| 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 |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/34356]  |
| 专题 | 生态环境研究中心_环境化学与生态毒理学国家重点实验室 |
| 推荐引用方式 GB/T 7714 | 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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