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题名: 极地环境中有机氯农药的分析方法及其分布特征研究
作者: 陈昭晶
学位类别: 硕士
答辩日期: 2015-05
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 张庆华
关键词: 高分辨气相色谱/高分辨质谱,有机氯农药,南极,北极,土壤,植物,high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS), organochlorine pesticides (OCPs), Antarctica, the Arctic, soil, vegetation.
其他题名: Analytical Method and Environmental Distribution of Organochlorine Pesticides in Polar Regions
学位专业: 环境工程
中文摘要:     持久性有机污染物(Persistent Organic Pollutants, POPs)具有高毒性、环境持久性、生物富集性和长距离迁移能力。有机氯农药(organochlorine pesticides, OCPs)是环境中典型的POPs物质,主要来自于人为活动。大部分OCPs如六氯苯(HCB)、滴滴涕类(DDTs)、六六六类(HCHs)及氯丹类化合物(CHLs)等已被大部分国家禁止或限制使用多年,然而 OCPs在全球环境中仍存在普遍检出,包括极地和偏远山区。本论文即针对极地环境样品中痕量 OCPs,应用高分辨气相色谱-高分辨质谱联用技术(HRGC-HRMS),对南极长城站和北极黄河站区域的土壤、沉积物和植物等多种环境介质进行分析检测,揭示了污染物浓度水平、分布特征以及可能的来源。全文主要开展了以下三方面工作:
(1)优化了样品前处理过程,建立了同位素稀释(Isotopic dilution,ID)/HRGC-HRMS法同时分析极地样品中23种OCPs的分析方法。样品经冷冻干燥、研磨处理后用正己烷:二氯甲烷(1/1,v/v)混合溶剂进行加速溶剂萃取(ASE),萃取液经中性硅胶-氧化铝复合柱和 C18SPE柱净化后,进  HRGC/HRMS检测分析。以同位素标记的  OCPs同类物为内标,采用平均相对响应因子法对目标物进行定量,6点标准曲线响应因子的相对标准偏差(RSD)≤20%,标准曲线的线性范围为 0.4-800μgL-1.基质加标法测定的回收率在 62%-101%之间。将本方法应用于实际样品分析,OCPs在土壤、苔藓和地衣样品中的检出限(Limits  of detection,LODs)分别为 0.024-5.01pg•g-1,0.2-12.2 pg•g-1和0.020-13.7 pg•g-1,同文献报道的 GC-ECD和GC-MS方法相比检出限降低一个数量级以上,因此能够更好地满足极地环境样品中 OCPs的检测分析。
(2)应用该方法,针对南极长城站区域环境中   OCPs的浓度水平、分布特征和来源进行了研究。对土壤、底泥、苔藓和地衣样品的分析结果显示,OCPs浓度总体上相对较低。土壤和底泥、苔藓以及地衣中 OCPs总含量分别为412 (93.6-1260),492 (223-1053)以及635 (373-812)pgg-1干重(dw),粪土中OCPs含量高于普通土壤。六氯苯(HCB)、滴滴涕类(DDTs)和六六六类(HCHs)为主要的OCPs污染物,而氯丹类化合物(CHLs)、艾氏剂、狄氏剂、异狄氏剂和灭蚁灵的浓度及检出率相对偏低。对 OCPs单体比值的分析表明,该地区  HCHs受到工业产品和林丹两种源的共同影响,DDTs和  CHLs则分别受到工业滴滴涕和工业氯丹产品旧源的影响。土壤和底泥样品中多种   OCPs的浓度与相应的总有机碳(TOC)含量呈线性正相关。
(3)对北极新奥尔松和伦敦岛OCPs的污染水平、分布特征和来源进行了研究。OCPs在北极地区的环境样品中存在普遍检出。土壤样品中 Σ23OCPs的平均浓度为184pg g-1dw,浓度范围在 124-258pg g-1dw之间。六种植物样品中的Σ23OCPs的平均浓度在711pgg-1dw-3212pg g-1dw之间,比南极植物中  OCPs的浓度高出约一个数量级。六氯苯(HCB)、滴滴涕类(DDTs)、六六六类(HCHs)及氯丹类化合物(CHLs)是主要的 OCPs污染物。样品中  α-HCH/γ-HCH和   p,p'-DDE/p,p'-DDT的比值计算表明,该地区   HCHs的存在受到工业品   HCH和林丹(γ-HCH)的共同作用,而 DDTs的存在主要来自工业品   DDT的历史残留。对土壤-植物体系中 20种 OCP化合物的 BAFs值与其  LogKOW值之间关系的分析结果表明,植物对 LogKOW值在  6.1附近的  OCP化合物的生物富集因子最大。
英文摘要:     Persistent  organic  pollutants  (POPs)  have  high toxicity,  high  persistence  in  the environment, bioaccumulation  and   long-range  transport  potential.  Organochlorine pesticides (OCPs)  are defined as  a typical class  of POPs  in the environment,  mainly from anthropogenic sources. Usage of many OCPs (HCB, HCHs, DDTs and CHLs, etc.)has been banned or restricted in most countries for  many years, however, they are still detected ubiquitously in the  world. In this thesis, high  resolution gas chromatography coupled with high resolution mass spectrometry (HRGC/HRMS) was adopted for trace OCPs in Polar  Regions. The contamination levels,  distributions and sources of  OCPs were  investigated by  analysis  of soil,  sediment  and  vegetation samples  around  the Chinese  Antarctic Great  Wall Station  and  the Chinese  Arctic  Yellow River  Station areas.The main contents include the following three parts:
     First,  sample preparation  process was  optimized  and  an analytical  method  using isotope  dilution  (ID)/HRGC-HRMS   for  twenty-three  OCPs   was  developed.13C-labelled OCPs were  used as internal  standards. The average  relative response factors (RRF) calculated  by six  calibration standards  were applied  for the  quantification of target compounds,  of which  the relative  standard deviations (RSD)  were lower  than 20 %. The linear  range and the recoveries of  this method was 0.4-800μg L-1and 62-101 %, respectively. The limits of detection (LODs) of field samples were in the rangeof 0.024-5.01 pgg1 , 0.20-12.2 pg g1and 0.020-13.7 pg g1 in soils, mosses and lichens. Compared with reported GC-electron capture detector (ECD) and GC-MS methods, the LODs were  up to  one order of  magnitude lower,  which satisfy  the determination  of OCPs in polar environmental samples.
    Secondly, concentration levels, distributions and sources of twenty-three OCPs from west Antarctica were  investigated. Soil, sediment, moss  and lichen samples collected from  Fildes  Peninsula, King  George  Island  and  Ardley  Island in  2009-2010  were selected for analysis.  The concentrations of Σ23OCPs were at  quite low levels,  in the range of 412 (93.6-1260) pgg-1 dry weight (dw) in soil and sediment, 492(223-1053)dw in lichen. Higher OCP levels were found pg g-1dw in moss and 635 (373-812) pg g-1 in  the   dropping-amended  soil  than   the  natural  soil.   Hexachlorobenzene  (HCB), dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCH isomers)
were the most abundant contaminants in all the samples, whereas chlordane compounds,aldrin,  dieldrin, endrin,  and  mirex  were detected  at  low frequencies.  The  ratios  ofisomers indicated that  HCHs in Antarctica were  affected by the combined  sources of“old” technical HCH  and “recent” lindane, whereas  DDTs and chlordane compounds were  from  aged  source of  technical  DDT  and  chlordane,  respectively.  Significant dependence of  Σ23OCPs  concentrations on  total  organic carbon  (TOC) content  was observed, especially for HCB, HCH (α-, β-, γ-), p,p′-DDE, HCHs and DDTs (R  = 0.24-20.74; p ≤ 0.05).
    At last, twenty-three  OCPs were determined in soil,  moss, sooty sedge, arctic bell-heather,  mountain avens,  tufted  saxifrage and  alpine  hair grass  collected  from Ny-Ålesund and London Island, Svalbard, the Arctic during 2010 and 2011, to investigate their   levels,   distributions  and   sources.   OCPs   generally   exist   in  the   samples.Concentrations of Σ23OCPs  were in the range  of 184 (124-258)pg g-1 dw  in soil and711-3212pg g-1dw  in six  vegetations, which  were higher  than that  in the  Antarctic vegetations. HCB,  DDTs ,HCHs and  CHLs were the  most abundant contaminants  in the Arctic samples. The ratios of α-HCH/γ-HCH indicated that HCHs in the Arctic were
affected by the combined sources of technical HCH  and lindane, whereas the ratios of p,p'-DDE/p,p'-DDT   suggested   that  DDTs   mainly   from   the   historical   residues. Vegetations got the biggest BAFs to OCPs with LogKOW value around 6.1.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/34356
Appears in Collections:环境化学与生态毒理学国家重点实验室_学位论文

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Recommended Citation:
陈昭晶. 极地环境中有机氯农药的分析方法及其分布特征研究[D]. 北京. 中国科学院研究生院. 2015.
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