Validation of the Method for Determination

Me t h od 6 3 8 9 9
of Pesticide Residues by Gas Chromatography –
Triple-Stage Quadrupole Mass Spectrometry
Laszlo Hollosi, Katerina Bousova, Michal Godula
Thermo Fisher Scientific, Food Safety Response Center, Dreieich, Germany

Key Words
TraceFinder, TSQ, Chromatography, GC, GC-MS, Pesticide Residues,
QuEChERS, Triple Quadrupole

1. Schematic of Method

Homogenization

Sample + IS

1. Weigh 10 g sample in 50 mL extraction tube

Extraction
2. Introduction
Pesticide residue analysis in food is one of the most
2. Add 9.8 mL acetonitrile (20 mL water + 10 mL
important and challenging tasks in routine laboratory
acetonitrile for wheat flour) and 200 μL stock IS
practice. The European legislation, which is currently the
3. 
Shake for 10 min, centrifuge at 5000 rpm for 5 min
most strict legislation (European Regulation 396/2005
and Commission Directive 2006/125/EC), sets maximum
residue limits (MRL) of pesticides in different products
Clean up
of plant and animal origin. This presents a significant
analytical challenge with respect to the low limits of
4. Transfer supernatant into a 15 mL clean-up tube
quantification (LOQ) required for some specified food
5. Centrifuge samples at 5000 rpm for 5 min matrices. A variety of GC and HPLC methods have been
6. Transfer supernatant into a GC vial developed for multi-residue determination of pesticides
7. Add 50 µL sorbitol and 20 µL of injection standard employing a variety of sample preparation and cleanup
techniques. In recent years the QuEChERS method has
become widely adopted for preparing samples of fruit
GC-MS/MS and vegetables, but the continuous need for more
sensitive and accurate measurements requires new
developments from the instrument producers as well.
2

This method reports on in-house validation results and 6. Standard List

assessment of performance parameters of a complete
6.1 Pesticides
multi-residue pesticide analysis method employing
QuEChERS sample preparation kits, sample measure- All individual pesticide compounds – Acephate, Acrinathrin,
ment by the newly developed Thermo Scientific™ TSQ™ Amitraz, Azinphos-methyl, Azoxystrobin, Bifenthrin,
8000 Pesticide Analyzer system and rapid data analysis Bitertanol, Boscalid, Bromopropylate, Bromuconazole,
by Thermo Scientific™ TraceFinder™ software. Bupirimate, Buprofezin, Cadusafos, Captan, Carbaryl,
Carbofuran, Carboxin, Chlorfenapyr, Chlorfenvinphos,
3. Scope Chlorobenzilate, Chlorothalonil, Chlorpropham,
The objective of this validation study was to prove a Chlorpyrifos-ethyl, Chlorpyrifos-methyl, Cyfluthrin,
complete workflow solution (delivered by Thermo Cyhalothrin, Cypermethrin, Cyproconazole, Cyprodinil,
Scientific chemicals, consumables and instrumentation) DDD, DDE,DDT, Deltamethrin, Demeton-S-methyl,
that can be implemented for routine multi-residue Diazinon, Dichlofluanid, Dichloran, Dichlorbenzophenon,
pesticide analysis (approximately 140 priority pesticides) Dichlorvos, Dicofol, Difenoconazole, Dimethoate,
in representative matrices (strawberry, wheat flour and Dimethomorph, Diphenylamine, Endosulfan, Endosulfan
leek). This was achieved in accordance with current sulfate, EPN, Epoxiconazole, Ethion, Ethoprop (Ethop-
legislation requirements, demonstrating that sensitivity rophos), Etofenprox, Fenamiphos, Fenamiphos sulfone,
of the assay conforms with the MRL values at the limits Fenamiphos-sulfoxid, Fenarimol, Fenbuconazol,
of detection (LOQ).1-4 Fenitrothion, Fenoxycarb, Fenpropathrin, Fenpropidin,
Fenpropimorph, Fenthion, Fenvalerate, Fipronil,
4. Principle Fludioxonil, Fluquinconazole, Flusilazole, Flutolanil,
Sub-portions of previously homogenized (for some instable Flutriafol, Fluvalinate, Folpet, HCH alpha, HCH beta,
compound cryogenic milling is recommended) samples HCH gamma Lindane, Hexaconazole, Imazalil,
were treated according to a standard QuEChERS Iprodione, Isofenphos-methyl, Kresoxim-methyl, Linuron,
method protocol (extraction and clean-up) prior to Malathion, Mepanipyrim, Metalaxyl, Methacrifos,
injection in the TSQ 8000 Triple-Stage Quadrupole Methamidophos, Methidathion, Methiocarb, Metribuzin,
GC-MS system. 5, 6 Monocrotophos, Myclobutanil, Ortho-phenylphenol,
Oxadiazon, Oxadixyl, Paclobutrazol, Paraoxon-methyl,
Ready to use QuEChERS kit containing both extraction
Parathion (ethyl), Parathion-methyl, Pendimethalin,
and clean-up tubes and associated protocol were used for
Permethrin, Phenthoate, Phosalone, Phosmet, Phos-
sample preparation (Thermo Fisher Scientific, Runcorn
phamidon, Pirimicarb, Pirimicarb-p-desmetyl,
UK). Identification of pesticide residues was based on
Pirimiphos methyl, Prochloraz, Procymidone, Profenofos,
retention time and ion-ratio confirmation using selective
Propargite, Propiconazole, Propyzamide, Prothiofos,
reaction monitoring (SRM) of characteristic transition
Pyraclostrobin, Pyridaben, Pyrimethanil, Pyriproxyfen,
ions, while quantification was calculated on matrix
Quinoxyfen, Spirodiclofen, Tebuconazole, Tebufenocide,
matched calibration and internal standardization. All
Tebufenpyrad, Tefluthrin, Tetraconazole, Tetradifon,
method performance criteria were established according
Tetrahydrophthalimide, Thiabendazole, Tolclofos-methyl,
to the relevant guidelines.1-4, 7
Tolyfluanid, Triadimefon, Triadimenol, Trifloxystrobin,
5. Reagent List Part Number
Trifluralin, Triticonazole, Vinclozolin) were obtained from
Sigma-Aldrich® (Germany) and Laboratory Instruments
5.1 Acetone, HPLC Grade A/0606/17 Srl (CASTELLANA GROTTE, Italy).
5.2 Acetonitrile, LC-MS Grade A/0638/17 6.2 Internal standards
5.3 Methanol, Optima LC-MS grade A456-212 1-bromo-4-fluorobenzene (BFB), triphenylphosphate
(TPP) (both from Sigma-Aldrich, Germany)
5.4 Toluene, HPLC grade T/2200/08
5.5 Water, LC-MS grade W/0112/17 6.3 Quality Control Materials
FAPAS #19140QC (lettuce), FAPAS #19141QC (green
5.6 Sorbitol, 500 g 10396733
bean) and FAPAS #19142QC (melon puree)
Note: FAPAS samples were selected primarily on content of target pesticides. However,
due to limited availability, matrices are slightly different from the validated matrices.
 3

7. Standards and Reagent Preparation 8. Apparatus Part Number

7.1 Individual Pesticide Standard Stock Solutions 8.1 Fisher precision balance XP-1500FR
Prepared gravimetrically in ~1000 mg/L concentration
8.2 Sartorius analytical balance ME235S
by weighing 10 mg from each analyte into a 20 mL
amber screw cap vial on a five digit analytical balance 8.3 Thermo Barnstead EASYpure®II water 3125753
and dissolving in 10 mL of appropriate solvent (acetone,
8.4 ULTRA-TURRAX – G25 dispergation tool
®
1713300
toluene or acetonitrile depending on the individual
compound). Concentrations of each individual standard 8.5 ULTRA-TURRAX 3565000
stock solutions were calculated gravimetrically using 8.6 Vortex shaker 3205025
weight of added compounds and solvents. All individual
standard stocks were stored in a freezer at -20 °C. 8.7 Vortex universal cap 3205029
Validity of individual standard stock solutions was 8.8 Horizontal shaker 1069-3391
6 months.
8.9 Horizontal shaker plate 1053-0102
7.2 Intermediate Standard Stock and Working 8.10 Thermo Heraeus Freco 17 micro centrifuge 3208590
Standard Solutions
Prepared by pipetting the appropriate amount of each 8.11 Pesticide Analyzer (TSQ 8000 Triple Stage
Quadrupole GC-MS with Thermo Scientific™
individual standard stock and diluting it with acetoni-
TRACE™ 1310)
trile. The concentration of intermediate standard stock
solutions was 5000 ng/mL. Working standards were
prepared by diluting intermediate standard stock
solution accordingly. Intermediate standard stock 9. Consumables Part Number

solutions were stored in a freezer at -20 °C, and the 9.1 GC vial kit 60180-599
working solutions in a fridge at 4 °C. Validity of
intermediate stock solutions was 3 months. 9.2 Pipette Finnpipette 100–1000 µL 3214535
9.3 Pipette Finnpipette 10–100 µL 3166472
7.3 Individual Internal Standard Stock Solutions
Prepared gravimetrically in ~1000 mg/L concentration 9.4 Pipette Finnpipette 500–5000 µL 3166473
by weighing 10 mg from each analyte into a 20 mL 9.5 Pipette holder 3651211
amber screw cap vial on a five digit analytical balance
and dissolving in 10 mL of acetone for TPP and 10 mL 9.6 Pipette tips 0.5–250 µL, 500/box 3270399
toluene for BFB. Exact concentration values were 9.7 Pipette tips 1–5 mL, 75/box 3270420
determined based on the gravimetrical values of both
9.8 Pipette tips 100–1000 µL, 200/box 3270410
weighed compound and added solvent. Individual
internal standard stock solutions were stored in a freezer 9.9 Spatula, 18/10 steel 3458179
at -20 °C. Validity of individual internal standard stock 9.10 Spatula, nylon 3047217
solutions was 6 months.
9.11 Centrifuge tube rack 1066-3721
7.4 Working Internal Standard Stock Solutions
9.12 QuEChERS extraction tube, 50 mL, 250 pack 60105-216
Prepared individually by pipetting the appropriate
amount of each individual standard stock solution and 9.13 QuEChERS clean-up tube, 15 mL, 50 pack 60105-225
diluting it with acetonitrile. The concentration of 9.14 GC column Thermo Scientific TraceGOLD
™ ™

working internal standard stock solutions was 5000 ng/mL TG-5SilMS, 30 m × 0.25 × 0.25 mm 10177894
and was used for direct spiking of the samples. Validity
9.15 PTV Baffle Liner (Siltek), Deactivated,
of working stock solutions was 3 months.
2 mm ID × 2.75 mm OD × 120 mm Length 453T2120
7.5 1% Sorbitol Solution (Analyte Protectant) 9.16 2 mL vial rack 12211001
Prepared in 70/30 v/v% ACN/H 2O and used for adding
prior to injection. Protectant solution was added to the
sample prior to injection in order to prevent undesired
10. Glassware Part Number
analyte interaction and consequent losses during the
injection.8 10.1 Volumetric flask, 10 mL FB50143
10.2 Volumetric flask, 25 mL FB50147
10.3 40 mL screw cap vial 1054-1593
10.4 Caps for 40 mL screw cap vial 1009-0962
10.5 500 mL bottle 9653640
10.6 100 mL bottle 1006-8060
4

11. Procedure 11.2 GC-MS/MS Analysis

11.1 Sample Preparation Sample measurements were carried out using the
Blank matrix samples (strawberry (SB), wheat flour TRACE 1310 gas chromatograph coupled to the TSQ
(WF) and leek (LK)) used for validation experiments 8000 Triple Stage Quadrupole Mass Spectrometer
were purchased in local retail stores and were homog- (Pesticide Analyzer). For instrument control, analysis,
enized with an Ultra-Turrax homogenizer, extracted and data review and reporting TraceFinder 3.1 software
cleaned-up prior to sample preparation. Matrix extracts was used.
were used as matrix blank samples and dilution solvents 11.2.1 GC method settings
for matrix-matched calibration. Ready to use Thermo
The injector settings were as follows:
Scientific QuEChERS extraction kits were used for
sample preparation, and contained 4 g MgSO4, 1 g Injector: Thermo Scientific™ TriPlus RSH Autosampler
NaCl, 1 g trisodiumcitrate dehydrate and 0.5 g disodi- with 10 μL injection syringe
umcitrate sesquihydrate for buffered extraction of target
Liner: PTV Baffle Liner (Siltek), Deactivated,
compounds. Pre-prepared clean-up tubes contained 2 mm ID × 2.75 mm OD × 120 mm Length
1200 mg MgSO4, 400 mg PSA and 400 mg C18 for (recommended to be changed after
increased clean-up efficiency for more complex matrices 40 injections of matrix samples)
such as leek. The same QuEChERS protocol was applied
Injection mode: splitless PTV, basic mode
for all of the matrices.
Carrier mode: constant flow
11.1.1 Homogenization of Matrices
11.1.1.1 Select larger amount of strawberry (~500 g) Inlet temp: 75 °C
and bunch of leek matrices and put into an Split flow: 50 mL/min
appropriate size beaker and label it.
Splitless time: 1 min
11.1.1.2 Attach the G25 dispergation tool to the
Injection volume: 1 μL
Ultra-Turrax homogenizer. (For better recovery
for some unstable compounds cryogenic Plunger strokes: 3
homogenization is advised). Air filling mode: auto
11.1.1.3 Start homogenization at middle rotation speed Carrier flow: 1.2 mL/min
(speed level 2–3) and continue to form a
PTV injection time: 0.1 min
smooth homogenate.
PTV transfer rate: 2.5 °C/s
11.1.2 Sample Extraction and Clean-up
11.1.2.1 Weigh 10 g sample into a 50 mL QuEChERS PTV transfer temp: 300 °C
extraction tube containing 4 g MgSO4, 1 g PTV transfer time: 3 min
NaCl, 1 g trisodiumcitrate dehydrate and 0.5 g
PTV cleaning rate: 14.5 °C
disodiumcitrate sesquihydrate.
PTV cleaning temp: 330 °C
11.1.2.2 Add 200 µL 5000 ng/mL internal standard
#141 to the samples. PTV cleaning time: 20 min

11.1.2.3 Add 10 mL ACN to SB and LK samples. For PTV cleaning flow: 75 mL/min
WF, first add 20 mL H 2O to the samples, let it PTV cleaning phase: post cycle temperature cool down
completely wet the sample and then add 10 mL
ACN to it.
The GC oven settings were as follows:
11.1.2.4 Shake samples for 10 min on a horizontal
shaker and centrifuge with 5000 rpm for 5 min. Carrier gas: 1.2 mL/min Helium (constant flow)
Transfer supernatant (~8 mL) into the 15 mL
PTV cleaning phase: post cycle temperature cool down
QuEChERS clean-up tubes containing 1200 mg
MgSO4, 400 mg PSA and 400 mg C18.
Table 1. GC temperature programming
11.1.2.5 Vortex for 1 min and centrifuge samples with
Rate Temperature Hold Time
5000 rpm for 5 min. #
[°C/min] [°C] [min]
11.1.2.6 Collect supernatant and transfer 1 mL into a Initial 40 1.5
GC vial for instrumental analysis.
1 25 90 1.5
11.1.2.7 Add 50 µL sorbitol solution (protectant) and 2 25 180 0
20 µL 5000 ng/mL injection standard (BFB) to
3 5 280 0
the GC vials prior to injection.
4 10 300 5
 5

11.2.2 Triple Quadrupole MS Settings Calculations of sample amount in each sample (the
Mass spectrometric detection was carried out using the absolute amount of pesticide extracted from the sample):
TSQ 8000 triple-quadrupole mass spectrometer in
A analyte X IS
X analyte =

+
timed-SRM mode. All method and SRM settings were
taken from the Thermo Scientific TSQ 8000 Pesticide A IS Rf

+
Analyzer system method.6 Ion ratio values were revised
and adapted for each investigated matrices. Xanalyte – the absolute amount of pesticide that was extracted from
the sample
The settings were as follows:
A analyte – the area of pesticide peak in the sample
Scan type: timed-SRM (details in Table 2) A[IS] – the area of the internal standard peak in the sample

Ionization: EI + X[IS] – the absolute amount of internal standard added to the sample
Calculations of sample amount in each sample (the
MS transfer line temp: 250 °C
absolute amount of pesticide extracted from the sample):
Ion source temp: 300 °C
Cycle time: 0.3 s X analyte
C=
Minimum baseline peak width: 3 s m
Desired scans per peak: 10 m – the weight of sample [g]

Minimum dwell time: 0.001 s Xanalyte – absolute analyte amount [ng]

Q1 resolution: normal (0.7 Da) 12. Method Performance Characteristics

In-house validation of the method was carried out on all
11.3 Calculation of Results matrices and target pesticides. European guidelines for
single laboratory validation and pesticide residue
Internal standardization was applied for quantification
analysis were used for establishing method performance
of target pesticides. The relevant response factors (R f)
criteria.1, 2 All method performance parameters were
were defined by the equation below. Calculation of final
compared to the relevant legislative requirements and
result was performed using the following equations.
maximum residue limit (MRLs). 2-4, 7 For compounds
11.3.1 Equations containing more isoforms, only one performance criteria
Calculation of the response factor: was established.

12.1 Selectivity
A St c [IS]
+

Rf = Method (SRM) selectivity was assessed based on the

A [IS] c St presence of specific ion transitions (quantifier ion and
+

two transitions for compound confirmation) at the

Rf – the response factor
corresponding retention time (Table 2), as well as the
A St – the area of the pesticide peak in the calibration standard observed ion ratio values corresponding to those of the
A[IS] – the area of the internal standard peak of the calibration standard standards. Acceptance criteria for retention time and ion
cSt – pesticide concentration of the calibration standard solution ratios were set according to current quality control
c[IS] – the internal standard concentration of the calibration criteria.1, 3 Matrix blank samples were also inspected for
standard solution the presence of interfering peaks in close vicinity of the
target retention times for which (according to SANCO
guideline definitions) <30% of LOQ acceptance criteria
was applied. 3 Additional peaks in close vicinity of target
peaks in blank samples were observed for chlorpropham
(LK), demethon-s-methyl (SB), fenhexamide (WF, LK),
fenitrothion (WF, LK), procymidon (WF), phosphalone
(SB), permethrin (WF, LK), fenpropathrin (LK),
o-phenylphenol (WF) and carbofuran (SB, WF).
However, they were all clearly resolved by retention time
from the target peaks (Rs>1.5) except carbofuran in SB
and WF and propargite in WF and LK matrices.
6

12.2 Linearity, Response Factor, Matrix Effect compounds in these matrices have to be measured with
The calibration curves were created at six levels (matrix- separate, specially optimized analytical methods.
matched) and injected in duplicate. R f values for internal Method bias was established by means of external
standardization were determined from the calibration quality control materials obtained from FAPAS (York,
curves for all matrices and internal standards by UK). Available FAPAS materials were #19140QC
calculating cumulative average response factor over the (lettuce puree), #19141QC (green bean puree) and
whole calibration range. The linearity of calibration #19142QC (melon puree). The available Fapas samples
curves was assessed in three groups of compounds represented only a limited number of the target com-
(depending on the relevant MRL values) in calibration pounds and different matrices from those targeted.
ranges of 0–200, 0–1000 and 0–2000 ng/g, respectively, However, measured values showed good agreement with
(details and results in Table 3). Calibration levels were the assigned values in all cases except carbofuran, in
equidistantly distributed over the calibration range. which the measured value was slightly below the
Linear function was evaluated according to Mandel’s acceptance range. This could be due to differences
fitting test and plotting of residuals for which <20% between the two different matrix characteristics. Details
acceptance limit was set. 3 Correlation coefficient values on the measured FAPAS values are listed in Table 7.
were additionally established for which an artificial
12.4 (Intermediate) Precision
0.985 was set as an acceptance limit, as no legislative
Instrument injection precision was tested for both
limits are defined for them. The set value wasn’t met for
retention time and peak area for all target compounds
fenpropathrin and dichlofluanid (LK) and propargite
by subsequent injections (n=6) of low concentration level
(WF) based on the high LOQ values related to the
(L1) standard solutions. Instrument injection precision
calibration levels. No weighted function was applied.
for retention time was below 0.5% for all compounds
Matrix effects were evaluated by (Youden-) plotting of and between 1.2–18.04% (fipronil and fenamiphos-
measured relative peak areas of calibration standards in sulfoxide) for peak area without internal standard
solvent against the areas in the relevant matrix. No compensation indicating reliable instrument perfor-
matrix effect is observed if the difference of the slope mance. Method within-day and between-day precision
(dif%) of the fitted line is less than 20% from the ideal values were determined for each matrix at middle
(y=x) curve, while matrix effects are observed when the spiking level (L2) and expressed as %RSD over 3 days
difference is between 20–50% (minor matrix effect) or with individually prepared samples (n=6). Mean
exceeds 50% (major matrix effect). Matrix effect results within-day precision values were determined as an
are listed in Table 3. For the compounds with demon- average of the 3 individual days’ mean precision, while
strated matrix effect application of matrix matched between-day precision was expressed as mean of the
calibration is required. overall precision data. According to SANCO require-
ments <20% was set as acceptance criteria for the target
12.3 Accuracy
compounds and matrices. 3 Measured values are shown
Method trueness was assessed by recovery studies using in Table 5.
blank matrices spiked at three concentration levels (L1,
L2 and L3) and injected in six individually prepared 12.5 Limit of Detection, Limit of Quantification
replicates. (Table 4). Spiking of samples occurred prior Limits of detection and quantification were estimated
to sample preparation. Found concentrations, recovery following the IUPAC. Measured method LOD, LOQ
and relative standard deviation (% RSD) were calculated and the relevant legislative limits (MRLs) are listed in
(Table 5). According to SANCO requirements recovery Table 6.7 An artificial MRL=10 ng/g was set as target
values are deemed acceptable if between 70–120%. 3 value for compounds, for which no MRL values are
Values were calculated only for those cases in which legislatively defined. The expectation of the method was
spiking levels were higher than the compound LOQ in to meet MRL values at least at LOQ level which was
the particular matrix. Recovery values could not been achieved for the vast majority of target compounds. For
established for amitraz in WF and captan, chlorthalonil methiocarb (WF, LK), carbofuran (SW), oxadyxil (WF)
and tolyfluanid in LK matrices due to the high LOQ and propargite (WF, LK) the established LOQ values
values measured relative to the spiked levels. Strong were below the targeted MRLs’ value. However, with
influence of matrix on the results were observed in exchanging of quantifier and qualifier ions the target
several cases and results could not been established at values can be reached. For fenpropathrin (WF, LK),
one or two spiking levels based on the measured amitraz (WF) and tebufenocid (all matrices), the target
different LOD/LOQ values in the different matrices values could not be reached even when exchanging the
(details in Table 4). For routine measurement these quantifier and qualifier ions.
 7

12.6 Robustness 14. References

A robustness study was performed by varying parameters 1. European Commission 2002/657/EC
like laboratory personnel, extraction and clean-up
2. European Commission 2006/125/EC
batches. Results were compared to the original method
and significant differences were sought based on 3. European Commission SANCO/12495/2011
ANOVA analysis. None of the parameters which were
4. European Commission 788/2012/EC
varied led to significant differences in measured values,
consequently indicating that the method was robust. 5. Fussell et al. (2007) Food Additives & Contam,
24:1247-1256
13. Conclusion
Full in-house validation of a complete method intended 6. T hermo Scientific TSQ 8000 Pesticide Analyzer
for routine pesticide residue measurements was carried Brochure, https://static.thermoscientific.com/images/
out. The goal of the study was to obtain an objective D22018~.pdf
and realistic overview of the analytical performance of a 7. E
 U Pesticides Database, http://ec.europa.eu/sanco_
widely used and accepted sample preparation method pesticides/public/index.cfm
combined with state of the art analytical instrumentation.
The method performance parameters indicate that the 8. A
 nastassiades et al. (2003) J. Chromatogr A,
performance for the majority of target compounds complies 1015:163-184
with current regulatory requirements. Independent,
external quality control materials were additionally
applied to improve confidence in the measurement
results. In some cases method performance parameters
could not be established or measured values fell outside
of the targeted range due to individual properties of
compounds or strong matrix influences on the analytical
results. For those compounds (in the relevant matrix),
individually optimized sample preparation (additional or
special clean-up) and instrumental methods have to be
applied. From a practical point of view (especially for
instable or active compounds) the best performance can
be achieved by replacing the liner (and septum) after
40–50 injections. Overall it can be concluded that the
complete workflow solution offered by Thermo Fisher
Scientific in conjunction with the newly developed
TSQ 8000 GC-MS system delivers the required system
performance for the target compounds especially
regarding sensitivity, selectivity and recovery.
8

15. Annex
Tables and Figures

Table 2. Selectivity parameters for the target compounds * retention times for all isomers ** internal standard compound

Quantifier Ion Qualifier Ion 1 Qualifier Ion 2 Ion Ratio

RT Precursor Product Collision Precursor Product Collision Precursor Product Collision (for qualifier ion 1/
Name
(min) Mass Mass Energy Mass Mass Energy Mass Mass Energy qualifier ion 2)
[m/z] [m/z] [V] [m/z] [m/z] [V] [m/z] [m/z] [V] [% of quant. ion]
Acephate 9.36 95.5 65.4 8 136.0 42.1 8 136.0 94.0 12 0.2 / 99
Acrinathrin 24.33 181.0 152.0 22 208.1 180.9 8 289.0 93.1 8 110 / 52
Amitraz 24.03 121.0 106.1 10 131.9 117.1 16 161.9 132.0 8 85 / 78
Azinphos-methyl 23.29 132.0 77.0 12 160.0 50.9 34 160.0 77.0 16 55 / 120
Azoxystrobin 30.33 344.1 156.0 34 344.1 171.9 36 344.1 329.0 14 100 / 250
Bifenthrin 22.08 165.1 163.6 24 181.0 165.9 10 181.0 179.0 12 3800 / 400
Bitertanol 25.25 170.0 115.1 34 170.0 141.1 20 170.0 169.1 16 140 / 40
Boscalid
27.09 112.0 76.0 12 139.9 76.0 22 139.9 112.0 10 240 / 350
(Nicobifen)
Bromopropylate 22.09 184.9 75.5 30 184.9 156.9 12 340.8 185.0 14 2500 / 600
21.87/
Bromuconazole 172.9 74.0 38 172.9 109.0 26 172.9 144.9 16 100 / 150
22.6*
Bupirimate 18.08 208.1 140.1 12 208.1 165.0 12 273.1 193.2 8 260 / 60
Buprofezin 18.08 105.1 50.9 32 105.1 77.0 18 175.0 132.1 12 275 / 75
Cadusafos 11.5 159.0 96.9 16 159.0 130.9 8 213.0 89.1 12 550 / 15
Captan 16.35 149.0 70.0 20 149.0 78.8 14 149.0 105.0 6 120 / 130
Carbaryl 14.13 115.0 89.0 16 144.0 115.1 22 144.0 116.1 10 800 / 400
Carbofuran 11.98 149.1 77.0 24 149.1 121.1 8 164.0 149.1 8 120 / 120
Carboxin 18.11 87.0 43.0 6 143.0 43.0 16 143.0 87.0 8 200 / 100
Chlorfenapyr 18.37 136.9 102.0 12 248.9 112.0 24 248.9 137.1 18 45 / 30
Chlorfenvinphos 16.13 266.9 159.0 16 266.9 203.0 10 323.0 266.9 14 25 / 80
Chlorobenzilate 18.89 111.0 75.1 14 139.0 74.9 26 139.0 111.0 12 215 / 440
Chlorothalonil 12.72 228.8 168.0 8 265.8 133.0 36 265.8 170.0 24 350 / 160
Chlorpropham 11.17 171.0 127.0 8 213.0 127.0 14 213.0 171.0 6 65 / 45
Chlorpyrifos-ethyl 14.88 196.7 107.0 36 196.7 168.9 12 313.9 257.9 12 240 / 135
Chlorpyrifos-
13.67 125.0 47.0 12 125.0 79.0 6 285.9 93.0 20 110 / 55
methyl
Cyfluthrin 26.67 163.0 65.1 26 163.0 91.1 12 163.0 127.1 6 100 / 25
Cyhalothrin 23.94 180.9 151.9 22 197.0 141.1 10 208.1 180.9 8 95 / 80
27.28/
27.53/
Cypermethrin 163.0 91.1 12 163.0 127.1 6 180.9 152.1 20 100 / 50
27.63/
27.72*
Cyproconazole 18.53 222.0 82.1 10 222.0 89.3 38 222.0 125.0 20 35 / 210
Cyprodinil 15.85 224.1 196.9 20 224.1 208.0 18 225.1 209.7 16 500 / 40
DDD p,p 19.16 235.0 165.1 20 235.0 199.0 14 236.8 165.0 20 21 / 48
DDE p, p 17.85 246.0 176.1 28 317.8 246.0 20 317.8 248.0 18 28 / 30
DDT p,p 20.39 235.0 165.1 22 235.0 199.5 10 236.8 165.0 22 1.5 / 48
Deltamethrin 30.04 181.0 152.1 22 252.8 92.9 16 252.8 172.0 8 40 / 35
Demeton-S-
10.91 88.0 59.8 6 109.0 79.0 6 141.9 79.0 12 10.1 / 25
methyl
Diazinon 12.51 137.1 54.1 20 137.1 84.1 12 179.1 121.5 26 170 / 10
 9

Table 2 continued * retention times for all isomers ** internal standard compound

Quantifier Ion Qualifier Ion 1 Qualifier Ion 2 Ion Ratio

RT Precursor Product Collision Precursor Product Collision Precursor Product Collision (for qualifier ion 1/
Name
(min) Mass Mass Energy Mass Mass Energy Mass Mass Energy qualifier ion 2)
[m/z] [m/z] [V] [m/z] [m/z] [V] [m/z] [m/z] [V] [% of quant. ion]
Dichlofluanid 14.69 123.0 51.0 32 123.0 77.0 18 223.9 123.0 10 210 / 120
Dichloran 12.03 175.9 148.0 10 205.9 147.9 20 205.9 176.0 10 50 / 160
Dichlorbenzophe-
16.61 139.0 110.9 15 249.9 139.0 10 0.3
non, p,p'-
Dichlorvos 8.10 109.0 79.0 6 185.0 93.0 12 186.9 93.0 12 60 / 16
Dicofol 24.18 111.0 74.9 12 139.0 111.0 12 251.0 139.0 15 460 / 160
29.51/
Difenoconazole 265.0 139.0 36 265.0 202.1 16 323.0 265.0 14 90 / 220
29.62*
Dimethoate 11.92 87.0 42.1 10 93.0 63.0 8 125.0 79.0 8 70 / 55
30.51/
Dimethomorph 165.0 77.0 18 165.0 137.0 10 301.0 165.1 12 390 / 130
31.00*
Diphenylamine 10.96 167.1 139.4 26 167.1 140.1 18 167.1 166.1 16 130 / 550
17.19/
Endosulfan 194.7 125.0 22 194.7 159.4 8 240.6 205.9 14 140 / 120
19
Endosulfan
20.23 238.7 203.9 12 271.7 234.9 12 271.7 236.8 12 47 / 550
sulfate
EPN 22.04 157.0 77.0 22 169.0 77.0 22 169.0 141.0 8 120 / 210
Epoxiconazole 21.34 165.0 138.0 8 192.0 111.0 22 192.0 138.0 12 150 / 300
Ethion 19.17 153.0 97.0 10 230.9 128.9 22 90
Ethoprop
11.02 157.9 96.9 16 157.9 113.9 6 200.0 158.0 6 75 / 70
(Ethoprophos)
Etofenprox 27.66 163.1 77.1 32 163.1 107.1 16 163.1 135.1 10 300 / 350
Fenamiphos 17.39 154.0 139.0 10 216.9 202.0 12 303.1 195.2 8 85 / 50
Fenamiphos
21.74 320.0 213.9 14 320.0 249.1 18 320.0 292.1 8 95 / 420
sulfone
Fenamiphos-
21.59 304.0 196.0 10 304.0 234.0 10 35
sulfoxid
Fenarimol 24.16 139.0 74.9 26 139.0 111.0 14 219.0 107.0 10 185 / 80
Fenbuconazol 26.31 129.0 77.8 18 129.0 102.0 14 198.1 129.1 8 230 / /370
Fenitrothion 14.44 125.0 79.0 8 277.0 109.0 16 277.0 260.0 6 45 / 48
Fenoxycarb 22.19 116.0 44.1 16 116.0 88.0 8 255.1 186.1 10 460 / 60
Fenpropathrin 22.39 97.1 55.1 6 181.0 126.8 28 181.0 151.9 22 22 / 92
Fenpropidin 14.38 98.2 41.5 18 98.2 55.1 14 98.2 70.0 10 1650 / 1850
Fenpropimorph 15.06 128.1 41.7 24 128.1 70.1 12 128.1 110.1 8 400 / 300
Fenthion 14.98 245.3 125.0 12 278.0 109.0 18 278.0 169.0 14 1300 / 500
Fenvalerate 28.73 125.0 89.0 18 167.0 89.0 32 167.0 125.0 10 45 / 300
Fipronil 15.96 366.9 212.9 28 366.9 244.9 20 368.8 214.9 30 30 / 65
Fludioxonil 17.61 153.7 127.0 8 248.0 127.0 26 248.0 153.8 18 290 / 160
Fluquinconazole 25.61 340.0 108.1 36 340.0 298.0 16 340.0 313.0 14 160 / 65
Flusilazole 18.05 206.0 151.3 14 233.0 151.9 14 233.0 164.9 16 230 / 350
Flutolanil 17.47 173.0 95.0 28 173.0 145.0 14 281.0 173.0 10 350 / 56
Flutriafol 17.31 123.0 75.0 24 123.0 95.0 12 219.0 123.0 12 180 / 72
10

Table 2 continued * retention times for all isomers ** internal standard compound

Quantifier Ion Qualifier Ion 1 Qualifier Ion 2 Ion Ratio

Name
RT Precursor Product Collision Precursor Product Collision Precursor Product Collision (for qualifier ion 1/
(min) Mass Mass Energy Mass Mass Energy Mass Mass Energy qualifier ion 2)
[m/z] [m/z] [V] [m/z] [m/z] [V] [m/z] [m/z] [V] [% of quant. ion]
29.03/
Fluvalinate 180.8 152.1 22 250.0 55.1 16 250.0 199.9 18 45 / 35
29.16*
Folpet 16.54 104.0 76.0 10 130.0 102.0 12 259.9 130.1 14 92 / 62
HCH alpha 11.71 216.9 180.9 8 218.8 182.9 8 95
HCH beta 12.19 216.9 180.9 8 218.8 182.9 8 90
HCH gamma_
12.39 216.9 180.9 8 218.8 182.9 8 100
Lindane
Hexaconazole 17.54 213.9 123.5 28 213.9 159.0 18 231.0 175.0 10 950 / 1100
Imazalil 17.58 172.8 109.0 26 174.7 147.0 16 215.0 173.0 8 90 / 130
Iprodione 21.77 314.0 245.0 10 315.7 247.0 10 315.7 273.0 8 50 / 22
Isofenphos-methyl 15.65 199.0 65.0 34 199.0 121.0 10 241.1 121.1 20 395 / 70
Kresoxim-methyl 18.12 116.0 62.9 24 116.0 89.0 14 130.9 130.1 10 324 / 102
Linuron 14.63 159.8 133.0 12 187.0 124.0 20 248.0 61.1 8 70 / 120
Malathion 14.68 92.8 63.0 8 125.0 79.0 8 173.1 99.0 12 110 / 300
Mepanipyrim 17.21 222.0 206.0 26 222.0 207.1 14 223.1 207.4 24 220 / 41
Metalaxyl 14.01 131.9 117.0 12 160.1 130.0 18 160.1 144.8 10 100 / 80
Methacrifos 9.8 125.0 79.0 8 180.0 93.0 10 240.0 180.0 10 55 / 40
Methamidophos 8.03 141.0 64.0 18 141.0 79.0 20 141.0 94.8 8 420 / 520
Methidathion 16.7 145.0 58.0 14 145.0 85.0 6 302.6 284.9 14 370
Methiocarb 14.98 153.0 45.0 12 153.0 109.1 6 168.1 153.0 10 225 / 554
Metribuzin 13.67 198.0 55.0 26 198.0 82.1 16 198.0 110.0 10 300 / 100
Monocrotophos 11.4 96.9 82.0 10 127.0 95.0 16 127.0 109.0 10 105 / 350
Myclobutanil 17.98 179.0 90.0 28 179.0 125.0 14 179.0 151.7 8 320 / 60
Ortho-phenyl-
10.09 141.1 115.1 14 170.1 115.0 34 170.1 141.1 22 91 / 100
phenol
Oxadiazon 17.87 174.9 76.0 28 174.9 112.0 12 174.9 147.2 6 226 / 52
Oxadixyl 19.12 131.9 117.0 16 163.1 117.0 24 163.1 132.1 8 110 / 260
Paclobutrazol 16.97 125.0 89.0 18 236.0 125.0 12 236.0 167.0 10 290 / 90
Paraoxon-methyl 12.83 95.9 65.0 12 109.0 79.0 6 230.0 105.9 16 140 / 110
Parathion (ethyl) 15.07 109.0 81.0 10 124.9 97.0 6 291.0 109.0 12 75 / 48
Parathion-methyl 13.85 124.9 47.0 12 124.9 79.0 6 263.0 109.0 12 105 / 60
Pendimethalin 15.81 252.1 161.0 14 252.1 162.0 8 252.1 191.3 8 130 / 85
25.38/
Permethrin 163.0 91.1 12 183.1 153.0 12 183.1 168.0 12 100 / 105
25.64*
Phenthoate 16.25 121.0 77.0 22 246.0 121.0 8 274.0 121.0 10 100 / 120
Phosalone 23.15 121.1 65.0 10 182.0 74.8 30 182.0 111.0 14 105 / 190
Phosmet 21.89 160.0 50.9 38 160.0 76.9 22 160.0 133.0 10 170 / 110
Phosphamidon 13.47 127.0 94.9 16 127.0 109.0 12 264.1 127.0 12 380 / 100
Pirimicarb 13.08 166.1 55.0 18 166.1 96.0 12 238.1 166.1 10 120 / 230
Pirimicarb-p-
13.36 152.1 42.0 25 152.1 96.0 10 224.1 152.1 10 230 / 120
desmetyl
Pirimiphos methyl 14.37 290.1 125.0 20 290.1 233.0 8 305.1 180.1 8 60 / 70
Prochloraz 25.74 69.9 42.0 8 180.1 138.1 12 308.0 147.1 12 160 / 10
Procymidone 16.4 95.9 53.0 16 95.9 67.1 8 283.0 96.1 8 400 / 65
 11

Table 2 continued * retention times for all isomers ** internal standard compound

Quantifier Ion Qualifier Ion 1 Qualifier Ion 2 Ion Ratio

Name
RT Precursor Product Collision Precursor Product Collision Precursor Product Collision (for qualifier ion 1/
(min) Mass Mass Energy Mass Mass Energy Mass Mass Energy qualifier ion 2)
[m/z] [m/z] [V] [m/z] [m/z] [V] [m/z] [m/z] [V] [% of quant. ion]
Profenofos 17.73 296.7 268.9 10 336.9 266.9 12 336.9 308.9 8 190 / 35
Propargite 20.97 135.1 77.1 26 135.1 107.1 12 150.1 135.1 8 310 / 110
20.19/
Propiconazole 172.9 74.0 38 172.9 109.0 26 172.9 145.0 16 110 / 155
20.39*
Propyzamide 12.5 172.9 74.0 38 172.9 109.0 26 172.9 145.0 14 105 / 190
Prothiofos 17.57 266.7 220.9 18 266.7 238.9 8 308.9 239.0 14 142 / 160
Pyraclostrobin 28.89 132.0 51.1 35 132.0 77.0 20 164.0 132.1 10 230 / 220
Pyridaben 25.62 147.1 117.1 20 147.1 119.1 8 147.1 132.1 12 55 / 58
Pyrimethanil 12.66 198.1 117.9 30 198.1 157.6 18 198.1 182.9 14 10 / 120
Pyriproxyfen 23.54 136.1 78.0 20 136.1 96.0 10 226.1 186.1 12 90 / 10
Quinoxyfen 20.18 237.0 208.0 26 271.8 237.1 12 307.0 237.0 18 55 / 33
Spirodiclofen 25.09 156.9 73.0 20 156.9 86.7 32 312.2 259.0 8 60 / 105
Tebuconazole 20.85 125.0 89.0 16 125.0 99.0 16 250.0 125.0 20 50 / 110
Tebufenocide 22.58 145.1 117.0 10 160.1 145.1 12 8
Tebufenpyrad 22.58 276.1 171.0 10 318.1 131.1 14 318.1 145.1 14 43 / 31
Tefluthrin 12.79 177.0 127.0 14 177.0 137.0 16 197.0 141.1 10 34 / 40
Tetraconazole 15.18 100.9 51.0 10 159.0 123.4 16 336.0 204.0 28 8 / 100
Tetradifon 22.97 159.0 74.8 32 159.0 111.0 20 159.0 131.0 10 125 / 252
Tetrahydroph-
9.96 151.0 77.1 30 151.0 79.9 6 151.0 122.1 8 140 / 80
thalimide (THPI)
Thiabendazole 16.36 174.0 103.0 18 174.0 130.1 10 201.0 174.0 14 110 / 700
Tolclofos-methyl 13.86 265.0 219.9 20 265.0 250.0 12 266.8 252.0 12 285 / 80
Tolyfluanid 16.1 137.0 65.1 28 137.0 91.1 18 238.0 137.0 10 150 / 110
Triadimefon 15.17 208.0 111.0 20 208.0 126.7 12 208.0 180.8 8 65 / 120
Triadimenol 16.39 112.0 57.6 8 128.0 65.0 18 168.2 70.0 10
Trifloxystrobin 20.16 116.1 63.0 24 116.1 89.0 14 145.0 95.0 14 295 / 40
Trifluralin 11.17 306.1 159.7 20 306.1 206.0 10 306.1 264.1 8 150 / 900
Triphenylphos-
21.01 215.0 168.1 16 326.1 168.6 28 326.1 325.3 10 6 / 62
phate (TPP)**
Triticonazole 23.17 217.0 167.0 18 235.1 181.9 12 235.1 217.1 8 92 / 120
Vinclozolin 13.73 241.1 58.1 12 241.1 184.1 10 284.9 269.9 12 160
12

Table 3. Linearity and matrix effect results (see text 12.2 for details on Youden plot slope results). – residue plot RSD% <20% – residue plot RSD% >20%

Strawberry Wheat Flour Leek

Calibration Residue Youden Residue Youden Residue Youden
Compound Range Plot Plot Plot Plot Plot Plot
[ng/g] r2 r2 r2
Deviation Slope Deviation Slope Deviation Slope
[%RSD] [diff%] [%RSD] [diff%] [%RSD] [diff%]
Acephate 0-200 0.9998 12 0.9995 9 0.9998 35
Acrinathrin 0-200 0.9976 9 0.9985 270 0.9976 61
Amitraz 0-2000 0.9884 39 n.d. n.d. n.d. 0.9920 38
Azinphos-methyl 0-1000 0.9885 20 0.9956 0 0.9890 52
Azoxystrobin 0-1000 0.9911 24 0.9979 130 0.9918 63
Bifenthrin 0-200 0.9997 10 0.9939 12 0.9947 24
Bitertanol 0-200 0.9993 24 0.9956 67 0.9986 18
Boscalid (Nicobifen) 0-200 0.9983 16 0.9946 61 0.9976 8
Bromopropylate 0-200 0.9986 9 0.9908 2 0.9988 19
Bromuconazole 0-200 0.9989 6 0.9965 7 0.9994 17
Bupirimate 0-1000 0.9970 5 0.9981 3 0.9995 21
Buprofezin 0-1000 0.9993 16 0.9984 13 0.9961 31
Cadusafos 0-200 1.0000 3 0.9997 14 0.9970 27
Captan 0-200 0.9963 63 0.9967 56 n.d. n.d. n.d.
Carbaryl 0-1000 0.9995 54 0.9991 50 0.9833 68
Carbofuran 0-200 0.9987 11 0.9907 31 0.9816 64
Carboxin 0-200 0.9989 6 0.9988 16 0.9998 18
Chlorfenapyr 0-1000 0.9991 16 0.9971 18 0.9994 35
Chlorfenvinphos 0-200 0.9996 9 0.9958 97 0.9982 10
Chlorobenzilate 0-200 0.9999 2 0.9971 5 0.9991 17
Chlorothalonil 0-200 0.9952 77 0.9991 25 n.d. n.d. n.d.
Chlorpropham 0-200 0.9999 1 0.9997 11 0.9971 18
Chlorpyrifos-ethyl 0-200 0.9998 11 0.9995 6 0.9994 22
Chlorpyrifos-methyl 0-200 0.9998 25 0.9995 32 0.9991 39
Cyfluthrin 0-200 0.9995 4 0.9918 130 0.9899 5
Cyhalothrin 0-200 0.9979 15 0.9972 39 0.9973 16
Cypermethrin 0-200 0.9993 10 0.9947 105 0.9900 15
Cyproconazole 0-200 0.9994 17 0.9975 29 0.9997 2
Cyprodinil 0-200 0.9594 5 0.9970 5 0.9993 10
DDD p,p 0-200 0.9984 4 0.9982 20 0.9987 7
DDE p, p 0-200 0.9999 11 0.9985 21 0.9983 9
DDT p,p 0-200 0.9974 21 0.9963 26 0.9926 18
Deltamethrin 0-200 0.9994 7 0.9935 149 0.9911 40
Demeton-S-methyl 0-1000 0.9997 0 0.9994 2 0.9995 6
Diazinon 0-200 0.9998 18 0.9996 23 0.9928 36
Dichlofluanid 0-1000 0.9962 6 0.9997 10 0.7016 99
Dichloran 0-200 0.9996 7 0.9993 21 0.9994 25
Dichlorbenzophenon, p,p'- 0-200 0.9976 24 0.9988 65 0.9904 99
Dichlorvos 0-200 0.9996 15 0.9992 37 0.9993 20
Dicofol 0-200 0.9989 2 0.9952 11 0.9991 20
Difenoconazole 0-200 0.9989 13 0.9965 225 0.9995 51
Dimethoate 0-200 0.9996 17 0.9997 4 0.9996 20
 13

Table 3 continued – residue plot RSD% <20% – residue plot RSD% >20%

Strawberry Wheat Flour Leek

Calibration Residue Youden Residue Youden Residue Youden
Compound Range Plot Plot Plot Plot Plot Plot
[ng/g] r2 r2 r2
Deviation Slope Deviation Slope Deviation Slope
[%RSD] [diff%] [%RSD] [diff%] [%RSD] [diff%]
Dimethomorph 0-200 0.9995 37 0.9996 181 0.9984 42
Diphenylamine 0-200 0.9999 12 0.9994 24 0.9969 22
Endosulfan 0-1000 0.9994 7 0.9961 4 0.9969 17
Endosulfan sulfate 0-200 0.9988 4 0.9920 2 0.9980 20
EPN 0-200 0.9960 2 0.9947 56 0.9926 0
Epoxiconazole 0-200 0.9992 5 0.9966 14 0.9994 8
Ethion 0-200 0.9977 11 0.9967 21 0.9995 3
Ethoprop (Ethoprophos) 0-200 0.9998 7 0.9997 16 0.9978 17
Etofenprox 0-200 0.9985 15 0.9939 60 0.9986 3
Fenamiphos 0-200 0.9996 2 0.9992 40 0.9999 41
Fenamiphos sulfone 0-200 0.9968 16 0.9981 74 0.9933 25
Fenamiphos-sulfoxid 0-2000 0.9907 10 0.9940 101 0.8709 44
Fenarimol 0-200 0.9979 2 0.9958 8 0.9987 22
Fenbuconazol 0-200 0.9990 7 0.9949 33 0.9991 6
Fenitrothion 0-200 0.9994 15 0.9993 15 0.9992 23
Fenoxycarb 0-200 0.9990 9 0.9970 52 0.9989 4
Fenpropathrin 0-200 0.9981 7 0.9972 45 0.9146 6
Fenpropidin 0-1000 0.9998 18 0.9997 7 0.9962 17
Fenpropimorph 0-200 0.9998 10 0.9997 5 0.9943 27
Fenthion 0-200 0.9987 17 0.9998 21 0.9997 5
Fenvalerate 0-200 0.9999 10 0.9949 84 0.9973 19
Fipronil 0-200 0.9998 8 0.9984 26 0.9991 29
Fludioxonil 0-200 0.9800 1 0.9979 11 0.9992 23
Fluquinconazole 0-200 0.9976 22 0.9990 153 0.9995 39
Flusilazole 0-200 0.9984 2 0.9953 13 0.9977 11
Flutolanil 0-200 0.9989 15 0.9996 38 0.9997 7
Flutriafol 0-200 0.9996 1 0.9991 14 0.9996 23
Fluvalinate 0-200 0.9995 20 0.9956 131 0.9938 1
Folpet 0-2000 0.9959 76 0.9984 48 n.d. n.d. n.d.
HCH alpha 0-200 0.9999 8 0.9951 8 0.9977 15
HCH beta 0-200 0.9999 14 0.9993 16 0.9981 29
HCH gamma_Lindane 0-200 0.9999 12 0.9945 17 0.9961 21
Hexaconazole 0-1000 0.9938 8 0.9995 11 0.9999 11
Imazalil 0-1000 0.9987 14 0.9985 14 0.9998 26
Iprodione 0-200 0.9981 5 0.9984 34 0.9917 13
Isofenphos-methyl 0-200 0.9996 6 0.9996 54 0.9992 6
Kresoxim-methyl 0-200 0.9990 15 0.9974 15 0.9992 35
Linuron 0-1000 0.9986 50 0.9967 55 0.9996 42
Malathion 0-200 0.9985 14 0.9995 11 0.9816 30
Mepanipyrim 0-200 0.9993 24 0.9928 38 0.9995 11
Metalaxyl 0-1000 0.9999 20 0.9996 30 0.9980 37
Methacrifos 0-200 0.9994 3 0.9983 16 0.9951 19
14

Table 3 continued – residue plot RSD% <20% – residue plot RSD% >20%

Strawberry Wheat Flour Leek

Calibration Residue Youden Residue Youden Residue Youden
Compound Range Plot Plot Plot Plot Plot Plot
[ng/g] r2 r2 r2
Deviation Slope Deviation Slope Deviation Slope
[%RSD] [diff%] [%RSD] [diff%] [%RSD] [diff%]
Methamidophos 0-200 0.9995 0 0.9995 9 0.9967 33
Methidathion 0-200 0.9984 13 0.9997 14 0.9988 32
Methiocarb 0-2000 0.9988 2 0.9963 20 0.9876 33
Metribuzin 0-1000 0.9997 21 0.9996 22 0.9995 28
Monocrotophos 0-1000 0.9997 36 0.9990 11 0.9982 45
Myclobutanil 0-200 0.9994 2 0.9979 8 0.9991 20
Ortho-phenylphenol 0-200 0.9999 4 0.9995 18 0.9945 24
Oxadiazon 0-200 0.9999 8 0.9968 11 0.9956 28
Oxadixyl 0-200 0.9997 5 0.9969 4 0.9989 25
Paclobutrazol 0-200 0.9996 4 0.9997 1 0.9988 15
Paraoxon-methyl 0-1000 0.9957 40 0.9964 27 0.9875 43
Parathion (ethyl) 0-1000 0.9968 7 0.9956 4 0.9964 20
Parathion-methyl 0-200 0.9996 24 0.9985 30 0.9997 35
Pendimethalin 0-200 0.9950 15 0.9910 121 0.9937 75
Permethrin 0-200 0.9951 27 0.9961 70 0.9970 13
Phenthoate 0-1000 0.9991 18 0.9989 25 0.9996 32
Phosalone 0-200 0.9976 2 0.9921 33 0.9939 12
Phosmet 0-200 0.9972 28 0.9961 34 0.9922 61
Phosphamidon 0-200 0.9989 42 0.9997 37 0.9961 70
Pirimicarb 0-200 0.9998 16 0.9997 22 0.9990 32
Pirimicarb-p-desmetyl 0-1000 0.9999 26 0.9998 28 0.9994 36
Pirimiphos methyl 0-200 0.9987 15 0.9980 4 0.9986 25
Prochloraz 0-1000 0.9924 9 0.9974 37 0.9925 12
Procymidone 0-200 0.9999 17 0.9996 6 0.9969 26
Profenofos 0-200 0.9988 2 0.9992 >200 0.9940 34
Propargite 0-200 0.9991 9 0.8967 17 0.9997 51
Propiconazole 0-200 0.9986 13 0.9976 15 0.9877 10
Propyzamide 0-200 0.9999 9 0.9995 14 0.9946 25
Prothiofos 0-200 0.9993 20 0.9987 80 0.9986 4
Pyraclostrobin 0-200 0.9997 6 0.9954 56 0.9964 1
Pyridaben 0-200 0.9961 29 0.9967 79 0.9953 14
Pyrimethanil 0-200 0.9999 13 0.9997 13 0.9963 20
Pyriproxyfen 0-200 0.9982 1 0.9964 12 0.9996 17
Quinoxyfen 0-200 0.9977 15 0.9979 28 0.9998 2
Spirodiclofen 0-200 0.9995 7 0.9974 8 0.9950 34
Tebuconazole 0-200 0.9995 17 0.9969 22 0.9986 3
Tebufenocide 0-1000 0.9980 11 0.9975 34 0.9984 12
Tebufenpyrad 0-200 0.9987 8 0.9996 126 0.9996 4
Tefluthrin 0-200 1.0000 14 0.9994 20 0.9929 31
Tetraconazole 0-1000 0.9997 17 0.9997 13 0.9975 33
Tetradifon 0-200 0.9998 10 0.9959 11 0.9989 30
Tetrahydrophthalimide 0-200 0.9645 106 0.9638 51 0.8388 93
 15

Table 3 continued – residue plot RSD% <20% – residue plot RSD% >20%

Strawberry Wheat Flour Leek

Calibration Residue Youden Residue Youden Residue Youden
Compound Range Plot Plot Plot Plot Plot Plot
[ng/g] r2 r2 r2
Deviation Slope Deviation Slope Deviation Slope
[%RSD] [diff%] [%RSD] [diff%] [%RSD] [diff%]
Thiabendazole 0-1000 0.9987 9 0.9996 8 0.9998 28
Tolclofos-methyl 0-200 0.9998 27 0.9990 57 0.9987 6
Tolyfluanid 0-1000 0.9970 6 0.9989 47 n.d. n.d. n.d.
Triadimefon 0-1000 0.9987 7 0.9996 8 0.9995 22
Triadimenol 0-1000 0.9993 2 0.9991 8 0.9992 26
Trifloxystrobin 0-200 0.9985 17 0.9978 61 0.9994 3
Trifluralin 0-200 0.9913 311 0.9973 62 0.9821 30
Triticonazole 0-200 0.9977 27 0.9975 70 0.9983 20
Vinclozolin 0-200 0.9996 18 0.9983 22 0.9973 27

Table 4: Recovery values [%] at 10 ng/g (level 1),

20 ng/g (level 2) and 100 ng/g (level 3) spike levels. * spiking levels are 50, 100 & 500 ng/g ** spiking levels are 100, 200 & 1000 ng/g <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Compound
Level 1 Level 2 Level 3 Level 1 Level 2 Level 3 Level 1 Level 2 Level 3
Acephate 84 88 63 68 75 60 68 72 56
Acrinathrin 100 79 67 121 118 85 129 69 24
Amitraz** 98 79 57 n.d. n.d. n.d. 126 95 69
Azinphos-methyl* 127 102 79 101 128 99 126 88 68
Azoxystrobin* 101 87 67 111 123 95 78 88 82
Bifenthrin 101 104 73 94 117 76 94 108 84
Bitertanol 101 109 82 116 118 81 82 109 88
Boscalid (Nicobifen) 93 101 81 111 116 83 111 111 86
Bromopropylate 92 109 90 117 114 82 97 111 89
Bromuconazole 87 106 90 108 114 79 88 106 88
Bupirimate* 83 111 101 105 113 83 93 120 99
Buprofezin* 82 112 97 100 112 80 100 125 97
Cadusafos 78 109 88 96 111 85 68 111 95
Captan 74 42 71 42 32 66 n.d. n.d. n.d.
Carbaryl* 106 81 65 110 100 71 83 76 72
Carbofuran 87 99 85 106 133 107 <LOQ 54 43
Carboxin 96 107 94 99 100 80 83 107 89
Chlorfenapyr* 86 112 100 104 118 83 84 118 99
Chlorfenvinphos 101 110 89 105 119 91 84 98 79
Chlorobenzilate 87 114 94 115 123 73 85 123 97
Chlorothalonil 133 73 36 76 56 62 n.d. n.d. n.d.
Chlorpropham 84 113 94 87 109 86 73 118 100
Chlorpyrifos-ethyl 86 110 87 95 113 88 91 132 100
Chlorpyrifos-methyl 114 112 80 100 121 95 93 135 103
Cyfluthrin 102 103 77 127 114 73 119 98 67
Cyhalothrin 103 85 79 117 118 86 104 77 65
16

Table 4 continued * spiking levels are 50, 100 & 500 ng/g ** spiking levels are 100, 200 & 1000 ng/g <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Compound
Level 1 Level 2 Level 3 Level 1 Level 2 Level 3 Level 1 Level 2 Level 3
Cypermethrin 84 86 73 181 136 84 112 112 80
Cyproconazole 83 103 88 111 112 80 73 107 89
Cyprodinil 21 30 24 106 109 81 84 120 92
DDD p,p 96 105 86 88 108 85 79 120 100
DDE p, p 76 104 85 89 100 75 80 121 96
DDT p,p 97 94 68 124 141 120 82 118 90
Deltamethrin 100 77 56 114 107 70 93 84 58
Demeton-S-methyl* 93 106 84 97 111 93 96 122 92
Diazinon 87 113 91 95 110 86 77 125 101
Dichlofluanid* 110 72 62 37 48 73 <LOD <LOD 55
Dichloran 83 109 95 106 120 92 78 116 90
Dichlorbenzophenon, p,p'- 77 104 86 <LOD <LOQ 84 <LOQ 105 103
Dichlorvos 89 122 92 98 118 112 98 112 85
Dicofol 86 98 85 114 114 80 83 103 85
Difenoconazole 93 104 80 101 113 90 66 87 69
Dimethoate 86 95 82 79 113 95 94 117 86
Dimethomorph 92 99 73 90 124 114 86 102 81
Diphenylamine 102 107 74 56 70 79 75 122 95
Endosulfan* 86 101 78 114 121 67 76 118 97
Endosulfan sulfate 102 109 87 126 129 86 114 122 95
EPN 121 113 84 134 123 96 122 122 85
Epoxiconazole 103 116 88 109 119 86 89 116 95
Ethion 112 110 84 116 120 86 77 116 97
Ethoprop (Ethoprophos) 91 99 73 99 111 89 72 114 97
Etofenprox 91 101 79 119 114 78 89 103 82
Fenamiphos 90 103 92 68 84 71 75 103 87
Fenamiphos sulfone 106 95 66 119 117 92 63 51 57
Fenamiphos-sulfoxid** 144 150 117 119 137 131 65 89 91
Fenarimol 95 100 79 111 115 79 85 101 83
Fenbuconazol 100 110 85 123 123 85 92 113 92
Fenitrothion 105 102 83 107 123 94 111 129 96
Fenoxycarb 98 103 85 114 120 89 97 112 91
Fenpropathrin 86 105 91 <LOD <LOD 82 <LOD <LOD 77
Fenpropidin* 35 36 23 43 29 26 n.d. 9 20
Fenpropimorph 59 79 65 68 79 62 40 80 73
Fenthion 87 100 108 61 84 77 108 122 102
Fenvalerate 82 93 79 111 118 85 99 109 81
Fipronil 89 110 92 119 119 96 74 104 83
Fludioxonil <LOD <LOD 55 104 117 68 87 117 98
Fluquinconazole 99 102 82 96 108 84 92 110 91
Flusilazole 90 119 99 123 112 85 75 99 101
Flutolanil 88 116 100 93 114 86 87 122 99
Flutriafol 85 108 91 77 114 66 81 114 92
Fluvalinate 35 97 77 121 122 91 98 101 76
Folpet** 133 34 45 66 36 29 <LOD <LOD <LOQ
 17

Table 4 continued * spiking levels are 50, 100 & 500 ng/g ** spiking levels are 100, 200 & 1000 ng/g <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Compound
Level 1 Level 2 Level 3 Level 1 Level 2 Level 3 Level 1 Level 2 Level 3
HCH alpha 79 109 87 113 121 88 84 135 108
HCH beta 85 111 90 109 110 85 87 138 109
HCH gamma_Lindane 87 110 89 115 123 88 81 132 106
Hexaconazole* 95 97 84 95 103 75 90 111 88
Imazalil* 72 97 84 87 102 67 69 96 78
Iprodione 109 111 86 120 124 94 109 102 84
Isofenphos-methyl 85 111 92 99 112 89 94 128 103
Kresoxim-methyl 86 111 96 114 119 85 86 120 101
Linuron* 126 118 95 95 100 63 126 133 98
Malathion 108 106 90 83 122 101 150 121 88
Mepanipyrim 82 111 96 123 138 72 93 121 95
Metalaxyl* 84 111 91 97 115 90 75 115 95
Methacrifos 89 108 78 82 109 96 66 130 103
Methamidophos 56 60 63 59 61 50 97 73 51
Methidathion 110 106 84 99 118 94 106 125 98
Methiocarb** 85 98 81 <LOD <LOD 75 <LOD <LOQ 78
Metribuzin* 87 111 98 89 117 84 94 129 99
Monocrotophos* 90 92 74 110 99 60 107 87 63
Myclobutanil 91 115 96 104 109 83 77 116 94
Ortho-phenylphenol 95 102 74 63 75 78 61 120 99
Oxadiazon 84 115 95 111 117 81 69 117 100
Oxadixyl 89 108 87 116 118 84 76 108 93
Paclobutrazol 81 106 91 95 109 85 90 111 91
Paraoxon-methyl* 102 108 109 137 146 111 132 117 73
Parathion (ethyl)* 69 98 101 54 95 95 120 132 100
Parathion-methyl 83 107 98 108 129 95 101 138 105
Pendimethalin 45 81 118 51 73 85 117 132 96
Permethrin 109 107 83 109 115 81 91 112 94
Phenthoate* 83 111 105 124 124 95 99 125 97
Phosalone 115 106 82 97 87 83 103 108 86
Phosmet 114 87 71 104 115 88 107 85 63
Phosphamidon 109 112 95 115 131 98 53 64 120
Pirimicarb 85 110 87 90 113 90 77 118 94
Pirimicarb-p-desmetyl* 79 99 81 85 106 82 82 122 89
Pirimiphos methyl 90 109 93 116 113 93 71 111 92
Prochloraz* 117 94 72 112 124 87 76 86 71
Procymidone 85 107 87 84 115 86 82 119 98
Profenofos 112 107 89 112 108 90 119 89 77
Propargite 104 104 90 <LOD <LOD 58 62 89 88
Propiconazole 89 95 74 102 110 77 79 107 90
Propyzamide 84 110 89 100 116 88 90 133 103
Prothiofos 73 96 92 95 99 82 89 104 81
Pyraclostrobin 100 116 90 128 139 97 101 123 92
Pyridaben 111 110 86 108 114 81 92 108 87
Pyrimethanil 78 103 84 84 103 84 70 118 95
18

Table 4 continued * spiking levels are 50, 100 & 500 ng/g ** spiking levels are 100, 200 & 1000 ng/g <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Compound
Level 1 Level 2 Level 3 Level 1 Level 2 Level 3 Level 1 Level 2 Level 3
Pyriproxyfen 101 107 84 106 113 81 90 112 92
Quinoxyfen 89 97 79 95 100 75 81 105 85
Spirodiclofen 91 88 78 132 113 75 <LOQ 96 71
Tebuconazole 80 95 75 100 111 79 89 110 91
Tebufenocide* 86 101 43 <LOD <LOQ 84 <LOQ 106 87
Tebufenpyrad 80 102 89 101 104 89 70 91 78
Tefluthrin 85 109 87 86 109 86 72 126 102
Tetraconazole* 84 108 93 98 115 89 79 118 101
Tetradifon 77 119 106 104 112 78 75 116 95
Tetrahydrophthalimide (THPI) <LOQ <LOQ 90 <LOQ 117 115 <LOQ 111 95
Thiabendazole* 77 96 82 83 88 67 75 97 79
Tolclofos-methyl 81 108 89 102 110 84 91 119 83
Tolyfluanid* 111 71 67 87 79 77 n.d. n.d. n.d.
Triadimefon* 76 106 98 95 111 88 91 121 100
Triadimenol* 79 106 87 96 110 82 77 103 90
Trifloxystrobin 103 111 87 103 112 87 94 123 97
Trifluralin 121 84 59 54 39 50 77 50 87
Triticonazole 101 105 82 106 112 81 88 106 86
Vinclozolin 89 114 94 130 107 75 67 111 90

Table 5. Method precision and intermediate precision values [RSD %]

at 10 ng/g (level 1), 20 ng/g (level 2) and 100 ng/g (level3). * spiking levels are 50, 100 & 500 ** spiking levels are 100, 200 & 1000 <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Precision Precision Precision
Compound Intermediate Intermediate Intermediate
Level Level Level Precision Level Level Level Precision Level Level Level Precision
1 2 3 1 2 3 1 2 3
Acephate 7 7 12 15 29 4 27 9 12 18 8 22
Acrinathrin 32 51 18 37 9 3 7 5 4 20 17 22
Amitraz** 5 11 11 14 n.d. n.d. n.d. n.d. 3 7 15 27
Azinphos-methyl* 2 4 7 5 6 1 6 3 6 10 7 23
Azoxystrobin* 3 6 2 7 12 4 4 12 5 6 10 11
Bifenthrin 6 10 3 9 13 6 5 9 15 12 8 13
Bitertanol 2 3 2 4 4 2 4 2 2 6 11 10
Boscalid (Nicobifen) 3 3 2 3 3 2 3 2 6 2 11 7
Bromopropylate 7 8 4 10 10 5 6 8 5 13 7 13
Bromuconazole 2 4 2 4 7 3 4 3 2 6 9 11
Bupirimate* 6 3 3 4 3 3 3 3 6 5 9 6
Buprofezin* 6 4 3 5 4 3 3 4 2 4 8 4
Cadusafos 7 9 3 8 15 3 12 5 2 7 6 6
Captan 31 64 15 75 28 21 52 66 n.d. n.d. n.d. n.d.
Carbaryl* 10 13 8 25 18 3 20 9 <LOQ 22 15 29
Carbofuran 18 5 4 16 27 5 17 11 11 40 20 50
Carboxin 7 4 2 7 6 4 3 6 4 5 7 7
 19

Table 5 continued * spiking levels are 50, 100 & 500 ** spiking levels are 100, 200 & 1000 <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Precision Precision Precision
Compound Intermediate Intermediate Intermediate
Level Level Level Precision Level Level Level Precision Level Level Level Precision
1 2 3 1 2 3 1 2 3
Chlorfenapyr* 5 7 5 6 11 5 6 6 4 5 6 8
Chlorfenvinphos 4 5 4 7 33 5 15 37 3 4 8 10
Chlorobenzilate 3 7 4 6 5 3 38 4 3 5 8 6
Chlorothalonil 4 18 18 16 38 9 27 11 n.d. n.d. n.d. n.d.
Chlorpropham 4 5 3 4 20 4 12 6 4 8 5 5
Chlorpyrifos-ethyl 5 7 2 6 11 7 10 8 13 7 7 6
Chlorpyrifos-methyl 5 3 5 6 17 3 12 6 8 5 6 5
Cyfluthrin 6 7 3 7 4 2 5 3 9 19 13 19
Cyhalothrin 8 25 9 19 3 3 3 3 3 20 15 18
Cypermethrin 6 12 5 9 11 2 3 3 17 9 12 13
Cyproconazole 5 4 3 4 4 2 2 3 5 6 7 4
Cyprodinil 3 8 3 6 7 5 8 7 8 6 6 8
DDD p,p 2 3 2 5 2 4 3 4 4 5 6 7
DDE p, p 7 7 4 6 6 4 2 5 4 6 5 16
DDT p,p 4 9 4 18 10 3 7 6 3 4 9 9
Deltamethrin 9 32 11 23 15 2 4 6 5 18 13 19
Demeton-S-methyl* 1 6 4 5 12 4 13 9 5 4 7 11
Diazinon 7 9 3 6 14 4 13 6 12 8 6 6
Dichlofluanid* 8 25 12 20 56 20 17 17 <LOD <LOD 90 n.d.
Dichloran 11 10 4 8 11 5 16 6 10 8 5 8
Dichlorbenzophenon, p,p'- 14 18 5 14 <LOD <LOQ 11 n.d. <LOQ 16 7 18
Dichlorvos 5 7 8 13 28 5 19 9 8 7 10 9
Dicofol 9 4 2 5 5 1 4 4 5 2 10 8
Difenoconazole 7 4 3 10 19 5 5 14 10 5 3 12
Dimethoate 10 10 6 12 17 3 11 10 5 5 6 8
Dimethomorph 5 3 3 11 18 7 9 13 5 7 9 6
Diphenylamine 7 7 3 6 33 12 19 21 8 12 7 8
Endosulfan* 9 10 5 8 6 7 46 21 17 8 6 6
Endosulfan sulfate 9 3 4 5 4 3 4 3 4 6 9 6
EPN 4 3 3 11 8 4 4 11 4 6 9 6
Epoxiconazole 4 5 2 4 6 3 6 2 5 4 7 5
Ethion 1 3 2 3 4 2 3 2 8 7 9 5
Ethoprop (Ethoprophos) 2 7 2 5 16 4 13 12 4 6 6 5
Etofenprox 3 5 2 6 4 2 2 2 3 3 9 6
Fenamiphos 9 7 3 8 10 4 7 6 5 9 12 10
Fenamiphos sulfone 11 30 10 27 12 2 5 11 15 19 17 16
Fenamiphos-sulfoxid** 8 22 7 28 26 3 12 17 9 5 21 9
Fenarimol 3 3 1 3 7 2 3 3 3 5 9 9
Fenbuconazol 3 5 3 4 3 3 3 2 1 6 10 5
Fenitrothion 9 7 4 8 16 4 11 8 5 5 7 7
Fenoxycarb 3 3 2 3 6 5 5 7 2 7 8 8
Fenpropathrin 9 4 2 4 <LOD <LOD 8 n.d. <LOD <LOD 13 n.d.
Fenpropidin* 27 26 11 21 29 12 61 15 n.d. 37 17 42
20

Table 5 continued * spiking levels are 50, 100 & 500 ** spiking levels are 100, 200 & 1000 <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Precision Precision Precision
Compound Intermediate Intermediate Intermediate
Level Level Level Precision Level Level Level Precision Level Level Level Precision
1 2 3 1 2 3 1 2 3
Fenpropimorph 7 11 3 7 14 6 8 8 18 10 9 9
Fenthion 16 5 6 13 30 12 9 48 12 13 5 10
Fenvalerate 5 8 3 7 7 2 3 2 3 4 12 9
Fipronil 8 5 3 7 24 4 18 17 11 4 4 17
Fludioxonil <LOD <LOD 6 n.d. 7 5 46 5 6 9 5 8
Fluquinconazole 7 7 5 7 13 4 4 11 3 6 10 16
Flusilazole 12 14 3 9 7 7 4 7 14 15 6 15
Flutolanil 5 2 2 5 8 4 6 5 4 8 8 8
Flutriafol 6 1 2 5 23 2 40 5 6 6 7 8
Fluvalinate 8 12 5 9 6 5 4 4 9 14 14 14
Folpet** 30 71 21 74 27 12 43 22 <LOD <LOD <LOQ n.d.
HCH alpha 7 9 3 6 9 4 11 5 3 8 5 13
HCH beta 7 8 3 7 18 4 10 7 7 8 7 12
HCH gamma_Lindane 10 9 1 7 12 4 11 4 10 9 6 10
Hexaconazole* 14 12 3 9 11 6 4 7 13 4 10 8
Imazalil* 7 4 3 4 9 5 10 4 6 4 10 8
Iprodione 12 4 4 5 6 5 8 7 7 7 11 10
Isofenphos-methyl 3 3 3 3 13 4 9 6 4 4 7 7
Kresoxim-methyl 1 6 4 5 5 2 5 3 8 4 6 5
Linuron* 5 5 7 18 18 6 20 12 5 4 10 9
Malathion 3 8 4 8 14 4 14 10 10 11 10 12
Mepanipyrim 10 4 3 6 13 4 22 8 4 7 9 5
Metalaxyl* 5 5 5 5 17 5 12 6 2 7 4 6
Methacrifos 11 11 3 7 75 3 17 8 7 11 6 11
Methamidophos 15 12 14 31 23 7 25 8 7 14 9 22
Methidathion 6 7 5 7 14 3 13 5 5 4 8 6
Methiocarb** 15 15 5 17 <LOD <LOD 11* n.d. <LOD <LOQ 11 n.d.
Metribuzin* 8 7 6 9 15 5 11 6 5 7 7 7
Monocrotophos* 13 13 11 20 9 2 13 6 6 15 10 18
Myclobutanil 5 3 3 6 1 5 3 4 6 9 5 7
Ortho-phenylphenol 4 7 3 6 31 12 15 20 4 8 6 6
Oxadiazon 3 9 4 7 5 4 6 4 9 8 6 8
Oxadixyl 4 4 4 5 8 2 4 3 7 5 8 8
Paclobutrazol 3 6 5 4 16 4 10 7 4 4 8 6
Paraoxon-methyl* 7 10 12 17 12 4 17 10 4 16 16 16
Parathion (ethyl)* 8 10 3 12 25 8 11 17 4 5 7 5
Parathion-methyl 13 11 6 9 8 7 12 8 4 5 7 4
Pendimethalin 22 20 5 25 17 13 11 32 8 9 6 14
Permethrin 3 4 3 4 2 3 4 3 4 10 11 8
Phenthoate* 5 7 4 6 5 3 13 23 3 5 8 4
Phosalone 2 5 2 4 42 3 3 22 4 10 8 10
Phosmet 7 10 9 14 6 1 8 4 6 23 13 26
Phosphamidon 7 9 10 21 20 2 15 8 76 42 24 62
 21

Table 5 continued * spiking levels are 50, 100 & 500 ** spiking levels are 100, 200 & 1000 <LOD/LOQ – spiking value below LOD/LOQ value

Strawberry Wheat Flour Leek

Precision Precision Precision
Compound Intermediate Intermediate Intermediate
Level Level Level Precision Level Level Level Precision Level Level Level Precision
1 2 3 1 2 3 1 2 3
Pirimicarb 9 7 5 6 13 5 12 6 7 9 6 7
Pirimicarb-p-desmetyl* 12 16 8 11 13 3 12 5 4 8 9 5
Pirimiphos methyl 6 6 4 5 10 4 11 22 6 7 6 5
Prochloraz* 4 3 4 7 9 5 7 10 5 6 14 6
Procymidone 8 6 4 7 16 2 8 10 8 6 7 9
Profenofos 19 12 7 13 14 8 12 12 13 27 12 31
Propargite 5 4 4 11 <LOD <LOD 56 n.d. 10 9 8 16
Propiconazole 2 2 3 4 8 4 11 3 3 6 8 6
Propyzamide 4 6 3 5 11 3 11 5 2 7 5 5
Prothiofos 9 3 4 6 17 5 8 17 8 10 6 11
Pyraclostrobin 5 3 3 8 2 2 3 2 2 3 11 5
Pyridaben 3 2 3 4 3 2 2 3 6 8 12 9
Pyrimethanil 4 7 2 6 13 3 8 5 3 9 7 6
Pyriproxyfen 3 4 2 4 4 1 3 1 2 4 8 6
Quinoxyfen 2 4 2 3 4 2 2 5 5 3 8 3
Spirodiclofen 10 6 5 13 14 5 10 10 <LOQ 11 12 17
Tebuconazole 3 2 1 3 6 3 7 2 3 3 9 7
Tebufenocide* 6 5 2 6 <LOD <LOQ 6 7 <LOQ 6 9 7
Tebufenpyrad 3 6 3 5 18 7 10 16 3 8 8 6
Tefluthrin 7 7 4 5 16 5 11 6 4 8 6 6
Tetraconazole* 4 6 4 4 13 4 11 6 4 4 6 4
Tetradifon 11 7 4 5 7 2 6 4 7 6 7 7
Tetrahydrophthalimide (THPI) <LOQ <LOQ 8 n.d. <LOQ 27 11 23 <LOQ 9 6 8
Thiabendazole* 5 3 4 3 16 3 14 6 4 5 9 7
Tolclofos-methyl 4 6 6 9 15 6 15 18 5 8 5 20
Tolyfluanid* 9 22 10 20 21 8 17 10 n.d. n.d. n.d. n.d.
Triadimefon* 4 4 2 5 12 3 9 6 1 6 6 7
Triadimenol* 9 7 3 7 10 3 9 10 9 7 7 5
Trifloxystrobin 4 4 2 3 6 4 3 3 4 8 8 6
Trifluralin 3 16 8 17 1 12 13 20 2 12 8 32
Triticonazole 7 3 3 3 4 3 2 3 5 6 9 6
Vinclozolin 15 4 6 8 16 6 14 14 23 9 7 10
22

Table 6: Method LOD, LOQ and current legislative residue level values (all values in ng/g). * default value of 10 ng/g set as no MRL values defined

Strawberry Wheat Flour Leek

Compound
LOD LOQ MRL LOD LOQ MRL LOD LOQ MRL
Acephate 0.3 1 20 0.6 2 20 1.5 5 20
Acrinathrin 6 20 200 2.7 9 50 6 20 50
Amitraz 6 20 50 300 1000 50 12 40 50
Azinphos-methyl 3 10 50 0.9 3 50 2.4 8 50
Azoxystrobin 0.9 3 1000 0.3 1 300 1.5 5 1000
Bifenthrin 6 20 500 4.8 16 500 7.5 25 50
Bitertanol 0.9 3 50 0.6 2 50 0.6 2 50
Boscalid (Nicobifen) 0.3 1 1000 0.15 0.5 500 0.6 2 5000
Bromopropylate 3 10 10 2.1 7 10 1.5 5 10
Bromuconazole 2.4 8 50 0.27 0.9 200 1.2 4 50
Bupirimate 3 10 1000 3 10 50 4.5 15 50
Buprofezin 6 20 3000 15 50 50 4.5 15 50
Cadusafos 1.5 5 10 0.3 1 10 1.5 5 10
Captan 3 10 3000 3 10 20 1000 1500 2000
Carbaryl 4.5 15 50 4.5 15 500 4.5 15 50
Carbofuran 9 30 20 3 10 20 4.5 15 20
Carboxin 1.8 6 20 6 20 20 0.6 2 20
Chlorfenapyr 4.5 15 10* 1.5 5 10* 3 10 10*
Chlorfenvinphos 1.5 5 10* 0.3 1 10* 1.2 4 10*
Chlorobenzilate 0.9 3 20 0.3 1 20 1.2 4 20
Chlorothalonil 12 40 5000 0.3 1 100 1500 2500 40000
Chlorpropham 1.5 5 50 0.6 2 20 1.2 4 50
Chlorpyrifos-ethyl 1.5 5 10* 0.3 1 10* 1.5 5 10*
Chlorpyrifos-methyl 1.5 5 500 0.3 1 3000 0.75 2.5 50
Cyfluthrin 4.5 15 20 3.6 12 20 2.4 8 20
Cyhalothrin 1.8 6 10* 0.9 3 10* 1.5 5 10*
Cypermethrin 4.5 15 70 15 50 2000 4.5 15 500
Cyproconazole 1.5 5 50 1.8 6 100 1.5 5 50
Cyprodinil 1.2 4 5000 0.3 1 500 1.5 5 50
DDD p,p 0.3 1 50 0.21 0.7 50 0.75 2.5 50
DDE p,p 0.3 1 10* 0.24 0.8 10* 1.2 4 10*
DDT o,p 0.6 2 10* 0.9 3 10* 0.6 2 10*
Deltamethrin 4.5 15 200 2.4 8 2000 7.5 25 200
Demeton-S-methyl 1.5 5 10* 1.5 5 10* 1.2 4 10*
Diazinon 0.3 1 10 0.3 1 20 0.3 1 10
Dichlofluanid 13.5 45 10* 3 10 10* 150 500 10*
Dichloran 4.5 15 300 3 10 10 2.4 8 100
Dichlorbenzophenon, p,p'- 3 10 10* 15 50 10* 4.5 15 10*
Dichlorvos 3 10 10 3 10 10 2.7 9 10
Dicofol 2.4 8 20 1.5 5 20 1.5 5 20
Difenoconazole 1.5 5 400 1.2 4 100 0.9 3 500
Dimethoate 1.2 4 20 0.6 2 50 0.6 2 20
Dimethomorph 1.5 5 10* 1.5 5 10* 0.6 2 10*
 23

Table 6 continued * default value of 10 ng/g set as no MRL values defined

Strawberry Wheat Flour Leek

Compound
LOD LOQ MRL LOD LOQ MRL LOD LOQ MRL
Diphenylamine 0.3 1 50 0.3 1 50 0.6 2 50
Endosulfan 1.5 5 50 6 20 50 1.2 4 50
Endosulfan sulfate 0.6 2 10* 1.5 5 10* 0.9 3 10*
EPN 2.1 7 10* 2.1 7 10* 0.9 3 10*
Epoxiconazole 1.2 4 50 0.6 2 600 0.6 2 50
Ethion 1.2 4 10 0.9 3 10 0.6 2 10
Ethoprop (Ethoprophos) 0.3 1 20 0.6 2 20 0.9 3 20
Etofenprox 0.9 3 1000 0.9 3 500 0.6 2 10
Fenamiphos 1.2 4 20 1.2 4 20 0.9 3 20
Fenamiphos sulfone 3.6 12 10* 0.9 3 10* 1.5 5 10*
Fenamiphos-sulfoxid 0.9 3 10* 10.5 35 10* 7.5 25 10*
Fenarimol 0.9 3 300 0.3 1 20 0.3 1 20
Fenbuconazol 0.6 2 50 0.6 2 100 0.75 2.5 50
Fenitrothion 3 10 10 1.5 5 50 2.4 8 10
Fenoxycarb 0.9 3 50 1.2 4 50 0.75 2.5 50
Fenpropathrin 7.5 25 2000 30 100 10 30 100 10
Fenpropidin 4.5 15 50 12 40 500 7.8 26 50
Fenpropimorph 0.15 0.5 1000 0.3 1 500 1.2 4 1000
Fenthion 1.5 5 10 1.8 6 10 1.5 5 10
Fenvalerate 2.25 7.5 20 1.5 5 50 0.9 3 20
Fipronil 0.3 1 5 1.5 5 5 0.9 3 10
Fludioxonil 30 100 3000 1.2 4 200 1.2 4 50
Fluquinconazole 0.6 2 50 0.3 1 100 0.6 2 50
Flusilazole 4.5 15 20 2.4 8 100 1.5 5 20
Flutolanil 0.6 2 50 0.3 1 50 0.6 2 50
Flutriafol 0.3 1 500 0.9 3 500 0.45 1.5 50
Fluvalinate 6 20 10* 3.6 12 10* 4.5 15 10*
Folpet 75 250 3000 450 1500 2000 600 2000 20
HCH alpha 0.3 1 10 0.3 1 20 0.3 1 10
HCH beta 0.3 1 10 0.3 1 20 0.3 1 10
HCH gamma_Lindane 0.15 0.5 10 0.3 1 10 0.6 2 10
Hexaconazole 9 0 200 4.5 15 100 4.5 15 20
Imazalil 1.5 0 50 6 20 50 1.8 6 50
Iprodione 1.5 5 1000 1.5 5 500 1.2 4 20
Isofenphos-methyl 0.3 1 10* 0.3 1 10* 1.2 4 10*
Kresoxim-methyl 1.5 5 1000 1.8 6 50 1.5 5 5000
Linuron 3 10 50 1.8 6 50 1.5 5 50
Malathion 3 10 20 10.5 35 8000 3.6 12 20
Mepanipyrim 1.8 6 2000 2.4 8 10 1.2 4 10
Metalaxyl 9 30 500 10.5 35 50 7.5 25 200
Methacrifos 0.9 3 50 1.8 6 50 0.9 3 50
Methamidophos 0.75 2.5 10 0.9 3 10 1.5 5 10
Methidathion 0.6 2 20 0.9 3 20 1.5 5 20
24

Table 6 continued * default value of 10 ng/g set as no MRL values defined

Strawberry Wheat Flour Leek

Compound
LOD LOQ MRL LOD LOQ MRL LOD LOQ MRL
Methiocarb 150 500 1000 300 1000 100 135 450 200
Metribuzin 0.6 2 100 1.8 6 100 2.1 7 100
Monocrotophos 3 10 10* 4.5 15 10* 3 10 10*
Myclobutanil 0.3 1 1000 1.2 4 20 1.2 4 20
Ortho-phenylphenol 1.5 5 10* 1.5 5 10* 1.5 5 10*
Oxadiazon 0.3 1 50 0.9 3 50 0.6 2 50
Oxadixyl 3 10 10 5.4 18 10 3 10 70
Paclobutrazol 0.9 3 500 0.3 1 20 1.2 4 20
Paraoxon-methyl 6 20 20 6 20 20 3 10 20
Parathion (ethyl) 12 40 10* 37.5 125 10* 12 40 10*
Parathion-methyl 0.6 2 10* 1.2 4 10* 1.5 5 10*
Pendimethalin 1.5 5 50 1.2 4 50 2.1 7 50
Permethrin 2.4 8 50 1.8 6 50 4.5 15 50
Phenthoate 12 40 10* 1.8 6 10* 7.5 25 10*
Phosalone 1.8 6 50 1.2 4 50 1.5 5 50
Phosmet 0.24 0.8 50 0.3 1 50 0.6 2 50
Phosphamidon 0.3 1 10 3 10 10 3 10 10
Pirimicarb 0.9 3 3000 0.9 3 500 0.6 2 1000
Pirimicarb-p-desmetyl 0.9 3 10* 1.2 4 10* 1.5 5 10*
Pirimiphos methyl 0.27 0.9 50 0.6 2 5000 3 10 50
Prochloraz 15.6 52 50 30 100 500 15 50 50
Procymidone 3 10 20 3.9 13 20 1.8 6 20
Profenofos 3 10 50 2.1 7 50 2.1 7 50
Propargite 3 10 10 30 100 10 7.5 25 10
Propiconazole 1.8 6 50 1.2 4 50 0.6 2 100
Propyzamide 0.21 0.7 20 0.9 3 20 0.6 2 20
Prothiofos 2.4 8 10* 0.9 3 10* 1.5 5 10*
Pyraclostrobin 0.75 2.5 1000 0.3 1 100 0.3 1 500
Pyridaben 0.9 3 1000 1.8 6 50 1.5 5 50
Pyrimethanil 0.9 3 5000 1.5 5 50 1.2 4 1000
Pyriproxyfen 0.3 1 50 1.2 4 50 0.6 2 50
Quinoxyfen 0.15 0.5 300 0.24 0.8 20 0.6 2 20
Spirodiclofen 6 20 2000 6 20 20 6 20 20
Tebuconazole 1.5 5 50 0.24 0.8 200 0.3 1 1000
Tebufenocide 30 100 50 60 200 50 30 100 50
Tebufenpyrad 0.3 1 500 0.6 2 50 0.6 2 50
Tefluthrin 0.15 0.5 50 0.3 1 50 1.5 5 50
Tetraconazole 2.4 8 200 1.5 5 100 1.2 4 20
Tetradifon 1.2 4 10 1.8 6 10 0.9 3 10
Tetrahydrophthalimide (THPI) 7.5 25 10* 4.5 15 10* 4.5 15 10*
Thiabendazole 4.5 15 50 1.5 5 50 2.7 9 50
Tolclofos-methyl 0.3 1 50 0.6 2 50 2.1 7 50
Tolyfluanid 7.5 25 5000 1.8 6 50 1000 3000 10*
 25

Table 6 continued * default value of 10 ng/g set as no MRL values defined

Strawberry Wheat Flour Leek

Compound
LOD LOQ MRL LOD LOQ MRL LOD LOQ MRL
Triadimefon 0.6 2 500 2.1 7 200 1.2 4 100
Triadimenol 7.5 25 500 2.1 7 200 2.7 9 100
Trifloxystrobin 1.5 5 500 1.2 4 50 1.2 4 200
Trifluralin 15 50 100 4.5 15 100 3 10 500
Triticonazole 1.5 5 10 0.6 2 10 1.5 5 10
Vinclozolin 2.4 8 50 0.9 3 50 2.7 9 50

Table 7: External quality control (FAPAS) results for the relevant compounds.

Fapas Sample Assigned Value Acceptance Range Measured Value

Compound
Number [µg/kg] [µg/kg] [µg/kg] (RSD%)
Carbaryl T19142 89 49.9-128.2 51.2 (22)
beta Endosulfan T19140 93.6 52.4-134.9 91.3 (7)
Chlorpyrifos-methyl T19141 86.0 48.2-123.9 88.8 (8)
Cypermethrin T19141 128.8 72.3-184.1 111.9 (8)
Cypermethrin T19142 140.4 80.0-200.7 120.2 (17)
DDT, o,p T19141 67.4 37.8-97.1 38.7 (16)
Dicloran T19142 66.3 37.1-95.5 63.1 (15)
Dimethoate T19141 69.0 38.6-99.4 62.3 (15)
Ethoprophos T19142 29.3 16.4-42.4 25.7 (10)
Methidathion T19141 29.0 16.3-41.8 29.1 (19)
Monocrotophos T19141 26.4 14.8-38.0 36.8 (13)
Phosalone T19140 70.4 39.4-101.4 68.3 (9)
Propyzamide T19140 89.9 50.4-129.5 94.7 (4)

Figure 1. Chromatogram of isofenphos-methyl in leek at at calibration level 2 [5ng/g].

26

Figure 2. Chromatogram of ethoprop in leek at calibration level2 [5ng/g].

Figure 3. Chromatogram of both permethrine peaks in leek at calibration level3 [10ng/g].

 Me t h od 6 3 8 9 9
Figure 4. Chromatogram of captan in wheat flour at calibration level6 [100 ng/g].

Figure 5. Chromatogram of o-phenylphenol wheat flour at calibration level4 [25ng/g].

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