Citation: | GAO Ran, RAO Zhu, GUO Xiao-chen. Analysis of 91 Pesticide Residues in Groundwater by Gas Chromatography-Mass Spectrometry[J]. Rock and Mineral Analysis, 2021, 40(6): 973-986. doi: 10.15898/j.cnki.11-2131/td.202011170148 |
Fast screening of multiple pesticides in groundwater is an important technical support for comprehensively characterizing groundwater quality and ensuring groundwater safety.
To establish a rapid, easy and highly efficient method for the determination of 91 pesticides in groundwater.
By selecting and optimizing the water sample pretreatment method and gas chromatography-mass spectrometry analysis conditions, a rapid analysis method for the simultaneous determination of 91 pesticides in groundwater by gas chromatography-mass spectrometry (GC-MS) was established. The targets were determined by GC-MS and quantified by an internal standard. After optimization, the target substance adopts pulsed splitless injection, separated by Zebron Multiresidue-2 chromatographic column, and segmented selective ion scanning.
Under the optimized conditions, pesticides showed good linearity with the correlation coefficient between 0.9901 and 0.9997 in the concentration range of 1.0-1000μg/L. The water sample was subjected to liquid-liquid extraction and concentration of dichloromethane and then tested on the machine, yielding method detection limits (MDLs) of 3.1-12.5ng/L, the average recoveries of 54.3%-129%, and the relative standard deviation (RSD) of 1.2% to 20%.
Compared to previous studies, the method not only greatly improves the efficiency, reduces the cost of analysis, ensures the effectiveness of sample analysis, but also has wide applicability, high accuracy and high sensitivity. The method is more suitable for analysis of large batches of samples, which ensures the timeliness of sample analysis. The method has been successfully applied to the national groundwater pollution survey.
[1] | 郭婕, 张燕, 胡振国, 等. 环境水样中农药污染分析技术研究进展[J]. 岩矿测试, 2021, 40(1): 16-32. Guo J, Zhang Y, Hu Z G, et al. A review of pesticide pollution analysis techniques for environmental water samples[J]. Rock and Mineral Analysis, 2021, 40(1): 16-32. |
[2] | 孙肖瑜, 王静, 金永堂. 我国水环境农药污染现状及健康影响研究进展[J]. 环境与健康杂志, 2009, 26(7): 649-652. Sun X Y, Wang J, Jin Y T. Advances in research on pesticide pollution to the aquatic environment and health impact in China[J]. Journal of Environmental Health, 2009, 26(7): 649-652. |
[3] | 叶凯, 孙玉川, 贾亚男, 等. 岩溶地下水水体中有机氯农药和多氯联苯的残留特征及健康风险评价[J]. 环境科学, 2020, 41(12): 5448-5457. Ye K, Sun Y C, Jia Y N, et al. Residual characteristics and health assessment analysis of OCPs and PCBs in karst groundwater[J]. Environmental Science, 2020, 41(12): 5448-5457. |
[4] | 周洋, 朱恒华, 刘治政, 等. 山东省海岸带地区地下水有机污染特征分析[J]. 山东国土资源, 2020, 36(8): 40-47. Zhou Y, Zhu H H, Liu Z Z, et al. Analysis on organic pollution characteristics of groundwater in coastal area of Shandong Province[J]. Shandong Land and Resources, 2020, 36(8): 40-47. |
[5] | Mahai G, Wan Y J, Xia W, et al. Neonicotinoid insecticides in surface water from the central Yangtze River, China[J]. Chemosphere, 2019, 229: 452-460. doi: 10.1016/j.chemosphere.2019.05.040 |
[6] | Zhou Y T, Wu J X, Wang B, et al. Occurrence, source and ecotoxicological risk assessment of pesticides in surface water of Wujin District (northwest of Taihu Lake), China[J]. Environmental Pollution, 2020, 265: 114953. doi: 10.1016/j.envpol.2020.114953 |
[7] | Rahman M, Hoque M S, Bhowmik S, et al. Monitoring of pesticide residues from fish feed, fish and vegetables in Bangladesh by GC-MS using the QuEChERS method[J]. Heliyon, doi.org/10.1016/j.heliyon.2021.e06390. |
[8] | 朱仁愿, 丁辉, 杨志敏, 等. 当归、党参、黄芪和甘草中农药多组分残留检测技术的研究进展[J]. 中国现代应用医学, 2021, 38(3): 371-376. Zhu R Y, Ding H, Yang Z M, et al. Research advances in the detection technology of pesticide residues in Angelicae Sinensis Radix, Codonopsis Radix, Astragali Radix and Glycyrrhizae Radix et Rhizoma[J]. Chinese Journal of Modern Applied Pharmacy, 2021, 38(3): 371-376. |
[9] | 吴剑平, 张婧, 周悦榕, 等. 超高效液相色谱-静电轨道阱质谱正负切换同时筛查定量谷物饲料中的51种农药残留[J]. 中国兽药杂志, 2018, 52(11): 47-58. Wu J P, Zhang J, Zhou Y R, et al. Synchronous screening and quantitation of 51 pesticides residue in grain feed by ultra performance liquid chromatography-orbitrap mass spectrometry with positive and negative switching mode[J]. Chinese Journal of Veterinary Drug, 2018, 52(11): 47-58. |
[10] | 叶茂盛, 孙秀梅, 郝青, 等. 水产品中有机磷农药多残留的固相萃取-气相色谱串联质谱测定[J]. 浙江海洋大学学报(自然科学版), 2019, 38(2): 174-179. doi: 10.3969/j.issn.1008-830X.2019.02.013 Ye M S, Sun X M, Hao Q, et al. Determination of organophosphorus pesticide residues in aquatic products by solid phase extraction coupled with gas chromatography tandem mass spectrometry[J]. Journal of Zhejiang Ocean University (Natural Science), 2019, 38(2): 174-179. doi: 10.3969/j.issn.1008-830X.2019.02.013 |
[11] | Acosta-Dacal A, Rial-Berriel C, Díaz-Díaz R, et al. Optimization and validation of a QuEChERS-based method for the simultaneous environmental monitoring of 218 pesticide residues in clay loam soil[J]. Science of the Total Environment, 2021, 753: 142015. doi: 10.1016/j.scitotenv.2020.142015 |
[12] | Tan H D, Li Q F, Zhang H J, et al. Pesticide residues in agricultural topsoil from the Hainan tropical riverside basin: Determination, distribution, and relationships with planting patterns and surface water[J]. Science of the Total Environment, 2020, 722: 137856. doi: 10.1016/j.scitotenv.2020.137856 |
[13] | 郭晓辰, 饶竹, 高冉. 气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留[J]. 岩矿测试, 2014, 33(3): 406-412. doi: 10.3969/j.issn.0254-5357.2014.03.020 Guo X C, Rao Z, Gao R. Determination of 24 pesticides including pyrethroids, organochlorines and chlorothalonil in underground water by gas chromatography[J]. Rock and Mineral Analysis, 2014, 33(3): 406-412. doi: 10.3969/j.issn.0254-5357.2014.03.020 |
[14] | Xiao Z W, He M, Chen B B, et al. Polydimethylsiloxane/metal-organic frameworks coated stir bar sorptive extraction coupled to gas chromatography-flame photometric detection for the determination of organophosphorus pesticides in environmental water samples[J]. Talanta, 2016, 156-157: 126-133. doi: 10.1016/j.talanta.2016.05.001 |
[15] | 王红斌, 赵田甜, 李桂镇, 等. 多壁碳纳米管固相萃取-高效液相色谱法测定水中7种三唑类农药残留[J]. 环境污染与防治, 2015, 37(4): 42-46. Wang H B, Zhao T T, Li G Z, et al. Determination of seven triazole pesticides residues in water by MWCNTs-SPE-HPLC[J]. Environmental Pollution and Prevention, 2015, 37(4): 42-46. |
[16] | Zhou Q X, Wu Y L, Sun Y, et al. Magnetic polyamidoamine dendrimers for magnetic separation and sensitive determination of organochlorine pesticides from water samples by high-performance liquid chromatography[J]. Journal of Environmental Sciences, 2021, 102: 64-73. doi: 10.1016/j.jes.2020.09.005 |
[17] | 严妍, 谢飞. 固相萃取GC-MS法测定生活饮用水中有机磷和拟除虫菊酯类农药残留[J]. 绿色科技, 2020(2): 98-100. . doi: 10.3969/j.issn.1674-9944.2020.02.033 Yan Y, Xie F. Determination of organophosphorus and pyrethroid pesticides residues in domestic water by solid phase extraction-GC-MS[J]. Journal of Green Science and Technology, 2020(2): 98-100. doi: 10.3969/j.issn.1674-9944.2020.02.033 |
[18] | Nasiri M, Ahmadzadeh H, Amiri A. Organophosphorus pesticides extraction with polyvinyl alcohol coated magnetic graphene oxide particles and analysis by gas chromatography-mass spectrometry: Application to apple juice and environmental water[J]. Talanta, 2021, 227: 122078. doi: 10.1016/j.talanta.2020.122078 |
[19] | Liu S Y, Huang X H, Hu K J, et al. Development of a multiresidue method for endocrine-disrupting pesticides by solid phase extraction and determination by UHPLC-MS/MS from drinking water samples[J]. Journal of Chromatographic Science, 2020, 58(3): 195-202. doi: 10.1093/chromsci/bmz089 |
[20] | 赖国银, 林立毅, 丁亦男, 等. 固相萃取-超高效液相色谱-四极杆-飞行时间质谱法分析地表水中26种农药[J]. 环境化学, 2019, 38(5): 1065-1073. Lai G Y, Lin L Y, Ding Y N, et al. Determination of 26 pesticides in surface water by solid phase extraction-ultra high performance liquid chromatography-quadrupole time-of-flight mass spectrometry[J]. Environmental Chemistry, 2019, 38(5): 1065-1073. |
[21] | 仇秀梅, 董学林, 刘亚东, 等. 液液萃取-气相色谱法同时测定地下水中16种有机氯农药[J]. 环境污染与防治, 2016, 38(11): 72-78. Qiu X M, Dong X L, Liu Y D, et al. Simultaneous determination of 16 organochlorine pesticides in groundwater by liquid-liquid extraction/gas chromatography[J]. Prevention and Control of Environmental Pollution, 2016, 38(11): 72-78. |
[22] | 陆一夫, 胡小键, 丁昌明, 等. 地表水中23种有机氯农药的自动固相萃取-气相色谱-高分辨质谱联用测定法[J]. 环境与健康杂志, 2017, 34(2): 146-148. Lu Y F, Hu X J, Ding C M, et al. Determination of 23 organochlorine pesticides in surface water by automatic solid phase extraction-gas chromatography-high resolution mass spectrometry[J]. Journal of Environmental Health, 2017, 34(2): 146-148. |
[23] | 张莉, 刘佳, 李晓亚, 等. 固相萃取膜富集-超声解吸-气相色谱法测定地下水中有机磷农药的含量[J]. 理化检验(化学分册), 2019, 55(7): 745-749. Zhang L, Liu J, Li X Y, et al. Determination of organophosphorus pesticides in groundwater by gas chromatography with enrichment on solid phase extraction membrane[J]. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2019, 55(7): 745-749. |
[24] | 常青, 马虹英, 王方杰, 等. 脉冲不分流进样气相色谱-质谱法分析血浆中的10种镇静催眠药[J]. 理化检验(化学分册), 2011, 29(11): 1082-1086. Chang Q, Ma H Y, Wang F J, et al. Determination of 10 sedative-hypnotics in human plasma using pulse splitless injection technique and gas chromatography-mass spectrometry[J]. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2011, 29(11): 1082-1086. |
Total ions chromatogram of 91 pesticides in fullscan mode (ZB—Multiresidue 2)
Response ratio in splitless with surge and splitless of 91 pesticides