廣東省農(nóng)耕土壤中TBBPA與HBCDs的含量、分布調(diào)查及蓄積水平估算
發(fā)布時(shí)間:2018-01-18 08:00
本文關(guān)鍵詞:廣東省農(nóng)耕土壤中TBBPA與HBCDs的含量、分布調(diào)查及蓄積水平估算 出處:《南方醫(yī)科大學(xué)》2017年碩士論文 論文類型:學(xué)位論文
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【摘要】:研究背景和目的:四溴雙酚A(Tetrabromobisphenol A,TBBPA)和六溴環(huán)十二烷(Hexabromocyclododecane,HBCDs)是目前使用量最大的有機(jī)阻燃劑,被廣泛應(yīng)用于工業(yè)生產(chǎn),已有研究證明二者對(duì)人體健康具有神經(jīng)毒性、發(fā)育毒性、內(nèi)分泌毒性等影響,作為新型的持續(xù)性有機(jī)污染物被廣泛關(guān)注,在空氣、水、河底泥等自然介質(zhì)中均有相關(guān)的檢出報(bào)導(dǎo),而土壤尤其是農(nóng)業(yè)土壤中的研究相對(duì)較少.本研究旨在考查并建立土壤中TBBPA以及HBCDs的3種異構(gòu)體(α-HBCD、β-HBCD、y-HBCD)的提取方法以及HPLC-MS-MS檢測(cè)方法,并用該方法對(duì)廣東省的農(nóng)耕土壤進(jìn)行檢測(cè),目的是探明廣東省農(nóng)耕土壤中兩種阻燃劑的含量、分布、異構(gòu)體的構(gòu)成特征,并對(duì)廣東省農(nóng)耕土壤中TBBPA與HBCDs的蓄積情況進(jìn)行評(píng)估,以期為兩者的污染防治提供依據(jù)。研究方法:1.建立土壤中TBBPA以及HBCDs的3種異構(gòu)體(α-HBCD、β-HBCD、γ-HBCD)的提取方法以及HPLC-MS-MS檢測(cè)方法,并作方法學(xué)考查;2.廣東省農(nóng)耕土壤的采樣;3.用HPLC-MS-MS對(duì)樣品進(jìn)行檢測(cè);4.用SPSS軟件對(duì)檢測(cè)結(jié)果進(jìn)行統(tǒng)計(jì)分析。研究結(jié)果:1.建立了快速、簡(jiǎn)便、穩(wěn)定的HPLC-MS-MS檢測(cè)大批量土壤中的TBBPA和HBCDs的方法,TBBPA以及α-HBCD、β-HBCD、γ-HBCD的定量限分別為0.01、0.02、0.01、0.03 pg·g-1dw,回收率均在 85%~115%之間;2.采集了粵北、粵東、粵西、珠三角地區(qū)6個(gè)市18個(gè)縣的360份土壤樣品;3.廣東省農(nóng)耕土壤中TBBPA與∑HBCDs(α、β、γ-HBCD之和)的含量范圍分別為ND~7.43 ng·g-1dw 和 ND~3.84 ng·g-1dw,均值分別為 0.61 ng·g-1dw 和 0.68 ng·g-1dw;4.在采樣涉及的6個(gè)市中,TBBPA平均含量高低順序?yàn)榉鹕?0.91 ng·g-1dw)湛江(0.90 ng·g-1dw)汕頭(0.82 ng·g-1dw)肇慶(0.44 ng·g-1dw)惠州(0.34 ng·g-1dw)韶關(guān)(0.24 ng·g-1dw),∑HBCDs 平均含量高低順序?yàn)樯穷^(0.98 ng·g-1dw)惠州(0.97 ng·g-1dw)佛山(0.77 ng·g-1dw)湛江(0.72 ng·g-1dw)肇慶(0.35 ng·g-1dw)韶關(guān)(0.28 ng·g-1dw);各采樣市之間的農(nóng)耕土壤中TBBPA濃度和HBCDs濃度均有顯著的地區(qū)差異(方差分析,P0.001),工業(yè)和經(jīng)濟(jì)更發(fā)達(dá)的珠三角地區(qū)農(nóng)耕土壤中的TBBPA與HBCDs濃度明顯高于粵北山區(qū);當(dāng)?shù)刈枞紕┦褂孟嚓P(guān)工業(yè)年產(chǎn)值與∑HBCDs在農(nóng)耕土壤中的污染濃度均有強(qiáng)相關(guān)性(P =0.021,Spearman 相關(guān)系數(shù)=0.829);5.廣東省農(nóng)耕土壤中α、β、γ-HBCD的平均豐度分別為36.1%、9.0%、54.9%,與工業(yè)產(chǎn)品中三者的比例有所不同,說(shuō)明HBCDs在環(huán)境蓄積過(guò)程中發(fā)生了轉(zhuǎn)化與重排;6.廣東省農(nóng)耕土壤中的TBBPA蓄積量為4.57 t,HBCDs的蓄積量為5.10 t,說(shuō)明該兩種化合物在廣東省農(nóng)耕土壤中已經(jīng)達(dá)到一定程度的蓄積。研究結(jié)論:1.廣東省農(nóng)耕土壤中廣泛檢出TBBPA和HBCDs,且二者的濃度要高于工業(yè)不發(fā)達(dá)地區(qū),但蓄積量還未達(dá)到PBDEs的程度;2.TBBPA與HBCDs的分布有明顯的地區(qū)差異,且HBCDs的濃度與阻燃劑相關(guān)工業(yè)的年產(chǎn)值有正相關(guān)性;3.HBCDs的三種異構(gòu)體在環(huán)境中會(huì)發(fā)生轉(zhuǎn)化。
[Abstract]:Background and objective: Tetrabromobisphenol A. TBBPA) and Hexabromocyclododecane (HBCDs) are the most widely used organic flame retardants, which are widely used in industrial production. It has been proved that both have neurotoxicity, developmental toxicity, endocrine toxicity and other effects on human health. As a new type of persistent organic pollutants, they are widely concerned in air and water. There are related reports of detection in natural media such as river bottom mud. The purpose of this study was to investigate and establish three isomers of TBBPA and HBCDs (偽 -HBCD, 尾 -HBCD) in soil, especially in agricultural soil. The extraction method and HPLC-MS-MS detection method of y-HBCD were used to detect the content of two kinds of flame retardants in agricultural soil of Guangdong province. Distribution, composition of isomers, and the accumulation of TBBPA and HBCDs in agricultural soils of Guangdong Province were evaluated. Methods: 1. To establish three isomers of TBBPA and HBCDs (偽 -HBCD, 尾 -HBCD) in soil. The extraction method and HPLC-MS-MS detection method of 緯 -HBCD, and the methodological examination; 2. Sampling of agricultural soil in Guangdong Province; 3. HPLC-MS-MS was used to detect the samples. 4. The test results were analyzed by SPSS software. The result of the study was: 1.The rapid and simple method was established. Stable HPLC-MS-MS was used to detect TBBPA and HBCDs in large quantities of soil, and 偽 -HBCD, 尾 -HBCD. The quantitative limit of 緯 -HBCD was 0.01g 路g-1dw. the recoveries of 緯 -HBCD were between 85% and 115%. 2. 360 soil samples were collected from 18 counties of 6 cities in northern Guangdong, eastern Guangdong, western Guangdong and Pearl River Delta. 3. TBBPA and 鈭,
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