合成麝香和甲基硅氧烷在典型区域的环境行为及生物暴露研究

CORC > 生态环境研究中心 > 中国科学院生态环境研究中心 > 环境化学与生态毒理学国家重点实验室

题名	合成麝香和甲基硅氧烷在典型区域的环境行为及生物暴露研究
作者	刘楠楠
学位类别	博士
答辩日期	2014-05
授予单位	中国科学院研究生院
授予地点	北京
导师	蔡亚岐
关键词	甲基硅氧烷合成麝香分析方法环境介质暴露水平 Methyl siloxanes Synthetic musks Analytical methods Environmental matrices Human exposure
其他题名	Occurrence and biological exposure of synthetic musks and methyl siloxanes in typical areas of China
学位专业	环境科学
中文摘要	本文的研究工作主要围绕典型区域环境介质中合成麝香（SMs）和甲基硅氧烷的污染水平、分布特征及生物和人群暴露情况展开，论文分为以下六章：第一章介绍 SMs和甲基硅氧烷污染现状、环境行为、生物毒性效应等领域相关研究的发展趋势。第二章建立并优化了气相色谱/质谱联用 (GC/MS)技术检测水体、沉积物、大气、灰尘/土壤、生物样本及人体血液等样品中 SMs（硝基麝香和多环麝香）和甲基硅氧烷（D4-D6，L4-L16）的分析方法，讨论了方法的检出限、回收率、精密度和线性范围等。结果表明，分析方法可靠、准确，各项指标均可满足实际样品的分析检测。第三章详细讨论了 SMs和甲基硅氧烷在全国 42个污水处理厂消化污泥中的污染水平和分布特征，同时评估了这两类污染物所带来的生态风险。结果发现一些人口密度大的大城市，如北京、杭州、广东中山等污水处理厂样品中 SMs的浓度较高。环形硅氧烷的浓度高于线形硅氧烷，且与污水处理厂的处理量成明显正相关关系。东营某石化产业园区内污水处理厂中硅氧烷浓度水平远高于其他地区。通过考察影响污泥中目标污染物浓度的潜在因素发现，污水来源、污泥 TOC、污水处理量及污水处理厂服务人口等可以影响到消化污泥中污染物的浓度水平。通过风险评估发现，当这些污泥被用作生物肥料施肥于农田时，两类污染物所带来的生态风险比较低或者可以忽略。SMs和甲基硅氧烷在污水处理厂中较高的浓度及检出率说明了这两大类污染物在中国存在普遍污染状况。第四章系统研究了东营某石化产业园区甲基硅氧烷的污染情况。结果表明甲基硅氧烷广泛存在于产业园区、周边各种环境介质及生物样品中。产业园区内部的室外大气和灰尘样品中的甲基硅氧烷浓度比对照区域高 1-2个数量级，且其在大气和土壤中的浓度以产业园区为中心向周边各个方向辐射降低。与对照地区及周边环境相比，产业园区内部环境介质中检出的甲基硅氧烷种类较多，检出频率较高，平均浓度较高。上述结果说明石化产业能够带来较为严重的硅氧烷污染。第五章系统研究了 SMs和甲基硅氧烷在职业和普通场所室内灰尘中的污染状况，评估了职业与普通人群的 SMs暴露情况。结果发现职业场所（理发店）室内灰尘中 SMs和甲基硅氧烷的浓度比普通场所中高约 1-2个数量级，理发师对 SMs的高暴露水平已经达到了 2791 ng/d。然而，通过对职业和普通人群的全血样本检测发现，SMs在职业人群中的浓度仅略高于普通人群（p < 0.05），说明SMs在人体血液中不易累积。但是，由于这类污染物的亲脂性结构，其在人体脂肪或器官中的累积问题应引起人们重视。第六章研究了装修过程中的房屋、普通家庭及汽车内部空气中的硅氧烷污染水平特征。结果表明，装修过程中的房屋室内大气中甲基硅氧烷的浓度最高，其次是普通家庭，汽车中甲基硅氧烷浓度最低。三类场所室内空气中硅氧烷的浓度都远远高于对照室外大气。说明室内装修、居民日常生活及汽车使用都能带来较为广泛的甲基硅氧烷污染。
英文摘要	The objective of this dissertation is to investigate the occurrence and fate of synthetic musks and methyl siloxanes in environmental matrices, organisms and human blood in typical areas of China, and their human exposure to targets compounds. It consists of the following seven chapters. In the first part, pollution occurrence, environmental behavior, toxicological effects, and determination of synthetic musks and methyl siloxanes were reviewed. In the second part, the analytical methods were developed to measure synthetic musks and cyclic/linear methyl siloxanes in human blood, sediment, dust/soil, water, air and fish samples. The methods are accurate, rapid and suitable for the inspection of target compouds in real samples. In the third part, we systematically investigated occurrence and distribution patterns of seven synthetic musks (SMs) and 17 siloxanes in anaerobic digested sludge samples collected at the dewatering process from 42 wastewater treatment plants (WWTPs) in China. SMs in sludge from different WWTPs exhibited similar composition profiles, and their total concentrations ranged from 47.3 ng/g to 68.2 µg/g dry weight (dw). The total concentrations of cyclic siloxanes ranged from In the fourth part, the occurrence and fate of three cyclic (D4-D6) and 13 linear (L4-L16) siloxanes were studied in environmental matrices and biological sample around a petrochemical industrial park of Dongying, China. In the studied industrial park, the siloxanes in air and soil had significantly higher concentrations and detection frequencies than those from outside the park. The total concentrations of methyl siloxanes ranged from 4.18 - 76.6 μg/m3, which were much higher than those in the reference park (90.6 - 356 ng/m3).The total concentrations of VMS (D4-D6, L4 and L5, 4.13 - 76.1 μg/m-3) were up to 2 - 4 orders of magnitude higher than those of semivolatile methyl siloxanes (ΣSVMS, 20 - 205 ng/m3) including L6 - L16 in the air from this studied park. The concentrations of siloxanes in soil samples from 11 factories (mean: 645.3 ng/g) were higher than those along the roadsides inside the studied park (mean: 110.4 ng/g), than for those outside the park (65.2 ng/g). The different profiles of siloxanes in surface water and sedimentin R1 (river 1), R2 (river 2) and R3 (river 3) indicated that, R3 had different siloxane pollution sources with R1 and R2. Meanwhile, an apparent influence of petrochemical industries on R1 and R2 was observed. The concentrations of methyl siloxanes in 12 fish collected from R2 were higher than those in previous studies. On the whole, the petrochemical industry might bring the serious methyl siloxanes pollution to the environment, and the caused ecological risk should not be neglected. In the fifth part, the levels of two nitro musks and five polycyclic musks, three cyclic (D4-D6) and 13 linear (L4-L16) siloxanes in indoor dust were measured. These samples were collected from barbershops, dormitories, bathhouses and households. The concentrations of∑SMs and∑siloxanes in barbershop dusts were 10 to 100 times higher than those from the other three indoor microenvironments. Polycyclic musks accounted for 89.4% of∑SMs on average in all samples, of which two compounds, HHCB and AHTN jointly dominated 97.9% of polycyclic musks. The levels of HHCB and AHTN varied from 12.2 to 8.39×105 and from 13.2 to 3.49×105 ng/g, respectively. As for siloxanes in dust samples, D4-D6 and L9-L14 were the dominat compounds. The concentrations of D5 and L11 were the highest, the mean concentrations of which were 2.56×103 and 2.13×103 ng/g. The daily intakes (DIs) of ∑SMs through house dust ingestion were estimated using the model of high dust ingestion and worst-case exposure (P95), and the corresponding exposure rates were 2791, 135 and 727 ng d−1 for the hairdressers, general population and toddlers, respectively. SMs were also detected in blood samples collected from the hairdressers and normal adults (n = 50 and 10, respectively). The concentrations of SMs in hairdressers were slightly higher than those from general population (p < 0.05). Despite the absence of significant gap about SMs concentrations among two populations’ blood, we should not overlook the potential occupational health risks due to their high SMs ingestion rate. In the sixth part, the occurrence and distribution of both cyclic and linear methyl siloxanes were systematically studied in indoor air samples collected from the houses under decoration, common housing and the cars. The results showed that the levels of siloxanes detected in houses under decoration were higher than those from the common housing and the cars. Siloxanes in common housing were mainly from the use of personal care products. High levels and detection rates of methyl siloxanes in houses under decoration indicated that the decorative building material (oil paint,furnitures, sealants and wall stickers) may induce methyl siloxanes contamination. The siloxanes polutions from the decoration and car oil in cars should not be ignored.
公开日期	2015-07-07
内容类型	学位论文
源URL	[http://ir.rcees.ac.cn/handle/311016/15633]
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	刘楠楠. 合成麝香和甲基硅氧烷在典型区域的环境行为及生物暴露研究[D]. 北京. 中国科学院研究生院. 2014.