液相色谱-串联质谱法测定中药浙八味中30种有机磷农药残留

虞淼; 姚芳; 张寒; 王娇; 齐沛沛; 王新全

doi:10.16801/j.issn.1008-7303.2021.0184

液相色谱-串联质谱法测定中药浙八味中30种有机磷农药残留

doi: 10.16801/j.issn.1008-7303.2021.0184

虞淼^1,,
姚芳²,
张寒¹,
王娇³,
齐沛沛³,
王新全^3, ,

1.
浙江省植保检疫与农药管理总站，杭州 310004
2.
绍兴市上虞区质检计量测试所，浙江绍兴 312300
3.
浙江省农业科学院农产品质量安全与营养研究所，农产品质量安全危害因子与风险防控国家重点实验室，杭州 310021

基金项目: 浙江省重点研发计划 (2020C02023).

详细信息

作者简介:
虞淼：yumiao2020@sina.com

通讯作者:
wangxinquan212@163.com

中图分类号: TQ450.263;O657.63;X592
计量
- 文章访问数: 114
- HTML全文浏览量: 38
- 被引次数: 0
出版历程
- 收稿日期: 2021-09-30
- 录用日期: 2021-11-12
- 网络出版日期: 2021-12-23

Determination of 30 organophosphorus pesticides in eight famous herbals in Zhejiang(Zhebawei) by liquid chromatography-tandem mass spectrometry

1.
Zhejiang Provincial Plant Protection Quarantine and Pesticide Management Institute, Hangzhou 310004, China
2.
Shaoxing Shangyu District Quality Inspection and Measurement Testing Institute 312300, Shaoxing Zhejiang, China
3.
Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences; State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products, Hangzhou 310021, China

Funds: the Key R&D Program of Zhejiang Province (2020C02023)

摘要

摘要: 建立了浙八味中30种有机磷 (OPPs)农药残留分析的检测方法。针对中草药基质复杂、净化难度大的问题，采用纳米材料二氧化锆 (nano-ZrO₂)和介孔分子筛 (MCM-41)作为分散固相萃取 (d-SPE)净化吸附剂，以延胡索为代表基质对净化过程进行系统的优化，并采用液相色谱-串联质谱 (LC-MS/MS)进行分析。结果表明：以30 mg nano-ZrO₂和50 mg MCM-41为净化吸附剂时，延胡索基质中，除苯腈磷、敌百虫 (0.002 ~ 0.25 mg/L)和敌敌畏 (0.005 ~ 0.25 mg/L)外，各农药在0.001 ~ 0.25 mg/L范围内线性关系良好，相关系数 (r)均大于0.99。方法定量限 (LOQ)除敌敌畏 (0.050 mg/kg)外，均为0.010 mg/kg。8种基质在0.05 mg/kg添加水平下，除倍硫磷和敌敌畏外，其余农药平均回收率范围为64 % ~ 125 %，相对标准偏差 (RSDs)在0.05% ~ 11%之间。该方法简单、快速、准确、重现性好，并且在浙八味中有较好的适用性，弥补了浙八味中有机磷农药残留检测技术缺乏的空白。
- 液相色谱-串联质谱：浙八味 /
- /
- 有机磷农药 /
- QuEChERS /
- 农药多残留 /
- 中药材
Abstract: A method for simultaneous determination of 30 organophosphorus pesticides in eight famous herbals in Zhejiang (called Zhebawei) was established. Considering the complexity of Chinese herbal medicine and difficulty in purification, nano-ZrO₂ and mesoporous molecular sieve MCM-41 were selected as dispersive solid phase extraction (d-SPE) cleanup adsorbents. The cleanup process was systematically optimized with Corydalis as the representative matrix, and combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The results showed that using 30 mg nano-ZrO₂ and 50 mg MCM-41 as d-SPE cleanup adsorbents, the linearity for the pesticides was good in the concentration range of 0.001-0.25 mg/L and the correlation coefficient (r) was greater than 0.99, except for cyanofenphos, trichlorphon (0.002-0.25 mg/L) and dichlorvos (0.005-0.25 mg/L). The limit of quantitation (LOQ) was 0.010 mg/kg except for dichlorvos (0.050 mg/kg). Except for fenthion and dichlorvos, the average recoveries of the pesticides in the eight herbal samples ranged from 64 % to 125 % at spiking level of 0.05 mg/kg, and the relative standard deviations (RSDs) ranged from 0.05 % to 11 %. The method is simple, rapid, accurate and reproducible, and has good applicability in the eight herbals in Zhejiang, which makes up for the lack of detection technology of organophosphorus pesticide residues in eight herbals of Zhejiang.
- ultra performance liquid chromatography-tandem mass spectrometry /
- Zhebawei /
- organophosphorus pesticides /
- QuEChERS /
- pesticide multi-residue /
- Chinese herbal medicine

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图 1 延胡索中农药在不同nano-ZrO₂用量条件下的回收率(n=3)

1 ~ 30分别对应于表1序号。

Figure 1. Recoveries of pesticides in Rhizoma Corydalis using different amount of nano-ZrO₂ as sorbents (n=3)

No.1-30 respectively correspond to the No. in Table 1.

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图 2 延胡索样品经不同MCM-41用量和30 mgnano-ZrO₂净化后颜色的变化

Figure 2. The color change of the Rhizoma Corydalis samples after cleaned-up with different amount of MCM-41 and 30 mg nano-ZrO₂

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图 3 不同用量MCM-41对部分农药基质效应 (R_a) 的影响 (nano-ZrO₂的用量为30 mg)

21个农药编号分别对应于表1序号。

Figure 3. The effect of different amount of MCM-41 (with 30 mg nano-ZrO₂) on matrix effects (R_a)

21 numbers correspond to the No. in Table 1, respectively.

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表 1 30种有机磷农药多级反应监测分析参数

Table 1. MRM parameters for residue analysis of 30 OPPs

编号 No.	化合物 Compound	保留时间 Retention time/min	前体离子 Parent ion, m/z	产物离子 Product ion, m/z	Q₁偏差 Q₁ pre-rod/V	碰撞电压 CE/ V	Q₃偏差 Q₃ pre-rod/V
1	倍硫磷 fenthion	4.985	279.2	169.0*；247.0	−30；−30	−17；−12	−18；−18
2	苯腈磷 cyanofenphos	4.753	304.1	77.25*；122.2	−20；−11	−60；−19	−16；−25
3	苯线磷 fenamiphos	4.753	304.1	217.1*；202.0	−15；−15	−22；−36	−23；−21
4	丙硫磷 prothiophos	6.498	344.8	240.9*；275.0	−17；−17	−18；−13	−26；−30
5	丙溴磷 profenofos	5.560	372.9	302.8*；345.0	−18；−18	−19；−12	−30；−24
6	除线磷 dichlofenthion	5.816	315.0	258.8*；286.9	−27；−27	−16；−11	−28；−20
7	哒嗪硫磷 pyridaphenthion	4.494	341.1	189.1*；205.1	−17；−23	−22；−22	−20；−22
8	敌百虫 trichlorfon	3.202	256.9	108.9*；220.8	−29；−29	−17；−10	−19；−23
9	敌敌畏 dichlorvos	3.784	221.0	109.1*；79.1	−23；−23	−16；−27	−11；−30
10	敌瘟磷 edifenphos	4.921	311.0	282.9*；111.0	−24；−24	−13；−21	−30；−21
11	毒死蜱 chlorpyrifos	5.888	351.9	199.9*；96.9	−27；−27	−18；−33	−21；−18
12	二嗪磷 diazinon	5.022	305.0	169.1*；153.1	−30；−30	−19；−20	−18；−16
13	伏杀硫磷 phosalone	5.103	368.0	182.0*；111.0	−30；−30	−14；−39	−19；−20
14	甲拌磷 phorate	5.189	261.0	75.0*；143.0	−29；−29	−10；−18	−30；−15
15	久效磷 monocrotophos	2.749	224.1	127.0*；193.0	−25；−25	−15；−8	−13；−20
16	乙丙硫磷 sulprofos	5.902	322.9	219.0*；139.2	−16；−16	−16；−30	−16；−15
17	硫线磷 cadusafos	5.302	271.1	159.0*；97.0	−30；−30	−14；−37	−29；−18
18	马拉硫磷 malathion	4.442	331.0	127.0*；99.0	−17；−17	−12；−23	−13；−18
19	马拉氧磷 malaoxon	3.765	314.9	98.9*；127.0	−15；−15	−24；−13	−19；−23
20	嘧啶磷 pirimiphos-ethyl	5.693	334.1	198.0*；182.1	−25；−25	−22；−22	−21；−19
21	三唑磷 triazophos	4.527	314.1	162.1*；119.1	−23；−23	−19；−35	−17；−21
22	杀虫畏 tetrachlorvinphos	4.829	364.9	127.0*；203.9	−27；−27	−14；−38	−13；−21
23	杀扑磷 methidathion	4.223	303.0	145.0*；85.1	−21；−21	−8；−22	−15；−30
24	双硫磷 temephos	5.567	467.0	419.0*；341.0	−23；−23	−19；−32	−30；−24
25	特丁硫磷 terbufos	5.645	289.0	103.1*；57.1	−14；−14	−9；−24	−18；−24
26	辛硫磷 phoxim	5.034	299.0	77.1*；129.1	−30；−30	−26；−10	−30；−13
27	亚胺硫磷 phosemet	4.252	318.0	160.0*；77.1	−16；−16	−13；−54	−17；−30
28	氧乐果 omethoate	2.329	214.1	183.0*；155.0	−15；−23	−23；−14	−15；−28
29	乙酰甲胺磷 acephate	2.238	184.2	143.0*；95.0	−20；−20	−8；−23	−15；−16
30	蝇毒磷 coumaphos	4.969	363.0	227.0*；307.1	−18；−18	−26；−18	−23；−21
注：定量离子。Note: quantitative ion.

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表 2 延胡索中30种有机磷的回归方程、相关系数(r)、基质效应、线性范围及检出限

Table 2. Method validation of the linearity, correlation coefficients (r), matrix effects, linear range, and LODs of the 30 OPPs in Rhizoma Corydalis

化合物　　　　 Compound	标准溶液 Standard solution	回归方程 Regression equation	相关系数 r	基质效应 Matrix effects	线性范围/mg/L Linear range	检出限 LOD/mg/L
倍硫磷 fenthion	基质 Matrix	y = 11186.5 x + 64206.7	0.9996	0.27	0.001 ~ 0.25	0.00038
倍硫磷 fenthion	溶剂 Solvent	y = 41100.0 x + 156743	0.9990		0.001 ~ 0.25
苯腈磷 cyanofenphos	基质 Matrix	y = 6712.28 x + 9725.17	0.9992	0.16	0.002 ~ 0.25	0.0016
苯腈磷 cyanofenphos	溶剂 Solvent	y = 41650.4 x + 46306.8	0.9998		0.002 ~ 0.25
苯线磷 fenamiphos	基质 Matrix	y = 85388.9 x + 16795.6	0.9996	0.14	0.001 ~ 0.25	0.00045
苯线磷 fenamiphos	溶剂 Solvent	y = 599509 x + 278328	0.9998		0.001 ~ 0.25
丙硫磷 prothiophos	基质 Matrix	y = 31005.3 x + 56113.3	0.9996	0.50	0.001 ~ 0.25	0.00053
丙硫磷 prothiophos	溶剂 Solvent	y = 62080.8 x + 42838.6	0.9998		0.001 ~ 0.25
丙溴磷 profenofos	基质 Matrix	y = 44979.0 x + 22741.5	0.9998	0.50	0.001 ~ 0.25	0.00051
丙溴磷 profenofos	溶剂 Solvent	y = 90314.6 x + 99936.6	0.9997		0.001 ~ 0.25
除线磷 dichlofenthion	基质 Matrix	y = 17313.0 x + 34036.4	0.9998	0.62	0.001 ~ 0.25	0.00071
除线磷 dichlofenthion	溶剂 Solvent	y = 27940.4 x - 1752.36	0.9998		0.001 ~ 0.25
哒嗪硫磷 pyridaphenthion	基质 Matrix	y = 102202 x + 968791	0.9997	0.31	0.001 ~ 0.25	0.00050
哒嗪硫磷 pyridaphenthion	溶剂 Solvent	y = 334406 x + 305843	0.9996		0.001 ~ 0.25
敌百虫 trichlorphon	基质 Matrix	y = 6983.58 x + 16255.9	0.9998	0.53	0.002 ~ 0.25	0.0014
敌百虫 trichlorphon	溶剂 Solvent	y = 13295.1 x - 36878.2	0.9987		0.002 ~ 0.25
敌敌畏 dichlorvos	基质 Matrix	y = 3750.36 x + 8692.80	0.9997	0.36	0.005 ~ 0.25	0.0026
敌敌畏 dichlorvos	溶剂 Solvent	y = 10361.8 x + 14173.9	0.9996		0.005 ~ 0.25
敌瘟磷 edifenphos	基质 Matrix	y = 750668 x - 43055.8	0.9999	0.24	0.001 ~ 0.25	0.00039
敌瘟磷 edifenphos	溶剂 Solvent	y = 3106700 x - 118601	0.9997		0.001 ~ 0.25
毒死蜱 chlorpyrifos	基质 Matrix	y = 27616.8 x + 209187	0.9998	0.40	0.001 ~ 0.25	0.00067
毒死蜱 chlorpyrifos	溶剂 Solvent	y = 68940.7 x + 22862.0	0.9999		0.001 ~ 0.25
二嗪磷 diazinon	基质 Matrix	y = 87125.4 x + 40800.7	0.9999	0.31	0.001 ~ 0.25	0.00021
二嗪磷 diazinon	溶剂 Solvent	y = 284411 x + 112947	0.9999		0.001 ~ 0.25
伏杀硫磷 phosalone	基质 Matrix	y = 13279.8 x + 1655.59	0.9999	0.12	0.001 ~ 0.25	0.00059
伏杀硫磷 phosalone	溶剂 Solvent	y = 111449 x + 106651	0.9998		0.001 ~ 0.25
甲拌磷 phorate	基质 Matrix	y = 7245.59 x + 2553.84	0.9998	0.16	0.001 ~ 0.25	0.00058
甲拌磷 phorate	溶剂 Solvent	y = 45622.5 x + 26065.4	0.9999		0.001 ~ 0.25
久效磷 monocrotophos	基质 Matrix	y = 9066.93 x + 4349.27	0.9998	0.25	0.001 ~ 0.25	0.0010
久效磷 monocrotophos	溶剂 Solvent	y = 36960.4 x + 24774.2	0.9993		0.001 ~ 0.25
乙丙硫磷 sulprofos	基质 Matrix	y = 17865.6 x + 18199.5	0.9999	0.29	0.001 ~ 0.25	0.00048
乙丙硫磷 sulprofos	溶剂 Solvent	y = 61161.1 x + 19350.2	0.9998		0.001 ~ 0.25
硫线磷 cadusafos	基质 Matrix	y = 213565 x + 63957.6	0.9999	0.40	0.001 ~ 0.25	0.00046
硫线磷 cadusafos	溶剂 Solvent	y = 537674 x - 165154	0.9999		0.001 ~ 0.25
马拉硫磷 malathion	基质 Matrix	y = 25105.2 x + 11069.0	0.9998	0.19	0.001 ~ 0.25	0.00092
马拉硫磷 malathion	溶剂 Solvent	y = 134823 x + 52546.8	0.9999		0.001 ~ 0.25
马拉氧磷 malaoxon	基质 Matrix	y = 257712 x + 64825.1	0.9998	0.30	0.001 ~ 0.25	0.00016
马拉氧磷 malaoxon	溶剂 Solvent	y = 859152 x + 372042	0.9998		0.001 ~ 0.25
嘧啶磷 pirimiphos-ethyl	基质 Matrix	y = 397456 x + 35639.9	0.9999	0.51	0.001 ~ 0.25	0.00014
嘧啶磷 pirimiphos-ethyl	溶剂 Solvent	y = 781657 x - 267204	0.9997		0.001 ~ 0.25
三唑磷 triazophos	基质 Matrix	y = 289410 x + 122747	0.9999	0.31	0.001 ~ 0.25	0.00013
三唑磷 triazophos	溶剂 Solvent	y = 929411 x - 228026	0.9999		0.001 ~ 0.25
杀虫畏 tetrachlorvinphos	基质 Matrix	y = 8073.80 x - 1514.11	0.9999	0.12	0.001 ~ 0.25	0.00094
杀虫畏 tetrachlorvinphos	溶剂 Solvent	y = 67348.3 x + 102981	0.9997		0.001 ~ 0.25
杀扑磷 methidathion	基质 Matrix	y = 13872.9 x + 1968.04	0.9999	0.22	0.001 ~ 0.25	0.00031
杀扑磷 methidathion	溶剂 Solvent	y = 63367.9 x + 54929.0	0.9995		0.001 ~ 0.25
双硫磷 temephos	基质 Matrix	y = 23922.2 x + 67354.1	0.9997	0.63	0.001 ~ 0.25	0.00055
双硫磷 temephos	溶剂 Solvent	y = 38083.5 x + 64683.7	0.9997		0.001 ~ 0.25
特丁硫磷 terbufos	基质 Matrix	y = 15305.8 x + 176447	0.9998	0.43	0.001 ~ 0.25	0.00091
特丁硫磷 terbufos	溶剂 Solvent	y = 35899.8 x + 136459	0.9998		0.001 ~ 0.25
辛硫磷 phoxim	基质 Matrix	y = 21771.8 x + 24226.9	0.9999	0.18	0.001 ~ 0.25	0.00053
辛硫磷 phoxim	溶剂 Solvent	y = 119213 x + 122252	0.9997		0.001 ~ 0.25
亚胺硫磷 phosemet	基质 Matrix	y = 71042.2 x + 46146.5	0.9998	0.24	0.001 ~ 0.25	0.00027
亚胺硫磷 phosemet	溶剂 Solvent	y = 300883 x + 25401.3	0.9999		0.001 ~ 0.25
氧乐果 omethoate	基质 Matrix	y = 46401.9 x + 826062	0.9996	0.81	0.001 ~ 0.25	0.00039
氧乐果 omethoate	溶剂 Solvent	y = 57136.3 x + 62540.0	0.9994		0.001 ~ 0.25
乙酰甲胺磷 acephate	基质 Matrix	y = 55667.2 x + 52404.0	0.9999	0.56	0.001 ~ 0.25	0.00044
乙酰甲胺磷 acephate	溶剂 Solvent	y = 99817.4 x + 161494	0.9990		0.001 ~ 0.25
蝇毒磷 coumaphos	基质 Matrix	y = 66053.1 x + 43518.5	0.9999	0.30	0.001 ~ 0.25	0.00023
蝇毒磷 coumaphos	溶剂 Solvent	y = 218234 x + 467439	0.9996		0.001 ~ 0.25

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表 3 延胡索中30种有机磷在不同添加水平下的回收率及相对标准偏差(n=3)

Table 3. Recoveries and RSDs of the 30 OPPs in Rhizoma Corydalis at different spiking levels (n=3)

化合物　　　　 Compound	0.010 mg/kg		0.050 mg/kg		0.10 mg/kg
化合物　　　　 Compound	回收率 Recovery/%	相对标准偏差 RSD/%	回收率 Recovery/%	相对标准偏差 RSD/%	回收率 Recovery/%	相对标准偏差 RSD/%
倍硫磷 fenthion	99	5.9	108	0.7	105	1.9
苯腈磷 cyanofenphos	100	6.4	107	2.3	97	1.9
苯线磷 fenamiphos	104	2.9	108	1.8	96	2.1
乙丙硫磷 sulprofos	107	12	110	2.2	114	0.8
丙溴磷 profenofos	100	8.6	111	1.5	98	1.7
除线磷 dichlofenthion	107	2.7	109	5.8	99	0.4
哒嗪硫磷 pyridaphenthion	107	1.8	108	6.1	92	5.2
敌百虫 trichlorphon	93	10	101	7.2	96	2.2
敌敌畏 dichlorvos	--	--	103	6.2	94	1.7
敌瘟磷 edifenphos	97	3.1	104	0.9	96	2.1
毒死蜱 chlorpyrifos	97	2.7	108	3.3	94	1.2
二嗪磷 diazinon	107	3.4	108	3.9	95	2.0
伏杀硫磷 phosalone	102	3.7	112	1.1	102	3.1
甲拌磷 phorate	105	4.2	112	2.9	96	2.1
久效磷 monocrotophos	92	12	84	2.7	95	0.8
硫丙磷 bolstar	103	17	108	5.3	99	1.6
硫线磷 cadusafos	101	2.3	116	0.5	97	0.3
马拉硫磷 malathion	96	4.9	117	3.3	97	5.7
马拉氧磷 malaoxon	103	2.8	107	2.9	94	0.7
嘧啶磷 pirimiphos-ethyl	103	1.9	107	2.5	94	0.9
三唑磷 triazophos	102	5.8	113	3.0	100	3.2
杀虫畏 tetrachlorvinphos	97	9.7	114	0.6	93	4.5
杀扑磷 methidathion	100	17	94	11.0	96	13
双硫磷 temephos	107	2.0	114	0.9	98	1.5
特丁硫磷 terbufos	107	1.4	109	0.7	97	2.0
辛硫磷 phoxim	99	3.9	114	3.4	96	4.1
亚胺硫磷 phosemet	102	8.4	117	1.6	97	6.3
氧乐果 omethoate	100	2.0	88	0.5	104	2.0
乙酰甲胺磷 acephate	81	2.7	79	0.7	90	3.2
蝇毒磷 coumaphos	93	2.3	103	1.7	95	0.8
注：--表示未检出。Note: -- indicates not detected.

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表 4 白芍、浙贝母、玄参、郁金、白术、麦冬和杭白菊中30种有机磷农药在添加水平为0.050 mg/kg下的回收率 (n=3)

Table 4. Recoveries of the 30 OPPs in Radix Paeoniae Alba, Bulbus Fritillariae Thunbergii, Radix Scrophulariae, Radix Curcumae, Rhizoma Atractylodis Macrocephalae, Radix Ophiopogonis, and Dendranthema Morifolium samples at spiked concentration of 0.050 mg/kg (n=3)

化合物　　 Compound	白芍 Radix Paeoniae Alba			浙贝母 Bulbus Fritillariae Thunbergii		玄参 Radix Scrophulariae		郁金 Radix Curcumae		白术 Rhizoma Atractylodis Macrocephalae		麦冬 Radix Ophiopogonis		杭白菊 Dendranthema Morifolium
化合物　　 Compound	回收率/ %	RSD/ %		回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %	回收率/ %	RSD/ %
倍硫磷 fenthion	110		4.0	96	7.9	101	0.91	--	--	113	5.2	101	5.3	--	--
苯腈磷 cyanofenphos	104		1.5	96	0.89	96	3.0	103	2.7	96	0.59	102	3.5	108	3.3
苯线磷 fenamiphos	104		2.6	96	2.0	95	2.5	98	3.2	97	0.57	103	1.4	114	3.6
丙硫磷 prothiophos	100		11	105	4.8	110	7.4	105	3.5	106	4.7	119	8.5	92	0.43
丙溴磷 profenofos	117		0.74	104	2.2	112	2.0	108	4.1	106	4.6	111	1.9	102	4.6
除线磷 dichlofenthion	106		2.3	108	9.1	99	7.6	97	4.2	108	7.7	114	3.1	99	4.1
哒嗪硫磷 pyridaphenthion	108		1.9	104	0.89	110	3.6	108	2.4	103	2.4	116	2.3	121	0.31
敌百虫 trichlorphon	99		3.8	98	5.6	104	5.1	104	4.7	95	4.3	113	0.60	112	0.91
敌敌畏 dichlorvos	105		4.3	108	2.1	--	--	--	--	98	4.9	--	--	104	7.5
敌瘟磷 edifenphos	103		0.65	103	2.0	110	1.6	105	2.5	103	1.5	110	2.3	115	3.0
毒死蜱 chlorpyrifos	113		3.0	102	6.9	108	0.94	103	4.8	99	5.6	110	1.8	97	1.6
二嗪磷 diazinon	104		1.7	102	5.3	107	3.6	103	5.1	97	2.9	103	3.2	108	0.81
伏杀硫磷 phosalone	114		4.6	104	1.2	116	4.1	103	0.93	99	5.0	111	1.7	117	0.31
甲拌磷 phorate	116		0.35	120	1.2	114	2.2	107	5.2	114	0.69	118	1.1	105	0.68
久效磷 monocrotophos	80		5.2	80	5.0	86	1.5	84	1.7	81	1.0	89	1.2	90	0.83
乙丙硫磷 sulprofos	112		5.7	102	3.7	107	5.1	97	8.1	102	1.2	112	2.2	98	1.4
硫线磷 cadusafos	111		3.0	106	2.7	114	2.9	109	4.2	104	1.7	116	1.0	119	1.4
马拉硫磷 malathion	104		1.4	103	2.2	101	2.6	106	1.7	91	1.3	120	4.5	108	0.65
马拉氧磷 malaoxon	106		1.6	98	2.3	105	3.5	109	3.4	103	1.1	110	0.85	104	0.26
嘧啶磷 pirimiphos-ethyl	84		4.1	83	8.0	80	3.0	77	4.7	71	4.1	80	3.2	70	7.3
三唑磷 triazophos	109		2.1	101	1.8	110	2.0	110	4.4	102	1.7	117	0.87	118	0.55
杀虫畏 tetrachlorvinphos	107		1.4	105	3.4	105	3.9	100	2.3	106	3.1	114	4.3	106	2.9
杀扑磷 methidathion	107		4.0	94	3.2	106	3.4	100	3.2	105	1.3	116	4.2	106	1.5
双硫磷 temephos	116		2.7	105	3.5	116	1.1	101	3.9	109	7.8	114	5.6	110	2.0
特丁硫磷 terbufos	108		0.34	98	8.2	108	1.3	102	1.0	97	6.1	105	4.3	108	0.67
辛硫磷 phoxim	113		1.4	105	2.7	110	2.0	101	3.5	104	2.9	106	2.0	103	3.3
亚胺硫磷 phosemet	108		4.6	123	1.5	120	1.4	121	5.2	125	3.2	112	3.6	109	0.52
氧乐果 omethoate	65		2.0	70	2.8	66	2.4	69	2.0	65	0.50	70	1.5	68	0.50
乙酰甲胺磷 acephate	69		2.1	66	2.1	66	0.51	70	2.3	65	0.57	71	2.2	70	1.1
蝇毒磷 coumaphos	112		2.7	109	4.3	112	1.5	98	3.7	101	5.9	113	0.52	107	0.049

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表 5 实际样品的残留测定结果

Table 5. The concentrations of pesticide residues in real samples

样品　　 Sample	批次 Batch	检出农药残留量 Pesticide detection/(mg/kg)
样品　　 Sample	批次 Batch	丙溴磷 profenofos	毒死蜱 chlorpyrifos	马拉硫磷 malathion	三唑磷 triazophos	辛硫磷 phoxim
浙贝母 Bulbus Fritillariae Thunbergii	1					0.038
	2					0.021
	3					0.021
麦冬 Radix Ophiopogonis	4		0.027
	5	0.027	0.015
	6		0.049
杭白菊 Dendranthema Morifolium	7	0.019
	8		0.018
	9				0.012
	10	0.017	0.028
	11		0.020	0.26
	12	0.0090	0.044
	13	0.023	0.15
	14	0.016	0.038
	15	0.013	0.16

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