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.     

复合垂直流构建湿地净化酞酸酯的初步研究

为考察湿地对特殊污染物酞酸酯的净化作用，在温室中建造了专门用于酞酸酯研究的2套下行流-上行流湿地小试系统，1号系统邻苯二甲酸二丁酯（DBP）和邻苯二甲酸二（2-乙基已基）酯（DEHP）污染负荷分别为19.86mgL^-1和3.16mgL^-1,2号系统DBP和DEHP污染负荷分别为9.84mgL^-1和1.58mgL^-1，试验时间为45d。水力负荷为420Ld^-1。结果表明：构建湿地对人工配置污水中的酞酸酯有很好的净化效果。平均去除率达到99.95%以上，出水酞酸酯质量浓度为10^-9级，均低于国家排放标准（GB8978-1996）.     

复合人工湿地对有机污染物的去除效果初步研究

研究了由不同植物配置(驯化和未驯化)的两组下行和上行植物床组成的复合人工湿地对生活污水的净化效果。结果表明,CODCr和BOD5的去除率达67.3%,68.1%,总氮(TN)的去除率为26.9%,总磷(TP)的去除主要发生在上行床,去除率为81.6%。环芳烃(PAHs)中苊(Ace)、荧蒽(Flu)、芘(Py)、苯并[a]蒽(BaA)、屈(Chr)、苯并[b]荧蒽(BbF)、苯并[a]芘(BaP)、茚并[1,2,3-cd]芘(InP)和苯并[g,h,i](BPR)经下行床后,去除率超过80%,上行床去除较少。驯化床和未驯化床对PAHs的去除效果差异不显著。邻苯二甲酸酯(PAEs)中邻苯二甲酸二乙酯(DEP)和邻苯二甲酸二异丁酯(DiBP)经驯化床后,质量浓度显著升高,经未驯化床后邻苯二甲酸二(2-乙基)己酯(DEHP)含量显著降低。蚕豆根尖微核实验表明,不同植物配置对微核率影响差异并不显著,毒害物质经下行床后大部分被去除。     

城区大气和塑料大棚空气中酞酸酯的分析

本文报道了济南市大气飘尘和塑料蔬菜大棚空气中酞酸酯的污染情况，探讨了大气飘尘中酞酸酯随季节变化和昼夜更替的变化情况。     

Phthalate exposure in pregnant women and their children in central Taiwan

Phthalate exposure was found to be associated with endocrine disruption, respiratory effects, reproductive and developmental toxicity. The intensive use of plastics may be increasing the exposure to phthalates in Taiwanese population, particularly for young children.We studied phthalate metabolites in pregnant women and their newborns in a prospective cohort from a medical center in Central Taiwan. One hundred maternal urine samples and 30 paired cord blood and milk samples were randomly selected from all of participants (430 pregnant women). Eleven phthalate metabolites (MEHP, 5OH-MEHP, 2cx-MEHP, 5cx-MEPP, 5oxo-MEHP, MiBP, MnBP, MBzP, OH-MiNP, oxo-MiNP, and cx-MiNP) representing the exposure to five commonly used phthalates (DEHP, di-isobutyl phthalate (DiBP), DnBP, BBP, DiNP) were measured in urine of pregnant women, cord serum and breast milk after delivery, and in urine of their children. Exposure was estimated with excretion factors and correlation among metabolites of the same parent compound. Thirty and 59 urinary samples from 2 and 5 years-old children were randomly selected from 185 children successfully followed.Total urinary phthalate metabolite concentration (geometric mean, μg L⁻¹) was found to be higher in 2-years-olds (398.6) and 5-years-olds (333.7) than pregnant women (205.2). Metabolites in urine are mainly from DEHP. The proportion of DiNP metabolites was higher in children urine (4.39 and 8.31%, ages 2 and 5) than in adults (0.83%) (p < 0.01). Compared to urinary levels, phthalate metabolite levels are low in cord blood (37.45) and milk (14.90). DEHP metabolite levels in women’s urine and their corresponding cord blood are significantly correlated. Compared to other populations in the world, DEHP derived metabolites in maternal urine were higher, while phthalate metabolite levels in milk and cord blood were similar. The level of phthalate metabolites in milk and cord blood were comparable to those found in other populations. Further studies of health effects related to DEHP and DiNP exposure are necessary for the children.     

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.     

Occurrence and migration of microplastics and plasticizers in different wastewater and sludge treatment units in municipal wastewater treatment plant

● Reduce the quantifying MPs time by using Nile red staining. ● The removal rate of MPs and PAEs in wastewater and sludge were investigated. ● MPs and PAEs were firstly analyzed during thermal hydrolysis treatment. ● The removal of PAEs from wastewater and sludge was mainly biodegradation. Microplastics (MPs) and plasticizers, such as phthalate esters (PAEs), were frequently detected in municipal wastewater treatment plants (MWTP). Previous research mainly studied the removal of MPs and PAEs in wastewater. However, the occurrence of MPs and PAEs in the sludge was generally ignored. To comprehensively investigate the occurrence and the migration behaviors of MPs and PAEs in MWTP, a series of representative parameters including the number, size, color, shape of MPs, and the concentrations of PAEs in wastewater and sludge were systematically investigated. In this study, the concentrations of MPs in the influent and effluent were 15.46±0.37 and 0.30±0.14 particles/L. The MP removal efficiency of 98.1% was achieved and about 73.8% of MPs were accumulated in the sludge in the MWTP. The numbers of MPs in the sludge before and after digestion were 4.40±0.14 and 0.31±0.01 particles/g (dry sludge), respectively. Fourier Transform Infrared Spectroscopy (ATR FT-IR) analysis showed that the main types of MPs were polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polystyrene (PS). Six PAEs, including phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), ortho dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), and bis(2-ethyl) hexyl phthalate (DEHP), were detected in the MWTP. The concentrations of total PAEs (ΣPAEs) in the influent and effluent were 76.66 and 6.28 µg/L, respectively. The concentrations of ΣPAEs in the sludge before and after digestion were 152.64 and 31.70 µg/g, respectively. In the process of thermal hydrolysis, the number and size of MPs decreased accompanied by the increase of the plasticizer concentration.     

有机磷酸酯阻燃剂的人群暴露和甲状腺毒性的研究进展

有机磷酸酯(organophosphate esters,OPEs)是使用最为广泛的有机磷阻燃剂,并兼具增塑剂、消泡剂和萃取剂等功能,被广泛用于电子产品、建筑材料和塑料材料等中,导致其在环境介质中普遍存在,对生态系统和人体健康构成巨大威胁.作为一种新型环境污染物,OPEs的人群暴露特征和生物毒性成为环境健康领域的研究热...     

A miniature stainless steel net dumbbell-shaped stir-bar for the extraction of phthalate esters in instant noodle and rice soup samples

Abstract

This work reports the development of a very-simple-to-construct stir-bar extraction device so called “a dumbbell-shaped stainless steel stir-bar.” The extraction device was assembled from a rolled up stainless steel net filled with an XAD-2 sorbent and a metal rod to allow the use of a magnetic stirrer during extraction. The dumbbell-shaped stainless steel stir-bar was used to extract diethyl phthalate (DEP), dibutyl phthalate (DBP), and di(2-ethylhexyl) phthalate (DEHP) before analysis by a gas chromatograph equipped with an electron capture detector (GD-ECD). Under the optimal conditions, the developed method provided a good linearity from 10.0 to 1,000.0?ng mL^?1 for all three compounds. Limits of detection and limits of quantification were 9.37?±?0.29?ng mL^?1 and 31.22?±?0.95?ng mL^?1 for DEP, 5.73?±?0.31?ng mL^?1 and 19.1?±?1.0?ng mL^?1 for DBP and 3.30?±?0.06?ng mL^?1 and 11.0?±?0.19?ng mL^?1 for DEHP, respectively. Good recoveries in the range of 81.89?±?0.17 to 109.5?±?2.0% were achieved when the method was used to extract phthalate esters in five instant noodle and two rice soup samples.     

快速溶剂萃取-凝胶净化-高效液相色谱法测定土壤中6种邻苯二甲酸酯

建立一种快速溶剂萃取(ASE)-凝胶净化(GPC)-高效液相色谱(HPLC)法测定土壤中6种邻苯二甲酸酯(PAEs)的方法。土壤样品经二氯甲烷-丙酮(体积比为1∶1)快速溶剂萃取后,过Bio-Beads SX-3凝胶层析柱净化,收集12~28 min的GPC洗脱液,并进行HPLC-DAD检测分析。通过分段收集,消除了土壤中共存的16种多环芳烃在225 nm紫外波长下对6种PAEs测定的干扰。采用ZORBAX Eclipse Plus C_(18)(150×4.6 mm,5μm)反相色谱柱,以乙腈-水为流动相进行梯度洗脱,流速为1 mL/min。结果表明,6种PAEs的线性关系良好,相关系数大于0.999 9,方法检出限为2.7~11.5μg/kg,精密度的相对标准偏差为1.5%~9.5%,加标回收率为66.5%~102%。该方法适用于含多环芳烃的土壤中PAEs的准确测定。