53 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.012 |
0.053 |
1.441 |
0.015 |
0.029 |
0.009 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.015 |
0.075 |
2.957 |
0.053 |
0.200 |
0.111 |
|
Rel. limit of repeatability |
22.55% |
21.71% |
45.99% |
14.32% |
10.61% |
15.27% |
|
|
Rel. limit of reproducibility |
28.44% |
30.98% |
94.35% |
50.99% |
73.69% |
195.53% |
|
|
No. of laboratories after elimination of outliers |
5 |
6 |
9 |
7 |
6 |
6 |
|
|
No. of measurement values without outliers |
10 |
11 |
17 |
13 |
12 |
12 |
Table 12: Diisodecyl phthalate (DIDP)[10] – Results of data evaluation
|
S001 |
S002 |
S003 |
S004 |
S005 |
S006 |
||
|
No. of laboratories that submitted compliant results |
8 |
7 |
8 |
7 |
7 |
8 |
|
|
Mean |
mg/l |
0.096 |
0.103 |
0.677 |
0.152 |
0.186 |
1.828 |
|
Median |
mg/l |
0.102 |
0.107 |
0.540 |
0.152 |
0.181 |
1.660 |
|
Assigned value |
mg/l |
0.275 |
0.186 |
0.200 |
0.281 |
0.427 |
3.070 |
|
Rel. dev. assign. value |
-62.9% |
-42.5% |
170.0% |
-45.9% |
-57.6% |
-45.9% |
|
|
Repeatability s.d. |
mg/l |
0.009 |
0.018 |
0.477 |
0.048 |
0.027 |
0.202 |
|
Reproducibility s.d. |
mg/l |
0.025 |
0.018 |
0.505 |
0.058 |
0.109 |
1.676 |
|
Rel. repeatability s.d. |
3.42% |
9.61% |
238.49% |
17.11% |
6.27% |
6.57% |
|
|
Rel. reproducibility s.d. |
9.11% |
9.61% |
252.34% |
20.51% |
25.43% |
54.59% |
|
|
Modified Horwitz s.d. ** |
20.00% |
20.00% |
20.38% |
20.00% |
20.00% |
20.00% |
|
|
HORRATR |
0.46 |
0.48 |
12.38 |
1.03 |
1.27 |
2.73 |
|
|
Limit of repeatability, r (2.77 X sr) |
mg/l |
0.026 |
0.050 |
1.321 |
0.133 |
0.074 |
0.559 |
|
Limit of reproducibility, R (2.77 X sR) |
mg/l |
0.069 |
0.050 |
1.398 |
0.160 |
0.301 |
4.642 |
|
Rel. limit of repeatability |
9.46% |
26.62% |
660.61% |
47.40% |
17.37% |
18.21% |
|
|
Rel. limit of reproducibility |
25.25% |
26.62% |
698.98% |
56.82% |
70.44% |
151.21% |
|
|
No. of laboratories after elimination of outliers |
7 |
5 |
7 |
7 |
7 |
7 |
|
|
No. of measurement values without outliers |
14 |
10 |
13 |
14 |
14 |
14 |
6. References
- Report on the Method Performance Study of a Method to Determine Phthalates in Wine Determination of Ten Phthalates in Wine by Gas Chromatography Mass Spectrometry (GC-MS), Wenzl Thomas, Karasek Lubomir, Giri Anupam. Publications Office of the European Union 2015 doi :10.2787/666948 (online) https://publications.europa.eu/en/publication-detail/-/publication/b3ebef67-f1db-4fb2-97ce-bfc301c8ce68/language-en
[1] Type IV method
[2] Type II method
[3] Type II method
[4] Type II method
[5] Type II method
[6] Type II method
[7] Type IV method
[8] Type IV method
[9] Type IV method
[10] Type IV method