北京地区水环境中有机氯农药的研究
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摘要
本论文采用固相萃取前处理技术和气相色谱(电子捕获检测器)方法分析
研究了北京地区重点污染点源(包括工业废水和生活污水)和地表水中有机氯
农药的污染残留情况。论文调查分析了化工废水、冶金废水、医院及其洗涤中
心废水、印钞废水和城市污水等五类重点污染点源中的有机氯农药残留，以及
永定河、妫水河、潮白河、温榆河、密云水库、京密引水渠、洵河、小中河、
大石河、拒马河、小清河、凤河等共12个河流水系的地表水中的有机氯农药残
留。
针对化工废水、冶金废水、医院及其洗涤中心废水、印钞废水和城市污水
五类典型的企事业单位废水的研究结果表明：北京市工业废水和生活污水中检
测到的有机氯农药包括：α-六六六、β-六六六、γ-六六六、δ-六六六、4,4’一
滴滴涕和硫丹I，它们的检出率分别为63．2％、60．5％、92．1％、15．8％、47．4％
和5．26％，检出浓度在0．38～69．6ng／I之间。各种有机氯农药的浓度占总检出浓
度的百分比由大到小分别为：β-六六六(45．1％)>γ-六六六(23．4％)>4，4’-
滴滴涕(19．7％)>α-六六六(8．37％)>δ-六六六(1．82％)>硫丹I(1．58％)，
可见，工业废水和生活污水中的主要有机氯农药污染残留为β-六六六、γ-六六
六和4,4’-滴滴涕。
对污水处理厂的进水(即初沉出水)和出水(即二沉出水)分别进行研究，
发现除了方庄污水处理厂的出水中六六六浓度比进水中略有升高外，清河、高
碑店和北小河三个污水处理厂的出水中的六六六浓度均比进水中浓度有明显的
降低，这说明污水处理厂通过空气曝气活性污泥法，利用微生物的新陈代谢，
能够使污水中的六六六类有机氯农药得到有效去除。
地表水样品共采集了北京周边永定河、妫水河、潮白河、温榆河、密云水
库、京密引水渠、洵河、小中河、大石河、拒马河、小清河、凤河等12个河流
水系的共32个水样。结果表明，地表水样品中检测到的有机氯农药残留包括：
α-六六六、β-六六六、γ-六六六、δ-六六六、4,4’-滴滴涕和硫丹I，它们的
检出率分别为75％、81．2％、90.6％、34.4％、37.5％和9.38％，检出浓度在
0.3l～77.9ng／L之间。地表水样品中检测到的六六六(HCHs=α-HCH+β-HCH+
γ-HCH+δ-HCH)的总浓度为O.54～25.4ng／L,平均值为7.41ng／L，占有机氯农
药总含量的47.3％，滴滴涕的浓度为2.85～77.9ng／L，平均值为20.24ng／L，占总
含量的51．6％。
地表水样品中检测到的六六六各异构体组分含量特征为：β-六六六>γ-
六六六>α-六六六>δ-六六六。这是由于β-六六六的对称性强，化学性质和
物理性质较其他异构体稳定，是环境中最稳定和最难降解的六六六异构体，其
他异构体在环境中会转型为β-六六六以达最稳定状态。
地表水样品中检测到的六六六残留的α／γ值在O.16～3.51之间，且多数样
点的比值小于1，说明样品中的六六六主要来源于以往所使用有机氯农药的残
留，并且没有新的污染输入来源。地表水样品中仅检出了滴滴涕母体化合物，
而没有检出降解产物滴滴伊和滴滴滴，由此可以推断有新的滴滴涕污染排放源。
This paper investigates the residual levels of OCPs in water from the industrial
and urban sewage and several rivers in Beijing by using solid phase extraction(SPE)
and gas-chromatography/electron-capture detection (GC/ECD). This paper
analyzed the residual levels of OCPs in water not only from five kinds of important
contaminative sewage such as chemical industrial sewage, washing sewage, urban
sewage and so on, but also from twelve rivers which concluded Yongdinghe River,
Chaobaihe River, Miyun Reservoir and so on.
The result indicated that there were α-HCH, β-HCH, γ-HCH, δ-HCH, p,p'-DDT
and Endosulfan I which were detected in the industrial and urban sewage water.
Their frequency of check-up were respectively 63.2%, 60.5%, 92.1%, 15.8%, 47.4%
and 5.26%, the concentration of them were 0.38-69.6ng/L. The order of their
concentration percentage were: β-HCH (45.1%)> γ-HCH (23.4%)> p,p'-DDT
(19.7%) > α-HCH (8.37%) > δ-HCH (1.82%) > Endosulfan I (1.58%). It is obviously
that the primary residual OCPs were β-HCH, γ-HCH and p,p'-DDT.
It was found that the concentration of outflow water were reduced greatly than
the enter water in the sewage plant. This showed than the sewage plant can
effectively wipe off the OCPs by the metabolism function of animalcule.
There were α-HCH, β-HCH, γ-HCH, δ-HCH, p,p'-DDT and Endosulfan I
which were also detected in the surface water. Their frequency of check-up were
respectively 75%, 81.2%, 90.6%, 34.4%, 37.5% and 9.38%, the concentration of
them were 0.31-77.9ng/L. The total concentration of HCHs was 0.54-25.4ng/L and
the average value was 7.41ng/L, which occupied 47.3% of OCPs. The concentration
of the p,p'-DDT was 2.85-77.9ng/L and it's average value was 20.24ng/L which
occupied 51.6% of OCPs.
The content order of isomers of HCH was: β-HCH > γ-HCH > α-HCH > δ-HCH.
It was because that β-HCH was very steady and not easy to decomposed and other
isomers would transit into β-HCH.
The values of α/γ in surface water were in the range of 0.16-3.51 and most of
them were less than 1. It indicated that the detected OCPs were most rooted in the
remains of what used before and there were no new contamination origin. It could be
concluded that there were new contamination origin of DDT somewhere because of
there were no DDE and DDD but only matrix compound of DDT were detected in
surface water.
研究了北京地区重点污染点源(包括工业废水和生活污水)和地表水中有机氯
农药的污染残留情况。论文调查分析了化工废水、冶金废水、医院及其洗涤中
心废水、印钞废水和城市污水等五类重点污染点源中的有机氯农药残留，以及
永定河、妫水河、潮白河、温榆河、密云水库、京密引水渠、洵河、小中河、
大石河、拒马河、小清河、凤河等共12个河流水系的地表水中的有机氯农药残
留。
针对化工废水、冶金废水、医院及其洗涤中心废水、印钞废水和城市污水
五类典型的企事业单位废水的研究结果表明：北京市工业废水和生活污水中检
测到的有机氯农药包括：α-六六六、β-六六六、γ-六六六、δ-六六六、4,4’一
滴滴涕和硫丹I，它们的检出率分别为63．2％、60．5％、92．1％、15．8％、47．4％
和5．26％，检出浓度在0．38～69．6ng／I之间。各种有机氯农药的浓度占总检出浓
度的百分比由大到小分别为：β-六六六(45．1％)>γ-六六六(23．4％)>4，4’-
滴滴涕(19．7％)>α-六六六(8．37％)>δ-六六六(1．82％)>硫丹I(1．58％)，
可见，工业废水和生活污水中的主要有机氯农药污染残留为β-六六六、γ-六六
六和4,4’-滴滴涕。
对污水处理厂的进水(即初沉出水)和出水(即二沉出水)分别进行研究，
发现除了方庄污水处理厂的出水中六六六浓度比进水中略有升高外，清河、高
碑店和北小河三个污水处理厂的出水中的六六六浓度均比进水中浓度有明显的
降低，这说明污水处理厂通过空气曝气活性污泥法，利用微生物的新陈代谢，
能够使污水中的六六六类有机氯农药得到有效去除。
地表水样品共采集了北京周边永定河、妫水河、潮白河、温榆河、密云水
库、京密引水渠、洵河、小中河、大石河、拒马河、小清河、凤河等12个河流
水系的共32个水样。结果表明，地表水样品中检测到的有机氯农药残留包括：
α-六六六、β-六六六、γ-六六六、δ-六六六、4,4’-滴滴涕和硫丹I，它们的
检出率分别为75％、81．2％、90.6％、34.4％、37.5％和9.38％，检出浓度在
0.3l～77.9ng／L之间。地表水样品中检测到的六六六(HCHs=α-HCH+β-HCH+
γ-HCH+δ-HCH)的总浓度为O.54～25.4ng／L,平均值为7.41ng／L，占有机氯农
药总含量的47.3％，滴滴涕的浓度为2.85～77.9ng／L，平均值为20.24ng／L，占总
含量的51．6％。
地表水样品中检测到的六六六各异构体组分含量特征为：β-六六六>γ-
六六六>α-六六六>δ-六六六。这是由于β-六六六的对称性强，化学性质和
物理性质较其他异构体稳定，是环境中最稳定和最难降解的六六六异构体，其
他异构体在环境中会转型为β-六六六以达最稳定状态。
地表水样品中检测到的六六六残留的α／γ值在O.16～3.51之间，且多数样
点的比值小于1，说明样品中的六六六主要来源于以往所使用有机氯农药的残
留，并且没有新的污染输入来源。地表水样品中仅检出了滴滴涕母体化合物，
而没有检出降解产物滴滴伊和滴滴滴，由此可以推断有新的滴滴涕污染排放源。
This paper investigates the residual levels of OCPs in water from the industrial
and urban sewage and several rivers in Beijing by using solid phase extraction(SPE)
and gas-chromatography/electron-capture detection (GC/ECD). This paper
analyzed the residual levels of OCPs in water not only from five kinds of important
contaminative sewage such as chemical industrial sewage, washing sewage, urban
sewage and so on, but also from twelve rivers which concluded Yongdinghe River,
Chaobaihe River, Miyun Reservoir and so on.
The result indicated that there were α-HCH, β-HCH, γ-HCH, δ-HCH, p,p'-DDT
and Endosulfan I which were detected in the industrial and urban sewage water.
Their frequency of check-up were respectively 63.2%, 60.5%, 92.1%, 15.8%, 47.4%
and 5.26%, the concentration of them were 0.38-69.6ng/L. The order of their
concentration percentage were: β-HCH (45.1%)> γ-HCH (23.4%)> p,p'-DDT
(19.7%) > α-HCH (8.37%) > δ-HCH (1.82%) > Endosulfan I (1.58%). It is obviously
that the primary residual OCPs were β-HCH, γ-HCH and p,p'-DDT.
It was found that the concentration of outflow water were reduced greatly than
the enter water in the sewage plant. This showed than the sewage plant can
effectively wipe off the OCPs by the metabolism function of animalcule.
There were α-HCH, β-HCH, γ-HCH, δ-HCH, p,p'-DDT and Endosulfan I
which were also detected in the surface water. Their frequency of check-up were
respectively 75%, 81.2%, 90.6%, 34.4%, 37.5% and 9.38%, the concentration of
them were 0.31-77.9ng/L. The total concentration of HCHs was 0.54-25.4ng/L and
the average value was 7.41ng/L, which occupied 47.3% of OCPs. The concentration
of the p,p'-DDT was 2.85-77.9ng/L and it's average value was 20.24ng/L which
occupied 51.6% of OCPs.
The content order of isomers of HCH was: β-HCH > γ-HCH > α-HCH > δ-HCH.
It was because that β-HCH was very steady and not easy to decomposed and other
isomers would transit into β-HCH.
The values of α/γ in surface water were in the range of 0.16-3.51 and most of
them were less than 1. It indicated that the detected OCPs were most rooted in the
remains of what used before and there were no new contamination origin. It could be
concluded that there were new contamination origin of DDT somewhere because of
there were no DDE and DDD but only matrix compound of DDT were detected in
surface water.
引文
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