Control

Guy JAMET PhD
SCL: Service Commun des Laboratoires
Leader of a pesticide residues unit in
Strasbourg
Deputy of France for pesticides normalisation
at the CEN institute in Berlin
Past president and active member of EPRW
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Guy Jamet – STRBG

Lay out of the presentation
‣ Organisation of plant protection products in France
‣ Competences of each partner
‣ The controls
‣ Requirements of labs dealing with PPP
‣ Characterization, validation and accreditation
‣ Sanco mandatory and possible application
‣ Statistical tools
‣ The different steps of GC/MS validation in our lab
‣ The “Dossier” of validation
‣ Opening on the QuEChERS method and LC-MS/MS
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Guy Jamet – STRBG

Organisation of plant protection
‣ Ministry of agriculture : DGAL
‣ No official laboratories
‣ Recognition of labs in department
‣ Ministry of finances
products in France
‣ Directory of competition, consumers and frauds
repression: DGCCRF
‣ Directory of food and feed: Laboratories: SCL
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Guy Jamet – STRBG

Competences of each partner
‣ Ministry of agriculture:
‣ Authorization of use for PPP
‣ Directory of food and feed:
‣ Follow up of good agricultural practices
‣ Controls in the fields before selling
‣ Control by application of PPP
‣ Posses its own system of enforcement
‣ Directory of competition, consumers and frauds repression.
‣ Controls at selling points of local production and import
‣ Respect of MRL, detection of misusing, frauds
‣ Enforcement is different
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Guy Jamet – STRBG

The controls
‣ Official labs depending of the Finances Ministry
‣ Official controls
‣ EU monitoring
‣ National enforcement
‣ Report to DGCCRF
‣ Partnership with DGAL on recognition
‣ State a formal conformity or non conformity
‣ Department labs depending of the executive organism of the
department
‣ Recognised by DGAL
‣ May be mandated by DGCCRF
‣ Advise about of the legality of the sample
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Guy Jamet – STRBG

Enforcement and Sampling
DU SCL
SCL LAB
Samples
Results
Conclusions
CCRF Inspectorates
Survey
Remaining of the rules
2 nd Control sampling predicted
Corrupted
Sample
Control
1) Document in dispute
2) Destruction of the
commodity
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Guy Jamet – STRBG

Requirements of labs dealing
with PPP
‣ Accreditation
‣ According ISO 17025
‣ Validated Methods
‣ According EU 2002-657
‣ DG Sanco guidelines
‣ According accreditation bodies requirements
‣ Fix or flexible scope
‣ Reference to recognized methods
‣ Participation to
‣ Proficiency testing
‣ EUPT if they are involved in the EU monitoring
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Guy Jamet – STRBG

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Guy Jamet – STRBG
Characterization, validation and
accreditation
‣ Characterization of a method:
‣ Evaluation of the steps introducing variability
‣ Validation of method:
‣ Statement according the characterization results if the
method is fit for the purpose via an acceptable measured
uncertainty
‣ Accreditation:
‣ Statement a lab is providing a recognized level of safety
‣ Validation is a part of accreditation
‣ Traceability is the other wider part.

Sanco mandatory and possible
application
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Guy Jamet – STRBG

Sample
Mandatory
Characterization
‣ Sampling
‣ Transport
‣ Sample processing
‣ Contamination and interference
‣ Test portions weighing
‣ Extraction condition
‣ Purification
‣ Concentration of extract
‣ Dilution
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Guy Jamet – STRBG

Standards
Mandatory
Characterization
‣ Identity ‣ Identity to the library
‣ Purity
‣ Consistent spectra
‣ Storage of stock standards
‣ Storage of working standards
‣ Frequency of replacement
‣ Stability of stock standards
‣ Stability of working
standards
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Guy Jamet – STRBG

Calibration
Mandatory
‣ Limits and MRL
Characterization
‣ LCL, LOD, LOQ:
‣ Not calculated
‣ But determination of RSD
‣ Interpolation
‣ Visual inspection of calibration
and curves
‣ Dynamic range of calibration
‣ Interpolation: Difference
between 2 levels

Sequences
Mandatory
‣ Length of the sequence
Characterization
‣ Calibration standard
‣ 2 dilutions per samples x n
samples
‣ Calibration standard
‣ Maintenance of the system
‣ Drift (20-30%)
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Guy Jamet – STRBG

Representative analytes
Mandatory
‣ Choice of representative
analytes
‣ Frequency of calibration and
recalibration
‣ Each batch for representative
‣ Calibration of not integrated
residues
‣ Recovery
Characterization
‣ 15 analytes + 25% if the
scope is 40 pesticides
‣ Effect on calibration (multi
residue)
‣ Mixture of isomers
‣ Degradation of products
(metabolites included in the
residue)
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Guy Jamet – STRBG

Matrix effect
Mandatory
‣ Different group
‣ Choice of representative
Matrix
‣ Extraction recovery with
appropriate standard
‣ Choice of the quantification
method
‣ Choice of analyte protectants
Characterization
‣ Calibration against solvent
‣ Extracted matrix calibration
‣ Matrix matched
‣ 3 portions
‣ Knowledge of amount
‣ Standard addition
‣ Spiking at the same level
‣ Priming in GC
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Guy Jamet – STRBG

Chromatographic integration
Mandatory
‣ Chromatograms must be
visually inspected
‣ Consistent approach must be
adopted ( Capability of
instrument)
‣ Chromatographic integration
and baseline adjustment
Characterization
‣ Characteristic ion
chromatograms
‣ Selectivity
‣ Compromise to integrate in
one step
‣ List of Residue amenable
one by one
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Guy Jamet – STRBG

Performance-criteria qualitative
screening method validation
Mandatory
Characterization
‣ Low probability of presence
‣ Confidence established at a
certain concentration level
‣ Representative of for the
matrix scope
‣ No regard of linearity and
recovery
‣ False positive excluded with
blank samples
‣ Repeatability of presence
‣ Depending if method is
conducted in solvent or
matrix
‣ All residues
‣ Confidence by repeatability
of quantification when MS
spectra is amenable
‣ False positive from past
injection must be avoided
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Guy Jamet – STRBG

Acceptability of analytical performance:
Initial validation
Mandatory
Characterization
‣ Mean recovery at each spiking
level 70-120%
‣ Lower recoveries acceptable
under conditions
‣ At least for one representative
matrix
‣ RSD r and RSD IP

Acceptability of analytical performance:
on going performance validation
Mandatory
‣ Recovery with each batch of
analyses
‣ Rolling programme
‣ At 1-10 times a relevant level
‣ Routinely at the MRL
‣ Range 60-140%
‣ Internal standard surrogated
‣ Variability between 2 test
portion of same sample
Characterization
‣ Recovery matrix by matrix
‣ MRPL and LMR
‣ Profile of accuracy
‣ Extraction standard
‣ Internal standard
‣ LMR exceeded on real
samples
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Guy Jamet – STRBG

Proficiency testing
Mandatory
‣ Participation to relevant
proficiency test is mandatory
for official labs
Characterization
‣ National
‣ Private
‣ EUPT
‣ In-house material must be
analysed regularly
‣ Minimum one
‣ Representative to activity
‣ Not than 10%
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Guy Jamet – STRBG

Confirmation results
Mandatory
‣ Negative results below LCL
not confirmed if recovery is
acceptable
‣ LCL
‣ Recovery
‣ Positive results confirmed
case-by-case
‣ Suspected MRL violation,
misusing or unusual residues
must be confirmed
Characterization
‣ Each consistent MS spectra
is a confirmation
‣ Each amenable MS spectra
induce a quantification
‣ Danger of transfer due to the
matrix polarity on the column
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Guy Jamet – STRBG

Requirements
Mandatory
‣ RRT tolerance of +/- 0.5%
‣ Mass spectra must be
consistent with the analyte
‣ Higher m/z than lower are
more selective
‣ Overlapping of ion
chromatograms
‣ Similarity with calibration
standards
‣ Avoiding interferences by
carefully peak subtraction
Characterization
‣ Own standards library
‣ Rearrangement are a
precious help
‣ High Intensity m/z
‣ 2 different software for
identification
‣ RRT or RT similar to
calibration curve
‣ Multi level calibration
‣ Noise subtracted
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Guy Jamet – STRBG

Reporting results
Mandatory
Characterization
‣ Mg/kg;

Mandatory of accreditation body
‣ Scope of the Accreditation
‣ Group or list of matrices
‣ List of residues sought for
‣ Organochlorines
‣ Organophosphates
‣ Part of the method
‣ Extraction
‣ Purification
‣ Physical analysis
‣ Method references
‣ EN NF 12393 part N
‣ EN NF 15662
‣ Standard accreditation
‣ Type A1: carry out of the
validated version no
modification permitted
‣ Type A2: new version are
implemented without
updating control from
accreditation body
‣ Type A3: refers to
competences or a scope
of possibilities
‣ flexible scope Type B:
‣ Extension of A3 between
to audits
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Guy Jamet – STRBG

Statistical tools
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Guy Jamet – STRBG

‣ ISO 5725 (required for reproducibility
between labs, not for lab intermediate
fidelity IF)
‣ NF V03-110 re adapted for IF in the
consumption of Accuracy profile
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Guy Jamet – STRBG

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Guy Jamet – STRBG
NF V03-110 as validation tools
‣ Based on the regulation ISO 5725 (for inter lab reproducibility)
‣ Adapted to repeatability and intermediate fidelity (intra lab
reproducibility)
‣ Taking in account
‣The determination of variability at each levels
‣The variability within the series
‣The variability between the series
‣TSS=RSS+ESS
‣The risk of the analyst at 95% confidence level
‣The risk of the client with a postulated amount (80%) of results
within acceptable limits
‣Defined by a minimum 3 times 3 repetitions per level
‣Implementing the variability of the actors and follow up in
time
‣ Extending data may be added later

Relative accuracy
Profile of accuracy (NF V03-110)
‣The risk of the analyst at 95% confidence level
‣The risk of the client with a postulated amount
(80%) of results within acceptable limits
Profile of accuracy
1
0,8
0,6
0,4
0,2
0
-0,2
1 2 3 4 5 6 7 8 9 10 11 12
-0,4
-0,6
-0,8
-1
Concentration in ng/L
Low er tolerable limit Low er acceptable limit Bias Upper acceptable limit Upper tolerable limit
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Guy Jamet – STRBG

Homogeneity, stability
Real
sample
@x mg/kg
T1
T2 T3 T4 T5
Homogeneity
T1
Ɵ1
T1
Ɵ2
T2
Ɵ1
T2
Ɵ2
ῩH, σ
Stability
Ῡ1, U= ῩH ±1,96σ
Stability
Ῡ2, U= ῩH ±1,96σ
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Guy Jamet – STRBG

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Guy Jamet – STRBG
Repetition for repeatability or
intermediate precision
M + C1 =
R11
M + C1 =
R12
Mean1, sdr1, rsdr1
M + C1 =
R13
Blank
matrix
M + C2 =
R21
M + C2 =
R22
Mean2, sdr2, rsdr2
M + C2 =
R23

Variability
Precision and accuracy in validation
Control chart
30%
20%
10%
0%
-10%
-20%
-30%
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
Control values
Good precision
Good accuracy
Risk analyst 95%
Low er tolerance Values Upper tolerance
Method is considered as validated
but 40% of unexplainable results
are exceeding the tolerance limit of
+/-20%
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Guy Jamet – STRBG
Precision and accuracy in validation
Low precision
Low accuracy
Risk analyst 95%
Method is considered as NOT
validated because of the low
precision and low accuracy

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Guy Jamet – STRBG
NF V03-110 as validation tools
Good precision
Good accuracy
Risk analyst 95%
Risk client 20%
Method should be considered as
NOT validated because 40% of
results are exceeding the tolerance
limit of +/-20%

Variability
NF V03-110 as validation tools
Method is considered as validated
because 5 values (16.7%) are outside of
the +/-20% tolerance limit despite the low
precision and the low accuracy
Control chart
30%
20%
10%
0%
-10%
Low precision
Low accuracy
95% Risk analyst
20% Risk client
-20%
-30%
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
Control Values
Low er tolerance Values Upper tolerance
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Guy Jamet – STRBG
Historical knowledge
‣ Ten years identification with 2 columns ECD - NPD, ECD
– FPD
‣ Systematic confirmation by MS
‣ Systematic identification and confirmation of difficult
substances
‣ Every samples were checked for 250 molecules with 1 – 3
ions and baseline subtraction
‣ Quantification of confirmed residues on specific detectors
and/or MS in SIM mode
‣ Different results from a detector to the other
‣ A lot of work
‣ Time consuming

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Guy Jamet – STRBG
Improvement of the Method
‣ Budget reduction
‣ GC ECD – FPD, GC MS
‣ No GPC purification
‣ Increasing of validation mandatory
‣Increasing of new molecule
‣Increasing of validation amount
‣ Solution
‣Validation of a simple method GC/MS full scan
mode for identification/confirmation and
quantification

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Guy Jamet – STRBG
The different steps of GC/MS
validation in our lab

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Guy Jamet – STRBG
GC Multi residue method
First proposal
‣ Characterization of our method without
purification
‣ Repeatability, Intermediate fidelity based on
recovery at the 3 MRPL 0.01, 0.02, 0.05 mg/kg
‣ Characterization in salads
‣ Extension to apples and carrots
‣ Detection limits in order to deal with organic
products

Avoiding contamination
‣ Premises
‣ Standards preparation
‣ Samples treatment
‣ Physical analysis
‣ SOP
‣ Rooms
‣ Solvents
‣ Tools
PR167/99/LOC/01
‣ No validation requested
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Guy Jamet – STRBG

Sampling and transport
‣ Sampling:
‣ Done by the inspectorate in the department
‣ At the selling point or import point
‣ Power to control of all the surrounding of the selling
‣ Enquiry samples
‣ Control samples
‣ According EU 2002-63
‣ Transport
‣ By organism or direct
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Guy Jamet – STRBG

Control at reception
‣ Mandatory
‣Respect of quality required
‣Respect of packaging
‣Respect of quantity
‣Description of samples and
specific wishes
‣ Decision
‣ Acceptation or Rejection
of the laboratory sample
‣ Action
‣ Opening of analytical
report
‣ Orientation of the essays
‣ SOP
IN167/80/EXT/02
Validation
‣ capability of acting people
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Guy Jamet – STRBG
Description of the sample
‣ Packaging: Sampling plastic bag closed
‣ Sampling label: Pesticides residues
‣ Country of origin: Argentina
‣ Weight: 1.020 kg
‣ Unit: 12
‣ Quality of the sample: fresh in good
integrity

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Guy Jamet – STRBG
Amenable Essays
Code Method title Th. weight
of test
potion (g)
12075 PESTICIDES BY GC [Internal method derived from NF EN
12393]
Essay and
real
weight of
potion test
(g)
50 YES
TP 1 50.10
TP 2 50.20
12480 PESTICIDES by LC-MS/MS [QUECHERS method (NF EN
15662)]
12368 DITHIOCARBAMATES (Internal method derived from NF
EN 12396-1)
5995 MALEIC HYDRAZID [VADUKUL (ANALYST, VOL116,
N°12, P735-739)]
5607 BROMIDS (EN ION BR-) [CLHP/I] 10
8413 NITRATES (Expressed in NO3-) [CLHP/I NF EN 12014-2 I/C
V 03-010-2 ]
10
50
10
10

Preparation of test sample and
test portions
‣ Test sample preparing
‣ According R396/2005
‣ Test sample reduction
‣ Within 72 h
‣ On fresh material
‣Method of opposite quarters
for big unit
‣ All the test sample for small
unit
‣ Test portions
‣Weighted and frozen
‣ Detailed in SOP
IN167/80/ANA/01
Validation
‣ capability of acting
people
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Guy Jamet – STRBG

Carry out of the GC/MS extract
‣ Extraction
‣ Partition
‣ Drying
‣ Re dilution
‣ EN NF 12393 part 2 method
“N” without GPC purification
detailed SOP
IN167/80/ANA/02
Validation
‣ Capability of acting
people
‣ Solvent and additives
‣ Drying instruments
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Guy Jamet – STRBG

Carry out of the GC/MS analysis
‣ GC
‣ Maintenance
‣ MS
‣ Maintenance
‣ Tuning
‣ Method
‣ Parameters
‣ Sequence
‣ Calibration standards
‣ Sample extract and
1/10 dilution each
‣ Detailed SOP
IN167/80/ANA/19
IN167/80/MAT/05
IN167/80/MAT/10
Validation
‣ Capability of acting people
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Guy Jamet – STRBG

Interpretation of the data
‣ Qualitatively
‣ Identification in the
calibration standards
corresponding to MRPL
‣ Identification of Aldrin
‣ Identification of
Bromophos methyl
‣ Identification and
confirmation by full scan in
sample
‣ Quantitatively
‣ Calibration curves
‣ Integration parameters
‣ Detailed SOP
IN167/80/ANA/13
IN167/80/ANA/17
IN167/80/MAT/11
Validation
‣ Capability of acting people
‣ Parameters of instruments
‣ Parameters of the methods
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Guy Jamet – STRBG

Standards
‣ Quality ‣ >95% purity from supplier
‣ New lot of routine standard
‣ New standard
‣ Conservation
‣ Stock solutions
‣ Working solutions
‣ Verification of identity with
library
‣ Consistence of the spectra
‣ 10 years
‣ 1000 ppm mother solution (3-5
years)
‣ Dilution 10, 1, 0.1 ppm (2 months)
‣ No recovery from old standard
IN167/80/ANA/20
Validation
‣ Capability of acting people
‣ Identity of the standard
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Guy Jamet – STRBG

Capability of acting people
‣Sample reception
‣Sample preparation
‣GC extract
‣Standards
‣MS analysis
‣Interpretation
‣ Learning period
‣Practice in parallel
‣Evaluation in practice alone
‣End results
‣Learning period
‣Double control of results
‣IN167/99/PER/03
‣IM167/99/PER/13
‣IM167/99/PER/14
‣IM167/99/PER/15
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Guy Jamet – STRBG

Characterization of the GC
‣ GC parameters
‣ Injector
‣ Oven temp
‣ Detector
‣ Quality of the column
‣ Done globally by the
analytical on going controls
‣ After each sequence
‣ Monthly cleaning
‣ RRT
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Guy Jamet – STRBG

Characterization of the MS
‣ MS parameters ‣ Tuning
‣ At the beginning before each
sequence
‣ Monthly after the maintaining
‣ Done globally by the
analytical on going controls
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Guy Jamet – STRBG

Characterization of the parameters of
decision
‣ Parameters of instruments
‣ Parameters of the methods
‣ Limits permitted for
identification
‣ Area reject
‣ Peak width
‣ Integration threshold
‣ Working range
‣ LCL
‣ LOD
‣ LOQ
‣ Repeatability
‣ Intermediate fidelity
‣ Reproducibility
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Guy Jamet – STRBG

Characterization of standards
‣ Identity of the standard
‣ Consistence of MS spectra
IM167/80/ANA/23
‣ RRT
IN167/80/ANA/17
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Guy Jamet – STRBG

Consistence of a spectra
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Guy Jamet – STRBG

Explanation of a spectra
O
O
N
Cl
N
H
N
Cl
N
H
+
minus Cl -
minus Cl -
+
m/z 307
, m/z 309
m/z 307
, m/z 309
O
O
N
H
+
N
Cl
N
Cl
minus Cl -
+
Chloropyridin oxonium
m/z 307
, m/z 309
m/z 140
, m/z 142
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Guy Jamet – STRBG

RRT
RT Aldrin 17,18
RRT / IS
Residue
column HPAS 5
RT-0.3 RT RT+0.3 MS fragmentation
6890/5973
ACEPHATE 0,53 8,8 9,11 9,4 136 125 183
ACRINATHRIN 1,46 24,3 25,08 25,8 181 208 289
ALDRIN 1,00 16,7 17,18 17,7 263 261 265 293
ALLETHRINE 1,08 18,0 18,55 19,1 123 107 168
ALPHACYPERMETHRIN 1,63 27,2 28,00 28,8 163 161 181 209
AMITRAZE 1,48 24,7 25,45 26,2 121 132 147 162 293
ATRAZINE 0,81 13,5 13,92 14,3 200 215 173
AZAMETIPHOS 1,28 21,4 22,06 22,7 109 215 324
AZINPHOS ETHYL 1,47 24,5 25,25 26,0 132 160 198
AZINPHOS METHYL 1,41 23,5 24,22 25,0 160 132
AZOXYSTROBINE 2,01 33,5 34,53 35,6 344 388 372 403
BENALAXYL 1,27 21,2 21,82 22,5 148 206 234 266 325
BENDIOCARBE 0,74 12,3 12,71 13,1 151 126 166 223
BIFENTHRIN 1,36 22,7 23,36 24,1 181 166 165
TRITICONAZOLE 1,41 23,5 24,22 25,0 235 115 217 182 299
VAMIDOTHION 1,11 18,5 19,07 19,6 87 145 109
VINCHLOZOLIN 0,93 15,5 15,93 16,4 212 198 285 187 178
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Guy Jamet – STRBG
1 st step of the characterisation
‣ Characterization of the most occurring
residues at time
‣ Matrices: salad with further extension to
carrot and apple
‣ Spiking samples before extraction at 0.01
and 0.05 mg/kg
‣ Submission to the routine extraction
procedure
‣ Spiking extracted matrix at the same
concentration
‣ Injection of the same concentration in
solvent
‣ Identification with an explainable mass
spectra: qualitative evaluation
‣ Determination of the recovery against the
solvent and the spiked extract in SIM
mode
‣ Characterisation tool
‣ NF V03-110
‣ SANCO guide line response of
instrument
REPRESENTATIVE ANALYTES
BIFENTHRINE
λ CYHALOTHRIN
BROMOPROPYLATE
MALATHION
CARBARYL
METALAXYL
CHLORFENVINPHOS ORTHOPHENYLPHENOL
CHLORPROPHAM
OXADIXYL
CHLORPYRIPHOS
PARATHION
CHLORPYRIPHOS-METHYL PARATHION-METHYL
α CYPERMETHRIN
PHOSALONE
CYPRODINIL
PROCYMIDONE
DELTAMETHRIN
PROPARGITE
ETHION
PROPYZAMIDE
DIMETHOATE
PYRIMETHANIL
DIPHENYLAMINE
QUINTOZENE
α ENDOSULFAN
TAU-FLUVALINATE
β ENDOSULFAN
TEBUCONAZOLE
ENDOSULFAN sulphate TEBUFENPYRAD
FLUDIOXONIL TOLCLOPHOS-METHYL
IPRODIONE
VINCLOZOLINE
KRESOXIM METHYL ALDRIN (IS Qualifier)

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Guy Jamet – STRBG
Recovery at requested limits
‣ Determination of the recovery at 2 MRPL values:
‣ 0.01, 0.05 mg/kg
‣ Multilevel calibration against solvent
‣ Different days or technicians
‣ Identification on specific detectors
‣ Confirmation on MS full scan mode
‣ (Quantification on specific detectors)
‣ Quantification on MS SIM mode
‣ Estimation of the variability at each level

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Working plan
‣ RE : Extraction of spiked salad at 0.01 and 0.05 mg/kg
‣ ER: Extraction of salad and spiking at 0.01 and 0.05 mg/kg
‣ C: calibration: equivalent of 0.01 and 0.05 m/kg in solvent
MRPL level
0,01
0,05
Day / Technician Calibration Recovery before extraction Recovery after extraction
D_1 C_111 C_112 C_113 RE_111 RE_112 RE_113 ER_111 ER_112 ER_113
D_2 C_121 C_122 C_123 RE_121 RE_122 RE_123 ER_121 ER_122 ER_123
D_3 C_131 C_132 C_133 RE_131 RE_132 RE_133 ER_131 ER_132 ER_133
D_1 C_211 C_212 C_213 RE_111 RE_112 RE_113 ER_111 ER_112 ER_113
D_2 C_221 C_222 C_223 RE_121 RE_122 RE_123 ER_121 ER_122 ER_123
D_3 C_231 C_232 C_233 RE_131 RE_132 RE_133 ER_131 ER_132 ER_133

Results
Confirmation
Recovery
M ET H OD SC A N
0.01 0.05
SIM ( after full Scan)
0.01 0.05 LOD
solvant blank S solvant blank S RRT RSD Target Qualifier T/Q RSD Blank/S mg/kg
BIFENTHRIN m w w s 1,36 1,0% 181 165 3,28 6% 72% 89% 0.01
BROM OPROPYLATE w w 0 m 1,36 1,0% 183 341 0,63 10% 101% 93% 0.01
CARBARYL 0 w 0 w 0,94 1,0% 144 115 1,06 50% 88% 80% 0.01
CHLORFENVINPHOS m m s s 1,08 1,0% 267 323 1,45 3% 91% 88% 0.01
CHLORPROPHAM w m m s 0,72 1,0% 127 213 0,37 6% 72% 97% 0.01
CHLORPYRIPHOS s w s s 1,06 1,0% 314 316 1,38 9% 83% 90% 0.01
CHLORPYRIPHOS M ETHYL s s s s 1,01 1,0% 286 288 1,33 2% 82% 91% 0.01
α CYPERM ETHRIN 0 w 0 w 1,18 1,0% 181 163 0,73 7% 70% 103% 0.01
CYPRODINIL m s w s 1,06 1,0% 224 225 1,50 1% 87% 72% 0.01
DELTAM ETHRIN 0 w 0 w 1,94 1,0% 253 181 0,94 14% 70% 75% 0.01
ETHION w w s s 0,81 1,0% 231 153 1,53 24% 90% 85% 0.01
DIM ETHOATE w w s m 0,39 1,0% 87 125 1,45 14% 90% 89% 0.01
DIPHENYLAM INE m s m w 0,70 1,0% 169 168 1,62 2% 84% 88% 0.01
α Endosulfan 0 w 0 w 1,21 1,0% 195 237 1,78 5% 65% 104% 0.01
ENDOSULFAN Beta 0 w 0 w 1,28 1,0% 195 241 1,50 19% 68% 88% 0.01
ENDOSULFAN Sulphate 0 w 0 w 1,16 1,0% 272 274 0,94 20% 72% 106% 0.01
FLUDIOXONIL w 0 0 w 1,18 1,0% 248 127 1,89 30% 73% 85% 0.01
IPRODIONE 0 w 0 m 1,44 1,0% 314 316 1,55 3% 99% 99% 0.01
KRESOXIM M ETHYL 0 w 0 m 1,18 1,0% 116 131 1,64 49% 89% 67% 0.01
λ CYHALOTHRIN 0 w w m 1,63 1,0% 181 197 1,24 7% 71% 92% 0.01
M ALATHION m m s s 0,99 1,0% 173 125 1,19 13% 82% 58% 0.01
M ETALAXYL M w w s s 0,95 1,0% 206 220 2,18 6% 70% 91% 0.01
ORTHOPHENYLPHENOL m m w 0 0,61 1,0% 170 141 3,03 7% 87% 89% 0.01
OXADIXYL w m 0 m 1,24 1,0% 163 132 1,41 1% 98% 99% 0.01
PARATHION ETHYL w w m m 1,01 1,0% 291 109 1,30 96% 82% 84% 0.01
PARATHION M ETHYL 0 w m m 0,93 1,0% 263 / / / 78% 83% 0.01
PENTACHLOROANILINE w m w s 0,90 1,0% 265 263 1,65 4% 75% 90% 0.01
PHOSALONE w w s m 1,42 1,0% 182 367 3,34 13% 103% 99% 0.01
PROCYM IDONE w w 0 w 1,09 1,0% 283 285 1,68 1% 85% 77% 0.01
PROPARGITE 0 w 0 w 1,31 1,0% 135 173 3,61 20% 84% 83% 0.01
PROPYZAM IDE w w w m 0,84 1,1% 173 255 4,53 16% 70% 90% 0.01
PYRIM ETHANIL w m m w 0,85 1,0% 198 199 1,99 2% 87% 89% 0.01
QUINTOZENE 0 w w m 0,83 1,2% 237 295 1,50 2% 71% 85% 0.01
TAU FLUVALINATE 0 w w m 1,82 1,0% 250 252 2,71 11% 71% 76% 0.01
TEBUCONAZOLE 0 w w m 1,31 1,0% 250 125 0,99 28% 92% 98% 0.01
TEBUFENPYRAD w w w m 1,37 1,0% 171 318 0,95 35% 84% 91% 0.01
TOLCLOPHOS M ETHYL s w s m 0,94 1,0% 265 125 2,71 3% 84% 92% 0.01
VINCLOZOLIN 0 m w m 0,93 1,0% 285 212 1,05 15% 75% 89% 0.01
Legend m: middle w: weak s: strong
60
Guy Jamet – STRBG

61
Guy Jamet – STRBG
2 nd Proposal restriction of the scope and
characterisation of the instrument response
‣ Follow up of the response
of different ions when
amenable
‣ Ion ratio
‣ Limits of detection:
amenable mass spectra
‣ LCL, LOD, LOQ Upper
saturating limit
‣ Multilevel calibration
standards
‣ REPRESENTATIVE
ANALYTES
‣ CHLORFENVINPHOS
‣ CYPRODINIL
‣ ETHION
‣ IPRODIONE
‣ OXADIXYL
‣ PROCYMIDONE
‣ PYRIMETHANIL
‣ VINCLOZOLINE

Conclusion after the 1 st step
‣ Not all the molecules are visible
in the solvent at 0.01 mg/kg
‣ Just a few analytes are not
visible at 0.05 mg/kg
‣ The SIM mode seems to
improve the detection
‣ Salad matrix shows a positive
protection of the molecules
‣ The real recovery is in the
interval 70-120% except for α-
ENDOSULFAN and β-
ENDOSULFAN
‣ The co elution of PARATHION
METHYL with
VINCLOZOLINE and
CHLORPYRIPHOS METHYL
is not easy to manage
‣ Remarks of accreditation bodies
‣ Recovery approach OK
‣ Repeatability OK
‣ Intermediate fidelity OK
‣ LOD OK
‣ LOQ have to be improved
‣ Decision must be made
with analytes not passing
the requirements
‣ Uncertainty must be
assessed
62
Guy Jamet – STRBG

63
Guy Jamet – STRBG
Instrument response: working plan
‣ Estimation of the variability at
each level: repeatability and
intermediate fidelity
‣ Visual examination on profile
accuracy plot
‣ Determination of the LCL
‣ Determination of the upper
acceptable quantification level
‣ Choice of the quantification ion
‣ Choice of qualifier ions
Concentration (ppb) D_1 D_2 D_3
10 C_111 C_211 C_311
10 C_112 C_212 C_312
10 C_113 C_213 C_313
20 C_121 C_221 C_321
20 C_122 C_222 C_322
20 C_123 C_223 C_323
100 C_131 C_231 C_331
100 C_132 C_232 C_332
100 C_133 C_233 C_333
500 C_141 C_241 C_341
500 C_142 C_242 C_342
500 C_143 C_243 C_343
2000 C_151 C_251 C_351
2000 C_152 C_252 C_352
2000 C_153 C_253 C_353
5000 C_161 C_261 C_361
5000 C_162 C_262 C_362
5000 C_163 C_263 C_363

64
Guy Jamet – STRBG
CHLORFENVINPHOS (LCL)
Chlorfenvinphos
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -83 -47 -8 -19 -10 -30
267 Bias 33 -4 -2 -7 -1 -8
Upper tolerable limit 148 39 5 6 8 14
Upper acceptable limit 50 50 50 50 50 50

65
Guy Jamet – STRBG
CYPRODINIL (LCL)
Cyprodinil
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -33 -102 -23 -25 -33 -184
224 Bias 25 23 8 -4 1 -14
Upper tolerable limit 83 147 38 18 35 155
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -28 -30 -27 -23 -28 -20
225 Bias 13 13 6 -3 0 -3
Upper tolerable limit 55 57 39 16 28 15
Upper acceptable limit 50 50 50 50 50 50

66
Guy Jamet – STRBG
ETHION (LCL)
Ethion
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -56 -87 -58 -139 -38 -18
125 Bias 42 47 37 10 27 8
Upper tolerable limit 141 181 132 160 92 35
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -38 -47 -44 -46 -19 -14
153 Bias 27 4 30 7 15 6
Upper tolerable limit 92 55 104 60 49 26
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -99 -52 -19 -5 -5 -5
231 Bias -9 6 0 1 3 -1
Upper tolerable limit 82 65 19 7 10 3
Upper acceptable limit 50 50 50 50 50 50

67
Guy Jamet – STRBG
λ CYHALOTHRIN (LCL)
λ Cyhalothrin
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -76 -52 -18 -23 -11 -12
181 Bias 3 19 30 20 7 7
Upper tolerable limit 83 91 78 62 24 25
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -69 -22 -12 -16 -6 -14
197 Bias 16 2 14 6 8 3
Upper tolerable limit 101 26 40 28 22 21
Upper acceptable limit 50 50 50 50 50 50

68
Guy Jamet – STRBG
OXADIXYL (LCL)
Oxadixyl
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -40 -54 -54 -371 -75 -60
132 Bias 26 -14 17 8 22 24
Upper tolerable limit 92 27 87 388 119 109
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -91 -101 -47 -60 -56 -25
163 Bias 5 -25 8 4 8 18
Upper tolerable limit 101 51 62 68 73 61
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -22 -89 -22 -59 -82 -145
233 Bias 18 -26 15 22 66 82
Upper tolerable limit 59 37 51 103 214 309
Upper acceptable limit 50 50 50 50 50 50

69
Guy Jamet – STRBG
IPRODIONE (LCL)
Iprodione
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -26 -119 -62 -46 -51 -59
187 Bias 35 3 66 60 39 74
Upper tolerable limit 97 125 195 166 130 208
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -85 -101 -137 -118 -129 -199
189 Bias -24 13 2 -5 107 67
Upper tolerable limit 37 126 141 108 343 334
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -32 -59 -49 -33 -43 -29
314 Bias 18 22 6 9 10 6
Upper tolerable limit 68 103 61 51 63 40
Upper acceptable limit 50 50 50 50 50 50

70
Guy Jamet – STRBG
PROCYMIDONE (LCL)
Procymidone
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -15 -54 -10 -4 -9 -17
283 Bias 3 6 0 2 0 -1
Upper tolerable limit 21 66 10 9 8 15
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -9 -129 -4 -7 -8 -16
285 Bias 4 8 2 0 1 -1
Upper tolerable limit 18 145 9 8 10 15
Upper acceptable limit 50 50 50 50 50 50

71
Guy Jamet – STRBG
PYRIMETHANIL (LCL)
Pyrimethanyl
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -41 -14 -19 -18 -18 -14
198 Bias 10 17 7 -1 -1 -3
Upper tolerable limit 61 49 32 16 16 8
Upper acceptable limit 50 50 50 50 50 50
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -204 -67 -37 -21 -22 -14
199 Bias 78 7 5 -1 0 -3
Upper tolerable limit 361 80 48 18 22 8
Upper acceptable limit 50 50 50 50 50 50

72
Guy Jamet – STRBG
VINCLOZOLINE (LCL)
Vinclozoline
Injected concentrations (ppb)
Ion Limits 10 20 100 500 2000 5000
Lower accptable limit -50 -50 -50 -50 -50 -50
Lower tolerable limit -64 -45 -19 -63 -22 -12
212 Bias 40 30 11 10 1 1
Upper tolerable limit 144 106 41 82 23 14
Upper acceptable limit 50 50 50 50 50 50

73
Guy Jamet – STRBG
Conclusion on limits
‣ 10 and 20 ppb are really difficult to reach
‣ In some cases 50 ppb can be seen
‣ 100 ppb can be considered in most cases as LCL that corresponds to
but with a low frequency
‣ 500 ppb will be an acceptable LCL in the other cases
‣ Reported to the extracting method
‣ The LOD is 0.001 to 0.005 mg/kg
‣ The LOQ is 0.01 to 0.05 mg/kg
‣ The variability is wider as the permitted limits of DG SANCO (50%)
‣ The upper limit is between 2000 and 5000 ppb for all compounds.

74
Guy Jamet – STRBG
Characterisation of the instrument
deviation
‣ Different days
‣ One ion or fragment of the
molecule
‣ Calibration on area with out
internal standard
‣ Calibration with
BROMOPHOS METHYL as
internal standard
‣ Determination of the range of
quantification
‣ Variability of the calibration
curve along the time
‣ Variability at each calibration
level
‣ REPRESENTATIVE
ANALYTES
CHLORFENVINPHOS
CYPRODINIL
IPRODIONE
λ CYHALOTHRIN
OXADIXYL
PROCYMIDONE
PYRIMETHANIL
TOLCLOPHOS METHYL
VINCLOZOLINE

75
Guy Jamet – STRBG
Instrument deviation: working plan
‣ Calibration in bracket
‣ Length of a GC-MS sequence
‣ Sd at each concentration
‣ Fitting function of mean response, rsdr, rsdFI
‣ 6 routine levels not exceeding a factor 4 between each other
‣ Full scan mode but characteristic ion: intensity max at highest m/z
Concentration (ppb) D_1 D_2 D_3 D_4 D_5 D_6 D_7 D_8 D_9
100 C_11 C_12 C_13 C_14 C_15 C_16 C_17 C_18 C_19
200 C_21 C_22 C_23 C_24 C_25 C_26 C_27 C_28 C_29
500 C_31 C_32 C_33 C_34 C_35 C_36 C_37 C_38 C_39
1000 C_41 C_42 C_43 C_44 C_45 C_46 C_47 C_48 C_49
2000 C_51 C_52 C_53 C_54 C_55 C_56 C_57 C_58 C_59
5000 C_61 C_62 C_63 C_64 C_65 C_66 C_67 C_68 C_69

76
Guy Jamet – STRBG
CHLORFENVINPHOS (Cal)
Chlorfenvinphos
ppb Min Mean Max
100 10765 36125 61485
200 -11861 80140 172141
500 108437 224974 341511
1000 306261 490017 673773
2000 795736 1033424 1271112
5000 2238694 2837381 3436068
Chlorfenvinphos (IS)
ppb Min Mean Max
100 0,07 0,13 0,19
200 0,08 0,27 0,46
500 0,52 0,8 1,08
1000 0,69 1,45 2,21
2000 2,60 2,91 3,22
5000 6,17 6,85 7,53

Response
CHLORFENVINPHOS (Cal)
Chlorfenvinphos
4000000
3500000
3000000
2500000
y = 573,76x - 57833
R 2 = 0,9989
2000000
1500000
1000000
500000
0
0 1000 2000 3000 4000 5000 6000
-500000
Concentration (ppb)
Min Mean Max Linéaire (Mean)
77
Guy Jamet – STRBG

Response
78
Guy Jamet – STRBG
CHLORFENVINPHOS (Cal)
Chlorfenvinphos (IS)
8,00
7,00
y = 0,0014x + 0,0626
R 2 = 0,9992
6,00
5,00
4,00
3,00
2,00
1,00
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )

CYPRODINIL (Cal)
Cyprodinil
ppb Min Mean Max
100 79283 147367 215451
200 20032 294585 569138
500 428330 802116 1175902
1000 1006644 1885101 2763558
2000 3308435 3981270 4654105
5000 8918419 11433870 13949321
Cyprodinil (IS)
ppb Min Mean Max
100 0,28 0,55 0,82
200 0,41 0,99 1,57
500 1,67 2,48 3,29
1000 3,95 5,68 7,41
2000 9,14 11,44 13,74
5000 22,97 27,81 32,65
79
Guy Jamet – STRBG

Response
80
Guy Jamet – STRBG
CYPRODINIL (Cal)
Cyprodinil
16000000
14000000
12000000
10000000
y = 2316,6x - 306961
R 2 = 0,9975
8000000
6000000
4000000
2000000
0
0 1000 2000 3000 4000 5000 6000
-2000000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

Response
81
Guy Jamet – STRBG
CYPRODINIL (Cal)
Cyprodinil (IS)
35,00
30,00
25,00
y = 0,0056x - 0,0472
R 2 = 0,9996
20,00
15,00
10,00
5,00
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )

ETHION (Cal)
Ethion
ppb Min Mean Max
100 35814 61220 86626
200 13207 114845 216483
500 177328 335848 494368
1000 498211 710715 923219
2000 1175367 1501107 1826847
5000 3332820 4350940 5369060
Ethion (IS)
ppb Min Mean Max
100 0,12 0,24 0,36
200 0,00 0,46 0,92
500 0,64 1,33 2,02
1000 0,86 2,1 3,34
2000 3,66 4,25 4,85
5000 9,17 10,49 11,81
82
Guy Jamet – STRBG

Response
ETHION (Cal)
Ethion
6000000
5000000
4000000
y = 878,98x - 110063
R 2 = 0,9971
3000000
2000000
1000000
0
0 1000 2000 3000 4000 5000 6000
-1000000
Concentration (ppb)
Min Mean Max Linéaire (Mean)
83
Guy Jamet – STRBG

Response
ETHION (Cal)
Ethion (IS)
14,00
12,00
10,00
y = 0,0021x + 0,0963
R 2 = 0,9993
8,00
6,00
4,00
2,00
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )
84
Guy Jamet – STRBG

OXADIXYL (Cal)
Oxadixyl
ppb Min Mean Max
100 4086 10189 16292
200 5933 16808 27683
500 17606 28957 40308
1000 20336 60165 99994
2000 109320 137510 165700
5000 271382 363783 456184
Oxadixyl (IS)
ppb Min Mean Max
100 0,03 0,04 0,05
200 0,01 0,07 0,13
500 0,04 0,09 0,14
1000 0,10 0,19 0,28
2000 0,29 0,4 0,51
5000 0,68 0,89 1,10
85
Guy Jamet – STRBG

Response
86
Guy Jamet – STRBG
OXADIXYL (Cal)
Oxadixyl
500000
450000
400000
350000
y = 72,868x - 3971,4
R 2 = 0,9978
300000
250000
200000
150000
100000
50000
0
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

Response
OXADIXYL (Cal)
Oxadixyl (IS)
1,20
1,00
0,80
y = 0,0002x + 0,0237
R 2 = 0,9973
0,60
0,40
0,20
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )
87
Guy Jamet – STRBG

IPRODIONE (Cal)
Iprodione
ppb Min Mean Max
100 4536 18899 33262
200 1528 38209 74890
500 50686 96545 142404
1000 131232 214082 296932
2000 346225 432781 519337
5000 1041685 1289214 1536743
Iprodione (IS)
ppb Min Mean Max
100 0,02 0,06 0,10
200 -0,01 0,14 0,29
500 0,21 0,39 0,57
1000 0,20 0,64 1,08
2000 0,97 1,24 1,51
5000 2,62 3,15 3,68
88
Guy Jamet – STRBG

Response
89
Guy Jamet – STRBG
IPRODIONE (Cal)
Iprodione
1800000
1600000
1400000
1200000
y = 259,79x - 32734
R 2 = 0,9961
1000000
800000
600000
400000
200000
0
0 1000 2000 3000 4000 5000 6000
-200000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

Response
IPRODIONE (Cal)
Iprodione (IS)
4,00
3,50
3,00
y = 0,0006x + 0,0212
R 2 = 0,9993
2,50
2,00
1,50
1,00
0,50
0,00
-0,50
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )
90
Guy Jamet – STRBG

PROCYMIDONE (Cal)
Procymidone
ppb Min Mean Max
100 6088 28447 50806
200 10449 66552 122655
500 108545 169602 230659
1000 230132 364133 498134
2000 597140 741789 886438
5000 1549554 2046967 2544380
Procymidone (IS)
ppb Min Mean Max
100 0,04 0,1 0,16
200 0,08 0,24 0,40
500 0,46 0,62 0,78
1000 0,43 1,09 1,75
2000 1,71 2,12 2,53
5000 4,15 4,95 5,75
91
Guy Jamet – STRBG

Response
PROCYMIDONE (Cal)
Procymidone
3000000
2500000
2000000
y = 412,29x - 35118
R 2 = 0,9987
1500000
1000000
500000
0
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire (Mean)
92
Guy Jamet – STRBG

Response
93
Guy Jamet – STRBG
PROCYMIDONE (Cal)
Procymidone (IS)
7,00
6,00
5,00
y = 0,001x + 0,0804
R 2 = 0,9989
4,00
3,00
2,00
1,00
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )

94
Guy Jamet – STRBG
PYRIMETHANIL (Cal)
Pyrimethanil
ppb Min Mean Max
100 38945 165722 292499
200 -161917 275839 713595
500 37650 801074 1564498
1000 352795 2351969 4351143
2000 4155867 5267258 6378649
5000 11419877 15145726 18871575
Pyrimethanil (IS)
ppb Min Mean Max
100 0,30 0,56 0,82
200 -0,30 0,96 2,22
500 0,64 2,64 4,64
1000 2,38 6,87 11,36
2000 11,52 15,14 18,76
5000 29,23 36,86 44,49

Response
95
Guy Jamet – STRBG
PYRIMETHANIL (Cal)
Pyrimethanil
20000000
15000000
y = 3097,5x - 541770
R 2 = 0,9972
10000000
5000000
0
0 1000 2000 3000 4000 5000 6000
-5000000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

Response
96
Guy Jamet – STRBG
PYRIMETHANIL (Cal)
Pyrimethanil (IS)
50,00
40,00
30,00
20,00
10,00
0,00
0 1000 2000 3000 4000 5000 6000
-10,00
Concentration (ppb)
Min Mean Max Linéaire (Max) Linéaire (Min) Linéaire ( Mean )

λ CYHALOTHRIN (Cal)
λ Cyhalothrin
ppb Min Mean Max
100 42946 66894 90842
200 101059 136751 172443
500 322848 370238 417628
1000 647020 772100 897180
2000 1394438 1608348 1822258
5000 3625622 4708600 5791578
λ Cyhalothrin (IS)
ppb Min Mean Max
100 0,11 0,28 0,45
200 -0,11 0,59 1,29
500 0,68 1,57 2,46
1000 0,75 2,36 3,97
2000 3,51 4,71 5,91
5000 9,01 11,58 14,15
97
Guy Jamet – STRBG

Response
98
Guy Jamet – STRBG
λ CYHALOTHRIN (Cal)
λ Cyhalothrin
7000000
6000000
5000000
4000000
y = 949,33x - 115193
R 2 = 0,9967
3000000
2000000
1000000
0
0 1000 2000 3000 4000 5000 6000
-1000000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

Response
λ CYHALOTHRIN (Cal)
λ Cyhalothrin (IS)
16,00
14,00
12,00
10,00
y = 0,0023x + 0,1691
R 2 = 0,999
8,00
6,00
4,00
2,00
0,00
0 1000 2000 3000 4000 5000 6000
-2,00
Concentration (ppb)
Min Mean Max Linéaire ( Mean )
99
Guy Jamet – STRBG

TOLCLOPHOS METHYL (Cal)
Tolclophos methyl
ppb Min Mean Max
100 77359 135479 193599
200 44603 265494 486385
500 445738 775196 1104654
1000 1128583 1567476 2006369
2000 2528860 3258840 3988820
5000 7044167 9019420 10994673
Tolclophos methyl (IS)
ppb Min Mean Max
100 0,30 0,54 0,78
200 0,70 0,96 1,22
500 2,64 3,12 3,60
1000 1,77 4,65 7,53
2000 7,97 9,22 10,47
5000 19,50 21,74 23,98
100
Guy Jamet – STRBG

Response
101
Guy Jamet – STRBG
TOLCLOPHOS METHYL (Cal)
Tolclophos Methyl (IS)
30,00
25,00
y = 0,0043x + 0,4151
R 2 = 0,9982
20,00
15,00
10,00
5,00
0,00
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire ( Mean )

Response
102
Guy Jamet – STRBG
TOLCLOPHOS METHYL (Cal)
Tolclophos Methyl
12000000
10000000
y = 1817x - 161340
R 2 = 0,9986
8000000
6000000
4000000
2000000
0
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire (Mean)

VINCLOZOLINE (Cal)
Vinclozoline
ppb Min Mean Max
100 18817 29915 41013
200 20367 55195 90023
500 94905 144233 193561
1000 192307 299077 405847
2000 489636 621366 753096
5000 1359205 1707544 2055883
Vinclozoline (IS)
ppb Min Mean Max
100 0,07 0,12 0,17
200 0,00 0,22 0,44
500 0,23 0,53 0,83
1000 0,43 0,9 1,37
2000 1,48 1,77 2,06
5000 3,62 4,14 4,66
103
Guy Jamet – STRBG

Response
VINCLOZOLINE (Cal)
Vinclozoline
2500000
2000000
y = 343,52x - 27605
R 2 = 0,9986
1500000
1000000
500000
0
0 1000 2000 3000 4000 5000 6000
Concentration (ppb)
Min Mean Max Linéaire (Mean)
104
Guy Jamet – STRBG

Response
VINCLOZOLINE (Cal)
Vinclozoline (IS)
5,00
4,00
y = 0,0008x + 0,0829
R 2 = 0,9993
3,00
2,00
1,00
0,00
0 1000 2000 3000 4000 5000 6000
-1,00
Concentration (ppb)
Min Mean Max Linéaire ( Mean )
105
Guy Jamet – STRBG

106
Guy Jamet – STRBG
Conclusion
‣ Internal standard is not helping a lot
‣ The mean response can be considered as linear
‣ Drift is evident along the time
‣ Drift is more important for molecules with RRT greater
than that of IS
‣ The variability is greater in the range 100-500 ppb
‣ Sequence must be limited
‣ Corresponding to daily work
‣ Calibration curves before and after the samples
‣ Calculation is conducted with the mean of both curves

107
Guy Jamet – STRBG
Calibration in range 100-500 ppb
‣ Profile of accuracy
‣ Repeatability
‣ Intermediate fidelity
‣ Estimation of the
variability
‣ REPRESENTATIVE
ANALYTES
CHLORFENVINPHOS
CYPRODINIL
ETHION
λ CYHALOTHRIN
PROCYMIDONE
PYRIMETHANIL
TOLCLOPHOS-METHYL
VINCLOZOLINE
‣ In solvent

108
Guy Jamet – STRBG
CHLORFENVINPHOS (LOD-LOQ)
concentration (ppb) 100 200 500
Chlorfenvinphos
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -114 1 -4
recovery -39 13 6
upper_acceptable_limit 37 25 16
upper_tolerance_limit 50 50 50
Chlorfenvinphos
Mean bias rsd_r rsd_Ro rsd_IP
100 61,26 -39% 83% 50% 83%
200 226,20 26% 4% 7% 6%
500 530,74 31% 2% 5% 5%

109
Guy Jamet – STRBG
CYPRODINIL (LOD-LOQ)
concentration (ppb) 100 200 500
Cyprodinil
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit 8 -6 2
recovery 23 15 7
upper_acceptable_limit 38 35 12
upper_tolerance_limit 50 50 50
Cyprodinil
Mean bias rsd_r rsd_Ro rsd_IP
100 122,90 23% 7% 9% 8%
200 229,07 29% 3% 9% 9%
500 534,89 35% 3% 4% 3%

110
Guy Jamet – STRBG
ETHION (LOD-LOQ)
concentration (ppb) 100 200 500
Ethion
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -26 -6 0
recovery -16 3 5
upper_acceptable_limit -5 11 11
upper_tolerance_limit 50 50 50
Ethion
Mean bias rsd_r rsd_Ro rsd_IP
100 84,25 -16% 5% 8% 7%
200 205,37 5% 4% 6% 5%
500 527,03 27% 3% 4% 3%

111
Guy Jamet – STRBG
λ CYHALOTHRIN (LOD-LOQ)
concentration (ppb) 100 200 500
λ Cyhalothrin
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit 2 1 -2
recovery 26 24 12
upper_acceptable_limit 50 47 25
upper_tolerance_limit 50 50 50
λ Cyhalothrin
Mean bias rsd_r rsd_Ro rsd_IP
100 126,12 26% 4% 10% 10%
200 247,80 48% 5% 10% 10%
500 557,72 58% 4% 7% 7%

112
Guy Jamet – STRBG
IPRODIONE (LOD-LOQ)
concentration (ppb) 100 200 500
Iprodione
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -153 -62 -3
recovery -75 -4 8
upper_acceptable_limit 3 54 18
upper_tolerance_limit 50 50 50
Iprodione
Mean bias rsd_r rsd_Ro rsd_IP
100 24,74 -75% 212% NaN 212%
200 191,65 -8% 41% 7% 41%
500 538,12 38% 7% 8% 7%

113
Guy Jamet – STRBG
PYRIMETHANIL (LOD-LOQ)
Pyrimethanil
concentration (ppb) 100 200 500
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -252 -197 -199
recovery 10 -8 77
upper_acceptable_limit 272 181 353
upper_tolerance_limit 50 50 50
Pyrimethanil
Mean bias rsd_r rsd_Ro rsd_IP
100 110,09 10% 6% 108% 110%
200 183,90 -16% 3% 93% 95%
500 884,54 385% 26% 95% 77%

114
Guy Jamet – STRBG
PROCYMIDONE (LOD-LOQ)
concentration (ppb) 100 200 500
Procymidone
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -73 -18 -15
recovery 4 19 6
upper_acceptable_limit 82 56 28
upper_tolerance_limit 50 50 50
Procymidone
Mean bias rsd_r rsd_Ro rsd_IP
100 104,29 4% 8% 28% 35%
200 238,43 38% 10% 18% 17%
500 531,28 31% 4% 10% 10%

115
Guy Jamet – STRBG
TOLCLOPHOS METHYL (LOD-LOQ)
concentration (ppb) 100 200 500
Tolclophos methyl
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -28 -8 -3
recovery -20 0 3
upper_acceptable_limit -12 8 9
upper_tolerance_limit 50 50 50
Tolclophos methyl
Mean bias rsd_r rsd_Ro rsd_IP
100 79,81 -20% 3% 6% 6%
200 199,50 -1% 5% 6% 5%
500 514,18 14% 4% 4% 4%

116
Guy Jamet – STRBG
Extension to other matrices at
0.01 mg/kg
‣ REPRESENTATIVE
MATRICES
‣ Salads representative
of leafy vegetables
‣ Carrots representative
of Roots vegetables
‣ Apples representative
of Fruit
‣ Relative big production
of each in Alsace
‣ REPRESENTATIVE
ANALYTES
‣ CHLORFENVINPHOS
‣ CYPRODINIL
‣ IPRODIONE
‣ λ CYHALOTHRIN
‣ PROCYMIDONE
‣ PYRIMETHANIL
‣ TOLCLOPHOS
METHYL
‣ VINCLOZOLINE

117
Guy Jamet – STRBG
CHLORFENVINPHOS (ACS)
Chlorfenvinphos
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -82 -175 -124
Recovery -6 -29 -52
Upper_tolerable_limt 70 117 19
Upper_acceptable_limit 50 50 50
Chlorfenvinphos
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 9,38 -1% 514% 518% 514%
Apple 7,09 -3% 29% 659% 670%
Salad 4,77 -5% 485% 115% 485%

118
Guy Jamet – STRBG
CYPRODINIL (ACS)
Cyprodinil
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -73 -94 -105
Recovery -16 -57 -32
Upper_tolerable_limt 41 -21 42
Upper_acceptable_limit 50 50 50
Cyprodinil
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 8,42 -2% 387% 208% 387%
Apple 4,26 -6% 231% 268% 242%
Salad 6,84 -3% 394% 510% 467%

119
Guy Jamet – STRBG
IPRODIONE (ACS)
Iprodione
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -114 -213 -186
Recovery -30 0 -14
Upper_tolerable_limt 54 213 158
Upper_acceptable_limit 50 50 50
Iprodione
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 6,97 -3% 222% 426% 446%
Apple 10,01 0% 1439% 150% 1439%
Salad 8,60 -1% 317% 178% 861%

120
Guy Jamet – STRBG
λ CYHALOTHRIN (ACS)
λ Cyhalothrin
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -102 -133 -112
Recovery -28 -58 -41
Upper_tolerable_limt 46 17 30
Upper_acceptable_limit 50 50 50
λ Cyhalothrin
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 7,19 -3% 231% 422% 409%
Apple 4,17 -6% 234% 427% 414%
Salad 5,87 -4% 262% 427% 408%

121
Guy Jamet – STRBG
PROCYMIDONE (ACS)
Procymidone
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -74 -106 -113
Recovery 14 -18 -30
Upper_tolerable_limt 101 71 53
Upper_acceptable_limit 50 50 50
Procymidone
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 11,37 1% 81% 396% 412%
Apple 8,22 -2% 236% 472% 472%
Salad 6,99 -3% 561% 605% 561%

122
Guy Jamet – STRBG
PYRIMETHANIL (ACS)
Pyrimethanil
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -82 -212 -128
Recovery 69 22 45
Upper_tolerable_limt 221 256 218
Upper_acceptable_limit 50 50 50
Pyrimethanil
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 16,94 7% 295% 769% 765%
Apple 12,22 2% 159% 1074% 1090%
Salad 14,50 5% 551% 959% 957%

123
Guy Jamet – STRBG
TOLCLOPHOS METHYL (ACS)
Tolclophos methyl
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -98 -71 -79
Recovery -39 -49 -52
Upper_tolerable_limt 21 -26 -26
Upper_acceptable_limit 50 50 50
Tolclophos methyl
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 6,13 -4% 140% 314% 310%
Apple 5,14 -5% 34% 82% 111%
Salad 4,77 -5% 107% 50% 157%

124
Guy Jamet – STRBG
VINCLOZOLINE (ACS)
Vinclozoline
limits
Carrots Apples Salads
Low er_acceptable_limit -50 -50 -50
Low er_tolerable_limit -110 -136 -148
Recovery -29 -53 -69
Upper_tolerable_limt 52 30 9
Upper_acceptable_limit 50 50 50
Vinclozoline
Matrix Mean bias sd_r sd_Ro sd_IP
Carrot 7,07 -3% 549% 555% 549%
Apple 4,73 -5% 273% 481% 464%
Salad 3,06 -7% 21% 356% 362%

125
Guy Jamet – STRBG
VINCLOZOLINE (LOD-LOQ)
concentration (ppb) 100 200 500
Vinclozoline
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -120 -54 -2
recovery -35 -2 8
upper_acceptable_limit 50 50 18
upper_tolerance_limit 50 50 50
Vinclozoline
Mean bias rsd_r rsd_Ro rsd_IP
100 64,92 -35% 89% 47% 89%
200 195,91 -4% 36% 11% 36%
500 538,80 39% 6% 4% 6%

126
Guy Jamet – STRBG
1 st step in qualitative accreditation
‣ Salads
‣ CYPRODINYL
‣ IPRODIONE
‣ λ CYHALOTHRIN
‣ PYRIMETHANYL
‣ LCL
‣ LOD
‣ LOQ
‣ Upper limit
‣ Repeatability of
recovery
‣ Intermediate fidelity

127
Guy Jamet – STRBG
3 rd proposal: determination of the recovery at
other concentrations on salads
‣ Follow up of the extraction at high
concentration level
‣ Determination of the response of a
diluted sample
‣ Using the 1 g/ml solution
‣ Further dilution
‣ Variability due to the dilution
‣ Multilevel calibration standards
‣ Aldrine as qualitative internal
standard
‣ No quantitative standard
‣ Different days
‣ Estimation of the variability at each
level
‣ Visual examination on profile
accuracy plot
‣ REPRESENTATIVE
ANALYTES
CYPRODINYL
IPRODIONE
λ CYHALOTHRIN
PYRIMETHANYL
‣ REPRESENTATIVE
MATRICE for LEAFY
VEGETABLES and huge
production in Alsace

128
Guy Jamet – STRBG
CYPRODINIL (high conc.)
Pesticde Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP
Cyprodinil 224
Cyprodinil 225
LMR/10s 1 1,16 0,16% 2,25% 24,62% 25,04%
LMR/10e 1 1,09 0,09% 2,55% 28,05% 28,53%
LMR/2e 5 5,19 0,19% 1,84% 10,69% 10,87%
LMRe 10 10,05 5,05% 9,94% 14,78% 2,88%
LMR/10s 1 1,15 0,15% 2,34% 23,59% 23,98%
LMR/10e 1 1,08 0,08% 2,39% 27,31% 27,77%
LMR/2e 5 5,23 0,23% 1,70% 10,96% 11,09%
LMRe 10 9,97 4,97% 9,70% 13,71% 2,77%
Pesticide limit LMR/10s LMR/10e LMR/2e LMRe
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit -47 -58 -20 -100
Cyprodinil 224 recovery 16 9 4 101
upper_tolerable_limit 78 77 28 302
upper_acceptable_limit 50 50 50 50
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit -45 -57 -20 -78
Cyprodinil 225 recovery 15 8 5 99
upper_tolerable_limit 75 74 29 277
upper_acceptable_limit 50 50 50 50

129
Guy Jamet – STRBG
IPRODIONE (high conc.)
Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP
LMR/10s 1 1,42 0,4% 4,0% 5,1% 4,6%
LMR/10e 1 1,37 0,4% 2,6% 2,3% 2,6%
Iprodione 314
LMR/2e 5 5,19 0,2% 2,4% 8,9% 8,9%
LMRe 10 11,34 6,3% 8,8% 9,1% 0,6%
LMR/10s 1 1,48 0,5% 3,1% 7,7% 7,6%
LMR/10e 1 1,43 0,4% 2,2% 4,9% 4,8%
Iprodione 316
LMR/2e 5 5,17 0,2% 2,6% 8,0% 8,0%
LMRe 10 11,47 6,5% 9,0% 7,3% 1,0%
Pesticide limit LMR/10s LMR/10e LMR/2e LMRe
low er_acceptable_limit -50 -50 -50 -50
Iprodione 314
Iprodione 316
low er_tolerable_limit 32 31 -15 96
recovery 42 37 4 127
upper_tolerable_limit 52 42 23 158
upper_acceptable_limit 50 50 50 50
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit 26 29 -13 81
recovery 48 43 3 129
upper_tolerable_limit 70 56 20 177
upper_acceptable_limit 50 50 50 50

130
Guy Jamet – STRBG
λ CYHALOTHRIN (high conc.)
Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP
LMR/10s 0.1 0,15 0,05% 4,10% 3,91% 4,10%
LMR/10e 0.1 0,15 0,05% 8,54% 8,06% 8,54%
λ Cyhalothrin 181
LMR/2e 0.5 0,61 0,11% 1,94% 9,64% 9,75%
LMRe 1.0 1,27 0,77% 7,37% 15,28% 0,47%
LMR/10s 0.1 0,14 0,04% 2,79% 2,87% 2,79%
LMR/10e 0.1 0,15 0,05% 7,50% 7,23% 7,50%
λ Cyhalothrin 197
LMR/2e 0.5 0,60 0,10% 1,97% 10,17% 10,30%
LMRe 1.0 1,28 0,78% 7,55% 15,85% 0,31%
Pesticide limit LMR/10s LMR/10e LMR/2e LMRe
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit 37 31 -4 90
λ Cyhalothrin 181 recovery 46 49 21 154
upper_tolerable_limit 55 68 46 218
upper_acceptable_limit 50 50 50 50
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit 38 31 -6 90
λ Cyhalothrin 197 recovery 44 48 21 157
upper_tolerable_limit 50 64 47 224
upper_acceptable_limit 50 50 50 50

131
Guy Jamet – STRBG
PYRIMETHANIL (high conc.)
Pesticide Conc mg/kg Mean bias rsd_r rsd_Ro rsd_IP
Pyrimethanil 198
Pyrimethanil 199
LMR/10s 0,2 0,43 0,2% 0,6% 15,6% 15,9%
LMR/10e 0,2 0,42 0,2% 1,9% 13,9% 14,5%
LMR/2e 1 1,10 0,1% 2,3% 17,2% 17,5%
LMRe 2 2,93 1,9% 13,7% 20,3% 2,3%
LMR/10s 0,2 0,44 0,2% 0,5% 14,0% 14,3%
LMR/10e 0,2 0,44 0,2% 1,7% 14,5% 14,8%
LMR/2e 1 1,10 0,1% 2,2% 17,1% 17,4%
LMRe 2 2,95 1,9% 13,7% 21,2% 2,1%
Pesticide limit LMR/10s LMR/10e LMR/2e LMRe
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit 40 46 -31 -884
Pyrimethanil 198 recovery 114 112 10 193
upper_tolerable_limit 188 178 52 1269
upper_acceptable_limit 50 50 50 50
low er_acceptable_limit -50 -50 -50 -50
low er_tolerable_limit 52 49 -31 -953
Pyrimethanil 199 recovery 121 119 10 195
upper_tolerable_limit 189 188 51 1342
upper_acceptable_limit 50 50 50 50

Mean, bias, RSD_r, RSD_FI (1)
Residues ppb Mean Bias rsd_r rsd_IP
100 119 19% 5% 11%
OPP 200 231 31% 7% 11%
500 533 33% 5% 5%
100 116 16% 7% 10%
Diphenylamine 200 232 32% 4% 9%
500 529 29% 4% 4%
100 34 -66% 150% 212%
Chlorpropham 200 235 35% 7% 13%
500 537 37% 5% 6%
100 0 -100% NaN NaN
Dimethoate 200 0 -200% NaN NaN
500 0 -500% NaN NaN
100 0 -100% NaN NaN
Dicloran 200 0 -200% NaN NaN
500 0 -500% NaN NaN
100 52 -48% 110% 110%
Propyzamide 200 156 -44% 43% 43%
500 523 23% 6% 6%
100 110 10% 6% 110%
Pyrimethanil 200 184 -16% 2% 95%
500 885 385% 26% 77%
100 99 -1% 18% 18%
Diazinon 200 171 -29% 64% 64%
500 459 -41% 40% 40%
100 9 -91% 300% 300%
Chlorothalonil 200 162 -38% 8% 8%
500 441 -59% 5% 6%
100 119 19% 6% 6%
Pyrimicarb 200 226 26% 2% 4%
500 540 40% 3% 6%
100 90 -10% 8% 8%
Chlorpyriphos methyl 200 206 6% 8% 8%
500 508 8% 4% 4%
132
Guy Jamet – STRBG

133
Guy Jamet – STRBG
Extension to other of analytes
‣ 0.01, 0.02, 0.05 mg/kg according
to R 396/2005
‣ 3 repetition each level
‣ Mean value
‣ RSD_r at each level
‣ 3 times
‣ 66 residues
‣ With BROMOPHOS METHYL
as internal standards
for quantification
‣ RSD_IP at each level
‣ Profile of accuracy

Mean, bias, RSD_r, RSD_FI (2)
Residues ppb Mean Bias rsd_r rsd_IP
100 65 -35% 89% 89%
Vinclozoline 200 196 -4% 36% 36%
500 539 39% 6% 6%
100 0 -100% NaN NaN
Parathion methyl 200 72 -128% 145% 152%
500 0 -500% NaN NaN
100 80 -20% 3% 6%
Tolclophos methyl 200 199 -1% 6% 6%
500 514 14% 4% 4%
100 14 -86% 300% 300%
Carbaryl 200 96 -104% 129% 129%
500 517 17% 27% 27%
100 116 16% 33% 33%
Metalaxyl 200 229 29% 34% 34%
500 549 49% 5% 5%
100 7 -93% 300% 300%
Fenitrothion 200 107 -93% 65% 105%
500 466 -34% 36% 36%
100 84 -16% 8% 14%
Pyrimiphos methyl 200 195 -5% 5% 5%
500 513 13% 3% 3%
100 84 -16% 14% 14%
Malathion 200 192 -8% 8% 8%
500 516 16% 4% 4%
100 71 -29% 50% 50%
Diethofencarbe 200 209 9% 10% 12%
500 525 25% 4% 4%
100 135 35% 13% 13%
Chlorpyriphos 200 240 40% 8% 8%
500 541 41% 5% 6%
100 129 29% 4% 6%
Chlorthal dimethyl 200 244 44% 5% 7%
500 543 43% 5% 5%
134
Guy Jamet – STRBG

Mean, bias, RSD_r, RSD_FI (3)
Residues ppb Mean Bias rsd_r rsd_IP
100 54 -46% 102% 102%
Tetraconazole 200 214 14% 3% 3%
500 526 26% 4% 4%
100 123 23% 7% 8%
Cyprodinil 200 229 29% 3% 9%
500 535 35% 3% 3%
100 57 -43% 129% 139%
Penconazole 200 257 57% 8% 11%
500 569 69% 3% 3%
100 28 -72% 150% 212%
Tolylfluanid 200 131 -69% 67% 67%
500 478 -22% 4% 10%
100 61 -39% 83% 83%
Chlorfenvinphos 200 226 26% 4% 6%
500 531 31% 2% 5%
100 0 -100% NaN NaN
Thiabenazole 200 2 -198% 300% 300%
500 77 -423% 210% 210%
100 0 -100% NaN NaN
Triadimenol 200 0 -200% NaN NaN
500 355 -145% 67% 76%
100 104 4% 8% 35%
Procymidone 200 238 38% 10% 17%
500 531 31% 4% 10%
100 180 80% 11% 69%
Methidathion 200 196 -4% 31% 92%
500 1020 520% 16% 65%
100 0 -100% NaN NaN
α Endosulfan 200 300 100% 87% 87%
500 416 -84% 49% 49%
100 90 -10% 6% 6%
Mepanipyrim 200 206 6% 4% 5%
500 526 26% 4% 4%
135
Guy Jamet – STRBG

Mean, bias, RSD_r, RSD_FI (4)
Residues ppb Mean Bias rsd_r rsd_IP
100 127 27% 11% 28%
Dieldrin 200 261 61% 9% 14%
500 525 25% 5% 12%
100 0 -100% NaN NaN
Fludioxonil 200 16 -184% 104% 104%
500 33 -467% 86% 86%
100 0 -100% NaN NaN
Myclobutanil 200 46 -154% 287% 287%
500 515 15% 32% 55%
100 135 35% 12% 12%
Buprofezine 200 182 -18% 51% 51%
500 555 55% 5% 6%
100 78 -22% 62% 62%
Flusilazole 200 229 29% 8% 10%
500 547 47% 4% 4%
100 94 -6% 17% 17%
Kresoxim methyl 200 218 18% 8% 11%
500 533 33% 5% 6%
100 0 -100% NaN NaN
Imazalil 200 0 -200% NaN NaN
500 18 -482% 300% 300%
100 35 -65% 116% 144%
Bupirimate 200 175 -25% 46% 46%
500 513 13% 7% 21%
100 0 -100% NaN NaN
β Endosulfan 200 178 -22% 46% 79%
500 373 -127% 62% 62%
100 84 -16% 5% 7%
Ethion 200 205 5% 4% 5%
500 527 27% 3% 3%
100 0 -100% NaN NaN
Oxadixyl 200 0 -200% NaN NaN
500 515 15% 37% 37%
136
Guy Jamet – STRBG

Mean, bias, RSD_r, RSD_FI (5)
Residues ppb Mean Bias rsd_r rsd_IP
100 89 -11% 12% 12%
Benalaxyl 200 208 8% 4% 8%
500 524 24% 6% 6%
100 0 -100% NaN NaN
Endosulfan sulphate 200 0 -200% NaN NaN
500 505 5% 9% 9%
100 0 -100% NaN NaN
Trifloxystrobin 200 1869 1669% 150% 212%
500 4304 3804% 107% 124%
100 0 -100% NaN NaN
Fenhexamid 200 0 -200% NaN NaN
500 614 114% 28% 28%
100 6 -94% 300% 300%
Tebuconazole 200 116 -84% 58% 80%
500 497 -3% 40% 40%
100 20 -80% 300% 300%
Propargite 200 147 -53% 110% 110%
500 702 202% 97% 97%
100 92 -8% 6% 17%
Pipronyl butoxyde 200 213 13% 5% 14%
500 553 53% 3% 10%
100 25 -75% 212% 212%
Iprodione 200 192 -8% 41% 41%
500 538 38% 7% 7%
100 0 -100% NaN NaN
Phosmet 200 0 -200% NaN NaN
500 0 -500% NaN NaN
100 356 256% 38% 85%
Bromopropylate 200 530 330% 49% 69%
500 894 394% 31% 103%
100 23 -77% 211% 211%
Bifenthrin 200 96 -104% 131% 131%
500 198 -302% 137% 137%
137
Guy Jamet – STRBG

Mean, bias, RSD_r, RSD_FI (6)
Residues ppb Mean Bias rsd_r rsd_IP
100 90 -10% 12% 14%
Tebufenpyrad 200 208 8% 7% 7%
500 542 42% 9% 9%
100 0 -100% NaN NaN
Phosalone 200 46 -154% 150% 212%
500 545 45% 9% 14%
100 0 -100% NaN NaN
Azinphos methyl 200 0 -200% NaN NaN
500 0 -500% NaN NaN
100 122 22% 6% 9%
Pyriproxyfen 200 240 40% 5% 8%
500 550 50% 4% 4%
100 126 26% 4% 10%
λ Cyhalothrine 200 248 48% 5% 10%
500 558 58% 4% 7%
100 64 -36% 149% 149%
Fenarimol 200 285 85% 10% 31%
500 619 119% 7% 20%
100 1 -99% 214% 214%
Bitertanol 200 39 -161% 151% 213%
500 718 218% 12% 34%
100 0 -100% NaN NaN
Boscalid 200 156 -44% 87% 87%
500 559 59% 8% 15%
100 82 -18% 40% 40%
α Cypermethrin 200 221 21% 9% 9%
500 540 40% 8% 8%
100 0 -100% NaN NaN
Deltamethrin 200 0 -200% NaN NaN
500 588 88% 10% 14%
100 0 -100% NaN NaN
Azoxystrobin 200 0 -200% NaN NaN
500 537 37% 35% 60%
138
Guy Jamet – STRBG

LOQ, LOD, LMR (1)
C_100 C_200 C_500 LOD LOQ LMR
OPP 0.01 0.02 0.05 0.001 0.01 0.01
Diphenylamine 0.01 0.02 0.05 0.001 0.01 0.05
Chlorpropham 0.02 0.05 0.002 0.02 0.05
Dimethoate 0.02
Dicloran 0.01
Propyzamide 0.05 0.005 0.05 0.02
Pyrimethanil 0.05 0.005 0.05 0.01
Diazinon 0.01 0.05 0.005 0.05 0.02
Chlorothalonil 0.02 0.05 0.002 0.02 0.01
Pyrimicarb 0.01 0.02 0.05 0.001 0.01 0.02
Chlorpyriphos methyl 0.01 0.02 0.05 0.001 0.01 0.05
Vinclozoline 0.02 0.05 0.002 0.02 0.05
Parathion methyl 0.02
Tolclophos methyl 0.01 0.02 0.05 0.001 0.01 0.01
Carbaryl 0.05 0.005 0.05 0.05
Metalaxyl 0.01 0.02 0.05 0.001 0.01 0.05
Fenitrothion 0.05 0.005 0.05 0.05
Pyrimiphos methyl 0.01 0.02 0.05 0.001 0.01 0.05
Malathion 0.01 0.02 0.05 0.001 0.01 0.02
Diethofencarb 0.01 0.02 0.05 0.001 0.01 0.01
Chlorpyriphos 0.01 0.02 0.05 0.001 0.01 0.05
Chlorthal dimethyl 0.01 0.02 0.05 0.001 0.01 0.01
Tetraconazole 0.02 0.05 0.002 0.02 0.01
Cyprodinil 0.01 0.02 0.05 0.001 0.01 0.01
Penconazole 0.02 0.05 0.002 0.02 0.05
Tolylfluanid 0.02 0.05 0.002 0.02 0.01
Chlorfenvinphos 0.02 0.05 0.002 0.02 0.02
Thiabenazole 0.05
Triadimenol 0.1
Procymidone 0.01 0.02 0.05 0.001 0.01 0.02
Methidathion 0.05 0.005 0.05 0.02
α Endosulfan 0.02 0.05 0.002 0.02 0.05
Mepanipyrim 0.01 0.02 0.05 0.001 0.01 0.02
139
Guy Jamet – STRBG

Capability of determination (1)
Residues MRL LOD LOQ MRL/LOQ
OPP 0,01 0,001 0,01 LOQ=MRL
Diphenylamine 0,05 0,001 0,01 LOQMRL
Dicloran 0,01 LOQ>>MRL
Propyzamide 0,02 0,005 0,05 LOQ>MRL
Pyrimethanil 0,01 0,005 0,05 LOQ>MRL
Diazinon 0,02 0,005 0,05 LOQ>MRL
Chlorothalonil 0,01 0,002 0,02 LOQ>MRL
Pyrimicarbe 0,02 0,001 0,01 LOQMRL
Procymidone 0,02 0,001 0,01 LOQMRL
α Endosulfan 0,05 0,002 0,02 LOQ

Capability of determination (2)
Residues MRL LOD LOQ MRL/LOQ
Dieldrine 0,01 0,001 0,01 LOQ=MRL
Fludioxonil 0,01 LOQ>>MRL
Myclobutanil 0,02 LOQ>>MRL
Buprofezine 0,01 0,001 0,01 LOQ=MRL
Flusilazole 0,01 0,001 0,01 LOQ=MRL
Kresoxim_methyl 0,05 0,001 0,01 LOQ>MRL
Bupirimate 0,01 0,002 0,02 LOQ>MRL
β Endosulfan 0,05 LOQ>>MRL
Ethion 0,01 0,001 0,01 LOQ=MRL
Oxadixyl 0,05 0,005 0,05 LOQ=MRL
Benalaxyl 0,05 0,001 0,01 LOQ>MRL
Fenhexamide 0,05 0,005 0,05 LOQ=MRL
Tebuconazole 0,01 0,002 0,02 LOQ>MRL
Propargite 0,01 0,005 0,05 LOQ>MRL
Pipronyl_butoxyde 0,05 0,001 0,01 LOQ>MRL
Bromopropylate 0,05 0,001 0,01 LOQMRL
141
Guy Jamet – STRBG

LOQ, LOD, LMR (2)
C_100 C_200 C_500 LOD LOQ LMR
Dieldrin 0.01 0.02 0.05 0.001 0.01 0.01
Fludioxonil 0.01
Myclobutanil 0.02
Buprofezine 0.01 0.02 0.05 0.001 0.01 0.01
Flusilazole 0.01 0.02 0.05 0.001 0.01 0.01
Kresoxim methyl 0.01 0.02 0.05 0.001 0.01 0.05
Imazalil 0.02
Bupirimate 0.02 0.05 0.002 0.02 0.01
β Endosulfan 0.05
Ethion 0.01 0.02 0.05 0.001 0.01 0.01
Oxadixyl 0.05 0.005 0.05 0.05
Benalaxyl 0.01 0.02 0.05 0.001 0.01 0.05
Endosulfan sulphate 0.05 0.005 0.05 0.05
Trifloxystrobin 0.05
Fenhexamid 0.05 0.005 0.05 0.05
Tebuconazole 0.02 0.05 0.002 0.02 0.01
Propargite 0.05 0.005 0.05 0.01
Pipronyl butoxyde 0.01 0.02 0.05 0.001 0.01 0.05
Iprodione 0.02 0.05 0.002 0.02 0.02
Phosmet 0.01
Bromopropylate 0.01 0.02 0.05 0.001 0.01 0.05
Bifenthrin 0.01 0.02 0.05 0.001 0.01 0.05
Tebufenpyrad 0.01 0.02 0.05 0.001 0.01 0.05
Phosalone 0.05 0.005 0.05 0.05
Azinphos methyl 0.01
Pyriproxyfen 0.01 0.02 0.05 0.001 0.01 0.01
λ Cyhalothrine 0.01 0.02 0.05 0.001 0.01 0.02
Fenarimol 0.02 0.05 0.002 0.02 0.02
Bitertanol 0.05 0.005 0.05 0.05
Boscalid 0.05 0.005 0.05 0.01
α Cypermethrin 0.01 0.02 0.05 0.001 0.01 0.05
Deltamethrin 0.05 0.005 0.05 0.05
Azoxystrobin 0.05
142
Guy Jamet – STRBG

143
Guy Jamet – STRBG
13 analytes with LOQ >> LMR
‣ Analytes with 1 or 2
characteristic ions
‣ AZINPHOS METHYL
‣ PHOSMET
‣ PARATHION METHYL
‣ THIABENDAZOLE
‣ Analytes with low response due
to isomers
‣ TRIADIMENOL
‣ Analytes with low response
‣ DIMETHOATE
‣ FLUDIOXONIL
‣ MYCLOBUTANIL
‣ DICHLORAN
‣ IMAZALIL
‣ β ENDOSULFAN
‣ TRIFLOXYSTROBIN
‣ AOXYSTROBIN

144
Guy Jamet – STRBG
11 analytes with LOD >LMR
‣ PROPYZAMIDE
‣ PYRIMETHANIL
‣ DIAZINON
‣ CHLOROTHALONIL
‣ TETRACONAZOLE
‣ TOLYLFLUANID
‣ METHIDATHION
‣ BUPIRIMATE
‣ TEBUCONAZOLE
‣ PROPARGITE
‣ BOSCALID

145
Guy Jamet – STRBG
20 analytes with LOD =LMR
‣ OPP
‣ TOLCLOPHOS METHYL
‣ CARBARYL
‣ FENITROTHION
‣ DIETHOFENCARB
‣ CHLORTHAL DIMETHYL
‣ CYPRODINIL
‣ DIELDRIN
‣ BUPROFEZIN
‣ FLUSILAZOLE
‣ ETHION
‣ OXADIXYL
‣ ENDOSULFAN Sulphate
‣ FENHEXAMID
‣ IPRODIONE
‣ PHOSALONE
‣ PYRIPROXYFEN
‣ FENARIMOL
‣ BITERTANOL
‣ DELTAMETHRIN

146
Guy Jamet – STRBG
22 analytes with LOD

147
Guy Jamet – STRBG
SUMMARY
‣ 63% of the analytes are amenable with the
method at the MRL
‣ 37% are not amenable at the MRL
‣ What’s about repeatability, intermediate
fidelity
‣ What’s about higher concentrations

148
Guy Jamet – STRBG
PROPYZAMIDE and CHLOROTHALONIL
(LOQ>MRL)
limits
c_100 c_200 c_500
limits
c_100 c_200 c_500
low er_tolerance_limt -50 -50 -50
low er_tolerance_limt -50 -50 -50
Propyzamide
low er_acceptable_limit -132 -72 -5
recovery -48 -22 5
Chlorothalonil
low er_acceptable_limit -129 -28 -20
recovery -91 -19 -12
upper_acceptable_limit 36 28 14
upper_acceptable_limit -54 -10 -3
upper_tolerance_limit 50 50 50
upper_tolerance_limit 50 50 50

149
Guy Jamet – STRBG
CHLORPYRIPHOS and MALATHION
(LOQ

150
Guy Jamet – STRBG
CYPERMETHRIN and MEPANIPYRIM
(LOQ>MRL)
Alpha_cypermethrine
limits c_100 c_200 c_500
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -66 -4 -4
recovery -18 11 8
upper_acceptable_limit 29 26 20
upper_tolerance_limit 50 50 50
Mepanipyrim
limits c_100 c_200 c_500
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -18 -5 -1
recovery -10 3 5
upper_acceptable_limit -2 11 11
upper_tolerance_limit 50 50 50

151
Guy Jamet – STRBG
Residues not amenable for every
matrices
0,01 mg/kg
Calibration Carott Apple
Salad
Mean Recovery
mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % real %
10 Pyrimicarb NA
11 Vinclozoline 11 4 33 7 6 80 6 4 72 72
13 Parathion methyl NA
19 Malathion 10 2 17 7 1 13 11 8 76 9 5 54 54
20 Diethofencarb 9 3 37 11 5 46 6 4 68 5 3 55 8 5 63 63
22 Chlorthal dimethyl 7 2 24 NA
26 Chlorfenvinphos 9 3 34 9 6 63 6 5 84 8 5 64 64
32 α Endosulfan NA
33 Mepanipyrim 10 6 55 16 20 121 7 2 26 11 13 122 122
34 Dieldrin 6 5 74 NA
35 Buprofezine NA
37 Imazalil 9 4 39 8 6 76 7 5 64 NA
40 Bupirimate 30 15 50 NA
41 Kresoxym methyl NA
42 β Endosulfan 5 5 103 8 7 95 NA
45 Benalaxyl 8 3 33 NA
47 Fenhexamid NA
48 Trifloxystrobin 15 5 31 40 24 59 35 34 97 NA
49 Piperonil butoxyde 22 10 45 32 16 50 37 19 50 U_150%
50 Tebuconazole NA
51 Propargite 2 2 86 6 4 78 12 13 111 NA
52 Iprodione NA
53 Phosmet NA
54 Bromopropylate 12 1 9 10 3 30 4 4 89 9 5 54 54
55 Bifenthrin 8 3 32 6 5 73 NA
58 Pyriproxyfen 10 2 21 NA
59 Azinphos_methyl 14 12 86 8 3 40 5 5 102 9 8 91 NA
63 α Cypermethrin NA

152
Guy Jamet – STRBG
BENALAXYL and KRESOXIM METHYL
(LOQ>MRL)
Benalaxyl
limits c_100 c_200 c_500
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -27 -12 -4
recovery -11 4 5
upper_acceptable_limit 6 21 14
upper_tolerance_limit 50 50 50
Kresoxim methyl
limits c_100 c_200 c_500
low er_tolerance_limt -50 -50 -50
low er_acceptable_limit -29 -12 -4
recovery -6 9 7
upper_acceptable_limit 18 29 17
upper_tolerance_limit 50 50 50

Residues amenable for every matrices
0,01 mg/kg
Calibration Carott Apple
Salad
Mean Recovery
mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % mean sd rsd % real %
1 OPP 8 1 14 11 1 8 9 1 14 9 4 42 10 1 14 14
2 Diphenylamine 9 3 37 9 2 27 5 3 62 6 2 40 7 3 43 43
3 Chlorpropham 13 5 37 16 4 22 13 5 39 9 4 41 13 4 33 33
4 Dimethoate 20 8 42 23 7 32 16 10 61 19 13 69 20 10 49 49
5 Dicloran 18 7 41 26 8 31 19 13 69 20 13 66 22 11 50 50
6 Propyzamide 12 4 37 10 4 38 9 5 62 9 6 64 10 5 49 49
7 Pyrimethanil 16 8 53 17 7 44 12 9 77 15 11 78 15 9 61 61
8 Diazinon 9 1 16 5 5 90 5 3 62 6 4 66 5 4 67 67
9 Chlorothalonil 10 4 36 14 4 26 13 6 51 9 5 59 12 5 42 42
12 Chlorpyriphos methyl 10 1 7 8 1 14 7 1 13 6 3 42 7 1 17 17
14 Tolclophos methyl 9 1 13 7 2 33 5 2 32 5 2 48 6 2 34 34
15 Carbaryl 15 8 56 17 11 68 17 12 68 14 13 89 17 11 68 68
16 Metalaxyl 15 6 38 12 8 62 12 6 54 12 10 83 13 8 62 62
17 Fenitrothion 13 5 43 16 5 29 11 7 64 11 7 66 13 6 48 48
18 Pyrimiphos methyl 9 1 12 6 3 40 4 2 43 5 3 56 5 2 45 45
20 Diethofencarb 9 3 37 11 5 46 6 4 68 5 3 55 8 5 63 63
21 Chlorpyriphos 9 1 14 6 3 50 5 2 44 5 3 62 6 3 47 1
23 Tetraconazole 8 4 44 10 1 7 7 5 71 11 7 61 9 5 49 49
24 Cyprodinil 12 1 8 8 4 43 5 3 54 7 4 64 7 4 52 52
25 Penconazole 15 7 48 16 11 67 10 11 108 15 14 96 14 12 83 83
27 Tolylfluanid 12 2 17 13 6 43 10 5 51 14 8 58 13 6 47 47
28 Thiabenazole 32 5 14 33 11 33 26 14 54 27 26 97 30 18 58 58
29 Triadimenol 18 4 23 28 18 63 15 11 74 24 20 86 23 17 73 73
30 Procymidone 13 6 48 11 5 41 8 5 64 7 5 74 9 5 55 55
31 Methidathion 13 5 41 27 24 88 13 8 57 12 7 57 18 16 88 88
36 Flusilazole 15 5 36 18 9 51 15 8 56 22 20 89 19 13 69 69
38 Fludixonyl 16 7 46 19 9 48 15 9 65 15 12 80 17 10 58 58
39 Myclobutanil 10 3 32 10 3 32 6 3 47 24 29 117 13 17 130 130
43 Oxadixyl 19 23 125 27 29 108 7 1 16 9 9 96 15 19 127 127
44 Ethion 17 8 51 27 8 31 14 3 18 11 7 63 19 9 47 47
46 Endosulfan sulphate 15 2 14 16 7 44 14 6 46 14 10 71 15 7 48 1
56 Tebufenpyrad 15 11 73 13 10 82 5 4 71 6 4 65 9 7 87 87
57 Phosalone 15 4 30 22 10 45 21 11 53 21 16 76 22 12 53 U_150%
60 λ Cyhalothrine 9 2 22 8 3 38 5 4 78 6 4 61 6 3 54 54
61 Fenarimol 17 17 100 26 21 80 21 16 78 20 16 81 23 17 74 74
62 Bitertanol 28 11 41 34 19 55 32 25 78 30 32 105 33 24 73 73
64 Deltamethrin 20 5 26 20 7 34 12 9 73 10 7 68 15 8 55 55
65 Azoxystrobin 18 7 36 19 10 54 16 10 63 14 12 88 17 10 62 62
153
Guy Jamet – STRBG

154
Guy Jamet – STRBG
Proficiency testing
‣ Goal
‣ Avoiding false +
‣ Avoiding false –
‣ Statement of the uncertainty
‣ According the routine
‣ Residues unknown
‣ Ratio with number of
samples
‣ National BIPEA
‣ Known residues for
quantitative aim only
‣ International paying
‣ FAPAS Residues unknown
‣ EU Mandatory
‣ EUPT Residues unknown

Prediction of the proficiency testing
NOM : Jamet Date : 15/02/07 Identifiant : 80 Visa :
Désignation : EIL
N°CAS :
Essai(s) concerné(s) :
Méthode multirésidus : Résidus de pesticides
Exigences spécifiées :
Maintien d’accréditation multirésidus avec extension matrice et quantitatif
Exigence OAV exercice communautaire
Compléter les rubriques nécessaires à valider la sélection :
FAPAS
Pertinant MRM
Fournisseurs
Critères
Références
Conditionnem
ent
EUPT
Obligatoire
OAV
Avril 2007
EUPT 09 +
blanc
Fraise
(Offre BIPEA non
pertinante MRM)
Juin 2007
1970 + blanc
salade purée
Portée actuel
Bipea
Méthodes
orphelines
Bipea
Méthodes
orphelines
Avril 2007 Septembre 2007
200g 100 g 100g 100g 100g
Tarif HT 135 205 265 265 205
Autres frais lié
à la
commande
HT
Délai de
livraison
Conservation
(durée – T°C -
…)
Antériorité de
la commande
FAPAS
Pertinant MRM
(Offre BIPEA non
pertinante MRM)
Janvier 2008
1975 + blanc
Pomme purée
Extension
- 85 + 55 - - 85 + 55
-18° -18° -18° -18° -18°
oui oui non non oui
Sélection
retenue
oui oui oui
Approbation de la direction Accord sur la sélection Pas d’accord sur la sélection ;
autre choix :
NOM : Date : Visa :
Mise à jour de la base de données informatique
Base à jour base non à jour, codification :…………….(si existe) ou à
créer :……………
Responsable gestion, mise en conformité de la base, le : / / Visa :
155
Guy Jamet – STRBG

156
Guy Jamet – STRBG
Proficiency testing
‣ EUPT6: Tomato
‣ EUPT7: Grapes
‣ EUPT8: Aubergine
‣ EUPT9: Strawberry
‣ EUPT10: Carrot
‣ EUPT11: Cauliflower
‣ EUPT12: Leek

Z-score EUPT
157
Guy Jamet – STRBG

Z-score EUPT by round
158
Guy Jamet – STRBG

Z-score EUPT by analytes and different
concentration
159
Guy Jamet – STRBG

Interpretation of Z-score
No
Z score
Yes
Not sought for
Yes
-2

4,4' DDE 1963 0,164 0,187
Azinphos methyl 19101 0,94 0,155
Bifenthrin 19101 0,244 0,139
Bifenthrine 1970 0,136 0,0948
Boscalid 19101 0,356 0,419
Bupirimate 1991 0,149 0,148
Carbaryl 1998 0,242 0,652
Chlorfenvinphos 1963 0,0743 0,098
Chlorpyriphos 1975 0,0457 0,0397
Cypermethrine 1963 0,602 0,43861
Dicloran 1998 0,228 0,429
Iprodione 1958 0,772 1,407
Iprodione 1991 0,539 0,366
Mecarbam 1963 0,0804 0,099
Metalaxyl 1958 0,186 0,465
Methidathion 1970 0,119 0,16874
Methidathion 1998 0,262 0,322
Pendimethaline 1998 0,299 0,328
Permethrine 1991 0,0475 0,0612
Propargite 1975 0,375 0,36
Pyrimicarbe 1975 0,0702 nd
PyrimME 1958 0,262 0,676
Quintozene 1958 0,0796 0,182
Tecnazene 1958 0,0862 0,242
161
Guy Jamet – STRBG
Thiabendazole 1991 0,0285 0,025
Trifloxystrobine 1991 0,278 0,217
Z-score FAPAS
Z score FAPAS /Residues
10
8
6
4
2
0
-2
-4
-6
Target Lab Z-score

162
Guy Jamet – STRBG
Reason of Z score EUPT
Round Residue Target Lab Z-score lab Matrix Comments
6 Azoxystrobin 0,225 ND -3,1 Tomato Homogeneity
6 Chlorothalonil 1,626 0,655 -2,4 Tomato Homogeneity
6 Diazinon 3,955 1,036 -3 Tomato Homogeneity
6 Dimethoate 0,132 0,028 -3,2 Tomato Homogeneity
6 Procymidone 0,412 0,0423 -3,5 Tomato Homogeneity
7 Dimethoate 0,139 0,04 -2,8 Grapes Residue
7 Fludioxonil 0,238 0,05 -3,2 Grapes Residue
7 Monocrotophos 0,643 0,1 -3,8 Grapes Residue
8 Fludioxonil 1,27 2,14 2,7 Aubergine Residue
8 Parathion 0,16 0,25 2,2 Aubergine Co elution
9 Fenhexamid 0,34 0,535 2,2 Straw berry Residue
9 Hexythiazox 1,05 1,81 2,9 Straw berry Residue
10 Endosulfan 0,106 0,194 2,4 Carrot Residue
10 Pendimethalin 0,076 ND -3,5 Carrot LOD
10 Phosmet 0,233 0,196 2,2 Carrot 1 ion
11 Azinphos 0,355 0,811 5,1 Cauliflow er 1 ion
11 Methidathion 0,472 0,06 -3,5 Cauliflow er Mass of ion
12 Azinphos methyl 0,048 ND -3,2 Leek 1 ion
12 Chlorothalonil 0,216 0,07 -2,7 Leek Residue
12 Fenpropathrin 0,062 ND -3,4 Leek LOD

Decision of the scope
‣ Sequence
‣ Routinely the sequence looks like following: solvent, std 5000 ppb, 2000 ppb, 1000 ppb,
500 ppb, 200 ppb, 100 ppb, 12 vials (representing the concentration of 10 g matrix per ml
and the 1/10 th dilution and finally 3x the re-injection of std 1000 ppb
‣ Characterisation of the sequence by
‣ The repeatability “r” of std 1000 ppb at each sequence
‣ The intermediate precision “IP” after 3 sequences (3 different days)
‣ The lower upper acceptable limits for the following residues
‣ OPP, DIPHENILAMINE, CCHLORPROPHAME, DIMETHOATE,
PROPYZAMIDE, PYRIMETHANIL, PYRIMICARB, VINCLOZOLIN,
CHLORPYRIPHOS METHYL, PARARTHION METHYL, TOLCLOPHOS
METHYL, CARBARYL, METALAXYL, MALATHION, CHLORPYRIPHOS,
CYPRODINIL, CHLORFENVINPHOS, TOLYLFLUANID, PPROCYMIDONE,
METHIDATHION, α ENDOSULFAN, IMAZALIL, FLUDIOXONIL, KRESOXIM
METHYL, β ENDOSULFAN, OXADIXYL, ETHION, ENDOSULFAN
SULPHATE, TEBUCONAZOLE, PROPARGITE, IPRODIONE, PHOSMET,
BROMOPROPYLAT, BIFENTHRINE,TEBUFENPYRAD, PHOSALONE, λ
CYHALOTHRIN, α CYPERMETHRIN, DELTAMETHRIN, AZOXYSTROBINE
‣ The results are issued from Excel using the profile of accuracy from these generated by
the GC/MS
163
Guy Jamet – STRBG

Validation of the deviation
Lim inf Tol inf M oyenne Tol sup Lim sup
OPP 800 918 1007 1096 1200
Diphenylamine 800 932 998 1064 1200
Chlorpropham 800 897 995 1093 1200
Dimethoate 800 806 1100 1394 1200
Propyzamide 800 944 993 1042 1200
Pyrimethanil 800 940 991 1042 1200
Pyrimicarb 800 928 1005 1083 1200
Vinclozoline 800 902 967 1031 1200
Chlorpyriphos methyl 800 953 996 1040 1200
Parathion methyl 800 767 1009 1251 1200
Tolclophos methyl 800 954 988 1021 1200
Carbaryl 800 916 1039 1163 1200
M etalaxyl 800 923 989 1054 1200
M alathion 800 942 983 1024 1200
Chlorpyriphos 800 942 969 996 1200
Cyprodinil 800 919 963 1007 1200
Chlorfenvinphos Z 800 938 999 1061 1200
Tolylfluanid 800 214 1324 2435 1200
Chlorfenvinphos E 800 910 987 1064 1200
Procymidone 800 940 972 1004 1200
M ethidathion 800 888 982 1076 1200
α Endosulfan 800 868 1009 1149 1200
Imazalil 800 -345 1009 2362 1200
Fludixonyl 800 -2 437 877 1200
Kresoxym methyl 800 867 933 999 1200
β Endosulfan 800 903 1063 1223 1200
Oxadixyl 800 766 870 973 1200
Ethion 800 835 908 982 1200
Endosulfan sulphate 800 715 1152 1589 1200
Tebuconazole 800 491 882 1274 1200
Propargite 800 684 1093 1502 1200
Iprodione 800 346 766 1186 1200
Phosmet 800 145 667 1189 1200
Bromopropylate 800 900 979 1058 1200
Bifenthrin 800 781 911 1040 1200
Tebufenpyrad 800 831 942 1054 1200
Phosalone 800 721 877 1034 1200
λ Cyhalothrin 800 754 882 1010 1200
α Cypermethrin 800 292 741 1191 1200
Deltamethrin 800 192 682 1173 1200
Azoxystrobin 800 -2752 932 4617 1200
164
Guy Jamet – STRBG

Variability
OPP
Dip
Chl
Dim
Pro
Pyri
Pyri
Vin
Chl
Par
Tolc
Car
Met
Mal
Chl
Cyp
Chl
Toly
Chl
Pro
Met
End
Ima
Flud
Kre
End
Oxa
Diet
End
Teb
Pro
Ipro
Pho
Bro
Bife
Teb
Pho
lam
Alp
Delt
Azo
165
Guy Jamet – STRBG
Validation of the residues
Limites d'acceptation absolues du point 1000 ppb
5000
4000
3000
2000
1000
0
-1000
-2000
-3000
-4000
Matières actives
#REF! Lim inf Tol inf Moyenne Tol sup Lim sup

Variability
OPP
Diphenylamine
Chlorprophame
Dimethoate
Propyzamide
Pyrimethanil
Pyrimicarbe
Vinclozoline
Chlorpyriphos methyl
Parathion methyl
Tolclophos methyl
Carbaryl
Metalaxyl
Malathion
Chlorpyriphos ethyl
Cyprodinil
Chlorfenvinphos Z
Chlorfenvinphos E
Procymidone
Methidathion
Bromopropylate
Bifenthrine
Tebufenpyrad
Oxadixyl
Diethion
Kresoxym methyl
lambda cyhalothryne
Phosalone
Endosulfan beta
Endosulfan alpha
166
Guy Jamet – STRBG
Amenable Residues
Residues with acceptable variability
25%
20%
15%
10%
5%
0%
-5%
-10%
-15%
-20%
-25%
Residues
Lim inf -20% rsdr % rsdFI % Biais (%) Lim sup 20%

Variability
Imazalil
Fludixonyl
Endosulfan sulfate
Tebuconazole
Propargite
Iprodione
Phosmet
Alpha cypermethrine
Deltamethrine
Azoxystrobine
Tolylfluanide
Not amenable Residues
Residues out of limits
140%
120%
100%
80%
60%
40%
20%
0%
-20%
-40%
-60%
-80%
Residues
Lim inf -20% rsdr % rsdFI % Biais (%) Lim sup 20%
167
Guy Jamet – STRBG

Sequence
Line Type Vial DataFile Method Sample
1 Sample 1 -------- PEST5SPE C1 5000
2 Sample 2 -------- PEST5SPE C1 2000
3 Sample 3 -------- PEST5SPE C1 1000
4 Sample 4 -------- PESTSSPE C1 500
5 Sample 5 -------- PEST5SPE C1 200
6 Sample 6 -------- PEST5SPE C1 100
7 Sample 7 -------- PEST5SPE Ech 1 1/1
8 Sample 8 -------- PEST5SPE Ech 1 1/10
9 Sample 9 -------- PEST5SPE Ech 2 1/1
10 Sample 10 -------- PEST5SPE Ech 2 1/10
11 Sample 11 -------- PEST5SPE Ech 3 1/1
12 Sample 12 -------- PEST5SPE Ech 3 1/10
13 Sample 13 -------- PEST5SPE Ech 4 1/1
14 Sample 14 -------- PEST5SPE Ech 4 1/10
15 Sample 15 -------- PEST5SPE Ech 5 1/1
16 Sample 16 -------- PEST5SPE Ech 5 1/10
17 Sample 17 -------- PEST5SPE Ech 6 1/1
18 Sample 18 -------- PEST5SPE Ech 6 1/10
19 Sample 19 -------- PEST5SPE Ech 7 1/1
20 Sample 20 -------- PEST5SPE Ech 7 1/10
21 Sample 21 -------- PEST5SPE Ech 8 1/1
22 Sample 22 -------- PEST5SPE Ech 8 1/10
23 Sample 23 -------- PEST5SPE Ech 9 1/1
24 Sample 24 -------- PEST5SPE Ech 9 1/10
25 Sample 25 -------- PEST5SPE Ech 10 1/1
26 Sample 26 -------- PEST5SPE Ech 10 1/10
27 Sample 27 -------- PEST5SPE Ech 11 1/1
28 Sample 28 -------- PEST5SPE Ech 11 1/10
29 Sample 29 -------- PEST5SPE Ech 12 1/1
30 Sample 30 -------- PEST5SPE Ech 12 1/10
31 Sample 3 -------- PESTSSPE C1 1000
32 Sample 3 -------- PESTSSPE C1 1000
33 Sample 3 -------- PESTSSPE C1 1000
34 Sample 1 -------- PEST5SPE C2 5000
35 Sample 2 -------- PEST5SPE C2 2000
36 Sample 3 -------- PEST5SPE C2 1000
37 Sample 4 -------- PEST5SPE C2 500
38 Sample 5 -------- PEST5SPE C2 200
39 Sample 6 -------- PEST5SPE C2 100
168
Guy Jamet – STRBG

169
Guy Jamet – STRBG
Deviation
Pyrimethanil
Concentration ppb Mean rsd_Mean
100 0,56 47%
200 0,96 131%
500 2,64 76%
1000 6,87 65%
2000 15,14 24%
5000 36,86 21%
Cyprodinil
Concentration ppb Mean rsd_Mean
100 0,55 48%
200 0,99 58%
500 2,48 33%
1000 5,68 30%
2000 11,44 20%
5000 27,81 17%
Iprodione
Concentration ppb Mean rsd_Mean
100 0,06 64%
200 0,14 107%
500 0,39 46%
1000 0,64 68%
2000 1,24 22%
5000 3,15 17%
λ Cyhalothrin
Concentration Mean rsd_Mean
100 0,28 60%
200 0,59 119%
500 1,57 57%
1000 2,36 68%
2000 4,71 25%
5000 11,58 22%

170
Guy Jamet – STRBG
Repeatability, Intermediate fidelity of
calibration
Pyrimethanil
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,558 -0,09 48% 35% 48%
C_200 0,963 -0,14 88% 86% 88%
C_500 2,635 -0,11 60% 51% 60%
C_1000 6,874 -0,03 44% 25% 4%
C_2000 15,141 0,10 15% 22% 2%
C_5000 36,865 0,08 11% 20% 1%
Cyprodinil
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,554 0,14 50% 46% 50%
C_200 0,993 -0,01 33% 35% 33%
C_500 2,484 0,03 31% 34% 31%
C_1000 5,675 0,02 15% 21% 5%
C_2000 11,443 0,04 15% 22% 2%
C_5000 27,808 0,02 12% 20% 1%
Iprodione
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,061 0,01 54% 73% 66%
C_200 0,141 0,02 39% 47% 43%
C_500 0,389 0,18 66% 37% 66%
C_1000 0,644 -0,04 18% 16% 6%
C_2000 1,240 0,01 16% 24% 3%
C_5000 3,147 -0,01 12% 19% 1%
λ Cyhalothrin
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,284 0,01 43% 51% 43%
C_200 0,594 0,08 61% 36% 61%
C_500 1,567 0,26 72% 32% 72%
C_1000 2,358 -0,03 22% 22% 5%
C_2000 4,711 0,01 23% 26% 3%
C_5000 11,578 0,00 18% 23% 1%

Response
171
Guy Jamet – STRBG
Profile of calibration PYRIMETHANIL
Pyrimethanil
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,56 -9% 48% 35% 48%
C_200 0,96 -14% 88% 86% 88%
C_500 2,64 -11% 60% 51% 60%
C_1000 6,87 -3% 44% 25% 4%
C_2000 15,14 10% 15% 22% 2%
C_5000 36,86 8% 11% 20% 1%
Pyrimethanil (IS)
50,00
40,00
30,00
20,00
Pyrimethanil
y = 0,0075x - 0,5055 R2 = 0,9991
y = -8E-08x2 + 0,0079x - 0,6962 R2 = 0,9992
10,00
0,00
0 1000 2000 3000 4000 5000 6000
-10,00
Concentration (ppb)
Min Mean Max Linéaire (Max) Linéaire (Min) Linéaire ( Mean )

Response
172
Guy Jamet – STRBG
Profile of calibration CYPRODINIL
Cyprodinil
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,55 14% 50% 46% 50%
C_200 0,99 -1% 33% 35% 33%
C_500 2,48 3% 31% 34% 31%
C_1000 5,68 2% 15% 21% 5%
C_2000 11,44 4% 15% 22% 2%
C_5000 27,81 2% 12% 20% 1%
Cyprodinil (IS)
35,00
30,00
25,00
20,00
15,00
10,00
Cyprodinyl
y = 0,0056x - 0,0472 R2 = 0,9996
y = -6E-08x2 + 0,0059x - 0,2035 R2 = 0,9998
5,00
0,00
0 1000 2000 3000 4000 5000 6000
-5,00
Concentration (ppb)
Min Mean Max Linéaire (Max) Linéaire ( Mean ) Linéaire (Min)

Response
173
Guy Jamet – STRBG
Profile of calibration IPRODIONE
Iprodione
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,06 1% 54% 73% 66%
C_200 0,14 2% 39% 47% 43%
C_500 0,39 18% 66% 37% 66%
C_1000 0,64 -4% 18% 16% 6%
C_2000 1,24 1% 16% 24% 3%
C_5000 3,15 -1% 12% 19% 1%
Iprodione (IS)
4,00
3,50
3,00
2,50
2,00
1,50
Iprodione
y = 0,0006x + 0,0212 R2 = 0,9993
y = 3E-09x2 + 0,0006x + 0,0296 R2 = 0,9993
1,00
0,50
0,00
0 1000 2000 3000 4000 5000 6000
-0,50
Concentration (ppb)
Min Mean Max Linéaire ( Mean ) Linéaire (Max) Linéaire (Min)

Response
174
Guy Jamet – STRBG
Profile of calibration λ CYHALOTHRIN
λ Cyhalothrin
Concentration Mean bias rsd_r rsd_Ro rsd_IP
C_100 0,28 1% 43% 51% 43%
C_200 0,59 8% 61% 36% 61%
C_500 1,57 26% 72% 32% 72%
C_1000 2,36 -3% 22% 22% 5%
C_2000 4,71 1% 23% 26% 3%
C_5000 11,58 0% 18% 23% 1%
λ Cyhalothrin (IS)
16,00
14,00
12,00
10,00
8,00
6,00
λ Cyhalothrin
y = 0,0023x + 0,1691 R2 = 0,999
y = -9E-11x2 + 0,0023x + 0,1689 R2 = 0,999
4,00
2,00
0,00
0 1000 2000 3000 4000 5000 6000
-2,00
Concentration (ppb)
Min Mean Max Linéaire (Min) Linéaire (Max) Linéaire ( Mean )

175
Guy Jamet – STRBG
Repeatability, Intermediate fidelity on
Salad at different concentrations
Pyrimethanil 198
Conc mg/kg Mean bias rsd_r rsd_R rsd_IP
LMR/10s 0,2 0,43 0,2% 0,6% 15,6% 15,9%
LMR/10e 0,2 0,42 0,2% 1,9% 13,9% 14,5%
LMR/2e 1 1,10 0,1% 2,3% 17,2% 17,5%
LMRe 2 2,93 1,9% 13,7% 20,3% 2,3%
Cyprodinil 224
Conc mg/kg Mean bias rsd_r rsd_R rsd_IP
LMR/10s 1 1,16 0,16% 2,25% 24,62% 25,04%
LMR/10e 1 1,09 0,09% 2,55% 28,05% 28,53%
LMR/2e 5 5,19 0,19% 1,84% 10,69% 10,87%
LMRe 10 10,05 5,05% 9,94% 14,78% 2,88%
Iprodione 314
Conc mg/kg Mean bias rsd_r rsd_R rsd_IP
LMR/10s 1 1,42 0,4% 4,0% 5,1% 4,6%
LMR/10e 1 1,37 0,4% 2,6% 2,3% 2,6%
LMR/2e 5 5,19 0,2% 2,4% 8,9% 8,9%
LMRe 10 11,34 6,3% 8,8% 9,1% 0,6%
λ Cyhalothrin 181
Conc mg/kg Mean bias rsd_r rsd_R rsd_IP
LMR/10s 0.1 0,15 0,05% 4,10% 3,91% 4,10%
LMR/10e 0.1 0,15 0,05% 8,54% 8,06% 8,54%
LMR/2e 0.5 0,61 0,11% 1,94% 9,64% 9,75%
LMRe 1.0 1,27 0,77% 7,37% 15,28% 0,47%

176
Guy Jamet – STRBG
Repeatability, Intermediate fidelity on
different matrices at 0.01 mg/kg
Pyrimethanil
Matrix Mean bias rsd_r rsd_IP
Carrot 169 6% 17% 45%
Apple 122 12% 13% 89%
Salad 168 12% 26% 69%
Cyprodinil
Matrix Mean bias rsd_r rsd_IP
Carrot 84 0% 46% 46%
Apple 43 9% 54% 57%
Salad 74 -1% 49% 49%
Iprodione
Matrix Mean bias rsd_r rsd_IP
Carrot 70 -24% 32% 64%
Apple 102 24% 141% 141%
Salad 87 78% 37% 101%
λ Cyhalothrin
Matrix Mean bias rsd_r rsd_IP
Carrot 72 -2% 32% 57%
Apple 57 -10% 21% 44%
Salad 74 1% 23% 27%

177
Guy Jamet – STRBG
On going control: identification and
confirmation

On going control
Cocktail C1-C2 (Accredited)
0.1 0.2 0.5
LMRP
RRT / ng/ml ng/ml ng/ml
Aldrin 0.01 0.02 0.05
mg/kg
mg/kg mg/kg mg/kg
Operator
α CYPERMETHRINE 1,5 0,05 Agi-AM Agi-AM Agi-AM NN
BIFENTHRIN 1,4 0,05 Agi-AM Agi-AM Agi-AM NN
BROMOPROPYLATE 1,4 0,05 Agi-AM Agi-AM Agi-AM NN
CARBARYL 0,9 0,05 AM AM AM NN
CHLORFENVINPHOS 1,1 0,02 Agi-AM Agi-AM Agi-AM NN
CHLORPROPHAM 0,7 0,05 Agi-AM Agi-AM Agi-AM NN
CHLORPYRIPHOS 1 0,05 Agi-AM Agi-AM Agi-AM NN
CHLORPYRIPHOS METHYL 0,9 0,05 Agi-AM Agi-AM Agi-AM NN
CYPRODINIL 1,1 0,01 Agi-AM Agi-AM Agi-AM NN
ETHION 1,2 0,01 Agi-AM Agi-AM Agi-AM NN
DIMETHOATE 0,8 0,02 Agi-AM Agi-AM Agi-AM NN
DIPHENYLAMINE 0,7 0,05 Agi-AM Agi-AM Agi-AM NN
α ENDOSULFAN 1,1 0,05 Agi-AM Agi-AM Agi-AM NN
β ENDOSULFAN 1,2 0,05 AM Agi-AM Agi-AM NN
ENDOSULFAN SULPHATE 1,3 0,05 AM AM AM NN
IPRODIONE 1,4 0,02 Agi-AM Agi-AM Agi-AM NN
KRESOXIM METHYL 1,2 0,05 Agi-AM Agi-AM Agi-AM NN
λ CYHALOTHRIN 1,5 0,02 Agi-AM Agi-AM Agi-AM NN
MALATHION 1 0,02 Agi-AM Agi-AM Agi-AM NN
METALAXYL 1 0,05 Agi-AM Agi-AM Agi-AM NN
OPP (2-Phénylphénol) 0,6 0,01 Agi-AM Agi-AM Agi-AM NN
OXADIXYL 1,2 0,05 AM NN
PARATHION METHYL 0,9 0,02 AM AM NN
PHOSALONE 1,4 0,05 Agi-AM Agi-AM Agi-AM NN
PROCYMIDONE 1,1 0,02 Agi-AM Agi-AM Agi-AM NN
PROPARGITE 1,3 0,01 Agi-AM Agi-AM Agi-AM NN
PROPYZAMIDE 0,8 0,02 Agi-AM Agi-AM Agi-AM NN
PYRIMETHANIL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN
TEBUCONAZOLE 1,3 0,01 Agi-AM Agi-AM Agi-AM NN
TEBUFENPYRAD 1,4 0,05 Agi-AM Agi-AM Agi-AM NN
TOLCLOPHOS METHYL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN
VINCHLOZOLINE 0,9 0,05 AM AM NN
178
Guy Jamet – STRBG

On going control
Sequence : 11/03/02
N° of samples: 12
Date : 11/03/03
Action : yes no
Cocktail C1-C2 (Not
ccredited)
RRT /
Aldrin
LMRP
mg/kg
0.1 ng/ml 0.2 ng/ml 0.5 ng/ml
0.01 0.02 0.05
mg/kg mg/kg mg/kg
Operator
AZINPHOS METHYL 1,4 0,01 AM Agi-AM Agi-AM NN
AZOXYSTROBIN 2 0,05 AM AM AM NN
BENALAXYL 1,3 0,05 AM Agi-AM Agi-AM NN
BITERTANOL 1,5 0,05 Agi Agi-AM Agi-AM NN
BOSCALID 1.6 0.01 AM Agi-AM Agi-AM NN
BUPIRIMATE 1,2 0,01 AM AM AM NN
BUPROFEZINE 1,2 0,01 AM AM AM NN
CHLOROTHALONIL 0,9 0,01 Agi-AM Agi-AM Agi-AM NN
CHLORTHAL DIMETHYL 1 0,01 AM AM AM NN
DELTAMETHRIN 1,9 0,05 AM AM AM NN
DIAZINON 0,9 0,02 Agi-AM Agi-AM Agi-AM NN
DICLORAN 0,8 0,01 AM AM AM NN
DIELDRIN 1,2 0,01 Agi-AM Agi-AM Agi-AM NN
DIETHOFENCARB 1 0,01 Agi-AM Agi-AM Agi-AM NN
FENARIMOL 1,5 0,02 Agi-AM Agi-AM Agi-AM NN
FENHEXAMID 1,3 0,05 AM AM Agi-AM NN
FENITROTHION 1 0,05 Agi-AM Agi-AM Agi-AM NN
FLUDIOXONIL 1,2 0,01 AM AM NN
FLUSILAZOLE 1,2 0,01 Agi-AM Agi-AM Agi-AM NN
IMAZALIL 1,2 0,02 AM AM AM NN
MAPANIPYRIM 1,1 0,02 Agi-AM Agi-AM Agi-AM NN
METHIDATHION 1,1 0,02 Agi-AM Agi-AM Agi-AM NN
MYCLOBUTANIL 1,2 0,02 Agi-AM Agi-AM Agi-AM NN
PENCONAZOLE 1,1 0,05 Agi-AM Agi-AM Agi-AM NN
PHOSMET 1,4 0,01 Agi-AM Agi-AM Agi-AM NN
PIPERONYL BUTOXYDE 1,3 0,05 AM AM AM NN
PYRIMICARB 0,9 0,02 Agi-AM Agi-AM Agi-AM NN
PYRIMIPHOS METHYL 1 0,05 Agi-AM Agi-AM Agi-AM NN
PYROPROXYFEN 1,4 0,01 Agi-AM Agi-AM Agi-AM NN
TETRACONAZOLE 1 0,01 Agi-AM Agi-AM Agi-AM NN
THIABENDAZOLE 1,1 0,05 Agi-AM Agi-AM Agi-AM NN
TOLYLFLUANID 1,1 0,01 AM AM AM NN
TRIADIMENOL 1,1 0,1 Agi-AM Agi-AM Agi-AM NN
TRIFLOXYSTOBIN 1,3 0,05 Agi-AM Agi-AM AM NN
179
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180
Guy Jamet – STRBG
Conclusion
‣ Pour profile for
PYRIMETHANIL,
‣ Large variability at 100 ppb
(0.01 mg/kg):
‣ IPRODIONE
‣ PROCYMIDONE
‣ CHLORFENVINPHOS
‣ VINCLOZOLINE
‣ λ CYHALOTHRIN
‣ Acceptable at every levels
‣ ETHION
‣ CYPRODINIL
‣ TOLCLOPHOS METHYL
‣ Remarks of accreditation bodies
‣ OK for leafy vegetables
‣ OK for representative analytes
‣ Uncertainty: Horwitz
‣ Not enough value for a
quantitative accreditation
‣ Qualitative accreditation
accorded based on the
identification and
proficiency testing

181
Guy Jamet – STRBG
2 nd step of the accreditation
Objective Measured parameters
Principe of the method Reference of the method
Qualitative determination of pesticide residues
α Cypermethrin Kresoxim Methyl
Bifenthrine
λ Cyhalothrin
Bromopropylate Malathion
Carbaryl
Metalaxyl
Chlorfenvinphos OPP (2 Phénylphénol)
Internal Method
Chlorprophame Oxadixyl
IN167/80/ANA/02
Chlorpyriphos Parathion Methyl Extraction w ith solvent
IN167/80/ANA/26
Salads Chlorpyriphos Methyl Phosalone
Purification by Liquid-liquid partition Adapted from standards
Cyprodinil
Procymidone
Analysis by GC/MS
NF EN 12393-1
Ethion
Propargite
NF EN 12393-2
Dimethoate
Propyzamide
NF EN 12393-3
Diphenylamine Pyrimethanil
Endosulfan Sulphate Tebuconazole
α Endosulfan
Tebufenpyrad
β Endosulfan
Tolclophos Methyl
Iprodione
Vinchlozoline

Amenable recovery on apples (60-140%)
mg/kg 0,02 0,06 0,12
OPP 88% 80% 75%
Chlorothalonil 105% 82% 78%
Vinclozoline 85% 77% 75%
Parathion Methtyl 65% 94% 83%
Tolclophos Methyl 83% 74% 73%
Metalaxyl 90% 75% 73%
Fenitrothion 77% 76% 78%
Malathion 88% 75% 71%
Chlorpyriphos 78% 76% 71%
Chlorthal dimethyl 73% 82% 74%
α Endosulfan 92% 72% 85%
Dieldrin 82% 79% 74%
Kresoxim Methyl 85% 86% 86%
Benalaxyl 78% 78% 75%
Endosulfan sulphate 70% 67% 93%
Iprodione 88% 78% 76%
Phosmet >140% 88% 117%
Bifenthrin 73% 81% 78%
Tebufenpyrad 82% 84% 83%
Phosalone 123% 109% 103%
Pyriproxyfen 80% 83% 81%
Fenarimol 118% 72% 64%
Bitertanol 95% 67% 62%
α Cypermethrin 97% 89% 84%
Azoxystrobin 105% 74% 66%
182
Guy Jamet – STRBG

183
Guy Jamet – STRBG
Low and exceeding recoveries on apples
mg/kg 0,02 0,06 0,12
Diphenylamine

184
Guy Jamet – STRBG
Extending recovery on apples
‣ 0.02, 0.06, 0.12 mg/kg
‣ 3 repetitions at each level
‣ Apples
‣ 3 series foreseen
‣ Results of the first round

Unexplainable recoveries on apples
Matrix
Straw berry Witloof Leek Leek Witloof Salad Straw berry Salad
mg/kg
0,02 0,05 0,10
Dieldrin >140%
Fludioxonil
Myclobutanil >140%
Buprofezine 74% 88% 72% 97% 78%
Flusilazole 66% 140%>140% >140% >140% >140%
Propargite
Pipronyl butoxyde >140%>140%>140%>140% 129% 134% >140%
Iprodione >140% 93%
Phosmet >140%
Bromopropylate 93% 75% 76% 76%
Bifenthrin 115%

186
Guy Jamet – STRBG
Exceeding recovery at low
concentration on apples
mg/kg 0,02 0,06 0,12
Dicloran >140% 97% 78%
Chlorpyriphos Methtyl >140% 90% 71%
Penconazole >140% 60% 140% 116% 116%
Azinphos Methyl >140% 64% 66%
Boscalid >140% 92% 77%
β Endosulfan >140% 90% 82%
Fenhexamid >140% 126% 120%

187
Guy Jamet – STRBG
Recoveries on different matrices (2)
Matrix Straw berry Witloof Leek Leek Witloof Salad Straw berry Salad
mg/kg
0,02 0,05 0,10
OPP 80% 140% >140% >140%
Tolclophos methyl >140% >140% 97% 92% >140% 102% 111% 117%
Metalaxyl 122% 75% 66% 84%
Pyrimiphos methyl >140% >140% >140% 108% 116% 119%
Malathion >140% 119% 120% >140%
Diethofencarb >140% 124% 113% >140%

Recoveries on different matrices (1)
Matrix Strawberry Witloof Leek Leek Witloof Salad Strawberry Salad
mg/kg
0,02 0,05 0,10
OPP 80% 140% >140% >140%
Tolclophos methyl >140% >140% 97% 92% >140% 102% 111% 117%
Metalaxyl 122% 75% 66% 84%
Pyrimiphos methyl >140% >140% >140% 108% 116% 119%
Malathion >140% 119% 120% >140%
Diethofencarb >140% 124% 113% >140%
Chlorthal dimethyl 74% 70% 140% >140% 98% >140%
Penconazole >140% 70% 71% 75% 68% 74%
Procymidone 78% 71% 73%
Buprofezine 74% 88% 72% 97% 78%
Flusilazole 66% 140% >140% >140%
Tebuconazole >140% >140% >140% >140% >140%
Pipronyl butoxyde >140% >140% >140% >140% 129% 134% >140%
Bromopropylate 93% 75% 76% 76%
Bifenthrin 115%

189
Guy Jamet – STRBG
Recoveries on different matrices
‣ Strawberries: 0.02, 0.05, 0.1 mg/kg
‣ Leeks: 0.05 mg/kg, 2 times
‣ Salads: 0.1 mg/kg, 2 times
‣ Witloof : 0.05, 0.1 mg/kg

190
Guy Jamet – STRBG
No recovery on different matrices (3)
‣ DIMETHOATE
‣ DICLORAN
‣ CHLOROTHALONIL
‣ PARATHION METHYL
‣ CARBARYL
‣ TOLYLFLUANID
‣ THIABENDAZOLE
‣ TRIADIMENOL
‣ α ENDOSULFAN
‣ DIELDRIN
‣ FLUDIOXONIL
‣ MYCLOBUTANIL
‣ IMAZALIL
‣ β ENDOSULFAN
‣ OXADIXYL
‣ ENDOSULFAN SULPHATE
‣ FENHEXAMID
‣ PHOSALONE
‣ AZINPHOS METHYL
‣ FENARIMOL
‣ PROPARGITE
‣ PHOSMET
‣ BITERTANOL
‣ BOSCALID
‣ DELTAMETHRIN
‣ AZOXYSTROBIN

Dossier of validation for GC-MS
191
Guy Jamet – STRBG

192
Guy Jamet – STRBG
Opening on the QuEChERS method
and LC-MS/MS

193
Guy Jamet – STRBG
Validation for LC-MS/MS
QuEChERS
EN NF 15662
‣ Determination of pesticides residues using
GC-MS and/or LC-MS/MS following
acetonitrile extraction/partitioning and
clean-up by dispersive SPE – QuEChERS
method

194
Guy Jamet – STRBG
Layout of the characterization
‣ Plan A:
‣ Response of the system
‣ Working range
‣ Plan B:
‣ Specificity:
‣ Recovery
‣ Plan C:
‣ Plan D
‣ Repeatability
‣ Intermediate Precision
‣ 10 levels from 0.003 to 2µg/ml
‣ Critical value
F(1, p(n – 1), 1 – α) by 1% of
accuracy
‣ apples, carrot, salad, lemon
‣ Regression slope = 1
‣ Blank, 0.02, 0.1, 1.0 mg/kg
‣ 3 repetitions, 3 levels
‣ sd repeatability
‣ 1 repetition, 3 levels
‣ sd Intermediate Precision
(

Working plan for the determination of all the
parameters
Recovery
Operator 1
D1
Operator 2
D7
Matrix Apple
Operator 3
D8
Operator 4
D9
Operator 5
D10
Repeatability Intermediate precision Intermediate precision Intermediate precision Intermediate precision
Blank x x x x x x x
0.02 mg/Kg x x x x x x x
0.1 mg/Kg x x x x x x x
1.0 mg/Kg x x x x x x x
Matrix Salad
Operator 1 Operator 2 Operator 3 Operator 4 Operator 5
Recovery
D6 D2 D8 D9 D10
Intermediate precision Repeatability Intermediate precision Intermediate precision Intermediate precision
Blank x x x x x x x
0.02 mg/Kg x x x x x x x
0.1 mg/Kg x x x x x x x
1.0 mg/Kg x x x x x x x
Matrix carrot
Operator 1 Operator 2 Operator 3 Operator 4 Operator 5
Recovery
D6 D7 D3 D9 D10
Intermediate precision Intermediate precision Repeatability Intermediate precision Intermediate precision
Blank x x x x x x x
0.02 mg/Kg x x x x x x x
0.1 mg/Kg x x x x x x x
1.0 mg/Kg x x x x x x x
Matrix lemon
Operator 1 Operator 2 Operator 3 Operator 4 Operator 5
Recovery
D6 D7 D8 D4 D10
Intermediate precision Intermediate precision Intermediate precision Repeatability Intermediate precision
Blank x x x x x x x
0.02 mg/Kg x x x x x x x
0.1 mg/Kg x x x x x x x
1.0 mg/Kg x x x x x x x
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Interpretation
Linearity
Specificity
YES
Linear model
No
YES
Specific method
No matrix effect
No
Working range of linear model
LOD
LOQ
Working range of quadratic model
LOD
LOQ
Calibration with standards in
solvent: acetonitrile
Calibration with standards in
matrix extract
Recovery
Intermediate Precision (IP)
YES
70%< Recovery

Response (area)
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Fitting of the response
‣ Response of LC in
solvent: acetonitrile
R (Pearson) = 0.979
3000000000
2500000000
Fittting of the response of Carbendazime
‣ Polynomial equation of
the 1 st degree: R 2 =0.954
2000000000
1500000000
1000000000
‣ Polynomial equation of
the 2 nd degree: R 2 =0.986
500000000
0
0,000 0,500 1,000 1,500 2,000 2,500
Concentration
‣ Polynomial equation of
the 3 rd degree: R 2 =0.999

Responses
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Specificity on a polynomial equation of
the 1 st degree
Specificity on polynomial equation of 1st degree
‣ Ideal fitting y = x, no
matrix effect
‣ Carrots: R 2 = 0.9994
‣ Salads: R 2 = 0.9867
‣ Apples: R 2 = 0.9977
Standards
‣ Lemons: R 2 = 0.9996

Predicted concentrations
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Specificity on a polynomial equation of
the 3 rd degree
0,600
0,500
0,400
Specificity on polynomial equation of 3rd degree
‣ Ideal fitting y = x, no
matrix effect
‣ Carrots: R 2 = 0.9996
‣ Salads: R 2 = 0.996
0,300
‣ Apples: R 2 = 0.9977
0,200
0,100
‣ Lemons: R 2 = 0.9997
0,000
0,000 0,100 0,200 0,300 0,400 0,500 0,600
Initial concentrations

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Recovery
‣ Against solvent
‣ On blank matrix spiked before extraction
‣ On blank matrix extract spiked after extraction
‣ Real recovery
‣ Matrix effect

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CARBENDAZIME real recovery at
0.02 mg/kg
Spiking level
0,02 mg/kg
Matrix carotts salads Apples Lemons All
Repet_1 87,5% 131,3% 33,3% 600,0%
Repet_2 100,0% 108,3% 88,2% 50,0%
Repet_3 111,1% 100,0% 133,3% 157,1%
Repet_4 100,0% 116,7% 146,2% 325,0%
mean 100% 114% 100% 283% 149%
sd 10% 13% 51% 240% 136%
rsd 9,7% 11,7% 50,9% 84,7% 91,0%

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CARBENDAZIME real recovery
at 0.1 mg/kg
Spiking level
0,1 mg/kg
Matrix carotts salads Apples Lemons All
Repet_1 83,1% 56,7% 170,6% 120,0%
Repet_2 122,2% 146,9% 114,3% 63,3%
Repet_3 104,7% 131,8% 292,3% 67,4%
Repet_4 105,8% 79,1% 107,7% 83,0%
mean 104% 104% 171% 83% 116%
sd 16% 43% 86% 26% 56%
rsd 15,4% 41,2% 49,9% 30,9% 48,9%

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Fitting and recovery of
CARBENDAZIME by LC/MS/MS
‣ Calibration curve: fitting
instrument response is not linear
‣ The fitting model introduced a
bias
‣ Minimised by the model 1/x
‣ Fitting of specificity depends of the
matrix
‣ At each matrix should
correspond a calculation
model
‣ Minimised by the model 1/x
‣ Calculation is conducted on the
model 1/x
‣ At 0.02 mg/kg the recovery doesn’t
show any matrix effect for carrots,
salads and apples
‣ RSD is
‣ < 30% and good for carrots and
salads,
‣ ~ 50% for apples
‣ Very bad (>80%) for lemons
‣ At 0.1 mg/kg the recovery doesn’t
show any matrix effect for carrots
and salads, but a positive one for
apples and negative one for lemons
‣ RSD is
‣ < 30% and good for carrots
‣

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Layout of Repeatability and
Reproducibility
‣ Repeatability based on
recovery
‣ 2 levels : 0.02, 0.1
mg/kg
‣ Pairing matrix,
analyst, day
‣ 3 repetitions a day
Repeatability
Concentration Matrix, day, Analyst Repetition 1 Repetition 2 Repetition 3
Apple D1 A1 0,008 0,007 0,004
0,02
Salad D2 A2 0,021 0,013 0,014
Carot D3 A3 0,020 0,009 0,014
Lemon D4 A4 0,014 0,010 0,012
Apple D1 A1 0,056 0,033 0,040
0,1
Salad D2 A2 0,090 0,075 0,081
Carot D3 A3 0,055 0,085
Lemon D4 A4 0,077 0,063 0,064

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Layout of Repeatability and
Reproducibility
‣ Reproducibility based on
recovery
‣ 2 levels : 0.02, 0.1
mg/kg
‣ Every matrices
extracted by each
technician
‣ 4 extracts per analyst
Intermediate Precision
Conc. Analyst, daysApple Salad Carrot Lemon
A1 D1-D6 0,008 0,021 0,007 0,018
A2 D2-D7 0,009 0,013 0,009 0,005
0,02 A3 D3-D8 0,015 0,026 0,020 0,011
A4 D4-D9 0,008 0,005 0,010 0,014
A5 D5-D10 0,019 0,021 0,024 0,013
A1 D1-D6 0,056 0,080 0,054 0,042
A2 D2-D7 0,029 0,075 0,033 0,019
0,1 A3 D3-D8 0,064 0,144 0,055 0,029
A4 D4-D9 0,038 0,029 0,045 0,077
A5 D5-D10 0,042 0,072 0,110 0,039

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Results of Repeatability and
Reproducibility
‣ Repeatability:
‣ The 30% of Sanco are not
fulfil at 0.02 mg/kg (2x
LCL)
‣ RSD at 0.1

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Results of Repeatability and
Reproducibility
‣ Reproducibility:
‣ The 30% of Sanco are
not fulfil at both
concentrations
‣ Horwitz is not fulfil at
0.1 mgkg
‣ The model should be
reviewed
Reproducibility
Concentrations 0,02 0,1
mean 0,0138 0,057
sd 0,005 0,031
limit 0,015 0,088
rsd 38% 55%
Horwitz 58% 45%

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Case of IMAZALIL
‣ Calibration curve OK
‣ Integration window as
narrow as possible
‣ Bad recovery
‣ Wide RSD
Standard
0.02
Sample
Sample
surrogated at
0.02

Dossier of validation for LC-MS/MS
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This presentation couldn’t be done without my team
Gerald LEDOUX
in charge of the QuEChERS method and LC-MS/MS
Sylvie GASSMANN and Emmanuel FLEURY
in charge of the GC and LC extraction
Claude WISSENMEYER and Philippe GAOUYAT
in charge of the GC-MS

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Thank you for your
attention
Any questions