-
摘要:
利用优化的QuEChERS法提取冷冻干燥后土壤样品中的农药残留, 包括24种有机氯类、8种有机磷类农药以及阿特拉津.采用气相色谱-三重四极杆串联质谱建立了同时测定土壤中33种农残的定性定量检测方法, 结果表明: 33种农药残留浓度在5.0~100 μg/L范围内, 线性良好; 方法检出限0.09×10-9~0.52×10-9, 方法定量限0.30×10-9~1.71×10-9, 方法精密度3.7%~17.2%, 回收率51.6%~118.8%.该方法具有简洁快速、回收率高、灵敏度高、抗基质干扰能力强的特点, 适用于土壤中有机氯类、有机磷类农药的痕量分析检测.
Abstract:The QuEChERS method is optimized to extract pesticide residues from frozen-drying soil samples, including 24 organochlorine pesticides (OCPs) and 8 organophosphorus pesticides (OPPs) as well as atrazine. An approach to simultaneous determination of 33 pesticide residues in soil is established by combining with gas chromatography-tandem mass spectrometry (GC-MS/MS). The results show that the concentration of 33 pesticide residues is 5.0-100 μg/L, in good linearity, with method limit of detection (LOD) 0.09×10-9-0.52×10-9, limit of quantitation (LOQ) 0.30×10-9-1.71×10-9, relative standard deviation (RSD) of precision 3.7%-17.2%, and recovery 51.6%-118.8%. The method is simple and rapid, characterized by high recovery and sensitivity, and strong resistance to matrix interference, which is suitable for trace analysis and detection of OCPs and OPPs in soil.
-
Key words:
- soil /
- pesticide residue /
- tandem mass spectrometry /
- QuEChERS /
- chemical analysis
-
-
表 1 33种农药保留时间、离子对、碰撞能量
Table 1. Retention time, ion pairs and collision energy of 33 pesticides
序号 目标物 保留时间/min 定量离子对/(m/z) 碰撞能量/eV 定性离子/(m/z) 碰撞能量/eV 1 敌敌畏 5.813 109.0 - 79.0 5 184.0 - 93.0 10 2 内吸磷-S 10.691 88.0 - 60.0 5 60.0 - 45.0 15 3 内吸磷-0 10.696 88.0 - 60.0 5 60.0 - 45.0 15 4 甲拌磷 11.732 121.0 - 65.0 10 121.0 - 47.0 30 5 a-六六六 11.861 180.8 - 145.0 15 218.7 - 182.9 5 6 六氯苯 12.054 283.8 - 213.9 30 281.8 - 211.9 30 7 阿特拉津 12.385 214.9 - 58.1 10 200.0 - 94.0 20 8 β-六六六 12.516 181.0 - 145.0 15 183.0 - 147.0 15 9 y-六六六 12.637 181.0 - 145.0 15 181.0 - 109.0 35 10 8-六六六 13.21 181.1 - 145.1 15 183.1 - 147.1 15 11 百菌清 13.331 265.8 - 133.0 45 263.8 - 168.0 30 12 甲基对硫磷 14.088 125.0 - 47.0 10 262.9 - 109.0 10 13 七氯 14.266 99.9 - 65.0 15 271.7 - 236.9 15 14 马拉硫磷 14.896 126.9 - 99.0 5 172.9 - 99.0 15 15 艾氏剂 15.045 262.9 - 192.9 35 254.9 - 220.0 20 16 对硫磷 15.18 138.9 - 109.0 5 138.9 - 81.0 15 17 三氯杀螨醇 15.235 139.0 - 111.0 15 139.0 - 75.0 35 18 环氧七氯 15.968 352.8 - 262.9 15 262.9 - 193.0 35 19 a-氯丹 16.543 372.7 - 266.0 25 372.7 - 301.0 10 20 a-硫丹 16.851 236.8 - 118.9 25 194.9 - 160.0 5 21 y-氯丹 16.912 271.7 - 236.9 15 372.8 - 265.8 15 22 p, p'-滴滴伊 17.419 245.8 - 176.1 35 247.8 - 176.1 35 23 狄氏剂 17.503 262.9 - 193.0 35 262.9 - 191.0 35 24 异狄氏剂 18.073 262.8 - 193.0 35 244.8 - 173.0 30 25 β-硫丹 18.321 206.9 - 172.0 15 194.9 - 158.9 10 26 p, p'-滴滴滴 18.522 234.8 - 165.1 30 164.9 - 115.0 40 27 o, p'-滴滴涕 18.613 234.8 - 165.1 30 236.8 - 165.1 30 28 异狄式剂醛 18.831 67.0 - 41.1 15 242.8 - 173.0 35 29 硫丹硫酸盐 19.482 271.7 - 236.9 15 273.7 - 238.9 15 30 p, p'-滴滴涕 19.538 236.8 - 165.1 30 245.8 - 176.1 35 31 异狄式剂酮 20.81 67.0 - 41.1 15 316.8 - 101.0 15 32 甲氧氯 21.183 227.0 - 169.1 30 227.0 - 141.0 40 33 灭蚁灵 22.446 271.7 - 236.9 20 236.8 - 118.9 35 
下载: 导出CSV
表 2 33种农药基质曲线线性关系
Table 2. Linear relation of 33 pesticides
序号 目标物 线性方程 R2值 1 敌敌畏 y 954.971424x-2982.153453 0.9993 2 内吸磷-S y 542.940276x-2149.645170 0.9994 3 内吸磷-0 y 546.862972x-2248.756143 0.999 4 甲拌磷 y 3155.573236x-9953.105161 0.9995 5 α-六六六 y 4463.121959x-8201.176879 0.9996 6 六氯苯 y 4889.302916x-2846.450065 0.9995 7 阿特拉津 y 645.170046x-2003.351126 0.9993 8 β-六六六 y 2116.091199x-4650.044009 0.9990 9 y-六六六 y 4679.588856x-2955.255333 0.9995 10 8-六六六 y 1257.065089x-4818.657801 0.9990 11 百菌清 y 199.811442x-908.081958 0.9992 12 甲基对硫磷 y 153.757221x-543.189911 0.999 13 七氯 y 4004.033239x-3091.692071 0.9997 14 马拉硫磷 y 340.136603x-1241.713805 0.9992 15 艾氏剂 y 1652.838794x-2444.855163 0.9997 16 对硫磷 y 242.753591x-873.749417 0.9986 17 三氯杀螨醇 y 7134.044840x-19021.881159 0.9987 18 环氧七氯 y 760.315969x-1080.065205 0.9997 19 a-氯丹 y 1018.977873x-1720.263715 0.9998 20 α-硫丹 y 193.640266x-183.437240 0.9989 21 y-氯丹 y 1458.351695x-2581.447800 0.9997 22 p, p'-滴滴伊 y 9360.289091x-23005.017779 0.9995 23 狄氏剂 y 775.879428x-916.301725 0.9997 24 异狄氏剂 y 529.690512x-899.186118 0.9997 25 β-硫丹 y 425.642809x-455.163541 0.9991 26 p, p'-滴滴滴 y 7466.023972x-20809.797969 0.9989 27 o, p'-滴滴涕 y 6113.323815x-22885.997996 0.9984 28 异狄式剂醛 y 835.183455x-1742.873843 0.9991 29 硫丹硫酸盐 y 432.646909x-1160.414848 0.9989 30 p, p'-滴滴涕 y 1743.835412x-6872.745864 0.9982 31 异狄式剂酮 y 726.586263x-1383.384902 0.9991 32 甲氧氯 y 1561.131516x-6277.471208 0.9981 33 灭蚁灵 y 7074.680738x-7630.548028 0.9982
下载: 导出CSV
表 3 33种农药检出限、定量限、精密度、回收率
Table 3. Limit of detection, limit of quantitation, relative standard deviation of precision, and recovery of 33 pesticides
目标物 LOD/10-9 LOQ/10-9 10 μg/L 50 μg/L 100 μg/L RSD/% 回收率/% RSD/% 回收率/% RSD/% 回收率/% 敌敌畏 0.15 0.5 5.5~14.2 54.0~104.4 3.9~11.2 65.1~110.3 3.9~9.6 72.4~118.5 内吸磷-S 0.15 0.5 5.4~13.4 63.8~118.2 3.7~10.9 66.6~113.0 3.9~11.2 74.8~100.1 内吸磷-0 0.19 0.63 6.5~16.3 73.4~110.3 6.9~11.5 85.6~111.5 4.4~15.1 73.3~110.2 甲拌磷 0.52 1.71 4.3~16.5 66.7~111.2 4.1~10.8 70.2~103.0 3.7~9.3 74.3~99.8 a-六六六 0.09 0.3 5.2~10.9 74.9~114.2 5.5~11.8 68.5~108.3 4.4~9.6 72.3~115.0 六氯苯 0.09 0.3 5.2~16.9 75.3~109.5 5.4~11.6 79.1~118.6 3.8~9.4 71.0~113.2 阿特拉津 0.15 0.5 4.4~12.6 65.3~123.3 5.2~17.1 70.4~103.5 4.1~9.4 73.8~116.2 β-六六六 0.15 0.50 5.9~11.7 66.7~99.7 4.2~11.5 72.9~103.1 3.8~12.2 73.3~95.2 y-六六六 0.15 0.50 5.5~11.6 61.0~105.3 4.7~10.1 61.6~116.1 3.9~10.6 71.4~111.5 8-六六六 0.09 0.30 5.0~13.0 68.7~105.5 4.2~10.2 65.2~106.9 4.1~8.8 82.6~105.2 百菌清 0.50 1.69 5.5~14.9 65.8~99.5 3.8~10.9 56.3~118.8 3.9~9.2 73.8~107.5 甲基对硫磷 0.38 1.27 4.3~12.7 64.7~117.3 4.4~11.9 79.2~115.3 3.7~12.9 71.9~98.2 七氯 0.10 0.33 6.9~16.4 57.5~113.8 4.2~11.8 63.5~114.6 4.3~12.2 71.9~98.9 马拉硫磷 0.28 0.93 5.0~10.6 67.3~113.9 5.2~8.5 76.0~100.9 4.4~16.5 74.7~112.8 艾氏剂 0.15 0.50 4.3~9.6 52.9~115.2 4.0~8.7 63.6~102.3 5.6~11.8 67.8~98.9 对硫磷 0.22 0.73 4.5~11.6 54.2~115.3 4.1~17.2 51.8~109.2 4.6~8.8 67.6~116.5 三氯杀螨醇 0.11 0.33 6.4~15.7 51.6~105.6 4.0~11.6 63.5~106.5 4.5~9.2 74.6~107.8 环氧七氯 0.13 0.41 4.1~12.1 76.2~113.1 4.6~10.9 64.2~118.2 5.6~8.9 72.6~113.9 a-氯丹 0.13 0.41 4.6~13.2 69.0~103.7 4.0~11.1 71.0~116.1 4.3~12.2 71.3~112.5 a-硫丹 0.17 0.57 4.3~15.6 69.6~104.4 3.8~12.1 77.8~114.9 4.9~9.6 72.2~116.2 y-氯丹 0.15 0.50 4.5~9.6 70.9~98.7 5.2~10.7 71.4~96.5 4.1~10.6 73.4~116.5 p, p'-滴滴伊 0.15 0.50 4.3~9.3 62.2~110.3 4.0~8.8 78.1~111.2 5.2~11.2 79.8~115.2 狄氏剂 0.16 0.50 5.1~12.0 66.7~101.9 3.6~10.8 72.3~97.8 3.1~10.2 82.8~103.8 异狄氏剂 0.18 0.60 5.4~9.8 64.2~112.5 4.1~7.8 77.9~97.8 4.6~8.2 71.2~105.3 β-硫丹 0.18 0.60 4.3~9.6 68.3~116.8 6.3~10.3 74.8~108.5 5.1~8.9 87.1~105.4 p, p'-滴滴滴 0.10 0.30 3.9~15.7 60.2~95.5 5.7~10.3 61.9~110.3 5.2~10.4 71.0~114.6 o, p'-滴滴涕 0.13 0.41 5.7~14.3 74.0~118.0 3.7~9.7 65.1~104.2 4.3~9.2 72.4~117.2 异狄式剂醛 0.20 0.67 4.2~14.8 53.8~108.9 3.8~11.7 66.6~101.4 5.3~9.2 74.8~105.6 硫丹硫酸盐 0.17 0.56 4.1~9.7 53.4~98.5 6.0~14.9 75.6~100.9 4.4~10.1 73.3~113.9 p, p'-滴滴涕 0.15 0.50 4.5~8.1 66.7~103.5 5.1~10.7 70.2~114.8 5.3~12.6 74.3~105.2 异狄式剂酮 0.13 0.43 4.2~11.3 64.9~110.9 5.1~10.8 78.5~105.3 4.8~9.3 72.3~98.5 甲氧氯 0.13 0.43 5.9~13.2 55.3~94.3 4.1~9.9 69.1~108.2 4.2~8.6 71.0~116.3 灭蚁灵 0.11 0.30 4.3~10.4 55.3~98.6 4.5~11.2 70.4~97.6 4.6~9.1 73.8~100.8
下载: 导出CSV
-
[1] 汪霞娟, 崔芬祺. 我国农田土壤有机农药污染现状及检测技术[J]. 黑龙江环境通报, 2019, 43(1): 32-33.
Wang X J, Cui F Q. Present situation and detection technology of organic pesticides pollution in farmland soils in China[J]. Heilongjiang Environmental Journal, 2019, 43(1): 32-33.
[2] 王宝金, 张天民, 严冬, 等. 持久性有机污染物对环境的影响及对策[J]. 地质与资源, 2007, 16(4): 293-296, 315. doi: 10.3969/j.issn.1671-1947.2007.04.010
Wang B J, Zhang T M, Yan D, et al. Persistent organic pollutants: Influence on environment and countermeasures[J]. Geology and Resources, 2007, 16(4): 293-296, 315. doi: 10.3969/j.issn.1671-1947.2007.04.010
[3] 缪宇腾, 卢一辰, 陆利霞, 等. 环境介质中有机磷农药残留检测方法的研究与进展[J]. 生物加工过程, 2022, 20(1): 95-103.
Liao Y T, Lu Y C, Lu L X, et al. Detection of organophosphorus pesticides in environmental matrices: A review[J]. Chinese Journal of Bioprocess Engineering, 2022, 20(1): 95-103.
[4] Grilo A, Moreira A, Carrapiço B, et al. Epidemiological study of pesticide poisoning in domestic animals and wildlife in Portugal: 2014-2020[J]. Frontiers in Veterinary Science, 2021, 7: 616293.
[5] 沙鸥, 姚佳伟, 许丽, 等. 有机磷农药中毒患者体内有机磷检测研究进展[J]. 化学试剂, 2021, 43(7): 857-864.
Sha O, Yao J W, Xu L, et al. Research progress on organophosphorus detection in patients with organophosphorus pesticide poisoning in diagnosis[J]. Chemical Reagents, 2021, 43(7): 857-864.
[6] 赵起越, 夏夜, 邹本东. 土壤中有机氯农药的前处理方法[J]. 分析试验室, 2022, 41(10): 1234-1240.
Zhao Q Y, Xia Y, Zou B D. Pretreatment of organochlorine pesticides in soil[J]. Chinese Journal of Analysis Laboratory, 2022, 41(10): 1234-1240.
[7] 朱霞萍, 王勇, 安艳, 等. 环境样中有机磷农药残留检测前处理技术研究进展[J]. 中国测试, 2021, 47(9): 52-60.
Zhu X P, Wang Y, An Y, et al. Development on pretreatment techniques for detection of organophosphorus pesticide residues in environmental samples[J]. China Measurement & Test, 2021, 47(9): 52-60.
[8] 陈林昌, 胡雅琴, 王鑫, 等. 加压流体萃取气相色谱法测定芡实种植底泥中有机氯农药残留[J]. 环境科技, 2021, 34(3): 69-72.
Chen L C, Hu Y Q, Wang X, et al. Pressurized fluid extraction GC residues of organochlorine pesticides in gorgon fruit planting sediment were determined[J]. Environmental Science and Technology, 2021, 34(3): 69-72.
[9] 王莎莎, 沈习习, 李曼曼, 等. QuEChERS-气相色谱-三重四级杆串联质谱法高通量检测生鲜肉中有机磷农药残留[J]. 食品与发酵工业, 2022, 48(5): 262-267.
Wang S S, Shen X X, Li M M, et al. High-throughput detection of organophosphorus pesticide residues in fresh meat by QuEChERS-GC-MS/MS[J]. Food and Fermentation Industries, 2022, 48(5): 262-267.
[10] 蔡霖, 席普宇, 谢晴, 等. QuEChERS方法联合HPLC-MS/MS和GC-MS测定土壤中110种农药残留[J]. 农业环境科学学报, 2017, 36(8): 1680-1688.
Cai L, Xi P Y, Xie Q, et al. Development of a multiresidue method for determination of 110 pesticide residues in soil using QuEChERS-HPLC-MS/MS and QuEChERS-GC-MS[J]. Journal of Agro-Environment Science, 2017, 36(8): 1680-1688.
[11] 曾凯, 孙国泉, 唐俊, 等. QuEChERS-气质联用法同时测定土壤中16种农药残留[J]. 农药, 2016, 55(7): 507-509, 523.
Zeng K, Sun G Q, Tang J, et al. Determination of 16 kinds of pesticide residues in soil by QuEChERS and gas chromatography-mass spectromter[J]. Agrochemicals, 2016, 55(7): 507-509, 523.
[12] 徐宜宏, 黄莹滢, 于丽, 等. 改良QuEChERS法测定土壤中的毒杀芬残留量[J]. 农药, 2018, 57(6): 435-437.
Xu Y H, Huang Y Y, Yu L, et al. Detection of toxaphene in soil by modified QuEChERS technique[J]. Agrochemicals, 2018, 57(6): 435-437.
[13] 谭华东, 赵淑巧, 吴东明, 等. 微量QuEChERS/气相色谱质谱法快速测定土壤中15种农药残留[J]. 化学试剂, 2020, 42(2): 147-153.
Tan H D, Zhao S Q, Wu D M, et al. Simultaneous determination of 15 pesticides residue in soil by Micro-QuEChERS coupled with gas chromatography-mass spectrometry[J]. Chemical Reagent, 2020, 42(2): 147-153.
[14] 林刚健, 杨挺, 方如意. GPC净化-GC-MS法测定甜玉米中17种有机氯类农药残留[J]. 现代食品, 2021, 27(10): 155-158.
Lin G J, Yang T, Fang R Y. Determination of 17 organochlorine pesticide residues in sweet corn by GPC-GC-MS[J]. Modern Food, 2021, 27(10): 155-158.
[15] 毕春磊. 加速溶剂萃取-凝胶渗透色谱法净化-气相色谱-串联质谱法测定农作物土壤中5种有机磷类农药的残留量[J]. 理化检验-化学分册, 2022, 58(4): 406-410.
Bi C L. Determination of residues of 5 organophosphorus pesticides in crop soil by gas chromatography-tandem mass spectrometry with accelerated solvent extraction and gel permeation chromatography purification[J]. Physical Testing and Chemical Analysis Part B: Chemical Analysis, 2022, 58(4): 406-410.
[16] 和莹, 孙谦, 张秦铭, 等. 气相色谱-三重四极杆质谱法测定土壤中有机氯农药[J]. 环境化学, 2022, 41(12): 4193-4196.
He Y, Sun Q, Zhang Q M, et al. Determination of organochlorine pesticide in soil by gas chromatography-triple quadrupole mass spectrometry[J]. Environmental Chemistry, 2022, 41(12): 4193-4196.
[17] 王贵玲, 陆川. 碳中和目标驱动下地热资源开采利用技术进展[J]. 地质与资源, 2022, 31(3): 412-425, 341. doi: 10.13686/j.cnki.dzyzy.2022.03.017
Wang G L, Lu C. Progress of geothermal resources exploitation and utilization technology driven by carbon neutralization target[J]. Geology and Resources, 2022, 31(3): 412-425, 341. doi: 10.13686/j.cnki.dzyzy.2022.03.017
[18] 刘强, 林楠, 王长琪, 等. 松嫩平原湿地演变及其驱动因素分析[J]. 地质与资源, 2023, 32(1): 96-103. doi: 10.13686/j.cnki.dzyzy.2023.01.012
Liu Q, Lin N, Wang C Q, et al. Wetland evolution and its driving factors in Songnen plain[J]. Geology and Resources, 2023, 32(1): 96-103. doi: 10.13686/j.cnki.dzyzy.2023.01.012
[19] 息朝庄, 吴林锋, 张鹏飞, 等. 贵州省惠水土壤-灌溉水-雨水-大气降尘中Cd、As等微量元素特征及来源讨论[J]. 中国地质, 2023, 50(1): 192-205.
Xi C Z, Wu L F, Zhang P F, et al. Characteristics and sources of Cd and As trace elements in soil-irrigation-rainwater-atmospheric dust-fall in Huishui County, Guizhou province[J]. Geology in China, 2023, 50(1): 192-205.
[20] 赵建, 孔繁鹏, 刘洪博, 等. 黑龙江省宝清县万金山乡土壤硒分布特征及其与土壤性质关系[J]. 地质与资源, 2023, 32(2): 233-237, 210. doi: 10.13686/j.cnki.dzyzy.2023.02.014
Zhao J, Kong F P, Liu H B, et al. Distribution of soil selenium and its relationship with soil properties in Wanjinshan of Baoqing county, Heilongjiang province[J]. Geology and Resources, 2023, 32(2): 233-237, 210. doi: 10.13686/j.cnki.dzyzy.2023.02.014
-
图(4)
表(3)
计量
- 文章访问数: 38
- PDF下载数: 11
- 施引文献: 0