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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 />
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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 />
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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 />
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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 />
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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 />
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Statistical tools<br />
25<br />
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‣ 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 />
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27<br />
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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 />
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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 />
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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 />
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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 />
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42<br />
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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 />
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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 />
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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 />
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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 />
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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
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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
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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 />
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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
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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%
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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%
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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 />
‣
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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
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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
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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%
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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 />
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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
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Thank you for your<br />
attention<br />
Any questions