【作者】 张劲；

【导师】 任国发；

【作者基本信息】 上海大学 ， 环境工程， 2018， 硕士

【摘要】 自早期广泛使用的溴代阻燃剂(多氯联苯和多溴联苯醚等)被例入《关于持久性有机污染物的斯德哥尔摩公约》(简称POPs公约)被禁止或限制使用后,有机磷酸酯(OPEs)作为其替代产品,需求量与使用量均得到大幅度的增长。中国作为有机磷酸酯生产和使用大国,已设立十多家有机磷酸酯工厂。目前OPEs作为一种新型污染物引起了世界范围内越来越多学者的关注,但仍然缺乏对点源(有机磷酸酯工厂)周边多环境介质中有机磷酸酯污染与人群内暴露数据。本研究以河北省衡水市某有机磷酸酯工厂附近多环境介质与暴露人群尿液样品为研究对象,采用气相色谱-质谱(GC-MS)对多环境介质中OPEs原型和液相色谱串联质谱法(LC-MS/MS)对人体尿液中OPEs代谢产物进行目标分析,并对有机磷酸酯在不同介质中的浓度水平、组成特征与分布特征,OPEs代谢产物内暴露量进行初步研究,并试图关联饮用水中OPEs的污染情况,该研究为=为点源污染的时间纵向评价提供了早期的科学数据,主要研究结果如下:(1)在该工厂附近纳污河流中检出TCEP、TCPP和TPP三种有机磷酸酯。点源周边纳污河流中沉积物与水体样品中的TPP浓度与国内外文献类似,两种介质中浓度范围分别为nd-1.48ng/g和0.9-4.4ng/L。而两种介质中TCEP与TCPP的浓度显著高于国内外研究,沉积物中TCEP和TCPP的浓度范围分别为61.07-79380.88ng/g和277.04-194020.8ng/g,水体样品中TCEP和TCPP的浓度范围分别为3021.4-14779.5ng/L和4098.1-18470.6ng/L,该工厂周边纳污河流中沉积物与水体样品中高浓度的TCEP与TCPP水平表明,此两种介质受该点源(OPEs工厂)污染影响;空间分布表明,沉积物与水体样品中TCEP和TCPP的浓度与其他研究中随着距点源距离的增大而降低的结论不同,本研究两种介质中TCEP和TCPP的污染浓度均出现先降低再升高后降低的趋势,且沉积物中污染物的衰减速率略高于水体样品中污染的衰减速率;水体样品与沉积物样品中TCEP和TCPP的组成分析显示,污染物在两类环境介质中的比例分配稍有不同,TCPP为沉积物中主要污染物,TCEP为水体样品中主要污染物,可能是因为两种OPEs单体不同的辛醇-水分配系数与溶解度造成的差异。(2)在点源周围土壤样品中TCEP、TCPP和TPP均有检出,其浓度远低于沉积物中浓度,三类污染物浓度范围分别为nd-8.6ng/g、nd-0.51ng/g和nd-0.31ng/g,推测该点源污染物在研究区域内主要通过污水排放对周围环境介质产生影响。与国内外相关研究对比,低于国内外垃圾拆解区周边土壤中OPEs污染浓度,甚至低至农村土壤研究中OPEs单体污染物的1-4倍。污染浓度空间分布显示,下风向(南侧)土壤中OPEs的污染浓度略高于上风向(北侧),说明该点源依旧对周边土壤环境带来污染但尚未造成严重污染。(3)在点源周边白杨树树皮样品均检出较高浓度的TCEP、TCPP,其浓度范围为4212.4-9092.3ng/g,1824.6-8878.3ng/g。同时也检出少量的TPP,其浓度范围为nd-2.3ng/g,说明该类污染物可以在植物体中累积,进一步推断出研究区域内植物可以通过根系吸收水体中溶解的OPEs在植物体内富集蓄积。(4)本研究测定不同地区(暴露区、非暴露区、城镇)人群尿液中OPEs代谢产物浓度,内暴露检测结果显示,暴露区(点源)附近村民尿液中主要OPEs代谢产物BCEP和BCPP的浓度与非暴露和城镇地区差异并不明显,可能与各地区不同的暴露途径有关。本研究试图关联饮用水与内暴露之间的关系,结果显示,工厂附近村民通过饮用水的暴露负荷较小,且暴露区饮用水中OPEs的含量对人体造成致癌与非致癌风险较低。更多还原

【Abstract】 Since the early use of bromine generation of flame retardants containing polychlorinated biphenyls and polybrominated diphenyl ether be banned or restricted use according the “Stockholm convention”,organic phosphate(OPEs)as its substitute products,the growth of the demand and usage are increased fastly.China,as a major producer of organic phosphate,has set up more than ten organic phosphate factories.OPEs now as a new type of pollutants caused more and more attention from scholars in the world,but still lack of data of point sources(organic phosphate factory)surrounding environment and the human exposure.This study research the environment medium sourrounding a organophosphate factory in hengshui city,hebei province and urine samples from exposed people,using gas chromatography-mass spectrometry(GC-MS)analysis environment medium OPEs and liquid chromatography tandem mass spectrometry(LC/MS/MS)analysis OPEs metabolites in urine,The system researches were carried to quantify the concentration levels,composition profiles and compared the concentration of OPEs metabolism in factory Valley and Urban human.And the research in the early stage of the OPEs factory is very important for the compairsion with the pollution levels after decades since the start of the production of OPEs.the main results were as follows:(1)The main products of the factory are TCEP,TCPP,and there may be a small amount productions of TPP.The TPP concentration in the sediment and water samples near the point source is similar to that of the domestic and foreign literatures.The concentration ranges of the two media are nd-1.48ng/g and 0.9-4.4ng/L respectively.The concentration of TCEP and TCPP in two kinds of medium was significantly higher than that of domestic and foreign research,sediment concentration range TCEP and TCPP were 61.07 and 79380.88 ng/g 277.04 194020.8 ng/g;water samples of TCEP and TCPP concentration range 3021.4 14779.5 ng/L respectively,and 4098.1 to 18470.6 ng/L,High concentration of TCEP in sediment and water samples nearby the factory shows that the two media are affected by the pollution of the point source(OPEs factory).Spatial distribution show that the concentration of TCEP and TCPP in sediment and water samples with other studies and decreased with the increase of distance from point source in the conclusion,this study two kinds of medium TCEP and TCPP rising pollution concentration in lower first and then decreases after trend,and the attenuation rate of pollutants in sediment slightly higher than the attenuation rate of pollution in water sample;In water sample and sediment samples TCEP and composition of TCPP analysis shows that the pollutants in the proportion of two types of environmental media distribution is slightly different,TCPP as the main pollutants in sediments,TCEP as the main pollutants in water samples,may be because the two different kinds of OPEs monomer logkow and the solubility of difference.(2)TCEP,TCPP and TPP can be detected in soil samples around the point-source,and these concentration is far lower than these in the sediment.Three kinds of pollutants concentration range is nd-8.6ng/g,nd-0.51ng/g and nd-0.31 ng/g respectively,speculated that the pulltion point source mainly through the sewage discharge medium impact on the surrounding environment.Compared with domestic and foreign studies,the pollution concentration of OPEs in the surrounding soil is lower than thar in the garbage removal area and rural soils.According to the spatial distribution,Pollution concentration of the wind(south)of OPEs in soil pollution concentration is slightly higher than the wind direction(north),shows that the point sources on surrounding soil environment pollution but still have not caused serious pollution.(3)Similar as the sediment and water,the TCEP and TCPP were detected with high concentration in the bark samples,and the concentration range was 4212.4-9092.3ng/g,1824.6-8878.3ng/g.Also detected the TPP with low oncentration,the concentration range of nd-2.3 ng/g,which can prove the accumulation of plants,also can further deduce the plants absorb the OPEs of dissolved in water through the root system to enrichmention to accumulation.(4)The factory surrounding environment have high concentration of TCEP and but concentration of their mebolism BCEP and BCPP in urine is not high,and it similar with other urban and background human’s urine.,may be because of the different path of expourse.This research attempts to find the relationship of the drinking water and the human exposure,the results show that the factory nearby villagers by the exposure of the drinking water load is small,and the exposed area of OPEs content in drinking water cause cancer to human body and the lower the risk of cancer.更多还原