QuEChERS-气相色谱-串联质谱法测定中药材水蛭中73种农药残留

郑坤明

doi:10.16801/j.issn.1008-7303.2021.0182

QuEChERS-气相色谱-串联质谱法测定中药材水蛭中73种农药残留

doi: 10.16801/j.issn.1008-7303.2021.0182

郑坤明^{1, 2, ,}

1.
福建中检华日食品安全检测有限公司，福州 350028
2.
贵州大学精细化工研究开发中心，绿色农药与农业生物工程国家重点实验室培育基地和教育部重点实验室，贵阳 550025

基金项目: 国家自然科学基金(21667007).

详细信息

通讯作者:
郑坤明，18198639783@163.com

中图分类号: O657.263；TQ450.2
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- 被引次数: 0
出版历程
- 收稿日期: 2021-08-30
- 录用日期: 2022-01-05
- 网络出版日期: 2022-04-07
- 刊出日期: 2022-06-10

Determination of 73 pesticides in traditional Chinese medicine Hirudo by QuEChERS-gas chromatography-tandem mass spectrometry

ZHENG Kunming^{1, 2
, ,}

1.
Fujian CCIC-Fairreach Food Safety Testing Co., Ltd, Fuzhou 350028, China
2.
Research and Development Center for Fine Chemicals, State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang 550025, China

Funds: Natural Science Foundation of China(21667007).

摘要

摘要: 建立了中药材水蛭中73种农药的QuEChERS-气相色谱-串联质谱(GC-MS/MS)检测方法。样品用水浸泡并经V(乙酸) : V(乙腈) = 1 : 99和1.5 g乙酸钠溶液作为缓冲体系提取，采用优化的净化剂150 mg乙二胺-N-丙基甲硅烷(PSA)和150 mg十八烷基键合硅胶(C₁₈)组合净化，经HP-5 MS色谱柱分离，在动态多反应监测模式下测定。结果表明：在优化的条件下，10.0~500 μg/L范围内，73种农药在水蛭中的峰面积与其质量浓度间呈良好的线性关系(r > 0.99)。在0.02、0.04和0.2 mg/kg 3个添加水平下，73种农药在水蛭中的回收率为71%~117%，相对标准偏差(RSD)(n = 6)为1.1%~12% (n = 6)，定量限(LOQ)为0.02 mg/kg，检出限为0.001~0.008 mg/kg。本方法简捷、灵敏、稳定，可以满足实际检测需求。
- QuEChERS /
- 气相色谱-串联质谱 /
- 中药材 /
- 水蛭 /
- 农药多残留
Abstract: An analytical method for the simultaneous determination of 73 pesticides in Hirudo using gas chromatography-tandem mass spectrometry(GC-MS/MS) and QuEChERS procedure was developed. After being soaked in water, the samples were extracted with acidic acetonitrile and cleaned up by a mixture of sorbents (150 mg PSA and 150 mg C₁₈). In order to obtain the optimum recovery rate of pesticide analysis, the amounts of the adsorbents were investigated. The analytes were separated by a HP-5 MS column connected to an electron impact ion source(EI) with dynamic multi-reaction monitoring MS mode. Under the optimized conditions, the results showed that the 73 pesticides had good linearity within the range of 10.0-500 μg/L, with correlation coefficients(r) higher than 0.99. The average recoveries ranged from 71%-117%, and the relative standard deviation(RSD) was 1.1%-12% (n=6) at three spiking levels (0.02, 0.04 and 0.2 mg/kg). The LOQs were 0.02 mg/kg and LODs were 0.001-0.008 mg/kg. The method is simple, sensitive, reliable, and can meet the requirements of practical detection for pesticides.
- QuEChERS /
- gas chromatography-tandem mass spectrometry(GC-MS/MS) /
- traditional Chinese medicine /
- Hirudo /
- pesticide multi-residues

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图 1 73种农药的总离子流图 (0.05 mg/L)

Figure 1. Total ion chromatogram of 73 pesticides (0.05 mg/L)

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图 2 不同吸附剂组成对提取回收率(70%~110%)的影响

Figure 2. Recoveries (70%-110%) of pesticides using different amounts of sorbents in the purification process

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图 3 3种复溶溶剂对水蛭空白样品的全扫描总离子流色谱图

a：丙酮和正己烷 (V/V, 1/1)(Acetone/N-hexane, V/V, 1/1)；b：乙酸乙酯 (Ethyl acetate)；c：丙酮 (Acetone)

Figure 3. The full scan total ion current chromatograms of the blank Hirudo sample in three different solvents

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表 1 73种农药质谱参数

Table 1. Mass spectrum acquisition parameters of 73 pesticides

编号 No.	农药 Pesticide	保留时间Retention time/min	离子对Ion pair, m/z	碰撞能量Collision energy/eV	编号 No.	农药 Pesticide	保留时间Retention time/min	离子对Ion pair, m/z	碰撞能量Collision energy/eV
1	敌敌畏 dichlorvos	6.14	109>79^* 184.9>93	5 10	40	多效唑 paclobutrazol	12.38	236>125.1^* 236>167	10 10
2	甲胺磷 methamidophos	6.76	141>95^* 141>79	5 15	41	腐霉利 procymidone	12.26	96>67.1^* 96>53.1	10 15
3	乙酰甲胺磷 acephate	8.43	136>94^* 136>42	10 5	42	己唑醇 hexaconazole	13.16	231>175^* 256>82.1	10 10
4	异丙威 isoprocarb	8.63	121>77.1^* 136>121.1	20 10	43	甲拌磷砜 phorate sulfone	12.09	153>97^* 124.9>96.9	10 5
5	α-六六六 α-HCH	9.83	218.9>183^* 216.9>181	5 42	44	甲拌磷亚砜 Phorate sulfoxide	12.07	96.9>64.9^* 199>142.9	20 10
6	二嗪磷 diazinon	10.09	137.1>84^* 137.1>54	10 20	45	三唑醇-1 triadimenol-1	12.20	168>70^* 128>65	10 25
7	甲拌磷 phorate	9.60	260>75^* 230.9>128.9	5 25	46	三唑醇-2 triadimenol-2	12.10	168>70^* 128>65	10 25
8	灭线磷 ethoprophos	9.14	157.9>97^* 157.9>114	15 5	47	水胺硫磷 isocarbophos	12.15	135.9>108^* 135.9>69	15 30
9	五氯硝基苯 pentachloronitrobenzene	10.23	295>237^* 236.9>142.9	20 30	48	4,4'-滴滴滴 p,p'-DDD	13.15	234.9>165.1^* 236.9>165.2	20 9
10	氧乐果 omethoate	9.82	155.9>110^* 109.9>79	5 15	49	2,4'-滴滴涕 o,p'-DDT	13.17	235>165.2^* 237>165.2	20 12
11	莠去津 atrazine	10.26	214.9>58.1^* 214.9>200.2	10 5	50	4,4'-滴滴涕 p,p'-DDT	13.30	235>165.2^* 237>165.2	20 40
12	治螟磷 sulfotep	9.48	201.8>145.9^* 237.8>145.9	10 10	51	狄氏剂 dieldrin	12.75	262.9>193^* 277>241	35 5
13	β-六六六 β-HCH	10.78	181>145^* 216.9>181	15 25	52	联苯菊酯 bifenthrin	13.45	181.2>165.2^* 181.2>166.2	25 10
14	γ-六六六 γ-HCH	10.88	181>145^* 216.9>181	15 10	53	硫环磷 phosfolan	13.21	196>140^* 168>140	10 5
15	久效磷 monocrotophos	10.38	127.1>109^* 127.1>95	10 15	54	杀扑磷 methidathion	12.84	144.9>85^* 144.9>58.1	5 15
16	抗蚜威 pirimicarb	11.09	238>166.2^* 166>55.1	10 20	55	倍硫磷砜 fenthion sulfone	13.66	309.9>105^* 135.9>92	10 10
17	乐果 dimethoate	10.76	86.9>46^* 142.9>111	15 10	56	倍硫磷亚砜 fenthion sulfoxide	13.64	278>109^* 278>169	15 15
18	氯唑磷 isazofos	10.75	161>119.1^* 161>146	5 5	57	敌瘟磷 edifenphos	13.66	172.9>109^* 201>109	5 10
19	西玛津 simazine	10.38	201.1>173.1^* 201.1>186.2	5 5	58	高效氯氟氰菊酯-1 lambda-cyhalothrin-1	13.89	197>141^* 197>161	10 17
20	乙草胺 acetochlor	10.89	222.9>132.2^* 222.9>147.2	20 5	59	高效氯氟氰菊酯-2 lambda-cyhalothrin-2	13.99	197>141^* 197>161	10 46
21	乙烯菌核利 vinclozolin	10.89	187>124^* 197.9>145	20 15	60	甲氰菊酯 fenpropathrin	12.89	207.9>181^* 264.9>210	5 10
22	δ-六六六 δ-HCH	11.20	217>181.1^* 181.1>145.1	5 25	61	三唑磷 triazophos	13.74	161.2>134.2^* 161.2>106.1	5 10
23	艾氏剂 aldrin	11.30	262.9>192.9^* 254.9>220	35 20	62	乙螨唑 etoxazole	13.80	141>113^* 141>63.1	15 30
24	毒死蜱 chlorpyrifos	11.59	196.9>169^* 198.9>171	15 15	63	异菌脲 iprodione	13.87	187>124^* 243.9>187	25 5
25	对硫磷 parathion	11.74	290.9>109^* 138.9>109	10 5	64	哒螨灵 pyridaben	15.09	147.2>117.1^* 147.2>132.2	20 10
26	二甲戊灵 pendimethalin	11.92	251.8>162.2^* 251.8>161.1	10 15	65	伏杀硫磷 phosalone	14.54	182>111^* 182>102.1	15 15
27	甲基毒死蜱 chlorpyrifos methyl	11.21	285.9>92.9^* 287.9>92.9	20 20	66	氟胺氰菊酯 fluvalinate	16.03	250>55^* 250>200	20 20
28	甲基对硫磷 parathion methyl	11.43	262.9>109^* 232.9>109	10 10	67	氟氯氰菊酯 cyfluthrin	15.26	226>206^* 198.9>170.1	15 6
29	甲基嘧啶磷 pirimiphos methyl	11.38	290>125^* 232.9>151	20 5	68	氟氰戊菊酯-1 flucythrinate-1	15.75	156.9>107.1^* 198.9>157	15 10
30	甲基异柳磷 isofenphos methyl	11.95	199>121^* 241.1>199.1	10 10	69	氟氰戊菊酯-2 flucythrinate-2	15.77	156.9>107.1^* 198.9>157	15 10
31	马拉硫磷 malathion	11.63	126.9>99^* 172.9>99	5 15	70	腈苯唑 fenbuconazole	16.19	128.9>102.1^* 197.9>129	15 5
32	三氯杀螨醇 dicofol	11.91	139>111^* 250.9>138.9	15 15	71	氯菊酯 permethrin	14.94	183.1>168.1^* 183.1>153	10 24
33	三唑酮 triadimefon	11.58	208>181.1^* 208>111	5 20	72	氯氰菊酯 cypermethrin	15.26	163>91^* 163>127	10 15
34	杀螟硫磷 fenitrothion	11.70	277>260^* 277>109	5 20	73	亚胺硫磷 phosmet	14.65	160>77.1^* 160>133.1	20 10
35	莠灭净 ametryn	11.42	227>58.1^* 227>170.1	10 10	74	苯醚甲环唑 difenoconazole	18.18	322.8>264.8^* 264.9>202	15 20
36	4,4'-滴滴伊 p,p'-DDE	12.62	246.1>176.2^* 315.8>246	30 9	75	氰戊菊酯-1 fenvalerate-1	16.64	167>125.1^* 224.9>119	5 21
37	倍硫磷 fenthion	11.96	278>109^* 278>169	15 15	76	氰戊菊酯-2 fenvalerate-2	16.88	167>125.1^* 224.9>119	5 15
38	丙溴磷 profenofos	12.72	207.9>63^* 338.8>268.7	30 15	77	溴氰菊酯 deltamethrin	17.92	252.9>93^* 250.7>172	15 5
39	丁草胺 butachlor	12.09	188.1>160.2^* 236.9>160.2	10 5
注：^：定量离子对；表中−1、−2 表示目标物的同分异构体。Note: ^: Quantitative ion pair; −1, −2 means isomers of compounds.

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表 2 73种农药在水蛭中的检出限、平均回收率及相对标准偏差

Table 2. LOD, average recoveries and relative standard deviations(RSD) of 73 pesticides in Hirudo

编号 No.	农药 Pesticide	添加水平 Spiked level						检出限 LOD/(mg/kg)	基质效应 M_e/%
		0.02 mg/kg		0.04 mg/kg		0.2 mg/kg
		回收率 Recovery/%	RSD/%	回收率 Recovery/%	RSD/%	回收率 Recovery/%	RSD/%
1	敌敌畏 dichlorvos	78	6.8	77	2.3	71	2.8	0.004	10.2
2	甲胺磷 methamidophos	88	5.9	95	2.7	83	2.0	0.003	16.3
3	乙酰甲胺磷 acephate	99	6.0	102	1.7	84	1.9	0.001	31.9
4	异丙威 isoprocarb	85	9.6	99	3.5	85	6.0	0.003	11.4
5	α-六六六 α-HCH	84	10	105	2.8	88	1.9	0.001	5.1
6	二嗪磷 diazinon	76	5.4	78	5.3	89	2.4	0.001	12.0
7	甲拌磷 phorate	88	9.2	104	3.2	89	2.1	0.001	17.1
8	灭线磷 ethoprophos	109	6.0	111	2.5	91	1.8	0.001	7.6
9	五氯硝基苯 pentachloronitrobenzene	86	5.0	91	1.9	95	2.1	0.002	−8.5
10	氧乐果 omethoate	83	5.1	97	2.1	94	2.7	0.001	20.3
11	莠去津 atrazine	91	4.3	96	2.7	93	1.6	0.002	3.1
12	治螟磷 sulfotep	91	3.3	96	2.6	95	1.7	0.003	5.7
13	β-六六六 β-HCH	89	3.5	98	2.4	97	1.7	0.002	4.8
14	γ-六六六 γ-HCH	90	6.1	93	4.3	95	2.7	0.002	4.5
15	久效磷 monocrotophos	100	6.5	101	3.4	105	4.0	0.003	14.0
16	抗蚜威 pirimicarb	92	5.2	101	2.7	95	2.5	0.001	6.4
17	乐果 dimethoate	93	5.9	93	3.8	93	2.3	0.002	12.3
18	氯唑磷 isazofos	96	6.5	104	3.5	95	2.0	0.005	10.5
19	西玛津 simazine	90	5.2	101	3.7	97	2.4	0.008	11.1
20	乙草胺 acetochlor	96	4.8	101	3.6	104	2.2	0.001	5.0
21	乙烯菌核利 vinclozolin	98	6.3	101	3.2	101	2.2	0.002	4.6
22	δ-六六六 δ-HCH	96	5.4	100	3.8	101	2.0	0.007	3.1
23	艾氏剂 aldrin	97	5.5	101	3.4	103	2.5	0.004	−0.5
24	毒死蜱 chlorpyrifos	97	6.6	104	3.1	101	1.8	0.005	0.7
25	对硫磷 parathion	87	5.4	104	3.3	103	1.9	0.003	22.8
26	二甲戊灵 pendimethalin	87	7.0	105	3.3	101	3.0	0.002	19.0
27	甲基毒死蜱 chlorpyrifos methyl	96	5.5	105	2.8	101	1.7	0.002	2.0
28	甲基对硫磷 parathion methyl	101	5.8	106	3.7	106	2.0	0.004	12.1
29	甲基嘧啶磷 pirimiphos methyl	91	8.1	95	5.1	105	1.3	0.001	4.5
30	甲基异柳磷 isofenphos methyl	89	3.6	102	3.1	102	1.3	0.003	5.1
31	马拉硫磷 malathion	96	4.2	108	4.0	107	2.8	0.007	16.0
32	三氯杀螨醇 dicofol	79	5.8	109	4.0	110	2.4	0.004	−2.5
33	三唑酮 triadimefon	98	7.9	98	4.5	112	1.3	0.003	4.6
34	杀螟硫磷 fenitrothion	98	5.6	103	4.1	107	2.4	0.004	25.7
35	莠灭净 ametryn	100	5.8	105	2.7	89	2.7	0.003	−1.4
36	4,4′-滴滴伊 p,p′-DDE	101	5.0	100	2.4	91	3.4	0.002	2.5
37	倍硫磷 fenthion	91	4.9	97	2.6	88	3.4	0.002	−27.6
38	丙溴磷 profenofos	102	5.8	103	2.6	93	3.0	0.003	16.1
39	丁草胺 butachlor	96	5.4	100	2.5	91	3.1	0.006	16.6
40	多效唑 paclobutrazol	96	5.6	102	3.4	92	3.3	0.001	16.1
41	腐霉利 procymidone	101	5.2	105	2.5	93	2.9	0.005	0.2
42	己唑醇 hexaconazole	96	6.7	103	4.0	90	3.2	0.005	−3.9
43	甲拌磷砜 phoratesulfone	96	5.9	102	2.9	91	2.7	0.008	16.0
44	甲拌磷亚砜 phoratesulfoxide	98	8.9	110	4.6	96	4.8	0.007	14.5
45	三唑醇-1 triadimenol-1	99	9.8	117	4.1	97	5.0	0.004	15.8
46	三唑醇-2 triadimenol-2	102	7.4	106	4.3	92	3.9	0.007	11.2
47	水胺硫磷 isocarbophos	101	5.0	104	3.2	92	2.5	0.008	22.4
48	4,4′-滴滴滴 p,p′-DDD	109	8.9	113	4.6	99	3.5	0.001	19.2
49	2,4′-滴滴涕 o,p′-DDT	104	8.0	107	4.1	89	3.7	0.002	1.8
50	4,4′-滴滴涕 p,p′-DDT	105	7.9	109	3.8	90	2.9	0.002	18.3
51	狄氏剂 dieldrin	107	9.6	110	6.1	91	4.1	0.002	−4.2
52	联苯菊酯 bifenthrin	108	8.0	109	4.8	91	3.7	0.002	14.7
53	硫环磷 phosfolan	100	8.6	113	5.5	94	3.5	0.002	38.4
54	杀扑磷 methidathion	113	7.5	114	4.4	94	5.2	0.005	16.3
55	倍硫磷砜 fenthion sulfone	99	9.3	114	5.0	94	5.1	0.001	−31.7
56	倍硫磷亚砜 fenthion sulfoxide	111	9.4	97	5.9	93	5.8	0.003	−39.8
57	敌瘟磷 edifenphos	99	9.5	105	6.4	89	6.9	0.003	19.3
58	高效氯氟氰菊酯-1 lambda-cyhalothrin-1	98	9.9	96	6.5	89	6.2	0.002	30.9
59	高效氯氟氰菊酯-2 lambda-cyhalothrin-2	92	8.1	100	5.5	88	7.6	0.002	28.4
60	甲氰菊酯 fenpropathrin	91	12	96	7.5	91	2.1	0.004	11.2
61	三唑磷 triazophos	92	9.8	98	6.8	87	3.9	0.007	17.1
62	乙螨唑 etoxazole	93	8.2	97	7.2	89	7.2	0.006	14.2
63	异菌脲 iprodione	98	2.6	99	9.2	90	3.6	0.006	17.3
64	哒螨灵 pyridaben	102	3.8	102	11	90	3.7	0.002	30.8
65	伏杀硫磷 phosalone	94	3.4	94	4.8	89	3.3	0.004	28.2
66	氟胺氰菊酯 fluvalinate	95	9.5	100	8.3	91	3.0	0.006	48.7
67	氟氯氰菊酯 cyfluthrin	94	2.0	107	9.3	90	2.8	0.006	18.1
68	氟氰戊菊酯-1 flucythrinate-1	96	2.7	98	10	91	3.7	0.001	31.8
69	氟氰戊菊酯-2 flucythrinate-2	99	1.4	93	1.9	88	1.1	0.002	32.2
70	腈苯唑 fenbuconazole	103	2.7	98	2.1	93	1.7	0.003	30.0
71	氯菊酯 permethrin	101	2.5	100	2.7	91	2.3	0.008	18.1
72	氯氰菊酯 cypermethrin	96	5.6	99	2.6	89	2.5	0.002	18.1
73	亚胺硫磷 phosmet	102	2.7	109	2.4	93	1.1	0.007	30.2
74	苯醚甲环唑 difenoconazole	93	3.7	103	4.3	89	1.2	0.006	51.6
75	氰戊菊酯-1 fenvalerate-1	95	2.7	102	3.4	91	2.1	0.002	99.0
76	氰戊菊酯-2 fenvalerate-2	115	2.2	114	2.7	95	2.7	0.007	102.9
77	溴氰菊酯 deltamethrin	98	3.2	109	3.8	92	1.6	0.002	15.2
注：表中−1、−2 表示化合物的同分异构体。Note: −1，−2 means isomers of compounds.

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