某工业园区丰水期地下水有机氯农药分布
Distribution of organochlorine pesticides in groundwater of industrial parks during the wet season
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摘要:目的 解析江汉平原工业园区地下水有机氯农药(organochlorine pesticides, OCPs)污染水平。方法 在江汉平原13个工业园区中, 采用整群随机抽样的方法抽取5个工业园区, 采集地下水样本43个, 采用固相萃取结合气相色谱-串联质谱(gas chromatography-tandem mass spectrometry, GC-MS/MS)测定16种OCPs含量; 基于浓度统计与空间对比刻画污染分布; 采用DDTs/HCHs诊断比值、聚类热图以及主成分分析进行组成特征及多变量分析; 采用Spearman秩相关分析探讨OCPs之间及其与水质化学参数的相关性。结果 目标OCPs中, 15种检出率>50%, 其中六氯苯(hexachlorobenzene, HCB)检出率为100%, δ-六氯环己烷(δ-1, 2, 3, 4, 5, 6-Hexachlorocyclohexane, δ-BHC)未检出。ΣOCPs浓度中位数为113.15 ng/L(范围8.38~2 537.35 ng/L), 不同园区地下水中ΣOCPs水平存在统计学差异(P=0.009), B园区ΣOCPs浓度中位数(278.90 ng/L)最高。HCB和2, 2-双(对氯苯基)-1, 1, 1-三氯乙烷(1, 1, 1-trichloro-2, 2-bis(p chlorophenyl)ethane, p, p'-DDT)是各园区地下水中最主要的贡献组分。(DDE+DDD)/ΣDDT整体偏低, α/γ-HCH约为1。聚类分析A、B园区聚为一类, 多数OCPs呈相对高水平富集, 而特征污染组分存在差异。主成分分析结果显示前两主成分累计解释73.9%的总变异, 可较好反映不同地下水样品中OCPs组成差异。OCPs之间普遍呈显著正相关(rs=0.46~0.88)。水化学参数与ΣOCPs线性相关整体较弱, 多元回归与主成分回归解释率有限。结论 工业园区地下水OCPs普遍检出, 局部存在高风险点位与高贡献化合物, 应将HCB及p, p'-DDT等作为优先监测与源头管控对象。Abstract:Objective To characterize the contamination levels of organochlorine pesticides (OCPs) in groundwater from industrial parks in the Jianghan Plain, China.Methods Five industrial parks were selected using cluster random sampling as survey clusters from all 13 industrial parks in the Jianghan plain, and a total of 43 groundwater samples were collected, and the concentrations of 16 OCPs were determined by solid-phase extraction coupled with gas chromatography-tandem mass spectrometry. Based on concentration statistics and spatial comparison, the pollution distribution of OCPs was characterized. Diagnostic ratios of dichlorodiphenyltrichloroethanes and hexachlorocyclohexanes, hierarchical clustering heatmap, and principal component analysis (PCA) were used for compositional characterization and multivariate analysis. Spearman rank correlation analysis was applied to explore the relationships among OCPs and between OCPs and water quality chemical parameters.Results Fifteen of the tested OCPs showed a detection frequency higher than 50%. Hexachlorobenzene (HCB) was detected in all samples, while δ-1, 2, 3, 4, 5, 6-hexachlorocyclohexane was not detected. The median concentration of ΣOCPs was 113.15 ng/L (8.38-2 537.35 ng/L). Significant differences in ΣOCPs levels were observed among groundwater samples from different industrial parks (P=0.009), with the highest median concentration found in Park B (278.90 ng/L). HCB and 1, 1, 1-trichloro-2, 2-bis(p-chlorophenyl)ethane were the dominant contributors to OCPs in groundwater across all parks. The overall (dichlorodiphenyldichloroethylene+dichlorodiphenyldichloroethane)/Σdichlorodiphenyltrichloroethanes ratio was relatively low, and the α/γ-hexachlorocyclohexanes ratio was approximately 1. Hierarchical clustering analysis showed that samples from Parks A and B were grouped together, with most OCPs exhibiting relatively high levels, although the characteristic pollutant compositions differed between the two parks. PCA revealed that the first two principal components explained 73.9% of the total variance, effectively reflecting the compositional differences of OCPs among groundwater samples. Significant positive correlations were generally observed among OCPs (rs=0.46-0.88). The linear correlations between water quality chemical parameters and ΣOCPs were generally weak, and the explanatory power of multiple regression and principal component regression was limited.Conclusion OCPs were widely detected in groundwater from industrial parks, and localized high-risk hotspots and high-contribution compounds were identified. HCB, 1, 1, 1-trichloro-2, 2-bis(p-chlorophenyl)ethane, and other dominant contributors should be prioritized for routine monitoring and source-oriented control.
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