1. Introduction

wine has high commercial value. The use of triple quadrupole gas chromatography-mass spectrometry can efficiently and sensitively analyze pesticide residues in wine matrix . The release of the national food safety standard "GB 23200.7-2016 Determination of 497 pesticides and related chemicals residues in honey, juice and fruit wine by gas chromatography-mass spectrometry" meets the needs of pesticide residue determination in fruit wine foods. Referring to GB 23200.7-2016, this paper tested 237 pesticide residue compounds in wine based on the independently developed GC -MS /MS platform, and evaluated the method linearity, precision, sensitivity and recovery rate. The experimental results show that the triple quadrupole MRM method has strong anti-interference ability and good sensitivity for the determination of pesticide residues in wine matrix.

2.2 Reagents, materials and standards

The reagents, materials, and standards used in the experiments are listed in Table 1.

Table 1 Reagents, materials and standards

Reagent name	Purity	Source
2 42 pesticides and their metabolites	/	Anpel
Heptachlor epoxide B	Chromatographic grade	Anpel
Acetonitrile	Analytical grade	Anpel
acetone	Chromatographic grade	Anpel
Dichloromethane	Analytical grade	Thermo Fisher
Toluene	Analytical grade	Anpel
Anhydrous sodium sulfate	Analytical grade	Sinopharm
n-Hexane	Analytical grade	Sarao

2.3 Test Method

Table 2 Test conditions

G C Conditions	Carrier gas	Helium
	Constant current	1. 0 mL/min
	Chromatographic columns	DB-17MS ( 30 m * 0.25 mm *0.25 μ m） (-20 ℃ -320 ℃ )
	Inlet temperature	2 8 0℃
	Injection volume	1 μL
	Whether to divert	No split
	Run time	40 min
	Heating program	Heating rate ( ℃/ min)Temperature(℃)Holding time (min)/40140120052400123008
MS conditions	Ionization energy	70 e V
	EI source temperature	2 60 ℃
	Transfer line temperature	2 8 0 ℃
	Data collection	MRM
	Solvent delay time	3 min

Table 3 Ion pairs and collision energies of 242 pesticide residues monitored

Serial number	Name	Precursor ion	Product ions	Collision Energy	Precursor ion	Product ions	Collision Energy
	Heptachlor epoxide B	352.8	262.9	15	354.8	264.9	15
1	2,4-D 2-Ethylhexyl Ester	331.5	69.9	30	221.7	99.6	15
2	Acephate	136	94	10	136	42	5
3	Acetochlor	222.9	132.2	20	222.9	147.2	5
4	Benthiocarb	212.1	182.2	10	264.1	194.2	15
5	Acrinathrin	288.9	92.8	10	207.8	181.1	10
6	Alachlor	188.1	160.2	10	160	132.1	10
7	Aldrin	262.9	192.9	35	254.9	220	20
8	Allethrin	123	81	10	107	91	10
9	Amethoxazole	227	58.1	10	227	170.1	10
10	Cypermethrin	225.9	184	5	225.9	157	10
11	Atlaton	211	169.1	5	169	154.1	5
12	Atrazine	214.9	58.1	10	214.9	200.2	5
13	Desethyl Atrazine	172	94	15	187	172	5
14	Yilanphos	132	77.1	15	160	77.1	20
15	Flubutyric Acid	176.1	91.1	10	221	193.1	5
16	Bensulfuron	148	77	35	148	105.1	20
17	Herbicide	199	170	10	170	134	15
18	Ethyl fluazifop	292	264	5	292	206	10
19	α-BHC	218.9	183	5	216.9	181	5
	β-BHC	181	145	15	216.9	181	5
	γ-BHC	181	145	15	216.9	181	5
	δ-BHC	217	181.1	5	181.1	145.1	15
20	Benzyl ester	340.9	309.9	10	189.1	126	20
21	Bifenthrin	181.2	165.2	25	181.2	166.2	10
22	Biphenyl	154.1	153.1	15	153.1	152.1	15
23	Boscalid	140	112	10	140	76	25
24	Herbicide	205	188	15	207	190	15
25	Bromophenazine	266.9	159.1	15	268.9	161.1	15
26	Bromophos	330.8	315.8	15	328.8	313.8	15
27	Ethyl Bromothion	358.7	302.8	15	302.8	284.7	15
28	Bromoxifen	185	157	15	183	155	15
29	Bromoxynil	276.9	87.9	30	127	57.1	5
30	Ethylpyrimidine sulfonate	272.9	193.1	5	272.9	108	15
31	Butachlor	188.1	160.2	10	236.9	160.2	5
32	Glufosinate	285.9	202	15	200	92	10
33	Carbofuran	164.2	149.1	10	164.2	131.1	15
33	3-Hydroxycarbofuran	180	162	5	180	137	10
34	trithion	153	96.9	10	199	143	10
35	Cis-Chlordane	372.9	265.9	20	271.9	236.9	15
35	Trans-Chlordane	372.8	265.8	15	271.7	236.9	15
36	Chlorfenapyr	246.9	227	15	136.9	102	15
37	Miconazole	175	111	10	111	75	15
38	Fenpyrachlor	266.9	159.1	15	322.8	266.8	10
39	Benzyl ether	316.6	286.6	15	235.9	172.9	25
40	Chlorpheniramine ethyl ester	139.1	111	10	251.1	139.1	15
41	Chloroanisole	191	113	15	191	141	10
42	Propyl chlorfenapyr	251.1	139.1	15	139.1	111	15
43	Chlorpheniramine	153	90	25	153	125.1	10
44	Chlorpyrifos	196.9	169	15	198.9	171	15
45	Chlorpyrifos-methyl	285.9	92.9	20	287.9	92.9	20
46	Methyl chlorothiazide	300.9	223	25	298.9	221	25
47	Acarid Phosphorus A	324.8	268.9	10	296.8	268.9	5
48	Clomazone	125	89	15	204.1	107.1	20
49	Coumaphos	210	182	10	361.9	109	15
50	Cyclohexidine	154.1	83.1	5	154.1	72.1	5
51	Cyfluanid	118.1	90	10	118.1	89	25
52	Cyfluthrin a	226	206	15	198.9	170.1	25
53	Cyhalothrin a	197	141	10	197	161	5
54	Cypermethrin A	163	91	10	163	127	5
55	Cyproconazole a	139	111	15	222	125.1	15
56	Cyprodinil	225.2	224.3	10	224.2	208.2	20
57	2,4'-Didi	235	165.2	20	237	165.2	20
	2,4'-DDT	235	165.2	20	237	165.2	20
	2,4'-DiDi	246	176.2	30	248	176.2	30
	4,4'-Didi	234.9	165.1	20	236.9	165.2	20
	4,4'-DDT	235	165.2	20	237	165.2	20
	4,4'-DiDiY	246.1	176.2	30	315.8	246	15
58	Defoliation Phosphorus	202	147	5	169	57.1	5
59	Deltamethrin A	252.9	93	15	250.7	172	5
60	Dichlorvos	213	58.1	10	213	171.2	5
61	Diazinon	137.1	84	10	137.1	54	20
62	Dimethoate	278.9	222.9	15	222.9	204.9	15
63	Dichlobenil	171	100	25	171	136.1	15
63	2,6-Dichlorobenzamide	189	173	5	173	145	15
64	Dichlorvos	109	79	5	184.9	93	10
65	Diclofop-butyl	253	162.1	15	339.9	252.9	10
66	Chlornithine	206.1	176	10	160.1	124.1	10
67	Dicofol a	139	111	15	139	75	15
68	Dicrotophos	127	109	15	127	95	15
69	Dieldrin	262.9	193	35	277	241	5
70	Difenoconazole	322.8	264.8	15	264.9	202	20
71	Sclerotium net	243	215	5	243	187	5
72	Dimethoate	86.9	46	15	142.9	111	10
73	Diniconazole	267.9	232.1	10	269.9	232	10
74	Dimethoate	271	96.9	30	152.9	96.9	10
75	Diphenylamine	169	168.2	15	168	167.2	15
76	Isopropylamine	255.1	222.1	10	255.1	180.1	20
77	Sterile Phosphate	130	102.1	10	148	130.1	10
78	Diflubenzuron	172.9	109	5	201	109	10
79	α-Endosulfan	194.9	159	5	194.9	125	20
	β-Endosulfan	206.9	172	15	194.9	124.9	25
	Endosulfan sulfate	273.8	238.9	15	271.9	237	15
80	Endrin	262.8	193	35	244.8	173	30
	Endrin aldehyde	278.9	209	25	249.9	214.9	30
	Endrin Ketone	316.8	280.7	5	316.8	100.8	10
81	Enoxastrobin	190	102	35	145	102	30
82	Fenthion	169	141.1	5	169	77.1	25
83	Epoxiconazole	192	138.1	10	192	111	25
84	Phyllanthus sphaerocephalus	171	99	20	169	97	20
85	Ethyl Butyl Fluoride	275.9	202.1	15	315.9	275.9	10
86	Dithiocarb	100	72	5	161	100	5
87	Ethion	230.9	129	20	230.9	175	10
88	Ethofuroxol	206.9	161.1	5	161	105.1	10
89	Ethoprophos	157.9	97	15	157.9	114	5
90	Ethofenprox	163	135.1	10	163	107.1	20
91	Ethoxazole	141	113	15	141	63.1	30
92	Tebuconazole	211.1	183	10	183	140	15
93	Ethiophos	181	153.1	5	168	153.1	5
94	Fenamiphos	218	109	15	218	79	30
95	Fenamidone	238	237.2	10	268	180.2	20
96	Enoxabiodinium	132	104	10	132	77	20
97	Fenpyrimidine	219	107.1	10	251	139.1	10
98	Fenbuconazole	128.9	102.1	15	197.9	129	5
99	Fenitrothion	277	260	5	277	109	20
100	Fenbuterol	121	77	20	121	103.1	15
101	Fenthiocarb	160.1	72.1	10	72	56	10
102	Cypermethrin	207.9	181	5	264.9	210	10
103	Fenthophos	291.8	156	15	291.8	108.8	15
104	Fenthion	278	109	15	278	169	15
	Fenthion Sulfone	309.9	105	10	135.9	92	10
	Fenthion sulfoxide	278	109	15	278	169	15
105	Triphenyltin hydroxide	351	196.9	25	351	119.9	35
106	Cypermethrin	167	125.1	5	224.9	119	15
107	Fipronil	366.8	212.8	25	368.8	214.8	25
	Fluorocarbonitrile	388	333	15	388	281	35
	Fipronil sulfide	420	350.9	10	351	254.9	20
	Fipronil Sulfone	384.8	256.8	20	382.8	254.9	20
108	Fluazifop-P-ethyl	281.9	91	20	281.9	238	20
109	Flucythrina	156.9	107.1	15	198.9	157	10
110	Fludioxonil	248	154.1	20	248	182.1	10
111	Butyclothion	320	285	10	320	250	20
112	Flumorph	284.6	164.7	10	164.7	76.9	20
113	Fluopyram	346.9	171.8	30	208.9	181.9	15
114	Fluopyram	172.9	94.9	30	172.9	74.9	50
115	trifloxyfen	190	126.1	10	190	75	20
116	Fluorobifen	303	273	15	301	271	10
117	Fluquinoxaline	340	298	15	108	57	15
119	Fluoramide	173	145.1	15	280.9	173	10
120	Fluvalinate	250	55	20	250	200	20
121	Fonfothion	136.9	109	5	245.9	137	5
122	Anthiophos	170	93	5	197.9	92.9	10
123	Thiazofosfamide	195	103	5	195	60	20
124	GABA	141	76.9	5	141	51	35
125	Haloxyfop-Phthiophene	375	316	10	316	91	20
126	Heptachlor	273.7	236.9	15	271.7	236.9	15
127	Heptylphosphine	124	89	10	124	63	35
128	Hexachlorobenzene	283.8	213.9	30	283.8	248.8	15
129	Hexaconazole	231	175	10	256	82.1	10
130	Hexazinone	171	71.1	10	171	85.1	10
131	Methoprene	139	111.1	5	139	55.1	20
132	Imazalil	214.9	173	5	216.8	175	5
133	Imidazole	125	99	20	125	89	20
134	Indigoferon	159	103	15	159	77	30
135	Isoprolin	203.9	91	5	121.9	121	15
136	Iprodione	187	124	25	243.9	187	5
137	Chlorpheniramine	161	119.1	5	161	146	5
138	Isothiophene	212.9	121.1	10	212.9	185.1	5
139	Oxofosfate	229	200.9	10	229	121	25
140	Isothioate-methyl	199	121	10	241.1	199.1	10
141	Isoprocarb	121	77.1	20	136	121.1	10
142	Rice Blast	162.1	85	20	162.1	134	5
143	Oxazophos	177.1	130	10	177.1	116.1	15
144	Methoprene	149	93	5	149	77	15
145	Kresoxim-methyl	116	89	15	116	63	30
146	Bromophenphos	171	77.1	15	154.9	77.1	15
147	Malaoxon	126.9	99	5	126.9	55	5
148	Malathion	126.9	99	5	172.9	99	15
149	2-Methyl-4-chloroisooctyl ester	200	141	5	200	77.1	35
150	Mefenacet	192	136.1	15	192	109.1	30
151	Pyraclostrobin	223.2	222.2	10	222.2	207.2	15
152	Metalaxyl	234	146.1	20	220	192.1	5
153	Acaricide	207.9	180.1	5	207.9	93	10
154	Methamidophos	141	95	5	141	79	15
155	Methidathion	144.9	85	5	144.9	58.1	15
156	Methoxychlor	227.1	121.1	10	227.1	91.1	35
157	Isopropylamine	238	162.2	10	162.2	133.2	15
158	Mefenphos	127	109	10	127	95	15
159	Mirex	273.8	238.8	15	271.8	236.8	15
160	Graminicide	126.2	55.1	10	126.2	83.1	5
161	Monocrotophos	127.1	109	10	127.1	95	15
162	Green Valley Takashi	214	61	10	126	99	15
163	Myclobutanil	179	125.1	10	179	90	30
164	dibromophosphine	108.9	79	5	144.9	109	15
165	Napropamide	128	72.1	5	128	100.1	10
166	Benzene	202	139.1	20	282.9	253	10
167	Oxydemeton-methyl	155.9	110	5	109.9	79	15
168	Oxadiazon	212.7	184.9	5	212.7	150	10
169	Oxadiazon	174.9	112	15	174.9	76	35
170	Frost Spirit	163	132.1	5	163	117.1	25
171	Sulfoxide	142	78.9	20	78.9	47	10
	Demeton-methyl	142	78.9	10	112	79	5
	Sulfone	169.1	125.1	5	169.1	109	15
172	Oxyfluorfen	252	196	20	252	146	30
173	Paclobutrazol	236	125.1	10	236	167	10
174	Paraoxon	148.9	119	5	108.9	91	5
175	Methyl paraoxon	229.9	106.1	15	229.9	136.1	5
176	Parathion	290.9	109	10	138.9	109	5
177	Methyl parathion	262.9	109	10	232.9	109	10
178	Penconazole	248	157.1	25	248	192.1	15
179	Pendimethalin	251.8	162.2	10	251.8	161.1	15
180	Pentachloroaniline	262.8	192	20	264.9	194	20
181	Pentachloronitrobenzene	295	237	20	236.9	142.9	30
182	Permethrin A	183.1	168.1	10	183.1	153	15
183	Cyanostrobin	216	197	15	216	187	15
184	Phorate	260	75	5	230.9	128.9	25
	Phorate sulfone	153	97	10	124.9	96.9	5
	Phorate sulfoxide	96.9	64.9	20	199	142.9	10
185	Phosalone	182	111	15	182	102.1	15
186	Sulfate	196	140	10	168	140	5
187	Phosmet	160	77.1	20	160	133.1	10
188	Phosphamide	127	109	10	127	95	15
189	Piperonyl Butyl	176.1	103.1	25	176.1	131.1	15
190	Piperidin	320	122	10	140	98.1	10
191	Pirimicarb	238	166.2	10	166	55.1	20
192	Pyriphos	318.1	166.1	10	318.1	182	10
193	Pirimiphos-methyl	290	125	20	232.9	151	5
194	Pretilachlor	162.1	132.2	20	262	202	5
195	Procymidone	284.8	96	10	282.8	96	10
196	Profenofos	207.9	63	30	338.8	268.7	15
197	Ciprofloxacin	317.9	199	15	317.9	54.8	10
198	Promethazine	226	184.2	10	199	184.1	5
199	Propyzamide	173	145	15	175	147	15
200	Propanil	161	99	30	161	90	25
201	Pulmonary	214.2	172.2	10	229.1	58.1	10
202	Afenacet	138	110	10	138	64	15
203	Propiconazole	172.9	145	15	172.9	74	45
204	Carbosulfan	110	63	25	110	64	15
205	Prothiophos	266.9	239	5	308.9	238.9	15
206	Pyraclostrobin	132	104	10	132	77	20
207	Pyraclostrobin	221	193.1	10	232	204.1	10
208	Pyridaben	147.2	117.1	20	147.2	132.2	10
209	Pyridazinphos	340	199	5	204	203.1	5
210	Pyriproxyfen	136.1	96	15	136.1	78.1	20
211	Quinalphos	146	118	10	146	91	30
212	Quinoxyfen	237	208.1	30	271.9	237.1	10
213	Fly	285	269.9	15	286.9	272	15
214	simazine	201.1	173.1	5	201.1	186.2	5
215	Phosphorus	201.8	145.9	10	237.8	145.9	10
216	Tebuconazole	250	125	20	250	153	10
217	Tebufenpyrad	275.9	171.1	10	332.9	171	15
218	Butylpyrimidinphos	233.9	110.1	15	260.8	137.2	15
219	Tetrachloronitrobenzene	260.9	203	10	214.9	179	10
220	Terbuthion	230.9	175	10	230.9	129	20
220	Terbuthion Sulfone	152.9	96.9	10	198.9	96.9	20
221	Terbutinzine	228.9	173.1	5	172.9	172	5
222	Terbutaline	185	170.1	5	241.1	170.2	15
223	Chlorpyrifos	328.9	109	15	330.9	109	15
224	Tetrafluconazole	336	217.9	20	336	203.8	30
225	Sulfonamide	226.9	199	15	158.9	131	10
226	Tetramethrin A	164	107.1	10	164	77.1	25
227	Grass Dan	100	72	5	124.9	89	15
228	Fenphos	143	79	10	175	79	10
229	Tolclofos-methyl	265	250	15	265	93	25
230	Triadimefon	208	181.1	5	208	111	20
231	Triadimenol	168	70	10	128	65	25
232	Wild wheat	268	184.1	20	142.9	83	15
233	Triazophos	161.2	134.2	5	161.2	106.1	10
234	Toxic soil phosphorus	296.8	268.9	10	298.8	270.9	10
235	Weed Killer	187.1	159.1	10	173.1	145	15
236	Trifloxystrobin	116	89	15	131	89	30
237	Vinclozolin	187	124	20	197.9	145	15

* Among them, 20 compounds have isomers (with an a after the name), and 12 compounds have metabolites (serial numbers combined) .

2.4 Sample preparation

Refer to Part 7 of GB 23200.7-2016 for the pretreatment method of fruit wine samples.

2.5 Preparation of standard working solution

Accurately pipette a certain amount of the mixed standard solution and use the wine matrix solution prepared in step 2.4 to gradually release it into standard working solutions containing external standards with mass concentrations of 0.005 μg/ mL , 0.01 μg / mL , 0.025 μg/ mL , 0.05 μg/mL, 0.1 μg / mL , 0.15 μg/ mL and 0.2 μg / mL and an internal standard of 0.05 μg / mL heptachlor epoxide for determination by gas chromatography-mass spectrometry.

3. Results and Discussion

3.1 Typical spectra

The standard working solutions of 0.1 μg/mL were prepared with n-hexane solvent and wine matrix solution respectively and then measured on the instrument. The spectra of the standard solutions with different solvents are shown below.

Figure 2 TIC chart of 237 pesticide residues at 100 ppb in solvent

Figure 3 TIC graph of 237 pesticide residues at 100 ppb in wine matrix

Figure 4 Single channel overlay of 237 pesticide residues at 100 ppb in wine matrix

By comparing the spectra of solvent standard and matrix standard, it can be seen that the wine matrix standard has a large matrix interference at 21-34 min . The matrix standard solution overlay obtained by scanning in MRM mode has a better peak shape.

The peak time of each compound is shown in the table below.

Table 4 Peak time statistics (DB-17MS)

Compound	Peak time	Compound	Peak time	Compound	Peak time
Dithiocarb	6.38	Toxic soil phosphorus	22.16	Propyl chlorfenapyr	27.17
Sulfoxide	6.45	Metribuzin	22.22	Myclobutanil	27.33
Dichlorvos	7.61	Terbutaline	22.24	Endrin	27.43
dibromophosphine	7.61	Methyl chlorothiazide	22.32	Diniconazole	27.54
Methamidophos	9.02	Isopropylamine	22.38	Cyproconazole a	27.54
Biphenyl	10.01	Triadimefon	22.39	Methoprene	27.54
Dichlobenil	10.12	Chlorpyrifos	22.43	Sulfate	27.63
Tebuconazole	11.39	Tetrafluconazole	22.55	Oxazophos	27.63
Mefenphos	11.62	Fipronil Sulfide	22.59	Benzene	27.71
3-Hydroxycarbofuran	12.07	Fipronil	22.59	2,4'-DDT	27.79
Demeton-methyl	12.57	Malaoxon	22.69	Kresoxim-methyl	27.8
Acaricide	12.58	Malathion	22.69	Bromoxynil	27.98
Chloroanisole	13.16	Grass Dan	22.7	Rice Blast	27.99
Ethyl Butyl Fluoride	13.26	Allethrin	22.74	4,4'-Didi	28.02
Acephate	13.32	Fenitrothion	22.77	Terbuthion	28.02
Ethyl fluazifop	13.47	Ethofuroxol	22.79	Ethion	28.03
Graminicide	13.58	Paraoxon	22.93	Fludioxonil	28.14
Isoprocarb	13.91	Pyriphos	22.93	β-Endosulfan	28.25
Cyclohexidine	14.66	Parathion	22.93	Benzyl ether	28.7
Tetrachloronitrobenzene	14.69	Oxofosfate	23.13	4,4'-DDT	28.8
Heptylphosphine	14.94	Flubutyric Acid	23.23	Piperonyl Butyl	28.8
Fenbuterol	15.18	Fluopyram	23.29	Trifloxystrobin	28.85
Ethoprophos	15.35	Dicofol a	23.33	Propiconazole	28.87
Chlorpheniramine	15.4	Pendimethalin	23.53	Quinoxyfen	28.91
Fenphos	15.41	Bromophos	23.54	Fenthophos	28.92
Ciprofloxacin	15.6	Isothioate-methyl	23.67	Fluopyram	28.98
Carbosulfan	16.01	Fenthion	23.67	Benthiocarb	28.99
Diphenylamine	16.02	Haloxyfop-Phthiophene	23.81	Bifenthrin	29.02
Hexachlorobenzene	16.32	Isothiophene	23.89	Endrin aldehyde	29.06
Phosphorus	16.42	Terbuthion Sulfone	24.04	Bensulfuron	29.06
Phorate	16.59	Phorate sulfoxide	24.05	Tebuconazole	29.23
Methoprene	16.73	Phorate sulfone	24.05	Fenthion sulfoxide	29.37
α-BHC	17.08	Penconazole	24.06	Fenamiphos	29.37
Oxydemeton-methyl	17.19	Herbicide	24.13	Diclofop-butyl	29.39
Desethyl Atrazine	17.37	Triadimenol	24.14	Fenthion Sulfone	29.45
Propyzamide	17.73	Cyprodinil	24.22	Triazophos	29.72
Butylpyrimidinphos	17.81	Butachlor	24.22	Frost Spirit	29.79
Monocrotophos	18.03	2-Methyl-4-chloroisooctyl ester	24.23	Acrinathrin	29.81
Dicrotophos	18.05	Trans-Chlordane	24.33	Bromoxifen	29.85
Pulmonary	18.15	Ethyl Bromothion	24.41	Ethoxazole	29.92
Diazinon	18.18	Isocarb	24.53	Diflubenzuron	29.95
Pentachloronitrobenzene	18.19	Fenpyrachlor	24.58	Cypermethrin	29.96
Afenacet	18.27	Sulfone	24.59	Lambda-cyhalothrin	29.96
Atlaton	18.32	Procymidone	24.69	Tebufenpyrad	29.99
Wild wheat	18.38	Cis-Chlordane	24.83	Iprodione	29.99
Green Valley Takashi	18.44	2,4'-DiDi	24.9	Oxadiazon	30.13
Atrazine	18.51	4,4'-DiDiY	24.9	Epoxiconazole	30.14
Imidazole	18.58	2,4-D 2-Ethylhexyl Ester	24.93	Tetramethrin A	30.36
Terbutinzine	18.61	α-Endosulfan	24.98	Piperidin	30.36
Clomazone	18.62	Quinalphos	25.04	Fenthion	30.63
Chlornithine	18.62	Paclobutrazol	25.04	Hexazinone	30.72
γ-BHC	18.78	trithion	25.06	Methoxychlor	30.76
simazine	18.8	Sclerotium net	25.07	Pyridazinphos	30.88
2,6-Dichlorobenzamide	18.86	Pretilachlor	25.25	Benzyl ester	31
Fonfothion	18.9	Fipronil Sulfone	25.31	Endosulfan sulfate	31
Ethiophos	19.16	Oxadiazon	25.39	Mirex	31.02
Dimethoate	19.33	Thiazofosfamide	25.43	Endrin Ketone	31.06
Pyrimethanil	19.36	Prothiophos	25.53	Cypermethrin	31.12
Methoprene	19.47	Defoliation Phosphorus	25.55	Sulfonamide	31.22
Fluorocarbonitrile	19.61	Herbicide	25.55	Indigoferon	31.26
Isoprolin	19.71	Fluorosulfuron	25.66	Pyriproxyfen	31.28
β-BHC	19.78	Hexaconazole	25.72	Bromophenphos	31.28
Carbofuran	19.82	Fluazifop-P-ethyl	25.73	Phosalone	31.33
Dimethoate	19.84	trifloxyfen	25.79	Phosmet	31.49
Dimethoate	19.87	Glufosinate	25.83	Fenamidone	31.51
Heptachlor	19.94	Oxyfluorfen	25.84	Pyraclostrobin	31.6
Chlorpheniramine	20.02	Butyclothion	25.93	Permethrin A	31.9
Vinclozolin	20.27	Chlorpyrifos	25.99	Fenpyrimidine	32.03
Acetochlor	20.31	Fluoramide	26.06	Pyridaben	32.22
Pentachloroaniline	20.52	Fenthiocarb	26.16	Mefenacet	32.31
Methyl paraoxon	20.77	Dieldrin	26.16	Pyraclostrobin	32.45
Alachlor	20.79	Bromophenazine	26.27	Enoxabiodinium	32.45
Weed Killer	20.85	Acarid Phosphorus A	26.29	Cyfluthrin a	32.58
Pirimicarb	20.97	Profenofos	26.39	Yilanphos	32.73
δ-BHC	20.97	Imazalil	26.39	Coumaphos	32.89
Chlorpyrifos-methyl	21.18	Napropamide	26.51	Cypermethrin A	32.94
Fly	21.19	Cyanostrobin	26.56	Flucythrina	33.01
Aldrin	21.21	Chlorfenapyr	26.62	Fluquinoxaline	33.02
Phosphamide	21.43	Dimethoate	26.62	Triphenyltin hydroxide	33.15
Propanil	21.5	Chlorpheniramine ethyl ester	26.66	Fluvalinate	33.54
Dichlorvos	21.54	Methidathion	26.77	Ethofenprox	33.56
Promethazine	21.64	GABA	26.77	Fenbuconazole	33.79
Tolclofos-methyl	21.82	Phyllanthus sphaerocephalus	26.79	Cypermethrin	34.46
Pirimiphos-methyl	21.86	Cyfluanid	26.8	Flumorph	34.8
Methyl parathion	21.88	Miconazole	26.86	Boscalid	34.83
Amethoxazole	21.98	2,4'-Didi	26.86	Deltamethrin A	36.21
Metalaxyl	21.98	Ethylpyrimidine sulfonate	26.94	Difenoconazole	36.55
Anthiophos	22.05	Pyraclostrobin	26.99	Enoxastrobin	38.71
Isopropylamine	22.07	Sterile Phosphate	27.05

* 20 compounds have isomers (names with a after them)

3.2 Linear

relative peak area of the quantitative ion chromatogram of each target as the ordinate and the mass concentration ( ng / mL ) of the target standard solution as the abscissa. The 237 compounds had good linearity and the correlation coefficients were all greater than 0.995. The statistics of the standard curves of some compounds are shown in the following table.

Table 5 Statistics of quantitative curves of target substances

Compound Name	Correlation coefficient	Compound Name	Correlation coefficient	Compound Name	Correlation coefficient
Dithiocarb	0.9986	Toxic soil phosphorus	0.9970	Myclobutanil	0.9982
Sulfoxide	0.9989	Terbutaline	0.9986	Endrin	0.9966
dibromophosphine	0.9985	Methyl chlorothiazide	0.9993	Diniconazole	0.9977
Dichlorvos	0.9986	Isopropylamine	0.9995	Cyproconazole a	0.9997
Methamidophos	0.9970	Triadimefon	0.9988	Oxazophos	0.9966
Biphenyl	0.9997	Chlorpyrifos	0.9988	Sulfate	0.9983
Dichlobenil	0.9992	Tetrafluconazole	0.9992	Benzene	0.9988
Tebuconazole	0.9980	Fipronil sulfide	0.9983	2,4'-DDT	0.9974
Mefenphos	0.9981	Fipronil	0.9997	Kresoxim-methyl	0.9996
3-Hydroxycarbofuran	0.9993	Malaoxon	0.9975	Bromoxynil	0.9988
Demeton-methyl	0.9981	Malathion	0.9982	Rice Blast	0.9975
Acaricide	0.9976	Grass Dan	0.9997	Terbuthion	0.9964
Chloroanisole	0.9984	Allethrin	0.9966	4,4'-Didi	0.9992
Ethyl Butyl Fluoride	0.9987	Fenitrothion	0.9961	Ethion	0.9975
Acephate	0.9977	Ethofuroxol	0.9972	Fludioxonil	0.9996
Ethyl fluazifop	0.9989	Paraoxon	0.9963	β-Endosulfan	0.9971
Graminicide	0.9991	Pyriphos	0.9979	Benzyl ether	0.9992
Isoprocarb	0.9983	Parathion	0.9984	Piperonyl Butyl	0.9986
Cyclohexidine	0.9989	Oxythiophene	0.9983	4,4'-DDT	0.9990
Tetrachloronitrobenzene	0.9981	Flubutyric Acid	0.9986	Trifloxystrobin	0.9981
Heptylphosphine	0.9991	Fluopyram	0.9971	Propiconazole	0.9988
Fenbuterol	0.9993	Dicofol a	0.9981	Quinoxyfen	0.9998
Ethoprophos	0.9982	Pendimethalin	0.9961	Fenthophos	0.9968
Chlorpheniramine	0.9982	Bromophos	0.9986	Fluopyram	0.9976
Fenphos	0.9999	Fenthion	0.9971	Benthiocarb	0.9974
Ciprofloxacin	0.9987	Isothioate-methyl	0.9987	Bifenthrin	0.9994
Carbosulfan	0.9975	Haloxyfop-Phthiophene	0.9986	Endrin aldehyde	0.9976
Diphenylamine	0.9989	Isothiophene	0.9969	Bensulfuron	0.9987
Hexachlorobenzene	0.9989	Terbuthion Sulfone	0.9976	Tebuconazole	0.9988
Phosphorus	0.9970	Phorate sulfoxide	0.9982	Fenamiphos	0.9986
Phorate	0.9980	Phorate sulfone	0.9983	Fenthion sulfoxide	0.9994
Methoprene	0.9993	Penconazole	0.9989	Diclofop-butyl	0.9982
α-BHC	0.9991	Herbicide	0.9987	Fenthion Sulfone	0.9989
Oxydemeton-methyl	0.9997	Triadimenol	0.9989	Triazophos	0.9977
Desethyl Atrazine	0.9974	Butachlor	0.9977	Frost Spirit	0.9994
Propyzamide	0.9991	Cyprodinil	0.9984	Acrinathrin	0.9994
Butylpyrimidinphos	0.9987	2-Methyl-4-chloroisooctyl ester	0.9987	Bromoxifen	0.9983
Monocrotophos	0.9996	Trans-Chlordane	0.9966	Ethoxazole	0.9973
Dicrotophos	0.997	Ethyl Bromothion	0.9989	Diflubenzuron	0.9993
Pulmonary	0.9973	Fenpyrachlor	0.9992	Cypermethrin	0.9986
Diazinon	0.9973	Sulfone	0.9988	Lambda-cyhalothrin	0.9989
Pentachloronitrobenzene	0.9989	Procymidone	0.9988	Tebufenpyrad	0.9986
Afenacet	0.9981	Cis-Chlordane	0.9969	Iprodione	0.9996
Atlaton	0.9992	4,4'-DiDiY	0.9972	Oxadiazon	0.9964
Wild wheat	0.9993	2,4'-DiDi	0.999	Epoxiconazole	0.9981
Green Valley Takashi	0.9987	2,4-D 2-Ethylhexyl Ester	0.9987	Piperidin	0.9960
Atrazine	0.9990	α-Endosulfan	0.997	Tetramethrin A	0.9995
Imidazole	0.9987	Paclobutrazol	0.9988	Fenthion	0.9993
Terbutinzine	0.9986	Quinalphos	0.9994	Hexazinone	0.9998
Clomazone	0.9988	trithion	0.9978	Methoxychlor	0.9996
Chlornithine	0.9997	Sclerotium net	0.9993	Pyridazinon	0.9976
γ-BHC	0.9994	Pretilachlor	0.9978	Benzyl ester	0.9972
simazine	0.9992	Fipronil Sulfone	0.998	Endosulfan sulfate	0.9996
2,6-Dichlorobenzamide	0.9994	Oxadiazon	0.9978	Mirex	0.9984
Fonfothion	0.9996	Thiazofosfamide	0.9989	Endrin Ketone	0.9991
Ethiophos	0.9996	Prothiophos	0.9974	Cypermethrin	0.9992
Dimethoate	0.9989	Herbicide	0.997	Sulfonamide	0.9995
Methoprene	0.9991	Defoliation Phosphorus	0.9996	Indigoferon	0.9980
Fluorocarbonitrile	0.9993	Fluorobifen	0.9984	Pyriproxyfen	0.9979
Isoprolin	0.9985	Hexaconazole	0.9976	Bromophenphos	0.9990
β-BHC	0.9973	Fluazifop-P-ethyl	0.9997	Phosalone	0.9972
Carbofuran	0.9980	trifloxyfen	0.9983	Phosmet	0.9986
Dimethoate	0.9976	Glufosinate	0.9965	Fenamidone	0.9993
Dimethoate	0.9989	Oxyfluorfen	0.9988	Pyraclostrobin	0.9977
Heptachlor	0.9989	Butyclothion	0.9981	Permethrin A	0.9982
Chlorpheniramine	0.9978	Chlorpyrifos	0.9976	Fenpyrimidine	0.9981
Vinclozolin	0.9979	Fluoramide	0.9987	Pyridaben	0.9993
Acetochlor	0.998	Dieldrin	0.9979	Mefenacet	0.9971
Pentachloroaniline	0.9987	Fenthiocarb	0.9984	Enoxabiodinium	0.9982
Methyl paraoxon	0.9981	Bromophenazine	0.9998	Pyraclostrobin	0.9994
Alachlor	0.9976	Acarid Phosphorus A	0.9985	Cyfluthrin a	0.9974
Weed Killer	0.9973	Profenofos	0.9989	Yilanphos	0.9982
δ-BHC	0.9993	Imazalil	0.9995	Coumaphos	0.9957
Pirimicarb	0.9994	Napropamide	0.9992	Cypermethrin A	0.9970
Chlorpyrifos-methyl	0.9993	Cyanostrobin	0.9972	Flucythrina	0.9980
Fly	0.9995	Chlorfenapyr	0.9976	Fluquinoxaline	0.9996
Aldrin	0.9982	Chlorpheniramine ethyl ester	0.998	Triphenyltin hydroxide	0.9978
Phosphamide	0.9989	Methidathion	0.9987	Fluvalinate	0.9974
Propanil	0.9993	GABA	0.9996	Ethofenprox	0.9982
Dichlorvos	0.9984	Phyllanthus sphaerocephalus	0.9988	Fenbuconazole	0.9963
Promethazine	0.9986	Cyfluanid	0.9977	Cypermethrin	0.9994
Tolclofos-methyl	0.9985	Miconazole	0.9985	Flumorph	0.9996
Pirimiphos-methyl	0.9992	2,4'-Didi	0.9994	Boscalid	0.9987
Methyl parathion	0.9961	Ethylpyrimidine sulfonate	0.9986	Deltamethrin A	0.9994
Amethoxazole	0.9989	Pyraclostrobin	0.9979	Difenoconazole	0.9976
Anthiophos	0.9988	Sterile Phosphate	0.9983	Enoxastrobin	0.9986
Isopropylamine	0.9997	Propyl chlorfenapyr	0.9975

3.3 Repeatability

The repeatability of the peak area was investigated by continuous analysis 8 times at two matrix standard concentrations of 30 ppb and 120 ppb, and the results are shown in Table 5. Among the 23 7 pesticide residues and their isomers, the repeatability RSD of 8 analyses at 30 ppb was <15%, and the repeatability RSD of 8 analyses at 120 ppb was <10% .

Table 6 Precision statistics of 237 pesticide residues at 30 ppb

30ppb repeatability RSD				120ppb repeatability RSD
Sample Information	RSD	Sample Information	RSD	Sample Information	RSD	Sample Information	RSD
Dithiocarb	4.73	Cis-Chlordane	6.95	Dithiocarb	1.68	Cis-Chlordane	3.25
Sulfoxide	5.13	2,4'-DiDi	3.82	Sulfoxide	4.80	2,4'-DiDi	2.86
Dichlorvos	5.65	4,4'-DiDiY	4.47	Dichlorvos	2.28	4,4'-DiDiY	2.61
dibromophosphine	6.03	2,4-D 2-Ethylhexyl Ester	4.85	dibromophosphine	4.40	2,4-D 2-Ethylhexyl Ester	1.73
Methamidophos	3.17	α-Endosulfan	11.41	Methamidophos	4.00	α-Endosulfan	7.37
Biphenyl	8.01	Quinalphos	8.93	Biphenyl	2.85	Quinalphos	1.93
Dichlobenil	4.56	Paclobutrazol	10.28	Dichlobenil	3.38	Paclobutrazol	7.70
Tebuconazole	6.09	Sclerotium net	5.86	Tebuconazole	4.87	Sclerotium net	8.82
Mefenphos	4.41	trithion	10.16	Mefenphos	4.17	trithion	5.93
3-Hydroxycarbofuran	8.32	Pretilachlor	3.27	3-Hydroxycarbofuran	8.79	Pretilachlor	2.48
Insect acaricide	3.75	Fipronil Sulfone	4.50	Insect acaricide	4.02	Fipronil Sulfone	3.43
Demeton-methyl	8.09	Oxadiazon	5.52	Demeton-methyl	6.11	Oxadiazon	2.35
Chloroanisole	4.61	Fosthiazate	12.41	Chloroanisole	4.07	Fosthiazate	7.16
Ethyl Butyl Fluorine	11.48	Prothiophos	9.33	Ethyl Butyl Fluoride	6.12	Prothiophos	7.11
Acephate	10.69	Defoliation Phosphorus	12.86	Acephate	6.41	Defoliation Phosphorus	2.57
Ethyl fluazifop	10.48	Herbicide	5.56	Ethyl fluazifop	8.87	Herbicide	3.12
Graminicide	3.70	Fluorobifen	11.01	Graminicide	2.93	Fluorobifen	6.46
Isoprocarb	4.55	Hexaconazole	12.14	Isoprocarb	3.45	Hexaconazole	8.07
Cyclohexidine	10.86	Fluazifop-P-ethyl	5.34	Cyclohexidine	6.14	Fluazifop-P-ethyl	4.66
Tetrachloronitrobenzene	11.37	trifloxyfen	12.64	Tetrachloronitrobenzene	6.88	trifloxyfen	8.42
Heptylphosphine	3.79	Glufosinate	11.35	Heptylphosphine	2.89	Glufosinate	7.40
Fenbuterol	1.58	Oxyfluorfen	9.75	Fenbuterol	3.70	Oxyfluorfen	8.82
Ethoprophos	3.42	Butyclothion	9.18	Ethoprophos	3.09	Butyclothion	4.09
Chlorpheniramine	11.12	Chlorpyrifos	10.47	Chlorpheniramine	6.53	Chlorpyrifos	5.20
Fenphos	6.32	Fluoramide	6.05	Fenphos	3.52	Fluoramide	3.19
Ciprofloxacin	11.30	Fenthiocarb	6.01	Ciprofloxacin	7.23	Fenthiocarb	4.74
Carbosulfan	5.55	Dieldrin	10.15	Carbosulfan	4.66	Dieldrin	5.71
Diphenylamine	5.13	Bromophenazine	7.05	Diphenylamine	3.19	Bromophenazine	2.99
Hexachlorobenzene	3.92	Acaricide	8.06	Hexachlorobenzene	5.55	Acaricide	4.15
Phosphorus	11.13	Profenofos	8.90	Phosphorus	3.22	Profenofos	4.06
Methoprene	4.14	Imazalil	8.86	Methoprene	3.33	Imazalil	5.42
α-BHC	4.39	Napropamide	11.46	α-BHC	4.39	Napropamide	4.82
Oxydemeton-methyl	10.24	Cyanostrobin	9.69	Oxydemeton-methyl	7.28	Cyanostrobin	7.41
Desethyl Atrazine	3.24	Chlorfenapyr	9.86	Desethyl Atrazine	2.06	Chlorfenapyr	7.72
Phorate	11.25	Chlorpheniramine ethyl ester	9.66	Phorate	7.15	Chlorpheniramine ethyl ester	5.89
Propyzamide	5.82	Methidathion	10.93	Propyzamide	3.26	Methidathion	7.64
Butylpyrimidinphos	11.24	GABA	4.72	Butylpyrimidinphos	4.60	GABA	4.73
Dicrotophos	9.01	Phyllanthus sphaerocephalus	12.06	Dicrotophos	6.14	Phyllanthus sphaerocephalus	5.63
Pulmonary	3.89	Cyfluanid	8.13	Pulmonary	3.29	Cyfluanid	8.25
Diazinon	2.55	2,4'-DDT	8.97	Diazinon	2.76	2,4'-DDT	5.37
Pentachloronitrobenzene	10.97	2,4'-Didi	4.70	Pentachloronitrobenzene	8.68	2,4'-Didi	3.56
Afenacet	11.98	Miconazole	5.49	Afenacet	3.36	Miconazole	4.14
Atlaton	9.63	Ethylpyrimidine sulfonate	12.86	Atlaton	6.01	Ethylpyrimidine sulfonate	3.77
Wild wheat	6.10	Pyraclostrobin	13.92	Wild wheat	6.25	Pyraclostrobin	7.47
Green Valley Takashi	9.28	Sterile Phosphate	12.44	Green Valley Takashi	5.45	Sterile Phosphate	3.70
Atrazine	7.84	Propyl chlorfenapyr	9.47	Atrazine	5.34	Propyl chlorfenapyr	4.03
Imidazole	2.56	Myclobutanil	12.60	Imidazole	3.84	Myclobutanil	4.80
Clomazone	7.11	Dimethoate	10.04	Clomazone	3.56	Dimethoate	3.72
Terbutinzine	4.37	Diniconazole	13.11	Terbutinzine	5.38	Diniconazole	8.22
Chlornithine	11.52	Sulfate	11.04	Chlornithine	7.94	Sulfate	4.62
γ-BHC	3.69	Oxazophos	9.47	γ-BHC	3.91	Oxazophos	8.62
simazine	4.42	Cyproconazole	10.65	simazine	3.36	Cyproconazole	7.42
2.6-Dichlorobenzamide	8.75	Benzene	13.46	2.6-Dichlorobenzamide	4.97	Benzene	8.64
Fenfothion	9.33	Kresoxim-methyl	3.95	Fenfothion	3.92	Kresoxim-methyl	2.69
Monocrotophos	9.28	Bromoxynil	10.91	Monocrotophos	7.79	Bromoxynil	7.15
Ethiophos	11.57	Rice Blast	5.99	Ethiophos	5.10	Rice Blast	5.64
Dimethoate	11.03	4,4'-Didi	4.80	Dimethoate	4.84	4,4'-Didi	5.90
Methoprene	11.73	Ethion	9.37	Methoprene	8.35	Ethion	7.02
Fluorocarbonitrile	2.41	Terbuthion	9.99	Fluorocarbonitrile	2.41	Terbuthion	5.14
Isoprolin	7.95	Fludioxonil	8.89	Isoprolin	2.43	Fludioxonil	7.74
β-BHC	4.97	β-Endosulfan	8.15	β-BHC	3.77	β-Endosulfan	4.56
Carbofuran	7.90	Benzyl ether	11.60	Carbofuran	6.31	Benzyl ether	7.61
Dimethoate	6.64	4,4'-DDT	11.41	Dimethoate	2.86	4,4'-DDT	6.34
Dimethoate	9.06	Piperonyl Butyl	12.25	Dimethoate	6.08	Piperonyl Butyl	3.95
Heptachlor	6.56	Trifloxystrobin	12.48	Heptachlor	3.77	Trifloxystrobin	4.58
Chlorpheniramine	7.16	Quinoxyfen	5.91	Chlorpheniramine	3.20	Quinoxyfen	6.66
Vinclozolin	4.53	Fenthophos	8.26	Vinclozolin	3.27	Fenthophos	5.69
Acetochlor	4.79	Propiconazole	5.86	Acetochlor	3.69	Propiconazole	4.42
Pentachloroaniline	6.40	Benthiocarb	13.20	Pentachloroaniline	4.71	Benthiocarb	6.68
Methyl paraoxon	10.34	Fluopyram	11.87	Methyl paraoxon	7.90	Fluopyram	6.53
Alachlor	3.28	Bifenthrin	4.86	Alachlor	2.66	Bifenthrin	2.29
Weed Killer	4.74	Endrin aldehyde	13.27	Weed Killer	6.93	Endrin aldehyde	6.21
Pirimicarb	3.82	Bensulfuron	6.10	Pirimicarb	3.43	Bensulfuron	3.45
δ-BHC	4.14	Tebuconazole	12.84	δ-BHC	3.90	Tebuconazole	6.41
Chlorpyrifos-methyl	10.30	Fenthion sulfoxide	9.27	Chlorpyrifos-methyl	5.36	Fenthion sulfoxide	7.15
Fly	6.58	Fenamiphos	9.05	Fly	3.22	Fenamiphos	5.74
Aldrin	4.69	Diclofop-butyl	13.22	Aldrin	2.33	Diclofop-butyl	6.28
Phosphamide	9.89	Fenthion Sulfone	6.92	Phosphamide	5.35	Fenthion Sulfone	7.51
Propanil	5.40	Tebufenpyrad	7.34	Propanil	5.24	Tebufenpyrad	5.30
Dichlorvos	6.44	Triazophos	9.81	Dichlorvos	6.74	Triazophos	7.29
Promethazine	10.88	Frost Spirit	8.43	Promethazine	4.06	Frost Spirit	5.54
Tolclofos-methyl	7.28	Bromoxifen	9.60	Tolclofos-methyl	4.14	Bromoxifen	2.12
Methyl parathion	12.17	Ethoxazole	10.30	Methyl parathion	8.70	Ethoxazole	4.67
Anthiophos	8.88	Diflubenzuron	10.74	Anthiophos	3.72	Diflubenzuron	4.39
Pirimiphos-methyl	10.82	Acrinathrin	7.55	Pirimiphos-methyl	5.29	Acrinathrin	4.32
Amethoxazole	5.41	Lambda-cyhalothrin	7.43	Amethoxazole	4.76	Lambda-cyhalothrin	2.95
Metalaxyl	2.64	Iprodione	6.18	Metalaxyl	4.14	Iprodione	6.70
Isopropylamine	4.12	Oxadiazon	13.02	Isopropylamine	4.13	Oxadiazon	6.33
Toxic soil phosphorus	11.63	Epoxiconazole-2	12.69	Toxic soil phosphorus	5.49	Epoxiconazole-2	7.60
Terbutaline	4.85	Piperidin	13.48	Terbutaline	5.08	Piperidin	8.54
Methyl chlorothiazide	3.98	Tetramethrin	13.11	Methyl chlorothiazide	3.26	Tetramethrin	3.94
Isopropylamine	6.99	Cypermethrin	9.73	Isopropylamine	4.64	Cypermethrin	3.33
Triadimefon	9.58	Fenthiophos	11.21	Triadimefon	5.15	Fenthiophos	7.89
Chlorpyrifos	6.38	Hexazinone	8.98	Chlorpyrifos	4.25	Hexazinone	6.21
Tetrafluimidazole	7.16	Methoxychlor	6.47	Tetrafluimidazole	4.31	Methoxychlor	5.46
Fipronil	9.66	Pyridazinphos	12.50	Fipronil	8.48	Pyridazinphos	8.41
Fipronil sulfide	4.75	Benzyl ester	13.28	Fipronil sulfide	5.04	Benzyl ester	7.57
Malathion	10.56	Mirex	5.78	Malathion	4.76	Mirex	8.11
Allethrin	8.78	Endosulfan sulfate	5.30	Allethrin	6.21	Endosulfan sulfate	7.09
Malaoxon	10.76	Endrin Ketone	7.89	Malaoxon	4.40	Endrin Ketone	8.77
Grass Dan	7.98	Bromophenylphosphine	8.07	Grass Dan	3.74	Bromophenylphosphine	4.25

Fenitrothion	11.60	Indigoferon	12.81	Fenitrothion	7.21	Indigoferon	4.88
Ethofuroxol	7.91	Sulfonamide	6.45	Ethofuroxol	2.32	Sulfonamide	7.84
Paraoxon	10.94	Pyriproxyfen	10.12	Paraoxon	8.10	Pyriproxyfen	3.33
Pyriphos	12.52	Cypermethrin	12.89	Pyriphos	7.84	Cypermethrin	7.75
Parathion	10.51	Fenamidone	13.69	Parathion	7.42	Fenamidone	6.33
Oxofosfate	12.98	Phosalone	11.80	Oxythiophene	3.71	Phosalone	7.22
Flubutyric Acid	4.94	Phosmet	12.28	Flubutyric Acid	3.49	Phosmet	4.81
Fluopyram	2.76	Pyraclostrobin	13.57	Fluopyram	2.89	Pyraclostrobin	7.90
Dicofol	8.44	Permethrin	6.82	Dicofol	4.88	Permethrin	5.43
Pendimethalin	12.96	Fenpyrimidine	9.83	Pendimethalin	8.12	Fenpyrimidine	6.86
Bromophos	6.58	Damanlin	9.62	Bromophos	3.43	Damanlin	3.91
Heptachlor epoxide B	9.96	Mefenacet	10.98	Heptachlor epoxide B	7.23	Mefenacet	5.14
Fenthion	10.15	Pyraclostrobin	4.74	Fenthion	7.24	Pyraclostrobin	7.97
Isothioate-methyl	10.83	Enoxabiodinium	9.43	Isothioate-methyl	6.85	Enoxabiodinium	6.41
Haloxyfop-Phthiophene	4.85	Yilanphos	9.73	Haloxyfop-Phthiophene	4.58	Yilanphos	8.27
Isothiophene	12.41	Cyfluthrin	10.43	Isothiophene	5.97	Cyfluthrin	7.46
Terbuthion Sulfone	11.58	Ethofenprox	3.46	Terbuthion Sulfone	5.57	Ethofenprox	2.01
Phorate sulfoxide	11.57	Coumaphos	10.74	Phorate sulfoxide	4.71	Coumaphos	8.44
Phorate sulfone	9.33	Fluquinoxaline	11.95	Phorate sulfone	6.09	Fluquinoxaline	7.08
Penconazole	7.46	Flucythrinate	11.18	Penconazole	3.13	Flucythrinate	8.16
Triadimenol	9.42	Cypermethrin	12.39	Triadimenol	6.16	Cypermethrin	8.16
Herbicide	5.14	Triphenyltin hydroxide	7.94	Herbicide	2.83	Triphenyltin hydroxide	8.79
Butachlor	11.40	Fluvalinate	12.73	Butachlor	3.95	Fluvalinate	8.64
Cyprodinil	5.86	Fenbuconazole	8.52	Cyprodinil	3.59	Fenbuconazole	7.18
2-Methyl-4-chloroisooctyl ester	7.62	Fenvalerate	11.57	2-Methyl-4-chloroisooctyl ester	5.17	Fenvalerate	8.73
Chlordane-trans	7.27	Flumorph	7.12	Chlordane-trans	3.88	Flumorph	6.30
Ethyl Bromothion	10.14	Boscalid	8.18	Ethyl Bromothion	5.00	Boscalid	6.23
Sulfone	10.62	Deltamethrin	11.65	Sulfone	8.71	Deltamethrin	8.50
Fenpyrol	8.58	Difenoconazole	13.08	Fenpyrol	2.63	Difenoconazole	7.82
Procymidone	5.06	Enoxastrobin	10.88	Procymidone	5.07	Enoxastrobin	8.71

3.4 Sensitivity

The detection limit of 237 pesticide residues is 0.0004-0.002 mg/ kg, which far meets the requirements of the standard (the quantitative limit in the standard is 0.008-0.4 mg/kg). The lowest linear point of some compounds is equivalent to a pesticide residue concentration of 0.0004 mg/kg. The quantitative channel spectrum response of some compounds is shown in the figure below.

3.5 Recovery rate

The wine samples were spiked and recovered with spike concentrations of 30 ppb and 120 ppb (equivalent to 0.002 mg/kg and 0.008 mg/kg), and the recovery rates of the compounds were statistically between 59.37% and 133.59%.

Table 7 Sensitivity statistics of 237 pesticide residues

4. In conclusion

In this paper, referring to GB23200.7-2016 standard, 5231 was used in combination with DB-7MS column to test 237 pesticide residues in wine matrix, and the linearity, sensitivity and repeatability of the method were investigated. The results showed that the 237 pesticide compounds had good linearity within the concentration range (r² ^>0.995 ), the detection limit of each pesticide residue compound was between 0.0004-0.002mg/kg, the precision was good, the repeatability analysis RSD near LOQ was < 15 % , and the repeatability analysis RSD near 4 times LOQ was < 10 % ; the spike recovery rate was between 59.3-133.4%. Using EXPEC 5231 can accurately, sensitively and efficiently perform quantitative analysis of multiple residues in wine.

GC-MSMS | Determination of 237 pesticide residues in wine