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典型工业地区及流域沉积物中持久性有机物的分布特征研究

标题: 典型工业地区及流域沉积物中持久性有机物的分布特征研究
英文标题: Distribution of Persistent Organic Pollutants (POPs) in Sediments of Typical Industrial Areas and Basin in China
作者: 刘立丹
出版时间: 2011-01-01
所在大学: 河北农业大学
关键词: 二噁英,多氯联苯,有机氯农药,沉积物,高分辨气相色谱-高分辨质谱
英文关键词: PCDD/Fs,PCBs,OCPs,sediment,HRGC-HRMS
论文级别: 硕士
学位: 学位论文
导师: 王玲%高丽荣
专业: 分析化学
提交时间: 2011
摘要: 持久性有机污染物(Persistent Organic Pollutants,POPs),具有高毒性、难降解性和半挥发性,在环境中可长期存在,通过大气可以长距离传输,危害生态系统和人类健康.目前,探索痕量POPs在多种介质环境中的污染水平已经成为国内外研究的热点.本论文利用同位素稀释高分辨气相色谱高分辨质谱联用(HRGC-HRMS)以及气相色谱-质谱联用(GC-LRMS)分析方法研究了不同类型工业地区及典型流域中二噁英(PCDD/Fs)、多氯联苯(PCBs)、有机氯农药(OCPs)等POPs的污染水平和分布特征.(1)对典型热工业城市唐山以及著名化工生产基地天津塘沽的主要河流表层沉积物中的PCDD/Fs和dl-PCBs污染水平进行了研究.其中唐山陡河沉积物中PCDD/Fs浓度范围为4.14123.7 pg/g,TEQ浓度范围为0.293.55 pg WHO-TEQ/g,而塘沽地区主要河流沉积物中PCDD/Fs浓度范围高达40603.51180923.0 pg/g,TEQ范围为136.03272.3 pg WHO-TEQ/g.唐山和塘沽表层沉积物中dl-PCBs的浓度范围分别为6.73173.6 pg/g和1636.05007.0 pg/g,TEQ范围分别为0.010.16 pg WHO-TEQ/g和2.4447.28 pg WHO-TEQ/g.本研究结果表明,天津塘沽地区河流受到PCDD/Fs和dl-PCBs的严重污染,而唐山地区河流中含量较低,说明唐山的工业生产对河流沉积物中PCDD/Fs和dl-PCBs影响较小;PCDD/Fs同系物指纹图谱特征显示,塘沽地区PCDD/Fs主要来源于历史上PCP和Na-PCP生产.(2)本研究还考察了湖北地区鸭儿湖表层沉积物中有机氯农药残留及其分布特征,利用气相色谱-质谱联用法(GC-MS)对表层沉积物样品中主要的有机氯农药六六六(HCHs)、滴滴涕(DDTs)、六氯苯(HCB)进行了分析,这三类有机氯农药的浓度范围分别为0.8519.8 ng/g,2.234.5 ng/g和0.138.8 ng/g(干重),平均浓度分别为5.0 ng/g,8.7 ng/g和2.2 ng/g(干重).本研究分析结果远低于历史数据,表明鸭儿湖地区的有机氯农药污染已经得到了很大的缓解.与国内外其他地区表层沉积物相比,本研究分析结果及国内其他部分有机氯农药污染区含量相当.沉积物中HCHs和DDTs的分布特征研究表明,沉积物中有机氯农药主要来自于早期的历史残留,近期基本没有新的污染输入.将鸭儿湖地区现在有机氯农药残留与沉积物生态风险评估值相比较,存在一定的生态风险,但风险已较低,不对生态环境构成严重威胁.(3)在对不同特征工业地区研究的基础上,本文也对我国华北地区最大水系海河流域除塘沽段以外的其它河流沉积物中PCDD/Fs、dl-PCBs和OCPs的污染水平及其分布特征进行研究.结果表明,海河流域沉积物中PCDD/Fs和dl-PCBs的浓度范围分别为11.68115.1 pg/g和18.7759.0 pg/g,TEQ浓度范围分别为0.293.05 pg WHO-TEQ/g和0.0301.36 pg WHO-TEQ/g;HCHs、DDTs、HCB的浓度范围分别为0.131.57 ng/g,0.452.48 ng/g和0.374.18 ng/g.同上述污染源相比较,海河流域中PCDD/Fs和PCBs的污染水平与唐山地区相当,但远低于塘沽地区的污染水平,OCPs的污染水平明显低于鸭儿湖的污染水平;同其它地区相比较,海河流域的持久性有机污染物污染水平较低,但由于生物富集性,其污染仍不可忽视.
英文摘要: Persistent Organic Pollutants(POPs)are chemical substances that persist in the environment, bioaccumulate through the food web, and pose a risk of causing adverse effects to human health and the environment. Their persistence in various media facilitates their transport over long distances to remote regions where they have never been used or produced, posing threats to the environment of the whole globe. Consequently, the studies on the fate of POPs in the environment have been the focus of a number of environment field studies. By using isotope dilution/high resolution gas chromatography (HRGC) / high resolution mass spectrum (HRMS) and gas chromatography (GC)/low resolution mass spectrum (LRMS) method, the concentrations, PCDD/Fs, PCBs and OCPs from typical industrial cities and the typical polluted areas were studied. This thesis is mainly concerned with the following aspects:(1) In this study, the levels of PCDD/PCDFs and dl-PCBs in sediments from the rivers of typical thermal industrial city Tangshan and chemical industrial base Tianjin, Tanggu were investigated. The PCDD/Fs concentrations in sediments from Douhe river ranged from 4.14 to 123.7 pg/g, the TEQ concentrations of PCDD/Fs ranged from 0.293.55 pg WHO-TEQ/g. Meanwhile, the concentration of PCDD/Fs in sediments from the main rivers of Tanggu ranged as high as 40603.51180923.0 pg/g, the TEQ concentration reached 136.03272.3 pg WHO-TEQ/g. As to dl-PCBs, the concentration of the sediments from Tangshan and Tanggu were in range of 6.73173.6 pg/g and 1636.05007.0 pg/g respectively, the TEQ concentrations ranged 0.010.16 pg WHO-TEQ/g and 2.4447.28 pg WHO-TEQ/g. Our research demonstrated that Tianjin and Tanggu were heavily polluted by PCDD/Fs and dl-PCBs. Nevertheless, the result that the levels of PCDD/Fs and PCBs in rivers of Tangshan area was lower showed that the chemical industrial contamination in Tangshan was not serious. Moreover, through the PCDD/Fs homologue profiles analysis, the PCDD/Fs pollution in Tanggu area was likely to come from the previous production of PCP and PCP-Na.(2) Occurrence and distribution of organochlorine pesticides (OCPs) in surface sediments of the Ya-Er Lake: HCHs, DDTs and HCB were analyzed by gas chromatograph-mass spectrometery (GC-MS). The concentrations of HCHs, DDTs and HCB were 0.8519.8, 2.234.5 and 0.138.8 ng·g-1 respectively. The levels of OCPs in Ya-Er Lake had been greatly decreased compared with previous data in 1990s. Concentrations of OCPs in Ya-Er Lake were at the same magnitude compared with those of surface sediments collected from other polluted lakes in China. The distribution characters of HCHs and DDTs indicated that the OCPs mainly came from early residues. The risk of OCPs in surface sediments is relatively low when comparing with the ERL and ERM value of risk evaluation. The results indicate that there is no serious threat to the ecological environment.(3) In addition to the study of the various types of industrial areas, we also investigated the distribution characteristics and the status of the PCDD/Fs dl-PCBs and OCPs in the sediments of Haihe River Basin ( except Tanggu reach) which is the largest river system in Northern China. The PCDD/Fs and PCBs concentrations in sediments from Haihe River Basin ranged from 11.68115.1 pg/g and 18.7759.0 pg/g, respectively; The TEQ concentrations of PCDD/Fs and PCBs in sediments from Haihe River Basin ranged from 0.293.05 pg WHO-TEQ/g and 0.0301.36 pg WHO-TEQ/g, respectively. The concentrations of HCHs, DDTs and HCB were 0.131.57 ng/g, 0.452.48 ng/g and 0.374.18 ng/g, respectively. Compared with the pollution source above, the levels of PCDD/Fs and PCBs were almost with those of Tangshan but quite lower than those of Tianjin Tanggu area and the levels of OCPs was greatly lower than that of Ya-er Lake. Additionally, the comparison with other regions illustrated that the contamination level of POPs in Haihe River Basin was low, but due to the bioaccumulation, the pollution should not be ignored.