成都市土壤中有机磷阻燃剂的污染特征及来源分析

在建立土壤中痕量有机磷酸酯阻燃剂(OPEs)的GC-MS实验室分析方法基础上,定量分析了成都市主城区表层土壤中7种典型OPEs(磷酸三丁酯(Tn BP)、磷酸三异辛酯(TEHP)、磷酸三丁氧乙酯(TBEP)、磷酸三苯酯(TPh P)、磷酸三氯乙酯(TCEP)、磷酸三氯丙酯(TCPP)、磷酸三(2,3-二氯丙基)酯(TDCPP))的含量及分布特征,采用插值法和聚类分析研究其空间分布,运用相关性分析和正定矩阵因子分解法对土壤中OPEs的来源进行了探析.结果表明,成都市主城区表层土壤中7种OPEs(∑7OPEs)的含量水平在31.6~211 ng·g-1之间,算术平均值为99.9 ng·g-1.所有样品中TBEP均为含量最高的单体,其含量占∑7OPEs总含量的52%~92%.从空间分布来看,成都市西北至东南沿线为OPEs的主要分布带,三环外东北和西南则为OPEs的低值带.聚类分析结果表明,OPEs的谱特征与上述空间分布特征具有一致性,可分为2类地区:第1类地区位于主要分布带,属高值区(∑7OPEs平均值为133.1 ng·g-1),第2类地区位于低值区(∑7OPEs平均值为60.2 ng·g-1).两类地区的谱特征差异主要体现在TCEP与TBEP的百分含量上.相关性研究表明,Tn BP与TCEP之间可能有较强的同源性,TBEP、TPh P、Tn BP三者之间也可能具有较强的同源性,而TEHP与其他种类OPEs可能不具有同源性.正定矩阵因子分解结果表明,OPEs主要来源有2个,不饱和聚酯树脂产品制造业、建筑物装潢/室内源对成都市土壤中OPEs的贡献率分别为43%和57%.     

废旧塑料处置地沉积物中邻苯二甲酸酯污染特征及其生态风险

为了解废旧塑料处置活动对区域水体的影响,采用气相质谱联用仪(GC-MS),对河北省某废旧塑料处置地沉积物中16种PAEs(phthalate esters,邻苯二甲酸酯)的污染特征和生态风险进行了研究. 结果表明:研究样地的w(∑₁₆PAEs)为0.527~102 μg/g, 平均值为18.9 μg/g,其中,DEHP〔邻苯二甲酸(2-乙基己基)酯〕是PAEs最主要的污染单体,平均占w(∑PAEs)的66.6%. 对该处置地的污染物源分析表明,沉积物中PAEs主要来源于废旧塑料回收利用过程中的环境排放. 沉积物中w(DEHP)(14.2 μg/g)和w(DBP)(1.41 μg/g)(DBP为邻苯二甲酸二正丁酯)均超过各自环境风险限值(ERLs),w(DIBP)(DIBP为邻苯二甲酸二异丁酯)超过了美国华盛顿州颁布的沉积物质量警戒限值(0.610 μg/g). 研究显示,沉积物中DBP对鱼类的生态风险及DEHP对藻类和鱼类的生态风险水平不可接受,应引起足够重视.      

大气环境中气相和颗粒相上酞酸酯的分析

本文选用聚氨基甲酸酯泡沫塑料(PUFP)吸附块和玻璃纤维摅膜(GF)构成大气全态采样头,捕集大气中气相和颗粒相中酞酸酯化合物,样品经提取分离后用气相色谱(GC)进行测定。以呼和浩特市居民区相草原对照区为采样点,分析夏冬雨季大气中酞酸酯(DNBP和DEHP)。结果表明,冬季大气气相中,DNBP和DEHP平均浓度为0.46和1.89μg/m~3,夏季为2.19和1.82μg/m~3;大气颗粒物相,冬季平均为1.34和1.66μg/m~3,夏季为0.51和0.36μg/m~3。夏季大气气相酞酸酯含量高,冬季大气颗粒相酞酸酯含量高。草原对照区大气颗粒物上DNBP和DEHP的平均浓度为0.17和0.14μg/m~3,夏季为0.23和0.10μg/m~3。DNBP和DEHP在大气全态中的总含量冬季和夏季较为接近。     

A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

邻苯二甲酸酯降解细菌的多样性、降解机理及环境应用

邻苯二甲酸酯(phthalic acid esters,PAEs)是一类对人体内分泌系统有干扰作用的持续性有机污染物(persistent organic pol utants,POPs)。PAEs在环境介质如水体、底泥和土壤中长期赋存会对生物体产生毒害效应,其分布广、浓度高和难降解等特点是限制有效环境治理的主要因素。作为环境的重要组成部分,微生物对污染物有很强的适应能力和高效的降解能力,这为PAEs的生物修复提供了可能。与物理化学修复法相比,微生物修复技术具有可控性强、修复面广和灵活性高等优势。本文综述了已报道的大部分PAEs降解细菌的种类及其代谢机制,并分析了其在PAEs污染水体和土壤修复中的应用现状与前景,以期为PAEs环境行为与生物修复研究提供参考。     

Determination of three endocrine disrupting chemicals,triclosan, 4-n-nonylphenol,and di-n-butyl phthalate using stir bar sorptive extraction in samples of different matrices

Three endocrine disrupting chemicals (EDCs), triclosan (TCS), 4-n-nonylphenol (4-n-NP), and di-n-butyl phthalate (DBP) were determined using stir bar sorptive extraction (SBSE) along with high-performance liquid chromatography/photodiode array detection (HPLC/DAD). Benzyl butyl phthalate was used as an internal standard. The targeted analytes could be rapidly determined with limits of quantification (LOQ) ranging from 4.1 (DBP), 10 (TCS), to 34 (4-n-NP)?µg?L^?1 in real samples such as bottled waters, personal care products, soaps, lotions, and urine. The results show that the developed analytical scheme is solvent-saving, efficient, and capable of fast screening samples for these common EDCs.     

高能辐射去除饮用水中邻苯二甲酸酯的影响因素

为提高高能辐射去除邻苯二甲酸脂类化合物(PAEs)的能效,研究了辐射去除的主要影响因素:剂量、射线类型、初始浓度、气氛、pH值、共存物质以及PAE类型(邻苯二甲酸二甲酯,DMP;邻苯二甲酸二乙酯,DEP;邻苯二甲酸二丁酯,DBP).以DMP为研究对象,辐照功效(GD)随PAEs初始浓度增加而增加,但随吸收剂量的增加而下降;辐照存在剂量率效应,在同等剂量下,g 辐照比EB辐照能量利用率更高.不同气氛条件下辐照降解效率顺序为:充O2>饱和空气>充N2;在本试验浓度下,辐射降解的最适初始 pH值是5~10,较低或较高pH值都会降低去除效率;水中阴离子抑制剂存在会降低去除效果.不同类型PAEs辐照去除效率大小依次为DMP,DEP,DBP.     

住宅室内降尘中邻苯二甲酸酯污染特征及暴露评价

利用CH2Cl2和超声对天津市13户家庭住宅冬季和夏季26个室内降尘样品中6种邻苯二甲酸酯(DMP、DEP、DBP、BBP、DEHP、DOP)进行提取分离,并采用气相色谱-质谱定量分析,研究了邻苯二甲酸酯污染变化特征和暴露风险.结果表明,冬夏两季,室内降尘样品均以DEHP 浓度最大,DBP第二,且DBP 和DEHP之和占ΣPAEs 的比例达到80.0%以上;冬季,各采样点6种邻苯二甲酸酯总含量(∑PAEs)浓度在1.498~32.587μg/g之间,平均浓度为(6.772±8.154)μg/g;夏季,∑PAEs浓度在1.981~40.041μg/g之间,平均浓度为(13.406±12.911) μg/g;PAEs浓度季节变化差异显著,夏季降尘样品中PAEs浓度高于冬季.暴露评价显示儿童和成人的夏季邻苯二甲酸酯总暴露量均大于冬季;经口暴露水平大于皮肤;平均儿童的暴露水平是成人的10倍左右;成人和儿童对4种物质(DBP、DEHP、DEP、BBP)的总暴露量最大值均出现在夏季;天津室内降尘暴露量与我国6城市室内降尘总暴露水平相当(除DEHP外),与德国和美国的暴露水平相比,天津儿童和成人的暴露量偏小.但是,室内环境中PAEs污染对人体健康的影响仍要引起重视,尤其是对低龄儿童的健康危害.     

中国典型流域有机磷酸酯的污染特征与风险评估

有机磷酸酯（OPEs）作为溴代阻燃剂的替代品,在生产生活中被广泛使用,其环境污染和毒性效应受到广泛关注.梳理中国七大典型流域水体中OPEs的含量水平和分布特征,计算中国成人、青少年和儿童的OPEs日均饮水暴露量,对其健康风险进行评估,并通过蒙特卡洛模拟方法评价了结果的可靠性.检索整理了12种OPEs对水生生物的毒性效应浓度,构建物种敏感度分布（SSD）曲线,对生态风险进行评估.结果表明,低等暴露水平下,七大流域ΣOPEs的第5百分位浓度为52.61 ng·L^-1;中等暴露水平下,七大流域ΣOPEs的中位浓度为499.74 ng·L^-1,磷酸三氯乙酯（TCEP）、磷酸三乙酯（TEP）和磷酸三（1,3-二氯-2-丙基）酯（TDCP）为主要污染物;高等暴露水平下,七大流域ΣOPEs的第95百分位浓度为1904.4 ng·L^-1,是其中等暴露水平的3.8倍,长江流域的ΣOPEs浓度最高.健康风险评估表明,不同人群通过饮用水暴露于OPEs的非致癌风险均在可接受范围内.磷酸三甲酯（TMP）、磷酸三异丁酯（TiBP）和TCEP是致癌风险的主要贡献者.生态风险评估结果表明,TCEP在高等暴露水平下存在中等生态风险;磷酸三正丁酯（TnBP）在中等暴露水平下存在中等生态风险,在高等暴露水平下,有较高生态风险;磷酸三苯酯（TPhP）在低中高3种暴露水平下的风险商均大于1,有较高生态风险,需要重点关注.     

PTA废液回收利用技术

介绍了从精对苯二甲酸（PTA）废液中回收醋酸,邻、对苯二甲酸,醋酸钴锰盐的回收工艺。醋酸得率为90％,邻、对苯二甲酸得率为70％,醋酸钴锰盐得率为95％。该技术成熟、合理,具有较好的经济效益和环境效益。