analysis of pesticide residues in animal products … acetate extraction and detection with gc- ......

Tuija Pihlström

National Food Agency

Sweden

Analysis of pesticide residues in food using

ethyl acetate extraction and detection with GC-

MS/MS and LC-MS/MS (SweEt)

LAPRW 2015 Santiago de Chile


Outlines of presentation

SweEt an alternative method for analysis

of pesticides in food

Validation according to EU SNACO 12571/2013 ”Analytical Quality

Control Procedures for Pesticide Residue Analysis i Food and Feed”

Example of reinforced import control (EC 669/2009) using the SweEt

method

Official control of pesticides at the National Food

Agency (NFA) in Sweden How is it organized?

Laboratories

National Reference Laboratory (NRL) and one official laboratory

(Eurofins), both accredited

Method development

• Most of the method development at the NFA. Transfer of the methods

to the official laboratory for validation and for monitoring of pesticides

Analytical methods

Mainly multi residue methods based on ethyl acetate extraction and

determination using LC-MS/MS and GC-MS/MS

Analysis

• 1800 of 2000 of the samples analysed by OfL (Eurofins)

•

history of the SweEt method

• Multi residue methods are a self-evident choice for analysis of

pesticide residues in food

• Since 1989 multi residue method based on extraction with

ethyl acetate method has been used

• At that time GC with various detectors was the main detection

technique

• The method has since then continuously been improved

including simplified sample preparation and faster analysis

• Introduction of animal product 2009 has further enlarged the

scope of the method

The simplified NFA´s MRM for FV

(448 analytes; 145 GC, 303 LC)

Extraction

10 g sample + 3 g NaHCO3

20 ml ethyl acetate and 10 g Na2SO4

Falcon tube SpexSample Prep 3 minutes

Centrifugation

in 3 min. (3800 g)

Filtration

Filtrate the crude extract

0.20 µm PTFE filter

Inject to GC-MS/MS and UPLC-MS/MS

Sample conc. 0.5g/ml

The simplified SweEt

Extraction 10 g sample+20 ml EtoAc

Falcon tube SpexShaker prep 3 min

↓ Centrifugation

↓

↓

↓

Filtration↓

↓

Inject to GC-MS/MS 0.5 g/ml

Inject to UPLC-MS/MS

0.5 g/ml

Fruit and

vegetables, MRM

Ethyl acetate method

Extraction 75 g sample+200 ml EtoAc

Waring blendor 3 min

↓

Decant and filtrate through Na2 SO4

↓

Concentration and redissolve

↓

GPC clean up

Concentration and redissolve

↓

Filtration

↓

↓

Solvent switch for LC

↓

Inject to GC-MS/MS 1.5 g/ml

Inject to LC-MS/MS 2.5 g/ml

Steps MIn Min

Extraction 3 3

Centrifugation 3

Filtration 5 2

Concentration/redissolve 15

Clean up 45

Concentration/redissolve 10

Filtrate 2 2

Solvent change 15

95 10

Fat determination

↓ Extraction

0.5 g fat

10 ml EtAc:cyhex (1+1) 3 min Spex shaker

Na2SO4

↓

Centrifugation

Filtration

↓

GPC SX-3 (1+1 EtOAc/cyklohexane)

↓

Evaporation

↓

Reconstitution in EtOAc

↓ ↓

GC-MS/MS

UPLC-MS/MS

Extraction

10 g sample 20 ml EtAc+NaHCO3

3 min Spex shaker Na2SO4

↓ Centrifugation

Filtration

GC-MS/MS

UPLC-MS/MS

Extraction

5 g sample 10 ml water

10 ml EtAc (1 % Hac)

3 min Spex shaker Na2SO4

↓

Centrifugation

↓

Filtration

↓ ↓

GC-

MS/MS

UPLC-MS/MS

Extraction

5 g sample PSA + C18

10 ml EtAc 3 min Spex shaker

Na2SO4

315 96

Centrifugation

Filtration

GC-MS/MS

UPLC-MS/MS

FV +honey Cereals AO<10%fat AO>10% fat

↓ 76

National Food Agency,

Sweden


Advantages of the SweEt method • Fast and non-laborious

• Negligible sample work up costs

• No evaporative concentration steps

• The extract is injected directly into the GC and LC

• The need of clean up has been eliminated (almost)

• Low amounts of matrix components as proteins and sugar which

often interfere with the chromatographic are co extracted.


Sweden


The study of different extraction solvents and the amount of co extracted matrix components J. Klein and L. Alder: Development of a Multi-Analyte / Multi-Matrix

Method Based on LC-MS/MS; EPRW 2002. Rome 28.- 31.05.2002

Type of solvent

Matrix Matrix type Amount of extracted sample

Acetone /water

2+1

Acetonitrile /water 2+1

Methanol /water

2+1

Water Ethyl acetate

Tomato High water content 1.0g 38mg 36mg 34mg 33mg 8mg

Citrus High acid and

high water content

1.0g 79mg 69mg 81mg - 3mg

Raisins High sugar an

low water content

1.0g 370mg 148mg 333mg 302mg 4mg

Avocado High oil content 1.0g 33mg 40mg 30mg 43mg 332mg

Even the sun has spots……….

National Agency, Sweden LAPRW 2015 Santiago de Chile

Limitations

Distorted or split peak shapes

Solvent composition ”solvent effect”

• The injection solvent is stronger than the mobile phase (MP)

• EtOAc not diluted immediately with MP, some of the analyte molecules

are diluted and migrated with the MP resulting in split peaks

• Early Peaks (low k) most affected (2-5 min)

• It is important to keep the injection volume low 2 µl is recommended to

avoid the peak split.


Sweden


Oxydemetonmethyl in

MeOH

MP: Buffert/MeOH (90/10)

Oxydemetonmethyl in

EtOAc

National Food Agency

Sweden

Validation in multi residue methods

Requirements for official laboratories

1. Implementation of Guidance document on analytical

quality control and validation procedures for pesticide

residues analysis in food an feed SANCO12571/2013

1. Accredited according to the ISO/IEC 17 025 standard

1. Participation in EU Proficiency tests

Guidance document on analytical quality control and validation

procedures for pesticide residues analysis in food an feed

SANCO12571/2013

To reach a complete harmonization of quality assurance measures

for pesticide residue analysis within Europe

To help monitoring laboratories achieve an acceptable standard

The reported results are reliable and consistent with other similar

results

Why do we need the guidelines?

The key objectives of the guidelines

To harmonize cost effective AQC in the EU (to find an

optimum between cost and output

(efficiency/quality)

To ensure false positives or false negatives are not reported

To support compliance with ISO/IEC 17025 accreditation

standard

Guidance in

The whole analytical chain (from sampling to reporting

results)

To define minimum criteria for validation and analysis (allows

free choice of method)

Table of contents

• Accreditation

• Sampling, transport, processing and storage of samples

• Pesticide standards, calibration solutions, etc.

• Extraction and concentration

• Contamination and interference

• Analytical calibration, representative analytes

• Analytical methods and analytical performance

• Method validation

• Routine recovery determination

• Proficiency testing and analysis of reference materials

• Confirmation of results

• Reporting of results

Example of representative commodities fruit vegetables

Commodity Categories

Commodities included in this category

Typical representative commodities

1.High water content Pome fruit

Stone fruit

Apples, pears

Apricots, carrots

2.High acid content and high water content

Citrus fruit Lemon, mandarin, orange

3.High sugar and low

water content

Honey, dried fruit Honey, raisins, dried apricots, dried

plums, fruit jams

4a. High oil content

and very low water

content

Tree nuts Walnuts, hazelnuts, chestnuts

4b. High oil content

and intermediate water

content

Oily fruits and products Olives, avocados and pastes

thereof

Example of validation according to the SANCO

12571/2013

Full validation in three different commodity groups

high water and high acid content, e.g. orange

high water content, e.g. cucumber or carrot

high sugar and low water content, e.g. raisins

Recovery study:

5 spiked samples at target LOQ (0,01 mg/kg)

5 spiked samples at 2-10 * target LOQ (0,05 mg/kg)

Parameter What/how Criterion

Linearity Through calibration curve Residuals < ±20%

Matrix effect Comparison of response from

solvent standards and matrix-

matched standards

20% small effect

LOQ By definition: lowest level for which

it has been demonstrated that

criteria for trueness and precision

have been met

≤ MRL

Specificity Response in reagent blank and

control samples

< 30% of LOQ

Precision (RSDr) Determine repeatability RSDr,

determine for both spike levels

≤ 20%

Precision* (RSDwR) Determine within-laboratory

reproducibility*

≤ 20%

Robustness Can be derived from on-going

method validation / verification

through establishing average

recovery and RSDwR?

See above

Trueness (bias)

Determine the average recovery for

spike levels

70-120%

Table 1. Validation parameters criteria.

Validation results of fruit and vegetables GC analytes 145, LC ES+/ES- analytes 303

Matrix group Detection Spiking level

(mg/kg) Mean recovery

(%) Mean RSD

(%) Number of results

High acid content and high water content GC-MS/MS 0,01 97 8,95 204

High acid content and high water content GC-MS/MS 0,05 100 7,25 142

High acid content and high water content LC-MS/MS ES- 0,01 87 9,59 25

High acid content and high water content LC-MS/MS ES- 0,05 89 6,32 26

High acid content and high water content LC-MS/MS ES+ 0,01 89 7,51 262

High acid content and high water content LC-MS/MS ES+ 0,05 89 4,87 272

High sugar and low water content GC-MS/MS 0,01 100 8,72 148

High sugar and low water content GC-MS/MS 0,05 104 6,91 149

High sugar and low water content LC-MS/MS ES- 0,01 94 4,4 11

High sugar and low water content LC-MS/MS ES- 0,05 98 3,91 13

High sugar and low water content LC-MS/MS ES+ 0,01 94 4,52 274

High sugar and low water content LC-MS/MS ES+ 0,05 97 3,18 271

High Water Content GC-MS/MS 0,01 101 9,24 207

High Water Content GC-MS/MS 0,05 103 6,35 140

High Water Content LC-MS/MS ES- 0,01 93 8,13 23

High Water Content LC-MS/MS ES- 0,05 88 5,64 23

High Water Content LC-MS/MS ES+ 0,01 95 4,92 259

High Water Content LC-MS/MS ES+ 0,05 94 4,34 262

Matrix effects – Orange, LC-MS/MS

Only 24 of 219 pesticides have >20 % matrix effect.

– in samples were those are found, true matrix-matching is used.

Standard in blank carrot extract. Tested at 0.05 mg/kg. Agilent 6460.

-60,0

-40,0

-20,0

0,0

20,0

40,0

60,0

Matr

ix e

ffect

(%

)

Pesticide

-30,0

-20,0

-10,0

0,0

10,0

20,0

30,0

Matr

ix e

ffect

(%

)

Pesticide

Matrix effects – Orange, GC-MS/MS

Only 1 of 129 analyte has >20 % matrix effect (Tetrachloroaniline-2,3,5,6, +27 %). – in samples were

found, true matrix-matching is used.

Standard in blank cucumber extract. Tested at 0.05 mg/kg. Thermo TSQ Quantum XLS.

Matrix effects – Raisins, LC-MS/MS

-60,0

-40,0

-20,0

0,0

20,0

40,0

60,0

Matr

ix e

ffect

(%

)

Pesticide

• Only 17 of 219 pesticides have >20 % matrix effect.

– in samples were those are found, matrix-matching is used for quantification.

Standard in blank carrot extract. Tested at 0.05 mg/kg. Agilent 6460.

-35

-25

-15

-5

5

15

25

35

45

Matr

ix e

ffect

(%

)

Pesticide

Matrix effects – Raisins, GC-MS/MS

26 of 129 pesticides have a matrix effects >20 %) - in samples were those are found, matrix-matching is used.

Standard in blank cucumber extract. Tested at 0.05 mg/kg. Thermo TSQ Quantum XLS.

SweEt in EU RL Proficiency tests:

Proficiency Test 1-4 for cereals


Sweden


Fat content in selected food Ref. The Food Database. NFA

Product *Total fat % Triglycerides %

Milk 3 %

3.1 2.3

Egg

9.7 8.5

Liver

3.0 2.8

Butter

82 79.3

*Phospholipid. Triglycerides, stereols


Sweden


Analysis of pesticides in products with animal products

Extraction

5 g sample + 0.2 g PSA and 0.2 g C18

10 ml ethyl acetate

Spex SamplePrep 3 min

0.5 g Na2SO4

Centrifugation and filtration In 3 min. (3800 g). filtrate the crude extract with 0.20 µm PTFE filter

Inject to GC-MS/MS and UPLC-MS/MS

Sample conc. 0.5g/ml


Results EU PT AO 9 Test material: Liquid Whole Egg

National Food

Administration. Sweden

AOAC2015

Pesticide Conc mg/kg Conc mg/kg Conc mg/kg NFA Eurofins

Spiked Assigned Found Z score Z score

Dieldrin 0,03 0.0268 0.031 0,6 0,8

Endosulfansulfat 0,045 0.0289 0.036 0,9 1

Endrin 0,015 0.0141 0.011 -0,9 2

gamma-HCH (Lindane) 0,033 0.0256 0.033 1,2 0,9

Trans- Heptachlorepoxid 0,051 0.0438 nd -3,5 0,9

Diazinon 0,065 0.0588 0.062 0,2 0,6

Parathion 0,105 0.0862 0.097 0,5 1

Phoxim 0,15 0.122 0.17 1,6 0,4

Deltamethrin 0,075 0.0562 0.078 1,6 1,1

Permethrin 0,3 0.251 0.34 1,4 0,8


Fat determination Gravimetrical determination after extraction with EtOAc:Cyhe (1+1)

Extraction Amount of fresh sample that corresponds to 0.5 g of fat (2.5 g cream)

10 ml ethyl acetate + cyclohexane (1 + 1)

2.5g Na2SO4

Centrifugation & Filtration 3 min. 3800g

Filtrate crude extract 0.2 µm PFTE filter

Clean up 5.0 ml to GPC SX-3

Ethyl acetate + cyclohexane (1 +

1)

Evaporation To dryness with N2

Re-dissolve in 0.5 ml ethyl acetate

Inject into GC-MS/MS and LC-MS/MS Matrix conc. 0.5 g/ml

Multi method for analysis of pesticides in products with high fat content

76 analytes


Sweden


Butter – our challenge (slide from 2010. Heidi Pekar)

GPC Fat Profile 0.5 g butter

85

185

285

385

4 8 12 16 20 24 28 32 Time (min)

Resid

ue (m

g)

Pesticide Fraction Start

Pesticide Fraction End


Sweden


EU PT AO7 results 2012 - liquid cream

NFA. Sweden

(GPC)

Fat Content: 29%

Pesticide Z-scores

Bifentrin -0.2

cis-Chlordane -0.6

trans-Chlordane -0.2

DDE -1.0

Diazinon -0.5

Deltamethrin -0.1

Endosulfansulfate -0.5

Hexachlorbenzene -0.8

alfa-Endosulfan -0.1

alfa-HCH -0.6

beta-HCH -0.4

Lindane -0.9

Parathion-ethyl -0.1

Boscalid -0.5

Tetraconazole -0.4

Thiachloprid -1.3

Eurofins, Sweden

Mandatory pesticides

(GPC)

Fat Content: 29%

Pesticide Z-scores

Bifentrin -0.8

cis-Chlordane -0.4

trans-Chlordane -0.6

DDE -1.6

Diazinon -1.3

Deltamethrin -0.2

Endosulfansulfate -1.0

Hexachlorbenzene -1.4

alfa-Endosulfan -0.7

alfa-HCH -0.9

beta-HCH -0.9

Lindane -1.1

Paration-ethyl -1.0


Sweden


The presented method available: NMKL 195. 2013 ”Pesticide residues. Analysis in foods with ethyl acetate extraction using

gas and liquid chromatography with tandem mass spectrometric

determination“

EU RL website (fruit and vegetables only) Proposal at CEN level (animal products)

National Food

Administration. Sweden



Sweden


EU reinforced import control

Case: Vine leaves

Specific framework for the official feed and food controls

Regulation (EC) No 882/2004 includes requirements for the official

control of vegetables being imported from third countries. Article 15(5)

provides a list of certain products on the basis of known or emerging

risks and be subject to increased controls at points of entry into the EU.

The consignments may not be placed on the market before the

analysis is complete. Regulation 669/2009 implementing Regulation

882/2004 sets out rules for the increased level of official controls.


Sweden


Sample- vine leaves

Dolma is a family of stuffed vegetable dishes

originating from Ottoman Empire. The most-well

known type is stuffed vine leaves.

A lot of 8 300 kg vine leaves from Turkey was

subjected to the increased control.

The results originates

from a 4.5 kg

composite (bulk)

sample containing 10

bags of wine leaves á

450 g


Analyte Found residue MRL Analyte Found residue MRL

mg/kg mg/kg

Acetamiprid 0.014 0.01* Imidacloprid 0.063 2,00

Azoxystrobin 2,00 0.05* Indoxacarb 0.065 0.02*

Bifenthrin 0.052 0.05* Iprodion 0.86

Boscalid 1.4 0.05* Kresoxim-methyl 0.15 0.05*

Carbendazim 0.1 Lambda-cyhalothrin 0.046 0.02*

Chlorantraniliprole 0.019 20,0 Mandipropamid 0.005 0.01*

Chlorpyrifos 0.3 0.05* Metalaxyl 0.017

Cyflufenamid 0.019 0.02* Methoxyfenozide 0.5 0.02*

Cymoxanil 0.013 0.05* Metrafenone 0.82

Cypermethrin 0.016 Myclobutanil 0.03 0.02*

Deltamethrin 0.035 0.5 Penconazole 0.08 0.05*

Difenoconazole 0.036 0.05* Propargite 0.016

Dimethomorph 0.13 0.01* Proquinazid 0.011 0.02*

Dithiocarbamates 10.4 0.05* Pyrimethanil 0.92

Emamectin 0.014 0.01* Quinalphos 0.013 0.05*

Ethirimol 0.018 0.05* Tebuconazole 0.42 0.02*

Famoxadone 0.037 0.02* Tebufenpyrad 0.066 0.05*

Fenbutatin Oxide 10.9 0.05* Tetraconazole 0.052 0.02*

Fluopyram 0.084 0.01* Triadimefon (sum) 0.15 0.1

Hexythiazox 0.061 0.5 Trifloxystrobin 0.082 0.02*

Table 1 Results in vine leaves 40

analytes


Results

In total 40 residues were found thereof one pesticide using the single residue

method. In 26 cases the MRL was exceeded. Taking into account the 50%

measurement uncertainty, 17 pesticides (analytes) fulfilled the criteria for

enforcement.

However, none of the detected quantities of residues exceeded the acute

reference dose (ArfD).

Preliminary results from further analysis of the same lot (bulk sample) carried

out by

EURL FV, Almeria University (ES)

NVWA (NL)

Fera Science Ltd (U.K.)

EURL SRM; CVUA (DE)

EU RL CER, DTU (DK) (pending)

gave similar, consistent results

(taking into account the inhomogeneity in the bulk sample)


Analysis of vine leaves

Homogenate of same sample

Other individual sample

Homogenate of same sample

Other individual sample

Pesticide

NFA / Eurofins, Sweden mg/kg

EURL-FV, Spain mg/kg

NVWA, NL

mg/kg

Fera Science

Ltd U.K.

mg/kg

CVUA DE

mg/kg

Pesticide

NFA / Eurofins, Sweden mg/kg

EURL-FV, Spain mg/kg

NVWA, NL

mg/kg

Fera Science

Ltd U.K.

mg/kg

CVUA DE

mg/kg

Acetamiprid 0,014 0,019 n.d. n.d 0,001 Hexythiazox 0,061 0,095 0,010 n.d 0,006

Azoxystrobin 2,0 3,24 1,32 0,35 0,83 Imidacloprid 0,063 0,065 0,060 0,019 0,060

Bifenthrin 0,052 0,045 n.d. n.d 0,024 Indoxacarb 0,065 0,092 0,010 0,059 0,12

Boscalid 1,4 1,90 0,92 1,2 5.6 Iprodion 0,86 1,12 n.d. 0,22 0,015

Carbendazim 0,10 0,14

0,040 0,025 0,014

Kresoxim-methyl 0,15 0,25

0,13 0,15 0,41

Chlorantraniliprole 0,019 0,045 0,015 0,010 n.d Mandipropamid 0,005 0,018 n.d. n.d <0,001

Chlorpyrifos-ethyl 0,30 0,41 0,25 1,30 0,63 Metalaxyl 0,017 0,024 0,017 0,027 0,023

Cyflufenamid 0,019 0,022 0,040 0,007 0,014 Methoxyfenozie 0,50 0,832 0,44 0,33 0,46

Cyhalothrin-lambda 0,046 0,059 0,005 n.d 0,021 Metrafenone 0,82 n.a 1,13 0,5 2,2

Cymoxanil 0,013 0,014 n.d. n.d n.d Myclobutanil 0,03 0,046 0,018 n.d 0,015

Cypermethrin I-IV 0,016 n.d 0,012 n.d 0,013 Penconazole 0,08 0,11 0,10 0,04 0,084

Deltamethrin 0,035 0,03 <0,001 n.d 0,013 Propragite 0,016 0,041 n.d. n.d. 0,007

Difenoconazole I + II 0,036 0,072

0,033

0,008

0,002

Proquinazid 0,011 n.a

0,045 0,009 0,020

Dimetomorf 0,13 0,19 n.d n.d 0,008 Pyrimethanil 0.92 1,72 0,72 0,88 1,00

DITHIOCARBAMATES 10,4 n.a n.a 11 Quinalphos 0,013 0,008 n.d. n.d n.d

Emamectin 0,014 0,03 n.d. n.d 0,006 Tebuconazole 0,42 0,446 0,46 0,26 0,54

Ethirimol 0,018 0,009 0,009 0,022 0,009 Tebufenpyrad 0,066 0,088 0,073 0,005 0,061

Famoxadone 0,037 n.a n.d. n.d n.d Tetraconazole 0.052 0,076 n.d. 0,072 0,026

Fenbutatin-oxide 10,9 11,5 n.a 2 2.8 Triadimenol 0,15 0,11 0,12 0,56 0,172 Fluopyram 0,084 0,14 0,18 0,02 n.d Trfloxystrobin 0,082 0,18 n.d. n.d 0,003


No Additional pesticides

EURL-FV, Spain

NVWA, Netherlands

Fera Science Ltd U.K.

CVUA Stuttgart

mg/kg mg/kg mg/kg mg/kg

1 Cyprodinil 0,011 0,004 <0,005 0,006

2 Dicofol degr. (Chlorobenzilate) <0,001

3 Dicofol degr. (Dichlorobenzophenone-4,4) 0,0004

4 Flusilazole 0,088 0,11 0,26

5 Folpet degr. (Phthalimide) 0,008

6 Procymidone 0,008 0,002

7 Pyraclostrobin 0,046 <0,005

8 Sulfur (S8) 360

9 Spirodiclofen 0,014 0,031 0,016

10 Cyfluneamid 0,022

11 Flufenoxuron 0,041 0,001

12 Methyldinocap 0,078

13 Spirotetramat 0,034 0,036

14 Daminozide detected

15 Diniconazole 0,0058 0,008

16 Fenpropimorph <0.005

17 Fenzox detected

18 Fludioxnil <0.005 0,002

19 Foramsulfuron detected

20 Forchlorfenuron detected 0,10

21 Imidacloprid-olefin detected

22 Iprodione 0,22

23 Mebendazole detected 24 Ofurace <0,005


No Additional pesticides

EURL-FV, Spain

NVWA, Netherlands

Fera Science Ltd U.K.

CVUA Stuttgart

mg/kg mg/kg mg/kg mg/kg

25 Cabaryl 0,002

26 Diflubenzuron 0,001

27 Dodine 0,024

28 Etofenprox 0,003 29 Fenarimol 0,001 30 Imazalil 0,008

31 Spinetoram 0,006

32 Tebufenozid 0,008


Sweden



mg/kg mg/kg

Acetamiprid 0.016 0.01* Imidacloprid 0.068 2

Azoxystrobin 0.48 0.05* Indoxacarb 0.15 0.02*

Boscalid 0.5 0.05* Iprodion 0.29 0.02*

Carbaryl 0.019 0.01* Kresoxim-methyl 0.05 0.05*

Carbendazim 0.24 0.1* Lambda-cyhalothrin 0.018 0.02*

Chlorantraniliprole 0.014 20 Methoxyfenozide 0.64 0.02*

Chlorpyrifos 0.44 0.05* Metrafenone 0.4 0.05*

Cymoxanil 0.042 0.05* Myclobutanil 0.02 0.02*

Difenoconazole 0.073 0.05* Penconazole 0.063 0.05*

Dimethomorph 0.06 0.01* Pyraclostrobin 0.05 0.02*

Emamectin 0.016 0.01* Pyrimethanil 0.65 0.01*

Esfenvalerate (sum) 0.12 0.02* Tebuconazole 0.18 0.02*

Ethirimol 0.015 0.05* Tetraconazole 0.072 0.02*

Famoxadone 0.01 0.02* Triadimefon (sum) 0.061 0.1

Fenbutatin Oxide 5.4 0.05* Prokvinazid 0.008 0.02*

Fluopyram 0.058 0.01*

Results in vine leaves (subsequent sampling) 26 analytes


Sweden



mg/kg mg/kg

Acetamiprid 0.016 0.01* Imidacloprid 0.068 2

Azoxystrobin 0.48 0.05* Indoxacarb 0.15 0.02*

Boscalid 0.5 0.05* Iprodion 0.29 0.02*

Carbaryl 0.019 0.01* Kresoxim-methyl 0.05 0.05*

Carbendazim 0.24 0.1* Lambda-cyhalothrin 0.018 0.02*

Chlorantraniliprole 0.014 20 Methoxyfenozide 0.64 0.02*

Chlorpyrifos 0.44 0.05* Metrafenone 0.4 0.05*

Cymoxanil 0.042 0.05* Myclobutanil 0.02 0.02*

Difenoconazole 0.073 0.05* Penconazole 0.063 0.05*

Dimethomorph 0.06 0.01* Pyraclostrobin 0.05 0.02*

Emamectin 0.016 0.01* Pyrimethanil 0.65 0.01*

Esfenvalerate (sum) 0.12 0.02* Tebuconazole 0.18 0.02*

Ethirimol 0.015 0.05* Tetraconazole 0.072 0.02*

Famoxadone 0.01 0.02* Triadimefon (sum) 0.061 0.1

Fenbutatin Oxide 5.4 0.05* Prokvinazid 0.008 0.02*

Fluopyram 0.058 0.01*

Results in vine leaves (subsequent sampling)


Sweden


15-05-18 WS Tbilisi Georgien

analysis of pesticide residues in animal products … acetate extraction and detection with gc- ......

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