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题名: 典型区域土壤与大气中有机磷酸酯阻燃剂污染现状研究
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.
内容类型: 学位论文
URI标识: http://ir.rcees.ac.cn/handle/311016/34321
Appears in Collections:环境化学与生态毒理学国家重点实验室_学位论文

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Recommended Citation:
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.
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