Determination of 16 Typical Chlorinated Persistent Organic Pollutants in Groundwater by Gas Chromatography-High Resolution Mass Spectrometry
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摘要: 9种有机氯农药(α-HCH、β-HCH、γ-HCH、δ-HCH、六氯苯、p,p′-DDE、p,p′-DDD、o,p′-DDT和p,p′-DDT)和7种指示性多氯联苯(PCB 28、PCB 52、PCB 101、PCB 118、PCB 138、PCB 153和PCB 180)是我国地下水水质调查的必测和选测的持久性有机污染物。目前采用的气相色谱-电子捕获检测器和气相色谱-质谱-选择离子监测分析技术，无法对地下水中这16种痕量和超痕量典型含氯持久性有机污染物进行准确的定性和定量分析。本文建立了地下水中16种典型含氯持久性有机污染物的固相圆盘萃取-气相色谱-高分辨质谱分析方法，目标物检出限为0.10~0.20 ng/L，基体加标回收率为61.9%~93.3%，精密度(RSD，n=5)为2.41%~20.0%，能够对地下水中痕量目标物进行准确定性和定量。应用该方法检测了两个地区16个地下水样品中的目标物。结果表明，两地实际样品中均未检出多氯联苯，而普遍检出急性毒性最强的γ-HCH和致癌活性最高的α-HCH，根据α-HCH和γ-HCH浓度的比值可以初步判断，两个地区的地下水样品有受到新的HCH排放源污染的可能性。
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关键词:
- 地下水 /
- 有机氯农药 /
- 多氯联苯 /
- 气相色谱-高分辨质谱法
Abstract: 9 kinds of organochlorine pesticides (α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene, p,p′-DDE, p,p′-DDD, o,p′-DDT and p,p′-DDT) and 7 kinds of polychlorinated biphenyls (PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) were the target compounds of national ground water quality investigation. Until now, the low sensitivity of Gas Chromatography with Electron Capture Detector (GC-ECD) and Gas Chromatography-Mass Spectrometry/Selected Ion Monitoring (GC-MS/SIM) technique have been applied to monitor the quality of ground water, however, these analysis methods are unable to monitor trace and ultra-trace the persistent organic pollutants targeted in ground water. In this paper, a high sensitivity analysis method of the target compounds in groundwater by solid phase disk extraction coupled with Gas Chromatography-High Resolution Mass Spectrometry (GC-HRMS) is described. The detection limits for the target compounds were 0.10-0.20 ng/L, the recovery with standards were 61.9%-93.3% and RSD (n=5) were 2.41%-20.0%. The method was applied for detection of the target compounds in groundwater using samples from two different areas of China. The analytical results show that no PCBs were detected in any of the samples, but two water samples may be contaminated with a new γ-hexachlorocyclohexane emission source according to the detection of α-hexachlorocyclohexane and γ-hexachlorocyclohexane and their residual concentration ratios. -
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图 2 地下水样品中痕量α-HCH、β-HCH和γ-HCH的GC-HRMS色谱图
Figure 2. Analytical results of trace α-HCH, β-HCH and γ-HCH in groundwater sample by GC-HRMS
表 1 目标物的GC-HRMS方法参数、添加回收率和相对标准偏差
Table 1 Detection limits, parameters, and recovery tests of the method
化合物 特征离子 检出限/(ng·L-1) 1.0 ng/L 5.0 ng/L 20 ng/L 回收率/% RSD/% 回收率/% RSD/% 回收率/% RSD/% α-HCH 216.9145，218.9116 0.20 78.2 10.6 75.8 4.09 88.8 17.0 β-HCH 216.9147，218.9116 0.20 83.5 10.6 68.6 2.75 71.5 10.9 γ-HCH 216.9147，218.9116 0.20 83.1 11.4 65.7 12.7 84.4 12.5 δ-HCH 216.9147，218.9116 0.20 87.4 8.48 72.3 10.4 74.7 16.3 六氯苯 283.8102，285.8072 0.10 72.1 9.06 65.8 2.81 61.9 9.32 p,p′-DDE 246.0003，247.9975 0.20 71.6 7.98 62.4 3.69 82.3 8.03 p,p′-DDD 235.0081，237.0053 0.20 74.8 10.0 68.4 9.77 68.2 6.98 o,p′-DDT 235.0081，237.0053 0.20 93.3 12.8 76.2 2.41 63.5 10.5 p,p′-DDT 235.0081，237.0053 0.20 79.0 12.0 79.0 11.5 73.5 20.0 PCB 28 255.9613，257.9584 0.20 78.9 6.26 62.7 10.6 79.3 5.71 PCB 52 289.9224，291.9194 0.20 67.0 12.1 65.8 7.94 64.4 12.6 PCB 101 323.8834，325.8804 0.20 62.6 11.4 62.6 7.16 74.5 2.69 PCB 118 323.8843，325.8804 0.20 75.0 12.3 66.9 7.81 87.4 4.98 PCB 138 359.8415，361.8386 0.20 67.3 9.47 83.2 14.0 86.6 7.09 PCB 153 359.8415，361.8386 0.20 70.2 13.0 63.1 5.38 87.9 11.5 PCB 180 393.8025，395.7995 0.20 80.5 13.2 64.2 2.68 83.6 8.59 
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表 2 东北某地地下水中16种目标物的分析结果
Table 2 Analytical results of target compounds in groundwater from northeast areas of China
化合物 ρB/(ng·L-1) 灌溉水(4 m) 灌溉水(8 m) 饮用水(8 m) 饮用水(8 m) 饮用水(40 m) 饮用水(80 m) α-HCH 0.30 <0.20 <0.20 <0.20 <0.20 <0.20 β-HCH 3.00 1.48 <0.20 <0.20 <0.20 <0.20 γ-HCH 0.50 <0.20 <0.20 <0.20 <0.20 <0.20 δ-HCH <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 六氯苯 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 p,p′-DDE <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 p,p′-DDD <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 o,p′-DDT <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 p,p′-DDT <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 28 0.20 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 52 <0.20 0.22 <0.20 <0.20 <0.20 <0.20 PCB 101 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 118 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 138 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 153 0.37 <0.20 <0.20 <0.20 <0.20 <0.20 PCB 180 <0.20 <0.20 <0.20 <0.20 <0.20 <0.20
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