Analysis of 91 Pesticide Residues in Groundwater by Gas Chromatography-Mass Spectrometry
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摘要:
地下水中多种农药快速检测是全面表征地下水水质、确保地下水安全的重要技术支撑。本文结合现有检测标准和文献中农药需分类分别前处理和测试的问题，采用气相色谱-质谱仪，通过对水样前处理方法和气相色谱-质谱分析条件进行选择和优化，建立了地下水中91种农药气相色谱-质谱同时测定的快速分析方法。经优化，目标物采用脉冲不分流进样，Zebron Multiresidue-2色谱柱分离，分段选择离子扫描，内标法定量，多数农药在1.0~1000μg/L浓度范围内线性良好，相关系数在0.9901~0.9997之间。水样经二氯甲烷液液萃取浓缩后上机测试，各农药方法检出限为3.1~12.5ng/L，平均加标回收率在54.3%~129%之间，相对标准偏差（RSD）为1.2%~20%。本方法快速、简单，准确度高，不仅显著提高了地下水中多种类农药残留分析效率，降低了分析成本；而且方法更适合大批量地下水样品的快速筛查，从而保证了样品分析的时效性。该方法已成功应用于全国地下水污染调查专项。
Abstract:BACKGROUND Fast screening of multiple pesticides in groundwater is an important technical support for comprehensively characterizing groundwater quality and ensuring groundwater safety.
OBJECTIVES To establish a rapid, easy and highly efficient method for the determination of 91 pesticides in groundwater.
METHODS 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.
RESULTS 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%.
CONCLUSIONS 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.
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Key words:
- groundwater /
- pesticide residues /
- gas chromatography-mass spectrometry /
- fast analysis
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表 1 不同化合物的保留时间、定量及定性离子、线性范围、相关系数、检出限、平均回收率和相对标准偏差
Table 1. Retention time, quantitative and qualitative ions, linear ranges, correlation coefficients, method detection limits, average spiked recoveries and the relative standard deviations of different compounds
峰号 化合物 tR (min) 定量及定性离子(m/z) 线性范围(μg/L) 相关系数r MDLs (ng/L) US EPA 525.2 MDLs(ng/L) GB/T 14848—2017 Ⅰ类限值(ng/L) 20ng/L(n=7) 100ng/L(n=5) 1000ng/L(n=5) R(%) RSD(%) R(%) RSD(%) R(%) RSD(%) 1 绿麦隆 6.35 132*, 167, 169 1~1000 0.9993 6.8 / / 97.9 6.9 98.7 2.3 81.2 11 2 敌敌畏 6.50 109*, 185, 187 1~1000 0.9997 3.7 92 50 72.9 4.2 110 2.8 108 8.0 3 速灭磷 8.35 127*, 109, 192 1~1000 0.9948 3.2 79 / 113 4.0 106 7.7 90.5 7.8 4 苊-D10(IS1) 9.21 164*, 162, 160 — — — — — — — — — — — 5 2, 4, 5, 6-四氯间二甲苯(SS1) 10.88 244*, 242, 209 — — — — — 63.9 8.6 70.1 2.3 99.5 2.4 6 治螟磷 11.96 97*, 322, 202 1~1000 0.9952 5.9 / / 96.5 8.8 101 4.2 124 5.7 7 甲拌磷 12.46 75*, 121, 260 5~1000 0.9957 4.0 / / 102 5.4 111 5.9 94.0 4.5 8 脱乙基莠去津 12.66 172*, 174, 187 1~1000 0.9932 8.0 / / 116 13 88.7 8.7 62.9 6.8 9 六氯苯 12.94 284*, 286, 282 1~1000 0.9984 4.1 120 10 83.5 6.6 84.7 2.2 89.0 2.6 10 α-六六六 13.32 181*, 183, 219 1~1000 0.9995 6.1 200 10※ 98.3 7.5 94.7 2.0 91.9 3.2 11 内吸磷 10.67, 13.51 88*, 60, 89 1~1000 0.9940 10.5 / / 112 13 98.9 9.6 90.0 3.6 12 特丁硫磷 13.78 231*, 153, 97 1~1000 0.9963 4.3 77 / 117 6.5 109 8.7 96.6 2.3 13 二嗪磷 14.06 137*, 179, 304 1~1000 0.9983 3.5 110 / 122 1.9 109 3.4 98.0 2.0 14 扑灭津 14.13 214*, 172, 229 1~1000 0.9941 5.6 88 / 134 7.4 111 3.0 96.6 2.8 15 莠去津 14.34 200*, 215, 217 1~1000 0.9963 7.9 65 50 112 15 93.4 4.6 97.0 6.0 16 五氯硝基苯 14.66 237*, 249, 295 1~1000 0.9918 6.1 / / 96.8 7.6 101 2.5 94.9 2.3 17 乐果 15.03 87*, 93, 125 5~1000 0.9922 7.5 / 50 93.7 6.8 99.4 6.2 70.0 7.4 18 β-六六六 15.06 181*, 183, 219 0.2~1000 0.9972 6.8 280 10※ 92.4 8.3 94.2 2.3 93.6 3.5 19 乙拌磷 15.06 88*, 89, 97 0.2~1000 0.9910 3.5 1300 / 108 4.5 99.8 6.3 93.0 3.4 20 菲-D10(IS2) 15.45 188*, 189, 184 — — — — — — — — — — — 21 杀螟腈 15.72 109*, 125, 243 1~1000 0.9933 6.0 / / 107 9.0 105 2.8 94.6 2.9 22 异稻瘟净 15.75 91*, 204, 123 1~1000 0.9922 5.1 / / 118 7.1 112 5.6 93.2 2.3 23 抗蚜威 16.75 166*, 72, 238 1~1000 0.9925 10.5 / / 50.6 18 71.5 15 74.7 7.1 24 七氯 16.81 272*, 100, 274 1~1000 0.9916 6.3 140 10 113 9.5 93.4 4.7 93.3 2.8 25 乙草胺 16.84 146*, 162, 174 1~1000 0.9921 4.8 / / 125 4.9 108 4.7 94.2 3.0 26 γ-六六六 17.05 181*, 183, 219 1~1000 0.9994 6.6 120 10 97.2 6.3 98.2 1.6 94.0 3.0 27 甲草胺 17.39 160*, 188, 146 1~1000 0.9921 6.9 87 / 125 6.6 110 3.5 95.9 2.4 28 甲基毒死蜱 17.63 286*, 125, 288 1~1000 0.9934 3.6 / / 128 5.9 110 4.1 117 2.2 29 δ-六六六 18.34 181*, 183, 219 1~1000 0.9983 5.0 150 10※ 99.5 5.0 97.9 1.5 93.7 2.7 30 艾氏剂 18.52 66*, 263, 261 1~1000 0.9965 3.8 160 / 87.0 5.4 95.8 6.2 91.7 4.7 31 甲基对硫磷 18.87 109*, 125, 263 1~1000 0.9906 3.9 / 50 115 5.1 101 3.3 97.5 1.6 32 百菌清 19.09 266*, 264, 268 1~1000 0.9979 4.2 110 50 107 3.6 111 4.1 94.4 2.1 33 特丁净 19.16 226*, 185, 241 1~1000 0.9902 4.0 / / 103 3.1 109 6.7 95.5 2.1 34 异丙甲草胺 19.56 162*, 238, 240 5~1000 0.9901 5.0 840 / 112 4.4 119 5.8 98.5 1.6 35 马拉硫磷 19.92 127*, 93, 173 5~1000 0.9905 5.0 / 50 103 4.4 116 3.5 95.5 2.1 36 毒死蜱 20.05 197*, 199, 314 1~1000 0.9972 6.0 120 50 114 11 116 5.4 112 1.3 37 杀螟硫磷 20.19 125*, 109, 277 1~1000 0.9936 5.4 / / 120 10 94.6 9.6 93.2 1.2 38 乙霉威 20.30 124*, 225, 267 5~1000 0.9908 7.1 / / 113 13 110 3.6 103 1.5 39 三唑酮 20.50 208*, 181, 210 5~1000 0.9924 4.5 160 / 95.1 7.9 113 9.2 104 3.0 40 倍硫磷 21.19 278*, 125, 109 1~1000 0.9919 5.9 / / 101 6.0 118 5.2 96.6 2.2 41 对硫磷 21.22 291*, 109, 97 10~1000 0.9906 5.9 / / 112 7.3 106 3.8 96.6 2.0 42 溴硫磷 21.51 125*, 331, 329 1~1000 0.9978 3.4 / / 113 4.3 110 3.8 99.5 3.043 43 甲基异柳磷 21.71 199*, 121, 231 1~1000 0.9940 5.8 / / 121 10 115 8.2 99.8 1.6 44 水胺硫磷 22.08 136*, 121, 120 1~1000 0.9925 5.9 / / 121 2.9 108 1.9 118 2.0 45 外环氧七氯B 22.24 81*, 353, 355 10~1000 0.9992 4.1 93 / 99.8 7.1 101 2.2 99.1 4.2 46 4, 4’-二溴联苯(SS2) 22.45 152*, 312, 314 — — — — — 96.2 6.7 93.2 3.1 99.8 1.9 47 内环氧七氯A 22.68 81*, 183, 253 10~1000 0.9989 5.7 / / 97.4 11 95.4 2.8 96.6 4.4 48 氟菌唑 23.07 73*, 278, 179 5~1000 0.9936 8.6 / / 72.9 9.8 67.2 9.2 62.6 15.1 49 丁草胺 23.72 176*, 160, 188 1~1000 0.9908 6.6 39 / 90.8 9.7 121 6.6 99.9 3.0 50 稻丰散 23.85 121*, 125, 274 1~1000 0.9940 7.6 / / 123 11 105 9.4 95.2 3.5 51 喹硫磷 23.90 146*, 156, 157 1~1000 0.9928 3.8 / / 106 6.0 113 7.7 109 3.8 52 γ-氯丹 24.05 373*, 375, 377 1~1000 0.9979 6.4 50 / 94.5 12 95.7 4.5 97.5 3.7 53 三唑醇 23.60, 24.06 112*, 168, 128 5~1000 0.9932 5.1 / / 85.1 6.3 74.3 9.1 97.8 3.8 54 α-氯丹 24.49 373*, 375, 377 1~1000 0.9976 5.9 61 / 95.8 11 100 2.9 98.0 3.9 55 硫丹Ⅰ 24.65 195*, 241, 237 5~1000 0.9967 4.6 200 / 101 8.4 104 3.4 94.0 2.4 56 多效唑 24.97 236*, 125, 167 5~1000 0.9949 6.8 / / 95.1 9.6 95.7 6.6 102 3.1 57 己唑醇 26.10 83*, 175, 214 5~1000 0.9911 6.6 / / 84.6 12 93.3 8.4 102 3.4 58 杀扑磷 26.17 145*, 93, 125 5~1000 0.9919 5.4 / / 117 5.4 128 8.5 97.2 3.3 59 4, 4’-DDE-D8(IS3) 26.31 254*, 256, 327 — — — — — — — — — — — 60 p, p’-DDE 26.48 246*, 248, 318 5~1000 0.9976 7.1 70 10※ 94.8 14 98.6 3.1 94.8 4.2 61 狄氏剂 26.65 79*, 263, 380 1~1000 0.9995 5.0 120 / 99.7 9.0 95.2 3.4 96.2 5.3 62 丙溴磷 26.76 139*, 339, 337 5~1000 0.9931 4.9 / / 92.0 8.1 108 3.9 107 2.7 63 烯效唑 27.54 234*, 70, 236 1~1000 0.9913 8.8 / / 93.9 16 89.0 3.4 102 3.9 64 氟硅唑 28.32 233*, 234, 315 1~1000 0.9931 6.7 / / 90.1 12 99.7 6.3 104 1.7 65 异狄氏剂 28.55 81*, 263, 265 5~1000 0.9971 8.5 310 / 127 11 118 3.2 102 3.0 66 腈菌唑 29.11 179*, 150, 152 10~1000 0.9918 4.5 / / 120 7.5 98.7 2.3 103 4.5 67 o, p’-DDT 29.22 235*, 165, 237 1~1000 0.9929 8.1 / 10※ 79.0 15 101 6.0 104 4.8 68 乙硫磷 29.55 231*, 125, 153 1~1000 0.9905 7.6 / / 107 11 106 4.3 103 4.0 69 p, p’-DDD 30.16 235*, 165, 237 1~1000 0.9964 6.0 280 10※ 80.5 11 95.4 5.3 96.6 5.5 70 硫丹Ⅱ 30.36 195*, 241, 237 5~1000 0.996 4.8 380 / 91.5 5.7 94.1 5.1 97.6 5.4 71 三环唑 30.74 189*, 162, 161 5~1000 0.9911 8.2 2400 / 62.1 12 76.0 8.0 81.4 8.8 72 4, 4’-DDT-D8(IS4) 31.15 243*, 245, 173 — — — — — — — — — — — 73 异狄氏剂醛 31.29 67*, 250, 345 5~1000 0.9980 5.8 240 / 82.3 11 94.9 5.7 104 4.7 74 p, p’-DDT 31.27 235*, 165, 237 1~1000 0.9958 6.5 90 10※ 75.5 12 101 3.2 102 4.3 75 丙环唑 31.42, 31.63 69*, 173, 259 10~1000 0.9962 12.5 / / 63.0 20 80.1 12.9 97.0 4.7 76 三唑磷 31.84 161*, 162, 172 1~1000 0.9913 9.2 / / 99.6 15 119 4.9 117 3.7 77 硫丹硫酸盐 32.25 272*, 274, 387 1~1000 0.9946 4.6 120 / 90.7 8.7 101 7.5 97.9 6.3 78 戊唑醇 32.23 125*, 250, 252 1~1000 0.9941 8.3 / / 68.0 16 105 8.6 99.8 4.8 79 联苯菊酯 32.18 181*, 166, 165 1~1000 0.9972 6.1 / / 103 12 109 3.6 99.7 3.5 80 甲氰菊酯 33.22 181*, 97, 125 1~1000 0.9908 9.0 / / 97.9 16 100 5.7 101 3.7 81 二丁基氯菌酸酯(SS3) 33.28 388*, 390, 99 - - - - - 116 11 107 2.7 100 2.4 82 三氯杀螨醇 33.78 139*, 251, 253 5~1000 0.9923 8.4 / / 74.9 15 103 5.3 108 3.0 83 甲氧滴滴涕 33.75 227*, 228, 152 1~1000 0.9926 6.2 330 / 99.0 12 106 4.0 101 3.8 84 苯硫磷 33.76 157*, 169, 141 1~1000 0.9947 6.7 / / 93.1 12 105 5.5 118 2.7 85 异狄氏剂酮 34.00 67*, 317, 139 1~1000 0.9984 6.2 / / 87.5 12 94.5 2.5 99.8 4.3 86 䓛-D12(IS5) 34.20 240*, 236, 241 — — — — — — — — — — — 87 灭蚁灵 34.42 272*, 274, 237 1~1000 0.9984 6.1 / / 90.4 11 91.9 5.9 94.6 3.3 88 三氟氯氰菊酯 34.34 181*, 197, 208 5~1000 0.9957 8.5 / / 94.8 16 110 3.4 98.6 2.2 89 三氯杀螨砜 34.81 159*, 111, 227 1~1000 0.9964 3.1 / / 108 5.6 105 3.5 96.4 3.5 90 反式氯菊酯 35.92 183*, 163, 184 1~1000 0.9970 5.6 510 / 105 10 117 1.6 98.4 2.6 91 顺式氯菊酯 36.16 183*, 163, 184 1~1000 0.9972 7.2 31 / 96.0 13 111 3.0 98.2 3.2 92 氟氯氰菊酯 36.82, 36.99, 37.06, 37.12 206*, 163, 165 1~1000 0.9956 8.5 / / 88.0 7.0 108 9.2 100 3.6 93 氯氰菊酯 37.36, 37.54, 37.63, 37.84 181*, 163, 165 1~1000 0.9933 6.5 / / 113 9.2 94.8 7.8 96.7 6.5 94 氟氰戊菊酯 37.63, 37.89 157*, 199, 181 1~1000 0.9971 10.2 / / 104 19 102 2.4 103 2.6 95 醚菊酯 37.83 163*, 135, 107 1~1000 0.9994 4.8 / / 115 8.2 110 4.6 102 3.2 96 氟胺氰菊酯 38.36, 38.48 250*, 252, 181 1~1000 0.9946 8.7 / / 83.4 16 108 3.1 103 2.5 97 氰戊菊酯 38.83, 39.12 125*, 167, 419 1~1000 0.9982 6.0 / / 89.7 12 105 3.6 102 3.1 98 苝-D12(IS6) 39.61 264*, 260, 265 — — — — — — — — — — — 99 溴氰菊酯 40.16 181*, 253, 255 1~1000 0.9945 5.7 / / 106 9.7 88.9 6.0 102 3.2 100 苯醚甲环唑 40.22, 40.30 265*, 323, 325 1~1000 0.9936 3.7 / / 86.9 4.1 99.5 7.3 110 3.3 注：“IS”表示内标物；“SS”表示替代物；“*”表示定量离子；US EPA 525.2方法检出限数据来源于US EPA 525.2中C18圆盘固相萃取-四极杆质谱准确度、精密度、检出限数据表；“/”表示该方法未检测相应组分；“※”表示GB/T 14848—2017中其限值为总量，非单体。“—”表示没有相关数据。 
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表 2 91种农药及替代物圆盘萃取法和液液萃取法平均加标回收率对比(加标浓度100ng/L，n=3)
Table 2. Average recoveries of 91 pesticides and substitutes by disc extraction and liquid-liquid extraction at the spiked concentration of 100ng/L (n=3)
化合物 圆盘萃取法加标回收率(%) 液液萃取法加标回收率(%) Empore膜， 二氯甲烷 洗脱 ENVI膜， 二氯甲烷 洗脱 Empore膜，乙酸乙酯- 丙酮(3∶1,V∶V) 洗脱 ENVI膜，乙酸乙酯- 丙酮(3∶1,V∶V) 洗脱 二氯 甲烷 正己烷 二氯甲烷-正己烷 (1∶1,V∶V) 绿麦隆 73.1 49.4 106 69.7 95.3 3.6 42.2 敌敌畏 64.8 45.5 119 78.9 86.9 15.5 51.0 速灭磷 72.4 47.6 124 82.0 114 3.4 49.3 2,4,5,6-四氯 间二甲苯(SS) 13.5 12.8 20.8 10.1 74.8 82.7 82.8 治螟磷 64.8 53.1 98.7 67.3 104 121 119 甲拌磷 94.1 80.7 44.9 43.2 98.4 123 128 脱乙基莠去津 73.6 40.8 80.4 61.2 62.7 0 0 六氯苯 12.6 12.3 19.5 14.7 76.7 81.1 76.2 α-六六六 54.1 44.9 92.7 61.1 89.2 84.5 80.7 内吸磷 120 81.9 5.4 2.7 94.5 44.0 92.1 特丁硫磷 79.7 70.8 39.4 34.0 96.7 110 113 二嗪磷 62.2 50.0 97.4 64.4 99.7 94.0 107 扑灭津 68.8 46.8 104 67.8 97.0 64.1 95.2 莠去津 70.3 43.7 106 64.9 98.0 18.5 62.8 五氯硝基苯 37.7 33.4 68.8 49.4 87.6 90.2 89.0 乐果 41.0 23.4 60.7 40.3 82.9 13.2 28.6 β-六六六 52.4 44.2 90.6 60.5 88.9 83.4 77.4 乙拌磷 102 86.5 6.0 6.4 101 101 105 杀螟腈 63.8 53.0 107 69.9 112 107 121 异稻瘟净 68.8 50.3 108 73.6 92.0 38.4 101 抗蚜威 48.7 23.8 91.6 57.9 80.2 0 46.2 七氯 69.8 73.2 20.1 16.2 87.5 84.8 82.6 乙草胺 64.0 49.3 106 66.1 102 86.4 95.4 γ-六六六 55.4 44.4 93.5 61.4 94.9 87.9 82.5 甲草胺 61.4 49.4 106 68.9 106 98.7 105 甲基毒死蜱 54.6 46.7 89.0 61.0 102 108 109 δ-六六六 58.6 46.8 93.3 61.5 96.9 92.1 87.8 艾氏剂 1.9 2.2 3.2 3.4 94.0 85.0 84.1 甲基对硫磷 65.3 55.7 102 71.6 106 113 115 百菌清 63.6 49.4 119 78.1 107 116 114 特丁净 61.2 35.7 97.1 60.6 108 24.4 98.1 异丙甲草胺 67.9 50.8 104 68.5 108 75.3 101 马拉硫磷 95.2 78.8 130 87.0 104 93.0 107 毒死蜱 56.2 45.1 88.6 60.7 104 106 111 杀螟硫磷 61.5 48.6 96.3 62.5 104 107 107 乙霉威 52.6 51.5 78.2 59.6 88.3 78.5 106 三唑酮 62.5 57.4 98.2 64.7 125 54.9 113 倍硫磷 104 88.9 23.7 39.3 113 111 117 对硫磷 61.9 54.7 97.3 64.0 103 109 107 溴硫磷 54.2 48.3 93.3 61.2 114 108 114 甲基异柳磷 96.2 79.9 124 78.7 108 104 113 水胺硫磷 65.1 49.4 101 68.5 112 62.0 91.7 外环氧七氯B 52.9 44.8 83.4 58.6 108 90.7 90.0 4,4’-二溴联苯(SS) 47.7 41.1 71.1 45.4 99.8 103 100 内环氧七氯A 56.2 48.3 80.9 57.8 108 82.9 84.5 氟菌唑 74.3 31.1 84.4 49.8 86.4 0 24.4 丁草胺 69.7 59.1 97.9 64.7 116 103 109 稻丰散 69.7 60.7 95.9 63.8 129 111 116 喹硫磷 66.2 55.3 96.0 61.3 115 119 119 γ-氯丹 90.5 77.7 60.8 41.2 94.3 96.1 90.6 三唑醇 57.0 40.4 93.3 61.9 105 12.0 36.4 α-氯丹 85.4 80.4 73.9 48.8 95.3 101 95.6 硫丹Ⅰ 55.3 51.6 91.9 60.9 92.6 102 95.2 多效唑 60.7 43.5 94.5 57.2 82.8 0 102 己唑醇 52.9 45.6 85.6 60.5 85.4 0 95.6 杀扑磷 69.3 55.4 94.4 62.9 115 97.2 109 p,p’-DDE 88.3 81.9 48.9 36.5 96.5 104 95.8 狄氏剂 57.2 49.8 88.5 62.6 95.5 99.8 93.3 丙溴磷 70.8 61.1 96.8 66.1 85.9 85.7 139 烯效唑 51.8 49.5 89.2 63.7 92.0 0 58.4 氟硅唑 75.3 51.7 93.8 63.5 100 3.9 72.2 异狄氏剂 61.0 47.8 84.7 66.4 107 99.5 104 腈菌唑 71.5 49.4 98.0 65.1 114 0 35.3 p,p’-DDD 48.4 44.2 59.8 43.6 94.4 97.0 91.4 乙硫磷 90.5 80.3 87.0 63.1 98.4 97.3 91.4 o,p’-DDT 57.5 49.3 82.0 60.1 93.8 96.6 92.2 硫丹Ⅱ 59.6 74.1 86.9 56.4 97.8 92.4 83.5 三环唑 58.3 39.4 87.5 51.0 54.3 0 0 异狄氏剂醛 59.3 42.5 87.9 61.8 99.1 90.0 71.3 p,p’-DDT 55.4 47.7 70.2 54.3 94.7 100.0 93.3 丙环唑 44.5 11.3 85.8 68.1 87.7 28.6 44.5 三唑磷 62.0 61.7 82.5 56.7 94.8 53.3 95.3 硫丹硫酸盐 98.8 84.3 93.5 61.7 98.2 97.5 92.9 戊唑醇 59.1 63.7 79.4 58.1 77.9 29.7 57.5 联苯菊酯 58.5 44.9 66.3 48.3 114 93.5 91.7 甲氰菊酯 72.5 61.5 54.0 47.8 115 102 99.1 二丁基氯菌酸酯(SS) 61.2 39.8 47.1 41.0 125 99.1 90.5 三氯杀螨醇 68.7 54.4 125 83.2 77.9 131 147 甲氧滴滴涕 65.6 53.1 93.9 63.8 115 102 105 苯硫磷 63.8 54.1 91.6 62.7 107 92.7 93.3 异狄氏剂酮 65.5 63.5 97.7 72.1 112 110 111 灭蚁灵 102 89.6 50.4 45.9 94.1 87.6 78.9 三氟氯氰菊酯 61.2 47.9 55.2 42.6 95.4 106 97.5 三氯杀螨砜 60.9 50.8 97.4 66.0 105 97.8 95.9 反式氯菊酯 61.6 47.0 62.6 54.7 99.0 89.7 90.4 顺式氯菊酯 64.4 47.8 65.1 54.3 107 89.4 93.7 氟氯氰菊酯 73.1 54.6 63.5 55.9 81.6 59.0 60.9 氯氰菊酯 70.3 47.3 67.7 55.4 94.5 73.1 75.3 氟氰戊菊酯 66.3 51.1 59.0 52.2 101 80.2 83.0 醚菊酯 61.3 46.0 57.9 46.0 101 96.3 94.2 氟胺氰菊酯 55.2 37.1 69.5 48.6 94.0 79.0 78.1 氰戊菊酯 61.0 57.7 66.0 51.1 97.8 82.8 79.8 溴氰菊酯 70.0 50.4 63.1 47.8 110 148 131 苯醚甲环唑 89.5 83.9 94.4 90.7 97.7 84.0 88.6
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表 3 化合物分段扫描离子和驻留时间
Table 3. Scanning ions in segments and dwell time of each compound
段数 扫描离子(m/z) 切割时间(min) 驻留时间(ms) 1 109, 127, 132, 167, 169, 185, 187, 192 4.5~7.5 100 2 160, 162, 164 7.5~9.0 100 3 60, 88, 89, 209, 242, 244 9.0~10.0 100 4 97, 202, 322 10.0~11.5 100 5 75, 121, 172, 174, 187, 260, 282, 284, 286 11.5~12.3 50 6 60, 88, 89, 181, 183, 219 12.3~13.1 100 7 97, 137, 153, 172, 179, 200, 214, 215, 217, 229, 231, 304 13.1~13.65 50 8 87, 88, 89, 93, 97, 125, 181, 183, 219, 237, 249, 295 13.65~14.9 50 9 91, 109, 123, 125, 184, 188, 189, 204, 243 14.9~15.3 50 10 72, 100, 146, 162, 166, 174, 181, 183, 219, 238, 272, 274 15.3~16.5 50 11 125, 146, 160, 188, 286, 288 16.5~17.25 100 12 66, 181, 183, 219, 261, 263 17.25~18.1 100 13 109, 125, 162, 185, 226, 238, 240, 241, 263, 264, 263, 268 18.1~19.4 50 14 93, 109, 124, 125, 127, 173, 181, 197, 199, 208, 210, 225, 267, 277, 314 19.4~19.8 50 15 97, 109, 121, 125, 199, 231, 278, 291, 329, 331 19.8~21.0 50 16 81, 120, 121, 136, 152, 183, 253, 312, 314, 353, 355 21.0~21.9 50 17 73, 179, 278 21.9~22.9 100 18 112, 121, 125, 128, 146, 156, 157, 160, 168, 176, 188, 274, 373, 375, 377 22.9~23.45 50 19 125, 167, 195, 236, 237, 241, 373, 375, 377 23.45~24.85 100 20 79, 83, 93, 125, 139, 145, 175, 214, 246, 248, 254, 256, 263, 318, 327, 337, 339, 380 24.85~25.8 50 21 70, 81, 233, 234, 236, 263, 265, 315 25.8~28.1 100 22 125, 150, 152, 153, 165, 179, 195, 231, 235, 237, 241 28.1~28.9 50 23 67, 69, 161, 162, 165, 172, 173, 189, 235, 237, 243, 245, 250, 259, 345 28.9~31.0 50 24 97, 99, 125, 165, 166, 181, 250, 252, 272, 274, 387, 388, 390 31.0~33.1 50 25 67, 139, 141, 152, 157, 169, 227, 228, 251, 253, 317 33.1~33.6 50 26 181, 197, 208, 236, 237, 240, 241, 272, 274 33.6~34.1 50 27 111, 159, 163, 183, 184, 227 34.1~35.8 100 28 107, 135, 157, 163, 165, 181, 199, 206 35.8~36.6 100 29 125, 167, 181, 250, 252, 419 36.6~38.2 100 30 181, 253, 255, 260, 264, 265, 323, 325 38.2~40.0 100
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表 4 中国7个省市231个地下水样品农药检出汇总
Table 4. Pesticides detected in 231 groundwater samples of 7 provinces in China
采样地区序号 样品数 样品检出数 农药检出数 农药检出种类 样品检出率(%) 总样品检出率(%) 地区1 13 2 2 莠去津、脱乙基莠去津 15.39 15.58 地区2 28 11 3 莠去津、乙草胺、顺式氯菊酯 39.29 地区3 112 17 12 敌敌畏、速灭磷、六氯苯、乙草胺、α-六六六、γ-六六六、β-六六六、δ-六六六、o, p’-DDT、p, p’-DDT、p, p’-DDD、顺式氯菊酯 15.18 地区4 34 3 3 敌敌畏、莠去津、脱乙基莠去津 8.82 地区5 19 2 1 莠去津 10.53 地区6 2 0 0 / 0.00 地区7 23 1 1 甲基异柳磷 4.35 总计 231 36 15 / / 注：“/”表示没有检出农药。
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