AU2021106323A4 - Method for determining pesticide residues - Google Patents

Abstract

The invention discloses a method for determining pesticide residues, and belongs to the technical field of pesticide determination. The UPLC-QTOF-MS method was used to determine the contents of various pesticide components in the samples to be tested; pesticide ingredients include both insecticides and fungicides. Liquid chromatography conditions include: mobile phase A is methanol, mobile phase B is ammonium acetate aqueous solution or formic acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure of mobile phase A is 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17min, 98%; 17-17.1min, 98-2%;17.1-20min, 2%;mass spectrometry conditions include: electrospray ionization source, positive ion mode; full scanning mode with scanning quality ranging from 50-1000 m/z. The method has good sensitivity, accuracy and precision, and can accurately and efficiently detect pesticide residues in vegetables and fruits. 1

Description

DESCRIPTION Method for determining pesticide residues

TECHNICAL FIELD

The invention relates to the technical field of pesticide determination, in particular to a

method for determining pesticide residues.

BACKGROUND

In the process of agricultural production, a large amount of insecticides need to be

applied to ensure the output of agricultural products. However, pesticide residues have

become one of the main risk factors affecting the quality and safety of agricultural products.

At present, more than 1,100 kinds of pesticides have been used in agricultural production in

China, and there are many kinds of insecticides with different uses. The list of banned and

authorized pesticides on agricultural products such as vegetables and fruits is constantly

changing. Many insecticides do not have relevant national, industrial or local standards, which

limits the daily monitoring of these pesticides.

Traditional pesticide residues detection technologies are mostly targeted detection

technologies based on gas/liquid chromatography, gas/liquid chromatography-mass

spectrometry and gas/liquid chromatography-tandem mass spectrometry. Due to the complex

matrix of agricultural products, wide sources of samples, many kinds of insecticides, wide

concentration range and great differences in physical and chemical properties of screening

objects, it is difficult for the existing targeted detection technology to comprehensively

analyze or simultaneously analyze pesticides and toxic metabolites in agricultural products,

and it is difficult to effectively implement the monitoring and prevention of multi-residue

drugs in agricultural products.

SUMMARY

DESCRIPTION The purpose of the present invention is to provide a method for determining pesticide residues,

which can at least accurately and efficiently detect the residual amount of at least one of

insecticides and fungicides in a sample to be detected.

The invention provides a method for determining pesticide residues ,which uses UPLC

QTOF-MS method to determine the contents of various pesticide components in samples to

be determined, wherein the pesticide components include insecticides and fungicides at the

same time;

the liquid chromatographic conditions in the determination process include: mobile

phase A is methanol, and mobile phase B is ammonium acetate aqueous solution or formic

acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure of mobile phase

A is 0-0.5 min, 2%; 0.5-15 min, 2-98%; 15-17 min, 98%; 17-17.1 min, 98-2%; 17.1-20

min, 2%;

the mass spectrometry conditions in the determination process include: the ion source

adopts electrospray ionization source and positive ion mode; full scanning mode, scanning

quality range is 50-1000 m/z; the flow rate of CUR is 32-38 psi; the flow rate of spray gas is

48-52 psi, and the flow rate of auxiliary heating gas is 48-52 psi. Ionization voltage is 5450

5550 V; the temperature is 490-510°C; the de-clustering voltage is 78-82 V; collision energy

is 20-50 eV; automatically calibrate the reference ion is C 3 3 H4 N 2 0 9 with mass-to-charge ratio

of 609.28766; the reference characteristic ions in MS/MS mode include CIIH12NO with mass

to-charge ratio of 174.09130, CioH1 1 04 with mass-to-charge ratio of 195.06520, C 1 3H1 8 N0 3

with mass-to-charge ratio of 236.12810, C 2 2H 2 5 N 2 0 3 with mass-to-charge ratio of 365.18600,

and C2 3 H 2 9N 2 0 4 with mass-to-charge ratio of 397.21220, C2 3 H3 0 N0 8 with mass-to-charge

ratio of 448.19660, C 3 3H4 0N 2 0 9 with mass-to-charge ratio of 609.28066.

In a preferred embodiment, the flow rate in liquid chromatography is 0.4 mL/min, and

the flow rate of CUR in mass spectrometry is 35 psi; the flow rate of spray gas is 50 psi, and

DESCRIPTION that of auxiliary heating gas is 50 psi; ionization voltage is 5500 V; the temperature is 500°C;

the de-clustering voltage is 80 V.

In an alternative embodiment, the mobile phase B is preferably an ammonium acetate

aqueous solution with a concentration of 4.5-5.5 mmol/L, more preferably an ammonium

acetate aqueous solution with a concentration of 5 mmol/L.

In an alternative embodiment, the column temperature in the liquid chromatography

process is 30-50°C, more preferably 45°C.

In an alternative embodiment, the injection amount in the process of liquid

chromatography is 3-5 pL, more preferably 3 pL.

In an alternative embodiment, further comprising the following pretreatment of the

sample to be measured: extracting the slurry pulped by the sample to be tested with an

extractant, then mixing with sodium chloride, centrifuging, mixing the supernatant with water,

and filtering the filtrate.

In an alternative embodiment, the extractant is acetonitrile;

In an alternative embodiment, the extraction is to mix the extractant with the slurry, and

then perform vortex extraction for 15-25 min, and then perform ultrasonic extraction for 4-6

min.

In an alternative embodiment, further comprising determining with the standard solution

corresponding to the pesticide component under the same conditions as the sample to be

determined, so as to compare the determination results of the sample to be determined.

In an alternative embodiment, the insecticides comprise at least one of 3

hydroxycarbofuran, abamectin Bla, dicrotophos, azinphos-methyl, fenthion, fenthion-sulfone,

fenthion-sulfoxide, EPN, fenamiphos, fenamiphos-sulfone, fenamiphos-sulfoxide, fenoxycarb,

pyriproxyfen, imidacloprid, profenofos, propoxur, tebufenozide, pyrethrin I, pyrethrin II,

diflubenzuron, pyridaphenthion, phenthoate, fonofos, trichlorfon, dichlorvos, flufiprole,

DESCRIPTION acetamiprid, chlorfenvinphos, chlorpyrifos, parathion, spinosad A, spinosad D, bendiocarb,

diazinon, fensulfothion, fensulfothion-sulfone, demeton-S-sulfoxide, dinotefuran, furathiocarb,

phosalone, tau-fluvalinate, flubendiamide, teflubenzuron, fipronil, fipronil-sulfone,

flufenoxuron, sulfoxaflor, flonicamid, chlorfluazuron, hexaflumuron, flucythrinate, novaluron,

heptenophos, chromafenozide, emamectin Bla, methamidophos, phorate-sulfone, phorate

sulfoxide, chlorpyrifos-methyl, demeton-S-methyl-sulfone, phosfolan-methyl, pirimiphos

methyl, isofenphos-methyl, carbaryl, fenpropathrin, methoxyfenozide, monocrotophos,

pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, phosphamidon, phosfolan,

thiodicarb, cadusafos, spirotetramat, spirotetramat-mono-hydroxy, spirotetramat-keto

hydroxy, spirotetramat-enol, spirotetramat-enol-glucoside, chlorantraniliprole, cyhalothrin,

permethrin, cypermethrin, imidaclothiz, isazofos, malathion, malaoxon, promecarb,

etofenprox, cyromazine, chlorbenzuron, metaflumizone, fenvalerate, clothianidin, thiacloprid,

thiamethoxam, buprofezin, pyridalyl, triazophos, chlordimeform, triflumuron, fenitrothion,

methidathion, oxamyl, oxamyl oxime, lufenuron, mevinphos, terbufos-sulfone, terbufos

sulfoxide, aldoxycarb, aldicarb-sulfoxide, pirimicarb-desmethyl-formamido, pirimicarb

desmethyl, nitenpyram, phoxim, cyantraniliprole, deltamethrin, vamidothion, phosmet,

oxydemeton-methyl, fensulfothion oxon, fensulfothion oxon sulfone, omethoate, phosmet

oxon, ivermectin, disulfoton-sulfone, disulfoton-sulfoxide, demeton-S-sulfone, ethiprole,

spinetoram A, spinetoram B, ethion, etrimfos, acephate, isoprocarb, indoxacarb, coumaphos,

rotenone, sulfotep, fenobucarb, and tolfenpyrad.

In a preferred embodiment, the insecticides simultaneously comprise imidacloprid,

acetamiprid, dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin

cypermethrin, clothianidin, thiamethoxam and triflumuron .

In an alternative embodiment, the fungicides comprise at least one of fenpyrazamine,

dichlofluanid, metrafenone, difenoconazole, benalaxyl, zoxamide, fenpropidin, penthiopyrad,

DESCRIPTION pyraclostrobin, isopyrazam, diclobutrazol, propiconazole, albendazole, proquinazid,

isoprothiolane, fenoxanil, meptyldinocap-phenol, edifenphos, coumoxystrobin, pyrisoxazole,

boscalid, picoxystrobin, carbendazim, hymexazol, oxadixyl, famoxadone, flutriafol,

fluopicolide, fluopyram, flusilazole, epoxiconazole, triflumizole, triflumizole metabolite FM

6-1, flumorph, flutolanil, sedaxane, penflufen, procymidone, fludioxonil, silthiofam,

cyproconazole, cyflufenamid, fenhexamid, hexaconazole, tolylfluanid, tolclofos-methyl,

thiophanate-methyl, metalaxyl, fenbuconazole, myclobutanil, bromuconazole, quinoxyfen,

bitertanol, fenarimol, prochloraz, prochloraz metabolite BTS44595, prochloraz metabolite

BTS44596, fenamidone, dimoxystrobin, kresoxim-methyl, cyprodinil, azoxystrobin,

pyrimethanil, triticonazole, mepronil, cyazofamid, cyazofamid metabolite CCIM, phenamacril,

thifluzamide, thiabendazole, tricyclazole, triadimenol, triadimefon, mandipropamid,

propamocarb, tetraconazole, prothioconazole-desthiometabolite, trifloxystrobin, pencycuron,

penconazole, tebuconazole, fenaminstrobin, enestroburin, dimethomorph, diniconazole,

iprovalicarb, imibenconazole, metconazole, diethofencarb, ethirimol, bupirimate, iprobenfos,

imazalil, amisulbrom, ipconazole, pyrametostrobin, pyraoxystrobin, and ametoctradin.

In a preferred embodiment, the fungicide simultaneously comprises difenoconazole,

pyraclostrobin, boscalid, carbendazim, fluopyram , thiophanate-methyl , myclobutanil,

prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb

and ethirimol.

In an alternative embodiment the pesticide component further comprises at least one of

acaricide, molluscicide, nematicide and synergist.

In an alternative embodiment, the acaricide comprises at least one of fenothiocarb,

pyridaben, cyflumetofen, fenazaquin, bifenazate, spiromesifen, spirodiclofen, propargite,

hexythiazox, clofentezine, etoxazole, and fenpyroximate.

In a preferred embodiment, the acaricide comprises bifenazate.

DESCRIPTION In an alternative embodiment, the molluscicide comprises at least one of methiocarb

sulfone and methiocarb-sulfoxide.

In an alternative embodiment, the nematicide comprises at least one of ethoprophos and

fosthiazate .

In a preferred embodiment, the nematicide comprises fosthiazate

. In an alternative embodiment, the synergist comprises piperonyl butoxide.

In an alternative embodiment the pesticide component further comprises herbicides.

In an alternative embodiment, the herbicide includes at least one of the following

components: ethametsulfuron-methyl, tribenuron-methyl, saflufenacil, metamitron, mefenacet,

pyraflufen-ethyl, fluazifop-butyl, diflufenican, pyrazosulfuron-ethyl, metazachlor,

prosulfocarb, bensulfuron-methyl, pretilachlor, propyrisulfuron, oxadiargyl, propanil,

napropamide, diuron, butachlor, tebuthiuron, propachlor, oxadiazon, oxaziclomefone,

metamifop, pendimethalin, rimsulfuron, flurtamone, triflusulfuron-methyl, flucetosulfuron,

haloxyfop-methyl, picolinafen, fomesafen, flufenacet, thiobencarb, molinate, diclofop-methyl,

cyclosulfamuron, hexazinone, pyriftalid, sulcotrione, alachlor, sulfentrazone, metsulfuron

methyl, iodosulfuron-methyl-sodium, mesosulfuron-methyl, imazapic, bifenox, fenoxaprop-p

ethyl, dimethenamid-P, quizalofop-ethyl, linuron, chlorotoluron, halosulfuron-methyl,

fluroxypyr, fluroxypyr-meptyl, chlorsulfuron, chlorimuron-ethyl, imazaquin, imazethapyr,

triasulfuron, cinosulfuron, orthosulfamuron, pyribenzoxim, dimepiperate, prometryn,

metazosulfuron, fluthiacet-methyl, metribuzin, cyanazine, cyhalofop-butyl, propyzamide,

clodinafop-propargyl, lactofen, thifensulfuron-methyl, tritosulfuron, tralkoxydim, chloridazon,

anilofos, florasulam, terbuthylazine, phenmedipham, propaquizafop, penoxsulam, simetryn,

simazine, clethodim, clethodim-sulfone, clethodim-sulfoxide, sethoxydim, amidosulfuron,

mesotrione, nicosulfuron, triallate, fluoroglycofen-ethyl, ethofumesate, oxyfluorfen,

DESCRIPTION ethoxysulfuron, propisochlor, metolachlor, isoproturon, clomazone, isoxaflutole, ametryn,

atrazine, butralin, carfentrazone-ethyl, pinoxaden, and flumetsulam.

In an alternative embodiment, the pesticide component further comprises a plant growth

regulator.

In an alternative embodiment, the plant growth regulator comprises at least one of

diethyl aminoethyl hexanoate, paclobutrazol, flumetralin, trinexapac-ethyl, forchlorfenuron,

thidiazuron, and uniconazole.

In an alternative embodiment, the sample to be determined is an agricultural product;

preferably, the sample to be tested is fruits and/or vegetables.

The application has the beneficial effects that:

In this application, an analytical method for simultaneous and rapid determination of

high-throughput pesticides (at least including insecticides and fungicides) based on high

resolution mass spectrometry technology is established, which is simple to operate. The linear

correlation coefficient r2 of all pesticides in the established detection method is greater than

0.990, the detection limit (LOD) range is 0.6-10 pg/kg, the limit of quantification (LOQ)

range is 2.0-30 gg/kg, and the LOQs of 98.1% pesticides are less than 10 pg/kg. The method

is accurate, reliable and sensitive, and can effectively avoid false detection and missed

detection. It can be used for high-throughput qualitative screening and quantitative analysis of

various pesticide residues in vegetables and fruits.

DESCRIPTION OF THE INVENTION

In order to make the objectives, technical solutions and advantages of the embodiments

of the present invention clearer, the technical solutions of the embodiments of the present

invention will be described clearly and completely below. If the specific conditions are not

indicated in the embodiment, the conventional conditions or the conditions suggested by the

DESCRIPTION manufacturer shall be followed. The reagents or instruments used are conventional products

that can be obtained through commercial purchase without indicating the manufacturer.

The determination method of pesticide residues provided in this application will be

described in detail below.

The application provides a method for determining pesticide residues, which adopts

UPLC-QTOF-MS (Ultra Performance Liquid Chromatography-Quadrupole Time-of-Flight

Mass Spectrometry) to determine the content of various pesticide components in a sample to

be measured, and the pesticide components simultaneously include insecticides and

fungicides.

In the present invention, the liquid chromatography flow rate may be 0.3 mL/min, 0.35

mL/min, 0.4mL/min, 0.45 mL/min or 0.5 mL/min.

In a preferred embodiment, the mobile phase B is an aqueous solution of ammonium

acetate, and its concentration can be 4.5-5.5 mmol/L, preferably 5 mmol/L. That is, in the

preferred embodiment, the mobile phase is compounded by methanol (mobile phase A) and

ammonium acetate aqueous solution (mobile phase B). The flow rate is preferably 0.4

mL/min.

In an alternative embodiment, the column temperature in the liquid chromatography

process may be 30-50°C, such as 30°C, 35C, 40°C, 45C or 50°C, and preferably 45C. In the

process of liquid chromatography, the injection amount can be 3-5 pL, such as 3 pL, 3.5 pL, 4

ptL, 4.5 L or 5 pL, and preferably 3 pL.

In the mass spectrometry condition described in the present invention, the flow rate of

the CUR can be 32 psi, 33 psi, 34 psi, 35 psi, 36 psi, 37 psi or 38 psi, or any other value in the

range of 32-38 psi.

The flow rate of spray gas can be 48 psi, 49 psi, 50 psi, 51psi, 52 psi, etc., or any other

value in the range of 48-52 psi.

DESCRIPTION The flow rate of the auxiliary heating gas can also be 48psi, 49psi, 50psi, 51psi or 52psi,

or any other value within the range of 48-52psi.

Ionization voltage can be 5450 V, 5500 V or 5550 V, or any other value within the range

of 5450-5550V.

The temperature can be 490°C, 495°C, 500°C, 505°C or 510°C, or any other value in the

range of 490-510 °C.

The de-clustering voltage can be 78 V, 79 V, 80 V, 81 V or 82 V, or any other value in

the range of 78-82 V.

In a preferred embodiment, the flow rate of CUR in mass spectrometry conditions is 35

psi; the flow rate of spray gas is 50 psi, and that of auxiliary heating gas is 50 psi. Ionization

voltage is 5500 V; the temperature is 500°C; the de-clustering voltage is 80 V.

It is worth noting that the specific materials of the CUR, spray gas and auxiliary heating

gas used in this application can refer to the prior art, and will not be described in detail here.

The time-of-flight mass spectrometry has the advantages of accurate mass determination

and high resolution, has high sensitivity and selectivity when obtaining precursor ion and

fragment ion information, can accurately determine the mass of molecules and fragment ions,

and then accurately determine the quality, avoid false detection and missed detection, can

quickly and accurately screen multiple residual insecticides in unknown samples, and improve

the efficiency and reliability of qualitative screening.

For reference, before the detection, the sample to be detected also includes the following

pretreatment: extracting the slurry beaten by the sample to be detected with an extractant, then

mixing with sodium chloride, centrifuging, taking the supernatant and mixing with water, and

filtering the membrane.

In a preferred embodiment, the extractant is acetonitrile. Acetonitrile is mainly used to

extract pesticide components from slurry, and the amount of impurities extracted in the

DESCRIPTION extraction process is small, and its recovery rate in extracting various pesticides is within an

acceptable range; if acetone is used, more impurities will be extracted, which will affect the

subsequent determination results, and the safety is not good.

In an alternative embodiment, the extraction may be performed by mixing the extractant

with the slurry, and then performing vortex extraction for 15-25 min (e.g., 20min), and then

performing ultrasonic extraction for 4-6 min (e.g., 5 min).

The NaCl used in the pretreatment process can make water and acetonitrile have a good

stratification effect, and can also remove part of protein.

Specifically, the pretreatment can refer to: weigh 10-20 g homogenized samples (such as

vegetables and fruits) in a 50 mL polypropylene centrifuge tube, add 10-20 mL acetonitrile,

perform vortex extraction for 15-25 min, perform ultrasonic extraction for 4-6 min, then add

3-5 g sodium chloride, perform vortex extraction for 1-2 min, and centrifuge at 4800-5200

r/min for 4-6 min, take lmL supernatant into 10 mL glass test tube, add 1mL ultrapure water,

vortex and mix for 25-35 s, put the extract through 0.22 pm nylon filter, and bottle it for

testing.

Preferably, the determination method provided by the application can at least

simultaneously determine imidacloprid, acetamiprid, dinotefuran, flonicamid, hexaflumuron,

chlorantraniliprole, cyhalothrin, cypermethrin, clothianidin, thiamethoxam, triflumuron,

difenoconazole, pyraclostrobin, boscalid, carbendazim, fluopyram, thiophanate-methyl,

myclobutanil, prochloraz, cyprodinil, azoxystrobin, pyrimethanil, triadimenol, triadimefon,

propamocarb, ethirimol, bifenazate and fosthiazate in the sample to be determined.

Further, the determination method of this application can also include: using the standard

solution corresponding to the pesticide components to be detected, performing determination

under the same conditions as the sample to be determined, and taking the determination result

of the standard solution as a control.

DESCRIPTION Specifically, the preparation of standard solutions can refer to: using acetone as solvent,

preparing multiple groups of standard solutions into a group of lpg/ml mixed standard

solutions containing all insecticides, storing at 4C away from light, and reconfiguring once

every two months.

Therefore, the application can accurately and efficiently detect the above 373 pesticides

in vegetables and fruits by using the high-resolution mass spectrometry technology combined

with a simple and rapid pretreatment method, and can satisfy the trace detection and analysis

of multi-residue pesticides in vegetables and fruits. The linear correlation coefficient r2 of all

insecticides in the detection method established in this application is greater than 0.990. The

limits of detection (LOD) ranged from 0.6-10 pg/kg, and the limits of quantification (LOQ)

ranged from 2.0-30 gg/kg. The limits of quantification of 98.1% of pesticides did not exceed

gg/kg. When strawberry was used as the substrate and the pesticide concentration was 10

gg/kg, 50 gg/kg and 100 pg/kg respectively, the results of 6 parallel determinations at each

level showed that the recovery rate of 352 pesticides (94.4%) ranged from 70% to 120%, and

among the other 21 pesticides, the recovery rate of abamectin Bla was 130% at 10 pg/kg. The

recovery rates of tribenuron-methyl, diclobutrazol, proquinazid, tebuthiuron, pyrisoxazole,

heptenophos, fenazaquin, bifenthrin, forchlorfenuron, imidaclothiz, etofenprox, cyromazine,

tricyclazole, chloridazon, mevinphos, pencycuron, clethodim, sethoxydim, fensulfothion oxon,

and metconazole were lower than 70% (30%-67%) .The relative standard deviation (RSD) of

all insecticides was less than 20%(0.7%-14.7%). The method has good sensitivity, accuracy

and precision, and is simple to operate, which can meet the requirements of relevant domestic

and foreign laws and policies for the analysis of pesticide residues in vegetables and fruits.

The characteristics and performance of the present invention will be further described in

detail with examples below.

Example 1

DESCRIPTION The embodiment provides a method for determining pesticide residues, which is as

follows:

Sample pretreatment: weigh 10 g homogenized sample (strawberry) in a 50 mL

polypropylene centrifuge tube, add 10 mL acetonitrile, perform vortex extraction for 20 min,

perform ultrasonic extraction for 5 min, then add 5 g sodium chloride, perform vortex

extraction for 1 min, centrifuge for 5 min at a rotating speed of 5000 r/min, take 1 mL

supernatant into a 10 mL glass test tube, add 1 mL ultrapure water, vortex mix for 30 s, put

the extract through a 0.22 pm nylon filter.

Preparation of standard solution: Twenty-six groups of standard solutions were prepared

into a group of1 pg/ml mixed standard solutions containing all insecticides with acetone as

solvent, which were stored at 4C away from light and reconfigured every two months.

The UPLC-QTOF-MS method was used to determine the contents of various pesticide

components in the sample under the following conditions, and the results were compared with

those of the standard solution under the same determination conditions.

The liquid chromatographic conditions in the determination process include: mobile

phase A is methanol, mobile phase B is ammonium acetate aqueous solution with

concentration of 5 mmol/L; the flow rate is 0.4 mL/min; the elution procedure of mobile

phase A (gradient elution) is 0-0.5 min, 2%; 0.5-15min, 2-98%; 15-17 min, 98%; 17-17.1

min, 98-2%; 17.1-20 min, 2%; column temperature is 45C; the amount of injection was 3

piL.

The mass spectrometry conditions in the determination process include: electrospray

ionization source (ESI), positive ion mode; full scanning mode, scanning quality range is 50

1000 m/z; the flow rate of CUR is 35 psi; the flow rate of spray gas (GS1) is 50 psi; and the

flow rate of auxiliary heating gas (GS2) is 50 psi. Ionization voltage (ISVF) is 5500 V;

temperature (TEM) is 500°C; the de-clustering voltage (DP) is 80 V; collision energy (CE) is

DESCRIPTION ±15 eV; automatically calibrate the reference ion is C3 3H 4 N 2 0 9 with mass-to-charge ratio

(m/z) of 609.28766; the reference characteristic ions in MS/MS mode include CH1 2N0

with mass-to-charge ratio of 174.09130, CioH 1 04 with mass-to-charge ratio of 195.06520,

C13H18NO3 with mass-to-charge ratio of 236.12810, C2 2 H 2 5N 2 0 3 with mass-to-charge ratio of

365.18600, and C 2 3 H2 9N 2 0 4 with mass-to-charge ratio of 397.21220, C2 3 H 30N0 8 with mass

to-charge ratio of 448.19660, C 3 3 H 40N 2 0 9 with mass-to-charge ratio of 609.28066.

The validation parameters and results of 373 pesticides determined by UPLC-QTOF/MS

method are shown in table 1, in which the adduct is +H, +NH4 or +Na.

Table 1 Measurement results

Product Product Linear LOD LOQ Recover rate/% RSD/% Retention Quality Chinese name time error/ppm ion 1 ion 2 r2 pg/kg pg/kg g/kg g/kg g/kg g/kg g/kg g kg

Ethametsulfuron-methyl 7.65 0.6 196.0823 168.0509 0.9981 0.6 2.0 108 107 104 6.4 7.0 6.1 Tribenuron-methyl 7.33 0.9 155.0921 181.0712 0.9984 1.0 3.0 52 64 54 7.0 4.6 3.4 Saflufenacil 9.63 0.5 348.9987 366.0261 0.9992 1.0 3.0 109 106 101 5.2 3.8 6.0 Metamitron 6.65 1.0 175.0980 104.0497 0.9978 0.6 2.0 80 83 71 7.7 6.7 6.1 Mefenacet 11.87 0.5 120.0790 148.0740 0.9998 0.6 2.0 109 105 104 5.6 4.9 4.3 Pyraflufen-ethyl 12.76 -0.7 338.9887 288.9929 0.9996 1.0 3.0 110 99 94 4.8 4.7 1.6 Fluazifop-butyl 13.77 | 0.7 282.0713 328.0770 | 0.9990 1.0 | 3.0 | 107 103 | 101 4.0 5.8 3.5 Diflufenican 13.34 1.3 266.0407 246.0353 0.9991 1.0 3.0 108 106 102 5.4 4.8 5.6 Pyrazosulfuron-ethyl 7.93 0.4 182.0548 139.0490 0.9988 1.0 3.0 81 75 73 5.9 4.0 3.5 Metazachlor 10.38 1.1 134.0960 210.0685 0.9985 1.0 3.0 105 104 103 5.0 5.6 4.8 Prosulfocarb 13.52 0.0 91.0533 128.1060 0.9996 0.6 2.0 76 76 79 4.4 3.1 2.2 Bensulfuron-methyl 9.75 1.0 149.0600 182.0570 0.9983 1.0 3.0 97 94 88 5.2 4.8 5.0 Pretilachlor 13.63 0.6 252.1148 176.1436 0.9981 1.0 3.0 104 99 97 4.3 4.9 3.4 Propyrisulfuron 8.90 0.1 218.0218 196.0626 0.9997 0.6 2.0 73 92 94 3.8 4.1 1.9 Oxadiargyl 12.98 1.1 223.0037 151.0184 0.9996 2.0 6.0 108 105 101 4.9 5.6 4.4 Propanil 11.20 0.4 127.0184 161.9871 0.9996 1.0 3.0 109 103 98 6.2 6.3 4.2 Napropamide 12.10 0.2 171.0804 129.1143 0.9995 0.6 2.0 86 81 75 3.3 3.6 2.7 Diuron 10.47 1.0 72.0441 159.9700 0.9972 0.6 2.0 104 104 95 6.9 6.0 6.2 Butachlor 14.07 0.7 238.0989 162.1278 0.9987 2.0 6.0 106 104 98 6.8 3.9 5.2 Tebuthiuron 9.34 0.0 172.0890 116.0256 0.9999 0.6 2.0 58 44 39 5.3 1.4 3.2 Propachlor 10.38 0.4 170.0363 94.0648 0.9984 1.0 3.0 107 107 106 7.8 5.1 4.7 Oxadiazon 13.99 0.8 219.9550 184.9865 0.9987 1.0 3.0 104 104 104 5.3 5.3 4.3 Oxazielomefone 13.74 1.6 190.0859 161.0592 0.9991 1.0 3.0 109 105 101 5.1 5.9 3.9 Metamifop 13.75 0.1 288.0413 180.0813 0.9993 1.0 3.0 107 103 98 5.2 5.2 3.8 Pendimethalin 14.24 0.7 212.0669 194.0571 0.9975 3.0 10.0 96 95 89 7.2 6.7 5.7 Rimsulfuron 6.07 1.0 182.0560 325.0957 0.9944 2.0 6.0 89 87 109 8.6 10.2 7.9 Flurtamone 11.19 0.8 247.0728 178.0775 0.9999 0.6 2.0 102 74 88 2.6 3.5 2.2 Triflusulfuron-methyl 9.52 -0.3 264.0688 238.0907 0.9998 0.6 2.0 80 77 77 5.0 3.9 2.9 Flucetosulfuron 7.51 1.6 156.0751 273.0322 0.9979 1.0 3.0 117 115 109 2.0 4.7 4.6 Haloxyfop-methyl 13.30 0.1 316.0316 288.0361 0.9990 0.6 2.0 107 105 102 4.1 6.1 3.7 Picolinafen 13.80 -0.3 238.0467 359.0795 0.9993 0.6 2.0 81 78 73 3.5 2.2 2.1 Fomesafen 10.48 -0.1 343.9931 300.0025 0.9968 2.0 6.0 104 103 101 3.6 5.7 3.7 Flufenacet 12.01 0.7 152.0510 124.0556 0.9997 0.6 2.0 82 76 87 4.5 4.1 2.2 Thiobencarb 13.09 1.1 125.0147 89.0387 0.9996 2.0 6.0 107 103 98 7.1 5.0 4.8 Molinate 11.74 0.5 55.0540 126.0906 0.9991 2.0 6.0 104 98 98 5.4 4.4 2.9 Diclofop-methyl 13.79 1.2 281.0132 120.0571 0.9980 2.0 6.0 107 107 103 6.7 5.7 5.2 Cyclosulfamuron 10.29 1.0 218.0219 261.0277 0.9979 0.6 2.0 101 102 99 5.4 5.9 5.4 Hexazinone 9.16 0.9 171.0865 71.0592 0.9969 1.0 3.0 104 102 99 7.7 6.8 5.3 Pyriftalid 11.07 0.8 139.0497 179.0156 0.9985 0.6 2.0 106 106 103 6.2 5.7 4.1 Sulcotrione 4.62 0.9 139.0383 111.0436 0.9991 2.0 6.0 102 100 97 6.4 6.0 5.0 Alachlor 12.23 1.6 162.1278 238.1018 0.9991 2.0 6.0 103 100 99 6.3 4.7 4.8 Sulfentrazone 9.05 -0.7 306.9937 273.0324 0.9999 1.0 3.0 88 76 83 6.7 10.2 5.7 Metsulfuron-methyl 5.99 0.7 167.0565 199.0055 0.9987 1.0 3.0 109 108 105 5.8 5.9 5.4 Iodosulfuron-methyl- 8.03 0.0 389.8912 163.0579 0.9989 1.0 3.0 77 99 106 6.5 7.2 1.9 sodium Mesosulfuron-methyl 7.62 1.2 182.0564 306.0107 0.9990 1.0 3.0 109 106 103 7.5 5.3 4.8 Imazapic 3.75 1.0 163.0504 231.1130 0.9988 1.0 3.0 100 99 94 4.9 6.1 5.3 Bifenox 13.18 1.2 188.9487 309.9669 0.9985 3.0 10.0 106 108 99 5.6 5.5 5.2 Fenoxaprop-P-ethyl 13.69 0.8 288.0420 244.0524 0.9990 0.6 2.0 97 97 89 5.1 5.2 3.9 Dimethenamid-P 11.41 1.3 244.0546 168.0835 0.9992 0.6 2.0 100 103 100 4.7 5.6 4.2 Quizalofop-ethyl 13.73 1.0 299.0578 271.0627 0.9997 3.0 10.0 107 98 93 4.7 5.9 4.0 Linuron 11.08 -0.5 159.9707 182.0231 0.9994 1.0 3.0 91 77 71 2.6 3.6 4.1

DESCRIPTION Chlorotoluron 10.00 1.0 72.0443 140.0261 0.9987 1.0 3.0 104 104 105 7.0 7.3 4.9 Halosulfuron-methyl 8.09 0.2 182.0544 139.0488 0.9981 1.0 3.0 104 104 102 8.7 6.6 6.7 Fluroxypyr 14.30 0.9 180.9730 208.9688 0.9977 5.0 15.0 104 101 93 6.0 5.6 6.5 Fluroxypyr-meptyl 14.30 0.2 208.9668 180.9720 0.9994 2.0 6.0 90 96 89 5.3 4.5 4.3 Chlorsulfuron 6.54 1.0 141.0770 167.0564 0.9978 1.0 3.0 106 108 109 5.7 7.1 5.5 Chlorimuron-ethyl 8.67 1.1 186.0055 184.9898 0.9982 1.0 3.0 97 100 100 4.9 6.5 5.1 Imazaquin 6.29 2.0 199.0487 267.1104 0.9994 0.6 2.0 98 94 92 5.8 6.2 3.5 Imazethapyr 5.00 1.7 245.1303 177.0666 0.9995 1.0 3.0 99 99 97 5.6 5.9 4.6 Triasulfuron 7.19 1.0 167.0566 141.0772 0.9987 0.6 2.0 108 104 102 7.8 5.3 8.0 Cinosulfuron 6.69 0.9 183.0503 157.0711 0.9991 0.6 2.0 102 107 99 8.2 5.7 5.5 Orthosulfamuron 9.00 1.3 227.0493 199.0832 0.9965 3.0 10.0 88 95 87 8.4 5.0 6.8 Pyribenzoxim 13.91 -1.0 413.1055 180.0793 0.9997 2.0 6.0 108 96 86 4.1 3.8 4.5 Dimepiperate 13.45 0.4 146.0636 119.0861 0.9989 3.0 10.0 104 103 100 5.6 5.1 6.3 Prometryn 12.07 2.3 158.0485 200.0953 0.9975 0.6 2.0 105 104 103 4.0 4.8 4.8 Metazosulfuron 8.08 -0.3 182.0560 295.0260 0.9998 0.6 2.0 84 96 91 5.2 8.5 2.4 Fluthiacet-methyl 12.63 -0.1 273.9952 344.0061 0.9995 0.6 2.0 96 94 85 5.6 7.2 6.3 Metribuzin 8.95 1.4 187.1018 84.0807 0.9975 2.0 6.0 108 94 83 9.0 6.8 3.4 Cyanazine 8.76 1.8 214.0844 132.0314 0.9957 1.0 3.0 101 101 99 7.4 6.7 5.7 Cyhalofop-butyl 13.44 0.3 256.0769 120.0567 0.9993 3.0 10.0 111 102 101 3.7 4.6 5.9 Propyzamide 11.62 1.2 172.9566 189.9821 0.9983 1.0 3.0 101 98 91 6.2 6.7 4.0 Clodinafop-propargyl 12.53 1.5 266.0368 238.0413 0.9987 1.0 3.0 108 103 101 5.7 5.2 4.6 Lactofen 13.83 0.8 343.9915 300.0021 0.9994 1.0 3.0 101 102 101 4.7 5.5 5.2 Thifensulfuron-methyl 5.98 0.7 167.0562 204.9618 0.9970 0.6 2.0 112 110 109 7.0 5.4 4.7 Tritosulfuron 8.79 0.5 195.0481 221.0272 0.9993 1.0 3.0 83 79 83 4.6 4.1 3.6 Tralkoxydim 11.27 0.4 138.0538 284.1642 0.9999 1.0 3.0 97 85 94 2.3 2.2 3.1 Chloridazon 6.91 -0.3 104.0483 92.0488 0.9994 0.6 2.0 30 60 63 4.4 3.6 2.3 Anilofos 12.77 -0.7 124.9811 170.9686 0.9986 1.0 3.0 102 100 96 5.3 6.5 4.5 Florasulam 6.38 2.2 129.0377 191.9908 0.9985 0.6 2.0 112 111 113 6.0 5.2 3.3 Terbuthylazine 11.43 0.8 174.0536 132.0319 0.9993 0.6 2.0 100 99 91 6.3 6.4 5.6 Pherunedipham | 10.92 1.4 136.0396 168.0659 0.9934 2.0 6.0 105 112 113 5.8 3.9 2.7 Propaquizafop 13.87 -1.0 299.0573 100.0750 0.9999 0.6 2.0 80 73 77 2.8 1.9 2.3 Penoxsulam| 8.46 0.7 195.0745 444.0562 0.9996 0.6 2.0 106 106 106 6.6 6.1 6.6 Simetryn 10.25 0.6 124.0864 144.0587 0.9951 0.6 2.0 100 103 99 6.1 5.0 5.2 Simazine 9.05 0.8 132.0331 124.0875 0.9976 1.0 3.0 99 98 96 7.8 6.3 4.4 Clethodim 10.74 0.6 164.0699 166.0854 0.9981 1.0 3.0 99 44 38 2.7 13.4 9.3 Clethodim-sulfone 7.31 0.4 164.0706 208.1332 0.9978 2.0 6.0 81 86 83 8.2 5.5 2.0 Clethodim-sulfoxide 7.39 0.9 206.1172 164.0706 0.9980 2.0 6.0 107 114 116 6.8 1.2 1.1 Sethoxydim 11.31 0.6 178.0854 282.1522 0.9997 0.6 2.0 102 47 39 2.5 9.7 9.0 Amidosulfuron 5.60 1.2 218.0219 261.0278 0.9993 1.0 3.0 103 102 91 7.7 6.1 9.1 Mesotrione 3.95 0.2 227.9947 104.0124 0.9994 2.0 6.0 99 105 105 9.7 7.8 7.0 Nicosulfuron 5.51 0.5 182.0553 213.0318 0.9983 1.0 3.0 101 97 88 8.3 4.7 7.8 Triallate 14.17 -0.6 142.9207 82.9432 0.9998 0.6 2.0 87 87 82 6.4 11.1 3.9 Fluoroglycofen-ethyl 13.46 0.6 343.9900 300.0005 0.9997 2.0 6.0 104 104 105 6.8 5.3 4.5 Ethofumesate 11.12 0.3 121.0639 161.0584 0.9995 1.0 3.0 90 80 72 3.2 1.6 1.3 Oxyfluorfen 13.68 -0.8 237.0385 316.0008 0.9992 1.0 3.0 84 82 75 10.9 9.8 3.0 Ethoxysulfuron 8.87 1.0 218.0220 261.0284 0.9989 0.6 2.0 94 97 99 8.2 6.3 6.1 Propisochlor 12.75 0.2 148.1115 224.0821 0.9995 2.0 6.0 77 73 84 4.4 4.4 5.1 Metolachlor 12.35 2.1 252.1136 176.1428 0.9987 1.0 3.0 107 104 102 5.2 5.0 5.5 Isoproturon 10.35 0.6 72.0443 165.1017 0.9966 0.6 2.0 110 108 107 6.6 4.6 5.3 Clomazone 10.91 0.4 125.0140 89.0377 0.9994 0.6 2.0 104 102 98 5.5 6.6 4.8 Isoxaflutole 10.43 0.8 250.9977 189.0155 0.9988 1.0 3.0 116 84 71 1.6 3.5 2.1 Ametryn 11.24 0.6 186.0797 96.0548 0.9982 0.6 2.0 103 105 98 4.2 4.3 4.0 Atrazine 10.23 1.4 174.0534 103.9998 0.9981 1.0 3.0 99 105 92 6.7 6.2 5.1 Butralin 14.49 2.0 240.0991 222.0889 0.9986 2.0 6.0 102 92 88 6.4 5.8 5.9 Carfentrazone-ethyl 12.63 0.1 345.9941 366.0002 0.9986 2.0 6.0 105 101 93 5.8 3.3 3.9 Pinoxaden 13.13 1.0 317.1836 57.0694 0.9969 2.0 6.0 105 105 105 4.6 5.5 6.2 Flumetsulam 5.03 -0.1 129.0373 262.0892 0.9991 1.0 3.0 73 75 77 2.4 2.8 3.4 3-Hydroxycarbofuran 6.84 0.2 163.0757 135.0806 0.9996 3.0 10.0 73 90 76 2.4 2.1 1.1 AbamectinBIa 15.19 0.8 305.2100 567.3305 0.9989 3.0 10.0 130 110 108 5.5 7.3 3.8 Dicrotophos 6.00 -0.5 127.0144 72.0439 0.9987 1.0 3.0 77 82 90 3.8 3.7 2.4 Azinphos-methyl 10.98 1.0 132.0442 124.9825 0.9968 3.0 10.0 105 105 100 8.3 5.6 4.0 Fenthion 12.69 1.3 169.0129 247.0006 0.9995 2.0 6.0 94 76 72 6.5 4.9 2.8 Fenthion-sulfone 9.80 0.6 124.9827 278.9925 0.9988 1.0 3.0 100 98 96 6.8 4.9 4.4 Fenthion-sulfoxide 9.53 1.2 279.9989 109.0047 0.9984 0.6 2.0 117 116 115 4.2 3.3 2.0 EPN 13.26 0.1 157.9861 296.0138 0.9999 1.0 3.0 81 79 73 3.4 5.0 5.0 Fenamiphos 12.41 0.7 217.0077 201.9846 0.9994 1.0 3.0 92 83 76 5.7 7.8 3.0 Fenamiphos-sulfone 9.57 1.1 266.0237 188.0462 0.9991 0.6 2.0 104 103 100 4.9 5.1 3.7 Fenamiphos-sulfoxide 9.37 0.6 233.0027 171.0469 0.9978 1.0 3.0 114 113 116 2.5 2.2 2.5 Fenoxycarb 12.32 1.5 88.0393 116.0704 0.9991 2.0 6.0 101 95 79 6.1 6.8 3.7 Pyriproxyfen 14.04 0.9 96.0437 185.0596 0.9985 0.6 2.0 96 97 82 4.4 5.1 5.7 Imidacloprid 6.25 1.9 209.0598 175.0984 0.9985 1.0 3.0 98 94 92 7.7 6.3 5.9 Profenofos 13.69 0.6 304.8599 286.8495 0.9988 1.0 3.0 104 103 99 5.9 4.8 5.2 Propoxur 8.95 -0.4 111.0436 93.0328 0.9999 2.0 6.0 103 82 90 3.4 7.8 4.4 Tebufenozide 12.50 0.8 133.0630 105.0678 0.9978 3.0 10.0 104 105 105 4.6 3.7 5.1 Pyrethrin I 14.50 1.3 161.0950 143.0847 0.9995 3.0 10.0 100 86 84 7.7 5.4 5.3 Pyrethrin I| 13.48 0.4 161.0961 143.0841 0.9990 2.0 6.0 106 101 99 4.5 5.2 4.2 Diflubenzuron 12.33 2.0 158.0411 141.0146 0.9997 2.0 6.0 111 106 104 4.7 6.2 4.9 Pyridaphenthion 11.78 1.3 189.0654 205.0430 0.9998 0.6 2.0 93 78 86 3.1 2.0 2.7 Phenthoate 12.55 1.2 124.9814 135.0437 0.9998 2.0 6.0 106 105 101 5.3 5.9 5.1 Fonofos 12.78 -0.3 108.9875 80.9558 0.9993 3.0 10.0 103 97 94 6.4 6.3 6.9 Trichlorfon 6.60 0.5 109.0043 78.9933 0.9991 2.0 6.0 105 108 102 5.3 6.3 5.7 Dichlorvos 8.79 0.6 109.0054 127.0150 0.9982 2.0 6.0 95 98 97 7.3 4.3 3.7 Flufiprole 12.84 -1.1 421.9965 404.9937 0.9986 3.0 10.0 109 105 99 4.4 6.9 4.1 Acetamiprid 6.91 0.8 126.0102 90.0332 0.9986 1.0 3.0 101 104 96 6.2 5.8 6.8 Chlorfenvinphos 12.80 -0.1 204.9364 169.9675 0.9999 0.6 2.0 85 75 82 3.4 3.1 2.9 Chlorpyrifos 14.10 -1.4 197.9261 96.9504 0.9989 0.6 2.0 85 74 78 2.1 8.4 4.0 Parathion 12.49 1.0 235.9772 123.0315 0.9981 2.0 6.0 105 105 101 7.6 4.3 5.3

DESCRIPTION Spinosad A 15.62 0.2 142.1218| 184.0729 0.9991 2.0 6.0 104 98 100 6.2 4.5 3.6 Spinosad D 15.84 -1.1 142.1223 189.1126 0.9961 2.0 6.0 104 105 110 5.7 4.8 3.5 Bendiocarb 8.98 0.6 109.0280 81.0333 0.9993 2.0 6.0 106 99 86 9.3 4.7 4.8 Diazinon 12.89 0.2 169.0786 153.1015 0.9987 1.0 3.0 105 103 101 4.3 4.7 3.8 Fensulfothion 10.39 0.0 234.9644 252.9749 0.9998 0.6 2.0 103 82 73 2.6 2.9 2.7 Fensulfothion-sulfone 10.57 0.2 268.9699 190.9924 0.9999 0.6 2.0 72 79 76 1.9 3.5 2.6 Demeton-S-sulfoxide 7.17 -0.3 140.9756 109.0041 0.9994 0.6 2.0 70 85 78 3.1 3.6 3.1 Dinotefuran 4.21 0.9 129.0892 114.1021 0.9993 3.0 10.0 85 95 92 6.9 5.5 4.7 Furathiocarb 13.83 -0.7 195.0473 167.0524 0.9991 1.0 3.0 113 105 88 1.6 1.5 2.5 Phosalone 13.07 1.2 182.0001 138.0100 0.9998 1.0 3.0 107 105 101 6.3 5.8 6.4 tau-Fluvalinate 14.96 -1.9 181.0643 208.0754 0.9992 2.0 6.0 82 74 74 6.2 3.5 4.3 Flubendiamide 12.53 -1.6 530.9792 570.9692 0.9998 0.6 2.0 91 79 84 3.0 3.8 4.6 Teflubenzuron 13.91 0.4 158.0410 141.0145 0.9987 3.0 10.0 107 104 102 6.4 4.0 4.1 Fipronil 12.41 0.5 367.9511 289.9784 0.9993 2.0 6.0 111 105 102 5.2 5.9 7.9 Fipronil-sulfone 12.79 -0.9 319.9842 243.9720 0.9986 2.0 6.0 95 88 85 7.5 5.5 3.9 Flufenoxuron 14.32 -0.9 158.0413 141.0143 0.9975 1.0 3.0 97 104 100 5.7 5.2 5.3 Sulfoxaflor 7.00 1.7 174.0525 154.0461 0.9995 3.0 10.0 109 104 99 5.6 6.7 7.2 Flonicamid 4.97 1.7 203.0403 148.0365 0.9990 1.0 3.0 95 104 95 6.3 6.0 5.2 Chlorfluazuron 14.58 0.5 382.9354 158.0414 0.9992 3.0 10.0 101 99 94 6.6 6.7 4.5 Hexaflumuron 13.46 0.2 158.0415 141.0143 0.9989 3.0 10.0 108 103 105 7.7 4.9 8.9 Flucythrinate 14.27 -0.5 412.1502 199.0926 0.9986 2.0 6.0 91 92 88 8.0 6.7 5.1 Novaluron 13.54 -1.2 158.0402 141.0136 0.9983 2.0 6.0 106 102 100 6.0 5.3 5.7 Heptenophos 10.47 0.5 127.0152 125.0146 0.9998 1.0 3.0 81 65 64 2.1 1.8 3.2 Chromafenozide 12.09 0.9 175.0745 133.0639 0.9998 0.6 2.0 85 72 75 2.1 2.0 2.9 EmamectinBla 15.02 -2.2 158.1150 302.1928 0.9983 1.0 3.0 104 105 102 6.9 6.0 4.6 Methamidophos 2.46 -0.3 94.0039 124.9794 1.0000 3.0 10.0 102 78 75 2.5 3.4 7.1 Phorate-sulfone 10.20 1.7 96.9506 114.9608 0.9990 1.0 3.0 106 105 103 5.5 4.9 4.1 Phorate-sulfoxide 10.03 1.6 142.9374 96.9501 0.9991 1.0 3.0 110 109 107 5.1 5.3 6.5 Chlorpyrifos-methyl 13.23 0.3 124.9820 289.8772 0.9995 1.0 3.0 107 105 104 6.4 5.9 4.8 Demeton-S-methyl- 5.24 -0.9 169.0076 125.9810 0.9981 1.0 3.0 94 84 100 4.6 2.5 3.5 sulfone Phosfolan-methyl 5.60 0.6 167.9868 109.0038 0.9992 0.6 2.0 101 103 99 5.8 5.2 3.9 Pirimiphos-methyl 13.14 1.5 164.1162 108.0539 0.9997 1.0 3.0 110 106 103 5.3 5.7 6.1 Isofenphos-methyl 12.62 -2.5 230.9865 121.0283 0.9989 2.0 6.0 99 94 84 5.1 4.0 6.7 Carbaryl 9.47 0.5 145.0643 127.0544 0.9952 10.0 30.0 87 86 77 6.9 10.6 4.6 Fenpropathrin 14.45 1.4 125.0961 97.1024 0.9993 2.0 6.0 91 90 84 4.9 4.5 4.6 Methoxyfenozide 11.83 1.2 149.0588 133.0645 0.9997 2.0 6.0 106 105 104 7.3 4.5 5.4 Monocrotophos 5.60 1.1 127.0160 109.0055 0.9991 1.0 3.0 99 96 91 6.9 3.4 4.6 Pirimicarb 10.11 1.8 72.0432 182.1275 0.9992 2.0 6.0 98 95 88 7.5 7.3 5.9 Carbofuran 9.06 0.6 123.0435 165.0905 0.9998 2.0 6.0 101 76 115 3.6 4.7 2.9 Quinalphos 12.59 0.8 163.0320 147.0547 0.9985 2.0 6.0 107 105 100 3.9 5.6 4.8 Dimethoate 6.73 1.7 124.9809 170.9688 0.9996 0.6 2.0 95 97 96 9.9 7.2 5.1 Bifenthrin 15.39 -0.9 181.1012 166.0781 0.9995 2.0 6.0 55 49 43 7.7 7.6 9.5 Phosphamidon 8.60 1.2 127.0158 174.0689 0.9988 0.6 2.0 106 104 103 7.3 5.4 3.6 Phosfolan 7.96 1.2 139.9546 61.0101 0.9999 1.0 3.0 71 71 71 6.5 3.4 3.4 Thiodicarb 10.08 1.5 88.0216 107.9939 0.9987 3.0 10.0 107 108 108 3.6 5.1 4.4 Cadusafos 13.37 1.2 130.9382 158.9697 0.9993 1.0 3.0 105 106 104 6.7 5.2 5.5 Spirotetramat 12.11 0.7 216.0999 270.1465 0.9997 1.0 3.0 107 105 102 7.0 5.3 3.6 Spirotetramat-mono- 9.05 0.9 254.1542 211.1476 0.9998 0.6 2.0 87 89 91 3.0 3.9 2.7 hydroxy Spirotetramat-keto- 10.66 -0.3 214.0853 300.1588 0.9997 0.6 2.0 97 88 97 3.5 4.0 2.2 hydroxy Spirotetramat-enol 7.49 0.8 216.1017 270.1494 0.9989 1.0 3.0 106 108 101 8.4 5.5 3.7 Spirotetramat-enol- 6.32 0.4 302.1755 270.1484 0.9994 1.0 3.0 71 77 75 3.3 5.8 4.2 glucoside Chlorantraniliprole 10.96 -0.3 452.9305 285.9193 0.9986 0.6 2.0 104 101 96 6.7 5.6 3.7 Cyhalothrin 14.52 0.9 255.0297 208.0766 0.9979 2.0 6.0 99 94 91 6.0 5.7 4.3 Permethrin 15.23 -0.2 183.0805 155.0854 0.9981 2.0 6.0 94 80 80 9.9 6.4 2.2 Cypermethrin 14.69 0.4 191.0028 181.0642 0.9994 3.0 10.0 104 93 88 6.3 7.5 5.8 Imidaclothiz 6.51 0.8 181.0538 122.0705 1.0000 1.0 3.0 61 57 55 5.1 3.0 2.4 Isazofos 11.91 2.1 119.9951 162.0632 0.9986 0.6 2.0 103 110 110 5.5 4.8 4.0 Malathion 11.67 0.9 99.0068 124.9814 0.9989 1.0 3.0 107 107 105 6.6 4.5 4.4 Malaoxon 9.28 0.6 99.0071 127.0382 0.9999 0.6 2.0 95 74 78 2.9 3.3 3.6 Promecarb 11.35 0.1 109.0637 91.0541 0.9998 1.0 3.0 88 77 74 4.5 4.1 2.8 Etofenprox 15.36 -0.8 177.1264 135.0794 0.9991 1.0 3.0 71 64 64 8.0 2.4 5.3 Cyromazine 3.72 -0.3 68.0236 85.0507 0.9990 2.0 6.0 45 37 38 4.8 5.5 4.2 Chlorbenzuron 12.62 0.6 156.0213 138.9945 0.9996 2.0 6.0 91 92 87 8.2 9.0 7.5 Metaflumizone 13.81 0.2 178.0475 287.0805 0.9981 2.0 6.0 101 104 99 4.2 4.9 5.3 Fenvalerate 14.75 0.7 167.0605 125.0141 0.9999 1.0 3.0 78 74 79 5.2 3.3 3.1 Clothianidin 6.32 1.6 131.9669 169.0547 0.9993 0.6 2.0 90 84 78 9.1 7.4 7.9 Thiacloprid 7.60 1.6 126.0089 98.9981 0.9990 0.6 2.0 98 98 88 6.9 4.8 4.5 Thiamethoxam 5.24 0.9 181.0548 211.0647 0.9983 1.0 3.0 111 110 97 7.0 4.0 4.3 Buprofezin 13.97 0.4 106.0648 201.1058 0.9989 0.6 2.0 102 105 100 5.8 4.3 4.9 Pyridalyl 15.66 -0.6 110.9596 108.9598 1.0000 0.6 2.0 95 91 89 5.1 4.3 3.4 Triazophos 11.90 -1.7 162.0647 119.0597 0.9990 0.6 2.0 110 106 103 6.9 6.3 4.8 Chlordimeform 10.03 0.0 117.0562 125.0149 0.9991 1.0 3.0 80 85 78 1.3 3.2 2.0 Triflumuron 13.00 0.4 156.0207 138.9944 0.9998 1.0 3.0 107 102 99 4.8 6.1 5.1 Fenitrothion 11.77 1.3 124.9805 245.9976 0.9981 2.0 6.0 103 105 100 6.8 5.3 5.2 Methidathion 10.76 0.3 85.0391 145.0069 0.9981 1.0 3.0 106 105 100 5.6 5.5 5.4 Oxamyl 4.67 -2.1 72.0432 90.0543 0.9973 5.0 15.0 86 109 78 4.0 6.1 3.4 Oxamyl oxime 3.71 -1.0 72.0441 90.0002 0.9992 2.0 6.0 84 104 93 5.4 5.3 5.5 Lufenuron 14.05 -0.2 158.0411 141.0146 0.9998 3.0 10.0 98 96 91 8.5 4.8 5.8 Mevinphos 7.62 0.4 127.0143 109.0039 0.9999 2.0 6.0 51 45 47 10.5 6.5 3.8 Terbufos-sulfone 11.17 0.9 114.9611 171.0241 0.9996 1.0 3.0 106 107 105 6.5 4.9 5.0 Terbufos-sulfoxide 11.19 1.1 130.9372 187.0001 0.9993 1.0 3.0 107 106 104 3.7 4.3 4.7 Aldoxycarb 4.47 0.8 86.0596 148.0422 0.9995 2.0 6.0 104 103 105 7.4 4.6 5.0 Aldicarb-sulfoxide 4.14 0.9 89.0408 132.0467 0.9991 3.0 10.0 85 85 91 6.7 7.5 8.2

DESCRIPTION Pirimicarb-desmethyl- 9.08 3.8 72.0435 225.1319 0.9996 0.6 2.0 99 104 92 3.7 5.4 3.6 formamido Pirimicarb-desmethyl 8.27 -0.3 72.0440 168.1125 0.9995 1.0 3.0 86 94 90 4.8 6.2 4.7 Nitenpyram 4.67 0.9 126.0092 237.0879 0.9994 0.6 2.0 91 88 82 7.5 4.6 2.0 Phoxim 12.96 1.2 77.0387 129.0448 0.9992 2.0 6.0 107 104 104 4.8 5.8 3.8 Cyantraniliprole 9.89 -0.3 285.9204 443.9686 0.9990 2.0 6.0 96 100 94 6.1 6.4 5.9 Deltamethrin 14.69 -0.4 280.8971 181.0626 0.9984 3.0 10.0 94 87 86 7.5 4.8 6.0 Vamidothion 6.86 1.0 146.0627 118.0315 0.9994 1.0 3.0 101 98 96 5.7 4.9 3.6 Phosmet 11.01 1.5 160.0391 133.0279 0.9962 5.0 15.0 103 107 105 7.5 6.2 5.7 Oxydemeton-methyl 5.04 1.3 109.0032 169.0073 0.9987 0.6 2.0 100 98 98 7.2 5.0 3.1 Fensulfothion oxon 8.04 -0.1 236.9976 157.0311 0.9998 0.6 2.0 67 66 64 4.9 3.7 2.4 Fensulfothion oxon 8.27 -0.1 175.0146 252.9922 0.9997 0.6 2.0 86 76 74 2.4 2.2 4.4 sulfone Omethoate 3.44 0.8 77.0382 124.9814 0.9983 1.0 3.0 89 73 70 5.9 4.5 1.7 Phosmet oxon 8.42 0.9 160.0385 133.0269 0.9995 0.6 2.0 93 84 87 3.8 1.4 3.3 Ivernectin 15.78 -0.7 307.2279 551.3384 0.9958 3.0 10.0 109 108 105 5.9 4.9 5.6 Disulfoton-sulfone 10.13 0.5 96.9502 124.9814 0.9991 0.6 2.0 77 84 76 5.0 2.7 3.8 Disulfoton-sulfoxide 9.97 -0.2 156.9530 184.9845 0.9994 0.6 2.0 71 85 80 5.1 2.6 3.1 Demeton-S-sulfone 7.40 -0.1 140.9758 234.9850 0.9992 0.6 2.0 96 96 80 2.8 1.7 2.2 Ethiprole 11.37 0.3 350.9462 254.9683 0.9990 1.0 3.0 108 104 99 6.7 5.3 4.8 Spinetoram A 15.87 -1.2 142.1222 203.1286 0.9965 3.0 10.0 104 104 104 6.5 6.6 3.9 Spinetoram B 16.05 -0.8 142.1218 98.0955 0.9998 0.6 2.0 104 108 94 2.7 5.5 4.9 Ethion 14.05 0.4 142.9376 170.9695 0.9990 0.6 2.0 106 101 91 2.8 4.9 5.5 Etrimfos 12.65 0.2 124.9817 265.0398 0.9999 1.0 3.0 78 80 77 0.9 2.4 1.8 Acephate 3.20 -0.8 142.9932 124.9822 0.9988 2.0 6.0 84 70 71 8.0 5.2 5.3 Isoprocarb 10.12 0.9 95.0485 77.0387 0.9966 3.0 10.0 110 108 108 4.5 4.4 5.2 Indoxacarb 13.31 0.2 150.0098 218.0410 0.9989 1.0 3.0 106 106 105 5.8 4.6 5.5 Coumaphos 12.92 0.1 226.9899 306.9560 0.9984 1.0 3.0 109 106 101 2.9 4.5 4.1 Rotenone 12.40 0.8 213.0906 192.0779 0.9991 1.0 3.0 108 106 103 5.9 5.3 5.1 Sulfotep 12.66 0.8 114.9611 142.9925 0.9987 2.0 6.0 108 105 104 5.0 5.7 3.7 Fenobucarb 11.03 0.1 95.0492 77.0388 0.9986 3.0 10.0 105 101 99 7.6 5.0 5.4 Tolfenpyrad 13.94 0.4 197.0969 171.0328 0.9990 2.0 6.0 105 105 102 5.3 4.6 5.8 Fenpyrazamine 11.83 0.8 216.1117 230.1281 0.9999 0.6 2.0 93 82 76 2.2 2.6 3.4 Dichlofluanid 11.99 1.3 123.0124 223.9484 0.9993 2.0 6.0 114 106 106 5.3 3.7 4.8 Metrafenone 13.14 -0.8 209.0797 226.9695 0.9994 0.6 2.0 76 74 80 2.9 5.3 2.8 Difenoconazole 13.25 0.5 251.0023 337.0404 0.9994 0.6 2.0 108 100 99 4.5 5.8 4.7 Benalaxyl 12.93 0.6 148.1106 91.0528 0.9994 1.0 3.0 106 104 102 5.4 5.2 3.1 Zoxamide 12.88 0.9 186.9706 158.9756 0.9991 1.0 3.0 107 105 102 6.2 4.0 4.9 Fenpropidin 13.19 1.4 147.1166 132.0936 0.9996 1.0 3.0 101 98 98 4.9 5.6 4.1 Penthiopyrad 12.57 0.1 177.0270 256.0346 0.9997 0.6 2.0 73 74 78 1.4 3.2 2.5 Pyraclostrobin 12.99 -0.1 163.0614 194.0795 0.9986 0.6 2.0 110 104 102 5.8 4.8 4.2 Isopyrazam| 13.22 -0.9 224.0871 320.1746 0.9992 1.0 3.0 85 75 73 2.1 1.8 2.3 Diclobutrazol 12.52 0.4 70.0399 158.9747 0.9986 1.0 3.0 51 47 46 7.5 3.1 2.7 Propiconazole 12.83 0.7 158.9759 69.0706 0.9992 1.0 3.0 104 100 97 6.9 6.3 7.1 Albendazole 11.31 -0.1 234.0688 191.0139 0.9997 0.6 2.0 84 94 84 2.9 2.6 1.9 Proquinazid 14.69 0.3 288.9457 330.9922 0.9992 0.6 2.0 66 55 54 2.4 5.7 3.4 Isoprothiolane 11.65 0.8 188.9669 144.9774 0.9990 1.0 3.0 103 103 101 6.2 7.1 5.1 Fenoxanil 12.41 1.5 188.9861 302.0693 0.9980 2.0 6.0 110 108 106 6.1 6.0 4.3 Meptyldinocap-phenol 13.63 -2.8 254.1120 176.1430 0.9970 3.0 10.0 108 103 97 4.8 5.4 5.1 Edifenphos 12.76 0.3 109.0091 111.0249 0.9999 2.0 6.0 106 101 97 3.9 4.9 4.4 Coumoxystrobin 14.06 0.1 145.0630 205.0848 0.9995 2.0 6.0 109 103 93 6.5 4.1 4.2 Pyrisoxazole 11.94 1.6 120.0436 151.0864 0.9998 1.0 3.0 63 53 56 1.6 3.6 2.5 Boscalid 11.47 1.1 307.0645 271.0875 0.9996 0.6 2.0 102 101 97 6.3 4.8 5.2 Picoxystrobin 12.42 0.4 145.0644 205.0865 0.9986 1.0 3.0 107 107 107 5.7 4.4 4.8 Carbendazim 7.54 1.7 160.0499 132.0555 0.9995 1.0 3.0 90 94 93 5.4 4.4 3.3 Hymexazol 1.13 -1.1 54.0343 82.0284 0.9992 3.0 10.0 84 75 72 8.6 12.3 4.5 Oxadixyl 8.52 2.6 149.0234 132.0807 0.9992 3.0 10.0 103 106 97 7.5 8.0 4.0 Famoxadone 12.84 -0.5 239.0915 195.0796 0.9990 3.0 10.0 110 107 104 4.8 6.2 5.8 Flutriafol 10.22 2.3 70.0391 123.0235 0.9985 1.0 3.0 105 99 90 8.5 8.3 7.2 Fluopicolide 11.60 0.6 172.9558 364.9635 0.9999 1.0 3.0 104 101 97 5.8 5.0 4.9 Fluopyram 11.92 0.3 208.0110 173.0187 0.9984 1.0 3.0 106 106 103 6.6 5.0 4.8 Flusilazole 12.37 1.4 165.0688 247.0734 0.9998 1.0 3.0 108 105 100 6.9 5.5 5.3 Epoxiconazole 12.23 | 1.4 121.0432 123.0227 | 0.9998 0.6 | 2.0 | 92 92 | 87 8.0 | 5.9 3.7 Triflumizole 13.50 0.9 278.0568 73.0646 0.9992 2.0 6.0 104 88 80 5.6 4.3 4.1 Triflumizole metabolite 11.89 1.6 215.0169 176.0054 0.9994 0.6 2.0 91 79 73 3.0 2.6 1.7 FM-6-1 Flumorph 10.74 0.4 285.0924 165.0544 0.9986 1.0 3.0 104 104 99 6.7 6.3 4.6 Flutolanil 11.58 0.9 242.0605 262.0669 0.9988 1.0 3.0 106 105 99 6.8 4.8 6.2 Sedaxane 11.75 0.9 159.0356 292.1439 0.9997 0.6 2.0 78 77 72 3.2 3.1 2.9 Penflufen 12.55 0.3 141.0452 234.1028 0.9991 0.6 2.0 99 99 115 2.9 3.3 2.6 Procynidone 11.94 -0.4 256.0261 284.0225 0.9985 3.0 10.0 94 79 77 10.5 13.1 7.3 Fludioxonil 11.37 0.8 229.0411 158.0398 0.9971 2.0 6.0 100 91 82 4.3 9.1 7.4 Silthiofam 12.49 -0.2 252.0872 139.0205 0.9997 1.0 3.0 91 88 82 4.5 2.2 3.4 Cyproconazole 12.32 -1.4 70.0403 125.0153 0.9988 1.0 3.0 99 95 89 6.6 6.9 4.3 Cyflufenamid 12.96 -2.2 295.0857 241.0384 0.9997 0.6 2.0 86 81 76 3.3 2.3 1.9 Fenhexamid 11.97 1.1 97.1014 55.0541 0.9985 2.0 6.0 107 102 94 5.3 6.8 5.6 Hexaconazole 12.89 0.0 70.0404 158.9772 0.9997 1.0 3.0 105 102 98 7.0 6.3 6.0 Tolylfluanid 12.64 0.6 137.0290 237.9653 0.9991 2.0 6.0 101 101 97 5.2 4.7 4.1 Tolclofos-methyl 13.04 1.0 174.9711 268.9358 0.9995 2.0 6.0 101 101 98 5.4 5.4 3.8 Thiophanate-methyl 9.10 1.0 151.0306 160.0491 0.9997 2.0 6.0 87 80 71 6.9 5.1 7.6 Metalaxyl 10.55 1.2 160.1113 192.1371 0.9982 2.0 6.0 105 100 96 8.0 5.3 4.1 Fenbuconazole 12.28 2.0 125.0154 70.0401 0.9984 2.0 6.0 97 95 87 7.2 4.4 5.5 Myclobutanil 11.72 1.3 70.0392 125.0149 0.9988 1.0 3.0 105 103 101 5.5 5.3 3.7 Bromuconazole 11.81 0.5 158.9750 160.9732 0.9991 0.6 2.0 77 70 76 6.4 0.7 2.3 Quinoxyfen 14.16 0.9 196.9789| 272.0269 |0.9994 0.6 2.0 99 99 97 5.4 5.2 4.6 Bitertanol 13.03 1.4 70.0405 99.0805 0.9985 3.0 10.0 107 106 100 3.3 | 5.3 5.7 Fenarimol 12.05 1.5 268.0513 259.0074 0.9990 2.0 6.0 100 99 93 4.4 4.8 5.2

DESCRIPTION Prochloraz 13.07 1.0 308.0016 265.9550 0.9995 1.0 3.0 94 96 86 8.2 6.6 4.9 Prochloraz metabolite 12.83 0.0 282.0209 129.1021 0.9999 0.6 2.0 87 79 73 4.7 2.9 1.6 BTS44595 Prochloraz metabolite 12.76 -0.5 308.0001 265.9531 0.9999 0.6 2.0 90 78 84 6.0 0.8 1.7 BTS44596 Fenamidone 11.26 0.6 236.1174 92.0488 0.9999 0.6 2.0 91 78 80 2.4 1.7 2.6 Dimoxystrobin 12.45 0.9 116.0490 205.0969 0.9996 0.6 2.0 92 91 96 3.9 3.9 2.1 Kresoxim-methyl 12.57 0.7 222.0910 223.0978 0.9991 2.0 6.0 106 107 101 3.5 3.1 4.8 Cyprodinil 12.71 0.8 210.1024 93.0569 0.9980 1.0 3.0 100 101 97 4.9 7.2 5.2 Azoxystrobin 11.26 0.7 372.0941 344.0995 0.9982 0.6 2.0 109 107 104 5.7 5.5 4.8 Pyrimethanil 11.24 1.2 183.0919 182.0841 0.9972 1.0 3.0 101 105 99 6.2 5.9 5.4 Triticonazole 12.04 0.9 70.0393 125.0149 0.9993 1.0 3.0 78 82 74 4.8 1.1 1.3 Mepronil 11.72 1.1 119.0486 228.1019 0.9994 1.0 3.0 106 103 99 5.3 5.6 5.3 Cyazofamid 12.25 1.2 108.0115 217.0411 0.9979 1.0 3.0 97 100 92 3.9 6.9 4.0 Cyazofamid metabolite 10.24 -1.9 183.0783 139.0302 0.9993 1.0 3.0 70 70 77 3.7 1.4 7.1 CUJM Phenamacril 8.86 0.4 104.0486 171.0542 0.9999 2.0 6.0 91 87 78 5.5 3.9 4.6 Thifluzamide 12.21 0.3 488.8340 148.0019 0.9988 5.0 15.0 100 95 87 5.8 4.7 3.0 Thiabendazole 8.51 1.8 175.0313 131.0593 0.9996 1.0 3.0 84 86 90 5.1 7.3 6.5 Tricyclazole 7.98 1.5 163.0324 136.0213 0.9948 0.6 2.0 61 55 55 6.3 8.4 3.4 Triadimenol 11.87 0.8 70.0404 227.0856 0.9982 3.0 10.0 101 103 99 5.5 5.4 6.3 Triadimefon 11.74 1.5 197.0734 69.0701 0.9993 1.0 3.0 104 102 99 6.6 5.5 4.3 Mandipropamid 11.51 0.6 328.1097 125.0148 0.9991 2.0 6.0 104 103 102 6.3 6.8 4.2 Propamocarb 5.07 -0.8 102.0546 74.0241 0.9995 1.0 3.0 83 79 76 3.3 4.7 3.1 Tetraconazole 11.98 -0.1 158.9754 70.0401 0.9998 1.0 3.0 74 81 74 2.4 4.0 3.2

12.27 1.6 70.0393 125.0143 0.9987 2.0 6.0 91 95 91 8.6 3.0 7.0 desthiomesabolite Trifloxystrobin 13.39 1.0 186.0519 206.0809 0.9988 1.0 3.0 107 107 107 5.7 5.6 4.8 Pencycuron 13.14 -1.1 125.0144 218.0733 0.9996 0.6 2.0 62 41 42 9.1 1.4 2.5 Penconazole 12.62 0.6 158.9766 70.0395 0.9994 2.0 6.0 97 93 86 6.8 7.2 5.4 Tebuconazole 12.69 0.6 70.0398 125.0146 0.9998 1.0 3.0 80 81 76 6.2 5.7 5.2 Fenaminstrobin 13.49 -0.9 170.9757 205.0967 0.9994 0.6 2.0 85 78 83 2.5 4.7 1.9 Enestroburin 13.73 -0.7 137.0144 178.0410 0.9996 0.6 2.0 86 75 77 2.0 1.9 2.2 Dimethomorph 11.60 0.1 301.0617 165.0543 0.9995 1.0 3.0 102 97 97 7.0 5.7 4.5 Diniconazole 13.19 1.8 70.0397 158.9762 0.9992 0.6 2.0 100 98 96 5.6 7.1 3.8 Iprovalicarb 11.99 0.7 119.0845 116.0702 0.9998 1.0 3.0 84 72 83 5.1 3.3 2.6 Imibenconazole 13.91 1.0 125.0146 341.9636 0.9985 2.0 6.0 92 98 94 7.0 5.2 4.4 Metconazole 12.92 0.0 70.0402 125.0149 0.9989 0.6 2.0 52 60 78 5.1 4.5 2.7 Diethofencarb 11.21 1.7 124.0385 152.0698 0.9988 3.0 10.0 105 107 102 5.2 5.2 5.0 Ethirimol 10.41 0.9 140.1055 98.0586 0.9980 0.6 2.0 82 91 86 8.5 6.4 4.7 Bupirimate 12.45 0.6 166.0970 210.1596 0.9999 0.6 2.0 108 74 82 3.8 3.1 1.9 Iprobenfos 12.60 1.0 91.0538 205.0072 0.9981 1.0 3.0 103 107 104 3.9 5.0 4.1 Imazalil 12.75 0.3 158.9746 200.9853 0.9970 0.6 2.0 100 100 91 4.6 4.4 5.0 Amisulbrom 13.52 -0.6 226.9741 225.9674 0.9999 0.6 2.0 85 75 72 6.5 2.8 3.2 Ipconazole 13.45 -0.9 70.0397 125.0146 0.9999 0.6 2.0 88 79 81 3.8 4.2 6.3 Pyrametostrobin 12.60 0.1 163.0616 149.0461 0.9996 2.0 6.0 103 104 99 6.6 4.1 4.8 Pyraoxystrobin 13.03 0.7 145.0644 205.0853 0.9991 1.0 3.0 107 103 100 5.3 6.8 4.2 Ametoctradin 13.39 1.1 176.0919 149.0792 0.9987 3.0 10.0 108 105 97 4.9 6.0 5.4 Fenothiocarb 12.46 0.8 72.0437 160.0795 0.9995 1.0 3.0 107 105 100 5.6 5.0 4.9 Pyridaben 14.88 0.6 147.1145 309.0786 0.9988 2.0 6.0 85 77 75 6.9 5.3 4.8 Cyflumetofen 13.58 -1.5 173.0201 249.0738 0.9998 0.6 2.0 80 77 83 3.6 1.8 2.9 Fenazaquin 14.94 0.3 57.0695 161.1315 0.9967 1.0 3.0 71 64 56 6.0 4.3 4.5 Bifenazate 11.83 -2.2 170.0963 198.0914 0.9979 10.0 30.0 109 101 96 8.0 8.7 10.0 Spiromesifen 14.39 0.4 273.1464 255.1363 1.0000 1.0 3.0 93 75 79 4.7 3.0 6.2 Spirodiclofen 14.70 -0.3 313.0389 71.0857 0.9988 2.0 6.0 99 91 88 6.1 5.3 5.3 Propargite 14.37 0.1 175.1103 231.1729 0.9980 1.0 3.0 103 102 97 5.1 4.9 4.8 Hexythiazox 14.20 1.1 168.0552 228.0215 0.9995 2.0 6.0 98 101 94 6.0 4.2 5.0 Clofentezine 13.06 1.5 138.0107 102.0339 0.9967 2.0 6.0 102 104 99 7.8 6.1 4.3 Etoxazole 14.42 0.9 141.0135 304.1128 0.9981 0.6 2.0 77 84 76 6.3 10.1 8.6 Fenpyroximate 14.62 -1.4 366.1410 135.0422 0.9991 0.6 2.0 81 81 81 8.1 5.3 5.7 Methiocarb-sulfone 7.22 0.8 122.0708 201.0639 1.0000 1.0 3.0 114 78 81 7.1 3.2 8.0 Methiocarb-sulfoxide 6.63 -0.4 185.0625 122.0717 0.9986 1.0 3.0 106 110 110 4.2 1.9 2.7 Ethoprophos 12.16 1.1 130.9377 96.9506 0.9997 1.0 3.0 101 99 98 5.8 5.0 4.7 Fosthiazate 9.93 0.5 104.0160 227.9912 0.9976 0.6 2.0 103 102 100 6.5 6.6 4.5 Piperonyl-butoxide 14.07 0.7 177.0883 119.0837 0.9990 1.0 3.0 106 104 100 7.5 5.0 5.9 Diethyl aminoethyl 10.45 0.0 143.1061 100.1124 0.9988 5.0 15.0 107 97 92 4.3 4.9 5.2 hexanoate Paclobutrazol 11.55 1.1 70.0394 125.0147 0.9984 1.0 3.0 107 103 102 6.5 4.8 6.4 Flumetralin 14.34 0.3 143.0042 - 0.9987 3.0 10.0 105 101 79 5.2 9.6 6.9 Trinexapac-ethyl 6.39 0.9 69.0334 165.0180 0.9991 2.0 6.0 112 111 103 5.8 7.5 3.1 Forchlorfenuron 10.59 1.4 129.0207 93.0445 0.9992 0.6 2.0 64 57 53 12.3 14.7 6.2 Thidiazuron 9.15 0.0 102.0123 127.9916 0.9990 1.0 3.0 91 97 90 8.8 7.3 5.1 Uniconazole 12.32 -1.4 70.0405 125.0158 0.9984 2.0 6.0 100 96 91 6.2 6.5 3.3

Example 2

The embodiment provides a method for determining pesticide residues, which is as

follows:

DESCRIPTION Sample pretreatment: weigh 15 g homogenized sample (cucumber) in a 50 mL

polypropylene centrifuge tube, add 15 mL acetonitrile, perform vortex extraction for 15 min,

perform ultrasonic extraction for 4 min, then add 3 g sodium chloride, perform vortex

extraction for 1.5 min, centrifuge at 4800 r/min for 4min, take lmL supernatant into 10 mL

glass test tube, add 1 mL ultrapure water, perform vortex mixing for 25 s. The extract was

then filtered through a 0.22 pm nylon syringe filter.

Preparation of standard solution: Twenty-six groups of standard solutions were prepared

into a group of gg/ml mixed standard solutions containing all pesticides with acetone as

solvent, which were stored at 4C away from light and reconfigured every two months.

The UPLC-QTOF-MS method was used to determine the contents of various pesticide

components in the sample under the following conditions, and the results were compared with

those of the standard solution under the same determination conditions.

The liquid chromatographic conditions in the determination process include: mobile

phase A is methanol, mobile phase B is ammonium acetate aqueous solution with

concentration of 4.5 mmol/L; the flow rate is 0.35 mL/min; the elution procedure of mobile

phase A (gradient elution) is 0-0.5min, 2%; 0.5-15min, 2-98%; 15-17 min, 98%; 17-17.1

min, 98-2%; 17.1-20 min, 2%; column temperature is 30°C; the amount of injection was 4

pL.

The mass spectrometry conditions in the determination process include:the ion source

adopts electrospray ionization source (ESI), positive ion mode; full scanning mode, scanning

quality range is 50-1000 m/z; the flow rate of CUR is 32 psi; the flow rate of spray gas (GS1)

is 48 psi, and the flow rate of auxiliary heating gas (GS2) is 50 psi; ionization voltage (ISVF)

is 5450 V;temperature (TEM) is 490°C; the de-clustering voltage (DP) is 78 V; collision

energy (CE) is 35±15 eV; automatically calibrate the reference ion is C3 3 H 4 N 2 0 9 with mass

to-charge ratio of 609.28766; the reference characteristic ions in MS/MS mode include

DESCRIPTION C1H12NO with mass-to-charge ratio of 174.09130, CioHiO4 with mass-to-charge ratio of

195.06520, C 13HiNO3 with mass-to-charge ratio of 236.12810, C2 2 H 2 5N 2 0 3 with mass-to

charge ratio of 365.18600, and C 2 3 H2 9N 2 0 4 with mass-to-charge ratio of 397.21220,

C 2 3 H 3 NOs 0 with mass-to-charge ratio of 448.19660, C 3 3 H4 0N 2 0 9 with mass-to-charge ratio of

609.28066.

Example 3

This example provides a method for determination of pesticide residues, which is similar

to the sample pretreatment in Example 1: weigh 20g homogenized sample (grape) in a 50mL

polypropylene centrifuge tube, add 20mL acetonitrile, vortex extract for 25min, ultrasonic

extract for 6min, then add 4g sodium chloride, vortex extract for 2min, centrifuge for 6min at

5200r/min, take supernatant from 1mL to 10mL glass tube, add 1 mL ultrapure water,

perform vortex mixing for 35 s. The extract was then filtered through a 0.22 tm nylon syringe

filter.

Preparation of standard solution: Twenty-six groups of standard solutions were prepared

into a group of1lpg/ml mixed standard solutions containing all insecticides with acetone as

solvent, which were stored at 4C away from light and reconfigured every two months.

The UPLC-QTOF-MS method was used to determine the contents of various pesticide

components in the sample under the following conditions, and the results were compared with

those of the standard solution under the same determination conditions.

The liquid chromatographic conditions in the determination process include: mobile

phase A is methanol, mobile phase B is ammonium acetate aqueous solution with

concentration of 5.5mmol/L; the flow rate is 0.5mL/min; the elution procedure of mobile

phase A (gradient elution) is 0-0.5min, 2%; 0.5-15min , 2-98%; 15-17min , 98%; 17

17.1min, 98-2%; 17.1-20min, 2%; Column temperature is 50°C; the injection volume was 5

pL.

DESCRIPTION The mass spectrometry conditions in the determination process include: electrospray

ionization source (ESI), positive ion mode; Full scanning mode, scanning quality range is 50

1000 m/z; the flow rate of CURtain gas (cur) is 38psi; the flow rate of spray gas (GS1) is

52psi, and that of auxiliary heating gas (GS2) is 50psi;. Ionization voltage (ISVF) is

5550V;temperature (TEM) is 510°C; the de-clustering voltage (DP) is 82 V; Collision energy

(CE) is 3515eV; automatically calibrate the reference ion is C 3 3 H4 0 N 2 0 9 with mass-to-charge

ratio of 609.28766; the reference characteristic ions in MS/MS mode include CnH1 2NO with

mass-to-charge ratio of 174.09130, CioH 1 1 04 with mass-to-charge ratio of 195.06520,

C 13 H 18NO3 with mass-to-charge ratio of 236.12810, C2 2 H 2 5N 2 0 3 with mass-to-charge ratio of

365.18600, and C 2 3 H2 9N 2 0 4 with mass-to-charge ratio of 397.21220, C23H3oNO8 with mass

to-charge ratio of 448.19660, C 3 3 H 40N 2 0 9 with mass-to-charge ratio of 609.28066.

Example 4

The only difference between this example and Example 1 is that the mobile phase B is

0.1 vt% formic acid aqueous solution.

Through determination, the methods provided in Example 2 and Example 3 can also

detect the contents of 373 pesticides in Table 1.

To sum up, the application of high-resolution mass spectrometry combined with simple

and rapid pretreatment method can accurately and efficiently detect the above 373 pesticides

in vegetables and fruits, and can satisfy the trace detection and analysis of multi-residue

pesticides in vegetables and fruits. The linear correlation coefficient r 2 of all pesticides in the

detection method established in this application is greater than 0.990. The limits of detection

(LOD) ranged from0.6-10pg/kg, and the limits of quantification (LOQ) ranged from 2.0

pg/kg. The limits of quantification of 98.1% of insecticides did not exceed 10 tg/kg. When

strawberry was used as the substrate and the pesticide concentration was 10 pg/kg, 50 pg/kg

and 100 gg/kg respectively, the results of 6 parallel determinations at each level showed that

DESCRIPTION the recovery rate of 352 pesticides (94.4%) ranged from 70% to 120%, and among the other

21 pesticides, the recovery rate of abamectin Bla was 130% at 10 pg/kg. The recovery rates

of tribenuron-methyl, diclobutrazol, proquinazid, tebuthiuron, pyrisoxazole, heptenophos,

fenazaquin, bifenthrin, forchlorfenuron, imidaclothiz, etofenprox, cyromazine, tricyclazole,

chloridazon, mevinphos, pencycuron, clethodim, sethoxydim, fensulfothion oxon, and

metconazole were lower than 70% (30%-67%). The relative standard deviation (RSD) of all

pesticides was less than 20% (0.7%-14.7%). The method has good sensitivity, accuracy and

precision, and is simple to operate, which can meet the requirements of relevant domestic and

foreign laws and policies for the analysis of pesticide residues in vegetables and fruits.

The above is only a preferred embodiment of the present invention, and is not used to

limit the present invention. For those skilled in the art, the present invention can be modified

and varied. Any modification, equivalent substitution, improvement, etc. made within the

spirit and principle of the present invention shall be included in the protection scope of the

present invention.

Claims (10)

1. CLAIMS 1. A method for determining pesticide residues is characterized by using UPLC-QTOF

   MS method to determine the contents of various pesticide components in samples to be

   determined, wherein the pesticide components include insecticides and fungicides at the same

   time;

   the liquid chromatographic conditions in the determination process include: mobile

   phase A is methanol, and mobile phase B is ammonium acetate aqueous solution or formic

   acid aqueous solution; the flow rate is 0.3-0.5 mL/min; the elution procedure of mobile phase

   A is 0-0.5 min, 2%; 0.5-15 min, 2-98%; 15-17 min, 98%; 17-17.1 min, 98-2%; 17.1-20

   min, 2%;

   the mass spectrometry conditions in the determination process include: the ion source

   adopts electrospray ionization source and positive ion mode; full scanning mode, scanning

   quality range is 50-1000 m/z; the flow rate of CUR is 32-38 psi; the flow rate of spray gas is

   48-52 psi, and the flow rate of auxiliary heating gas is 48-52 psi. Ionization voltage is 5450

   5550 V; the temperature is 490-510°C; the de-clustering voltage is 78-82 V; collision energy

   is 20-50 eV; automatically calibrate the reference ion is C 33H4 0 N20 9 with mass-to-charge ratio

   of 609.28766; the reference characteristic ions in MS/MS mode include CIH 12NO with mass

   to-charge ratio of 174.09130, CioH11 04 with mass-to-charge ratio of 195.06520, C 13H1 8 NO 3

   with mass-to-charge ratio of 236.12810, C 22 H25 N 2 0 3 with mass-to-charge ratio of 365.18600,

   and C2 3 H 2 9N 2 0 4 with mass-to-charge ratio of 397.21220, C2 3 H 30 NOs with mass-to-charge

   ratio of 448.19660, C 3 3 H4 0N 2 0 9 with mass-to-charge ratio of 609.28066.
2. 2. The determination method according to claim 1 is characterized in that the flow rate in

   liquid chromatography is 0.4 mL/min, and the flow rate of CUR in mass spectrometry is 35

   psi; the flow rate of spray gas is 50 psi, and that of auxiliary heating gas is 50 psi; ionization

   voltage is 5500 V; the temperature is 500°C; the de-clustering voltage is 80 V;

   CLAIMS preferably, the mobile phase B is preferably an ammonium acetate aqueous solution with

   a concentration of 4.5-5.5 mmol/L, more preferably an ammonium acetate aqueous solution

   with a concentration of 5 mmol/L;

   preferably, the column temperature in the liquid chromatography process is 30-50°C,

   more preferably 45°C;

   preferably, the injection amount in the process of liquid chromatography is 3-5 tL, more

   preferably 3 pL..
3. 3. The measuring method according to claim 2 further comprising the following

   pretreatment of the sample to be measured:

   extracting the slurry pulped by the sample to be tested with an extractant, then mixing

   with sodium chloride, centrifuging, mixing the supernatant with water, and filtering the

   filtrate;

   preferably, the extractant is acetonitrile;

   preferably, the extraction is to mix the extractant with the slurry, and then perform vortex

   extraction for 15-25 min, and then perform ultrasonic extraction for 4-6 min.
4. 4. The determination method according to claim 1, further comprising determining with

   the standard solution corresponding to the pesticide component under the same conditions as

   the sample to be determined, so as to compare the determination results of the sample to be

   determined.
5. 5. The measuring method according to any one of claims 1 to 4, wherein, the insecticide

   comprises at least one of the following components : 3-hydroxycarbofuran, abamectin Bla,

   dicrotophos, azinphos-methyl, fenthion, fenthion-sulfone, fenthion-sulfoxide, EPN,

   fenamiphos, fenamiphos-sulfone, fenamiphos-sulfoxide, fenoxycarb, pyriproxyfen,

   imidacloprid, profenofos, propoxur, tebufenozide, pyrethrin I, pyrethrin II, diflubenzuron,

   pyridaphenthion, phenthoate, fonofos, trichlorfon, dichlorvos, flufiprole, acetamiprid,

   CLAIMS chlorfenvinphos, chlorpyrifos, parathion, spinosad A, spinosad D, bendiocarb, diazinon,

   fensulfothion, fensulfothion-sulfone, demeton-S-sulfoxide, dinotefuran, furathiocarb,

   phosalone, tau-fluvalinate, flubendiamide, teflubenzuron, fipronil, fipronil-sulfone,

   flufenoxuron, sulfoxaflor, flonicamid, chlorfluazuron, hexaflumuron, flucythrinate, novaluron,

   heptenophos, chromafenozide, emamectin Bla, methamidophos, phorate-sulfone, phorate

   sulfoxide, chlorpyrifos-methyl, demeton-S-methyl-sulfone, phosfolan-methyl, pirimiphos

   methyl, isofenphos-methyl, carbaryl, fenpropathrin, methoxyfenozide, monocrotophos,

   pirimicarb, carbofuran, quinalphos, dimethoate, bifenthrin, phosphamidon, phosfolan,

   thiodicarb, cadusafos, spirotetramat, spirotetramat-mono-hydroxy, spirotetramat-keto

   hydroxy, spirotetramat-enol, spirotetramat-enol-glucoside, chlorantraniliprole, cyhalothrin,

   permethrin, cypermethrin, imidaclothiz, isazofos, malathion, malaoxon, promecarb,

   etofenprox, cyromazine, chlorbenzuron, metaflumizone, fenvalerate, clothianidin, thiacloprid,

   thiamethoxam, buprofezin, pyridalyl, triazophos, chlordimeform, triflumuron, fenitrothion,

   methidathion, oxamyl, oxamyl oxime, lufenuron, mevinphos, terbufos-sulfone, terbufos

   sulfoxide, aldoxycarb, aldicarb-sulfoxide, pirimicarb-desmethyl-formamido, pirimicarb

   desmethyl, nitenpyram, phoxim, cyantraniliprole, deltamethrin, vamidothion, phosmet,

   oxydemeton-methyl, fensulfothion oxon, fensulfothion oxon sulfone, omethoate, phosmet

   oxon, ivermectin, disulfoton-sulfone, disulfoton-sulfoxide, demeton-S-sulfone, ethiprole,

   spinetoram A, spinetoram B, ethion, etrimfos, acephate, isoprocarb, indoxacarb, coumaphos,

   rotenone, sulfotep, fenobucarb, and tolfenpyrad.

   Preferably, the insecticide simultaneously comprises imidacloprid, acetamiprid,

   dinotefuran, flonicamid, hexaflumuron, chlorantraniliprole, cyhalothrin , cypermethrin,

   clothianidin, thiamethoxam and triflumuron.
6. 6. The measuring method according to claim 5, wherein, the fungicide comprises at least

   one of the following components: fenpyrazamine, dichlofluanid, metrafenone,

   CLAIMS difenoconazole, benalaxyl, zoxamide, fenpropidin, penthiopyrad, pyraclostrobin, isopyrazam,

   diclobutrazol, propiconazole, albendazole, proquinazid, isoprothiolane, fenoxanil,

   meptyldinocap-phenol, edifenphos, coumoxystrobin, pyrisoxazole, boscalid, picoxystrobin,

   carbendazim, hymexazol, oxadixyl, famoxadone, flutriafol, fluopicolide, fluopyram,

   flusilazole, epoxiconazole, triflumizole, triflumizole metabolite FM-6-1, flumorph, flutolanil,

   sedaxane, penflufen, procymidone, fludioxonil, silthiofam, cyproconazole, cyflufenamid,

   fenhexamid, hexaconazole, tolylfluanid, tolclofos-methyl, thiophanate-methyl, metalaxyl,

   fenbuconazole, myclobutanil, bromuconazole, quinoxyfen, bitertanol, fenarimol, prochloraz,

   prochloraz metabolite BTS44595, prochloraz metabolite BTS44596, fenamidone,

   dimoxystrobin, kresoxim-methyl, cyprodinil, azoxystrobin, pyrimethanil, triticonazole,

   mepronil, cyazofamid, cyazofamid metabolite CCIM, phenamacril, thifluzamide,

   thiabendazole, tricyclazole, triadimenol, triadimefon, mandipropamid, propamocarb,

   tetraconazole, prothioconazole-desthiometabolite, trifloxystrobin, pencycuron, penconazole,

   tebuconazole, fenaminstrobin, enestroburin, dimethomorph, diniconazole, iprovalicarb,

   imibenconazole, metconazole, diethofencarb, ethirimol, bupirimate, iprobenfos, imazalil,

   amisulbrom, ipconazole, pyrametostrobin, pyraoxystrobin, and ametoctradin.

   Preferably, the fungicide simultaneously comprises difenoconazole, pyraclostrobin,

   boscalid, carbendazim, fluopyram , thiophanate-methyl, myclobutanil, prochloraz, cyprodinil,

   azoxystrobin, pyrimethanil, triadimenol, triadimefon, propamocarb and ethirimol.
7. 7. The determination method according to claim 6, wherein the pesticide component

   further comprises at least one of acaricide, molluscicide, nematicide and synergist;

   Preferably, the acaricide comprises at least one of fenothiocarb, pyridaben, cyflumetofen,

   fenazaquin, bifenazate, spiromesifen, spirodiclofen, propargite, hexythiazox, clofentezine,

   etoxazole, and fenpyroximate.; more preferably, the acaricide comprises bifenazate;

   CLAIMS Preferably, the molluscicide comprises at least one of methiocarb-sulfone and

   methiocarb-sulfoxide;

   Preferably, the nematicide comprises at least one of ethoprophos and fosthiazate; more

   preferably, the nematicide comprises fosthiazate;

   Preferably, the synergist comprises piperonyl butoxide.
8. 8. The determination method according to claim 7, wherein the pesticide component

   further comprises herbicides;

   Preferably, the herbicide includes at least one of the following components:

   ethametsulfuron-methyl, tribenuron-methyl, saflufenacil, metamitron, mefenacet, pyraflufen

   ethyl, fluazifop-butyl, diflufenican, pyrazosulfuron-ethyl, metazachlor, prosulfocarb,

   bensulfuron-methyl, pretilachlor, propyrisulfuron, oxadiargyl, propanil, napropamide, diuron,

   butachlor, tebuthiuron, propachlor, oxadiazon, oxaziclomefone, metamifop, pendimethalin,

   rimsulfuron, flurtamone, triflusulfuron-methyl, flucetosulfuron, haloxyfop-methyl,

   picolinafen, fomesafen, flufenacet, thiobencarb, molinate, diclofop-methyl, cyclosulfamuron,

   hexazinone, pyriftalid, sulcotrione, alachlor, sulfentrazone, metsulfuron-methyl, iodosulfuron

   methyl-sodium, mesosulfuron-methyl, imazapic, bifenox, fenoxaprop-p-ethyl, dimethenamid

   P, quizalofop-ethyl, linuron, chlorotoluron, halosulfuron-methyl, fluroxypyr, fluroxypyr

   meptyl, chlorsulfuron, chlorimuron-ethyl, imazaquin, imazethapyr, triasulfuron, cinosulfuron,

   orthosulfamuron, pyribenzoxim, dimepiperate, prometryn, metazosulfuron, fluthiacet-methyl,

   metribuzin, cyanazine, cyhalofop-butyl, propyzamide, clodinafop-propargyl, lactofen,

   thifensulfuron-methyl, tritosulfuron, tralkoxydim, chloridazon, anilofos, florasulam,

   terbuthylazine, phenmedipham, propaquizafop, penoxsulam, simetryn, simazine, clethodim,

   clethodim-sulfone, clethodim-sulfoxide, sethoxydim, amidosulfuron, mesotrione,

   nicosulfuron, triallate, fluoroglycofen-ethyl, ethofumesate, oxyfluorfen, ethoxysulfuron,

   CLAIMS propisochlor, metolachlor, isoproturon, clomazone, isoxaflutole, ametryn, atrazine, butralin,

   carfentrazone-ethyl, pinoxaden, and flumetsulam.
9. 9. The determination method according to claim 8, wherein the pesticide component

   further comprises a plant growth regulator;

   preferably, the plant growth regulator comprises at least one of diethyl aminoethyl

   hexanoate, paclobutrazol, flumetralin, trinexapac-ethyl, forchlorfenuron, thidiazuron, and

   uniconazole.
10. 10. The determination method according to claim 1 is characterized in that the sample to

    be determined is an agricultural product;

    preferably, the sample to be tested is fruits and/or vegetables.