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题名: 城市污水处理与工业应用过程中有机磷酸酯阻燃剂的 迁移转化研究
作者: 梁钪
学位类别: 博士
答辩日期: 2016-05
授予单位: 中国科学院研究生院
授予地点: 北京
导师: 刘景富
关键词: 有机磷酸酯阻燃剂,分析方法,污水处理厂,阻燃剂使用工厂,迁移 转化 ; Organophosphate flame retardants, Analysis method, Sewage treatment plant, Factory using flame retardants, Transport and transformation
其他题名: Transport and Transformation of Organophosphate Ester Flame Retardants in the Processes of Municipal Wastewater Treatment and Industrial Application
学位专业: 分析化学
中文摘要:     有机磷酸酯(Organophosphate  esters,OPEs)阻燃剂是一类常用的高产量阻燃剂。由于溴代阻燃剂在全球范围内的逐渐禁用及其本身良好的阻燃性能,OPEs被广泛应用于日常生活和工业生产的各个领域。在大量生产和使用的同时,OPEs会不断进入环境,目前已经在各种环境介质中被普遍检出。由于其潜在的环境和健康风险,近年来 OPEs成为了研究热点。目前,关于  OPEs的研究主要集中在分析方法、污染状况调查及毒理方面,而有关环境过程的研究却十分有限。本论文首先建立和完善了污水、污泥、土壤和灰尘等多种环境介质中OPEs的分析方法,在此基础上对典型环境过程中  OPEs污染现状、分布特征和迁移转化进行了研究,论文分为以下五章:
    第一章介绍了  OPEs阻燃剂在环境介质中的污染现状、环境行为和毒性效应等领域的研究进展,并对目前主流的 OPEs阻燃剂分析方法进行了讨论。
    第二章基于超高效液相色谱-串联质谱(UPLC-MS/MS)建立了污水、污泥、土壤和灰尘中 14种常用  OPEs的分析方法,以及人体尿液中  5种  OPEs代谢产物的分析方法。污水样品加标回收率为 43.6%-119%,检出限为 0.30-6.00 ng/L;污泥、土壤和灰尘样品的加标回收率分别在 68.1%-114%、53.1%-121%和54.0%-119%之间,检出限分别为 0.60-3.00 ng/g、0.03-1.38 ng/g和  0.60-9.68 ng/g;人体尿液样品的加标回收率为 54.2%-91.2%,检出限为 0.03-0.36 μg/L。各方法的加标回收率和重现性表现良好,适用于多种环境介质中  OPEs污染现状和迁移转化的研究。
    第三章对城市污水处理过程中  OPEs的迁移行为和去除进行了研究。选取北京某典型污水处理厂为研究对象,连续三天采集了各个处理流程的出水和污泥样品,在分析污水和污泥中OPEs浓度的基础上,应用质量通量和质量平衡计算,深入研究了 14种  OPEs在污水深度处理过程中的迁移和去除行为。结果表明,OPEs在所有污水和污泥样品中均有检出,其在污水进水水相、三级出水水相及脱水污泥中的总浓度分别为 1399 ng/L,833 ng/L和315 ng/g干重。进水中总OPEs分别有53.1%和 6.3%转移到出水和脱水污泥中,其余 39.9%和0.7%分别在生物处理和物化处理中被去除。在污水处理过程中,活性污泥处理系统对污水中 OPEs的去除起了重要作用,而由疏水作用主导的污泥吸附比较有限。各 OPE在活性污泥处理过程中降解程度与其分子结构相关。
    第四章研究了  OPEs在工业应用过程中的迁移和转化行为。选取北京某使用 OPEs生产建筑防火板的工厂为研究对象,研究了14种  OPEs在工厂内部及周边环境中的污染特征及环境行为,同时通过对职工尿液样品中OPEs代谢产物的分析考察了OPEs从厂内环境向人体的迁移转化行为。结果发现,工厂内宿舍和办公室的灰尘中 OPEs浓度水平(17.9-1456.5µg/g)远高于工厂内土壤中OPEs总浓度2.68-88.3µg/g),厂内土壤中 OPEs总浓度又远高于工厂周边土壤中的浓度(0.004 -2.18 µg/g);在工厂内及工厂周边土壤和灰尘样品中,工厂的主要生产原料磷酸三(2-氯)乙酯(Tri(2-chloroethyl)  phosphate,TCEP)是主要污染物,表明工厂的生产活动对厂内及周边环境造成了明显的污染;工厂周边土壤中 OPEs的浓度受盛行风向影响明显;同时,工厂职工尿液中TCEP代谢产物磷酸二(2-氯)乙酯(bis(2-chloroethyl)  phosphate,BCEP)的浓度水平(中位值 32.1 μg/L)明显高于对照组(中位值 3.10 μg/L)及国外报道,表明工厂的生产活动对职工身体健康造成潜在威胁。
    第五章主要基于 UPLC-MS/MS和固相萃取(SPE)技术,建立了污水和污泥中2,2-二(氯甲基)-1,3-丙二醇-双[双(2-氯乙基)磷酸酯   ](2,2-bis(chloromethyl)-propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate,V6)、双酚 A双二苯基磷酸酯(bisphenol  A bis(diphenylphosphate),BDP)和间苯二酚四苯基二磷酸酯(resorcinol bis(diphenylphosphate),RDP)三种低聚合 OPEs的分析方法,并将其用于分析北京市某污水处理厂中这三种物质的污染水平。污水和污泥水相样品和固相样品中三种物质的加标回收率分别在57.3%-125%与69.6%-136%之间,分析方法的检出限分别为 0.30-0.50  ng/L和  0.13-0.15 ng/g,该方法具有较高的灵敏度和选择性。将其应用于污水厂污水和污泥样品分析,在污水和污泥固相悬浮颗粒物中首次检测到了 BDP和  RDP。与其他 14种常用的单分子 OPEs相比,污水和污泥中  V6、BDP和  RDP浓度水平较低。










英文摘要:     Organophosphate esters  (OPEs) are  a high  volume production  retardants  with good  performance.  Owing  to  the  worldwide ban  of  brominated  flame  retardants (BFRs),  OPEs is  widely  used in  daily  life and  industrial  manufacture. With  their extensive production  and usage, OPEs  are widely present  in various  media. Due to their potential environmental  and health risk, OPEs  have become a research  hotspot in recent  years. At present,  the research  of OPEs is  mainly focused on  the analysis methods,   environmental    pollution   level   and    toxicology,   while   research    on environmental processes is very limited.
    The aim of  this dissertation is  to develop reliable analytical  methods for OPEs in various  matrices and investigate  the occurrence, distribution and  fate of OPEs  in some typical environmental processes. It consists of the following five parts.
    In  the  first  part,  we  reviewed  the  pollution  status,  environmental  behavior, toxicological effects and analytical methods of OPEs.
    In   the   second  part,   a   series   of   analytical   methods   were  developed   to simultaneously analyze  14 commonly used  OPEs in sewage  water, sludge,  soil and dust samples. At the same time, method for analysis of 5 OPEs metabolites in human urine was also  developed. For the aqueous samples  of sewage water and sludge,  the spiked recoveries and method detection limits (MDLs) of  14 OPEs were in the range of  43.6%-119% and  0.30-6.00 ng/L,  respectively;  for suspended  solids  of sewage water/sludge, soil  and indoor dust  samples, the spiked  recoveries were in  the range of 68.1%-114%,  53.1%-121%, and  54.0%-119%, respectively, and  the MDLs  were in the ranged  of 0.60-3.00 ng/g,  0.03-1.38 ng/g and  0.60-9.68 ng/g, respectively; as for   human  urine   samples,  the   spiked   recoveries  and   MDLs   were  ranged   in 54.2%-91.2%  and   0.03-0.36   μg/L,  respectively.   These   methods  were   reliable,showing high sensitivity, good recovery and repeatability. They can  meet the need of OPEs analysis in the environment.
    In the third part, we studied the distribution,  degradation and fate of OPEs in an advanced municipal  sewage treatment  plant (STPs)  in  Beijing, China.  A three-day sampling  was   carried  out   at  the   outlet  of   all  treatment   steps.  Based   on  the concentration of  OPEs in sewage  and sludge, mass  flow and mass  balance analysis were conducted to  gain an insight  into the behavior and  fate of 14  OPEs during the sewage treatment.  The results showed  that OPEs were detected  in all sewage  water and sludge samples with total OPE concentrations of 1399 ± 263 ng/L in raw sewage aqueous phase, 833 ± 175 ng/L in tertiary effluent  aqueous phase, and 315 ± 89 ng/g dry weight in  dewatered sludge. Mass  balance results showed  that 53.1% and 6.3% of  the  initial  OPE   mass  flow  were  eventually   transferred  to  the  effluents  and dewatered sludge,  respectively, while the  remaining 39.9% and  0.7% were lost  due to biodegradation and physical-chemical treatment, respectively. It was indicated that the activated sludge treatment  system with anaerobic/anoxic/aerobic bioreactors was a  major  factor  in  the removal  of  OPEs  from  the  raw  sewage,  while  transfer  to dewatered  sludge  governed  by  hydrophobic  interactions   was  limited  during  the sewage  treatment.  Meanwhile,  the   degradation  difference  of  OPEs  in   activated sludge   treatment  was   more  related  with   their   molecular  structure   over   their hydrophobicity.
    The  fourth  part  focused  on  the  transport  and  transformation  of  OPEs  in  a factory of producing fire-proof materials using OPEs. We studied  the occurrence and behavior of  14 OPEs in  both inside and  surrounding environment of  the factory, as well  as the  transport and  transformation  of OPEs  to/in  human body  based  on the analysis of OPEs metabolites  in workers’ urine samples. The results showed that  the OPEs concentrations  in  house dust  samples (17.9-1456.5µg/g)  of staff  dormitories and offices were  much higher than that of  soil samples inside the factory  (2.68-88.3µg/g), while  the OPEs concentrations  in soil samples  inside the  factory were much higher than that of soil samples surrounding the factory (0.004 -2.18 µg/g); The main raw  material  of  the  factory  production,  tri(2-chloroethyl)phosphate  (TCEP),  was found to be the predominant  OPEs in almost all the soil and dust  samples inside and surrounding the factory, indicating that the production of the factory caused pollution to its  inside  and surrounding  environment. The  horizontal  distribution of  OPEs in surface soil  surrounding  the factory  was significantly  influenced by  the prevailing wind direction;  Meanwhile, the  concentration level of  bis(2-chloroethyl) phosphate(BCEP) (median  32.1  μg/L) as  the metabolite  of TCEP  in workers’  urine samples was one order of magnitude higher than that in control group (median 3.10 μg/L) and European  countries, indicating  that  the production  of  the factory  pose  a  potential threat on workers’ health.
    In  the   last  part,  the   analytical  method   based  on  ultra-performance   liquid chromatography-tandem   mass   spectrometry   (UPLC-MS/MS)   and    solid   phase extraction (SPE)  was  developed for  analysis of  three  oligomeric phosphate  esters,including 2,2-bis(chloromethyl)-propane-1,3-diyltetrakis(2-chloroethyl)bisphosphate   (V6),  bisphenol   A   bis(diphenylphosphate)  (BDP)   and   resorcinol  bis(diphenylphosphate)  (RDP),  in  sewage  and  sludge  samples  collected  from  an advanced municipal  sewage  treatment plant  (STP)  in Beijing,  China. For  aqueous samples  and suspended  solids  of  sewage water  and  sludge, the  spiked  recoveries were in the range of 57.3%-125% and 69.6%-136%, and the MDLs were in the range of 0.30-0.50  ng/L and  0.13-0.15 ng/g,  respectively.  The method  was sensitive  and selective. In the STP, BDP and RDP were detected for the  first time in the suspended solids of the sewage  and sludge samples. Compared  to the other commonly used  14 monomeric OPEs, the concentration levels of V6, BDP and RDP were relatively low.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/36890
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梁钪. 城市污水处理与工业应用过程中有机磷酸酯阻燃剂的 迁移转化研究[D]. 北京. 中国科学院研究生院. 2016.
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