加速溶剂萃取-气相色谱-串联质谱法同时测定贝类中64种农药残留

doi:10.3724/SP.J.1123.2019.11003

摘要/Abstract

摘要：

建立了加速溶剂同步萃取净化-气相色谱-串联质谱（GC-MS/MS）同时测定贝类中64种农药残留的方法。加速溶剂萃取的萃取溶剂为90%（v/v）乙腈水溶液，萃取温度为85℃、冲洗体积60%萃取池体积、循环次数1次，同时使用0.8 g N-丙基乙二胺（PSA）和0.8 g石墨化炭黑（GCB）在线净化，提取液浓缩定容后，在多反应监测（MRM）模式下测定，外标法定量。结果表明，64种农药在10.0~1000 μg/L范围内呈现良好的线性关系，决定系数（r²）均大于0.989，方法的定量限为2.0~10.0 μg/kg；对文蛤空白基质进行加标回收试验，添加水平为5.0、10.0和100 μg/kg以及定量限水平，得到的平均回收率为69.4%~129.7%，精密度为0.7%~16.0%（n=6）。该方法提取和净化同步完成，操作简单，重复性好，灵敏度高，能够满足于贝类水产品中多种农药残留的同时筛查。

关键词: 气相色谱-串联质谱, 加速溶剂同步萃取净化, 多农药残留, 贝类

Abstract:

A method was established for the determination of 64 pesticide residues in shellfish using accelerated solvent simultaneous extraction and purification coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS). The target compounds were extracted from shellfish using 90% (v/v) acetonitrile aqueous solution with 60% of the pool volume at 85℃ via a single cycle of accelerated solvent extraction. The extracts were synchronously purified with primary secondary amine (PSA) and graphitized carbon black (GCB) added to the extracting cell. After concentration, the target compounds were detected by GC-MS/MS in the multiple reaction monitoring (MRM) mode, and quantified by using the external standard method. Under the optimized conditions, good linearities were obtained for the 64 pesticides in the range of 10.0-1000 μg/L, with coefficients of determination greater than 0.989. The limits of quantification for the method were between 2.0 μg/kg and 10.0 μg/kg. At four spiked levels (5.0, 10.0, 100 μg/kg, and the LOQ level) in clam, the recoveries of all the pesticides were between 69.4% and 129.7%, with the relative standard deviations varying from 0.7% to 16.0% (n=6). The method is simple, repeatable and sensitive, and it is suitable for the screening of various pesticide residues in shellfish products.

Key words: gas chromatography-tandem mass spectrometry (GC-MS/MS), accelerated solvent simultaneous extraction and purification, multi-pesticide residues, shellfish

张云青, 孟祥龙, 范广宇, 马桂珍, 唐秀, 李配婷. 加速溶剂萃取-气相色谱-串联质谱法同时测定贝类中64种农药残留[J]. 色谱, 2020, 38(6): 687-694.

ZHANG Yunqing, MENG Xianglong, FAN Guangyu, MA Guizhen, TANG Xiu, LI Peiting. Simultaneous determination of 64 pesticide residues in shellfish by accelerated solvent extraction coupled with gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(6): 687-694.

图/表 5

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Analyte	Chinese name	Retention time/min	Monitoring ion pair (m/z)	CE/eV
* Parent ion.
Alachlor	甲草胺	12.1	188.08^*, 160.07	10
Aldrin	艾氏剂	13.1	292.90^*, 222.92	20
Atrazine	莠去津	9.4	215.00^*, 200.00	10
Bifenthrin	联苯菊酯	25.4	181.05^*, 141.04	22
Chlorpyrifos	毒死蜱	13.7	315.93^*, 259.95	12
cis-Chlordane	顺式氯丹	15.8	409.80^*, 374.81	5
Clomazone	异恶草酮	9.4	204.06^*, 107.03	15
Coumaphos	蝇毒磷	30.5	362.01^*, 109.00	10
Cyfluthrin	氟氯氰菊酯	30.6	165.02^*, 91.01	15
Cyhalothrin	氯氟氰菊酯	29.4	208.50^*, 181.04	10
Cypermethrin	氯氰菊酯	33.4	181.03^*, 152.03	25
Deltamethrin	溴氰菊酯	36.2	252.80^*, 92.90	16
Desmetryn	敌草净	11.2	213.11^*, 171.08	10
Diazinon	二嗪农	10.3	304.10^*, 179.06	15
Dichlorvos	敌敌畏	4.9	186.90^*, 93.00	12
Diclofopmethyl	禾草灵	23.2	340.00^*, 253.00	10
Dicofol	三氯杀螨醇	13.6	250.94^*, 138.97	15
Dieldrin	狄氏剂	18.5	278.90^*, 242.92	15
Diflufenican	吡氟酰草胺	23.4	394.07^*, 266.05	10
Dimethoate	乐果	9.1	229.00^*, 87.00	10
Endosulfan Ⅰ	α-硫丹	16.7	264.88^*, 192.91	22
Endosulfan Ⅱ	β-硫丹	19.2	195.91^*, 158.93	16
Endosulfan sulfate	硫丹硫酸盐	21.3	271.88^*, 236.89	15
Endrin	异狄氏剂	18.5	280.90^*, 244.92	12
Ethion	乙硫磷	20.5	383.99^*, 230.99	10
Etofenprox	醚菊酯	33.7	163.09^*, 107.06	16
Fenpropathrin	甲氰菊酯	25.6	265.13^*, 89.04	10
Fenthion	倍硫磷	13.8	278.02^*, 109.01	18
Fenvalerate	氰戊菊酯	35.3	225.07^*, 119.04	10
Fipronil	锐劲特	16.0	366.95^*, 212.97	25
Flucythrinate	氟氰戊菊酯	33.7	199.07^*, 107.04	22
Fonofos	地虫硫磷	9.8	246.03^*, 137.02	10
Hexachlorobenzene	六氯苯	8.8	285.81^*, 250.83	20
Isocarbophos	水胺硫磷	14.0	136.00^*, 69.00	30
Malathion	马拉硫磷	13.5	173.02^*, 99.01	10
Methamidophos	甲胺磷	4.6	141.00^*, 64.00	18
Metolachlor	异丙甲草胺	13.5	238.11^*, 133.06	15
Myclobutanil	腈菌唑	18.4	179.07^*, 125.05	15
o, p′-Dichlorodiphenyltrichloroethane	o, p′-滴滴涕	21.9	236.94^*, 164.96	20
Oxadiazon	恶草酮	18.5	304.06^*, 260.05	10
Parathion	对硫磷	13.8	291.03^*, 109.01	15
Parathion methyl	甲基对硫磷	11.7	263.00^*, 109.00	15
Pentachloronitrobenzene	五氯硝基苯	9.7	294.84^*, 236.87	20
Permethrin	氯菊酯	30.6	183.04^*, 153.03	15
Phorate	甲拌磷	8.6	260.01^*, 75.00	5
Phosemet	亚胺硫磷	24.2	316.99^*, 160.00	5
Piperophos	戊草净	25.1	320.11^*, 122.04	10
p, p′-Dichlorodiphenyldichloroethane	p, p′-滴滴滴	20.1	236.97^*, 164.98	20
p, p′-Dichlorodiphenyldichloroethylene	p, p′-滴滴伊	18.0	318.00^*, 246.00	20
p, p′-Dichlorodiphenyltrichloroethane	p, p′-滴滴涕	21.9	236.94^*, 164.96	20
Procymidone	腐霉利	15.9	283.02^*, 96.01	10
Profenofos	溴丙磷	17.8	338.94^*, 268.95	20
Prometryn	扑草净	12.4	241.14^*, 184.10	15
Simetryn	西草净	11.9	213.11^*, 170.08	10
Tebuconazole	戊唑醇	22.5	252.12^*, 127.06	20
Terbufos	特丁硫磷	9.8	288.04^*, 231.04	15
Triadimefon	三唑酮	13.9	210.07^*, 183.06	10
Triadimenol	三唑醇	15.9	168.06^*, 70.03	10
Triazophos	三唑磷	21.3	161.00^*, 105.70	12
Trifluralin	氟乐灵	8.5	306.10^*, 160.05	15
α-Hexachlorocyclohexane	α-六六六	8.8	218.89^*, 182.91	10
β-Hexachlorocyclohexane	β-六六六	9.4	180.91^*, 144.93	8
γ-Hexachlorocyclohexane	γ-六六六	9.6	218.89^*, 144.93	8
δ-Hexachlorocyclohexane	δ-六六六	10.4	218.89^*, 182.91	8

Analyte	Chinese name	Retention time/min	Monitoring ion pair (m/z)	CE/eV
* Parent ion.
Alachlor	甲草胺	12.1	188.08^*, 160.07	10
Aldrin	艾氏剂	13.1	292.90^*, 222.92	20
Atrazine	莠去津	9.4	215.00^*, 200.00	10
Bifenthrin	联苯菊酯	25.4	181.05^*, 141.04	22
Chlorpyrifos	毒死蜱	13.7	315.93^*, 259.95	12
cis-Chlordane	顺式氯丹	15.8	409.80^*, 374.81	5
Clomazone	异恶草酮	9.4	204.06^*, 107.03	15
Coumaphos	蝇毒磷	30.5	362.01^*, 109.00	10
Cyfluthrin	氟氯氰菊酯	30.6	165.02^*, 91.01	15
Cyhalothrin	氯氟氰菊酯	29.4	208.50^*, 181.04	10
Cypermethrin	氯氰菊酯	33.4	181.03^*, 152.03	25
Deltamethrin	溴氰菊酯	36.2	252.80^*, 92.90	16
Desmetryn	敌草净	11.2	213.11^*, 171.08	10
Diazinon	二嗪农	10.3	304.10^*, 179.06	15
Dichlorvos	敌敌畏	4.9	186.90^*, 93.00	12
Diclofopmethyl	禾草灵	23.2	340.00^*, 253.00	10
Dicofol	三氯杀螨醇	13.6	250.94^*, 138.97	15
Dieldrin	狄氏剂	18.5	278.90^*, 242.92	15
Diflufenican	吡氟酰草胺	23.4	394.07^*, 266.05	10
Dimethoate	乐果	9.1	229.00^*, 87.00	10
Endosulfan Ⅰ	α-硫丹	16.7	264.88^*, 192.91	22
Endosulfan Ⅱ	β-硫丹	19.2	195.91^*, 158.93	16
Endosulfan sulfate	硫丹硫酸盐	21.3	271.88^*, 236.89	15
Endrin	异狄氏剂	18.5	280.90^*, 244.92	12
Ethion	乙硫磷	20.5	383.99^*, 230.99	10
Etofenprox	醚菊酯	33.7	163.09^*, 107.06	16
Fenpropathrin	甲氰菊酯	25.6	265.13^*, 89.04	10
Fenthion	倍硫磷	13.8	278.02^*, 109.01	18
Fenvalerate	氰戊菊酯	35.3	225.07^*, 119.04	10
Fipronil	锐劲特	16.0	366.95^*, 212.97	25
Flucythrinate	氟氰戊菊酯	33.7	199.07^*, 107.04	22
Fonofos	地虫硫磷	9.8	246.03^*, 137.02	10
Hexachlorobenzene	六氯苯	8.8	285.81^*, 250.83	20
Isocarbophos	水胺硫磷	14.0	136.00^*, 69.00	30
Malathion	马拉硫磷	13.5	173.02^*, 99.01	10
Methamidophos	甲胺磷	4.6	141.00^*, 64.00	18
Metolachlor	异丙甲草胺	13.5	238.11^*, 133.06	15
Myclobutanil	腈菌唑	18.4	179.07^*, 125.05	15
o, p′-Dichlorodiphenyltrichloroethane	o, p′-滴滴涕	21.9	236.94^*, 164.96	20
Oxadiazon	恶草酮	18.5	304.06^*, 260.05	10
Parathion	对硫磷	13.8	291.03^*, 109.01	15
Parathion methyl	甲基对硫磷	11.7	263.00^*, 109.00	15
Pentachloronitrobenzene	五氯硝基苯	9.7	294.84^*, 236.87	20
Permethrin	氯菊酯	30.6	183.04^*, 153.03	15
Phorate	甲拌磷	8.6	260.01^*, 75.00	5
Phosemet	亚胺硫磷	24.2	316.99^*, 160.00	5
Piperophos	戊草净	25.1	320.11^*, 122.04	10
p, p′-Dichlorodiphenyldichloroethane	p, p′-滴滴滴	20.1	236.97^*, 164.98	20
p, p′-Dichlorodiphenyldichloroethylene	p, p′-滴滴伊	18.0	318.00^*, 246.00	20
p, p′-Dichlorodiphenyltrichloroethane	p, p′-滴滴涕	21.9	236.94^*, 164.96	20
Procymidone	腐霉利	15.9	283.02^*, 96.01	10
Profenofos	溴丙磷	17.8	338.94^*, 268.95	20
Prometryn	扑草净	12.4	241.14^*, 184.10	15
Simetryn	西草净	11.9	213.11^*, 170.08	10
Tebuconazole	戊唑醇	22.5	252.12^*, 127.06	20
Terbufos	特丁硫磷	9.8	288.04^*, 231.04	15
Triadimefon	三唑酮	13.9	210.07^*, 183.06	10
Triadimenol	三唑醇	15.9	168.06^*, 70.03	10
Triazophos	三唑磷	21.3	161.00^*, 105.70	12
Trifluralin	氟乐灵	8.5	306.10^*, 160.05	15
α-Hexachlorocyclohexane	α-六六六	8.8	218.89^*, 182.91	10
β-Hexachlorocyclohexane	β-六六六	9.4	180.91^*, 144.93	8
γ-Hexachlorocyclohexane	γ-六六六	9.6	218.89^*, 144.93	8
δ-Hexachlorocyclohexane	δ-六六六	10.4	218.89^*, 182.91	8

Analyte	MDL/(μg/kg)	LOQ/(μg/kg)	ME/%	Recovery/% (RSD/%)
Analyte	MDL/(μg/kg)	LOQ/(μg/kg)	ME/%	2.0 μg/kg	5.0 μg/kg	10.0 μg/kg	100.0 μg/kg
-: pesticides were not spiked at this level.
Alachlor	1.0	3.0	-22	-	100.4 (5.1)	94.9 (5.7)	104.1 (3.0)
Aldrin	1.7	5.0	-23	-	82.6 (7.2)	88.8 (4.2)	89.9 (4.4)
Atrazine	2.0	6.0	-25	-	106.5 (7.0)	92.8 (5.5)	92.0 (2.4)
Bifenthrin	1.7	5.0	33	-	100.4 (3.6)	95.6 (3.4)	103.3 (2.8)
Chlorpyrifos	2.0	6.0	-5	-	108.1 (5.8)	109.8 (4.8)	118.9 (5.3)
cis-Chlordane	1.3	4.0	-10	-	88.5 (4.8)	91.3 (3.9)	95.5 (9.2)
Clomazone	1.7	5.0	-16	-	84.3 (2.3)	73.2 (3.4)	74.4 (2.0)
Coumaphos	3.3	10.0	15	-	117.5 (7.4)	123.7 (4.8)	125.0 (3.1)
Cyfluthrin	0.7	2.0	20	104.9 (10.4)	93.7 (8.9)	94.8 (3.0)	101.9 (2.6)
Cyhalothrin	0.7	2.0	80	110.1 (16.0)	121.1 (7.2)	109.3 (6.6)	114.6 (6.1)
Cypermethrin	0.7	2.0	55	94.6 (2.9)	94.7 (4.2)	105.6 (3.1)	110.6 (1.4)
Deltamethrin	1.3	4.0	67	-	129.7 (6.0)	122.8 (4.6)	116.0 (3.1)
Desmetryn	2.0	6.0	-10	-	76.9 (3.2)	85.2 (1.4)	91.8 (3.9)
Diazinon	1.3	4.0	-12	-	99.2 (3.0)	88.2 (3.8)	100.1 (4.1)
Dichlorvos	3.0	9.0	-56	-	73.7 (7.4)	76.2 (2.5)	87.2 (9.4)
Diclofopmethyl	1.3	4.0	27	-	98.1 (5.4)	94.0 (1.9)	106.9 (3.3)
Dicofol	0.7	2.0	12	96.3 (3.2)	97.3 (1.8)	94.0 (5.7)	97.9 (1.9)
Dieldrin	2.3	7.0	-32	-	88.2 (1.6)	98.0 (4.4)	98.5 (1.4)
Diflufenican	3.3	10.0	72		97.9 (4.1)	95.8 (2.8)	102.4 (3.2)
Dimethoate	1.7	5.0	-51	-	122.1 (5.9)	120.7 (2.8)	117.6 (9.5)
Endosulfan Ⅰ	1.3	4.0	12	-	83.0 (6.2)	85.6 (2.0)	101.5 (1.7)
Endosulfan Ⅱ	1.0	3.0	-20	-	97.0 (6.2)	96.0 (0.9)	113.8 (0.7)
Endosulfan sulfate	1.3	4.0	-35	-	117.5 (7.3)	106.3 (3.2)	110.7 (3.3)
Endrin	3.3	10.0	-3	-	70.1 (6.9)	73.9 (1.5)	74.0 (3.7)
Ethion	1.3	4.0	35	-	106.4 (8.7)	108.2 (2.4)	122.8 (3.3)
Etofenprox	1.3	4.0	-29	-	88.6 (8.6)	91.3 (1.5)	102.2 (2.0)
Fenpropathrin	1.3	4.0	55	102.9 (6.7)	95.4 (5.9)	96.0 (2.0)	106.1 (2.9)
Fenthion	1.3	4.0	-8	101.7 (7.2)	99.6 (5.2)	102.8 (8.3)	125.4 (4.1)
Fenvalerate	0.7	2.0	86	101.6 (6.0)	93.6 (11.0)	97.5 (2.2)	109.7 (1.1)
Fipronil	1.7	5.0	4	-	81.4 (12.0)	77.9 (6.4)	91.9 (4.7)
Flucythrinate	2.0	6.0	94	-	93.8 (5.4)	101.4 (5.0)	110.3 (1.7)
Fonofos	1.0	3.0	-13	-	124.5 (6.1)	114.9 (2.4)	97.1 (4.7)
Hexachlorobenzene	2.0	6.0	-31	-	69.4 (9.9)	79.8 (2.4)	89.7 (3.1)
Isocarbophos	1.7	5.0	-58	-	105.0 (13.0)	72.7 (4.3)	96.9 (2.1)
Malathion	2.0	6.0	-22	-	119.3 (11.0)	118.5 (6.7)	126.0 (5.6)
Methamidophos	2.7	8.0	95	-	79.6 (8.8)	72.7 (3.7)	77.3 (8.1)
Metolachlor	3.3	10.0	41	-	105.3 (8.7)	108.4 (1.4)	108.5 (2.0)
Myclobutanil	1.3	4.0	21	-	99.2 (10.0)	96.0 (3.9)	111.2 (2.5)
o, p′-Dichlorodiphenyltrichloroethane	1.7	5.0	19	-	80.0 (6.5)	82.4 (1.3)	86.1 (1.5)
Oxadiazon	0.7	2.0	44	124.6 (6.70)	108.3 (6.1)	107.8 (2.2)	114.4 (5.9)
Parathion	1.7	5.0	15	-	102.3 (13.0)	108.2 (3.3)	125.4 (3.1)
Parathion methyl	1.3	4.0	-43	-	125.6 (10.0)	123.8 (4.1)	124.8 (3.2)
Pentachloronitrobenzene	2.3	7.0	-14	-	92.0 (9.3)	93.4 (4.7)	106.9 (2.7)
Permethrin	1.0	3.0	67	-	92.8 (7.2)	95.1 (3.0)	102.1 (2.3)
Phorate	1.7	5.0	-8	-	71.6 (10.0)	79.0(6.6)	89.4 (4.2)
Phosemet	2.0	6.0	-56	-	106.7 (4.7)	109.4 (5.2)	95.7 (1.6)
Piperophos	1.3	4.0	29	-	96.0 (8.5)	97.8 (2.8)	107.8 (2.0)
p, p′-Dichlorodiphenyldichloroethane	1.3	4.0	26	-	80.5 (10.0)	80.2 (2.1)	88.2 (2.1)
p, p′-Dichlorodiphenyldichloroethylene	1.3	4.0	0	-	92.0 (9.0)	85.1 (4.1)	88.1 (4.8)
p, p′-Dichlorodiphenyltrichloroethane	1.3	4.0	10	-	79.5 (8.0)	80.6 (3.6)	80.2 (2.9)
Procymidone	0.7	2.0	11	116.3 (6.5)	102.7 (12.0)	102.2 (2.5)	113.4 (4.5)
Profenofos	1.3	4.0	6	-	103.1 (10.0)	107.3 (3.3)	123.3 (1.4)
Prometryn	1.3	4.0	12	-	94.8 (8.4)	91.2 (5.8)	91.6 (1.7)
Simetryn	1.0	3.0	-42	-	91.1 (4.1)	83.7 (2.4)	80.3 (3.6)
Tebuconazole	3.3	10.0	31	-	110.7 (13.0)	103.1 (3.8)	91.4 (2.0)
Terbufos	2.7	8.0	-11	-	76.7 (8.3)	82.7 (4.0)	96.3 (3.1)
Triadimefon	2.0	6.0	5	-	97.6 (4.2)	96.0 (2.8)	107.3 (3.3)
Triadimenol	0.7	2.0	13	127.3 (13.9)	126.6 (4.1)	114.6 (3.5)	108.4 (4.8)
Triazophos	1.3	4.0	19	-	117.9 (8.9)	115.8 (4.8)	122.2 (1.5)
Trifluralin	1.3	4.0	-9	-	95.3 (7.9)	93.8 (2.9)	105.4 (5.8)
α-Hexachlorocyclohexane	3.0	9.0	-28	-	93.6 (7.2)	93.9 (9.0)	110.8 (2.6)
β-Hexachlorocyclohexane	2.0	6.0	-20	-	96.0 (6.9)	92.0(5.2)	108.0 (2.6)
γ-Hexachlorocyclohexane	3.0	9.0	32	-	73.9 (6.0)	84.0 (5.1)	84.4 (4.3)
δ-Hexachlorocyclohexane	2.0	6.0	-63	-	94.6 (7.9)	97.0 (1.9)	96.4 (2.9)

Analyte	MDL/(μg/kg)	LOQ/(μg/kg)	ME/%	Recovery/% (RSD/%)
Analyte	MDL/(μg/kg)	LOQ/(μg/kg)	ME/%	2.0 μg/kg	5.0 μg/kg	10.0 μg/kg	100.0 μg/kg
-: pesticides were not spiked at this level.
Alachlor	1.0	3.0	-22	-	100.4 (5.1)	94.9 (5.7)	104.1 (3.0)
Aldrin	1.7	5.0	-23	-	82.6 (7.2)	88.8 (4.2)	89.9 (4.4)
Atrazine	2.0	6.0	-25	-	106.5 (7.0)	92.8 (5.5)	92.0 (2.4)
Bifenthrin	1.7	5.0	33	-	100.4 (3.6)	95.6 (3.4)	103.3 (2.8)
Chlorpyrifos	2.0	6.0	-5	-	108.1 (5.8)	109.8 (4.8)	118.9 (5.3)
cis-Chlordane	1.3	4.0	-10	-	88.5 (4.8)	91.3 (3.9)	95.5 (9.2)
Clomazone	1.7	5.0	-16	-	84.3 (2.3)	73.2 (3.4)	74.4 (2.0)
Coumaphos	3.3	10.0	15	-	117.5 (7.4)	123.7 (4.8)	125.0 (3.1)
Cyfluthrin	0.7	2.0	20	104.9 (10.4)	93.7 (8.9)	94.8 (3.0)	101.9 (2.6)
Cyhalothrin	0.7	2.0	80	110.1 (16.0)	121.1 (7.2)	109.3 (6.6)	114.6 (6.1)
Cypermethrin	0.7	2.0	55	94.6 (2.9)	94.7 (4.2)	105.6 (3.1)	110.6 (1.4)
Deltamethrin	1.3	4.0	67	-	129.7 (6.0)	122.8 (4.6)	116.0 (3.1)
Desmetryn	2.0	6.0	-10	-	76.9 (3.2)	85.2 (1.4)	91.8 (3.9)
Diazinon	1.3	4.0	-12	-	99.2 (3.0)	88.2 (3.8)	100.1 (4.1)
Dichlorvos	3.0	9.0	-56	-	73.7 (7.4)	76.2 (2.5)	87.2 (9.4)
Diclofopmethyl	1.3	4.0	27	-	98.1 (5.4)	94.0 (1.9)	106.9 (3.3)
Dicofol	0.7	2.0	12	96.3 (3.2)	97.3 (1.8)	94.0 (5.7)	97.9 (1.9)
Dieldrin	2.3	7.0	-32	-	88.2 (1.6)	98.0 (4.4)	98.5 (1.4)
Diflufenican	3.3	10.0	72		97.9 (4.1)	95.8 (2.8)	102.4 (3.2)
Dimethoate	1.7	5.0	-51	-	122.1 (5.9)	120.7 (2.8)	117.6 (9.5)
Endosulfan Ⅰ	1.3	4.0	12	-	83.0 (6.2)	85.6 (2.0)	101.5 (1.7)
Endosulfan Ⅱ	1.0	3.0	-20	-	97.0 (6.2)	96.0 (0.9)	113.8 (0.7)
Endosulfan sulfate	1.3	4.0	-35	-	117.5 (7.3)	106.3 (3.2)	110.7 (3.3)
Endrin	3.3	10.0	-3	-	70.1 (6.9)	73.9 (1.5)	74.0 (3.7)
Ethion	1.3	4.0	35	-	106.4 (8.7)	108.2 (2.4)	122.8 (3.3)
Etofenprox	1.3	4.0	-29	-	88.6 (8.6)	91.3 (1.5)	102.2 (2.0)
Fenpropathrin	1.3	4.0	55	102.9 (6.7)	95.4 (5.9)	96.0 (2.0)	106.1 (2.9)
Fenthion	1.3	4.0	-8	101.7 (7.2)	99.6 (5.2)	102.8 (8.3)	125.4 (4.1)
Fenvalerate	0.7	2.0	86	101.6 (6.0)	93.6 (11.0)	97.5 (2.2)	109.7 (1.1)
Fipronil	1.7	5.0	4	-	81.4 (12.0)	77.9 (6.4)	91.9 (4.7)
Flucythrinate	2.0	6.0	94	-	93.8 (5.4)	101.4 (5.0)	110.3 (1.7)
Fonofos	1.0	3.0	-13	-	124.5 (6.1)	114.9 (2.4)	97.1 (4.7)
Hexachlorobenzene	2.0	6.0	-31	-	69.4 (9.9)	79.8 (2.4)	89.7 (3.1)
Isocarbophos	1.7	5.0	-58	-	105.0 (13.0)	72.7 (4.3)	96.9 (2.1)
Malathion	2.0	6.0	-22	-	119.3 (11.0)	118.5 (6.7)	126.0 (5.6)
Methamidophos	2.7	8.0	95	-	79.6 (8.8)	72.7 (3.7)	77.3 (8.1)
Metolachlor	3.3	10.0	41	-	105.3 (8.7)	108.4 (1.4)	108.5 (2.0)
Myclobutanil	1.3	4.0	21	-	99.2 (10.0)	96.0 (3.9)	111.2 (2.5)
o, p′-Dichlorodiphenyltrichloroethane	1.7	5.0	19	-	80.0 (6.5)	82.4 (1.3)	86.1 (1.5)
Oxadiazon	0.7	2.0	44	124.6 (6.70)	108.3 (6.1)	107.8 (2.2)	114.4 (5.9)
Parathion	1.7	5.0	15	-	102.3 (13.0)	108.2 (3.3)	125.4 (3.1)
Parathion methyl	1.3	4.0	-43	-	125.6 (10.0)	123.8 (4.1)	124.8 (3.2)
Pentachloronitrobenzene	2.3	7.0	-14	-	92.0 (9.3)	93.4 (4.7)	106.9 (2.7)
Permethrin	1.0	3.0	67	-	92.8 (7.2)	95.1 (3.0)	102.1 (2.3)
Phorate	1.7	5.0	-8	-	71.6 (10.0)	79.0(6.6)	89.4 (4.2)
Phosemet	2.0	6.0	-56	-	106.7 (4.7)	109.4 (5.2)	95.7 (1.6)
Piperophos	1.3	4.0	29	-	96.0 (8.5)	97.8 (2.8)	107.8 (2.0)
p, p′-Dichlorodiphenyldichloroethane	1.3	4.0	26	-	80.5 (10.0)	80.2 (2.1)	88.2 (2.1)
p, p′-Dichlorodiphenyldichloroethylene	1.3	4.0	0	-	92.0 (9.0)	85.1 (4.1)	88.1 (4.8)
p, p′-Dichlorodiphenyltrichloroethane	1.3	4.0	10	-	79.5 (8.0)	80.6 (3.6)	80.2 (2.9)
Procymidone	0.7	2.0	11	116.3 (6.5)	102.7 (12.0)	102.2 (2.5)	113.4 (4.5)
Profenofos	1.3	4.0	6	-	103.1 (10.0)	107.3 (3.3)	123.3 (1.4)
Prometryn	1.3	4.0	12	-	94.8 (8.4)	91.2 (5.8)	91.6 (1.7)
Simetryn	1.0	3.0	-42	-	91.1 (4.1)	83.7 (2.4)	80.3 (3.6)
Tebuconazole	3.3	10.0	31	-	110.7 (13.0)	103.1 (3.8)	91.4 (2.0)
Terbufos	2.7	8.0	-11	-	76.7 (8.3)	82.7 (4.0)	96.3 (3.1)
Triadimefon	2.0	6.0	5	-	97.6 (4.2)	96.0 (2.8)	107.3 (3.3)
Triadimenol	0.7	2.0	13	127.3 (13.9)	126.6 (4.1)	114.6 (3.5)	108.4 (4.8)
Triazophos	1.3	4.0	19	-	117.9 (8.9)	115.8 (4.8)	122.2 (1.5)
Trifluralin	1.3	4.0	-9	-	95.3 (7.9)	93.8 (2.9)	105.4 (5.8)
α-Hexachlorocyclohexane	3.0	9.0	-28	-	93.6 (7.2)	93.9 (9.0)	110.8 (2.6)
β-Hexachlorocyclohexane	2.0	6.0	-20	-	96.0 (6.9)	92.0(5.2)	108.0 (2.6)
γ-Hexachlorocyclohexane	3.0	9.0	32	-	73.9 (6.0)	84.0 (5.1)	84.4 (4.3)
δ-Hexachlorocyclohexane	2.0	6.0	-63	-	94.6 (7.9)	97.0 (1.9)	96.4 (2.9)

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