Method for the Analysis of 22 Organochlorine Pesticides and 8 Polychlorinated Biphenyls in Soils and Sediments Using Gas Chromatography
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摘要: 近年来地下水、土壤和沉积物等介质中有机氯农药和多氯联苯分析方法的改善主要集中在样品前处理和分析测试条件等方面，而探讨布点、采样等方面的整套方法较少。本文建立了一套适用性较广的气相色谱法同时测定土壤和沉积物中22种有机氯农药和8种多氯联苯，方法检出限为0.09~0.48 ng/g，平均空白回收率为58.7%~133.7%。针对布点、采样、运输、保存、提取、净化、浓缩、仪器测试、数据处理和提交报告整个过程阐述了方法的有效性和实用性；并对提取、净化、测试等多个环节提供了两种或更多的选择，使方法具有更大的灵活性。本文提出，布点前应根据踏勘样品和前人资料考虑采集不同深度的样品；样品的布点、采集和制备均需选择样品，它们共同决定了样品的代表性；分析方法要灵活运用，对于很少检出的目标化合物可采用允许共峰但分析快速的方法，如果有检出再采用针对性的方法分别测定；样品的测定序列不应为了节约分析成本而过于简单。Abstract: In recent years, the main focus for improving detection methods for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in groundwater, soils and sediments has focused mainly on pretreatment and analysis conditions. Comprehensive methods including sampling point design and sample collection were seldom studied. A new method was has been developed for the simultaneous determination of 22 OCPs and 8 PCBs in soils and sediments by Gas Chromatography coupled with electron capture detection. Method detection limits range from 0.09 ng/g to 0.48 ng/g, and the average recoveries are 58.7%-133.7%. This developed method seems to be a relatively integrated and widely applicable method, including sampling point design, sample collection, transportation, preservation, extraction, clean-up, concentration, determination, data analysis and reporting. Alternative technologies were recommended for extraction, clean-up and Gas Chromatographic condition, etc, which improves the flexibility of the method. The results show that the sampling point design for the samples collected from different depths should be considered on the basis of scouting samples and pre-existing data since the representativeness of samples comprehensively depends on selecting procedure, sampling point design, sample collection and preparation. A flexible Gas Chromatographic condition can be used for those samples with rare target compounds, and a corresponding Gas Chromatographic condition can be used further if special target compounds need to be separated. Sequence of the samples should not be oversimplified in order to save cost.
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Keywords:
- soil /
- sediment /
- organochlorine pesticides /
- polychlorinated biphenyls /
- sampling point design /
- sampling /
- Gas Chromatography
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表 1 不同深度的土壤中DDTs的浓度
Table 1 Concentrations of DDTs in soils with different depth
化合物 土壤样品1
(数据单位：ng/g干重)土壤样品2
(数据单位：ng/g干重)0~20
cm20~40
cm40~60
cm60~80
cm0~20
cm20~40
cm40~60
cm60~80
cmp,p'-DDE 5.04 0.41 23.73 19.76 179.86 233.61 46.01 3.93 p,p'-DDD 1.40 < 0.10 2.27 3.96 1.44 10.43 0.94 < 0.10 o,p'-DDT 2.50 < 0.10 < 0.10 < 0.10 6.19 7.00 < 0.10 0.33 p,p'-DDT 15.11 < 0.10 4.18 3.94 42.41 85.10 7.85 1.33 ∑DDTs 24.05 0.41 30.18 27.66 229.90 336.14 54.80 5.59 
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表 2 不同净化处理的方法回收率
Table 2 Method recoveries for OCPs and PCBs with different clean-up procedures
有机氯农药化合物 方法回收率/% 浓硫酸磺化法 佛罗里硅土柱法 α-HCH 89.8 85.8 β-HCH 90.0 80.8 γ-HCH 89.2 84.3 δ-HCH 105.7 86.1 p,p'-DDE 111.4 96.4 p,p'-DDD 110.4 100.5 o,p'-DDT 117.7 94.0 p,p'-DDT 115.0 112.5 HCB 87.3 82.4 七氯 108.7 118.0 艾氏剂 85.5 76.7 环氧七氯 85.2 95.7 γ-氯丹 86.8 91.9 α-硫丹 86.2 84.1 α-氯丹 87.9 106.3 狄氏剂 27.3 97.9 异狄氏剂 41.7 123.6 β-硫丹 85.9 90.0 异狄氏剂醛 30.4 58.7 硫丹硫酸酯 78.1 86.7 异狄氏剂酮 95.7 88.0 甲氧滴滴涕 75.2 133.7 PCB 28 92.7 82.9 PCB 52 92.9 83.9 PCB 103 92.7 88.6 PCB 101 93.7 86.5 PCB 118 96.5 94.1 PCB 153 96.0 90.3 PCB 138 96.9 94.7 PCB 180 99.0 93.7
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表 3 样品测定序列
Table 3 Sequence of sample for detection
序列次序 分析内容 1 进样口裂解监测溶液 2 正己烷溶液1 3 标准曲线序列(一般4~7个标准) 4 正己烷溶液2 5 实验室空白 6 野外空白 7 样品组1(一般10~20个样品) 8 连续校准溶液1 9 正己烷溶液3 10 样品组2(一般10~20个样品) 11 连续校准溶液2 12 正己烷溶液4 13 重复7~12 14 重复3和4
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表 4 土壤和沉积物中22种有机氯农药和8种多氯联苯的方法检出限
Table 4 Method detection limits of 22 OCPs and 8 PCBs in soils and sediments
序号 目标化合物 方法检出限
/(ng·g-1)1 α-HCH 0.14 2 β-HCH 0.17 3 γ-HCH 0.15 4 δ-HCH 0.18 5 p,p'-DDE 0.14 6 p,p'-DDD 0.20 7 o,p'-DDT 0.29 8 p,p'-DDT 0.38 9 HCB 0.15 10 七氯 0.11 11 艾氏剂 0.12 12 环氧七氯 0.15 13 γ-氯丹 0.14 14 α-硫丹 0.26 15 α-氯丹 0.24 16 狄氏剂 0.24 17 异狄氏剂 0.28 18 β-硫丹 0.30 19 异狄氏剂醛 0.48 20 硫丹硫酸酯 0.27 21 异狄氏剂酮 0.29 22 甲氧滴滴涕 0.34 23 PCB 28 0.11 24 PCB 52 0.13 25 PCB 103 0.09 26 PCB 101 0.12 27 PCB 118 0.15 28 PCB 153 0.18 29 PCB 138 0.10 30 PCB 180 0.12
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