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Fapas® – Food Chemistry Proficiency Test Report 19248

Pesticide Residues in Lemon Purée

April-June 2018

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Food Chem. Report 19248

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PARTICIPANT LABORATORY NUMBER

Participants can log in to Fapas® SecureWeb at any time to obtain their laboratory number for this proficiency test. Laboratory numbers are displayed in SecureWeb next to the download link for this report.

REPORT INTEGRITY

Fapas® reports are distributed as digitally signed Adobe® PDF files. When these files are opened with Adobe® Reader v9 or later, a blue ribbon and information bar indicates that the certificate has been validated. This confirms that the author of the report is Fapas® and that the document has not been altered since it was signed [1, 2]. The integrity of hard copies of Fapas® reports cannot be assured in this way, i.e. printed copies are not controlled. A watermark stating this appears on every page when a Fapas® report is printed. End users of Fapas® reports should ensure that either the PDF file they are viewing displays a valid Fapas® digital signature or that the content of their hard copy exactly matches the content of a PDF file that displays a valid Fapas® digital signature.

QUALITY SYSTEMS

Fapas® – Food Chemistry is accredited by UKAS as complying with the requirements of ISO/IEC 17043:2010 [3]. Fera is an ISO 9001 certified organisation.

0009

Fera hereby excludes all liability for any claim, loss, demands or damages of any kind whatsoever (whether such claims, loss, demands or damages were foreseeable, known or otherwise) arising out of or in connection with the preparation of any technical or scientific report, including without limitation, indirect or consequential loss or damage; loss of actual or anticipated profits (including loss of profits on contracts); loss of revenue; loss of business; loss of opportunity; loss of anticipated savings; loss of goodwill; loss of reputation; loss or damage to or corruption of data; loss of use of money or otherwise, and whether or not advised of the possibility of such claim, loss demand or damages and whether arising in tort (including negligence), contract or otherwise. This statement does not affect your statutory rights. Nothing in this disclaimer excludes or limits Fera liability for: (a) death or personal injury caused by Fera negligence (or that of its employees, agents or directors); or (b) the tort of deceit; [or (c) any breach of the obligations implied by Sale of Goods Act 1979 or Supply of Goods and Services Act 1982 (including those relating to the title, fitness for purpose and satisfactory quality of goods);] or (d) any liability which may not be limited or excluded by law (e) fraud or fraudulent misrepresentation. The parties agree that any matters are governed by English law and irrevocably submit to the non-exclusive jurisdiction of the English courts. © Copyright Fera Science Ltd (Fera) 2018. All rights reserved.

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SUMMARY

1. The test materials for Fapas® – Food Chemistry proficiency test 19248 were dispatched in April 2018. Each participant received a lemon purée test material to be analysed for a selection of pesticide residues.

2. An assigned value (xa) was determined for each analyte and in conjunction with the

standard deviation for proficiency (σp) was used to calculate a z-score for each result.

3. Results for this proficiency test are summarised as follows:

analyte assigned value, xₐ µg/kg

number of scores, |z| ≤2

total number of scores

% |z|≤2

Acetochlor 88.3 39 45 87

Chlordane (cis) 34.4 37 50 74

Dimethoate 182 61 69 88

Endosulfan I (alpha) 125 58 64 91

EPN 48.6 46 52 88

Etofenprox 105 59 63 94

Fenamidone 62.4 52 59 88

Fluvalinate (tau) 75.5 46 56 82

Linuron 125 58 66 88

Pyriproxyfen 106 59 67 88

Tebuconazole 129 58 67 87

Triazophos 41.1 59 66 89

Triflumuron 103 46 54 85

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CONTENTS

1. INTRODUCTION 6

1.1. Proficiency Testing 6

2. TEST MATERIAL 6

2.1. Preparation 6

2.2. Homogeneity 6

2.3. Dispatch 6

3. RESULTS 6

4. STATISTICAL EVALUATION OF RESULTS 7

4.1. Calculation of the Assigned Value, xa 7

4.2. Standard Deviation for Proficiency, σp 8

4.3. Individual z-Scores 8

5. INTERPRETATION OF SCORES 8

6. REFERENCES 9

TABLES Table 1: Results and z-Scores for Acetochlor, Chlordane (cis) and Dimethoate 10

Table 2: Results and z-Scores for Endosulfan l (alpha), EPN and Etofenprox 15

Table 3: Results and z-Scores for Fenamidone, Fluvalinate (tau) and Linuron 20

Table 4: Results and z-Scores for Pyriproxyfen and Tebuconazole 25

Table 5: Results and z-Scores for Triazophos and Triflumuron 30

Table 6: Additional Pesticide Residues Reported 35 Table 7: Participants’ Comments 35

Table 8: Assigned Values and Standard Deviations for Proficiency 36

Table 9: Number and Percentage of z-Scores where |z| ≤2 36

FIGURES Figure 1: z-Scores for Acetochlor 37

Figure 2: z-Scores for Chlordane (cis) 38

Figure 3: z-Scores for Dimethoate 39

Figure 4: z-Scores for Endosulfan I (alpha) 40

Figure 5: z-Scores for EPN 41

Figure 6: z-Scores for Etofenprox 42

Figure 7: z-Scores for Fenamidone 43

Figure 8: z-Scores for Fluvalinate (tau) 44

Figure 9: z-Scores for Linuron 45

Figure 10: z-Scores for Pyriproxyfen 46

Figure 11: z-Scores for Tebuconazole 47

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Figure 12: z-Scores for Triazophos 48

Figure 13: z-Scores for Triflumuron 49

APPENDICES APPENDIX I: Analytical Methods Used by Participants 50

APPENDIX II: Fapas® SecureWeb, Protocol and Contact Details 62

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1. INTRODUCTION

1.1. Proficiency Testing

Proficiency testing aims to provide an independent assessment of the competence of participating laboratories. Together with the use of validated methods, proficiency testing is an essential element of laboratory quality assurance. Further details of the Fapas® – Food Chemistry proficiency testing scheme are available in our protocols [4, 5].

2. TEST MATERIAL

2.1. Preparation

Preparation of the samples for this proficiency test was sub-contracted to a laboratory meeting the quality requirements of the scheme’s accreditation [3]. The test material was prepared from fresh lemons. The bulk sample was split into two batches: one for spiking and one for the blank test material. Sub-samples were taken to screen for the possible presence of incurred residues and the remainder was stored at -20°C. No residues were detected at, or above, 15 μg/kg. Acetochlor, Chlordane (cis), Dimethoate, Endosulfan I (alpha), EPN, Etofenprox, Fenamidone, Fluvalinate (tau), Linuron, Pyriproxyfen, Tebuconazole, Triazophos and Triflumuron were spiked into the test material. Samples were stored at -20°C until dispatch.

2.2. Homogeneity

To test for homogeneity, randomly selected test materials were analysed in duplicate. Testing was sub-contracted to a laboratory meeting the quality requirements of the scheme’s accreditation [3]. These data showed sufficient homogeneity and were not included in the subsequent calculation of the assigned values.

2.3. Dispatch

The start date was 16 April 2018. Test materials were sent to 80 participants.

3. RESULTS

The instructions for reporting results were as follows: • Determine the level of pesticide residues present in the test material, in µg/kg, as

received, uncorrected for recovery, together with the percentage recovery and limit of quantification (LoQ).

• All pesticide residues are to be reported as the parent compound only, unless specified otherwise.

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• If any residues are reported not in the form specified, please note this in the comments box.

• For residues tested for but not detected, please enter an LoQ via the ‘review/resubmit your results’ link on your list of tests. This has to be done after you have submitted results for all pesticide residues detected.

• This is an identification and quantification test, therefore if you analyse for a pesticide that is in the test material, and do not identify it, and your limit of quantification is below the level needed for a satisfactory z-score or you do not submit an LoQ, you will be assessed as if your result was zero.

Results were submitted by 74 participants (93%) before the closing date for this test, 1 June 2018. Each participant was given a laboratory number, assigned in order of receipt of results. The reported analyte concentrations are given in Table 1-Table 5. If a participant analysed for a pesticide residue that was in the test material, but did not identify it, and their limit of quantification was below the level needed for a z-score of -3.0, they were assessed as if their result was zero. If a participant analysed for a pesticide residue that was in the test material, but did not identify it, and their limit of quantification was above the level needed for a z-score of -3.0, the result was recorded as <LoQ. Any participant identifying pesticide residues other than Acetochlor, Chlordane (cis), Dimethoate, Endosulfan I (alpha), EPN, Etofenprox, Fenamidone, Fluvalinate (tau), Linuron, Pyriproxyfen, Tebuconazole, Triazophos and Triflumuron at a level ≥15 µg/kg are listed in Table 6 together with the percentage recovery and LoQ. Participants’ comments are given in Table 7. The analytical methods used by each participant are summarised in APPENDIX I.

4. STATISTICAL EVALUATION OF RESULTS

The results submitted by participants were statistically analysed in order to provide an assigned value for each analyte. The assigned values were then used in combination with the standard deviation for proficiency, σp, to calculate a z-score [6] for each result. The procedure is detailed in the relevant protocols [4, 5]. Further background on the procedure followed can be found in the IUPAC International Harmonised Protocol for the Proficiency Testing of Analytical Chemistry Laboratories [7].

4.1. Calculation of the Assigned Value, xa

The assigned value, xa, for each analyte was derived from the consensus of the results submitted by participants. The following results were excluded from the calculation of the assigned value:

i) non numerical results i.e. qualitative or semi-quantitative results, ii) results reported as approximately 10, 100 or 1000 × greater or smaller than the

majority of submitted results (as these were considered to be reporting errors), iii) results where no percentage recovery was reported, iv) results whose recovery was outside the range 60-140% [8],

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v) results where no limit of quantification was reported. For all analytes, this procedure was straightforward and the robust mean was chosen as the assigned value. The assigned values for all analytes are shown in Table 8.

4.2. Standard Deviation for Proficiency, σp

The standard deviation for proficiency, σp, was set at a value that reflects best practice for the analyses in question. For all analytes, σp was derived from the appropriate form of the Horwitz equation [9]. The values for σp used to calculate z-scores from the reported results of this test are given in Table 8.

4.3. Individual z-Scores

Participants’ z-scores were calculated as:

p

axxzσ

)( −=

where x = the participant’s reported result,

xa = the assigned value and σp = the standard deviation for proficiency.

Participants’ z-scores for all analytes are given in Table 1-Table 5 and shown as histograms in Figures 1–13. It is possible for the z-scores published in this report to differ slightly from the z-score that can be calculated using the formula given above. These differences arise from the necessary rounding of the actual assigned values and standard deviations for proficiency prior to their publication in Table 8. The number and percentage of z-scores in the range -2 ≤ z ≤ 2 for all analytes are given in Table 9.

5. INTERPRETATION OF SCORES

In normal circumstances, over time, about 95% of z-scores will lie in the range -2 ≤ z ≤ 2. Occasional scores in the range 2 <|z| <3 are to be expected, at a rate of 1 in 20. Whether or not such scores are of importance can only be decided by considering them in the context of the other scores obtained by that laboratory. Scores where |z| >3 are to be expected at a rate of about 1 in 300. Given this rarity, such z-scores very strongly indicate that the result is not fit-for-purpose and almost certainly requires investigation. The consideration of a set or sequence of z-scores over time provides more useful information than a single z-score. Examples of suitable methods of comparison are provided in the IUPAC International Harmonised Protocol for the Proficiency Testing of Analytical Chemistry Laboratories [7].

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6. REFERENCES

1 Adobe Approved Trust List, https://helpx.adobe.com/acrobat/kb/approved-trust-list2.html#Whatisit accessed 01/06/2017.

2 GlobalSign PDF Signing Tool, https://www.globalsign.com/en/pdf-signing/ accessed 01/06/2017.

3 ISO/IEC 17043:2010, Conformity assessment – General requirements for proficiency testing.

4 Fapas®, 2017, Protocol for Proficiency Testing Schemes, Version 6, April 2017, Part 1 – Common Principles.

5 Fapas®, 2017, Protocol for Proficiency Testing Schemes, Version 5, April 2017, Part 2 – Fapas® Food Chemistry scheme (FAPAS).

6 AMC Tech Brief No. 74, z-Scores and other scores in chemical proficiency testing – their meanings, and some common misconceptions, Anal. Methods, 2016, 8, 5553.

7 Thompson, M., Ellison, S.L.R. and Wood, R., 2006, The International Harmonised Protocol for the Proficiency Testing of Analytical Chemistry Laboratories, Pure Appl. Chem., 78, No. 1, 145–196.

8 Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed, Document No. SANTE/11945/2015.

9 Thompson, M., 2000, Recent trends in inter-laboratory precision at ppb and sub-ppb concentrations in relation to fitness for purpose criteria in proficiency testing, Analyst, 125, 385-386.

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Table 1: Results and z-Scores for Acetochlor, Chlordane (cis) and Dimethoate

laboratory number

analyte

Acetochlor Chlordane (cis) Dimethoate

assigned value: 88.3 µg/kg assigned value: 34.4 µg/kg assigned value: 182 µg/kg

result % Rec LoQ z-score result % Rec LoQ z-score result % Rec LoQ z-score

001

91 92 10 0.1 35 91 10 0.1 185 94 10 0.1

002

95 90 10 0.3 40 94 10 0.7 175 81 10 -0.2

003

#

#

81.76 98.16 10 -2.7 004

93.6 112.2 5 0.3 113.5 77.8 10 10.4 153.0 115.4 5 -0.8

005

67.7 88 10 -1.1 26.4 107 10 -1.1 198.4 80 10 0.4

006

94 106 10 0.3 42 100 10 1.0 193 100 10 0.3

007

#

31.2 101.3 0.01 -0.4 152.2 83.1 0.01 -0.8

008

119 118 10 1.6 34 89 10 -0.1 199 102 10 0.5

009

93.2

10 0.3 33.9

10 -0.1 189

10 0.2

010

#

#

153 89 5 -0.8

011

76 100 10 -0.6 31 100 10 -0.5 188 100 10 0.2

012

#

#

171.7 96 10 -0.3

013

92 98 10 0.2 38 86 10 0.5 183 100 10 0.0

014

#

#

233 90.6 0.010 mg/kg

1.4

015

#

#

#

z-scores outside |z| >2 are shown in bold, see Section 5

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Table 1 (continued): Results and z-Scores for Acetochlor, Chlordane (cis) and Dimethoate

laboratory number

analyte




016

93.0 105 10 0.2 35.0 98 10 0.1 177.4 97 10 -0.1

017

78.4 118 10.0 -0.5 25.6 121 10.0 -1.2 > 200 124 10.0

018

#

#

136

10 -1.2

019

74.55

-0.7 29.29

-0.7 178.81

-0.1

020

115 63 0.01 1.4 42

0.01 1.0 352 52 0.01 4.5 021

#

#

184 26 10 0.1

022

#

#

#

023

#

#

398 95 10 5.8 024

95.2 78

0.4 30.3 80

-0.5 304.8 119

3.3

025

96.05 101.55 10 0.4 36.74 104.70 10 0.3 220.43 97.10 10 1.0

026

#

0

-4.5 179 104 10 -0.1

027

#

#

240.01 98.4 10 1.6

028

54 100 10 -1.8 31 100 10 -0.5 200 100 10 0.5

029

74.3 90 10 -0.7 28.9 82 10 -0.7 217.9 98 10 1.0

030

78 85 10 -0.5 0

-4.5 230 90 10 1.3


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laboratory number

analyte




031

90.4 104.8 10 0.1 35.1 102.2 34 0.1 127.8 84.6 34 -1.4

032

124 80.6 10 1.8 597 92.3 10 74.2 152 106.4 10 -0.8

033

0.076 106 0.005 -4.5 #

0.23 108 0.005 -4.8 034

#

#

198

10 0.4

035

94 108 5 0.3 35 103 5 0.1 186 90 5 0.1

036

73 100 10 -0.8 30 80 10 -0.6 155 90 10 -0.7

037

140 112.8 10 2.7 90 100 10 7.3 200 74.9 10 0.5

038

#

#

211 97 6 0.8

039

65.7 86 5 -1.2 27.8 91 5 -0.9 169 82 5 -0.3

040

#

#

195

0.4

041

63 99 5 -1.3 24 94 5 -1.4 162 81 5 -0.5

042

#

34.3 104.4 0.01 mg/kg 0.0 200 82.6 0.01 mg/kg 0.5

043

0

-4.5 0

-4.5 181 102 5 0.0

044

99.9 78.5 10 0.6 40.9 65 10 0.9 169.5 83.2 10 -0.3

045

84 101 10 -0.2 30 95 10 -0.6 153 117 10 -0.8


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laboratory number

analyte




046

#

#

152 78.8 10 -0.8

047

85 100 10 -0.2 37 100 10 0.3 211 100 10 0.8

048

#

23 89 10 -1.5 157 89 10 -0.7

049

#

18 85 10 -2.2 167 90 10 -0.4

050

84 92 10 -0.2 #

179 112 10 -0.1

051

#

#

305.05 171.47 10 3.3 052

#

#

166 87 20 -0.4

053

82 89 10 -0.3 35 94 10 0.1 219 106 10 1.0

054

#

#

210

0.8

055

#

0

5 -4.5 210 89.1 5 0.8

056

91.0 97.9 10 0.1 35.1 92.0 10 0.1 189.2 101.1 10 0.2

057

77

10 -0.6 40

10 0.7 172

10 -0.3

058

#

#

184.3 100 5 0.1

059

101 88 10 0.7 22 101 10 -1.6 250 97 10 1.8

060

#

90 139 10 7.3 212 105 10 0.8


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laboratory number

analyte




061

#

#

125.9

3 -1.5

062

100 95 10 0.6 36 95 10 0.2 216 95 10 0.9

063

80 110 10 -0.4 #

190 90 10 0.2

064

65 103 10 -1.2 0

-4.5 116 101 10 -1.7

065

100 125 10 0.6 34 95 10 -0.1 157 103 10 -0.7

066

#

#

#

067

87 91 10 -0.1 34 101 10 -0.1 275 96 10 2.5 068

#

31 90 5 -0.5 185 77 10 0.1

069

0

-4.5 115.59 92 10 10.7 136.41 87 10 -1.2

070

0

-4.5 135 86 10 13.3 143 112 10 -1.0

071

84 110 10 -0.2 34 90 10 -0.1 150 70 10 -0.8

072

0

-4.5 147.4 100 50 14.9 56.1 100 5 -3.3 073

105 112 10 0.9 29 81 10 -0.7 149 90 10 -0.9

074

#

#

#


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Table 2: Results and z-Scores for Endosulfan l (alpha), EPN and Etofenprox

laboratory number

analyte

Endosulfan I (alpha) EPN Etofenprox

assigned value: 125 µg/kg assigned value: 48.6 µg/kg assigned value: 105 µg/kg


001

145 89 10 0.7 44 95 10 -0.4 111 92 10 0.2

002

146 93 10 0.8 56 91 10 0.7 144 93 10 1.7

003

92.95 102.40 10 -1.2 #

#

004

113.8 75.7 10 -0.4 #

119.9 93.7 10 0.6

005

109 92 10 -0.6 33.3 86 10 -1.4 77.0 72 10 -1.2

006

159 100 10 1.2 51 100 10 0.2 115 94 10 0.4

007

98.9 100.4 0.01 -1.0 #

95.6 104.5 0.01 -0.4

008

158 109 10 1.2 62 100 10 1.3 118 107 10 0.5

009

130

10 0.2 13.1

10 -3.3 127

10 0.9

010

#

#

83 88 5 -1.0

011

138 100 10 0.5 41 100 10 -0.7 104 100 10 -0.1

012

83.1 82 10 -1.5 #

83.1 129 10 -1.0

013

125 84 10 0.0 49 86 10 0.0 111 116 10 0.2

014

154 93.1 0.010 mg/kg

1.0 45 96.9 0.010 mg/kg

-0.3 104 97.0 0.010 mg/kg

-0.1

015

#

#

#


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Table 2 (continued): Results and z-Scores for Endosulfan l (alpha), EPN and Etofenprox

laboratory number

analyte




016

161.3 99 10 1.3 49.5 103 10 0.1 98.3 92 10 -0.3

017

134 136 10.0 0.3 37.4 122 10.0 -1.0 95.8 124 10.0 -0.4

018

58.1

10 -2.5 #

#

019

100.84

-0.9 34.28

-1.3 85.76

-0.9

020

149

0.01 0.9 75

0.01 2.5 145 53 0.01 1.7

021

172 -14 10 1.7 #

100 -8.9 10 -0.2

022

#

#

#

023

#

#

#

024

132.4 82

0.3 47.0 78

-0.1 91.2 74

-0.6

025

139.68 105.27 10 0.5 54.96 104.24 10 0.6 109.54 105.73 10 0.2

026

113.4 89 10 -0.4 #

#

027

#

74.31 109.2 10 2.4 113.18 76 10 0.3

028

95 100 10 -1.1 39 100 10 -0.9 92 100 10 -0.6

029

131.2 94 10 0.2 46.1 103 10 -0.2 90.5 92 10 -0.6

030

130 95 10 0.2 27 80 10 -2.0 110 90 10 0.2


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laboratory number

analyte




031

149.9 124.7 34 0.9 48.3 127.2 34 0.0 114.7 163.0 10 0.4

032

127 85.3 50 0.1 40 80.5 10 -0.8 97 95.6 10 -0.4

033

0.11 112 0.005 -4.6 0.055 84 0.005 -4.5 0.12 94 0.005 -4.5 034

150

10 0.9 #

92

10 -0.6

035

142 94 5 0.6 62 113 5 1.3 127 115 5 0.9

036

95 100 10 -1.1 41 100 10 -0.7 91 70 10 -0.6

037

120 72.3 10 -0.2 #

140 96.6 10 1.5

038

105 98 3 -0.7 #

108 100 0.3 0.1

039

97.1 87 5 -1.0 31.3 95 5 -1.6 113 80 5 0.3

040

99

-1.0 28

-1.9 108

0.1

041

96 73 5 -1.1 33 93 5 -1.5 89 115 5 -0.7

042

162 107.1 0.01 mg/kg 1.3 56.5 105.1 0.01 mg/kg 0.7 108 107.9 0.01 mg/kg 0.1

043

97 103 10 -1.0 0

-4.5 0

-4.5 044

136.5 95 50 0.4 60.3 88.3 50 1.1 128.2 103.6 10 1.0

045

114 106 10 -0.4 40 106 10 -0.8 93 110 10 -0.5


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laboratory number

analyte




046

#

#

#

047

158 100 10 1.2 60 100 10 1.1 140 100 10 1.5

048

98 96 10 -1.0 39 81 10 -0.9 79 87 10 -1.1

049

72 85 10 -1.9 #

66 95 10 -1.7

050

#

49 91 10 0.0 #

051

#

#

#

052

151 92 10 0.9 45 102 10 -0.3 97 91 10 -0.4

053

134 93 10 0.3 50 97 10 0.1 105 102 10 0.0

054

101

-0.9 #

110

0.2

055

158 84.6 5 1.2 56 110.6 5 0.7 124 103.1 5 0.8

056

124.4 90.9 10 0.0 51.2 98.5 10 0.2 106.1 96.3 10 0.0

057

156

10 1.1 42

10 -0.6 89

10 -0.7

058

150.6 100 10 0.9 54.9 100 10 0.6 108.2 100 10 0.1

059

160 100 10 1.3 37 96 10 -1.1 130 100 10 1.1

060

133 131 10 0.3 56 82 10 0.7 140 115 10 1.5


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laboratory number

analyte




061

#

#

93.5

3 -0.5

062

110 95 10 -0.6 50 95 10 0.1 100 95 10 -0.2

063

60 70 10 -2.4 61 80 10 1.2 89 80 10 -0.7

064

119 94 10 -0.2 36 101 10 -1.2 79 103 10 -1.1

065

140 104 10 0.5 56 119 10 0.7 109 111 10 0.2

066

#

#

#

067

149 100 10 0.9 45 96 10 -0.3 126 99 10 0.9

068

140 79 5 0.5 55 120 10 0.6 110 107 10 0.2

069

0

-4.6 #

0

-4.5 070

31 81 10 -3.4 58 108 10 0.9 134 99 10 1.2

071

119 80 10 -0.2 40 120 10 -0.8 83 90 10 -1.0

072

0

-4.6 273.4 100 25 21.0 0

-4.5 073

103 91 10 -0.8 54 100 10 0.5 83 92 10 -1.0

074

89

10 -1.3 #

#


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Table 3: Results and z-Scores for Fenamidone, Fluvalinate (tau) and Linuron

laboratory number

analyte

Fenamidone Fluvalinate (tau) Linuron



001

72 93 10 0.7 72 98 10 -0.2 117 92 10 -0.3

002

73 94 10 0.8 80 90 10 0.3 107 91 10 -0.6

003

#

69.79 96.60 10 -0.3 #

004

97.0 109.0 5 2.5 87.6 83.2 10 0.7 0

-4.6 005

47.4 75 10 -1.1 50.5 78 10 -1.5 142.3 100 10 0.6

006

74 105 10 0.8 84 100 10 0.5 132 104 10 0.3

007

53.0 103.0 0.01 -0.7 60.6 108.3 0.01 -0.9 91.8 102.9 0.01 -1.2

008

76 108 10 1.0 92 96 10 1.0 142 102 10 0.6

009

76.4

10 1.0 13.2

10 -3.8 128

10 0.1

010

54 97 5 -0.6 44

5 -1.9 113 82 5 -0.4

011

62 100 10 0.0 84 100 10 0.5 110 100 10 -0.5

012

49.4 95 10 -0.9 72.2 92 10 -0.2 108.8 96 10 -0.6

013

59 100 10 -0.2 105 84 10 1.8 125 100 10 0.0

014

65 94.4 0.010 mg/kg

0.2 74 95.0 0.010 mg/kg

-0.1 138 89.8 0.010 mg/kg

0.5

015

#

#

#


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Table 3 (continued): Results and z-Scores for Fenamidone, Fluvalinate (tau) and Linuron

laboratory number

analyte




016

47.8 93 10 -1.1 84.2 122 10 0.5 0

-4.6 017

61.3 101 10.0 -0.1 81.0 124 10.0 0.3 129 124 10.0 0.2

018

#

#

#

019

50.32

-0.9 56.58

-1.1 127.8

0.1

020

89 77 0.01 1.9 111

0.01 2.1 177 83 0.01 1.9

021

#

78 13 10 0.1 131 0.2 10 0.2

022

#

#

#

023

49.83 93 10 -0.9 #

140 85 10 0.6

024

53.0 108

-0.7 74.1 86

-0.1 133.4 110

0.3

025

#

79.47 108.42 10 0.2 130.10 90.33 10 0.2

026

55.4 72 10 -0.5 #

61.1 92.8 10 -2.3 027

53.39 110.03 10 -0.7 #

130.35 115.9 10 0.2

028

65 100 10 0.2 73 100 10 -0.2 130 100 10 0.2

029

0

-4.5 101.7 103 10 1.6 115.3 112 10 -0.3

030

69 90 10 0.5 19 110 10 -3.4 127 95 10 0.1


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laboratory number

analyte




031

63.7 82.0 10 0.1 135 122.1 67 3.6 107.2 90.1 67 -0.6

032

62 113.1 10 0.0 #

125 123.3 10 0.0

033

0.063 98 0.005 -4.5 0.11 80 0.005 -4.5 0.14 95 0.005 -4.6 034

#

#

#

035

63 94 5 0.0 104 73 5 1.7 132 109 5 0.3

036

58 90 10 -0.3 67 70 10 -0.5 132 80 10 0.3

037

77 80.7 10 1.1 78 113.2 10 0.1 0

-4.6 038

#

#

120 99 0.8 -0.2

039

59.9 78 5 -0.2 58.1 88 5 -1.0 126 81 5 0.0

040

#

#

126

0.0

041

51 109 5 -0.8 53 67 5 -1.4 102 97 5 -0.8

042

65.4 111.5 0.01 mg/kg 0.2 69.7 87.2 0.01 mg/kg -0.4 134 104.4 0.01 mg/kg 0.3

043

78 87 5 1.1 0

-4.5 161 98 10 1.3

044

90.9 107.6 10 2.1 93 117.5 10 1.1 124.6 92 10 0.0

045

52 108 10 -0.8 69 105 10 -0.4 126 111 10 0.0


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Page 23 of 62


laboratory number

analyte




046

62.155 96.25 10 0.0 #

94 78.7 10 -1.1

047

72 100 10 0.7 80 100 10 0.3 145 100 10 0.7

048

47 77 10 -1.1 #

108 108 10 -0.6

049

63 90 10 0.0 49 95 10 -1.6 119 90 10 -0.2

050

#

#

115 99 10 -0.4

051

185.53 640.23 10 9.0 #

565.41 536.87 10 16.1 052

66 102 10 0.3 57 100 10 -1.1 136 82 10 0.4

053

66 106 10 0.3 67 96 10 -0.5 139 96 10 0.5

054

#

#

122

-0.1

055

66 99.7 5 0.3 52 94.4 5 -1.4 132 99.6 5 0.3

056

#

91.9 126.9 10 1.0 123.4 94.7 10 0.0

057

56

10 -0.5 71

10 -0.3 80

10 -1.6

058

67.7 100 10 0.4 105.3 100 10 1.8 145.9 100 10 0.8

059

54 99 10 -0.6 88 102 10 0.7 185 102 10 2.2 060

69 115 10 0.5 95 93 20 1.2 155 113 10 1.1


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Page 24 of 62


laboratory number

analyte




061

#

#

#

062

59 95 10 -0.2 80 95 10 0.3 130 95 10 0.2

063

52 90 10 -0.8 40 80 10 -2.1 141 80 10 0.6

064

51 107 10 -0.8 54 109 10 -1.3 106 86 10 -0.7

065

#

95 132 10 1.2 140 115 10 0.6

066

#

#

#

067

63 99 10 0.0 85 102 10 0.6 152 101 10 1.0

068

72 96 10 0.7 70 110 10 -0.3 108 101 10 -0.6

069

170.64 88 10 7.9 0

-4.5 135.96 89 10 0.4

070

80 89 10 1.3 32 84 10 -2.6 71 86 10 -2.0

071

40 80 10 -1.6 58 120 10 -1.1 100 100 10 -0.9

072

28.5 100 5 -2.5 0

-4.5 63.2 100 5 -2.3 073

38 104 10 -1.8 87 100 10 0.7 101 100 10 -0.9

074

56

20 -0.5 #

#


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Page 25 of 62

Table 4: Results and z-Scores for Pyriproxyfen and Tebuconazole

laboratory number

analyte

Pyriproxyfen Tebuconazole assigned value: 106 µg/kg assigned value: 129 µg/kg

result % Rec LoQ z-score result % Rec LoQ z-score

001

113 94 10 0.3 131 90 10 0.1

002

108 87 10 0.1 121 89 10 -0.3

003

40.76 109.00 10 -2.8 42.17 82.17 10 -3.1 004

94.6 100 5 -0.5 133.8 88.8 5 0.2

005

79.9 78 10 -1.1 90.3 78 10 -1.4

006

119 97 10 0.6 138 98 10 0.3

007

70.7 97.4 0.01 -1.5 93.8 93.5 0.01 -1.3

008

128 114 10 0.9 136 102 10 0.3

009

127

10 0.9 148

10 0.7

010

87 110 5 -0.8 112 96 5 -0.6

011

105 100 10 0.0 127 100 10 -0.1

012

81.3 96 10 -1.1 94.6 89 10 -1.2

013

117 92 10 0.5 132 84 10 0.1

014

117 92.8 0.010 mg/kg 0.5 160 94.4 0.010 mg/kg 1.1

015

#

#


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Page 26 of 62

Table 4 (continued): Results and z-Scores for Pyriproxyfen and Tebuconazole

laboratory number

analyte



016

109.1 99 10 0.1 123.0 89 10 -0.2

017

104 122 10.0 -0.1 131 112 10.0 0.1

018

#

#

019

85.2

-0.9 112.49

-0.6

020

151 51 0.01 1.9 209 70 0.01 2.9 021

125 -4.8 10 0.8 131 0.4 10 0.1

022

#

#

023

108.07 87 10 0.1 156.05 88 10 1.0

024

130.2 118

1.0 151.1 92

0.8

025

121.40 104.52 10 0.7 143.57 97.75 10 0.5

026

45.1 98 10 -2.6 106.9 88 10 -0.8

027

106.86 106.86 10 0.0 121.91 102 10 -0.2

028

125 100 10 0.8 132 100 10 0.1

029

75.3 105 10 -1.3 141.9 102 10 0.5

030

91 100 10 -0.6 140 90 10 0.4


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Page 27 of 62


laboratory number

analyte



031

132.4 103.6 10 1.1 120.7 84.0 34 -0.3

032

124 90.3 10 0.8 133 93.5 10 0.1

033

0.044 89 0.01 -4.5 0.15 108 0.01 -4.6 034

89

10 -0.7 214

10 3.0

035

135 108 5 1.2 155 102 5 0.9

036

88 110 10 -0.8 105 100 10 -0.9

037

200 78.3 10 4.0 210 93.2 10 2.9 038

#

#

039

107 87 5 0.0 138 87 5 0.3

040

125

0.8 172

1.5

041

67 76 5 -1.7 91 102 5 -1.4

042

#

115 110.9 0.01 mg/kg -0.5

043

83 114 10 -1.0 119 96 10 -0.4

044

131.2 85 10 1.1 176.6 100.1 10 1.7

045

93 94 10 -0.6 123 106 10 -0.2


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Page 28 of 62


laboratory number

analyte



046

83.71 108 10 -1.0 75 74.9 10 -1.9

047

142 100 10 1.5 172 100 10 1.5

048

87 93 10 -0.8 123 99 10 -0.2

049

68 95 10 -1.6 64 90 10 -2.3 050

#

129 89 10 0.0

051

16406.80 14133.16 10 698.3 #

052

118 102 10 0.5 143 102 10 0.5

053

127 107 10 0.9 151 97 10 0.8

054

114

0.3 152

0.8

055

127 100.2 5 0.9 153 107.5 5 0.9

056

122.0 98.2 10 0.7 154.1 97.4 10 0.9

057

55

10 -2.2 57

10 -2.6 058

127.1 100 10 0.9 135.8 100 10 0.2

059

100 99 10 -0.3 146 101 10 0.6

060

139 119 10 1.4 166 119 10 1.3


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Page 29 of 62


laboratory number

analyte



061

76.9

3 -1.3 33.9

3 -3.4 062

105 95 10 0.0 130 95 10 0.0

063

98 110 10 -0.3 105 80 10 -0.9

064

89 108 10 -0.7 96 97 10 -1.2

065

116 102 10 0.4 151 111 10 0.8

066

#

#

067

130 98 10 1.0 132 102 10 0.1

068

113 119 3 0.3 131 106 3 0.1

069

177.95 88 10 3.1 21.49 92 10 -3.8 070

126 107 10 0.9 135 92 10 0.2

071

100 80 10 -0.3 125 90 10 -0.1

072

18.3 100 5 -3.8 96.8 100 5 -1.1

073

95 88 10 -0.5 148 103 10 0.7

074

80

100 -1.1 #


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Page 30 of 62

Table 5: Results and z-Scores for Triazophos and Triflumuron

laboratory number

analyte

Triazophos Triflumuron assigned value: 41.1 µg/kg assigned value: 103 µg/kg


001

48 93 10 0.8 100 95 10 -0.1

002

43 93 10 0.2 91 88 10 -0.5

003

25.75 73.58 10 -1.7 #

004

65.7 102.9 5 2.7 92.1 108.4 5 -0.5

005

30.7 70 10 -1.1 114.4 95 10 0.5

006

51 112 10 1.1 107 103 10 0.2

007

37.4 93.5 0.01 -0.4 #

008

40 108 10 -0.1 120 112 10 0.8

009

44.6

10 0.4 78.0

10 -1.1

010

33 102 5 -0.9 82 103 5 -0.9

011

40 100 10 -0.1 80 100 10 -1.0

012

33.7 95 10 -0.8 #

013

50 106 10 1.0 99 102 10 -0.2

014

49 89.3 0.010 mg/kg 0.9 121 93.4 0.010 mg/kg 0.8

015

38.7 94.2 10 -0.3 #


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Page 31 of 62

Table 5 (continued): Results and z-Scores for Triazophos and Triflumuron

laboratory number

analyte



016

41.3 86 10 0.0 96.7 96 10 -0.3

017

41.0 123 10.0 0.0 123 120 10.0 0.9

018

#

#

019

35.94

-0.6 108.93

0.3

020

57

0.01 1.8 134

0.01 1.4

021

48 27 10 0.8 111 16 10 0.4

022

40.42 96.98 5 -0.1 #

023

#

180 85 10 3.4 024

42.8 90

0.2 120.0 119

0.8

025

42.38 100.59 10 0.1 #

026

45.9 105 10 0.5 63.8 70 10 -1.7

027

#

#

028

32 100 10 -1.0 104 100 10 0.1

029

37.8 105 10 -0.4 97 89 10 -0.2

030

42 100 10 0.1 112 90 10 0.4


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laboratory number

analyte



031

43.1 110.6 34 0.2 #

032

45 110.5 10 0.4 95 113.4 10 -0.3

033

0.051 96 0.005 -4.5 0

-4.5 034

0

-4.5 #

035

42 105 5 0.1 114 88 5 0.5

036

30 90 10 -1.2 85 120 10 -0.8

037

61 93.2 10 2.2 140 95.3 10 1.7

038

#

#

039

37.9 84 5 -0.4 89.7 88 5 -0.6

040

47

0.7 122

0.9

041

22 79 5 -2.1 30 115 5 -3.2 042

42.0 108.5 0.01 mg/kg 0.1 107 111 0.01 mg/kg 0.2

043

85 89 5 4.9 193 96 5 4.0 044

48.1 120 10 0.8 81.3 102.3 10 -0.9

045

36 88 10 -0.6 100 116 10 -0.1


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Page 33 of 62


laboratory number

analyte



046

#

#

047

43 100 10 0.2 118 100 10 0.7

048

37 98 10 -0.5 87 117 10 -0.7

049

28 85 10 -1.4 72 95 10 -1.4

050

41 88 10 0.0 #

051

#

#

052

43 102 10 0.2 #

053

43 101 10 0.2 136 99 10 1.5

054

43

0.2 99

-0.2

055

52 109.5 10 1.2 99 96.8 5 -0.2

056

43.2 94.5 10 0.2 #

057

35

10 -0.7 109

10 0.3

058

39.4 100 10 -0.2 #

059

43 99 10 0.2 130 99 10 1.2

060

44 108 10 0.3 0

10 -4.5


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Page 34 of 62


laboratory number

analyte



061

#

66.2

3 -1.6

062

49 95 10 0.9 97 95 10 -0.2

063

45 75 10 0.4 122 80 10 0.9

064

25 104 10 -1.8 94 86 10 -0.4

065

39 98 10 -0.2 #

066

#

#

067

32 99 10 -1.0 201 99 10 4.4 068

47 104 10 0.7 99 113 10 -0.2

069

36.35 89 10 -0.5 0

-4.5 070

44 109 10 0.3 77 84 10 -1.1

071

33 90 10 -0.9 92 100 10 -0.5

072

153.3 100 25 12.4 0

-4.5 073

36 100 10 -0.6 93 93 10 -0.4

074

33

10 -0.9 #


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Table 6: Additional Pesticide Residues Reported

laboratory number pesticide residue ≥15 μg/kg result μg/kg

recovery %

LoQ μg/kg

018 Cyhalothrin-lambda 31.1 10

023 Flonicamid 322.34 91 10

024 Chlordane (trans) 28.8 72

037 Chlordane (trans) 90 100 10

040 Chlordane (trans) 27

040 Dieldrin 62

043 Carbofuran 90 110 10

055 Chlordane (trans) 60 89.8 5

069 Endosulfan II (beta) 52.69 90 10

069 Fenpropimorph 53.66 91 10

072 2,4-D (free acid only) 462 100 10

072 Azinphos-ethyl 172.1 100 50

072 THPI 39.2 100 25

Table 7: Participants’ Comments

laboratory number comments

005 cis chlordane was calculated from a technichal mix of known purity.

023 Compound not in list but detected are Clethodim 114.3 ug/kg and Forchlorfenuron 145.36 ug/kg

027 We received the sample not in good condition. Stay 2 days in Fed Ex facilities without keeping in Freezer or Refrigerator.

034 on Blank sample Etofenprox detected but not quantified (< 10 ppb)

037 All results reported above are in ug/kg (ppb) as well as the LoQ. Please note that we as a Laboratory use Chlordane as a Technical mixture and report it as Chlordane and do not report it individually therefore we have included both as Cis and Trans and gi

047 We also found traces of Hexythiazox at 3 Âµg/kg

051 PT was held up in customs during shipment; it was shipped April 16 and arrived April 24. PT may not have been properly refrigerated during that time period and could have adversely affected our results.

055 Spuren von Hexythiazox gefunden

059 Hexythiazox has been detected below LoQ

070 We do not differentiate between cis or trans Chlordan, the MRL applies to the sum. For this submission we choose the cis entry.

comments are as submitted by participants but some may have been edited to maintain participant anonymity

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Table 8: Assigned Values and Standard Deviations for Proficiency

analyte data points, n

assigned value, xₐ µg/kg

uncertainty, u

standard deviation for proficiency, σp

Acetochlor 36 88.3 2.7 Horwitz [9] 19.4

Chlordane (cis) 39 34.4 1.3 Horwitz [9] 7.58

Dimethoate 56 182 5 Horwitz [9] 37.6

Endosulfan I (alpha) 50 125 4 Horwitz [9] 27.4

EPN 44 48.6 1.6 Horwitz [9] 10.7

Etofenprox 48 105 3 Horwitz [9] 23.2

Fenamidone 51 62.4 1.7 Horwitz [9] 13.7

Fluvalinate (tau) 45 75.5 3.0 Horwitz [9] 16.6

Linuron 54 125 3 Horwitz [9] 27.3

Pyriproxyfen 54 106 3 Horwitz [9] 23.3

Tebuconazole 57 129 3 Horwitz [9] 28.1

Triazophos 55 41.1 1.0 Horwitz [9] 9.04

Triflumuron 41 103 3 Horwitz [9] 22.6

Table 9: Number and Percentage of z-Scores where |z| ≤2

analyte number of scores where |z| ≤2

total number of scores

% |z|≤2

Acetochlor 39 45 87

Chlordane (cis) 37 50 74

Dimethoate 61 69 88

Endosulfan I (alpha) 58 64 91

EPN 46 52 88

Etofenprox 59 63 94

Fenamidone 52 59 88

Fluvalinate (tau) 46 56 82

Linuron 58 66 88

Pyriproxyfen 59 67 88

Tebuconazole 58 67 87

Triazophos 59 66 89

Triflumuron 46 54 85

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Figure 1: z-Scores for Acetochlor

43 69 70 72 33 28 41 64 39 5 36 29 19 11 57 30 17 63 53 45 50 71 47 67 31 1 56 13 16 9 4 6 35 2 24 25 44 62 65 59 73 20 8 32 37

127 µg/kg

88.3 µg/kg

49.4 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

z-score

Laboratory Number

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Page 38 of 62

Figure 2: z-Scores for Chlordane (cis)

26 30 43 55 64 49 59 48 41 17 5 39 29 73 19 36 45 24 11 28 68 7 9 8 65 67 71 42 1 16 35 53 31 56 62 25 47 13 2 57 44 6 20 37 60 4 69 70 72 32

49.6 µg/kg

34.4 µg/kg

19.3 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

z-score

Laboratory Number

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Page 39 of 62

Figure 3: z-Scores for Dimethoate

33 72 3 64 61 31 18 69 70 73 71 32 46 7 4 10 45 36 48 65 41 52 49 39 44 12 57 2 16 19 26 50 43 13 21 58 1 68 35 11 9 56 63 6 40 34 5 8 28 37 42 54 55 38 47 60 62 29 53 25 30 14 27 59 67 24 51 20 23

257 µg/kg

182 µg/kg

107 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

z-score

Laboratory Number

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Page 40 of 62

Figure 4: z-Scores for Endosulfan I (alpha)

69 72 33 70 18 63 49 12 74 3 28 36 41 43 39 48 7 40 19 54 73 38 5 62 26 4 45 64 71 37 56 13 32 9 30 29 24 60 17 53 44 11 25 65 68 35 1 2 20 67 31 34 58 52 14 57 8 47 55 6 59 16 42 21

180 µg/kg

125 µg/kg

70.5 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

z-score

Laboratory Number

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Page 41 of 62

Figure 5: z-Scores for EPN

43 33 9 30 40 39 41 5 19 64 59 17 28 48 32 45 71 11 36 57 1 14 52 67 29 24 31 13 50 16 53 62 6 56 73 58 25 68 2 55 60 65 42 70 47 44 63 8 35 27 20 72

69.9 µg/kg

48.6 µg/kg

27.2 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

z-score

Laboratory Number

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Page 42 of 62

Figure 6: z-Scores for Etofenprox

43 69 72 33 49 5 48 64 10 71 73 12 19 41 57 63 29 36 24 28 34 45 61 7 17 32 52 16 21 62 11 14 53 56 38 40 42 58 65 25 30 54 68 1 13 39 27 31 6 8 4 55 67 9 35 44 59 70 37 47 60 2 20

152 µg/kg

105 µg/kg

59.1 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

z-score

Laboratory Number

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Page 43 of 62

Figure 7: z-Scores for Fenamidone

29 33 72 73 71 48 5 16 12 23 19 41 64 45 63 7 24 27 10 59 26 57 74 36 13 62 39 17 11 32 46 35 49 67 31 14 28 42 52 53 55 58 30 60 1 47 68 2 6 8 9 37 43 70 20 44 4 69 51

89.8 µg/kg

62.4 µg/kg

34.9 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

z-score

Laboratory Number

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Figure 8: z-Scores for Fluvalinate (tau)

43 69 72 33 9 30 70 63 10 49 5 55 41 64 19 52 71 39 7 36 53 45 42 3 68 57 1 12 28 14 24 21 37 25 2 47 62 17 6 11 16 67 73 4 59 56 8 44 60 65 29 35 13 58 20 31

109 µg/kg

75.5 µg/kg

42.3 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

z-score

Laboratory Number

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Figure 9: z-Scores for Linuron

4 16 37 33 26 72 70 57 7 46 71 73 41 64 2 31 48 68 12 11 10 50 29 1 49 38 54 56 44 13 32 39 40 45 30 19 9 17 28 62 25 27 21 6 35 36 55 24 42 69 52 14 53 23 65 63 8 5 47 58 67 60 43 20 59 51

179 µg/kg

125 µg/kg

70.2 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

z-score

Laboratory Number

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Figure 10: z-Scores for Pyriproxyfen

33 72 3 26 57 41 49 7 29 61 5 74 12 43 46 19 10 48 36 34 64 30 45 4 73 63 59 71 17 11 62 27 39 2 23 16 1 68 54 65 13 14 52 6 25 56 32 21 28 40 70 9 53 55 58 8 67 24 44 31 35 60 47 20 69 37 51

153 µg/kg

106 µg/kg

59.4 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

z-score

Laboratory Number

NOT CONTROLL

ED WHEN PRIN

TED


Page 47 of 62

Figure 11: z-Scores for Tebuconazole

33 69 61 3 57 49 46 5 41 7 12 64 72 36 63 26 10 19 42 43 31 2 27 16 45 48 71 11 50 62 1 17 21 68 13 28 67 32 4 70 58 8 6 39 30 29 52 25 59 9 73 53 65 24 54 55 56 35 23 14 60 40 47 44 20 37 34

185 µg/kg

129 µg/kg

72.8 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

z-score

Laboratory Number

NOT CONTROLL

ED WHEN PRIN

TED


Page 48 of 62

Figure 12: z-Scores for Triazophos

34 33 41 64 3 49 36 5 28 67 10 71 74 12 57 19 45 73 69 48 7 29 39 15 65 58 8 11 22 17 50 16 30 35 42 25 24 2 47 52 53 54 59 31 56 60 70 9 32 63 26 40 68 1 21 44 14 62 13 6 55 20 37 4 43 72

59.2 µg/kg

41.1 µg/kg

23.0 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

z-score

Laboratory Number

NOT CONTROLL

ED WHEN PRIN

TED


Page 49 of 62

Figure 13: z-Scores for Triflumuron

33 60 69 72 41 26 61 49 70 9 11 44 10 36 48 39 2 71 4 73 64 32 16 29 62 13 54 55 68 1 45 28 6 42 19 57 21 30 35 5 47 8 24 14 40 63 17 59 20 53 37 23 43 67148 µg/kg

103 µg/kg

57.5 µg/kg

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

1.0

2.0

3.0

4.0

z-score

Laboratory Number

NOT CONTROLL

ED WHEN PRIN

TED


Page 50 of 62

APPENDIX I: Analytical Methods Used by Participants

Methods are tabulated according to the information supplied by participants, but some responses may have been combined or edited for clarity.

Accredited Method Used laboratory number

no 014 023 024 035 044 052

yes 001 002 003 004 005 006 007 008 009 010 011 012 013 015 016 017 019 020 021 022 026 027 029 030 031 032 033 036 037 038 041 042 045 046 047 049 050 051 053 054 055 057 058 059 060 061 062 063 064 066 068 071 073

Method Based On laboratory number

International Standard 002 008 010 013 014 020 023 026 027 029 030 032 033 035 036 037 041 042 044 045 046 050 053 057 059 060 063 064 066 067 068

National Standard 001 006 011 022 038 054 055

Paper Published In An International Journal

003 009 015 016 052 058 071

Manufacturer/Kit Instructions/Technical Note

007 021

In house method 004 005 012 017 019 024 031 047 049 051 061 062 073

Quoted percentage recovery measured in same analytical batch as test material

laboratory number

no 004 009 045 049 053 059 066

yes 001 002 003 005 006 007 008 010 011 012 013 014 015 016 017 019 020 021 022 023 024 026 027 029 030 031 032 033 035 036 037 038 041 042 044 046 047 050 051 052 054 055 057 058 060 062 063 064 068 071 073

If measured in this batch, stage spike added

laboratory number

prior to extraction 001 002 003 005 006 007 008 010 011 012 013 014 015 016 017 019 020 021 022 023 024 027 029 030 031 032 033 035 037 038 041 042 044 045 046 047 049 050 051 052 053 054 055 057 058 060 062 063 064 067 068 071 073

NOT CONTROLL

ED WHEN PRIN

TED


Page 51 of 62

If measured in this batch, stage spike added (continued)

laboratory number

prior to clean up 026

Concentration of Spike (µg/kg) laboratory number

≥5 - <10 018 022 036 055 063 068

≥10 - <25 003 007 013 017 021 027 029 032 033 041 044 045 046 049 050 052 057 058 071

≥25 - <50 047 054

≥50 - <100 002 004 006 008 010 011 012 015 016 019 020 024 030 035 051 060 064 073

≥100 001 005 014 023 026 038 042 053 059 062 067

Composition of Blank Commodity used for Spiking

laboratory number

blank provided 001 002 005 007 008 011 013 014 015 016 019 020 021 022 023 024 026 030 031 035 036 037 038 041 044 045 046 047 049 050 051 052 053 054 058 059 060 061 062 063 067 071 073

blank from our laboratory 033 057 068

blank commodity from former analysis 055

Carrot 017

comercial blank 010 027 032 042

Fresh lemon fruit 029

Matriz de limon 012

organic lemon 006

Calibration laboratory number

standard addition 006 041 047 051 062

matrix-matched 001 002 004 005 006 007 008 009 011 014 019 021 022 023 024 026 027 029 031 033 035 037 038 041 042 044 045 046 049 051 052 053 054 055 057 058 059 060 064 067 068

solvent 002 010 015 032 035 050 063

multi-level 002 003 010 012 013 015 016 017 018 020 024 030 035 036 041 042 051 052 055 057 061 064 066 071 073

single-level 002 006

NOT CONTROLL

ED WHEN PRIN

TED


Page 52 of 62

Internal Standard Added laboratory number

no 001 004 010 012 018 022 023 024 029 038 044 052 061 063

yes 002 005 006 007 008 009 011 013 014 015 016 017 019 020 021 027 030 031 032 033 035 036 037 041 042 045 046 047 049 050 051 053 054 055 057 058 059 060 062 064 066 068 071 073

Internal Standard Used laboratory number

ANTRACENO D10 and ISOPROTURON D6

009

Atrazine and Tionazin 032

Atrazine-d5 016

CAFFEINE 068

chlorpyrifos d10, difenoconazol d6, isoproturon d6

055

Isodrin, HCH-alpha 008

Linuron D6, Chlorpyrifos D10 041

only to check extraction efficiency 002

ORTOFENIL TRIFOSFATO 019

PCB 31/Sulfotep 011 059 067

PCB, HBB 006

PCB-108 062

PCB209 066

PCB52 027 046

Phenanthrene-d10, TDPP 064

Several 049

TPP 005 006 007 008 013 014 015 017 020 021 026 030 033 035 036 042 045 047 0051 54 058 060 062 064 071 073

Carbaryl-d7 058

Sulprophos 073

Carbendazime-D4, Acetamiprid-D3, Tiacloprid-D4, Clotianidina-D3

007

Pirimicarb D6 060

Malathion-d10, Carbendazim-d3, Dichlorvos-D6

014

Trifenil metano - Atrazina D5 - Nicarbazin

053

TRIS 050

NOT CONTROLL

ED WHEN PRIN

TED


Page 53 of 62

GC Method: Sample Weight (g) laboratory number

010

≥1 - <5 001 011 012 026 038 054 062

≥5 - <10 006 008 015 016 018 022 041 047 058 059 066 073

≥10 - <20 002 003 004 005 007 009 013 014 017 019 021 024 027 029 030 032 033 035 036 042 044 045 046 049 052 053 055 057 060 063 067 068 071

≥20 - <50 020 031 064

GC Method: Extraction Solvent Components

laboratory number

acetone 020 064

acetonitrile 001 002 004 005 006 007 008 009 011 012 013 014 015 016 017 018 019 021 022 024 026 027 029 031 033 036 038 041 042 044 045 046 047 052 053 054 055 057 058 059 060 062 063 066 067 068 071 073

ethyl acetate 003 020 032 049

water 020 041

Acetic acid 052

cyclohexane 020

Quechers extraction 035

GC Method: Extraction pH Adjusted laboratory number

no 003 004 005 009 011 012 019 021 022 024 030 031 032 035 036 038 044 045 047 051 052 053 059 063 066 068 071

yes 001 002 006 007 008 013 014 015 016 017 018 020 026 027 029 033 041 042 046 049 054 055 057 058 060 062 073

GC Method: Extraction Techniques Used

laboratory number

macerate at room temperature 031

QuEChERS 001 002 004 005 006 007 008 009 011 012 013 014 015 016 017 018 019 021 022 024 026 027 029 032 033 035 036 038 041 042 044 045 046 047 049 052 053 054 055 057 058 059 060 062 063 064 066 067 068 071 073

NOT CONTROLL

ED WHEN PRIN

TED


Page 54 of 62

GC Method: Extraction Techniques Used (continued)

laboratory number

liquid-liquid partition 003 030 064

DFG S19 020

GC Method: Sample Clean-up Technique

laboratory number

GPC/HPGPC 046

liquid-liquid partition 020 030

none 003 011 022 038 049 059 063 067

solid phase extraction (SPE) (column/cartridge)

016 031 064

solid phase extraction (SPE) (dispersive)

001 002 004 005 006 007 008 009 012 013 014 015 017 018 019 021 026 027 029 032 033 035 036 041 042 044 045 047 052 053 054 055 057 058 060 062 066 068 071 073

Quechers DSPE 024

GC Method: SPE Sorbent Type laboratory number

C18 004 005 007 013 024 027 030 032 041 059

Envicarb/GCB 026 031

PSA 001 002 004 006 008 009 012 014 015 017 018 019 021 024 029 033 035 036 042 044 045 046 052 053 054 055 057 058 060 062 066 068 071

Mixed Mode 016 047 073

MgSO4 024 071

GC Method: GC Column Packing laboratory number

65% methyl 35% phenyl polysiloxane 030

95% methyl 5% phenyl polysiloxane 001 002 003 004 005 006 007 008 009 011 013 014 016 017 018 019 020 021 022 024 026 029 032 033 038 041 044 045 046 047 049 052 053 054 055 057 058 059 060 062 063 066 067 068 073

5% diphenyl / 95 % dimethyl polysiloxane

027

5% Phenyl-Methyl Siloxane 071

5%DIPHENYL 95%DIMETHYL POLSYLOXANE

042

NOT CONTROLL

ED WHEN PRIN

TED


Page 55 of 62

GC Method: GC Column Packing (continued)

laboratory number

Agilent HP-5MS UI 035

DB-5MS ultra inert 015

Vf-5 012

GC Method: GC Detector Type laboratory number

ECD 018

FPD 022

MS 002 004 006 020 031 032 060 062 066

MS-MS 001 002 003 005 006 007 008 009 011 012 013 015 016 017 019 021 024 026 027 029 030 033 035 036 038 041 042 044 045 046 047 049 051 052 053 054 055 057 058 059 060 062 063 067 068 071 073

Orbitrap 014

PFPD 018

LC Method: Sample Weight (g) laboratory number

≥1 - <5 001 011 012 026 038 050 054 062

≥5 - <10 006 008 015 016 020 023 037 041 047 058 059 073

≥10 - <20 002 004 005 007 009 010 013 014 017 019 021 024 029 030 031 032 033 035 036 042 044 045 046 049 051 052 053 055 057 060 061 063 064 067 068 071

LC Method: Extraction Solvent Components

laboratory number

acetone 055

acetonitrile 001 002 004 005 006 007 008 009 010 011 012 013 014 015 016 017 019 020 021 023 024 026 029 031 032 033 036 038 041 042 044 045 046 047 049 050 051 052 053 054 055 057 058 059 060 061 062 063 064 067 068 071 073

methanol 037

Acetic Acid 052

Quechers extraction 035

water 041

NOT CONTROLL

ED WHEN PRIN

TED


Page 56 of 62

LC Method: Extraction pH Adjusted laboratory number

no 004 009 011 012 019 021 023 024 030 031 032 035 036 038 045 047 050 051 052 053 059 063 068 071

yes 001 002 006 007 008 010 013 014 015 016 017 020 029 033 041 042 044 046 049 054 055 057 058 060 061 062 073

LC Method: Extraction Techniques Used

laboratory number

QuEChERS 001 002 004 005 006 007 008 009 010 011 012 013 014 015 016 017 019 020 021 023 024 026 029 031 032 033 035 036 038 041 042 044 045 046 047 049 050 051 052 053 054 055 057 058 059 060 061 062 063 064 067 068 071 073

liquid-liquid partition 030 037

LC Method: Sample Clean-up Technique

laboratory number

GPC/HPGPC 046

liquid-liquid partition 030

none 009 011 014 031 035 037 038 047 049 059 063 067

solid phase extraction (SPE) (column/cartridge)

005 016 026

solid phase extraction (SPE) (dispersive)

001 002 004 006 007 008 010 012 013 015 017 019 020 021 023 029 032 033 036 041 042 044 045 050 051 052 053 054 055 057 058 060 061 062 064 068 071 073

Quechers DSPE 024

LC Method: SPE Sorbent Type laboratory number

C18 004 007 013 024 030 032 041 059

Envicarb/GCB 026

PSA 001 002 004 006 008 010 012 015 017 019 020 021 024 029 033 036 042 044 045 046 051 052 053 054 055 057 058 060 061 068 071

NH2 005

Mixed Mode 016 023 073

MgSO4 024 071

phase seperation 062

NOT CONTROLL

ED WHEN PRIN

TED


Page 57 of 62

LC Method: HPLC Column Packing laboratory number

C18 001 002 004 005 006 007 008 009 010 011 012 013 015 016 017 019 020 021 023 024 026 029 030 032 033 035 036 038 041 042 045 046 047 049 050 051 052 053 054 057 058 060 062 063 064 067 068 071 073

C8 014 059

Mixed Mode 037

biphenyl 044 061

LC method: Mobile Phase Components

laboratory number

ethanoic acid (acetic acid) 032 037

acetonitrile 001 004 005 011 012 029 031 032 033 050 054 055

ammonium acetate 006 007 031

ammonium formate 002 009 010 012 013 014 015 016 020 023 024 029 032 033 035 036 038 041 046 047 052 053 057 060 062 063 068 071 073

formic acid (methanoic acid) 005 007 012 013 014 017 024 029 033 041 046 052 055 062 073

methanol 002 004 006 007 008 010 013 015 016 017 020 021 023 024 035 036 037 041 042 044 045 046 047 049 051 052 057 058 059 060 061 062 067 068 071 073

water 002 004 005 006 007 010 011 012 015 016 017 020 021 024 026 029 030 032 033 035 036 037 041 042 044 046 047 050 051 052 055 060 061 062 063 064 071 073

LC Method: Detector Type laboratory number

MS-MS 001 002 004 005 006 007 008 009 010 011 012 013 015 016 017 019 020 021 023 024 026 029 030 031 032 033 035 036 037 038 041 042 044 045 046 047 049 050 051 052 053 054 055 057 058 059 060 061 062 064 067 068 071 073

Orbitrap 014

Q-TOF 063

NOT CONTROLL

ED WHEN PRIN

TED


Page 58 of 62

Acetochlor

Method Principle laboratory number

GC 024 053 062 071

LC 032

Identification by Mass Spectrometry laboratory number

yes 024 032 053 062 071

Chlordane (cis)


GC 007 024 032 042 053 060 062 071


yes 007 024 032 042 053 060 062 071

Dimethoate


GC 018 021 042 052 053

LC 007 010 023 024 032 051 060 062 071


no 018

yes 007 010 021 023 024 032 042 051 052 053 060 062 071

Endosulfan I (alpha)


GC 007 018 021 024 032 042 052 053 060 062 071

NOT CONTROLL

ED WHEN PRIN

TED


Page 59 of 62


no 018

yes 007 021 024 032 042 052 053 060 062 071

EPN


GC 024 042 052 060 062 071

LC 032


yes 024 032 042 052 060 062 071

Etofenprox


GC 007 021 024 042 052 060 062

LC 010 032 071


yes 007 010 021 024 032 042 052 060 062 071

Fenamidone


GC 042 052

LC 007 010 023 024 032 051 060 062 071


yes 007 010 023 024 032 042 051 052 060 062 071

NOT CONTROLL

ED WHEN PRIN

TED


Page 60 of 62

Fluvalinate (tau)


GC 007 021 024 042 052 060 062 071

LC 010 053


yes 007 010 021 024 042 052 053 060 062 071

Linuron


GC 042

LC 007 010 021 023 024 032 051 052 060 062 071


yes 007 010 021 023 024 032 042 051 052 060 062 071

Pyriproxyfen


GC 007 021 052 053 060 071

LC 010 023 024 032 051 062


yes 007 010 021 023 024 032 051 052 060 062 071

Tebuconazole


GC 021 042 052 062 071

NOT CONTROLL

ED WHEN PRIN

TED


Page 61 of 62

Method Principle (continued) laboratory number

LC 007 010 023 024 032 060


yes 007 010 021 023 024 032 042 052 060 062 071

Triazophos


GC 007 021 024 042 052

LC 010 032 060 062 071


yes 007 010 021 024 032 042 052 060 062 071

Triflumuron


LC 010 021 023 024 032 042 062 071


no 021

yes 010 023 024 032 042 062 071

NOT CONTROLL

ED WHEN PRIN

TED


Page 62 of 62

APPENDIX II: Fapas® SecureWeb, Protocol and Contact Details

1. Fapas® SECUREWEB

Access to the secure area of our website is only available to participants in our proficiency tests. Please contact us if you require a UserID and Password. Fapas® SecureWeb allows participants to:

• Obtain their laboratory numbers for the proficiency tests in which they have participated.

• View the results they submitted in past and current proficiency tests. • Submit their results and methods for current tests. • Review future tests they have ordered. • Order proficiency tests, reference materials and quality control materials. • Freely download copies of reports (PDF file), of proficiency tests in which they have

participated. • View charts of their z-scores obtained in previous Fapas® – Food Chemistry

proficiency tests.

2. PROTOCOL

The Protocols [4, 5] set out how Fapas® – Food Chemistry is organised. Copies can be downloaded from our website.

3. CONTACT DETAILS

This report was prepared and authorised on behalf of Fapas® by Simon Hunter (Round Coordinator). Participants with any comments or concerns about this proficiency test should contact:

Fapas® Fera Science Ltd (Fera)

National Agri-Food Innovation Campus Sand Hutton

York YO41 1LZ

UK

Tel: +44 (0)1904 462100 Fax: +44 (0)1904 500440

[email protected] www.fapas.com

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