典型区域土壤与大气中有机磷酸酯阻燃剂污染现状研究
文献类型：学位论文
| 作者 | 董媛 |
| 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 | 傅珊 |
| 关键词 | 有机磷酸酯阻燃剂，垃圾焚烧厂周边，土壤，大气，大气颗粒物，Organophosphate esters solid waste incineration region soil gas particulate matters. |
| 其他题名 | Pollution of organophosphate esters in soil and atmosphere in the typical regions |
| 学位专业 | 环境科学 |
| 中文摘要 | 有机磷酸酯阻燃剂（Organophosphate esters，OPEs）是一种添加型磷系阻燃剂，由于成本较低、阻燃效果好、且具有阻燃剂和增塑剂的双重性质，被广泛的应用于家具、纺织品、溴代阻燃剂的禁用电缆、建筑材料、绝缘材料、涂料、地板抛光剂、液压机液体、电子及日用品等行业。由于其添加在产品中与化合物没有形成稳定的化学键，因此易通过挥发的形式缓慢释放进入环境当中。同时，有机磷酸酯具有持久性有机污染物的半挥发性、脂溶性、与颗粒物有亲和力，能够随着大气进行长距离传输。近年来，随着溴代阻燃剂被禁用，有机磷酸酯作为一种替代型阻燃剂的使用量和生产量逐年增加。此外，有研究表明，有机磷酸酯阻燃剂具有致癌作用、神经毒性作用和内分泌干扰等作用。因此，有机磷酸酯阻燃剂成为环境研究领域的热点话题之一。 对有机磷酸酯阻燃剂的研究从上世纪九十年代才逐渐增加起来，相关研究还不完善。本研究首先建立了适用于土壤和大气样品中 12种有机磷酸酯目标物的分析检测方法。方法分别采用超声和索氏提取法对土壤和大气样品进行提取、硅胶/弗罗里硅土复合柱净化、气相色谱质谱联用进行分析检测。实验结果显示，体积比为 1:1的丙酮和正己烷混合溶液作为提取溶剂提取效果最好，净化过程采用体积比为 6:4的乙酸乙酯和正己烷混合液作为洗脱溶剂能够得到良好的回收率。空白和基质加标回收率的范围在 78%~120%和 72%~118%，相对标准偏差小于12%。采用内标法建立的内标标准曲线，12种目标物表现出了良好的线性相关性（R在 0.998~0.999之间）和方法精确度（RSD<6%）。12种OPEs在土壤样品中的 LOD在0.07~8.7 ng/g，在大气中的 LOD为3×10-3 ~9.8×10 -2ng/m3。 在建立上述分析检测方法的基础上对垃圾焚烧厂和背景区域 86个土壤样品和 32个大气样品（大气、总悬浮颗粒物、PM2.5-10和 PM2.5）中的有机磷酸酯进行分析检测。以背景区域土壤、大气样品中的平均浓度作为背景值。对垃圾焚烧厂周边土壤中有机磷酸酯的浓度水平、污染现状和迁移分布规律进行研究。结果发现，除 TBEP和TCrP没有被检出，其他10种目标物在所有样品中均被检出。垃圾焚烧厂区域土壤中有机磷酸酯总浓度在5.74~2.15×10ng/g，中值为 23.02ng/g，平均值 46.8 ng/g，约是背景值区域浓度的 2倍。有机磷酸酯在距离垃圾焚烧厂近的采样点浓度水平较高，随着距离的增加有下降的趋势，且主要以氯代TCEP、TCPP和非氯代的TPP为主要污染物，其中氯代 OPEs占总量的 76.0%。 对垃圾焚烧厂区域大气中有机磷酸酯的研究发现，气相和颗粒相的总浓度在1.8~30.1 ng/m3，中值为 24.3 ng/m3，平均值为 25.8 ng/m3，约是背景区域的3倍（平均值 8.94 ng/m3）。 OPEs在气相中的浓度水平很低，主要集中在颗粒相，其中以 PM2.5为最主要的污染介质（颗粒相中 79.1%的 OPEs富集在 PM2.5中）。气相中 OPEs以氯代 TCEP和 TCPP为主要污染物，颗粒物中 OPEs以氯代 TCEP、TCPP、TDCP和非氯代的 TPP为主要污染物。垃圾焚烧厂周边常住居民通过呼吸摄入的OPEs的初步风险评估水平明显低于现有的参考剂量，但是由于TCEP、TDCP、TCPP和 TBEP有致癌作用，TnBP和 TPP有神经毒性作用，仍不能忽视环境中 OPEs的存在。垃圾焚烧厂可能是周围环境中 OPEs的来源，但是目前数据还不充分，需要进一步的深入研究。 |
| 英文摘要 | Organophosphate esters (OPEs) are one of the families of persistent organic pollutants (POPs). Because of the low cost and excellent flame retardant properties,OPEs are extensively employed as flame retardant and plasticizers applied in furniture,textiles, cable, building materials, insulation materials, coatings, floor polishes,hydraulic fluids and electronic appliances. Because the additives in such products are not chemically bound to the compounds, they can be released to the surrounding environment over the entire life cycle of the products slowly by abrasion and volatilization. Moreover, OPEs have semi-volatility, lipid solubility and tend to combined with particulate matters, which lead to the long-distance transmission of OPEs. In recent years, with the ban of bromine flame retardants (BRFs), OPEs are considered as suitable alternatives for BFRs, and the usage and production increased rapidly. Besides, researches show that OPEs are carcinogenic, neurotoxic, and endocrine disruption. Therefore, OPEs has been one of the hot topics. Researches about OPEs begin to increase in 1990s, but now the information are deficient. This study was conducted to establish a analytical method for determination of 12 OPEs in soil and atmospheric samples. Soil and atmospheric samples were extracted using ultrasonic and soxhlet extraction with acetone/hexane (1:1, V/V) as the solvent, respectively. Then, cleaned up by silica gel and florisil with ethyl acetate/hexane (6:4, V/V), followed by gas chromatography-mass spectrometry. Experimental results showed that the recoveries of 12 OPEs from spiked blank samples and soil samples with developed method were in the range of 78%~120% and 71%~118%, with relative standard deviations (RSDs) of less than 12%. The correlation coefficients of 12 OPEs in internal standard curve method ranged from 0.998 to 0.999, and the RSDs below 6%. The limit of detections (LODs) in soil and atmospheric samples ranged from 0.07 to 8.7 ng/g and 3×10-3 to 9.8×10 -2ng/m3，respectively. The development method was applied to determine the amount of target OPEs in 86 soil samples and 32 atmospheric samples (include of gas, total suspended particulates (TSP), PM2.5-10 and PM2.5) that were collected from background region and solid waste incineration in Beijing, China. The average concentration of OPEs in soil and atmospheric samples were used as background values. This research was aimed to study the concentration level, pollution situation, regulation of migration and distribution of 12 OPEs in several environmental medium in the solid waste incineration region. The results showed that all target OPEs were detected in all samples, except for TBEP and TCrP. In soil samples in the solid waste incineration region, the total concentration of OPEs were 5.74~2.15×10 ng/g, median and mean concentration were 23.0 ng/g and 46.8 ng/g, which were twice of background values. Moreover, OPEs concentration were higher in the sample sites which near solid waste incineration region than others. Chlorinated TCEP and TCPP were the dominant contaminant, followed by non-chlorinated TPP, and the chlorinated OPEs accounted for 76.0% of the total OPEs. In atmospheric samples in the solid waste incineration region, the total concentration of OPEs (defined as the sum of 12 congeners in gas and TSP) were 21.8~30.1 ng/m3 , the median and mean concentration were 24.3 ng/m3 and 25.8 ng/m3 , which were 3 times higher than background values. The concentration of OPEs in gas samples was low, and OPEs mainly focused on particulate matters. Furthermore, 79.1% of OPEs were in PM2.5. In gas samples, the dominant OPEs were TCEP and TCPP. However, in particulate matters, the dominant OPEs were TCEP, TCPP, TDCP and TPP. Results from a previous risk assessment indicated that the risk to human health was low. However, due to the toxicity of TCEP, TDPP, TDCP, TBEP, TnBP and TPP,there is a potential threat associated with human exposure to OPEs for the residents near the solid waste incineration. As a result, solid waste incineration maybe a potential source of OPEs for environment, but due to the lacking of datas, it is needed to study further. |
| 源URL | [http://ir.rcees.ac.cn/handle/311016/34321]  |
| 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 | 董媛. 典型区域土壤与大气中有机磷酸酯阻燃剂污染现状研究[D]. 北京. 中国科学院研究生院. 2015. |
入库方式： OAI收割
来源：生态环境研究中心
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