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Guy JAMET PhD<br />

SCL: Service Commun des Laboratoires<br />

Leader of a pesticide residues unit in<br />

Strasbourg<br />

Deputy of France for pesticides normalisation<br />

at the CEN institute in Berlin<br />

Past president and active member of EPRW<br />

1<br />

Guy Jamet – STRBG


Lay out of the presentation<br />

‣ Organisation of plant protection products in France<br />

‣ Competences of each partner<br />

‣ The controls<br />

‣ Requirements of labs dealing with PPP<br />

‣ Characterization, validation and accreditation<br />

‣ Sanco mandatory and possible application<br />

‣ Statistical tools<br />

‣ The different steps of GC/MS validation in our lab<br />

‣ The “Dossier” of validation<br />

‣ Opening on the QuEChERS method and LC-MS/MS<br />

2<br />

Guy Jamet – STRBG


Organisation of plant protection<br />

‣ Ministry of agriculture : DGAL<br />

‣ No official laboratories<br />

‣ Recognition of labs in department<br />

‣ Ministry of finances<br />

products in France<br />

‣ Directory of competition, consumers and frauds<br />

repression: DGCCRF<br />

‣ Directory of food and feed: Laboratories: SCL<br />

3<br />

Guy Jamet – STRBG


Competences of each partner<br />

‣ Ministry of agriculture:<br />

‣ Authorization of use for PPP<br />

‣ Directory of food and feed:<br />

‣ Follow up of good agricultural practices<br />

‣ <strong>Control</strong>s in the fields before selling<br />

‣ <strong>Control</strong> by application of PPP<br />

‣ Posses its own system of enforcement<br />

‣ Directory of competition, consumers and frauds repression.<br />

‣ <strong>Control</strong>s at selling points of local production and import<br />

‣ Respect of MRL, detection of misusing, frauds<br />

‣ Enforcement is different<br />

4<br />

Guy Jamet – STRBG


The controls<br />

‣ Official labs depending of the Finances Ministry<br />

‣ Official controls<br />

‣ EU monitoring<br />

‣ National enforcement<br />

‣ Report to DGCCRF<br />

‣ Partnership with DGAL on recognition<br />

‣ State a formal conformity or non conformity<br />

‣ Department labs depending of the executive organism of the<br />

department<br />

‣ Recognised by DGAL<br />

‣ May be mandated by DGCCRF<br />

‣ Advise about of the legality of the sample<br />

5<br />

Guy Jamet – STRBG


Enforcement and Sampling<br />

DU SCL<br />

SCL LAB<br />

Samples<br />

Results<br />

Conclusions<br />

CCRF Inspectorates<br />

Survey<br />

Remaining of the rules<br />

2 nd <strong>Control</strong> sampling predicted<br />

Corrupted<br />

Sample<br />

<strong>Control</strong><br />

1) Document in dispute<br />

2) Destruction of the<br />

commodity<br />

6<br />

Guy Jamet – STRBG


Requirements of labs dealing<br />

with PPP<br />

‣ Accreditation<br />

‣ According ISO 17025<br />

‣ Validated Methods<br />

‣ According EU 2002-657<br />

‣ DG Sanco guidelines<br />

‣ According accreditation bodies requirements<br />

‣ Fix or flexible scope<br />

‣ Reference to recognized methods<br />

‣ Participation to<br />

‣ Proficiency testing<br />

‣ EUPT if they are involved in the EU monitoring<br />

7<br />

Guy Jamet – STRBG


8<br />

Guy Jamet – STRBG<br />

Characterization, validation and<br />

accreditation<br />

‣ Characterization of a method:<br />

‣ Evaluation of the steps introducing variability<br />

‣ Validation of method:<br />

‣ Statement according the characterization results if the<br />

method is fit for the purpose via an acceptable measured<br />

uncertainty<br />

‣ Accreditation:<br />

‣ Statement a lab is providing a recognized level of safety<br />

‣ Validation is a part of accreditation<br />

‣ Traceability is the other wider part.


Sanco mandatory and possible<br />

application<br />

9<br />

Guy Jamet – STRBG


Sample<br />

Mandatory<br />

Characterization<br />

‣ Sampling<br />

‣ Transport<br />

‣ Sample processing<br />

‣ Contamination and interference<br />

‣ Test portions weighing<br />

‣ Extraction condition<br />

‣ Purification<br />

‣ Concentration of extract<br />

‣ Dilution<br />

10<br />

Guy Jamet – STRBG


Standards<br />

Mandatory<br />

Characterization<br />

‣ Identity ‣ Identity to the library<br />

‣ Purity<br />

‣ Consistent spectra<br />

‣ Storage of stock standards<br />

‣ Storage of working standards<br />

‣ Frequency of replacement<br />

‣ Stability of stock standards<br />

‣ Stability of working<br />

standards<br />

11<br />

Guy Jamet – STRBG


Calibration<br />

Mandatory<br />

‣ Limits and MRL<br />

Characterization<br />

‣ LCL, LOD, LOQ:<br />

‣ Not calculated<br />

‣ But determination of RSD<br />

‣ Interpolation<br />

‣ Visual inspection of calibration<br />

and curves<br />

‣ Dynamic range of calibration<br />

‣ Interpolation: Difference<br />

between 2 levels


Sequences<br />

Mandatory<br />

‣ Length of the sequence<br />

Characterization<br />

‣ Calibration standard<br />

‣ 2 dilutions per samples x n<br />

samples<br />

‣ Calibration standard<br />

‣ Maintenance of the system<br />

‣ Drift (20-30%)<br />

13<br />

Guy Jamet – STRBG


Representative analytes<br />

Mandatory<br />

‣ Choice of representative<br />

analytes<br />

‣ Frequency of calibration and<br />

recalibration<br />

‣ Each batch for representative<br />

‣ Calibration of not integrated<br />

residues<br />

‣ Recovery<br />

Characterization<br />

‣ 15 analytes + 25% if the<br />

scope is 40 pesticides<br />

‣ Effect on calibration (multi<br />

residue)<br />

‣ Mixture of isomers<br />

‣ Degradation of products<br />

(metabolites included in the<br />

residue)<br />

14<br />

Guy Jamet – STRBG


Matrix effect<br />

Mandatory<br />

‣ Different group<br />

‣ Choice of representative<br />

Matrix<br />

‣ Extraction recovery with<br />

appropriate standard<br />

‣ Choice of the quantification<br />

method<br />

‣ Choice of analyte protectants<br />

Characterization<br />

‣ Calibration against solvent<br />

‣ Extracted matrix calibration<br />

‣ Matrix matched<br />

‣ 3 portions<br />

‣ Knowledge of amount<br />

‣ Standard addition<br />

‣ Spiking at the same level<br />

‣ Priming in GC<br />

15<br />

Guy Jamet – STRBG


Chromatographic integration<br />

Mandatory<br />

‣ Chromatograms must be<br />

visually inspected<br />

‣ Consistent approach must be<br />

adopted ( Capability of<br />

instrument)<br />

‣ Chromatographic integration<br />

and baseline adjustment<br />

Characterization<br />

‣ Characteristic ion<br />

chromatograms<br />

‣ Selectivity<br />

‣ Compromise to integrate in<br />

one step<br />

‣ List of Residue amenable<br />

one by one<br />

16<br />

Guy Jamet – STRBG


Performance-criteria qualitative<br />

screening method validation<br />

Mandatory<br />

Characterization<br />

‣ Low probability of presence<br />

‣ Confidence established at a<br />

certain concentration level<br />

‣ Representative of for the<br />

matrix scope<br />

‣ No regard of linearity and<br />

recovery<br />

‣ False positive excluded with<br />

blank samples<br />

‣ Repeatability of presence<br />

‣ Depending if method is<br />

conducted in solvent or<br />

matrix<br />

‣ All residues<br />

‣ Confidence by repeatability<br />

of quantification when MS<br />

spectra is amenable<br />

‣ False positive from past<br />

injection must be avoided<br />

17<br />

Guy Jamet – STRBG


Acceptability of analytical performance:<br />

Initial validation<br />

Mandatory<br />

Characterization<br />

‣ Mean recovery at each spiking<br />

level 70-120%<br />

‣ Lower recoveries acceptable<br />

under conditions<br />

‣ At least for one representative<br />

matrix<br />

‣ RSD r and RSD IP


Acceptability of analytical performance:<br />

on going performance validation<br />

Mandatory<br />

‣ Recovery with each batch of<br />

analyses<br />

‣ Rolling programme<br />

‣ At 1-10 times a relevant level<br />

‣ Routinely at the MRL<br />

‣ Range 60-140%<br />

‣ Internal standard surrogated<br />

‣ Variability between 2 test<br />

portion of same sample<br />

Characterization<br />

‣ Recovery matrix by matrix<br />

‣ MRPL and LMR<br />

‣ Profile of accuracy<br />

‣ Extraction standard<br />

‣ Internal standard<br />

‣ LMR exceeded on real<br />

samples<br />

19<br />

Guy Jamet – STRBG


Proficiency testing<br />

Mandatory<br />

‣ Participation to relevant<br />

proficiency test is mandatory<br />

for official labs<br />

Characterization<br />

‣ National<br />

‣ Private<br />

‣ EUPT<br />

‣ In-house material must be<br />

analysed regularly<br />

‣ Minimum one<br />

‣ Representative to activity<br />

‣ Not than 10%<br />

20<br />

Guy Jamet – STRBG


Confirmation results<br />

Mandatory<br />

‣ Negative results below LCL<br />

not confirmed if recovery is<br />

acceptable<br />

‣ LCL<br />

‣ Recovery<br />

‣ Positive results confirmed<br />

case-by-case<br />

‣ Suspected MRL violation,<br />

misusing or unusual residues<br />

must be confirmed<br />

Characterization<br />

‣ Each consistent MS spectra<br />

is a confirmation<br />

‣ Each amenable MS spectra<br />

induce a quantification<br />

‣ Danger of transfer due to the<br />

matrix polarity on the column<br />

21<br />

Guy Jamet – STRBG


Requirements<br />

Mandatory<br />

‣ RRT tolerance of +/- 0.5%<br />

‣ Mass spectra must be<br />

consistent with the analyte<br />

‣ Higher m/z than lower are<br />

more selective<br />

‣ Overlapping of ion<br />

chromatograms<br />

‣ Similarity with calibration<br />

standards<br />

‣ Avoiding interferences by<br />

carefully peak subtraction<br />

Characterization<br />

‣ Own standards library<br />

‣ Rearrangement are a<br />

precious help<br />

‣ High Intensity m/z<br />

‣ 2 different software for<br />

identification<br />

‣ RRT or RT similar to<br />

calibration curve<br />

‣ Multi level calibration<br />

‣ Noise subtracted<br />

22<br />

Guy Jamet – STRBG


Reporting results<br />

Mandatory<br />

Characterization<br />

‣ Mg/kg;


Mandatory of accreditation body<br />

‣ Scope of the Accreditation<br />

‣ Group or list of matrices<br />

‣ List of residues sought for<br />

‣ Organochlorines<br />

‣ Organophosphates<br />

‣ Part of the method<br />

‣ Extraction<br />

‣ Purification<br />

‣ Physical analysis<br />

‣ Method references<br />

‣ EN NF 12393 part N<br />

‣ EN NF 15662<br />

‣ Standard accreditation<br />

‣ Type A1: carry out of the<br />

validated version no<br />

modification permitted<br />

‣ Type A2: new version are<br />

implemented without<br />

updating control from<br />

accreditation body<br />

‣ Type A3: refers to<br />

competences or a scope<br />

of possibilities<br />

‣ flexible scope Type B:<br />

‣ Extension of A3 between<br />

to audits<br />

24<br />

Guy Jamet – STRBG


Statistical tools<br />

25<br />

Guy Jamet – STRBG


‣ ISO 5725 (required for reproducibility<br />

between labs, not for lab intermediate<br />

fidelity IF)<br />

‣ NF V03-110 re adapted for IF in the<br />

consumption of Accuracy profile<br />

26<br />

Guy Jamet – STRBG


27<br />

Guy Jamet – STRBG<br />

NF V03-110 as validation tools<br />

‣ Based on the regulation ISO 5725 (for inter lab reproducibility)<br />

‣ Adapted to repeatability and intermediate fidelity (intra lab<br />

reproducibility)<br />

‣ Taking in account<br />

‣The determination of variability at each levels<br />

‣The variability within the series<br />

‣The variability between the series<br />

‣TSS=RSS+ESS<br />

‣The risk of the analyst at 95% confidence level<br />

‣The risk of the client with a postulated amount (80%) of results<br />

within acceptable limits<br />

‣Defined by a minimum 3 times 3 repetitions per level<br />

‣Implementing the variability of the actors and follow up in<br />

time<br />

‣ Extending data may be added later


Relative accuracy<br />

Profile of accuracy (NF V03-110)<br />

‣The risk of the analyst at 95% confidence level<br />

‣The risk of the client with a postulated amount<br />

(80%) of results within acceptable limits<br />

Profile of accuracy<br />

1<br />

0,8<br />

0,6<br />

0,4<br />

0,2<br />

0<br />

-0,2<br />

1 2 3 4 5 6 7 8 9 10 11 12<br />

-0,4<br />

-0,6<br />

-0,8<br />

-1<br />

Concentration in ng/L<br />

Low er tolerable limit Low er acceptable limit Bias Upper acceptable limit Upper tolerable limit<br />

28<br />

Guy Jamet – STRBG


Homogeneity, stability<br />

Real<br />

sample<br />

@x mg/kg<br />

T1<br />

T2 T3 T4 T5<br />

Homogeneity<br />

T1<br />

Ɵ1<br />

T1<br />

Ɵ2<br />

T2<br />

Ɵ1<br />

T2<br />

Ɵ2<br />

ῩH, σ<br />

Stability<br />

Ῡ1, U= ῩH ±1,96σ<br />

Stability<br />

Ῡ2, U= ῩH ±1,96σ<br />

29<br />

Guy Jamet – STRBG


30<br />

Guy Jamet – STRBG<br />

Repetition for repeatability or<br />

intermediate precision<br />

M + C1 =<br />

R11<br />

M + C1 =<br />

R12<br />

Mean1, sdr1, rsdr1<br />

M + C1 =<br />

R13<br />

Blank<br />

matrix<br />

M + C2 =<br />

R21<br />

M + C2 =<br />

R22<br />

Mean2, sdr2, rsdr2<br />

M + C2 =<br />

R23


Variability<br />

Precision and accuracy in validation<br />

<strong>Control</strong> chart<br />

30%<br />

20%<br />

10%<br />

0%<br />

-10%<br />

-20%<br />

-30%<br />

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30<br />

<strong>Control</strong> values<br />

Good precision<br />

Good accuracy<br />

Risk analyst 95%<br />

Low er tolerance Values Upper tolerance<br />

Method is considered as validated<br />

but 40% of unexplainable results<br />

are exceeding the tolerance limit of<br />

+/-20%<br />

31<br />

Guy Jamet – STRBG


32<br />

Guy Jamet – STRBG<br />

Precision and accuracy in validation<br />

Low precision<br />

Low accuracy<br />

Risk analyst 95%<br />

Method is considered as NOT<br />

validated because of the low<br />

precision and low accuracy


33<br />

Guy Jamet – STRBG<br />

NF V03-110 as validation tools<br />

Good precision<br />

Good accuracy<br />

Risk analyst 95%<br />

Risk client 20%<br />

Method should be considered as<br />

NOT validated because 40% of<br />

results are exceeding the tolerance<br />

limit of +/-20%


Variability<br />

NF V03-110 as validation tools<br />

Method is considered as validated<br />

because 5 values (16.7%) are outside of<br />

the +/-20% tolerance limit despite the low<br />

precision and the low accuracy<br />

<strong>Control</strong> chart<br />

30%<br />

20%<br />

10%<br />

0%<br />

-10%<br />

Low precision<br />

Low accuracy<br />

95% Risk analyst<br />

20% Risk client<br />

-20%<br />

-30%<br />

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30<br />

<strong>Control</strong> Values<br />

Low er tolerance Values Upper tolerance<br />

34<br />

Guy Jamet – STRBG


35<br />

Guy Jamet – STRBG<br />

Historical knowledge<br />

‣ Ten years identification with 2 columns ECD - NPD, ECD<br />

– FPD<br />

‣ Systematic confirmation by MS<br />

‣ Systematic identification and confirmation of difficult<br />

substances<br />

‣ Every samples were checked for 250 molecules with 1 – 3<br />

ions and baseline subtraction<br />

‣ Quantification of confirmed residues on specific detectors<br />

and/or MS in SIM mode<br />

‣ Different results from a detector to the other<br />

‣ A lot of work<br />

‣ Time consuming


36<br />

Guy Jamet – STRBG<br />

Improvement of the Method<br />

‣ Budget reduction<br />

‣ GC ECD – FPD, GC MS<br />

‣ No GPC purification<br />

‣ Increasing of validation mandatory<br />

‣Increasing of new molecule<br />

‣Increasing of validation amount<br />

‣ Solution<br />

‣Validation of a simple method GC/MS full scan<br />

mode for identification/confirmation and<br />

quantification


37<br />

Guy Jamet – STRBG<br />

The different steps of GC/MS<br />

validation in our lab


38<br />

Guy Jamet – STRBG<br />

GC Multi residue method<br />

First proposal<br />

‣ Characterization of our method without<br />

purification<br />

‣ Repeatability, Intermediate fidelity based on<br />

recovery at the 3 MRPL 0.01, 0.02, 0.05 mg/kg<br />

‣ Characterization in salads<br />

‣ Extension to apples and carrots<br />

‣ Detection limits in order to deal with organic<br />

products


Avoiding contamination<br />

‣ Premises<br />

‣ Standards preparation<br />

‣ Samples treatment<br />

‣ Physical analysis<br />

‣ SOP<br />

‣ Rooms<br />

‣ Solvents<br />

‣ Tools<br />

PR167/99/LOC/01<br />

‣ No validation requested<br />

39<br />

Guy Jamet – STRBG


Sampling and transport<br />

‣ Sampling:<br />

‣ Done by the inspectorate in the department<br />

‣ At the selling point or import point<br />

‣ Power to control of all the surrounding of the selling<br />

‣ Enquiry samples<br />

‣ <strong>Control</strong> samples<br />

‣ According EU 2002-63<br />

‣ Transport<br />

‣ By organism or direct<br />

40<br />

Guy Jamet – STRBG


<strong>Control</strong> at reception<br />

‣ Mandatory<br />

‣Respect of quality required<br />

‣Respect of packaging<br />

‣Respect of quantity<br />

‣Description of samples and<br />

specific wishes<br />

‣ Decision<br />

‣ Acceptation or Rejection<br />

of the laboratory sample<br />

‣ Action<br />

‣ Opening of analytical<br />

report<br />

‣ Orientation of the essays<br />

‣ SOP<br />

IN167/80/EXT/02<br />

Validation<br />

‣ capability of acting people<br />

41<br />

Guy Jamet – STRBG


42<br />

Guy Jamet – STRBG<br />

Description of the sample<br />

‣ Packaging: Sampling plastic bag closed<br />

‣ Sampling label: Pesticides residues<br />

‣ Country of origin: Argentina<br />

‣ Weight: 1.020 kg<br />

‣ Unit: 12<br />

‣ Quality of the sample: fresh in good<br />

integrity


43<br />

Guy Jamet – STRBG<br />

Amenable Essays<br />

Code Method title Th. weight<br />

of test<br />

potion (g)<br />

12075 PESTICIDES BY GC [Internal method derived from NF EN<br />

12393]<br />

Essay and<br />

real<br />

weight of<br />

potion test<br />

(g)<br />

50 YES<br />

TP 1 50.10<br />

TP 2 50.20<br />

12480 PESTICIDES by LC-MS/MS [QUECHERS method (NF EN<br />

15662)]<br />

12368 DITHIOCARBAMATES (Internal method derived from NF<br />

EN 12396-1)<br />

5995 MALEIC HYDRAZID [VADUKUL (ANALYST, VOL116,<br />

N°12, P735-739)]<br />

5607 BROMIDS (EN ION BR-) [CLHP/I] 10<br />

8413 NITRATES (Expressed in NO3-) [CLHP/I NF EN 12014-2 I/C<br />

V 03-010-2 ]<br />

10<br />

50<br />

10<br />

10


Preparation of test sample and<br />

test portions<br />

‣ Test sample preparing<br />

‣ According R396/2005<br />

‣ Test sample reduction<br />

‣ Within 72 h<br />

‣ On fresh material<br />

‣Method of opposite quarters<br />

for big unit<br />

‣ All the test sample for small<br />

unit<br />

‣ Test portions<br />

‣Weighted and frozen<br />

‣ Detailed in SOP<br />

IN167/80/ANA/01<br />

Validation<br />

‣ capability of acting<br />

people<br />

44<br />

Guy Jamet – STRBG


Carry out of the GC/MS extract<br />

‣ Extraction<br />

‣ Partition<br />

‣ Drying<br />

‣ Re dilution<br />

‣ EN NF 12393 part 2 method<br />

“N” without GPC purification<br />

detailed SOP<br />

IN167/80/ANA/02<br />

Validation<br />

‣ Capability of acting<br />

people<br />

‣ Solvent and additives<br />

‣ Drying instruments<br />

45<br />

Guy Jamet – STRBG


Carry out of the GC/MS analysis<br />

‣ GC<br />

‣ Maintenance<br />

‣ MS<br />

‣ Maintenance<br />

‣ Tuning<br />

‣ Method<br />

‣ Parameters<br />

‣ Sequence<br />

‣ Calibration standards<br />

‣ Sample extract and<br />

1/10 dilution each<br />

‣ Detailed SOP<br />

IN167/80/ANA/19<br />

IN167/80/MAT/05<br />

IN167/80/MAT/10<br />

Validation<br />

‣ Capability of acting people<br />

46<br />

Guy Jamet – STRBG


Interpretation of the data<br />

‣ Qualitatively<br />

‣ Identification in the<br />

calibration standards<br />

corresponding to MRPL<br />

‣ Identification of Aldrin<br />

‣ Identification of<br />

Bromophos methyl<br />

‣ Identification and<br />

confirmation by full scan in<br />

sample<br />

‣ Quantitatively<br />

‣ Calibration curves<br />

‣ Integration parameters<br />

‣ Detailed SOP<br />

IN167/80/ANA/13<br />

IN167/80/ANA/17<br />

IN167/80/MAT/11<br />

Validation<br />

‣ Capability of acting people<br />

‣ Parameters of instruments<br />

‣ Parameters of the methods<br />

47<br />

Guy Jamet – STRBG


Standards<br />

‣ Quality ‣ >95% purity from supplier<br />

‣ New lot of routine standard<br />

‣ New standard<br />

‣ Conservation<br />

‣ Stock solutions<br />

‣ Working solutions<br />

‣ Verification of identity with<br />

library<br />

‣ Consistence of the spectra<br />

‣ 10 years<br />

‣ 1000 ppm mother solution (3-5<br />

years)<br />

‣ Dilution 10, 1, 0.1 ppm (2 months)<br />

‣ No recovery from old standard<br />

IN167/80/ANA/20<br />

Validation<br />

‣ Capability of acting people<br />

‣ Identity of the standard<br />

48<br />

Guy Jamet – STRBG


Capability of acting people<br />

‣Sample reception<br />

‣Sample preparation<br />

‣GC extract<br />

‣Standards<br />

‣MS analysis<br />

‣Interpretation<br />

‣ Learning period<br />

‣Practice in parallel<br />

‣Evaluation in practice alone<br />

‣End results<br />

‣Learning period<br />

‣Double control of results<br />

‣IN167/99/PER/03<br />

‣IM167/99/PER/13<br />

‣IM167/99/PER/14<br />

‣IM167/99/PER/15<br />

49<br />

Guy Jamet – STRBG


Characterization of the GC<br />

‣ GC parameters<br />

‣ Injector<br />

‣ Oven temp<br />

‣ Detector<br />

‣ Quality of the column<br />

‣ Done globally by the<br />

analytical on going controls<br />

‣ After each sequence<br />

‣ Monthly cleaning<br />

‣ RRT<br />

50<br />

Guy Jamet – STRBG


Characterization of the MS<br />

‣ MS parameters ‣ Tuning<br />

‣ At the beginning before each<br />

sequence<br />

‣ Monthly after the maintaining<br />

‣ Done globally by the<br />

analytical on going controls<br />

51<br />

Guy Jamet – STRBG


Characterization of the parameters of<br />

decision<br />

‣ Parameters of instruments<br />

‣ Parameters of the methods<br />

‣ Limits permitted for<br />

identification<br />

‣ Area reject<br />

‣ Peak width<br />

‣ Integration threshold<br />

‣ Working range<br />

‣ LCL<br />

‣ LOD<br />

‣ LOQ<br />

‣ Repeatability<br />

‣ Intermediate fidelity<br />

‣ Reproducibility<br />

52<br />

Guy Jamet – STRBG


Characterization of standards<br />

‣ Identity of the standard<br />

‣ Consistence of MS spectra<br />

IM167/80/ANA/23<br />

‣ RRT<br />

IN167/80/ANA/17<br />

53<br />

Guy Jamet – STRBG


Consistence of a spectra<br />

54<br />

Guy Jamet – STRBG


Explanation of a spectra<br />

O<br />

O<br />

N<br />

Cl<br />

N<br />

H<br />

N<br />

Cl<br />

N<br />

H<br />

+<br />

minus Cl -<br />

minus Cl -<br />

+<br />

m/z 307<br />

, m/z 309<br />

m/z 307<br />

, m/z 309<br />

O<br />

O<br />

N<br />

H<br />

+<br />

N<br />

Cl<br />

N<br />

Cl<br />

minus Cl -<br />

+<br />

Chloropyridin oxonium<br />

m/z 307<br />

, m/z 309<br />

m/z 140<br />

, m/z 142<br />

55<br />

Guy Jamet – STRBG


RRT<br />

RT Aldrin 17,18<br />

RRT / IS<br />

Residue<br />

column HPAS 5<br />

RT-0.3 RT RT+0.3 MS fragmentation<br />

6890/5973<br />

ACEPHATE 0,53 8,8 9,11 9,4 136 125 183<br />

ACRINATHRIN 1,46 24,3 25,08 25,8 181 208 289<br />

ALDRIN 1,00 16,7 17,18 17,7 263 261 265 293<br />

ALLETHRINE 1,08 18,0 18,55 19,1 123 107 168<br />

ALPHACYPERMETHRIN 1,63 27,2 28,00 28,8 163 161 181 209<br />

AMITRAZE 1,48 24,7 25,45 26,2 121 132 147 162 293<br />

ATRAZINE 0,81 13,5 13,92 14,3 200 215 173<br />

AZAMETIPHOS 1,28 21,4 22,06 22,7 109 215 324<br />

AZINPHOS ETHYL 1,47 24,5 25,25 26,0 132 160 198<br />

AZINPHOS METHYL 1,41 23,5 24,22 25,0 160 132<br />

AZOXYSTROBINE 2,01 33,5 34,53 35,6 344 388 372 403<br />

BENALAXYL 1,27 21,2 21,82 22,5 148 206 234 266 325<br />

BENDIOCARBE 0,74 12,3 12,71 13,1 151 126 166 223<br />

BIFENTHRIN 1,36 22,7 23,36 24,1 181 166 165<br />

TRITICONAZOLE 1,41 23,5 24,22 25,0 235 115 217 182 299<br />

VAMIDOTHION 1,11 18,5 19,07 19,6 87 145 109<br />

VINCHLOZOLIN 0,93 15,5 15,93 16,4 212 198 285 187 178<br />

56<br />

Guy Jamet – STRBG


57<br />

Guy Jamet – STRBG<br />

1 st step of the characterisation<br />

‣ Characterization of the most occurring<br />

residues at time<br />

‣ Matrices: salad with further extension to<br />

carrot and apple<br />

‣ Spiking samples before extraction at 0.01<br />

and 0.05 mg/kg<br />

‣ Submission to the routine extraction<br />

procedure<br />

‣ Spiking extracted matrix at the same<br />

concentration<br />

‣ Injection of the same concentration in<br />

solvent<br />

‣ Identification with an explainable mass<br />

spectra: qualitative evaluation<br />

‣ Determination of the recovery against the<br />

solvent and the spiked extract in SIM<br />

mode<br />

‣ Characterisation tool<br />

‣ NF V03-110<br />

‣ SANCO guide line response of<br />

instrument<br />

REPRESENTATIVE ANALYTES<br />

BIFENTHRINE<br />

λ CYHALOTHRIN<br />

BROMOPROPYLATE<br />

MALATHION<br />

CARBARYL<br />

METALAXYL<br />

CHLORFENVINPHOS ORTHOPHENYLPHENOL<br />

CHLORPROPHAM<br />

OXADIXYL<br />

CHLORPYRIPHOS<br />

PARATHION<br />

CHLORPYRIPHOS-METHYL PARATHION-METHYL<br />

α CYPERMETHRIN<br />

PHOSALONE<br />

CYPRODINIL<br />

PROCYMIDONE<br />

DELTAMETHRIN<br />

PROPARGITE<br />

ETHION<br />

PROPYZAMIDE<br />

DIMETHOATE<br />

PYRIMETHANIL<br />

DIPHENYLAMINE<br />

QUINTOZENE<br />

α ENDOSULFAN<br />

TAU-FLUVALINATE<br />

β ENDOSULFAN<br />

TEBUCONAZOLE<br />

ENDOSULFAN sulphate TEBUFENPYRAD<br />

FLUDIOXONIL TOLCLOPHOS-METHYL<br />

IPRODIONE<br />

VINCLOZOLINE<br />

KRESOXIM METHYL ALDRIN (IS Qualifier)


58<br />

Guy Jamet – STRBG<br />

Recovery at requested limits<br />

‣ Determination of the recovery at 2 MRPL values:<br />

‣ 0.01, 0.05 mg/kg<br />

‣ Multilevel calibration against solvent<br />

‣ Different days or technicians<br />

‣ Identification on specific detectors<br />

‣ Confirmation on MS full scan mode<br />

‣ (Quantification on specific detectors)<br />

‣ Quantification on MS SIM mode<br />

‣ Estimation of the variability at each level


59<br />

Guy Jamet – STRBG<br />

Working plan<br />

‣ RE : Extraction of spiked salad at 0.01 and 0.05 mg/kg<br />

‣ ER: Extraction of salad and spiking at 0.01 and 0.05 mg/kg<br />

‣ C: calibration: equivalent of 0.01 and 0.05 m/kg in solvent<br />

MRPL level<br />

0,01<br />

0,05<br />

Day / Technician Calibration Recovery before extraction Recovery after extraction<br />

D_1 C_111 C_112 C_113 RE_111 RE_112 RE_113 ER_111 ER_112 ER_113<br />

D_2 C_121 C_122 C_123 RE_121 RE_122 RE_123 ER_121 ER_122 ER_123<br />

D_3 C_131 C_132 C_133 RE_131 RE_132 RE_133 ER_131 ER_132 ER_133<br />

D_1 C_211 C_212 C_213 RE_111 RE_112 RE_113 ER_111 ER_112 ER_113<br />

D_2 C_221 C_222 C_223 RE_121 RE_122 RE_123 ER_121 ER_122 ER_123<br />

D_3 C_231 C_232 C_233 RE_131 RE_132 RE_133 ER_131 ER_132 ER_133


Results<br />

Confirmation<br />

Recovery<br />

M ET H OD SC A N<br />

0.01 0.05<br />

SIM ( after full Scan)<br />

0.01 0.05 LOD<br />

solvant blank S solvant blank S RRT RSD Target Qualifier T/Q RSD Blank/S mg/kg<br />

BIFENTHRIN m w w s 1,36 1,0% 181 165 3,28 6% 72% 89% 0.01<br />

BROM OPROPYLATE w w 0 m 1,36 1,0% 183 341 0,63 10% 101% 93% 0.01<br />

CARBARYL 0 w 0 w 0,94 1,0% 144 115 1,06 50% 88% 80% 0.01<br />

CHLORFENVINPHOS m m s s 1,08 1,0% 267 323 1,45 3% 91% 88% 0.01<br />

CHLORPROPHAM w m m s 0,72 1,0% 127 213 0,37 6% 72% 97% 0.01<br />

CHLORPYRIPHOS s w s s 1,06 1,0% 314 316 1,38 9% 83% 90% 0.01<br />

CHLORPYRIPHOS M ETHYL s s s s 1,01 1,0% 286 288 1,33 2% 82% 91% 0.01<br />

α CYPERM ETHRIN 0 w 0 w 1,18 1,0% 181 163 0,73 7% 70% 103% 0.01<br />

CYPRODINIL m s w s 1,06 1,0% 224 225 1,50 1% 87% 72% 0.01<br />

DELTAM ETHRIN 0 w 0 w 1,94 1,0% 253 181 0,94 14% 70% 75% 0.01<br />

ETHION w w s s 0,81 1,0% 231 153 1,53 24% 90% 85% 0.01<br />

DIM ETHOATE w w s m 0,39 1,0% 87 125 1,45 14% 90% 89% 0.01<br />

DIPHENYLAM INE m s m w 0,70 1,0% 169 168 1,62 2% 84% 88% 0.01<br />

α Endosulfan 0 w 0 w 1,21 1,0% 195 237 1,78 5% 65% 104% 0.01<br />

ENDOSULFAN Beta 0 w 0 w 1,28 1,0% 195 241 1,50 19% 68% 88% 0.01<br />

ENDOSULFAN Sulphate 0 w 0 w 1,16 1,0% 272 274 0,94 20% 72% 106% 0.01<br />

FLUDIOXONIL w 0 0 w 1,18 1,0% 248 127 1,89 30% 73% 85% 0.01<br />

IPRODIONE 0 w 0 m 1,44 1,0% 314 316 1,55 3% 99% 99% 0.01<br />

KRESOXIM M ETHYL 0 w 0 m 1,18 1,0% 116 131 1,64 49% 89% 67% 0.01<br />

λ CYHALOTHRIN 0 w w m 1,63 1,0% 181 197 1,24 7% 71% 92% 0.01<br />

M ALATHION m m s s 0,99 1,0% 173 125 1,19 13% 82% 58% 0.01<br />

M ETALAXYL M w w s s 0,95 1,0% 206 220 2,18 6% 70% 91% 0.01<br />

ORTHOPHENYLPHENOL m m w 0 0,61 1,0% 170 141 3,03 7% 87% 89% 0.01<br />

OXADIXYL w m 0 m 1,24 1,0% 163 132 1,41 1% 98% 99% 0.01<br />

PARATHION ETHYL w w m m 1,01 1,0% 291 109 1,30 96% 82% 84% 0.01<br />

PARATHION M ETHYL 0 w m m 0,93 1,0% 263 / / / 78% 83% 0.01<br />

PENTACHLOROANILINE w m w s 0,90 1,0% 265 263 1,65 4% 75% 90% 0.01<br />

PHOSALONE w w s m 1,42 1,0% 182 367 3,34 13% 103% 99% 0.01<br />

PROCYM IDONE w w 0 w 1,09 1,0% 283 285 1,68 1% 85% 77% 0.01<br />

PROPARGITE 0 w 0 w 1,31 1,0% 135 173 3,61 20% 84% 83% 0.01<br />

PROPYZAM IDE w w w m 0,84 1,1% 173 255 4,53 16% 70% 90% 0.01<br />

PYRIM ETHANIL w m m w 0,85 1,0% 198 199 1,99 2% 87% 89% 0.01<br />

QUINTOZENE 0 w w m 0,83 1,2% 237 295 1,50 2% 71% 85% 0.01<br />

TAU FLUVALINATE 0 w w m 1,82 1,0% 250 252 2,71 11% 71% 76% 0.01<br />

TEBUCONAZOLE 0 w w m 1,31 1,0% 250 125 0,99 28% 92% 98% 0.01<br />

TEBUFENPYRAD w w w m 1,37 1,0% 171 318 0,95 35% 84% 91% 0.01<br />

TOLCLOPHOS M ETHYL s w s m 0,94 1,0% 265 125 2,71 3% 84% 92% 0.01<br />

VINCLOZOLIN 0 m w m 0,93 1,0% 285 212 1,05 15% 75% 89% 0.01<br />

Legend m: middle w: weak s: strong<br />

60<br />

Guy Jamet – STRBG


61<br />

Guy Jamet – STRBG<br />

2 nd Proposal restriction of the scope and<br />

characterisation of the instrument response<br />

‣ Follow up of the response<br />

of different ions when<br />

amenable<br />

‣ Ion ratio<br />

‣ Limits of detection:<br />

amenable mass spectra<br />

‣ LCL, LOD, LOQ Upper<br />

saturating limit<br />

‣ Multilevel calibration<br />

standards<br />

‣ REPRESENTATIVE<br />

ANALYTES<br />

‣ CHLORFENVINPHOS<br />

‣ CYPRODINIL<br />

‣ ETHION<br />

‣ IPRODIONE<br />

‣ OXADIXYL<br />

‣ PROCYMIDONE<br />

‣ PYRIMETHANIL<br />

‣ VINCLOZOLINE


Conclusion after the 1 st step<br />

‣ Not all the molecules are visible<br />

in the solvent at 0.01 mg/kg<br />

‣ Just a few analytes are not<br />

visible at 0.05 mg/kg<br />

‣ The SIM mode seems to<br />

improve the detection<br />

‣ Salad matrix shows a positive<br />

protection of the molecules<br />

‣ The real recovery is in the<br />

interval 70-120% except for α-<br />

ENDOSULFAN and β-<br />

ENDOSULFAN<br />

‣ The co elution of PARATHION<br />

METHYL with<br />

VINCLOZOLINE and<br />

CHLORPYRIPHOS METHYL<br />

is not easy to manage<br />

‣ Remarks of accreditation bodies<br />

‣ Recovery approach OK<br />

‣ Repeatability OK<br />

‣ Intermediate fidelity OK<br />

‣ LOD OK<br />

‣ LOQ have to be improved<br />

‣ Decision must be made<br />

with analytes not passing<br />

the requirements<br />

‣ Uncertainty must be<br />

assessed<br />

62<br />

Guy Jamet – STRBG


63<br />

Guy Jamet – STRBG<br />

Instrument response: working plan<br />

‣ Estimation of the variability at<br />

each level: repeatability and<br />

intermediate fidelity<br />

‣ Visual examination on profile<br />

accuracy plot<br />

‣ Determination of the LCL<br />

‣ Determination of the upper<br />

acceptable quantification level<br />

‣ Choice of the quantification ion<br />

‣ Choice of qualifier ions<br />

Concentration (ppb) D_1 D_2 D_3<br />

10 C_111 C_211 C_311<br />

10 C_112 C_212 C_312<br />

10 C_113 C_213 C_313<br />

20 C_121 C_221 C_321<br />

20 C_122 C_222 C_322<br />

20 C_123 C_223 C_323<br />

100 C_131 C_231 C_331<br />

100 C_132 C_232 C_332<br />

100 C_133 C_233 C_333<br />

500 C_141 C_241 C_341<br />

500 C_142 C_242 C_342<br />

500 C_143 C_243 C_343<br />

2000 C_151 C_251 C_351<br />

2000 C_152 C_252 C_352<br />

2000 C_153 C_253 C_353<br />

5000 C_161 C_261 C_361<br />

5000 C_162 C_262 C_362<br />

5000 C_163 C_263 C_363


64<br />

Guy Jamet – STRBG<br />

CHLORFENVINPHOS (LCL)<br />

Chlorfenvinphos<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -83 -47 -8 -19 -10 -30<br />

267 Bias 33 -4 -2 -7 -1 -8<br />

Upper tolerable limit 148 39 5 6 8 14<br />

Upper acceptable limit 50 50 50 50 50 50


65<br />

Guy Jamet – STRBG<br />

CYPRODINIL (LCL)<br />

Cyprodinil<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -33 -102 -23 -25 -33 -184<br />

224 Bias 25 23 8 -4 1 -14<br />

Upper tolerable limit 83 147 38 18 35 155<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -28 -30 -27 -23 -28 -20<br />

225 Bias 13 13 6 -3 0 -3<br />

Upper tolerable limit 55 57 39 16 28 15<br />

Upper acceptable limit 50 50 50 50 50 50


66<br />

Guy Jamet – STRBG<br />

ETHION (LCL)<br />

Ethion<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -56 -87 -58 -139 -38 -18<br />

125 Bias 42 47 37 10 27 8<br />

Upper tolerable limit 141 181 132 160 92 35<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -38 -47 -44 -46 -19 -14<br />

153 Bias 27 4 30 7 15 6<br />

Upper tolerable limit 92 55 104 60 49 26<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -99 -52 -19 -5 -5 -5<br />

231 Bias -9 6 0 1 3 -1<br />

Upper tolerable limit 82 65 19 7 10 3<br />

Upper acceptable limit 50 50 50 50 50 50


67<br />

Guy Jamet – STRBG<br />

λ CYHALOTHRIN (LCL)<br />

λ Cyhalothrin<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -76 -52 -18 -23 -11 -12<br />

181 Bias 3 19 30 20 7 7<br />

Upper tolerable limit 83 91 78 62 24 25<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -69 -22 -12 -16 -6 -14<br />

197 Bias 16 2 14 6 8 3<br />

Upper tolerable limit 101 26 40 28 22 21<br />

Upper acceptable limit 50 50 50 50 50 50


68<br />

Guy Jamet – STRBG<br />

OXADIXYL (LCL)<br />

Oxadixyl<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -40 -54 -54 -371 -75 -60<br />

132 Bias 26 -14 17 8 22 24<br />

Upper tolerable limit 92 27 87 388 119 109<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -91 -101 -47 -60 -56 -25<br />

163 Bias 5 -25 8 4 8 18<br />

Upper tolerable limit 101 51 62 68 73 61<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -22 -89 -22 -59 -82 -145<br />

233 Bias 18 -26 15 22 66 82<br />

Upper tolerable limit 59 37 51 103 214 309<br />

Upper acceptable limit 50 50 50 50 50 50


69<br />

Guy Jamet – STRBG<br />

IPRODIONE (LCL)<br />

Iprodione<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -26 -119 -62 -46 -51 -59<br />

187 Bias 35 3 66 60 39 74<br />

Upper tolerable limit 97 125 195 166 130 208<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -85 -101 -137 -118 -129 -199<br />

189 Bias -24 13 2 -5 107 67<br />

Upper tolerable limit 37 126 141 108 343 334<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -32 -59 -49 -33 -43 -29<br />

314 Bias 18 22 6 9 10 6<br />

Upper tolerable limit 68 103 61 51 63 40<br />

Upper acceptable limit 50 50 50 50 50 50


70<br />

Guy Jamet – STRBG<br />

PROCYMIDONE (LCL)<br />

Procymidone<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -15 -54 -10 -4 -9 -17<br />

283 Bias 3 6 0 2 0 -1<br />

Upper tolerable limit 21 66 10 9 8 15<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -9 -129 -4 -7 -8 -16<br />

285 Bias 4 8 2 0 1 -1<br />

Upper tolerable limit 18 145 9 8 10 15<br />

Upper acceptable limit 50 50 50 50 50 50


71<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (LCL)<br />

Pyrimethanyl<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -41 -14 -19 -18 -18 -14<br />

198 Bias 10 17 7 -1 -1 -3<br />

Upper tolerable limit 61 49 32 16 16 8<br />

Upper acceptable limit 50 50 50 50 50 50<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -204 -67 -37 -21 -22 -14<br />

199 Bias 78 7 5 -1 0 -3<br />

Upper tolerable limit 361 80 48 18 22 8<br />

Upper acceptable limit 50 50 50 50 50 50


72<br />

Guy Jamet – STRBG<br />

VINCLOZOLINE (LCL)<br />

Vinclozoline<br />

Injected concentrations (ppb)<br />

Ion Limits 10 20 100 500 2000 5000<br />

Lower accptable limit -50 -50 -50 -50 -50 -50<br />

Lower tolerable limit -64 -45 -19 -63 -22 -12<br />

212 Bias 40 30 11 10 1 1<br />

Upper tolerable limit 144 106 41 82 23 14<br />

Upper acceptable limit 50 50 50 50 50 50


73<br />

Guy Jamet – STRBG<br />

Conclusion on limits<br />

‣ 10 and 20 ppb are really difficult to reach<br />

‣ In some cases 50 ppb can be seen<br />

‣ 100 ppb can be considered in most cases as LCL that corresponds to<br />

but with a low frequency<br />

‣ 500 ppb will be an acceptable LCL in the other cases<br />

‣ Reported to the extracting method<br />

‣ The LOD is 0.001 to 0.005 mg/kg<br />

‣ The LOQ is 0.01 to 0.05 mg/kg<br />

‣ The variability is wider as the permitted limits of DG SANCO (50%)<br />

‣ The upper limit is between 2000 and 5000 ppb for all compounds.


74<br />

Guy Jamet – STRBG<br />

Characterisation of the instrument<br />

deviation<br />

‣ Different days<br />

‣ One ion or fragment of the<br />

molecule<br />

‣ Calibration on area with out<br />

internal standard<br />

‣ Calibration with<br />

BROMOPHOS METHYL as<br />

internal standard<br />

‣ Determination of the range of<br />

quantification<br />

‣ Variability of the calibration<br />

curve along the time<br />

‣ Variability at each calibration<br />

level<br />

‣ REPRESENTATIVE<br />

ANALYTES<br />

CHLORFENVINPHOS<br />

CYPRODINIL<br />

IPRODIONE<br />

λ CYHALOTHRIN<br />

OXADIXYL<br />

PROCYMIDONE<br />

PYRIMETHANIL<br />

TOLCLOPHOS METHYL<br />

VINCLOZOLINE


75<br />

Guy Jamet – STRBG<br />

Instrument deviation: working plan<br />

‣ Calibration in bracket<br />

‣ Length of a GC-MS sequence<br />

‣ Sd at each concentration<br />

‣ Fitting function of mean response, rsdr, rsdFI<br />

‣ 6 routine levels not exceeding a factor 4 between each other<br />

‣ Full scan mode but characteristic ion: intensity max at highest m/z<br />

Concentration (ppb) D_1 D_2 D_3 D_4 D_5 D_6 D_7 D_8 D_9<br />

100 C_11 C_12 C_13 C_14 C_15 C_16 C_17 C_18 C_19<br />

200 C_21 C_22 C_23 C_24 C_25 C_26 C_27 C_28 C_29<br />

500 C_31 C_32 C_33 C_34 C_35 C_36 C_37 C_38 C_39<br />

1000 C_41 C_42 C_43 C_44 C_45 C_46 C_47 C_48 C_49<br />

2000 C_51 C_52 C_53 C_54 C_55 C_56 C_57 C_58 C_59<br />

5000 C_61 C_62 C_63 C_64 C_65 C_66 C_67 C_68 C_69


76<br />

Guy Jamet – STRBG<br />

CHLORFENVINPHOS (Cal)<br />

Chlorfenvinphos<br />

ppb Min Mean Max<br />

100 10765 36125 61485<br />

200 -11861 80140 172141<br />

500 108437 224974 341511<br />

1000 306261 490017 673773<br />

2000 795736 1033424 1271112<br />

5000 2238694 2837381 3436068<br />

Chlorfenvinphos (IS)<br />

ppb Min Mean Max<br />

100 0,07 0,13 0,19<br />

200 0,08 0,27 0,46<br />

500 0,52 0,8 1,08<br />

1000 0,69 1,45 2,21<br />

2000 2,60 2,91 3,22<br />

5000 6,17 6,85 7,53


Response<br />

CHLORFENVINPHOS (Cal)<br />

Chlorfenvinphos<br />

4000000<br />

3500000<br />

3000000<br />

2500000<br />

y = 573,76x - 57833<br />

R 2 = 0,9989<br />

2000000<br />

1500000<br />

1000000<br />

500000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-500000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)<br />

77<br />

Guy Jamet – STRBG


Response<br />

78<br />

Guy Jamet – STRBG<br />

CHLORFENVINPHOS (Cal)<br />

Chlorfenvinphos (IS)<br />

8,00<br />

7,00<br />

y = 0,0014x + 0,0626<br />

R 2 = 0,9992<br />

6,00<br />

5,00<br />

4,00<br />

3,00<br />

2,00<br />

1,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )


CYPRODINIL (Cal)<br />

Cyprodinil<br />

ppb Min Mean Max<br />

100 79283 147367 215451<br />

200 20032 294585 569138<br />

500 428330 802116 1175902<br />

1000 1006644 1885101 2763558<br />

2000 3308435 3981270 4654105<br />

5000 8918419 11433870 13949321<br />

Cyprodinil (IS)<br />

ppb Min Mean Max<br />

100 0,28 0,55 0,82<br />

200 0,41 0,99 1,57<br />

500 1,67 2,48 3,29<br />

1000 3,95 5,68 7,41<br />

2000 9,14 11,44 13,74<br />

5000 22,97 27,81 32,65<br />

79<br />

Guy Jamet – STRBG


Response<br />

80<br />

Guy Jamet – STRBG<br />

CYPRODINIL (Cal)<br />

Cyprodinil<br />

16000000<br />

14000000<br />

12000000<br />

10000000<br />

y = 2316,6x - 306961<br />

R 2 = 0,9975<br />

8000000<br />

6000000<br />

4000000<br />

2000000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-2000000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


Response<br />

81<br />

Guy Jamet – STRBG<br />

CYPRODINIL (Cal)<br />

Cyprodinil (IS)<br />

35,00<br />

30,00<br />

25,00<br />

y = 0,0056x - 0,0472<br />

R 2 = 0,9996<br />

20,00<br />

15,00<br />

10,00<br />

5,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )


ETHION (Cal)<br />

Ethion<br />

ppb Min Mean Max<br />

100 35814 61220 86626<br />

200 13207 114845 216483<br />

500 177328 335848 494368<br />

1000 498211 710715 923219<br />

2000 1175367 1501107 1826847<br />

5000 3332820 4350940 5369060<br />

Ethion (IS)<br />

ppb Min Mean Max<br />

100 0,12 0,24 0,36<br />

200 0,00 0,46 0,92<br />

500 0,64 1,33 2,02<br />

1000 0,86 2,1 3,34<br />

2000 3,66 4,25 4,85<br />

5000 9,17 10,49 11,81<br />

82<br />

Guy Jamet – STRBG


Response<br />

ETHION (Cal)<br />

Ethion<br />

6000000<br />

5000000<br />

4000000<br />

y = 878,98x - 110063<br />

R 2 = 0,9971<br />

3000000<br />

2000000<br />

1000000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-1000000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)<br />

83<br />

Guy Jamet – STRBG


Response<br />

ETHION (Cal)<br />

Ethion (IS)<br />

14,00<br />

12,00<br />

10,00<br />

y = 0,0021x + 0,0963<br />

R 2 = 0,9993<br />

8,00<br />

6,00<br />

4,00<br />

2,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )<br />

84<br />

Guy Jamet – STRBG


OXADIXYL (Cal)<br />

Oxadixyl<br />

ppb Min Mean Max<br />

100 4086 10189 16292<br />

200 5933 16808 27683<br />

500 17606 28957 40308<br />

1000 20336 60165 99994<br />

2000 109320 137510 165700<br />

5000 271382 363783 456184<br />

Oxadixyl (IS)<br />

ppb Min Mean Max<br />

100 0,03 0,04 0,05<br />

200 0,01 0,07 0,13<br />

500 0,04 0,09 0,14<br />

1000 0,10 0,19 0,28<br />

2000 0,29 0,4 0,51<br />

5000 0,68 0,89 1,10<br />

85<br />

Guy Jamet – STRBG


Response<br />

86<br />

Guy Jamet – STRBG<br />

OXADIXYL (Cal)<br />

Oxadixyl<br />

500000<br />

450000<br />

400000<br />

350000<br />

y = 72,868x - 3971,4<br />

R 2 = 0,9978<br />

300000<br />

250000<br />

200000<br />

150000<br />

100000<br />

50000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


Response<br />

OXADIXYL (Cal)<br />

Oxadixyl (IS)<br />

1,20<br />

1,00<br />

0,80<br />

y = 0,0002x + 0,0237<br />

R 2 = 0,9973<br />

0,60<br />

0,40<br />

0,20<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )<br />

87<br />

Guy Jamet – STRBG


IPRODIONE (Cal)<br />

Iprodione<br />

ppb Min Mean Max<br />

100 4536 18899 33262<br />

200 1528 38209 74890<br />

500 50686 96545 142404<br />

1000 131232 214082 296932<br />

2000 346225 432781 519337<br />

5000 1041685 1289214 1536743<br />

Iprodione (IS)<br />

ppb Min Mean Max<br />

100 0,02 0,06 0,10<br />

200 -0,01 0,14 0,29<br />

500 0,21 0,39 0,57<br />

1000 0,20 0,64 1,08<br />

2000 0,97 1,24 1,51<br />

5000 2,62 3,15 3,68<br />

88<br />

Guy Jamet – STRBG


Response<br />

89<br />

Guy Jamet – STRBG<br />

IPRODIONE (Cal)<br />

Iprodione<br />

1800000<br />

1600000<br />

1400000<br />

1200000<br />

y = 259,79x - 32734<br />

R 2 = 0,9961<br />

1000000<br />

800000<br />

600000<br />

400000<br />

200000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-200000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


Response<br />

IPRODIONE (Cal)<br />

Iprodione (IS)<br />

4,00<br />

3,50<br />

3,00<br />

y = 0,0006x + 0,0212<br />

R 2 = 0,9993<br />

2,50<br />

2,00<br />

1,50<br />

1,00<br />

0,50<br />

0,00<br />

-0,50<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )<br />

90<br />

Guy Jamet – STRBG


PROCYMIDONE (Cal)<br />

Procymidone<br />

ppb Min Mean Max<br />

100 6088 28447 50806<br />

200 10449 66552 122655<br />

500 108545 169602 230659<br />

1000 230132 364133 498134<br />

2000 597140 741789 886438<br />

5000 1549554 2046967 2544380<br />

Procymidone (IS)<br />

ppb Min Mean Max<br />

100 0,04 0,1 0,16<br />

200 0,08 0,24 0,40<br />

500 0,46 0,62 0,78<br />

1000 0,43 1,09 1,75<br />

2000 1,71 2,12 2,53<br />

5000 4,15 4,95 5,75<br />

91<br />

Guy Jamet – STRBG


Response<br />

PROCYMIDONE (Cal)<br />

Procymidone<br />

3000000<br />

2500000<br />

2000000<br />

y = 412,29x - 35118<br />

R 2 = 0,9987<br />

1500000<br />

1000000<br />

500000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)<br />

92<br />

Guy Jamet – STRBG


Response<br />

93<br />

Guy Jamet – STRBG<br />

PROCYMIDONE (Cal)<br />

Procymidone (IS)<br />

7,00<br />

6,00<br />

5,00<br />

y = 0,001x + 0,0804<br />

R 2 = 0,9989<br />

4,00<br />

3,00<br />

2,00<br />

1,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )


94<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (Cal)<br />

Pyrimethanil<br />

ppb Min Mean Max<br />

100 38945 165722 292499<br />

200 -161917 275839 713595<br />

500 37650 801074 1564498<br />

1000 352795 2351969 4351143<br />

2000 4155867 5267258 6378649<br />

5000 11419877 15145726 18871575<br />

Pyrimethanil (IS)<br />

ppb Min Mean Max<br />

100 0,30 0,56 0,82<br />

200 -0,30 0,96 2,22<br />

500 0,64 2,64 4,64<br />

1000 2,38 6,87 11,36<br />

2000 11,52 15,14 18,76<br />

5000 29,23 36,86 44,49


Response<br />

95<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (Cal)<br />

Pyrimethanil<br />

20000000<br />

15000000<br />

y = 3097,5x - 541770<br />

R 2 = 0,9972<br />

10000000<br />

5000000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-5000000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


Response<br />

96<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (Cal)<br />

Pyrimethanil (IS)<br />

50,00<br />

40,00<br />

30,00<br />

20,00<br />

10,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-10,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Max) Linéaire (Min) Linéaire ( Mean )


λ CYHALOTHRIN (Cal)<br />

λ Cyhalothrin<br />

ppb Min Mean Max<br />

100 42946 66894 90842<br />

200 101059 136751 172443<br />

500 322848 370238 417628<br />

1000 647020 772100 897180<br />

2000 1394438 1608348 1822258<br />

5000 3625622 4708600 5791578<br />

λ Cyhalothrin (IS)<br />

ppb Min Mean Max<br />

100 0,11 0,28 0,45<br />

200 -0,11 0,59 1,29<br />

500 0,68 1,57 2,46<br />

1000 0,75 2,36 3,97<br />

2000 3,51 4,71 5,91<br />

5000 9,01 11,58 14,15<br />

97<br />

Guy Jamet – STRBG


Response<br />

98<br />

Guy Jamet – STRBG<br />

λ CYHALOTHRIN (Cal)<br />

λ Cyhalothrin<br />

7000000<br />

6000000<br />

5000000<br />

4000000<br />

y = 949,33x - 115193<br />

R 2 = 0,9967<br />

3000000<br />

2000000<br />

1000000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

-1000000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


Response<br />

λ CYHALOTHRIN (Cal)<br />

λ Cyhalothrin (IS)<br />

16,00<br />

14,00<br />

12,00<br />

10,00<br />

y = 0,0023x + 0,1691<br />

R 2 = 0,999<br />

8,00<br />

6,00<br />

4,00<br />

2,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-2,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )<br />

99<br />

Guy Jamet – STRBG


TOLCLOPHOS METHYL (Cal)<br />

Tolclophos methyl<br />

ppb Min Mean Max<br />

100 77359 135479 193599<br />

200 44603 265494 486385<br />

500 445738 775196 1104654<br />

1000 1128583 1567476 2006369<br />

2000 2528860 3258840 3988820<br />

5000 7044167 9019420 10994673<br />

Tolclophos methyl (IS)<br />

ppb Min Mean Max<br />

100 0,30 0,54 0,78<br />

200 0,70 0,96 1,22<br />

500 2,64 3,12 3,60<br />

1000 1,77 4,65 7,53<br />

2000 7,97 9,22 10,47<br />

5000 19,50 21,74 23,98<br />

100<br />

Guy Jamet – STRBG


Response<br />

101<br />

Guy Jamet – STRBG<br />

TOLCLOPHOS METHYL (Cal)<br />

Tolclophos Methyl (IS)<br />

30,00<br />

25,00<br />

y = 0,0043x + 0,4151<br />

R 2 = 0,9982<br />

20,00<br />

15,00<br />

10,00<br />

5,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )


Response<br />

102<br />

Guy Jamet – STRBG<br />

TOLCLOPHOS METHYL (Cal)<br />

Tolclophos Methyl<br />

12000000<br />

10000000<br />

y = 1817x - 161340<br />

R 2 = 0,9986<br />

8000000<br />

6000000<br />

4000000<br />

2000000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)


VINCLOZOLINE (Cal)<br />

Vinclozoline<br />

ppb Min Mean Max<br />

100 18817 29915 41013<br />

200 20367 55195 90023<br />

500 94905 144233 193561<br />

1000 192307 299077 405847<br />

2000 489636 621366 753096<br />

5000 1359205 1707544 2055883<br />

Vinclozoline (IS)<br />

ppb Min Mean Max<br />

100 0,07 0,12 0,17<br />

200 0,00 0,22 0,44<br />

500 0,23 0,53 0,83<br />

1000 0,43 0,9 1,37<br />

2000 1,48 1,77 2,06<br />

5000 3,62 4,14 4,66<br />

103<br />

Guy Jamet – STRBG


Response<br />

VINCLOZOLINE (Cal)<br />

Vinclozoline<br />

2500000<br />

2000000<br />

y = 343,52x - 27605<br />

R 2 = 0,9986<br />

1500000<br />

1000000<br />

500000<br />

0<br />

0 1000 2000 3000 4000 5000 6000<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Mean)<br />

104<br />

Guy Jamet – STRBG


Response<br />

VINCLOZOLINE (Cal)<br />

Vinclozoline (IS)<br />

5,00<br />

4,00<br />

y = 0,0008x + 0,0829<br />

R 2 = 0,9993<br />

3,00<br />

2,00<br />

1,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-1,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean )<br />

105<br />

Guy Jamet – STRBG


106<br />

Guy Jamet – STRBG<br />

Conclusion<br />

‣ Internal standard is not helping a lot<br />

‣ The mean response can be considered as linear<br />

‣ Drift is evident along the time<br />

‣ Drift is more important for molecules with RRT greater<br />

than that of IS<br />

‣ The variability is greater in the range 100-500 ppb<br />

‣ Sequence must be limited<br />

‣ Corresponding to daily work<br />

‣ Calibration curves before and after the samples<br />

‣ Calculation is conducted with the mean of both curves


107<br />

Guy Jamet – STRBG<br />

Calibration in range 100-500 ppb<br />

‣ Profile of accuracy<br />

‣ Repeatability<br />

‣ Intermediate fidelity<br />

‣ Estimation of the<br />

variability<br />

‣ REPRESENTATIVE<br />

ANALYTES<br />

CHLORFENVINPHOS<br />

CYPRODINIL<br />

ETHION<br />

λ CYHALOTHRIN<br />

PROCYMIDONE<br />

PYRIMETHANIL<br />

TOLCLOPHOS-METHYL<br />

VINCLOZOLINE<br />

‣ In solvent


108<br />

Guy Jamet – STRBG<br />

CHLORFENVINPHOS (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Chlorfenvinphos<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -114 1 -4<br />

recovery -39 13 6<br />

upper_acceptable_limit 37 25 16<br />

upper_tolerance_limit 50 50 50<br />

Chlorfenvinphos<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 61,26 -39% 83% 50% 83%<br />

200 226,20 26% 4% 7% 6%<br />

500 530,74 31% 2% 5% 5%


109<br />

Guy Jamet – STRBG<br />

CYPRODINIL (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Cyprodinil<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit 8 -6 2<br />

recovery 23 15 7<br />

upper_acceptable_limit 38 35 12<br />

upper_tolerance_limit 50 50 50<br />

Cyprodinil<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 122,90 23% 7% 9% 8%<br />

200 229,07 29% 3% 9% 9%<br />

500 534,89 35% 3% 4% 3%


110<br />

Guy Jamet – STRBG<br />

ETHION (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Ethion<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -26 -6 0<br />

recovery -16 3 5<br />

upper_acceptable_limit -5 11 11<br />

upper_tolerance_limit 50 50 50<br />

Ethion<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 84,25 -16% 5% 8% 7%<br />

200 205,37 5% 4% 6% 5%<br />

500 527,03 27% 3% 4% 3%


111<br />

Guy Jamet – STRBG<br />

λ CYHALOTHRIN (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

λ Cyhalothrin<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit 2 1 -2<br />

recovery 26 24 12<br />

upper_acceptable_limit 50 47 25<br />

upper_tolerance_limit 50 50 50<br />

λ Cyhalothrin<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 126,12 26% 4% 10% 10%<br />

200 247,80 48% 5% 10% 10%<br />

500 557,72 58% 4% 7% 7%


112<br />

Guy Jamet – STRBG<br />

IPRODIONE (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Iprodione<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -153 -62 -3<br />

recovery -75 -4 8<br />

upper_acceptable_limit 3 54 18<br />

upper_tolerance_limit 50 50 50<br />

Iprodione<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 24,74 -75% 212% NaN 212%<br />

200 191,65 -8% 41% 7% 41%<br />

500 538,12 38% 7% 8% 7%


113<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (LOD-LOQ)<br />

Pyrimethanil<br />

concentration (ppb) 100 200 500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -252 -197 -199<br />

recovery 10 -8 77<br />

upper_acceptable_limit 272 181 353<br />

upper_tolerance_limit 50 50 50<br />

Pyrimethanil<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 110,09 10% 6% 108% 110%<br />

200 183,90 -16% 3% 93% 95%<br />

500 884,54 385% 26% 95% 77%


114<br />

Guy Jamet – STRBG<br />

PROCYMIDONE (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Procymidone<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -73 -18 -15<br />

recovery 4 19 6<br />

upper_acceptable_limit 82 56 28<br />

upper_tolerance_limit 50 50 50<br />

Procymidone<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 104,29 4% 8% 28% 35%<br />

200 238,43 38% 10% 18% 17%<br />

500 531,28 31% 4% 10% 10%


115<br />

Guy Jamet – STRBG<br />

TOLCLOPHOS METHYL (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Tolclophos methyl<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -28 -8 -3<br />

recovery -20 0 3<br />

upper_acceptable_limit -12 8 9<br />

upper_tolerance_limit 50 50 50<br />

Tolclophos methyl<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 79,81 -20% 3% 6% 6%<br />

200 199,50 -1% 5% 6% 5%<br />

500 514,18 14% 4% 4% 4%


116<br />

Guy Jamet – STRBG<br />

Extension to other matrices at<br />

0.01 mg/kg<br />

‣ REPRESENTATIVE<br />

MATRICES<br />

‣ Salads representative<br />

of leafy vegetables<br />

‣ Carrots representative<br />

of Roots vegetables<br />

‣ Apples representative<br />

of Fruit<br />

‣ Relative big production<br />

of each in Alsace<br />

‣ REPRESENTATIVE<br />

ANALYTES<br />

‣ CHLORFENVINPHOS<br />

‣ CYPRODINIL<br />

‣ IPRODIONE<br />

‣ λ CYHALOTHRIN<br />

‣ PROCYMIDONE<br />

‣ PYRIMETHANIL<br />

‣ TOLCLOPHOS<br />

METHYL<br />

‣ VINCLOZOLINE


117<br />

Guy Jamet – STRBG<br />

CHLORFENVINPHOS (ACS)<br />

Chlorfenvinphos<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -82 -175 -124<br />

Recovery -6 -29 -52<br />

Upper_tolerable_limt 70 117 19<br />

Upper_acceptable_limit 50 50 50<br />

Chlorfenvinphos<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 9,38 -1% 514% 518% 514%<br />

Apple 7,09 -3% 29% 659% 670%<br />

Salad 4,77 -5% 485% 115% 485%


118<br />

Guy Jamet – STRBG<br />

CYPRODINIL (ACS)<br />

Cyprodinil<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -73 -94 -105<br />

Recovery -16 -57 -32<br />

Upper_tolerable_limt 41 -21 42<br />

Upper_acceptable_limit 50 50 50<br />

Cyprodinil<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 8,42 -2% 387% 208% 387%<br />

Apple 4,26 -6% 231% 268% 242%<br />

Salad 6,84 -3% 394% 510% 467%


119<br />

Guy Jamet – STRBG<br />

IPRODIONE (ACS)<br />

Iprodione<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -114 -213 -186<br />

Recovery -30 0 -14<br />

Upper_tolerable_limt 54 213 158<br />

Upper_acceptable_limit 50 50 50<br />

Iprodione<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 6,97 -3% 222% 426% 446%<br />

Apple 10,01 0% 1439% 150% 1439%<br />

Salad 8,60 -1% 317% 178% 861%


120<br />

Guy Jamet – STRBG<br />

λ CYHALOTHRIN (ACS)<br />

λ Cyhalothrin<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -102 -133 -112<br />

Recovery -28 -58 -41<br />

Upper_tolerable_limt 46 17 30<br />

Upper_acceptable_limit 50 50 50<br />

λ Cyhalothrin<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 7,19 -3% 231% 422% 409%<br />

Apple 4,17 -6% 234% 427% 414%<br />

Salad 5,87 -4% 262% 427% 408%


121<br />

Guy Jamet – STRBG<br />

PROCYMIDONE (ACS)<br />

Procymidone<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -74 -106 -113<br />

Recovery 14 -18 -30<br />

Upper_tolerable_limt 101 71 53<br />

Upper_acceptable_limit 50 50 50<br />

Procymidone<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 11,37 1% 81% 396% 412%<br />

Apple 8,22 -2% 236% 472% 472%<br />

Salad 6,99 -3% 561% 605% 561%


122<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (ACS)<br />

Pyrimethanil<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -82 -212 -128<br />

Recovery 69 22 45<br />

Upper_tolerable_limt 221 256 218<br />

Upper_acceptable_limit 50 50 50<br />

Pyrimethanil<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 16,94 7% 295% 769% 765%<br />

Apple 12,22 2% 159% 1074% 1090%<br />

Salad 14,50 5% 551% 959% 957%


123<br />

Guy Jamet – STRBG<br />

TOLCLOPHOS METHYL (ACS)<br />

Tolclophos methyl<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -98 -71 -79<br />

Recovery -39 -49 -52<br />

Upper_tolerable_limt 21 -26 -26<br />

Upper_acceptable_limit 50 50 50<br />

Tolclophos methyl<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 6,13 -4% 140% 314% 310%<br />

Apple 5,14 -5% 34% 82% 111%<br />

Salad 4,77 -5% 107% 50% 157%


124<br />

Guy Jamet – STRBG<br />

VINCLOZOLINE (ACS)<br />

Vinclozoline<br />

limits<br />

Carrots Apples Salads<br />

Low er_acceptable_limit -50 -50 -50<br />

Low er_tolerable_limit -110 -136 -148<br />

Recovery -29 -53 -69<br />

Upper_tolerable_limt 52 30 9<br />

Upper_acceptable_limit 50 50 50<br />

Vinclozoline<br />

Matrix Mean bias sd_r sd_Ro sd_IP<br />

Carrot 7,07 -3% 549% 555% 549%<br />

Apple 4,73 -5% 273% 481% 464%<br />

Salad 3,06 -7% 21% 356% 362%


125<br />

Guy Jamet – STRBG<br />

VINCLOZOLINE (LOD-LOQ)<br />

concentration (ppb) 100 200 500<br />

Vinclozoline<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -120 -54 -2<br />

recovery -35 -2 8<br />

upper_acceptable_limit 50 50 18<br />

upper_tolerance_limit 50 50 50<br />

Vinclozoline<br />

Mean bias rsd_r rsd_Ro rsd_IP<br />

100 64,92 -35% 89% 47% 89%<br />

200 195,91 -4% 36% 11% 36%<br />

500 538,80 39% 6% 4% 6%


126<br />

Guy Jamet – STRBG<br />

1 st step in qualitative accreditation<br />

‣ Salads<br />

‣ CYPRODINYL<br />

‣ IPRODIONE<br />

‣ λ CYHALOTHRIN<br />

‣ PYRIMETHANYL<br />

‣ LCL<br />

‣ LOD<br />

‣ LOQ<br />

‣ Upper limit<br />

‣ Repeatability of<br />

recovery<br />

‣ Intermediate fidelity


127<br />

Guy Jamet – STRBG<br />

3 rd proposal: determination of the recovery at<br />

other concentrations on salads<br />

‣ Follow up of the extraction at high<br />

concentration level<br />

‣ Determination of the response of a<br />

diluted sample<br />

‣ Using the 1 g/ml solution<br />

‣ Further dilution<br />

‣ Variability due to the dilution<br />

‣ Multilevel calibration standards<br />

‣ Aldrine as qualitative internal<br />

standard<br />

‣ No quantitative standard<br />

‣ Different days<br />

‣ Estimation of the variability at each<br />

level<br />

‣ Visual examination on profile<br />

accuracy plot<br />

‣ REPRESENTATIVE<br />

ANALYTES<br />

CYPRODINYL<br />

IPRODIONE<br />

λ CYHALOTHRIN<br />

PYRIMETHANYL<br />

‣ REPRESENTATIVE<br />

MATRICE for LEAFY<br />

VEGETABLES and huge<br />

production in Alsace


128<br />

Guy Jamet – STRBG<br />

CYPRODINIL (high conc.)<br />

Pesticde Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP<br />

Cyprodinil 224<br />

Cyprodinil 225<br />

LMR/10s 1 1,16 0,16% 2,25% 24,62% 25,04%<br />

LMR/10e 1 1,09 0,09% 2,55% 28,05% 28,53%<br />

LMR/2e 5 5,19 0,19% 1,84% 10,69% 10,87%<br />

LMRe 10 10,05 5,05% 9,94% 14,78% 2,88%<br />

LMR/10s 1 1,15 0,15% 2,34% 23,59% 23,98%<br />

LMR/10e 1 1,08 0,08% 2,39% 27,31% 27,77%<br />

LMR/2e 5 5,23 0,23% 1,70% 10,96% 11,09%<br />

LMRe 10 9,97 4,97% 9,70% 13,71% 2,77%<br />

Pesticide limit LMR/10s LMR/10e LMR/2e LMRe<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit -47 -58 -20 -100<br />

Cyprodinil 224 recovery 16 9 4 101<br />

upper_tolerable_limit 78 77 28 302<br />

upper_acceptable_limit 50 50 50 50<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit -45 -57 -20 -78<br />

Cyprodinil 225 recovery 15 8 5 99<br />

upper_tolerable_limit 75 74 29 277<br />

upper_acceptable_limit 50 50 50 50


129<br />

Guy Jamet – STRBG<br />

IPRODIONE (high conc.)<br />

Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP<br />

LMR/10s 1 1,42 0,4% 4,0% 5,1% 4,6%<br />

LMR/10e 1 1,37 0,4% 2,6% 2,3% 2,6%<br />

Iprodione 314<br />

LMR/2e 5 5,19 0,2% 2,4% 8,9% 8,9%<br />

LMRe 10 11,34 6,3% 8,8% 9,1% 0,6%<br />

LMR/10s 1 1,48 0,5% 3,1% 7,7% 7,6%<br />

LMR/10e 1 1,43 0,4% 2,2% 4,9% 4,8%<br />

Iprodione 316<br />

LMR/2e 5 5,17 0,2% 2,6% 8,0% 8,0%<br />

LMRe 10 11,47 6,5% 9,0% 7,3% 1,0%<br />

Pesticide limit LMR/10s LMR/10e LMR/2e LMRe<br />

low er_acceptable_limit -50 -50 -50 -50<br />

Iprodione 314<br />

Iprodione 316<br />

low er_tolerable_limit 32 31 -15 96<br />

recovery 42 37 4 127<br />

upper_tolerable_limit 52 42 23 158<br />

upper_acceptable_limit 50 50 50 50<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit 26 29 -13 81<br />

recovery 48 43 3 129<br />

upper_tolerable_limit 70 56 20 177<br />

upper_acceptable_limit 50 50 50 50


130<br />

Guy Jamet – STRBG<br />

λ CYHALOTHRIN (high conc.)<br />

Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP<br />

LMR/10s 0.1 0,15 0,05% 4,10% 3,91% 4,10%<br />

LMR/10e 0.1 0,15 0,05% 8,54% 8,06% 8,54%<br />

λ Cyhalothrin 181<br />

LMR/2e 0.5 0,61 0,11% 1,94% 9,64% 9,75%<br />

LMRe 1.0 1,27 0,77% 7,37% 15,28% 0,47%<br />

LMR/10s 0.1 0,14 0,04% 2,79% 2,87% 2,79%<br />

LMR/10e 0.1 0,15 0,05% 7,50% 7,23% 7,50%<br />

λ Cyhalothrin 197<br />

LMR/2e 0.5 0,60 0,10% 1,97% 10,17% 10,30%<br />

LMRe 1.0 1,28 0,78% 7,55% 15,85% 0,31%<br />

Pesticide limit LMR/10s LMR/10e LMR/2e LMRe<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit 37 31 -4 90<br />

λ Cyhalothrin 181 recovery 46 49 21 154<br />

upper_tolerable_limit 55 68 46 218<br />

upper_acceptable_limit 50 50 50 50<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit 38 31 -6 90<br />

λ Cyhalothrin 197 recovery 44 48 21 157<br />

upper_tolerable_limit 50 64 47 224<br />

upper_acceptable_limit 50 50 50 50


131<br />

Guy Jamet – STRBG<br />

PYRIMETHANIL (high conc.)<br />

Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP<br />

Pyrimethanil 198<br />

Pyrimethanil 199<br />

LMR/10s 0,2 0,43 0,2% 0,6% 15,6% 15,9%<br />

LMR/10e 0,2 0,42 0,2% 1,9% 13,9% 14,5%<br />

LMR/2e 1 1,10 0,1% 2,3% 17,2% 17,5%<br />

LMRe 2 2,93 1,9% 13,7% 20,3% 2,3%<br />

LMR/10s 0,2 0,44 0,2% 0,5% 14,0% 14,3%<br />

LMR/10e 0,2 0,44 0,2% 1,7% 14,5% 14,8%<br />

LMR/2e 1 1,10 0,1% 2,2% 17,1% 17,4%<br />

LMRe 2 2,95 1,9% 13,7% 21,2% 2,1%<br />

Pesticide limit LMR/10s LMR/10e LMR/2e LMRe<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit 40 46 -31 -884<br />

Pyrimethanil 198 recovery 114 112 10 193<br />

upper_tolerable_limit 188 178 52 1269<br />

upper_acceptable_limit 50 50 50 50<br />

low er_acceptable_limit -50 -50 -50 -50<br />

low er_tolerable_limit 52 49 -31 -953<br />

Pyrimethanil 199 recovery 121 119 10 195<br />

upper_tolerable_limit 189 188 51 1342<br />

upper_acceptable_limit 50 50 50 50


Mean, bias, RSD_r, RSD_FI (1)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 119 19% 5% 11%<br />

OPP 200 231 31% 7% 11%<br />

500 533 33% 5% 5%<br />

100 116 16% 7% 10%<br />

Diphenylamine 200 232 32% 4% 9%<br />

500 529 29% 4% 4%<br />

100 34 -66% 150% 212%<br />

Chlorpropham 200 235 35% 7% 13%<br />

500 537 37% 5% 6%<br />

100 0 -100% NaN NaN<br />

Dimethoate 200 0 -200% NaN NaN<br />

500 0 -500% NaN NaN<br />

100 0 -100% NaN NaN<br />

Dicloran 200 0 -200% NaN NaN<br />

500 0 -500% NaN NaN<br />

100 52 -48% 110% 110%<br />

Propyzamide 200 156 -44% 43% 43%<br />

500 523 23% 6% 6%<br />

100 110 10% 6% 110%<br />

Pyrimethanil 200 184 -16% 2% 95%<br />

500 885 385% 26% 77%<br />

100 99 -1% 18% 18%<br />

Diazinon 200 171 -29% 64% 64%<br />

500 459 -41% 40% 40%<br />

100 9 -91% 300% 300%<br />

Chlorothalonil 200 162 -38% 8% 8%<br />

500 441 -59% 5% 6%<br />

100 119 19% 6% 6%<br />

Pyrimicarb 200 226 26% 2% 4%<br />

500 540 40% 3% 6%<br />

100 90 -10% 8% 8%<br />

Chlorpyriphos methyl 200 206 6% 8% 8%<br />

500 508 8% 4% 4%<br />

132<br />

Guy Jamet – STRBG


133<br />

Guy Jamet – STRBG<br />

Extension to other of analytes<br />

‣ 0.01, 0.02, 0.05 mg/kg according<br />

to R 396/2005<br />

‣ 3 repetition each level<br />

‣ Mean value<br />

‣ RSD_r at each level<br />

‣ 3 times<br />

‣ 66 residues<br />

‣ With BROMOPHOS METHYL<br />

as internal standards<br />

for quantification<br />

‣ RSD_IP at each level<br />

‣ Profile of accuracy


Mean, bias, RSD_r, RSD_FI (2)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 65 -35% 89% 89%<br />

Vinclozoline 200 196 -4% 36% 36%<br />

500 539 39% 6% 6%<br />

100 0 -100% NaN NaN<br />

Parathion methyl 200 72 -128% 145% 152%<br />

500 0 -500% NaN NaN<br />

100 80 -20% 3% 6%<br />

Tolclophos methyl 200 199 -1% 6% 6%<br />

500 514 14% 4% 4%<br />

100 14 -86% 300% 300%<br />

Carbaryl 200 96 -104% 129% 129%<br />

500 517 17% 27% 27%<br />

100 116 16% 33% 33%<br />

Metalaxyl 200 229 29% 34% 34%<br />

500 549 49% 5% 5%<br />

100 7 -93% 300% 300%<br />

Fenitrothion 200 107 -93% 65% 105%<br />

500 466 -34% 36% 36%<br />

100 84 -16% 8% 14%<br />

Pyrimiphos methyl 200 195 -5% 5% 5%<br />

500 513 13% 3% 3%<br />

100 84 -16% 14% 14%<br />

Malathion 200 192 -8% 8% 8%<br />

500 516 16% 4% 4%<br />

100 71 -29% 50% 50%<br />

Diethofencarbe 200 209 9% 10% 12%<br />

500 525 25% 4% 4%<br />

100 135 35% 13% 13%<br />

Chlorpyriphos 200 240 40% 8% 8%<br />

500 541 41% 5% 6%<br />

100 129 29% 4% 6%<br />

Chlorthal dimethyl 200 244 44% 5% 7%<br />

500 543 43% 5% 5%<br />

134<br />

Guy Jamet – STRBG


Mean, bias, RSD_r, RSD_FI (3)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 54 -46% 102% 102%<br />

Tetraconazole 200 214 14% 3% 3%<br />

500 526 26% 4% 4%<br />

100 123 23% 7% 8%<br />

Cyprodinil 200 229 29% 3% 9%<br />

500 535 35% 3% 3%<br />

100 57 -43% 129% 139%<br />

Penconazole 200 257 57% 8% 11%<br />

500 569 69% 3% 3%<br />

100 28 -72% 150% 212%<br />

Tolylfluanid 200 131 -69% 67% 67%<br />

500 478 -22% 4% 10%<br />

100 61 -39% 83% 83%<br />

Chlorfenvinphos 200 226 26% 4% 6%<br />

500 531 31% 2% 5%<br />

100 0 -100% NaN NaN<br />

Thiabenazole 200 2 -198% 300% 300%<br />

500 77 -423% 210% 210%<br />

100 0 -100% NaN NaN<br />

Triadimenol 200 0 -200% NaN NaN<br />

500 355 -145% 67% 76%<br />

100 104 4% 8% 35%<br />

Procymidone 200 238 38% 10% 17%<br />

500 531 31% 4% 10%<br />

100 180 80% 11% 69%<br />

Methidathion 200 196 -4% 31% 92%<br />

500 1020 520% 16% 65%<br />

100 0 -100% NaN NaN<br />

α Endosulfan 200 300 100% 87% 87%<br />

500 416 -84% 49% 49%<br />

100 90 -10% 6% 6%<br />

Mepanipyrim 200 206 6% 4% 5%<br />

500 526 26% 4% 4%<br />

135<br />

Guy Jamet – STRBG


Mean, bias, RSD_r, RSD_FI (4)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 127 27% 11% 28%<br />

Dieldrin 200 261 61% 9% 14%<br />

500 525 25% 5% 12%<br />

100 0 -100% NaN NaN<br />

Fludioxonil 200 16 -184% 104% 104%<br />

500 33 -467% 86% 86%<br />

100 0 -100% NaN NaN<br />

Myclobutanil 200 46 -154% 287% 287%<br />

500 515 15% 32% 55%<br />

100 135 35% 12% 12%<br />

Buprofezine 200 182 -18% 51% 51%<br />

500 555 55% 5% 6%<br />

100 78 -22% 62% 62%<br />

Flusilazole 200 229 29% 8% 10%<br />

500 547 47% 4% 4%<br />

100 94 -6% 17% 17%<br />

Kresoxim methyl 200 218 18% 8% 11%<br />

500 533 33% 5% 6%<br />

100 0 -100% NaN NaN<br />

Imazalil 200 0 -200% NaN NaN<br />

500 18 -482% 300% 300%<br />

100 35 -65% 116% 144%<br />

Bupirimate 200 175 -25% 46% 46%<br />

500 513 13% 7% 21%<br />

100 0 -100% NaN NaN<br />

β Endosulfan 200 178 -22% 46% 79%<br />

500 373 -127% 62% 62%<br />

100 84 -16% 5% 7%<br />

Ethion 200 205 5% 4% 5%<br />

500 527 27% 3% 3%<br />

100 0 -100% NaN NaN<br />

Oxadixyl 200 0 -200% NaN NaN<br />

500 515 15% 37% 37%<br />

136<br />

Guy Jamet – STRBG


Mean, bias, RSD_r, RSD_FI (5)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 89 -11% 12% 12%<br />

Benalaxyl 200 208 8% 4% 8%<br />

500 524 24% 6% 6%<br />

100 0 -100% NaN NaN<br />

Endosulfan sulphate 200 0 -200% NaN NaN<br />

500 505 5% 9% 9%<br />

100 0 -100% NaN NaN<br />

Trifloxystrobin 200 1869 1669% 150% 212%<br />

500 4304 3804% 107% 124%<br />

100 0 -100% NaN NaN<br />

Fenhexamid 200 0 -200% NaN NaN<br />

500 614 114% 28% 28%<br />

100 6 -94% 300% 300%<br />

Tebuconazole 200 116 -84% 58% 80%<br />

500 497 -3% 40% 40%<br />

100 20 -80% 300% 300%<br />

Propargite 200 147 -53% 110% 110%<br />

500 702 202% 97% 97%<br />

100 92 -8% 6% 17%<br />

Pipronyl butoxyde 200 213 13% 5% 14%<br />

500 553 53% 3% 10%<br />

100 25 -75% 212% 212%<br />

Iprodione 200 192 -8% 41% 41%<br />

500 538 38% 7% 7%<br />

100 0 -100% NaN NaN<br />

Phosmet 200 0 -200% NaN NaN<br />

500 0 -500% NaN NaN<br />

100 356 256% 38% 85%<br />

Bromopropylate 200 530 330% 49% 69%<br />

500 894 394% 31% 103%<br />

100 23 -77% 211% 211%<br />

Bifenthrin 200 96 -104% 131% 131%<br />

500 198 -302% 137% 137%<br />

137<br />

Guy Jamet – STRBG


Mean, bias, RSD_r, RSD_FI (6)<br />

Residues ppb Mean Bias rsd_r rsd_IP<br />

100 90 -10% 12% 14%<br />

Tebufenpyrad 200 208 8% 7% 7%<br />

500 542 42% 9% 9%<br />

100 0 -100% NaN NaN<br />

Phosalone 200 46 -154% 150% 212%<br />

500 545 45% 9% 14%<br />

100 0 -100% NaN NaN<br />

Azinphos methyl 200 0 -200% NaN NaN<br />

500 0 -500% NaN NaN<br />

100 122 22% 6% 9%<br />

Pyriproxyfen 200 240 40% 5% 8%<br />

500 550 50% 4% 4%<br />

100 126 26% 4% 10%<br />

λ Cyhalothrine 200 248 48% 5% 10%<br />

500 558 58% 4% 7%<br />

100 64 -36% 149% 149%<br />

Fenarimol 200 285 85% 10% 31%<br />

500 619 119% 7% 20%<br />

100 1 -99% 214% 214%<br />

Bitertanol 200 39 -161% 151% 213%<br />

500 718 218% 12% 34%<br />

100 0 -100% NaN NaN<br />

Boscalid 200 156 -44% 87% 87%<br />

500 559 59% 8% 15%<br />

100 82 -18% 40% 40%<br />

α Cypermethrin 200 221 21% 9% 9%<br />

500 540 40% 8% 8%<br />

100 0 -100% NaN NaN<br />

Deltamethrin 200 0 -200% NaN NaN<br />

500 588 88% 10% 14%<br />

100 0 -100% NaN NaN<br />

Azoxystrobin 200 0 -200% NaN NaN<br />

500 537 37% 35% 60%<br />

138<br />

Guy Jamet – STRBG


LOQ, LOD, LMR (1)<br />

C_100 C_200 C_500 LOD LOQ LMR<br />

OPP 0.01 0.02 0.05 0.001 0.01 0.01<br />

Diphenylamine 0.01 0.02 0.05 0.001 0.01 0.05<br />

Chlorpropham 0.02 0.05 0.002 0.02 0.05<br />

Dimethoate 0.02<br />

Dicloran 0.01<br />

Propyzamide 0.05 0.005 0.05 0.02<br />

Pyrimethanil 0.05 0.005 0.05 0.01<br />

Diazinon 0.01 0.05 0.005 0.05 0.02<br />

Chlorothalonil 0.02 0.05 0.002 0.02 0.01<br />

Pyrimicarb 0.01 0.02 0.05 0.001 0.01 0.02<br />

Chlorpyriphos methyl 0.01 0.02 0.05 0.001 0.01 0.05<br />

Vinclozoline 0.02 0.05 0.002 0.02 0.05<br />

Parathion methyl 0.02<br />

Tolclophos methyl 0.01 0.02 0.05 0.001 0.01 0.01<br />

Carbaryl 0.05 0.005 0.05 0.05<br />

Metalaxyl 0.01 0.02 0.05 0.001 0.01 0.05<br />

Fenitrothion 0.05 0.005 0.05 0.05<br />

Pyrimiphos methyl 0.01 0.02 0.05 0.001 0.01 0.05<br />

Malathion 0.01 0.02 0.05 0.001 0.01 0.02<br />

Diethofencarb 0.01 0.02 0.05 0.001 0.01 0.01<br />

Chlorpyriphos 0.01 0.02 0.05 0.001 0.01 0.05<br />

Chlorthal dimethyl 0.01 0.02 0.05 0.001 0.01 0.01<br />

Tetraconazole 0.02 0.05 0.002 0.02 0.01<br />

Cyprodinil 0.01 0.02 0.05 0.001 0.01 0.01<br />

Penconazole 0.02 0.05 0.002 0.02 0.05<br />

Tolylfluanid 0.02 0.05 0.002 0.02 0.01<br />

Chlorfenvinphos 0.02 0.05 0.002 0.02 0.02<br />

Thiabenazole 0.05<br />

Triadimenol 0.1<br />

Procymidone 0.01 0.02 0.05 0.001 0.01 0.02<br />

Methidathion 0.05 0.005 0.05 0.02<br />

α Endosulfan 0.02 0.05 0.002 0.02 0.05<br />

Mepanipyrim 0.01 0.02 0.05 0.001 0.01 0.02<br />

139<br />

Guy Jamet – STRBG


Capability of determination (1)<br />

Residues MRL LOD LOQ MRL/LOQ<br />

OPP 0,01 0,001 0,01 LOQ=MRL<br />

Diphenylamine 0,05 0,001 0,01 LOQMRL<br />

Dicloran 0,01 LOQ>>MRL<br />

Propyzamide 0,02 0,005 0,05 LOQ>MRL<br />

Pyrimethanil 0,01 0,005 0,05 LOQ>MRL<br />

Diazinon 0,02 0,005 0,05 LOQ>MRL<br />

Chlorothalonil 0,01 0,002 0,02 LOQ>MRL<br />

Pyrimicarbe 0,02 0,001 0,01 LOQMRL<br />

Procymidone 0,02 0,001 0,01 LOQMRL<br />

α Endosulfan 0,05 0,002 0,02 LOQ


Capability of determination (2)<br />

Residues MRL LOD LOQ MRL/LOQ<br />

Dieldrine 0,01 0,001 0,01 LOQ=MRL<br />

Fludioxonil 0,01 LOQ>>MRL<br />

Myclobutanil 0,02 LOQ>>MRL<br />

Buprofezine 0,01 0,001 0,01 LOQ=MRL<br />

Flusilazole 0,01 0,001 0,01 LOQ=MRL<br />

Kresoxim_methyl 0,05 0,001 0,01 LOQ>MRL<br />

Bupirimate 0,01 0,002 0,02 LOQ>MRL<br />

β Endosulfan 0,05 LOQ>>MRL<br />

Ethion 0,01 0,001 0,01 LOQ=MRL<br />

Oxadixyl 0,05 0,005 0,05 LOQ=MRL<br />

Benalaxyl 0,05 0,001 0,01 LOQ>MRL<br />

Fenhexamide 0,05 0,005 0,05 LOQ=MRL<br />

Tebuconazole 0,01 0,002 0,02 LOQ>MRL<br />

Propargite 0,01 0,005 0,05 LOQ>MRL<br />

Pipronyl_butoxyde 0,05 0,001 0,01 LOQ>MRL<br />

Bromopropylate 0,05 0,001 0,01 LOQMRL<br />

141<br />

Guy Jamet – STRBG


LOQ, LOD, LMR (2)<br />

C_100 C_200 C_500 LOD LOQ LMR<br />

Dieldrin 0.01 0.02 0.05 0.001 0.01 0.01<br />

Fludioxonil 0.01<br />

Myclobutanil 0.02<br />

Buprofezine 0.01 0.02 0.05 0.001 0.01 0.01<br />

Flusilazole 0.01 0.02 0.05 0.001 0.01 0.01<br />

Kresoxim methyl 0.01 0.02 0.05 0.001 0.01 0.05<br />

Imazalil 0.02<br />

Bupirimate 0.02 0.05 0.002 0.02 0.01<br />

β Endosulfan 0.05<br />

Ethion 0.01 0.02 0.05 0.001 0.01 0.01<br />

Oxadixyl 0.05 0.005 0.05 0.05<br />

Benalaxyl 0.01 0.02 0.05 0.001 0.01 0.05<br />

Endosulfan sulphate 0.05 0.005 0.05 0.05<br />

Trifloxystrobin 0.05<br />

Fenhexamid 0.05 0.005 0.05 0.05<br />

Tebuconazole 0.02 0.05 0.002 0.02 0.01<br />

Propargite 0.05 0.005 0.05 0.01<br />

Pipronyl butoxyde 0.01 0.02 0.05 0.001 0.01 0.05<br />

Iprodione 0.02 0.05 0.002 0.02 0.02<br />

Phosmet 0.01<br />

Bromopropylate 0.01 0.02 0.05 0.001 0.01 0.05<br />

Bifenthrin 0.01 0.02 0.05 0.001 0.01 0.05<br />

Tebufenpyrad 0.01 0.02 0.05 0.001 0.01 0.05<br />

Phosalone 0.05 0.005 0.05 0.05<br />

Azinphos methyl 0.01<br />

Pyriproxyfen 0.01 0.02 0.05 0.001 0.01 0.01<br />

λ Cyhalothrine 0.01 0.02 0.05 0.001 0.01 0.02<br />

Fenarimol 0.02 0.05 0.002 0.02 0.02<br />

Bitertanol 0.05 0.005 0.05 0.05<br />

Boscalid 0.05 0.005 0.05 0.01<br />

α Cypermethrin 0.01 0.02 0.05 0.001 0.01 0.05<br />

Deltamethrin 0.05 0.005 0.05 0.05<br />

Azoxystrobin 0.05<br />

142<br />

Guy Jamet – STRBG


143<br />

Guy Jamet – STRBG<br />

13 analytes with LOQ >> LMR<br />

‣ Analytes with 1 or 2<br />

characteristic ions<br />

‣ AZINPHOS METHYL<br />

‣ PHOSMET<br />

‣ PARATHION METHYL<br />

‣ THIABENDAZOLE<br />

‣ Analytes with low response due<br />

to isomers<br />

‣ TRIADIMENOL<br />

‣ Analytes with low response<br />

‣ DIMETHOATE<br />

‣ FLUDIOXONIL<br />

‣ MYCLOBUTANIL<br />

‣ DICHLORAN<br />

‣ IMAZALIL<br />

‣ β ENDOSULFAN<br />

‣ TRIFLOXYSTROBIN<br />

‣ AOXYSTROBIN


144<br />

Guy Jamet – STRBG<br />

11 analytes with LOD >LMR<br />

‣ PROPYZAMIDE<br />

‣ PYRIMETHANIL<br />

‣ DIAZINON<br />

‣ CHLOROTHALONIL<br />

‣ TETRACONAZOLE<br />

‣ TOLYLFLUANID<br />

‣ METHIDATHION<br />

‣ BUPIRIMATE<br />

‣ TEBUCONAZOLE<br />

‣ PROPARGITE<br />

‣ BOSCALID


145<br />

Guy Jamet – STRBG<br />

20 analytes with LOD =LMR<br />

‣ OPP<br />

‣ TOLCLOPHOS METHYL<br />

‣ CARBARYL<br />

‣ FENITROTHION<br />

‣ DIETHOFENCARB<br />

‣ CHLORTHAL DIMETHYL<br />

‣ CYPRODINIL<br />

‣ DIELDRIN<br />

‣ BUPROFEZIN<br />

‣ FLUSILAZOLE<br />

‣ ETHION<br />

‣ OXADIXYL<br />

‣ ENDOSULFAN Sulphate<br />

‣ FENHEXAMID<br />

‣ IPRODIONE<br />

‣ PHOSALONE<br />

‣ PYRIPROXYFEN<br />

‣ FENARIMOL<br />

‣ BITERTANOL<br />

‣ DELTAMETHRIN


146<br />

Guy Jamet – STRBG<br />

22 analytes with LOD


147<br />

Guy Jamet – STRBG<br />

SUMMARY<br />

‣ 63% of the analytes are amenable with the<br />

method at the MRL<br />

‣ 37% are not amenable at the MRL<br />

‣ What’s about repeatability, intermediate<br />

fidelity<br />

‣ What’s about higher concentrations


148<br />

Guy Jamet – STRBG<br />

PROPYZAMIDE and CHLOROTHALONIL<br />

(LOQ>MRL)<br />

limits<br />

c_100 c_200 c_500<br />

limits<br />

c_100 c_200 c_500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_tolerance_limt -50 -50 -50<br />

Propyzamide<br />

low er_acceptable_limit -132 -72 -5<br />

recovery -48 -22 5<br />

Chlorothalonil<br />

low er_acceptable_limit -129 -28 -20<br />

recovery -91 -19 -12<br />

upper_acceptable_limit 36 28 14<br />

upper_acceptable_limit -54 -10 -3<br />

upper_tolerance_limit 50 50 50<br />

upper_tolerance_limit 50 50 50


149<br />

Guy Jamet – STRBG<br />

CHLORPYRIPHOS and MALATHION<br />

(LOQ


150<br />

Guy Jamet – STRBG<br />

CYPERMETHRIN and MEPANIPYRIM<br />

(LOQ>MRL)<br />

Alpha_cypermethrine<br />

limits c_100 c_200 c_500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -66 -4 -4<br />

recovery -18 11 8<br />

upper_acceptable_limit 29 26 20<br />

upper_tolerance_limit 50 50 50<br />

Mepanipyrim<br />

limits c_100 c_200 c_500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -18 -5 -1<br />

recovery -10 3 5<br />

upper_acceptable_limit -2 11 11<br />

upper_tolerance_limit 50 50 50


151<br />

Guy Jamet – STRBG<br />

Residues not amenable for every<br />

matrices<br />

0,01 mg/kg<br />

Calibration Carott Apple<br />

Salad<br />

Mean Recovery<br />

mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % real %<br />

10 Pyrimicarb NA<br />

11 Vinclozoline 11 4 33 7 6 80 6 4 72 72<br />

13 Parathion methyl NA<br />

19 Malathion 10 2 17 7 1 13 11 8 76 9 5 54 54<br />

20 Diethofencarb 9 3 37 11 5 46 6 4 68 5 3 55 8 5 63 63<br />

22 Chlorthal dimethyl 7 2 24 NA<br />

26 Chlorfenvinphos 9 3 34 9 6 63 6 5 84 8 5 64 64<br />

32 α Endosulfan NA<br />

33 Mepanipyrim 10 6 55 16 20 121 7 2 26 11 13 122 122<br />

34 Dieldrin 6 5 74 NA<br />

35 Buprofezine NA<br />

37 Imazalil 9 4 39 8 6 76 7 5 64 NA<br />

40 Bupirimate 30 15 50 NA<br />

41 Kresoxym methyl NA<br />

42 β Endosulfan 5 5 103 8 7 95 NA<br />

45 Benalaxyl 8 3 33 NA<br />

47 Fenhexamid NA<br />

48 Trifloxystrobin 15 5 31 40 24 59 35 34 97 NA<br />

49 Piperonil butoxyde 22 10 45 32 16 50 37 19 50 U_150%<br />

50 Tebuconazole NA<br />

51 Propargite 2 2 86 6 4 78 12 13 111 NA<br />

52 Iprodione NA<br />

53 Phosmet NA<br />

54 Bromopropylate 12 1 9 10 3 30 4 4 89 9 5 54 54<br />

55 Bifenthrin 8 3 32 6 5 73 NA<br />

58 Pyriproxyfen 10 2 21 NA<br />

59 Azinphos_methyl 14 12 86 8 3 40 5 5 102 9 8 91 NA<br />

63 α Cypermethrin NA


152<br />

Guy Jamet – STRBG<br />

BENALAXYL and KRESOXIM METHYL<br />

(LOQ>MRL)<br />

Benalaxyl<br />

limits c_100 c_200 c_500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -27 -12 -4<br />

recovery -11 4 5<br />

upper_acceptable_limit 6 21 14<br />

upper_tolerance_limit 50 50 50<br />

Kresoxim methyl<br />

limits c_100 c_200 c_500<br />

low er_tolerance_limt -50 -50 -50<br />

low er_acceptable_limit -29 -12 -4<br />

recovery -6 9 7<br />

upper_acceptable_limit 18 29 17<br />

upper_tolerance_limit 50 50 50


Residues amenable for every matrices<br />

0,01 mg/kg<br />

Calibration Carott Apple<br />

Salad<br />

Mean Recovery<br />

mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % real %<br />

1 OPP 8 1 14 11 1 8 9 1 14 9 4 42 10 1 14 14<br />

2 Diphenylamine 9 3 37 9 2 27 5 3 62 6 2 40 7 3 43 43<br />

3 Chlorpropham 13 5 37 16 4 22 13 5 39 9 4 41 13 4 33 33<br />

4 Dimethoate 20 8 42 23 7 32 16 10 61 19 13 69 20 10 49 49<br />

5 Dicloran 18 7 41 26 8 31 19 13 69 20 13 66 22 11 50 50<br />

6 Propyzamide 12 4 37 10 4 38 9 5 62 9 6 64 10 5 49 49<br />

7 Pyrimethanil 16 8 53 17 7 44 12 9 77 15 11 78 15 9 61 61<br />

8 Diazinon 9 1 16 5 5 90 5 3 62 6 4 66 5 4 67 67<br />

9 Chlorothalonil 10 4 36 14 4 26 13 6 51 9 5 59 12 5 42 42<br />

12 Chlorpyriphos methyl 10 1 7 8 1 14 7 1 13 6 3 42 7 1 17 17<br />

14 Tolclophos methyl 9 1 13 7 2 33 5 2 32 5 2 48 6 2 34 34<br />

15 Carbaryl 15 8 56 17 11 68 17 12 68 14 13 89 17 11 68 68<br />

16 Metalaxyl 15 6 38 12 8 62 12 6 54 12 10 83 13 8 62 62<br />

17 Fenitrothion 13 5 43 16 5 29 11 7 64 11 7 66 13 6 48 48<br />

18 Pyrimiphos methyl 9 1 12 6 3 40 4 2 43 5 3 56 5 2 45 45<br />

20 Diethofencarb 9 3 37 11 5 46 6 4 68 5 3 55 8 5 63 63<br />

21 Chlorpyriphos 9 1 14 6 3 50 5 2 44 5 3 62 6 3 47 1<br />

23 Tetraconazole 8 4 44 10 1 7 7 5 71 11 7 61 9 5 49 49<br />

24 Cyprodinil 12 1 8 8 4 43 5 3 54 7 4 64 7 4 52 52<br />

25 Penconazole 15 7 48 16 11 67 10 11 108 15 14 96 14 12 83 83<br />

27 Tolylfluanid 12 2 17 13 6 43 10 5 51 14 8 58 13 6 47 47<br />

28 Thiabenazole 32 5 14 33 11 33 26 14 54 27 26 97 30 18 58 58<br />

29 Triadimenol 18 4 23 28 18 63 15 11 74 24 20 86 23 17 73 73<br />

30 Procymidone 13 6 48 11 5 41 8 5 64 7 5 74 9 5 55 55<br />

31 Methidathion 13 5 41 27 24 88 13 8 57 12 7 57 18 16 88 88<br />

36 Flusilazole 15 5 36 18 9 51 15 8 56 22 20 89 19 13 69 69<br />

38 Fludixonyl 16 7 46 19 9 48 15 9 65 15 12 80 17 10 58 58<br />

39 Myclobutanil 10 3 32 10 3 32 6 3 47 24 29 117 13 17 130 130<br />

43 Oxadixyl 19 23 125 27 29 108 7 1 16 9 9 96 15 19 127 127<br />

44 Ethion 17 8 51 27 8 31 14 3 18 11 7 63 19 9 47 47<br />

46 Endosulfan sulphate 15 2 14 16 7 44 14 6 46 14 10 71 15 7 48 1<br />

56 Tebufenpyrad 15 11 73 13 10 82 5 4 71 6 4 65 9 7 87 87<br />

57 Phosalone 15 4 30 22 10 45 21 11 53 21 16 76 22 12 53 U_150%<br />

60 λ Cyhalothrine 9 2 22 8 3 38 5 4 78 6 4 61 6 3 54 54<br />

61 Fenarimol 17 17 100 26 21 80 21 16 78 20 16 81 23 17 74 74<br />

62 Bitertanol 28 11 41 34 19 55 32 25 78 30 32 105 33 24 73 73<br />

64 Deltamethrin 20 5 26 20 7 34 12 9 73 10 7 68 15 8 55 55<br />

65 Azoxystrobin 18 7 36 19 10 54 16 10 63 14 12 88 17 10 62 62<br />

153<br />

Guy Jamet – STRBG


154<br />

Guy Jamet – STRBG<br />

Proficiency testing<br />

‣ Goal<br />

‣ Avoiding false +<br />

‣ Avoiding false –<br />

‣ Statement of the uncertainty<br />

‣ According the routine<br />

‣ Residues unknown<br />

‣ Ratio with number of<br />

samples<br />

‣ National BIPEA<br />

‣ Known residues for<br />

quantitative aim only<br />

‣ International paying<br />

‣ FAPAS Residues unknown<br />

‣ EU Mandatory<br />

‣ EUPT Residues unknown


Prediction of the proficiency testing<br />

NOM : Jamet Date : 15/02/07 Identifiant : 80 Visa :<br />

Désignation : EIL<br />

N°CAS :<br />

Essai(s) concerné(s) :<br />

Méthode multirésidus : Résidus de pesticides<br />

Exigences spécifiées :<br />

Maintien d’accréditation multirésidus avec extension matrice et quantitatif<br />

Exigence OAV exercice communautaire<br />

Compléter les rubriques nécessaires à valider la sélection :<br />

FAPAS<br />

Pertinant MRM<br />

Fournisseurs<br />

Critères<br />

Références<br />

Conditionnem<br />

ent<br />

EUPT<br />

Obligatoire<br />

OAV<br />

Avril 2007<br />

EUPT 09 +<br />

blanc<br />

Fraise<br />

(Offre BIPEA non<br />

pertinante MRM)<br />

Juin 2007<br />

1970 + blanc<br />

salade purée<br />

Portée actuel<br />

Bipea<br />

Méthodes<br />

orphelines<br />

Bipea<br />

Méthodes<br />

orphelines<br />

Avril 2007 Septembre 2007<br />

200g 100 g 100g 100g 100g<br />

Tarif HT 135 205 265 265 205<br />

Autres frais lié<br />

à la<br />

commande<br />

HT<br />

Délai de<br />

livraison<br />

Conservation<br />

(durée – T°C -<br />

…)<br />

Antériorité de<br />

la commande<br />

FAPAS<br />

Pertinant MRM<br />

(Offre BIPEA non<br />

pertinante MRM)<br />

Janvier 2008<br />

1975 + blanc<br />

Pomme purée<br />

Extension<br />

- 85 + 55 - - 85 + 55<br />

-18° -18° -18° -18° -18°<br />

oui oui non non oui<br />

Sélection<br />

retenue<br />

oui oui oui<br />

Approbation de la direction Accord sur la sélection Pas d’accord sur la sélection ;<br />

autre choix :<br />

NOM : Date : Visa :<br />

Mise à jour de la base de données informatique<br />

Base à jour base non à jour, codification :…………….(si existe) ou à<br />

créer :……………<br />

Responsable gestion, mise en conformité de la base, le : / / Visa :<br />

155<br />

Guy Jamet – STRBG


156<br />

Guy Jamet – STRBG<br />

Proficiency testing<br />

‣ EUPT6: Tomato<br />

‣ EUPT7: Grapes<br />

‣ EUPT8: Aubergine<br />

‣ EUPT9: Strawberry<br />

‣ EUPT10: Carrot<br />

‣ EUPT11: Cauliflower<br />

‣ EUPT12: Leek


Z-score EUPT<br />

157<br />

Guy Jamet – STRBG


Z-score EUPT by round<br />

158<br />

Guy Jamet – STRBG


Z-score EUPT by analytes and different<br />

concentration<br />

159<br />

Guy Jamet – STRBG


Interpretation of Z-score<br />

No<br />

Z score<br />

Yes<br />

Not sought for<br />

Yes<br />

-2


4,4' DDE 1963 0,164 0,187<br />

Azinphos methyl 19101 0,94 0,155<br />

Bifenthrin 19101 0,244 0,139<br />

Bifenthrine 1970 0,136 0,0948<br />

Boscalid 19101 0,356 0,419<br />

Bupirimate 1991 0,149 0,148<br />

Carbaryl 1998 0,242 0,652<br />

Chlorfenvinphos 1963 0,0743 0,098<br />

Chlorpyriphos 1975 0,0457 0,0397<br />

Cypermethrine 1963 0,602 0,43861<br />

Dicloran 1998 0,228 0,429<br />

Iprodione 1958 0,772 1,407<br />

Iprodione 1991 0,539 0,366<br />

Mecarbam 1963 0,0804 0,099<br />

Metalaxyl 1958 0,186 0,465<br />

Methidathion 1970 0,119 0,16874<br />

Methidathion 1998 0,262 0,322<br />

Pendimethaline 1998 0,299 0,328<br />

Permethrine 1991 0,0475 0,0612<br />

Propargite 1975 0,375 0,36<br />

Pyrimicarbe 1975 0,0702 nd<br />

PyrimME 1958 0,262 0,676<br />

Quintozene 1958 0,0796 0,182<br />

Tecnazene 1958 0,0862 0,242<br />

161<br />

Guy Jamet – STRBG<br />

Thiabendazole 1991 0,0285 0,025<br />

Trifloxystrobine 1991 0,278 0,217<br />

Z-score FAPAS<br />

Z score FAPAS /Residues<br />

10<br />

8<br />

6<br />

4<br />

2<br />

0<br />

-2<br />

-4<br />

-6<br />

Target Lab Z-score


162<br />

Guy Jamet – STRBG<br />

Reason of Z score EUPT<br />

Round Residue Target Lab Z-score lab Matrix Comments<br />

6 Azoxystrobin 0,225 ND -3,1 Tomato Homogeneity<br />

6 Chlorothalonil 1,626 0,655 -2,4 Tomato Homogeneity<br />

6 Diazinon 3,955 1,036 -3 Tomato Homogeneity<br />

6 Dimethoate 0,132 0,028 -3,2 Tomato Homogeneity<br />

6 Procymidone 0,412 0,0423 -3,5 Tomato Homogeneity<br />

7 Dimethoate 0,139 0,04 -2,8 Grapes Residue<br />

7 Fludioxonil 0,238 0,05 -3,2 Grapes Residue<br />

7 Monocrotophos 0,643 0,1 -3,8 Grapes Residue<br />

8 Fludioxonil 1,27 2,14 2,7 Aubergine Residue<br />

8 Parathion 0,16 0,25 2,2 Aubergine Co elution<br />

9 Fenhexamid 0,34 0,535 2,2 Straw berry Residue<br />

9 Hexythiazox 1,05 1,81 2,9 Straw berry Residue<br />

10 Endosulfan 0,106 0,194 2,4 Carrot Residue<br />

10 Pendimethalin 0,076 ND -3,5 Carrot LOD<br />

10 Phosmet 0,233 0,196 2,2 Carrot 1 ion<br />

11 Azinphos 0,355 0,811 5,1 Cauliflow er 1 ion<br />

11 Methidathion 0,472 0,06 -3,5 Cauliflow er Mass of ion<br />

12 Azinphos methyl 0,048 ND -3,2 Leek 1 ion<br />

12 Chlorothalonil 0,216 0,07 -2,7 Leek Residue<br />

12 Fenpropathrin 0,062 ND -3,4 Leek LOD


Decision of the scope<br />

‣ Sequence<br />

‣ Routinely the sequence looks like following: solvent, std 5000 ppb, 2000 ppb, 1000 ppb,<br />

500 ppb, 200 ppb, 100 ppb, 12 vials (representing the concentration of 10 g matrix per ml<br />

and the 1/10 th dilution and finally 3x the re-injection of std 1000 ppb<br />

‣ Characterisation of the sequence by<br />

‣ The repeatability “r” of std 1000 ppb at each sequence<br />

‣ The intermediate precision “IP” after 3 sequences (3 different days)<br />

‣ The lower upper acceptable limits for the following residues<br />

‣ OPP, DIPHENILAMINE, CCHLORPROPHAME, DIMETHOATE,<br />

PROPYZAMIDE, PYRIMETHANIL, PYRIMICARB, VINCLOZOLIN,<br />

CHLORPYRIPHOS METHYL, PARARTHION METHYL, TOLCLOPHOS<br />

METHYL, CARBARYL, METALAXYL, MALATHION, CHLORPYRIPHOS,<br />

CYPRODINIL, CHLORFENVINPHOS, TOLYLFLUANID, PPROCYMIDONE,<br />

METHIDATHION, α ENDOSULFAN, IMAZALIL, FLUDIOXONIL, KRESOXIM<br />

METHYL, β ENDOSULFAN, OXADIXYL, ETHION, ENDOSULFAN<br />

SULPHATE, TEBUCONAZOLE, PROPARGITE, IPRODIONE, PHOSMET,<br />

BROMOPROPYLAT, BIFENTHRINE,TEBUFENPYRAD, PHOSALONE, λ<br />

CYHALOTHRIN, α CYPERMETHRIN, DELTAMETHRIN, AZOXYSTROBINE<br />

‣ The results are issued from Excel using the profile of accuracy from these generated by<br />

the GC/MS<br />

163<br />

Guy Jamet – STRBG


Validation of the deviation<br />

Lim inf Tol inf M oyenne Tol sup Lim sup<br />

OPP 800 918 1007 1096 1200<br />

Diphenylamine 800 932 998 1064 1200<br />

Chlorpropham 800 897 995 1093 1200<br />

Dimethoate 800 806 1100 1394 1200<br />

Propyzamide 800 944 993 1042 1200<br />

Pyrimethanil 800 940 991 1042 1200<br />

Pyrimicarb 800 928 1005 1083 1200<br />

Vinclozoline 800 902 967 1031 1200<br />

Chlorpyriphos methyl 800 953 996 1040 1200<br />

Parathion methyl 800 767 1009 1251 1200<br />

Tolclophos methyl 800 954 988 1021 1200<br />

Carbaryl 800 916 1039 1163 1200<br />

M etalaxyl 800 923 989 1054 1200<br />

M alathion 800 942 983 1024 1200<br />

Chlorpyriphos 800 942 969 996 1200<br />

Cyprodinil 800 919 963 1007 1200<br />

Chlorfenvinphos Z 800 938 999 1061 1200<br />

Tolylfluanid 800 214 1324 2435 1200<br />

Chlorfenvinphos E 800 910 987 1064 1200<br />

Procymidone 800 940 972 1004 1200<br />

M ethidathion 800 888 982 1076 1200<br />

α Endosulfan 800 868 1009 1149 1200<br />

Imazalil 800 -345 1009 2362 1200<br />

Fludixonyl 800 -2 437 877 1200<br />

Kresoxym methyl 800 867 933 999 1200<br />

β Endosulfan 800 903 1063 1223 1200<br />

Oxadixyl 800 766 870 973 1200<br />

Ethion 800 835 908 982 1200<br />

Endosulfan sulphate 800 715 1152 1589 1200<br />

Tebuconazole 800 491 882 1274 1200<br />

Propargite 800 684 1093 1502 1200<br />

Iprodione 800 346 766 1186 1200<br />

Phosmet 800 145 667 1189 1200<br />

Bromopropylate 800 900 979 1058 1200<br />

Bifenthrin 800 781 911 1040 1200<br />

Tebufenpyrad 800 831 942 1054 1200<br />

Phosalone 800 721 877 1034 1200<br />

λ Cyhalothrin 800 754 882 1010 1200<br />

α Cypermethrin 800 292 741 1191 1200<br />

Deltamethrin 800 192 682 1173 1200<br />

Azoxystrobin 800 -2752 932 4617 1200<br />

164<br />

Guy Jamet – STRBG


Variability<br />

OPP<br />

Dip<br />

Chl<br />

Dim<br />

Pro<br />

Pyri<br />

Pyri<br />

Vin<br />

Chl<br />

Par<br />

Tolc<br />

Car<br />

Met<br />

Mal<br />

Chl<br />

Cyp<br />

Chl<br />

Toly<br />

Chl<br />

Pro<br />

Met<br />

End<br />

Ima<br />

Flud<br />

Kre<br />

End<br />

Oxa<br />

Diet<br />

End<br />

Teb<br />

Pro<br />

Ipro<br />

Pho<br />

Bro<br />

Bife<br />

Teb<br />

Pho<br />

lam<br />

Alp<br />

Delt<br />

Azo<br />

165<br />

Guy Jamet – STRBG<br />

Validation of the residues<br />

Limites d'acceptation absolues du point 1000 ppb<br />

5000<br />

4000<br />

3000<br />

2000<br />

1000<br />

0<br />

-1000<br />

-2000<br />

-3000<br />

-4000<br />

Matières actives<br />

#REF! Lim inf Tol inf Moyenne Tol sup Lim sup


Variability<br />

OPP<br />

Diphenylamine<br />

Chlorprophame<br />

Dimethoate<br />

Propyzamide<br />

Pyrimethanil<br />

Pyrimicarbe<br />

Vinclozoline<br />

Chlorpyriphos methyl<br />

Parathion methyl<br />

Tolclophos methyl<br />

Carbaryl<br />

Metalaxyl<br />

Malathion<br />

Chlorpyriphos ethyl<br />

Cyprodinil<br />

Chlorfenvinphos Z<br />

Chlorfenvinphos E<br />

Procymidone<br />

Methidathion<br />

Bromopropylate<br />

Bifenthrine<br />

Tebufenpyrad<br />

Oxadixyl<br />

Diethion<br />

Kresoxym methyl<br />

lambda cyhalothryne<br />

Phosalone<br />

Endosulfan beta<br />

Endosulfan alpha<br />

166<br />

Guy Jamet – STRBG<br />

Amenable Residues<br />

Residues with acceptable variability<br />

25%<br />

20%<br />

15%<br />

10%<br />

5%<br />

0%<br />

-5%<br />

-10%<br />

-15%<br />

-20%<br />

-25%<br />

Residues<br />

Lim inf -20% rsdr % rsdFI % Biais (%) Lim sup 20%


Variability<br />

Imazalil<br />

Fludixonyl<br />

Endosulfan sulfate<br />

Tebuconazole<br />

Propargite<br />

Iprodione<br />

Phosmet<br />

Alpha cypermethrine<br />

Deltamethrine<br />

Azoxystrobine<br />

Tolylfluanide<br />

Not amenable Residues<br />

Residues out of limits<br />

140%<br />

120%<br />

100%<br />

80%<br />

60%<br />

40%<br />

20%<br />

0%<br />

-20%<br />

-40%<br />

-60%<br />

-80%<br />

Residues<br />

Lim inf -20% rsdr % rsdFI % Biais (%) Lim sup 20%<br />

167<br />

Guy Jamet – STRBG


Sequence<br />

Line Type Vial DataFile Method Sample<br />

1 Sample 1 -------- PEST5SPE C1 5000<br />

2 Sample 2 -------- PEST5SPE C1 2000<br />

3 Sample 3 -------- PEST5SPE C1 1000<br />

4 Sample 4 -------- PESTSSPE C1 500<br />

5 Sample 5 -------- PEST5SPE C1 200<br />

6 Sample 6 -------- PEST5SPE C1 100<br />

7 Sample 7 -------- PEST5SPE Ech 1 1/1<br />

8 Sample 8 -------- PEST5SPE Ech 1 1/10<br />

9 Sample 9 -------- PEST5SPE Ech 2 1/1<br />

10 Sample 10 -------- PEST5SPE Ech 2 1/10<br />

11 Sample 11 -------- PEST5SPE Ech 3 1/1<br />

12 Sample 12 -------- PEST5SPE Ech 3 1/10<br />

13 Sample 13 -------- PEST5SPE Ech 4 1/1<br />

14 Sample 14 -------- PEST5SPE Ech 4 1/10<br />

15 Sample 15 -------- PEST5SPE Ech 5 1/1<br />

16 Sample 16 -------- PEST5SPE Ech 5 1/10<br />

17 Sample 17 -------- PEST5SPE Ech 6 1/1<br />

18 Sample 18 -------- PEST5SPE Ech 6 1/10<br />

19 Sample 19 -------- PEST5SPE Ech 7 1/1<br />

20 Sample 20 -------- PEST5SPE Ech 7 1/10<br />

21 Sample 21 -------- PEST5SPE Ech 8 1/1<br />

22 Sample 22 -------- PEST5SPE Ech 8 1/10<br />

23 Sample 23 -------- PEST5SPE Ech 9 1/1<br />

24 Sample 24 -------- PEST5SPE Ech 9 1/10<br />

25 Sample 25 -------- PEST5SPE Ech 10 1/1<br />

26 Sample 26 -------- PEST5SPE Ech 10 1/10<br />

27 Sample 27 -------- PEST5SPE Ech 11 1/1<br />

28 Sample 28 -------- PEST5SPE Ech 11 1/10<br />

29 Sample 29 -------- PEST5SPE Ech 12 1/1<br />

30 Sample 30 -------- PEST5SPE Ech 12 1/10<br />

31 Sample 3 -------- PESTSSPE C1 1000<br />

32 Sample 3 -------- PESTSSPE C1 1000<br />

33 Sample 3 -------- PESTSSPE C1 1000<br />

34 Sample 1 -------- PEST5SPE C2 5000<br />

35 Sample 2 -------- PEST5SPE C2 2000<br />

36 Sample 3 -------- PEST5SPE C2 1000<br />

37 Sample 4 -------- PEST5SPE C2 500<br />

38 Sample 5 -------- PEST5SPE C2 200<br />

39 Sample 6 -------- PEST5SPE C2 100<br />

168<br />

Guy Jamet – STRBG


169<br />

Guy Jamet – STRBG<br />

Deviation<br />

Pyrimethanil<br />

Concentration ppb Mean rsd_Mean<br />

100 0,56 47%<br />

200 0,96 131%<br />

500 2,64 76%<br />

1000 6,87 65%<br />

2000 15,14 24%<br />

5000 36,86 21%<br />

Cyprodinil<br />

Concentration ppb Mean rsd_Mean<br />

100 0,55 48%<br />

200 0,99 58%<br />

500 2,48 33%<br />

1000 5,68 30%<br />

2000 11,44 20%<br />

5000 27,81 17%<br />

Iprodione<br />

Concentration ppb Mean rsd_Mean<br />

100 0,06 64%<br />

200 0,14 107%<br />

500 0,39 46%<br />

1000 0,64 68%<br />

2000 1,24 22%<br />

5000 3,15 17%<br />

λ Cyhalothrin<br />

Concentration Mean rsd_Mean<br />

100 0,28 60%<br />

200 0,59 119%<br />

500 1,57 57%<br />

1000 2,36 68%<br />

2000 4,71 25%<br />

5000 11,58 22%


170<br />

Guy Jamet – STRBG<br />

Repeatability, Intermediate fidelity of<br />

calibration<br />

Pyrimethanil<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,558 -0,09 48% 35% 48%<br />

C_200 0,963 -0,14 88% 86% 88%<br />

C_500 2,635 -0,11 60% 51% 60%<br />

C_1000 6,874 -0,03 44% 25% 4%<br />

C_2000 15,141 0,10 15% 22% 2%<br />

C_5000 36,865 0,08 11% 20% 1%<br />

Cyprodinil<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,554 0,14 50% 46% 50%<br />

C_200 0,993 -0,01 33% 35% 33%<br />

C_500 2,484 0,03 31% 34% 31%<br />

C_1000 5,675 0,02 15% 21% 5%<br />

C_2000 11,443 0,04 15% 22% 2%<br />

C_5000 27,808 0,02 12% 20% 1%<br />

Iprodione<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,061 0,01 54% 73% 66%<br />

C_200 0,141 0,02 39% 47% 43%<br />

C_500 0,389 0,18 66% 37% 66%<br />

C_1000 0,644 -0,04 18% 16% 6%<br />

C_2000 1,240 0,01 16% 24% 3%<br />

C_5000 3,147 -0,01 12% 19% 1%<br />

λ Cyhalothrin<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,284 0,01 43% 51% 43%<br />

C_200 0,594 0,08 61% 36% 61%<br />

C_500 1,567 0,26 72% 32% 72%<br />

C_1000 2,358 -0,03 22% 22% 5%<br />

C_2000 4,711 0,01 23% 26% 3%<br />

C_5000 11,578 0,00 18% 23% 1%


Response<br />

171<br />

Guy Jamet – STRBG<br />

Profile of calibration PYRIMETHANIL<br />

Pyrimethanil<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,56 -9% 48% 35% 48%<br />

C_200 0,96 -14% 88% 86% 88%<br />

C_500 2,64 -11% 60% 51% 60%<br />

C_1000 6,87 -3% 44% 25% 4%<br />

C_2000 15,14 10% 15% 22% 2%<br />

C_5000 36,86 8% 11% 20% 1%<br />

Pyrimethanil (IS)<br />

50,00<br />

40,00<br />

30,00<br />

20,00<br />

Pyrimethanil<br />

y = 0,0075x - 0,5055 R2 = 0,9991<br />

y = -8E-08x2 + 0,0079x - 0,6962 R2 = 0,9992<br />

10,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-10,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Max) Linéaire (Min) Linéaire ( Mean )


Response<br />

172<br />

Guy Jamet – STRBG<br />

Profile of calibration CYPRODINIL<br />

Cyprodinil<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,55 14% 50% 46% 50%<br />

C_200 0,99 -1% 33% 35% 33%<br />

C_500 2,48 3% 31% 34% 31%<br />

C_1000 5,68 2% 15% 21% 5%<br />

C_2000 11,44 4% 15% 22% 2%<br />

C_5000 27,81 2% 12% 20% 1%<br />

Cyprodinil (IS)<br />

35,00<br />

30,00<br />

25,00<br />

20,00<br />

15,00<br />

10,00<br />

Cyprodinyl<br />

y = 0,0056x - 0,0472 R2 = 0,9996<br />

y = -6E-08x2 + 0,0059x - 0,2035 R2 = 0,9998<br />

5,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-5,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Max) Linéaire ( Mean ) Linéaire (Min)


Response<br />

173<br />

Guy Jamet – STRBG<br />

Profile of calibration IPRODIONE<br />

Iprodione<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,06 1% 54% 73% 66%<br />

C_200 0,14 2% 39% 47% 43%<br />

C_500 0,39 18% 66% 37% 66%<br />

C_1000 0,64 -4% 18% 16% 6%<br />

C_2000 1,24 1% 16% 24% 3%<br />

C_5000 3,15 -1% 12% 19% 1%<br />

Iprodione (IS)<br />

4,00<br />

3,50<br />

3,00<br />

2,50<br />

2,00<br />

1,50<br />

Iprodione<br />

y = 0,0006x + 0,0212 R2 = 0,9993<br />

y = 3E-09x2 + 0,0006x + 0,0296 R2 = 0,9993<br />

1,00<br />

0,50<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-0,50<br />

Concentration (ppb)<br />

Min Mean Max Linéaire ( Mean ) Linéaire (Max) Linéaire (Min)


Response<br />

174<br />

Guy Jamet – STRBG<br />

Profile of calibration λ CYHALOTHRIN<br />

λ Cyhalothrin<br />

Concentration Mean bias rsd_r rsd_Ro rsd_IP<br />

C_100 0,28 1% 43% 51% 43%<br />

C_200 0,59 8% 61% 36% 61%<br />

C_500 1,57 26% 72% 32% 72%<br />

C_1000 2,36 -3% 22% 22% 5%<br />

C_2000 4,71 1% 23% 26% 3%<br />

C_5000 11,58 0% 18% 23% 1%<br />

λ Cyhalothrin (IS)<br />

16,00<br />

14,00<br />

12,00<br />

10,00<br />

8,00<br />

6,00<br />

λ Cyhalothrin<br />

y = 0,0023x + 0,1691 R2 = 0,999<br />

y = -9E-11x2 + 0,0023x + 0,1689 R2 = 0,999<br />

4,00<br />

2,00<br />

0,00<br />

0 1000 2000 3000 4000 5000 6000<br />

-2,00<br />

Concentration (ppb)<br />

Min Mean Max Linéaire (Min) Linéaire (Max) Linéaire ( Mean )


175<br />

Guy Jamet – STRBG<br />

Repeatability, Intermediate fidelity on<br />

Salad at different concentrations<br />

Pyrimethanil 198<br />

Conc mg/kg Mean bias rsd_r rsd_R rsd_IP<br />

LMR/10s 0,2 0,43 0,2% 0,6% 15,6% 15,9%<br />

LMR/10e 0,2 0,42 0,2% 1,9% 13,9% 14,5%<br />

LMR/2e 1 1,10 0,1% 2,3% 17,2% 17,5%<br />

LMRe 2 2,93 1,9% 13,7% 20,3% 2,3%<br />

Cyprodinil 224<br />

Conc mg/kg Mean bias rsd_r rsd_R rsd_IP<br />

LMR/10s 1 1,16 0,16% 2,25% 24,62% 25,04%<br />

LMR/10e 1 1,09 0,09% 2,55% 28,05% 28,53%<br />

LMR/2e 5 5,19 0,19% 1,84% 10,69% 10,87%<br />

LMRe 10 10,05 5,05% 9,94% 14,78% 2,88%<br />

Iprodione 314<br />

Conc mg/kg Mean bias rsd_r rsd_R rsd_IP<br />

LMR/10s 1 1,42 0,4% 4,0% 5,1% 4,6%<br />

LMR/10e 1 1,37 0,4% 2,6% 2,3% 2,6%<br />

LMR/2e 5 5,19 0,2% 2,4% 8,9% 8,9%<br />

LMRe 10 11,34 6,3% 8,8% 9,1% 0,6%<br />

λ Cyhalothrin 181<br />

Conc mg/kg Mean bias rsd_r rsd_R rsd_IP<br />

LMR/10s 0.1 0,15 0,05% 4,10% 3,91% 4,10%<br />

LMR/10e 0.1 0,15 0,05% 8,54% 8,06% 8,54%<br />

LMR/2e 0.5 0,61 0,11% 1,94% 9,64% 9,75%<br />

LMRe 1.0 1,27 0,77% 7,37% 15,28% 0,47%


176<br />

Guy Jamet – STRBG<br />

Repeatability, Intermediate fidelity on<br />

different matrices at 0.01 mg/kg<br />

Pyrimethanil<br />

Matrix Mean bias rsd_r rsd_IP<br />

Carrot 169 6% 17% 45%<br />

Apple 122 12% 13% 89%<br />

Salad 168 12% 26% 69%<br />

Cyprodinil<br />

Matrix Mean bias rsd_r rsd_IP<br />

Carrot 84 0% 46% 46%<br />

Apple 43 9% 54% 57%<br />

Salad 74 -1% 49% 49%<br />

Iprodione<br />

Matrix Mean bias rsd_r rsd_IP<br />

Carrot 70 -24% 32% 64%<br />

Apple 102 24% 141% 141%<br />

Salad 87 78% 37% 101%<br />

λ Cyhalothrin<br />

Matrix Mean bias rsd_r rsd_IP<br />

Carrot 72 -2% 32% 57%<br />

Apple 57 -10% 21% 44%<br />

Salad 74 1% 23% 27%


177<br />

Guy Jamet – STRBG<br />

On going control: identification and<br />

confirmation


On going control<br />

Cocktail C1-C2 (Accredited)<br />

0.1 0.2 0.5<br />

LMRP<br />

RRT / ng/ml ng/ml ng/ml<br />

Aldrin 0.01 0.02 0.05<br />

mg/kg<br />

mg/kg mg/kg mg/kg<br />

Operator<br />

α CYPERMETHRINE 1,5 0,05 Agi-AM Agi-AM Agi-AM NN<br />

BIFENTHRIN 1,4 0,05 Agi-AM Agi-AM Agi-AM NN<br />

BROMOPROPYLATE 1,4 0,05 Agi-AM Agi-AM Agi-AM NN<br />

CARBARYL 0,9 0,05 AM AM AM NN<br />

CHLORFENVINPHOS 1,1 0,02 Agi-AM Agi-AM Agi-AM NN<br />

CHLORPROPHAM 0,7 0,05 Agi-AM Agi-AM Agi-AM NN<br />

CHLORPYRIPHOS 1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

CHLORPYRIPHOS METHYL 0,9 0,05 Agi-AM Agi-AM Agi-AM NN<br />

CYPRODINIL 1,1 0,01 Agi-AM Agi-AM Agi-AM NN<br />

ETHION 1,2 0,01 Agi-AM Agi-AM Agi-AM NN<br />

DIMETHOATE 0,8 0,02 Agi-AM Agi-AM Agi-AM NN<br />

DIPHENYLAMINE 0,7 0,05 Agi-AM Agi-AM Agi-AM NN<br />

α ENDOSULFAN 1,1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

β ENDOSULFAN 1,2 0,05 AM Agi-AM Agi-AM NN<br />

ENDOSULFAN SULPHATE 1,3 0,05 AM AM AM NN<br />

IPRODIONE 1,4 0,02 Agi-AM Agi-AM Agi-AM NN<br />

KRESOXIM METHYL 1,2 0,05 Agi-AM Agi-AM Agi-AM NN<br />

λ CYHALOTHRIN 1,5 0,02 Agi-AM Agi-AM Agi-AM NN<br />

MALATHION 1 0,02 Agi-AM Agi-AM Agi-AM NN<br />

METALAXYL 1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

OPP (2-Phénylphénol) 0,6 0,01 Agi-AM Agi-AM Agi-AM NN<br />

OXADIXYL 1,2 0,05 AM NN<br />

PARATHION METHYL 0,9 0,02 AM AM NN<br />

PHOSALONE 1,4 0,05 Agi-AM Agi-AM Agi-AM NN<br />

PROCYMIDONE 1,1 0,02 Agi-AM Agi-AM Agi-AM NN<br />

PROPARGITE 1,3 0,01 Agi-AM Agi-AM Agi-AM NN<br />

PROPYZAMIDE 0,8 0,02 Agi-AM Agi-AM Agi-AM NN<br />

PYRIMETHANIL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN<br />

TEBUCONAZOLE 1,3 0,01 Agi-AM Agi-AM Agi-AM NN<br />

TEBUFENPYRAD 1,4 0,05 Agi-AM Agi-AM Agi-AM NN<br />

TOLCLOPHOS METHYL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN<br />

VINCHLOZOLINE 0,9 0,05 AM AM NN<br />

178<br />

Guy Jamet – STRBG


On going control<br />

Sequence : 11/03/02<br />

N° of samples: 12<br />

Date : 11/03/03<br />

Action : yes no<br />

Cocktail C1-C2 (Not<br />

ccredited)<br />

RRT /<br />

Aldrin<br />

LMRP<br />

mg/kg<br />

0.1 ng/ml 0.2 ng/ml 0.5 ng/ml<br />

0.01 0.02 0.05<br />

mg/kg mg/kg mg/kg<br />

Operator<br />

AZINPHOS METHYL 1,4 0,01 AM Agi-AM Agi-AM NN<br />

AZOXYSTROBIN 2 0,05 AM AM AM NN<br />

BENALAXYL 1,3 0,05 AM Agi-AM Agi-AM NN<br />

BITERTANOL 1,5 0,05 Agi Agi-AM Agi-AM NN<br />

BOSCALID 1.6 0.01 AM Agi-AM Agi-AM NN<br />

BUPIRIMATE 1,2 0,01 AM AM AM NN<br />

BUPROFEZINE 1,2 0,01 AM AM AM NN<br />

CHLOROTHALONIL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN<br />

CHLORTHAL DIMETHYL 1 0,01 AM AM AM NN<br />

DELTAMETHRIN 1,9 0,05 AM AM AM NN<br />

DIAZINON 0,9 0,02 Agi-AM Agi-AM Agi-AM NN<br />

DICLORAN 0,8 0,01 AM AM AM NN<br />

DIELDRIN 1,2 0,01 Agi-AM Agi-AM Agi-AM NN<br />

DIETHOFENCARB 1 0,01 Agi-AM Agi-AM Agi-AM NN<br />

FENARIMOL 1,5 0,02 Agi-AM Agi-AM Agi-AM NN<br />

FENHEXAMID 1,3 0,05 AM AM Agi-AM NN<br />

FENITROTHION 1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

FLUDIOXONIL 1,2 0,01 AM AM NN<br />

FLUSILAZOLE 1,2 0,01 Agi-AM Agi-AM Agi-AM NN<br />

IMAZALIL 1,2 0,02 AM AM AM NN<br />

MAPANIPYRIM 1,1 0,02 Agi-AM Agi-AM Agi-AM NN<br />

METHIDATHION 1,1 0,02 Agi-AM Agi-AM Agi-AM NN<br />

MYCLOBUTANIL 1,2 0,02 Agi-AM Agi-AM Agi-AM NN<br />

PENCONAZOLE 1,1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

PHOSMET 1,4 0,01 Agi-AM Agi-AM Agi-AM NN<br />

PIPERONYL BUTOXYDE 1,3 0,05 AM AM AM NN<br />

PYRIMICARB 0,9 0,02 Agi-AM Agi-AM Agi-AM NN<br />

PYRIMIPHOS METHYL 1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

PYROPROXYFEN 1,4 0,01 Agi-AM Agi-AM Agi-AM NN<br />

TETRACONAZOLE 1 0,01 Agi-AM Agi-AM Agi-AM NN<br />

THIABENDAZOLE 1,1 0,05 Agi-AM Agi-AM Agi-AM NN<br />

TOLYLFLUANID 1,1 0,01 AM AM AM NN<br />

TRIADIMENOL 1,1 0,1 Agi-AM Agi-AM Agi-AM NN<br />

TRIFLOXYSTOBIN 1,3 0,05 Agi-AM Agi-AM AM NN<br />

179<br />

Guy Jamet – STRBG


180<br />

Guy Jamet – STRBG<br />

Conclusion<br />

‣ Pour profile for<br />

PYRIMETHANIL,<br />

‣ Large variability at 100 ppb<br />

(0.01 mg/kg):<br />

‣ IPRODIONE<br />

‣ PROCYMIDONE<br />

‣ CHLORFENVINPHOS<br />

‣ VINCLOZOLINE<br />

‣ λ CYHALOTHRIN<br />

‣ Acceptable at every levels<br />

‣ ETHION<br />

‣ CYPRODINIL<br />

‣ TOLCLOPHOS METHYL<br />

‣ Remarks of accreditation bodies<br />

‣ OK for leafy vegetables<br />

‣ OK for representative analytes<br />

‣ Uncertainty: Horwitz<br />

‣ Not enough value for a<br />

quantitative accreditation<br />

‣ Qualitative accreditation<br />

accorded based on the<br />

identification and<br />

proficiency testing


181<br />

Guy Jamet – STRBG<br />

2 nd step of the accreditation<br />

Objective Measured parameters<br />

Principe of the method Reference of the method<br />

Qualitative determination of pesticide residues<br />

α Cypermethrin Kresoxim Methyl<br />

Bifenthrine<br />

λ Cyhalothrin<br />

Bromopropylate Malathion<br />

Carbaryl<br />

Metalaxyl<br />

Chlorfenvinphos OPP (2 Phénylphénol)<br />

Internal Method<br />

Chlorprophame Oxadixyl<br />

IN167/80/ANA/02<br />

Chlorpyriphos Parathion Methyl Extraction w ith solvent<br />

IN167/80/ANA/26<br />

Salads Chlorpyriphos Methyl Phosalone<br />

Purification by Liquid-liquid partition Adapted from standards<br />

Cyprodinil<br />

Procymidone<br />

Analysis by GC/MS<br />

NF EN 12393-1<br />

Ethion<br />

Propargite<br />

NF EN 12393-2<br />

Dimethoate<br />

Propyzamide<br />

NF EN 12393-3<br />

Diphenylamine Pyrimethanil<br />

Endosulfan Sulphate Tebuconazole<br />

α Endosulfan<br />

Tebufenpyrad<br />

β Endosulfan<br />

Tolclophos Methyl<br />

Iprodione<br />

Vinchlozoline


Amenable recovery on apples (60-140%)<br />

mg/kg 0,02 0,06 0,12<br />

OPP 88% 80% 75%<br />

Chlorothalonil 105% 82% 78%<br />

Vinclozoline 85% 77% 75%<br />

Parathion Methtyl 65% 94% 83%<br />

Tolclophos Methyl 83% 74% 73%<br />

Metalaxyl 90% 75% 73%<br />

Fenitrothion 77% 76% 78%<br />

Malathion 88% 75% 71%<br />

Chlorpyriphos 78% 76% 71%<br />

Chlorthal dimethyl 73% 82% 74%<br />

α Endosulfan 92% 72% 85%<br />

Dieldrin 82% 79% 74%<br />

Kresoxim Methyl 85% 86% 86%<br />

Benalaxyl 78% 78% 75%<br />

Endosulfan sulphate 70% 67% 93%<br />

Iprodione 88% 78% 76%<br />

Phosmet >140% 88% 117%<br />

Bifenthrin 73% 81% 78%<br />

Tebufenpyrad 82% 84% 83%<br />

Phosalone 123% 109% 103%<br />

Pyriproxyfen 80% 83% 81%<br />

Fenarimol 118% 72% 64%<br />

Bitertanol 95% 67% 62%<br />

α Cypermethrin 97% 89% 84%<br />

Azoxystrobin 105% 74% 66%<br />

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Low and exceeding recoveries on apples<br />

mg/kg 0,02 0,06 0,12<br />

Diphenylamine


184<br />

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Extending recovery on apples<br />

‣ 0.02, 0.06, 0.12 mg/kg<br />

‣ 3 repetitions at each level<br />

‣ Apples<br />

‣ 3 series foreseen<br />

‣ Results of the first round


Unexplainable recoveries on apples<br />

Matrix<br />

Straw berry Witloof Leek Leek Witloof Salad Straw berry Salad<br />

mg/kg<br />

0,02 0,05 0,10<br />

Dieldrin >140%<br />

Fludioxonil<br />

Myclobutanil >140%<br />

Buprofezine 74% 88% 72% 97% 78%<br />

Flusilazole 66% 140%>140% >140% >140% >140%<br />

Propargite<br />

Pipronyl butoxyde >140%>140%>140%>140% 129% 134% >140%<br />

Iprodione >140% 93%<br />

Phosmet >140%<br />

Bromopropylate 93% 75% 76% 76%<br />

Bifenthrin 115%


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Exceeding recovery at low<br />

concentration on apples<br />

mg/kg 0,02 0,06 0,12<br />

Dicloran >140% 97% 78%<br />

Chlorpyriphos Methtyl >140% 90% 71%<br />

Penconazole >140% 60% 140% 116% 116%<br />

Azinphos Methyl >140% 64% 66%<br />

Boscalid >140% 92% 77%<br />

β Endosulfan >140% 90% 82%<br />

Fenhexamid >140% 126% 120%


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Recoveries on different matrices (2)<br />

Matrix Straw berry Witloof Leek Leek Witloof Salad Straw berry Salad<br />

mg/kg<br />

0,02 0,05 0,10<br />

OPP 80% 140% >140% >140%<br />

Tolclophos methyl >140% >140% 97% 92% >140% 102% 111% 117%<br />

Metalaxyl 122% 75% 66% 84%<br />

Pyrimiphos methyl >140% >140% >140% 108% 116% 119%<br />

Malathion >140% 119% 120% >140%<br />

Diethofencarb >140% 124% 113% >140%


Recoveries on different matrices (1)<br />

Matrix Strawberry Witloof Leek Leek Witloof Salad Strawberry Salad<br />

mg/kg<br />

0,02 0,05 0,10<br />

OPP 80% 140% >140% >140%<br />

Tolclophos methyl >140% >140% 97% 92% >140% 102% 111% 117%<br />

Metalaxyl 122% 75% 66% 84%<br />

Pyrimiphos methyl >140% >140% >140% 108% 116% 119%<br />

Malathion >140% 119% 120% >140%<br />

Diethofencarb >140% 124% 113% >140%<br />

Chlorthal dimethyl 74% 70% 140% >140% 98% >140%<br />

Penconazole >140% 70% 71% 75% 68% 74%<br />

Procymidone 78% 71% 73%<br />

Buprofezine 74% 88% 72% 97% 78%<br />

Flusilazole 66% 140% >140% >140%<br />

Tebuconazole >140% >140% >140% >140% >140%<br />

Pipronyl butoxyde >140% >140% >140% >140% 129% 134% >140%<br />

Bromopropylate 93% 75% 76% 76%<br />

Bifenthrin 115%


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Recoveries on different matrices<br />

‣ Strawberries: 0.02, 0.05, 0.1 mg/kg<br />

‣ Leeks: 0.05 mg/kg, 2 times<br />

‣ Salads: 0.1 mg/kg, 2 times<br />

‣ Witloof : 0.05, 0.1 mg/kg


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No recovery on different matrices (3)<br />

‣ DIMETHOATE<br />

‣ DICLORAN<br />

‣ CHLOROTHALONIL<br />

‣ PARATHION METHYL<br />

‣ CARBARYL<br />

‣ TOLYLFLUANID<br />

‣ THIABENDAZOLE<br />

‣ TRIADIMENOL<br />

‣ α ENDOSULFAN<br />

‣ DIELDRIN<br />

‣ FLUDIOXONIL<br />

‣ MYCLOBUTANIL<br />

‣ IMAZALIL<br />

‣ β ENDOSULFAN<br />

‣ OXADIXYL<br />

‣ ENDOSULFAN SULPHATE<br />

‣ FENHEXAMID<br />

‣ PHOSALONE<br />

‣ AZINPHOS METHYL<br />

‣ FENARIMOL<br />

‣ PROPARGITE<br />

‣ PHOSMET<br />

‣ BITERTANOL<br />

‣ BOSCALID<br />

‣ DELTAMETHRIN<br />

‣ AZOXYSTROBIN


Dossier of validation for GC-MS<br />

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Opening on the QuEChERS method<br />

and LC-MS/MS


193<br />

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Validation for LC-MS/MS<br />

QuEChERS<br />

EN NF 15662<br />

‣ Determination of pesticides residues using<br />

GC-MS and/or LC-MS/MS following<br />

acetonitrile extraction/partitioning and<br />

clean-up by dispersive SPE – QuEChERS<br />

method


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Layout of the characterization<br />

‣ Plan A:<br />

‣ Response of the system<br />

‣ Working range<br />

‣ Plan B:<br />

‣ Specificity:<br />

‣ Recovery<br />

‣ Plan C:<br />

‣ Plan D<br />

‣ Repeatability<br />

‣ Intermediate Precision<br />

‣ 10 levels from 0.003 to 2µg/ml<br />

‣ Critical value<br />

F(1, p(n – 1), 1 – α) by 1% of<br />

accuracy<br />

‣ apples, carrot, salad, lemon<br />

‣ Regression slope = 1<br />

‣ Blank, 0.02, 0.1, 1.0 mg/kg<br />

‣ 3 repetitions, 3 levels<br />

‣ sd repeatability<br />

‣ 1 repetition, 3 levels<br />

‣ sd Intermediate Precision<br />

(


Working plan for the determination of all the<br />

parameters<br />

Recovery<br />

Operator 1<br />

D1<br />

Operator 2<br />

D7<br />

Matrix Apple<br />

Operator 3<br />

D8<br />

Operator 4<br />

D9<br />

Operator 5<br />

D10<br />

Repeatability Intermediate precision Intermediate precision Intermediate precision Intermediate precision<br />

Blank x x x x x x x<br />

0.02 mg/Kg x x x x x x x<br />

0.1 mg/Kg x x x x x x x<br />

1.0 mg/Kg x x x x x x x<br />

Matrix Salad<br />

Operator 1 Operator 2 Operator 3 Operator 4 Operator 5<br />

Recovery<br />

D6 D2 D8 D9 D10<br />

Intermediate precision Repeatability Intermediate precision Intermediate precision Intermediate precision<br />

Blank x x x x x x x<br />

0.02 mg/Kg x x x x x x x<br />

0.1 mg/Kg x x x x x x x<br />

1.0 mg/Kg x x x x x x x<br />

Matrix carrot<br />

Operator 1 Operator 2 Operator 3 Operator 4 Operator 5<br />

Recovery<br />

D6 D7 D3 D9 D10<br />

Intermediate precision Intermediate precision Repeatability Intermediate precision Intermediate precision<br />

Blank x x x x x x x<br />

0.02 mg/Kg x x x x x x x<br />

0.1 mg/Kg x x x x x x x<br />

1.0 mg/Kg x x x x x x x<br />

Matrix lemon<br />

Operator 1 Operator 2 Operator 3 Operator 4 Operator 5<br />

Recovery<br />

D6 D7 D8 D4 D10<br />

Intermediate precision Intermediate precision Intermediate precision Repeatability Intermediate precision<br />

Blank x x x x x x x<br />

0.02 mg/Kg x x x x x x x<br />

0.1 mg/Kg x x x x x x x<br />

1.0 mg/Kg x x x x x x x<br />

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Interpretation<br />

Linearity<br />

Specificity<br />

YES<br />

Linear model<br />

No<br />

YES<br />

Specific method<br />

No matrix effect<br />

No<br />

Working range of linear model<br />

LOD<br />

LOQ<br />

Working range of quadratic model<br />

LOD<br />

LOQ<br />

Calibration with standards in<br />

solvent: acetonitrile<br />

Calibration with standards in<br />

matrix extract<br />

Recovery<br />

Intermediate Precision (IP)<br />

YES<br />

70%< Recovery


Response (area)<br />

197<br />

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Fitting of the response<br />

‣ Response of LC in<br />

solvent: acetonitrile<br />

R (Pearson) = 0.979<br />

3000000000<br />

2500000000<br />

Fittting of the response of Carbendazime<br />

‣ Polynomial equation of<br />

the 1 st degree: R 2 =0.954<br />

2000000000<br />

1500000000<br />

1000000000<br />

‣ Polynomial equation of<br />

the 2 nd degree: R 2 =0.986<br />

500000000<br />

0<br />

0,000 0,500 1,000 1,500 2,000 2,500<br />

Concentration<br />

‣ Polynomial equation of<br />

the 3 rd degree: R 2 =0.999


Responses<br />

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Specificity on a polynomial equation of<br />

the 1 st degree<br />

Specificity on polynomial equation of 1st degree<br />

‣ Ideal fitting y = x, no<br />

matrix effect<br />

‣ Carrots: R 2 = 0.9994<br />

‣ Salads: R 2 = 0.9867<br />

‣ Apples: R 2 = 0.9977<br />

Standards<br />

‣ Lemons: R 2 = 0.9996


Predicted concentrations<br />

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Specificity on a polynomial equation of<br />

the 3 rd degree<br />

0,600<br />

0,500<br />

0,400<br />

Specificity on polynomial equation of 3rd degree<br />

‣ Ideal fitting y = x, no<br />

matrix effect<br />

‣ Carrots: R 2 = 0.9996<br />

‣ Salads: R 2 = 0.996<br />

0,300<br />

‣ Apples: R 2 = 0.9977<br />

0,200<br />

0,100<br />

‣ Lemons: R 2 = 0.9997<br />

0,000<br />

0,000 0,100 0,200 0,300 0,400 0,500 0,600<br />

Initial concentrations


200<br />

Guy Jamet – STRBG<br />

Recovery<br />

‣ Against solvent<br />

‣ On blank matrix spiked before extraction<br />

‣ On blank matrix extract spiked after extraction<br />

‣ Real recovery<br />

‣ Matrix effect


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CARBENDAZIME real recovery at<br />

0.02 mg/kg<br />

Spiking level<br />

0,02 mg/kg<br />

Matrix carotts salads Apples Lemons All<br />

Repet_1 87,5% 131,3% 33,3% 600,0%<br />

Repet_2 100,0% 108,3% 88,2% 50,0%<br />

Repet_3 111,1% 100,0% 133,3% 157,1%<br />

Repet_4 100,0% 116,7% 146,2% 325,0%<br />

mean 100% 114% 100% 283% 149%<br />

sd 10% 13% 51% 240% 136%<br />

rsd 9,7% 11,7% 50,9% 84,7% 91,0%


202<br />

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CARBENDAZIME real recovery<br />

at 0.1 mg/kg<br />

Spiking level<br />

0,1 mg/kg<br />

Matrix carotts salads Apples Lemons All<br />

Repet_1 83,1% 56,7% 170,6% 120,0%<br />

Repet_2 122,2% 146,9% 114,3% 63,3%<br />

Repet_3 104,7% 131,8% 292,3% 67,4%<br />

Repet_4 105,8% 79,1% 107,7% 83,0%<br />

mean 104% 104% 171% 83% 116%<br />

sd 16% 43% 86% 26% 56%<br />

rsd 15,4% 41,2% 49,9% 30,9% 48,9%


203<br />

Guy Jamet – STRBG<br />

Fitting and recovery of<br />

CARBENDAZIME by LC/MS/MS<br />

‣ Calibration curve: fitting<br />

instrument response is not linear<br />

‣ The fitting model introduced a<br />

bias<br />

‣ Minimised by the model 1/x<br />

‣ Fitting of specificity depends of the<br />

matrix<br />

‣ At each matrix should<br />

correspond a calculation<br />

model<br />

‣ Minimised by the model 1/x<br />

‣ Calculation is conducted on the<br />

model 1/x<br />

‣ At 0.02 mg/kg the recovery doesn’t<br />

show any matrix effect for carrots,<br />

salads and apples<br />

‣ RSD is<br />

‣ < 30% and good for carrots and<br />

salads,<br />

‣ ~ 50% for apples<br />

‣ Very bad (>80%) for lemons<br />

‣ At 0.1 mg/kg the recovery doesn’t<br />

show any matrix effect for carrots<br />

and salads, but a positive one for<br />

apples and negative one for lemons<br />

‣ RSD is<br />

‣ < 30% and good for carrots<br />


204<br />

Guy Jamet – STRBG<br />

Layout of Repeatability and<br />

Reproducibility<br />

‣ Repeatability based on<br />

recovery<br />

‣ 2 levels : 0.02, 0.1<br />

mg/kg<br />

‣ Pairing matrix,<br />

analyst, day<br />

‣ 3 repetitions a day<br />

Repeatability<br />

Concentration Matrix, day, Analyst Repetition 1 Repetition 2 Repetition 3<br />

Apple D1 A1 0,008 0,007 0,004<br />

0,02<br />

Salad D2 A2 0,021 0,013 0,014<br />

Carot D3 A3 0,020 0,009 0,014<br />

Lemon D4 A4 0,014 0,010 0,012<br />

Apple D1 A1 0,056 0,033 0,040<br />

0,1<br />

Salad D2 A2 0,090 0,075 0,081<br />

Carot D3 A3 0,055 0,085<br />

Lemon D4 A4 0,077 0,063 0,064


205<br />

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Layout of Repeatability and<br />

Reproducibility<br />

‣ Reproducibility based on<br />

recovery<br />

‣ 2 levels : 0.02, 0.1<br />

mg/kg<br />

‣ Every matrices<br />

extracted by each<br />

technician<br />

‣ 4 extracts per analyst<br />

Intermediate Precision<br />

Conc. Analyst, daysApple Salad Carrot Lemon<br />

A1 D1-D6 0,008 0,021 0,007 0,018<br />

A2 D2-D7 0,009 0,013 0,009 0,005<br />

0,02 A3 D3-D8 0,015 0,026 0,020 0,011<br />

A4 D4-D9 0,008 0,005 0,010 0,014<br />

A5 D5-D10 0,019 0,021 0,024 0,013<br />

A1 D1-D6 0,056 0,080 0,054 0,042<br />

A2 D2-D7 0,029 0,075 0,033 0,019<br />

0,1 A3 D3-D8 0,064 0,144 0,055 0,029<br />

A4 D4-D9 0,038 0,029 0,045 0,077<br />

A5 D5-D10 0,042 0,072 0,110 0,039


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Results of Repeatability and<br />

Reproducibility<br />

‣ Repeatability:<br />

‣ The 30% of Sanco are not<br />

fulfil at 0.02 mg/kg (2x<br />

LCL)<br />

‣ RSD at 0.1


207<br />

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Results of Repeatability and<br />

Reproducibility<br />

‣ Reproducibility:<br />

‣ The 30% of Sanco are<br />

not fulfil at both<br />

concentrations<br />

‣ Horwitz is not fulfil at<br />

0.1 mgkg<br />

‣ The model should be<br />

reviewed<br />

Reproducibility<br />

Concentrations 0,02 0,1<br />

mean 0,0138 0,057<br />

sd 0,005 0,031<br />

limit 0,015 0,088<br />

rsd 38% 55%<br />

Horwitz 58% 45%


208<br />

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Case of IMAZALIL<br />

‣ Calibration curve OK<br />

‣ Integration window as<br />

narrow as possible<br />

‣ Bad recovery<br />

‣ Wide RSD<br />

Standard<br />

0.02<br />

Sample<br />

Sample<br />

surrogated at<br />

0.02


Dossier of validation for LC-MS/MS<br />

209<br />

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210<br />

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This presentation couldn’t be done without my team<br />

Gerald LEDOUX<br />

in charge of the QuEChERS method and LC-MS/MS<br />

Sylvie GASSMANN and Emmanuel FLEURY<br />

in charge of the GC and LC extraction<br />

Claude WISSENMEYER and Philippe GAOUYAT<br />

in charge of the GC-MS


211<br />

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Thank you for your<br />

attention<br />

Any questions

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