printed when controlled not - merieux nutrisciences › ... › files › 20171124.pdf ·...

NOT CONTROLL

ED WHEN PRIN

TED

of 47

Fapas® – Food Chemistry Proficiency Test Report 20143

Illegal Dyes in Hot Pepper Sauce

October-November 2017

NOT CONTROLL

ED WHEN PRIN

TED

Food Chem. Report 20143

of 47

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) 2017. All rights reserved.

NOT CONTROLL

ED WHEN PRIN

TED


of 47

SUMMARY

1. The test material for Fapas® – Food Chemistry proficiency test 20143 was dispatched in October 2017. Each participant received a hot pepper sauce test material. From a list of fourteen illegal dyes participants had to identify and, optionally, quantify those present.

2. The test material contained Sudan III, Sudan IV and Sudan Orange G. 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. However, those for Sudan

Orange G were given for information only.

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

Sudan III 399 46 67 69

Sudan IV 87.6 39 53 74

Sudan Orange G 128 22 41 54

italics indicate for information only

4. Qualitative results for this proficiency test are summarised as follows:

analyte number of satisfactory qualitative assessments

total number of qualitative assessments

(including <LOD and NS)

satisfactory %

Sudan III 8 15 53

Sudan IV 6 22 27

Sudan Orange G 7 10 70

NOT CONTROLL

ED WHEN PRIN

TED


of 47

CONTENTS

1. INTRODUCTION 5

1.1. Proficiency Testing 5

2. TEST MATERIAL 5

2.1. Preparation 5

2.2. Homogeneity 5

2.3. Dispatch 5

3. RESULTS 5

4. STATISTICAL EVALUATION OF RESULTS 6

4.1. Calculation of the Assigned Value, xa 7

4.2. Standard Deviation for Proficiency, σp 7

4.3. Individual z-Scores 7

4.4. Assessment of Qualitative Results 8

4.5. Additional Dyes Identified 8

5. INTERPRETATION OF SCORES 8

6. REFERENCES 9

TABLES Table 1: Qualitative Results and assessments for Sudan III and Sudan IV 10

Table 2: Qualitative Results and assessments for Sudan Orange G 12

Table 3: Quantitative Results and z-Scores for Sudan III and Sudan IV 13

Table 4: Quantitative Results and z-Scores for Sudan Orange G 17

Table 5: Additional Dyes Reported 21

Table 6: Participants’ Comments 22

Table 7: Summary of Qualitative Assessments 23

Table 8: Assigned Values and Standard Deviations for Proficiency 23

Table 9: Number and Percentage of z-Scores where |z| ≤2 23

FIGURES Figure 1: z-Scores for Sudan III 24

Figure 2: z-Scores for Sudan IV 25

Figure 3: z-Scores for Sudan Orange G 26

APPENDICES APPENDIX I: Analytical Methods Used by Participants 27

APPENDIX II: Fapas® SecureWeb, Protocol and Contact Details 47

NOT CONTROLL

ED WHEN PRIN

TED


of 47

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 hot pepper sauce was purchased from a retail source. Sudan III, Sudan IV, and Sudan Orange G were spiked into the test material. Samples were stored at ambient 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 4 October 2017. Test materials were sent to 89 participants.

3. RESULTS

The instructions for reporting results were as follows: 1) This sample may contain any of the illegal dyes listed below:

Dye (common name) CAS number Dye (common name) CAS number

Butter Yellow (Dimethyl yellow) 60-11-7 Sudan IV 85-83-6 Orange II 633-96-5 Sudan Black B 4197-25-5 Para Red 6410-10-2 Sudan Orange G 2051-85-6 Rhodamine B 81-88-9 Sudan Red B 3176-79-2 Sudan I 842-07-9 Sudan Red 7B 6368-72-5 Sudan II 3118-97-6 Sudan Red G 1229-55-6 Sudan III 85-86-9 Toluidine Red 2425-85-6

NOT CONTROLL

ED WHEN PRIN

TED


of 47

2) You may submit either qualitative OR quantitative results for each dye.

a) To submit a positive QUALITATIVE result, i.e. if you analysed for a dye and found it present, enter your result as ‘detected’.

b) To submit a positive QUANTITATIVE result, enter your result in µg/kg (corrected for recovery).

c) For negative results, i.e. if you analysed for a dye qualitatively and found it absent or quantitatively and it was below your LOD, enter your result as ‘not detected’.

d) In all cases: a. please enter an LOD via the ‘review/resubmit’ link on your list of tests. NB

this has to be done after you have submitted results for all dyes detected. Entering an LOD is important because if you analyse for a dye that is in the test material but you do not detect it, then your LOD is taken into account when assessing your result. If you do not give an LOD, your result will be assessed as if your LOD was zero.

b. please enter the percentage purity of the dye standard and whether or not your result was corrected for this percentage purity.

e) If you do not test for a dye please ensure you tick the ‘not tested’ box for that dye. 3) Your attention is drawn to Statutory Analysis Government Chemist Programme Ad Hoc

Project 1, October 2006, Analysis of Illegal Dyes in Paprika Powder by LC-MS/MS which concerns illegal dye determination and can be obtained in pdf format by using the following web address, https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/510960/Analysis_of_illegal_dyes_in_paprika_powder_by_LC_MSMS.pdf.

Results were submitted by 86 participants (97%) before the closing date for this test, 15 November 2017. Each participant was given a laboratory number, assigned in order of receipt of results. The reported analyte concentrations and assessments are given in Table 1 to Table 4. Participants’ comments are given in Table 6. 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].

NOT CONTROLL

ED WHEN PRIN

TED


of 47

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). For Sudan III and Sudan IV, this procedure was straightforward and the robust mean was chosen as the assigned value. For Sudan Orange G, the major mode was chosen as the assigned value due to the distribution of results being skewed, as shown in the kernel density plot in Figure 3. The assigned value and z-scores are given for information only for this analyte due to the high uncertainty. 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 three added illegal dyes, σp was derived from the appropriate form of the Horwitz equation [8]. 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 three added illegal dyes are given in Table 3 and Table 4, and shown as histograms in Figures 1–3. Those for Sudan Orange G are given for information only. 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.

NOT CONTROLL

ED WHEN PRIN

TED


of 47

4.4. Assessment of Qualitative Results

For Sudan III, Sudan IV, and Sudan Orange G participants who had reported their results qualitatively were assessed as follows: • For each of the three dyes reported as ‘detected’, participants were assessed as

satisfactory or not satisfactory. • Where participants had reported one of these three dyes as ‘not detected’ they were

assessed against their limit of detection (LOD). If their LOD was lower than the value required to receive a z-score of -3 they were assessed as ‘NS’ (not satisfactory). If their LOD was equal to or greater than the value required to receive a z-score of -3 then they are marked in Table 1 and Table 2 as ‘<LOD’. If no LOD was given, the participant’s result was assessed as if their LOD was zero.

Qualitative assessment of participants’ results are given in Table 1 and Table 2, and a summary of qualitative assessments is given in Table 7. For the three illegal dyes knowingly added to the matrix during test material preparation it can confidently be assumed that the participants’ consensus should be ‘detected’. Where a test material is known to be positive with respect to added dyes, results may be expressed as Satisfactory or Not Satisfactory.

4.5. Additional Dyes Identified

Any participants identifying dyes other than Sudan III, Sudan IV, and Sudan Orange G are listed in Table 5 together with the dyes reported, the level determined if applicable, and the LOD.

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].

NOT CONTROLL

ED WHEN PRIN

TED


of 47

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 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.

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 1: Qualitative Results and assessments for Sudan III and Sudan IV

laboratory number analyte

Sudan III Sudan IV expected result: detected

53% satisfactory expected result: detected

27% satisfactory

result LOD µg/kg

purity of standard

%

assessment result LOD µg/kg

purity of standard

%

assessment

001 detected 10 S detected 10 S

003 detected 2.706 S detected 4.728 S 004 not detected 1000 <LoD not detected 1000 <LoD

005 not detected NS 010 Detected NA NA S not detected NS

015 detected 3 S

018 not detected NS not detected NS 022 not detected 150 Y <LoD

023 DETECTED 250 N S DETECTED 250 N S 024 not detected 2000 <LoD not detected 2000 <LoD

025 detected 500 S not detected NS

026 not detected NS 031 not detected NS

036 not detected 500 <LoD not detected 500 <LoD 045 not detected 2.00 N NS

S = Satisfactory NS = Not Satisfactory

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 1 (continued): Qualitative Results and assessments for Sudan III and Sudan IV


Sudan III Sudan IV expected result: detected

53% satisfactory expected result: detected

27% satisfactory

result LOD µg/kg

purity of standard

%

assessment result LOD µg/kg

purity of standard

%

assessment

048 not detected NS

049 detected 50 S 050 detected 20 S detected 20 S

065 not detected NS not detected NS 066 not detected NS

069 not detected NS

070 not detected NS 071 not detected 500 Y <LoD not detected 500 Y <LoD

073 detected S detected S 076 not detected NS

079 detected 65 N S

082 detected S detected S 083 not detected 250 <LoD

086 not detected 300 70-130 <LoD


NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 2: Qualitative Results and assessments for Sudan Orange G


Sudan Orange G expected result: detected

70% satisfactory

result LOD µg/kg

purity of standard %

assessment

001 detected 10 S

003 detected 8.022 S

004 not detected 1000 <LoD

007 not detected 200 N <LoD

010 Detected NA NA S

025 detected S

049 detected 50 S

050 detected 20 S

071 not detected 500 Y <LoD

073 detected S

082 detected S

086 not detected 300 70-130 <LoD


NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 3: Quantitative Results and z-Scores for Sudan III and Sudan IV

laboratory number

analyte

Sudan III Sudan IV

assigned value 399 μg/kg assigned value 87.6 μg/kg

result LOD μg/kg

purity of standard, %

z-score result LOD μg/kg


z-score

001

002 452 10

0.7 99 5

0.6

003

004

005 585 500 98.1% Y 2.5

006 433.8 50 92.8 0.5 75.2 50 91.8 -0.6

007 460 200 N 0.8 360 200 N 14.1 008

009 260 10 78 N -1.9 50 10 80 N -2.0

010 011 259.00 10 105%; N (not

applied to result)

-1.9 17.00 10 113%; N (not applied to

result)

-3.7

012 122 10 80 (N) -3.8 75 10 80 (N) -0.7

013 273.3 100

-1.7 74.8 100

-0.7

014 478 10

1.1 83 10

-0.2

015 420 3

0.3 016 393 3,33 -0.1 017 500.5 100 N 1.4 135 100 N 2.5 018

019 308.99 40 Y -1.2 88.51 40 Y 0.0

020 592 10 97 Y 2.6 131 10 91 Y 2.2 021 367 10 Y -0.4 75 10 Y -0.7

022 927 150 Y 7.2 023

024 025

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

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 3 (continued): Quantitative Results and z-Scores for Sudan III and Sudan IV

laboratory number

analyte

Sudan III Sudan IV


result LOD μg/kg




z-score

026 667 500 Y 3.7 027 303.92 2.00 N, 100% -1.3 65.56 2.00 N, 99% -1.1

028 546 10 80%, Y 2.0 110 10 85%, Y 1.2

029 238 10 106%, N -2.2 030 804 10 5.5 77 10 -0.6

031 433 30 N 0.5 032 551 10 474% Y 2.1 86 10 367% Y -0.1

033 0.53 0.2 y -5.4 0.37 0.2 y -4.5 034 305 15 N -1.3 111 15 N 1.2

035 267 50 N -1.8 60 50 N -1.4

036 037 299.81 10 Y -1.4 128.25 10 Y 2.1 038 442 N 0.6 84 N -0.2

039 437.67 100 56% yes 0.5 79.03 100 65% yes -0.4

040 157 10 72% & Y -3.3 17 10 82% & Y -3.7 041 415.5 500 N 0.2 120.8 500 N 1.7

042 96 -4.1 81 -0.3

043 303 4 Y -1.3 51.7 4 Y -1.9

044 266.22 1 -1.8 76.33 1 -0.6

045 212.2 2.00 N -2.5 046 257.21 4 N -1.9 28.21 10 N -3.1 047 515 10 100, N 1.6 99 10 100, N 0.6

048 293 50 Y -1.4 049 050


NOT CONTROLL

ED WHEN PRIN

TED


of 47


laboratory number

analyte

Sudan III Sudan IV


result LOD μg/kg




z-score

051 > 200 5 83%, N

78 5 87%, N -0.5

052 694 50 100, Y 4.0 14 10 100, Y -3.8 053 506 4 102/y 1.5 51 10 74/y -1.9

054 642 30 73,8 % & Yes

3.3 123 30 83,5 % & Yes

1.8

055 515 50

1.6 117 50

1.5

056 463.473 4 N 0.9 93.555 10 N 0.3

057 426.8 50

0.4 187 50

5.2 058 334 LOQ =

10µg/kg 80% Y -0.9 56 LOQ =

10µg/kg 82% Y -1.6

059 293 20 -1.4 98.5 20 0.6

060 336.5 20 -0.9 103.5 20 0.8

061 547 5 N 2.0 103 10 110%, N 0.8

062 333 5 N -0.9 74 5 N -0.7

063 178 10 N -3.0 131 10 N 2.2 064 259.80

-1.9 92.19

0.2

065

066 240.93 10 -2.2 067 183.64

n -2.9 64.86

n -1.2

068 1133 10 97.3 corrected

10.0 80 10 89 corrected -0.4

069

201.114 5.8

5.9

070 352 10

-0.6

071 072 476 10 Y & 100 1.1 100 10 Y & 115 0.6

073

074 419.6 10 87% Y 0.3 075 312 100 N -1.2


NOT CONTROLL

ED WHEN PRIN

TED


of 47


laboratory number

analyte

Sudan III Sudan IV


result LOD μg/kg




z-score

076

077 475.20 1 N 1.0 102.83 1 N 0.8

078 689 20

4.0 118 20

1.6

079 287 65 N -1.5

080 137 30 99% Y -3.6 31 30 91% Y -2.9 081 472 2 PPb 80% (Y) 1.0 125 2 PPb 80%(Y) 1.9

082

083 370 250 Y -0.4 084 518 10 N 1.6 45 10 N -2.2 085 373 20 N -0.4 86 20 N -0.1

086 703 200 90-110, N 4.2


NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 4: Quantitative Results and z-Scores for Sudan Orange G


Sudan Orange G assigned value 128 μg/kg

result LOD μg/kg


z-score

001

002 189 10

2.2

003

004

005

006

007

008

009 120 10 63 N -0.3

010 011 137.00 10 91%; N (not applied

to result) 0.3

012 69 10 80 (N) -2.1

013

014 64 10

-2.3

015 110 3

-0.7

016 110 3,33 -0.7

017 74 100 N -1.9

018

019 322.81 40 Y 7.0

020 1297 10 95 Y 41.8

021 195 10 Y 2.4

022 023

024 025


NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 4 (continued): Quantitative Results and z-Scores for Sudan Orange G



result LOD μg/kg


z-score

026

027

028

029 138 10 91%, N 0.3

030 81 10

-1.7

031

032 587 10 108% Y 16.4

033

034 240 15 N 4.0

035 036

037 428.69 10 Y 10.7

038 557

N 15.3

039

040

041 042 70

-2.1

043 104 4 Y -0.9

044 57.84 1

-2.5

045 228.1 2.00 N 3.6

046 047 048

049 050


NOT CONTROLL

ED WHEN PRIN

TED


of 47




result LOD μg/kg


z-score

051 122 5 100%, N -0.2

052 85 50 100, Y -1.5

053

054 221 30 89,1 % & Yes 3.3

055 148 50

0.7

056

057

058

059 89.3 20 -1.4

060 103.8 20 -0.9

061 141 5 95%, N 0.5

062 190 5 N 2.2

063 28 10 N -3.6

064 136.73

0.3

065 405 200 N 9.9

066 146.92 10 0.7

067 145.96

n 0.6

068 175 10 94.9 corrected 1.7

069

070 177 10

1.7

071 072 318 10 Y & 81 6.8

073

074 152.7 10 82% Y 0.9

075


NOT CONTROLL

ED WHEN PRIN

TED


of 47




result LOD μg/kg


z-score

076

077

078

079

080 199 200 117% N 2.5

081

082

083

084 152 10 N 0.8

085 107 20 N -0.8

086


NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 5: Additional Dyes Reported

lab number

dye qualitative quantitative

result lod purity % corrected

result lod purity % corrected

007 Para Red

90 200 N

011 Sudan Red B 17 10 72%; N (not

applied to result)

015 Sudan Red B detected 3

025 Para Red detected

025 Sudan I detected 500

025 Sudan II detected 1000

025 Sudan Black B detected

025 Sudan Red G detected

025 Toluidine Red detected

033 Sudan II 0.28 0.2 y

037 Orange II 417.48 20 Y

052 Toluidine Red 42 10 100, Y

056 Sudan I 2.334 4 N

068 Sudan Red B 48.4 10 87 corrected

069 Butter Yellow (Dimethyl Yellow)

detected 4

069 Para Red 86.4 4

069 Sudan I 154.5 4.5

069 Sudan II 68 4.5

070 Sudan Red B 279 20

073 Sudan Red B detected

082 Sudan I detected

084 Sudan red B 45 10 N

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 6: Participants’ Comments

participant number comments

001 calculated amounts of detected analytes SOG, SIII, SIV as follows: 203, 490, 107 ug/kg respectively. (Not corrected to Recovery, n=6, RSD < 10%

003 Tests are done qualitative _ detected

008 Sudan I LOD 1000µg/kg

012 Trace of Sudan Black B

013 LODs of our method are 100µg/kg for all dyes but in fact we can quantifie 50µg/kg

015 Sudan IV and Sudan Red B coelute with the same transitions in our LC/MS system. Our 'quantitative' results are 100ppb of either single analyte, or some combination of the two.

018 NO this analysis is not under ISO scope.

020 Results are corrected for recovery

021 LOD for Para Red is 50ug/kg; LOD for Butter Yellow (Dimethyl Yellow) ,Sudan I,Sudan Black B,Sudan Red G ,Para Red,Sudan II,Sudan Red 7B,Toluidine Red are 10ug/kg

026 Recovery applied to result by ISTD

034 Matrix effect was taken to account

036 Results are below LOQ of our method

041 A working limit of 500 µg/kg is proposed as the reporting LOQ.

051 LOD means LOQ

054 Sudan Red B is a positional isomer of Sudan IV - we don't have possibilities to separate these parameters.

069 dimethyl yellow detected qualitativly

071 We don´t recieved the first sample. We requested a new sample to FAPAS that recieved en November. We can see peak at the same time that Para Red, Sudan II, Sudan III and Sudan Red 7B (under LOD), but they can not be spectroscopy identified

072 Coelution Sudan IV and Sudan Red B - result expressed in Sudan IV

074 We cannot separate Sudan IV and Sudan Red B, so we report them as a sum in routine. In this test we got a signal for these compounds, which is calculated with 48.7 µg/kg.

083 LOQ: 250 ug/kg for Sudan I,II,IV

086 ASTA Method 28.0 (2005) (HPLC-UV), LOD= 300 µg/kg, LOQ= 1000 µg/kg

comments are as submitted by participants

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Table 7: Summary of Qualitative Assessments

analyte number of satisfactory (S) qualitative assessments

total number of qualitative assessments

(S, NS & <LOD)

satisfactory %

Sudan III 8 15 53

Sudan IV 6 22 27


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, µg/kg

Sudan III 66 399 20 Horwitz [8] 73

Sudan IV 52 87.6 4.8 Horwitz [8] 19.3

Sudan Orange G 41 128 12 Horwitz [8] 28


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

analyte number of scores where |z| ≤2

total number of scores

% |z| ≤2

Sudan III 46 67 69

Sudan IV 39 53 74



NOT CONTROLL

ED WHEN PRIN

TED


of 47

Figure 1: z-Scores for Sudan III

33 42 12 80 40 63 67 45 29 66 46 11 64 9 44 35 13 79 48 59 37 43 27 34 19 75 62 58 60 70 21 83 85 16 41 74 15 57 31 6 39 38 2 7 56 81 77 72 14 17 53 47 55 84 28 61 32 5 20 54 26 78 52 86 30 22 68

545 µg/kg

399 µg/kg

252 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


of 47

Figure 2: z-Scores for Sudan IV

33 52 11 40 46 80 84 9 53 43 58 35 67 27 62 13 12 21 6 44 30 51 39 68 42 14 38 32 85 19 64 56 59 2 47 72 77 61 60 28 34 55 78 41 54 81 37 20 63 17 57 69 7

126.2 µg/kg

87.6 µg/kg

49.1 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


of 47

Figure 3: z-Scores for Sudan Orange G

this histogram is given for information only

63 44 14 12 42 17 30 52 59 60 43 85 15 16 9 51 64 11 29 61 67 66 55 84 74 68 70 2 62 21 80 54 45 34 72 19 65 37 38 32 20

184 µg/kg

128 µg/kg

72 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


of 47

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.

Is the Method Used Accredited? laboratory number

yes 004 005 008 009 011 015 019 020 021 022 026 027 028 032 036 037 043 045 047 052 053 060 061 065 069 073 074 080 081 083

no 006 007 010 018 025 034 035 041 048 054 055 057 063 067 068 072 078 079

What is Your Method Based On? laboratory number

International Standard 015 022 028 063 081

National Standard 047

Paper Published In An International Journal 020 043 068 069

Manufacturer/Kit Instructions/Technical Note 010 019 032 035 048 057

In house method 004 005 006 007 008 009 011 018 021 025 026 027 034 036 037 041 045 052 053 054 055 060 061 065 067 070 073 074 078 079 080 083

Sample Amount Used for Analysis (g) laboratory number

<1 018 055 083

≥1 - <2 004 010 011 043 045 048 052 067 068 073

≥2 - <5 007 008 022 025 026 027 032 035 037 041 047 053 054 061 065 069 070 078 079

≥5 - <10 005 006 009 034 036 057 063 072 074 080

≥10 - <15 020 028 081

≥20 - <30 019 021

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sample Treatment Prior to HPLC laboratory number

blend / homogenise with solvent 005 018 019 034 037 041 057 069 070 079 080

centrifuge 004 007 010 011 018 019 027 036 045 052 061 067 068

dilute 004 015 019 045 047 052 065 067 078

dissolve in water 006 010

evaporate 036

filter 005 009 015 018 019 022 036 037 052 063 065 067

hydrolysis 036

internal standard addition 019 061

liquid/liquid extraction 067

solid phase extraction (SPE) 057

solvent extraction 008 010 011 015 019 021 025 026 028 032 035 043 048 053 054 055 061 065 072 073 074 081 083

sonicat 068

sonicate 041

Syringe filter 020

Sample Clean-up Technique for Vet Drugs/Illegal Dyes

laboratory number

filter 005 007 008 011 020 021 022 034 035 036 037 048 055 060 063 065 069 070 073 074 079 080 081

GPC/HPGPC 009 026 037

liquid/liquid extraction 006 027 036 052 061 068 083

solid phase extraction (SPE) (column/cartridge)

032 057

solvent exchange 036

none 004 010 015 018 025 028 041 045 047 054 072 078

SPE Sorbent Type laboratory number

C18 032 057 069 081

none 025

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Calibrations laboratory number

solvent 011 018 035 041 055 057 065 073

matrix-matched 027 028 037 043 053 067 068 070 081 083

single-level 005 020

multi-level 006 007 008 009 022 026 032 034 036 037 048 063 065 069 072 074 079 080

standard addition 015 019 021 025 034 045 047 052 054 055 060 061 074 078

Type of Internal Standard Added laboratory number

none 006 009 015 018 021 022 025 028 032 034 035 041 048 052 057 063 065 069 072 080 083

Stable Isotope Labelled Analogue 019 026 027 045 055 070

structural analogue 073 074 078 081

addition of the same standard 054

Sudan1-D5 and Sudan 4-D6 011

HPLC Column Packing for Illegal Dyes laboratory number

C18 004 005 006 007 008 009 010 011 018 020 021 022 026 027 028 032 034 035 036 037 041 045 047 048 053 054 057 061 063 065 067 068 069 070 072 073 074 078 079 080 081 083

HPLC Column Temperature (°C) laboratory number

ambient 005 007 018 021 037 054 061 065 069 074 078 079 080 081

>ambient - <50 004 006 008 009 010 015 019 020 022 026 027 028 032 034 035 036 041 045 048 052 053 057 063 067 068 070 072 073 083

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Mobile Phase Components laboratory number

acetate 037 045

ethanoic acid (acetic acid) 005 026 067 079

acetone 004

acetonitrile 005 006 008 010 015 018 019 021 022 028 035 037 045 047 053 054 055 061 067 068 069 072 074 079 081 083

formic acid (methanoic acid) 010 011 015 019 032 037 045 054 061 072 074 083

ion pair agent 065

methanol 010 011 026 032 036 037 052 065 067 070 078

phosphate 065

water 004 007 009 011 015 018 019 020 021 026 028 032 035 036 037 047 052 054 055 057 061 063 067 068 072 074 078 079 083

0.1% Formic acid in water and in methanol 041

A:0.10% Formic acid in H2O, B: 0.10% Formic acid in MeOH

027

acetic acid 080

Ammonim formate/formic acid buffer/methanol

034

ammonium acetate 073

Buffer 0.04% TFA : ACN 048

Mobile Phase Programme laboratory number

isocratic 005 018 028 045 081

gradient 004 006 007 008 009 010 011 015 019 020 021 022 026 027 032 034 035 036 037 041 043 048 052 053 054 055 057 061 063 065 067 068 069 070 072 073 074 078 079 080 083

HPLC Detector Type laboratory number

Diode Array Detector 004 007 018 022 036 048 065 069 080

MS-MS 009 010 011 015 019 020 021 026 027 028 032 034 035 037 041 043 045 047 052 053 054 055 057 060 061 063 067 068 070 072 073 074 078 081 083

UV 006

UV/Vis 005 008 079

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Non HPLC Method Used laboratory number

direct sample analysys (DSA) coupled with MS-TOF

025

Sudan III

If a recovery was calculated for this analyte please state recovery

laboratory number

100 027 052

100.5% 021

102% 053

105% 011

107.9 019

474% 032

78 009 048

87 074

89.3 022

89.71 037

90 068

92% 007

92.8 006

95 083

96 020

98.1 005

99% 080

no 047

Standard Addition 063

Was your result corrected for recovery? laboratory number

yes 005 006 019 020 021 026 032 037 048 052 053 068 074 080 083

no 007 009 010 011 022 027 034 035 041 045 047 055 060 061 063 067 072 073 078

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Source of Standards laboratory number

Acros 006 080

Dr Ehrenstorfer 009 021 022 026 027 035 041 048 074 078

Sigma/Aldrich 005 007 010 011 020 032 034 037 045 052 060 061 063 068 072 073 083

Wako 019

ACCU 047

TRC 067

If the purity of the dye standard was determined please state purity

laboratory number

%98 067

>95% 041

100% 034

105.5% 061

85 068 080

90% 047

94,8 078

95% 072

96 052

96% 009

96%; Standard purity was determined by Sigma/ Aldrich.

011

96,0% 074

96.0% 021

96.1 083

96.5% 022

97 048

99% 027 032

99.9% 007

Did you correct for the purity of the dye standard?

laboratory number

yes 007 009 011 022 027 032 034 045 048 052 055 061 067 068 072 074 078 080 083

no 006 019 020 021 026 037 041 047 060 063 073

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Wavelength (nm) for DAD/UV detectors laboratory number

478 048

478 & 500 005

500 006

505 022

510 007 080

Ions monitored (MS/MS confirmation) laboratory number

156/197.1 010

156-196 073

353 078

353,2-197,2 / 128,1 / 156,1 074

353.0, 77.0 037

353.1/197 019

353.1>196.1 ; 353.1>197.1 052

353.1>197.1,128.0 045

353.1>76.9 026

353.19>77.06 063

353.1-92.1-197.1 083

353/128 009

353/77;353/196 032

353>196, 353>120 027

353>77, 92 041

353-120 061

353-156;353-120 021

353-77 072

77 034

es? 067

UPLC/MS/MS 047

yes 068

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sudan IV


laboratory number

100 052

102.5 037

107.9 019

113% 011

367% 032

74% 053

80 009

80% 080

91.8 006

92% 007

93 020

93.0% 021

99 027

no 047



yes 006 019 020 021 032 037 052 053 080

no 007 009 011 027 034 035 041 047 055 060 061 063 067 069 072 073 078


Acros 006 080

Dr Ehrenstorfer 009 021 027 035 041 047 078

Sigma/Aldrich 007 011 020 032 037 052 060 061 063 072 073

Wako 019

Institut of Leather Industry 034

sigma 069

TRC 067

NOT CONTROLL

ED WHEN PRIN

TED


of 47


laboratory number

%98 067

>95% 041

?80% 060

100 072

118.9% 061

85 080

88.5% 034

94% 009 047

96 020 052


011

99% 027 032 069

99,6 078

99.0% 021

99.9% 007


laboratory number

yes 007 009 011 027 032 034 052 055 060 061 067 069 072 078 080

no 006 019 020 021 037 041 047 063 073


488 069

500 006

510 007 080

NOT CONTROLL

ED WHEN PRIN

TED


of 47


381-224; 381-106 021

224-276 073

381 078

381.0, 91.0 037

381.1/224.1 019

381.1>224.1 ; 381.1>225.1 052

381.2- 224.2, 106.1 020

381.22>91.11 063

381/224 009

381/91;381/224 032

381>224, 381>91 027

381>91, 106 041

381-106 061

381-91 072

91 034

es? 067

UPLC/MS/MS 047

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sudan Orange G


laboratory number

100 052

107.9 019

108% 032

117% 080

63 009

82 074

86.9 037

89.5% 021

90 020

91% 011



yes 019 020 021 032 037 052 074

no 009 010 011 034 055 060 061 063 065 067 072 073 080


Acros 063 080

Dr Ehrenstorfer 009 021

Fluka 063

Sigma/Aldrich 010 011 020 032 034 037 045 052 060 061 063 065 072 073 074

Supelco 063

Wako 019

TRC 067

NOT CONTROLL

ED WHEN PRIN

TED


of 47


laboratory number

%98 067

100 072

85 080

85% 034

85.0 045


011

97 052

98,5% 074

98.5% 061

98.6% 009 021

99% 032


laboratory number

yes 009 011 032 034 045 055 061 067 072 074 080

no 019 020 021 037 060 063 065 073


401 080

430 065

NOT CONTROLL

ED WHEN PRIN

TED


of 47


212.9>92.1 ; 212.9>121.0 052

215,2-93,0 / 121,9 074

215.1, 93.1 037

215.1/92.9;215.1/122.1 032

215.1>93.0,122.0 045

215.13>93.13 063

215/93 009

215-122 061

215-93;215-122 021

251.1/93.1 019

381-91 072

92-120 073

93 034

93/122 010

es? 067

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Butter Yellow (Dimethyl Yellow)


no 069


sigma 069


laboratory number

96.2 069


laboratory number

yes 069


488 069

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Orange II


laboratory number

99.5 037


yes 037


Sigma/Aldrich 037


laboratory number

no 037


327.0, 171.1 037

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Para Red


laboratory number

92% 007


no 007 069


Sigma/Aldrich 007

sigma 069


laboratory number

95% 007 069


laboratory number

yes 007 069


488 069

510 007

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sudan I


no 069


sigma 069


laboratory number

99% 069


laboratory number

yes 069


488 069

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sudan II


no 069


sigma 069


laboratory number

87% 069


laboratory number

yes 069


488 069

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Sudan Red B


laboratory number

72% 011

90 068


yes 068

no 011 073


Sigma/Aldrich 011 068 073


laboratory number

85 068


011


laboratory number

yes 011 068

no 073


224-209-156-91 073

yes 068

NOT CONTROLL

ED WHEN PRIN

TED


of 47

Toluidine Red


laboratory number

100 052


yes 052


Sigma/Aldrich 052


laboratory number

96 052


laboratory number

yes 052


381.1>224.1 ; 381.1>225.1 052

NOT CONTROLL

ED WHEN PRIN

TED


of 47

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 Guy Beavis (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

printed when controlled not - merieux nutrisciences › ... › files › 20171124.pdf ·...

Documents