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Method of determination of phthalates by gas chromatography / mass spectrometry in wines (Type-II-and-IV)

OIV-MA-AS323-10 Method of determination of phthalates by gas chromatography/ mass spectrometry in wines

Type II/IV methods

  1. Scope

This method applies to the detection and assay of phthalates in wines.

  1. Principle

The sample is extracted using isohexane. The extract is concentrated by evaporation. The concentrated extract is analysed by gas chromatography/mass spectrometry (GC/MS) with deuterated internal standards.

  1. Reagents and materials

Unless otherwise specified, all the reagents used are of recognised analytical quality.

3.1.   DMP (dimethyl phthalate) [CAS N°: 131-11-3]

3.2.   DnBP (dibutyl phthalate) [CAS N°: 84-74-2]

3.3.   DEHP (bis (2-ethylhexyl) phthalate) [CAS N°: 117-81-7]

3.4.   BBP (butyl benzyl phthalate) [CAS N°: 85-68-7]

3.5.   DINP (di-isononyl phthalate) [CAS N°: 068515-48-0/028553-12-0]

3.6.   DIDP (di-isodecyl phthalate) [CAS N°: 068515-49-1/026761-40-0]

3.7.   DCHP (dicyclohexyl phthalate) [CAS N°: 84-61-7]

3.8.   DEP (diethyl phthalate) [CAS N°: 84-66-2]

3.9.   DiBP (di-isobutyl phthalate) [CAS N°: 84-74-2]

3.10.                     DnOP (di-n-octyl phthalate) [CAS N°: 117-84-0]

3.11.                     DMP-d4: internal standard [CAS N°: 93951-89-4]

3.12.                     DEP-d4: internal standard [CAS N°: 93952-12-6]

3.13.                     DiBP-d4: internal standard [CAS N°: 358730-88-8]

3.14.                     DnBP-d4: internal standard [CAS N°: 93952-11-5]

3.15.                     BBP-d4: internal standard [CAS N°: 93951-88-3]

3.16.                     DCHP-d4: internal standard [CAS N°: 358731-25-6]

3.17.                     DEHP–d4: internal standard [CAS N°: 93951-87-2]

3.18.                     DnOP-d4: internal standard [CAS N°: 93952-13-7]

3.19.                     Isohexane [CAS N°: 107-83-5] and Acetone [CAS N°: 67-64-1]

3.20.                     Standard solutions

All the volumetric flasks used to prepare the calibration solutions are to be rinsed with acetone then isohexane to avoid any contamination.

3.20.1.   Stock solutions

Phthalate - 1 g/L individual solution: for each phthalate weigh 100 mg into a 100 mL flask, dissolve in the isohexane and make up to 100 mL.

DINP-DIDP– 5 g/L individual solution: for each phthalate weigh 500 mg into a 100 mL flask, dissolve in the isohexane and make up to 100 mL.

Internal standard - 0.5 g/L individual solution: deuterated standards are packaged in sealed 25 mg ampoules; for each internal standard, all the contents of the bulb are transferred into a 50 mL volumetric flask; make up to 50 mL with isohexane.

3.20.2.   Working solutions

Phthalate 1 mg/L working solution (S1)

Take 100 µL of each 1 g/L and 5g/L stock solution (3.20.1), add the samples to a 100 mL flask, and make up to 100 mL with isohexane.

Phthalate 10 mg/L working solution (S2)

Take 1 mL of each 1 g/L and 5g/L stock solution (3.20.1), add the samples to a 100 mL flask, and make up to 100 mL with isohexane.

Internal standard 10 mg/L working solution (IS)

Take 1 mL of each deuterated standard 0.5 g/L stock solution (3.20.1), add the samples to a 50 mL flask, and make up to 50 mL with isohexane.

3.20.3.   Calibration range

The calibration range in isohexane is prepared from the various working solutions (3.20.2), directly into the injection vials that have been heat-treated, rinsed (see § 5.1) and dried under a hood beforehand, according to the following table:

Calibration points

Phthalate concn. (mg/L)*

Vol. of S1 surrogate soln. (μL)

Vol. of S2 surrogate soln. (μL)

Vol. of IS surrogate soln. (μL)

Vol. of isohexane (μL)

C1

0

0

0

50

1000

C2

0,05

50

0

50

950

C3

0,10

100

0

50

900

C4

0,20

200

0

50

800

C5

0,50

0

50

50

950

C6

0,80

0

80

50

920

C7

1,00

0

100

50

900

* to be multiplied by 5 for DINP and DIDP concentrations

  1. Equipment

4.1.   Glassware and volumetric laboratory equipment:

4.1.1. 50 mL and 100 mL class A volumetric flasks

4.1.2. 50 mL glass centrifuge tubes with stopper

4.1.3. 10 mL glass test tubes with stopper

4.1.4.  Micropipettes with variable volumes ranging from 25 µl to 1,000 µl, checked in accordance with ISO 8655-6

4.1.5. Nitrogen flow evaporator

4.2.   Analytical balance

4.3.   GC-MS System (e.g. Varian 450GC-300MS)

  1. Procedure

5.1.   Precautions

Due to the presence of phthalates in the laboratory environment, precautions must be taken throughout the analysis of these compounds:

  • Avoid any contact with plastic equipment (especially flexible PVC) as much as possible. If this is not possible, make sure there is no contamination.
  • Test the solvents used and dedicate bottles of solvent to these analyses.
  • Heat-treat all non-volumetric glassware (400°C for at least 2 hours). Rinse all the equipment carefully (with acetone then isohexane).
  • Make sure the septums of the injection vials are phthalate-free.
  • Before and after each injection, rinse the injection syringe several times.
  • If possible, work in a clean room or in a room reserved for these analyses.

5.2.   Preparing the samples

Place 12.5 mL of the sample in a 50 mL centrifuge tube. Add 10 mL of isohexane.

Shake vigorously (Vortex mixer) for at least one minute.

Let the mixture decant until the 2 phases have separated (30 minutes in a 50°C ultrasound bath will accelerate the separation). Recover 8 mL of the organic phase and transfer it into a 10 mL test tube. Evaporate under a flow of nitrogen (0.3 bar) at 35°C and avoid continuing to dryness (warning: the temperature must not exceed 40°C)

Resume with 1 mL of isohexane.

Add 50 μl of the 0.01 g/L internal standard solution to each extract.

Transfer into an injection vial.

NOTE: to minimise matrix effects during analysis by GC-MS, a “protective” agent can be added, such as methyl undecanoate [CAS N°: 1731-86-8].

Add 20 μL of this compound is added to each calibration solution and to the extracts from the samples prior to evaporation under a flow of nitrogen.

5.3.   Blank test

Prepare a “blank” test by following the procedure described in 5.2 without adding the sample.

5.4.   GC/MS analysis

Depending on the apparatus available and its performance, choose between SIM and MRM modes for the mass spectrometry.

For information purposes, analysis conditions are provided in Appendix I and a typical chromatogram is provided in Appendix II.

5.4.1. Calibration

First, carry out several solvent injections (at least 2). Next, inject the standard solutions (3.20.3) in duplicate in increasing order of concentration and end with at least two solvent injections.

Establish a calibration curve for each phthalate:

A: peak area

C: concentration

IS: internal standard

Each phthalate is quantified using to the corresponding deuterated standard, with the exception of DINP and DIDP which are quantified using to DnOP-d4.

5.4.2. Analysing the samples

 Start the analysis sequence by analysing the "blank" test (5.3).

Then inject the samples prepared (5.2) in duplicate.

Plan solvent injections after potentially highly contaminated samples.

End the series by injecting one or more calibration standards to check any signal drift during the analysis series and to check several solvent injections..

For each injection, measure the area of the identified peaks and internal standards, and use the calibration curve equation (5.4.1) to determine the concentration in the extract analysed.

5.4.3. Expressing the results

For each sample, calculate the average of the results obtained (5.4.2) for both injections.

The results are expressed in mg/L.

 

  1. Quality control

 

During each analysis series, quality control is provided by the analysis of a wine sample supplemented with phthalates at a concentration level of 0.020 mg/L.

The extract of the sample prepared as per 5.2 is analysed at the beginning of the series, and the results obtained, given in terms of recovery rate, are reflected on a control chart.

  1. Method characteristics

 

The analyses performed in the laboratory, under repeatability and intermediate precision conditions, on a red wine and a white wine supplemented with phthalates at two concentration levels (0.040 mg/L and 0.080 mg/L), gave the following repeatability (%), intermediate reproducibility (%), and recovery values:

Phthalates

Recovery %

%

%

DMP

(dimethyl phthalate)

67

5

8

DEP

(diethyl phthalate)

84

8

11

DiBP

(di-isobutyl phthalate)

93

7

10

DnBP

(dibutyl phthalate)

95

5

7

BBP

(butyl benzyl phthalate)

98

5

6

DCHP

(dicyclohexyl phthalate)

97

5

7

DEHP

(bis(2-ethylhexyl) phthalate)

98

6

7

DnOP

(dioctyl phthalate)

98

6

7

DINP

(di-isononyl phthalate)

104

7

8

DIDP

(di-isodecyl phthalate)

96

8

11

i.e. the following average values for all the phthalates:

Repeatability (given in CVr%): 6%

Intermediate precision (given in CVIP%): 8%

  1. Detection and quantification limits

For each phthalate being analysed for, the detection and quantification limits are provided in the following table:

Phthalates

Quantification limit (mg/L)

Detection limit (mg/L)

DMP

(dimethyl phthalate)

0.010

0.004

DEP

(diethyl phthalate)

0.010

0.004

DiBP

(di-isobutyl phthalate)

0.010

0.004

DnBP

(dibutyl phthalate)

0.010

0.004

BBP

(butyl benzyl phthalate)

0.010

0.004

DCHP

(dicyclohexyl phthalate)

0.010

0.004

DEHP

(bis(2-ethylhexyl) phthalate)

0.010

0.004

DnOP

(dioctyl phthalate)

0.010

0.004

DINP

(di-isononyl phthalate)

0.050

0.020

DIDP

(di-isodecyl phthalate)

0.050

0.020

  1. References
  • FV 1371. Detection and assay of phthalates in alcoholic beverages. 2011
  • FV 1234. Questions about phthalates. 2006

Appendix I

(for information)

  • Gas chromatography conditions
  • VF-5ms type capillary column: 30 m x 0.25 mm internal diameter, film thickness 0.25 µm 
  • Temperature programming:

For detection in SIM mode:

Oven maintained at 100°C for 1 min; increase to 230°C at a rate of 10°C/min; increase to 270°C at a rate of 10°C/min; maintain for 2 min, increase to 300°C at a rate of 25°C/min; maintain for 8 min.

Note: this programming separates the DEHP and DCHP peaks (which cannot be done with the MRM mode programming)

For detection in MRM mode:

Oven maintained at 80°C for 1 min; increase to 200°C at a rate of 20°C/min; increase to 300°C at a rate of 10°C/min; maintain for 8 min.

Injector: maintained at 150°C for 0.5 min; increase to 280°C at a rate of 200°C/min, in splitless mode at injection

Helium: 1 mL/min at a constant flow rate

Volume injected: 1 μL

Mass spectrometry (MS) conditions

Ionisation in EI mode at 70 eV

Source temperature: 250°C

Transfer line temperature: 300°C

Manifold: 40°C

Phthalate quantification and identification parameters

For an analysis in SIM mode, table 1 provides the quantification ion and the two qualifier ions for each phthalate and its deuterated homologue.

For an analysis in MRM mode, table 2 reflects the quantifying and qualifying transitions for each phthalate and its deuterated homologue.

Note: DIDP and DINP are each a mixture of compounds. Chromatography cannot separate them completely. They are therefore assayed as a "group".

Appendix I

(for information)

Table 1

Quantification ion m/z

Qualifier ions m/z

1

Qualifier ions m/z

2

DMP

(dimethyl phthalate)

163

77

194

DMP-d4

167

81

198

DEP

(diethyl phthalate)

149

177

222

DEP-d4

153

181

226

DiBP

(di-isobutyl phthalate)

149

167

223

DiBP-d4

153

171

227

DnBP

(dibutyl phthalate)

149

205

223

DnBP-d4

153

209

227

BBP

(butyl benzyl phthalate)

149

91

206

BBP-d4

153

95

210

DCHP

(dicyclohexyl phthalate)

149

167

249

DCHP-d4

153

171

253

DEHP

(bis(2-ethylhexyl) phthalate)

149

167

279

DEHP-d4

153

171

283

DnOP

(dioctyl phthalate)

149

167

279

DnOP-d4

153

171

283

DINP

(di-isononyl phthalate)

149

293

DIDP

(di-isodecyl phthalate)

149

307

Table 2

Quantifying transition

Qualifying transition

DMP

(dimethyl phthalate)

194>163

194>77

DMP-d4

198>167

198>81

DEP

(diethyl phthalate)

177>149

177>93

DEP-d4

181>153

181>97

DiBP

(di-isobutyl phthalate)

223>149

205>149

DiBP-d4

227>153

209>153

DnBP

(dibutyl phthalate)

223>149

205>149

DnBP-d4

227>153

209>153

BBP

(butyl benzyl phthalate)

206>149

149>121

BBP-d4

210>153

153>125

DCHP

(dicyclohexyl phthalate)

249>149

249>93

DCHP-d4

253>153

253>97

DEHP

(bis(2-ethylhexyl) phthalate)

279>149

279>93

DEHP-d4

283>153

283>97

DnOP

(dioctyl phthalate)

279>149

279>93

DnOP-d4

283>153

283>93

DINP

(di-isononyl phthalate)

293>149

DIDP

(di-isodecyl phthalate)

307>149

Appendix II

(for information)

GC/MS chromatograms of a phthalate standard solution and deuterated internal standards.

Appendix III

(for information)

Validation of analysis of phthalates in wines

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

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

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 () was compared to the relative standard deviation derived from the modified Horwitz equation (,) 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 ().

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.

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

References

[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