济南冬春季室内空气PM_(2.5)中多环芳烃污染特征及健康风险评价

2010年冬春季,在济南典型室内环境(超市、办公室和餐厅)采集了PM2.5样品,并对其多环芳烃(PAHs)进行了分析.结果表明,采样期间办公室的PAHs平均浓度最高,为93.11 ng.m-3,超市和餐厅的PAHs平均浓度分别为42.97 ng.m-3和26.65 ng.m-3.超市和办公室的多环芳烃均以室外源(燃煤)为主,吸烟导致办公室轻环多环芳烃浓度升高,高于室外相应物种的浓度,餐厅的轻环多环芳烃和重环多环芳烃分别来源于室内烹饪和室外的机动车尾气.与室外相比,超市和办公室PAHs中的菲(Phe)和苯并[b+k]荧蒽(BbkF)占总PAHs的比例较高,达到10%—15%,这与冬季室内使用中央空调取暖密不可分.超市、办公室和餐厅的毒性当量浓度值(BEQ)分别为7.05 ng.m-3、10.75 ng.m-3和0.75 ng.m-3.其中办公室的毒性当量浓度高于我国规定10 ng.m-3.超市,办公室和餐厅的PAHs暴露致终身肺癌风险度分别为0.6×10-3、0.9×10-3和6.5×10-5,均超过了世界卫生组织的建议值(10-5),超市和办公室的终身致癌健康风险高于美国最高法院规定的10-3的显著水平,说明生活在超市和办公室致癌风险高.     

北京市不同区域采暖期大气颗粒物中多环芳烃的分布特征

利用分级采样器分别采集北京市不同区域采暖期的大气颗粒物,分析多环芳烃的组成及含量.结果表明北京市大气总悬浮颗粒物中总多环芳烃的含量城乡结合带为7486—43687ng·m-3,郊区为11993—39786ng·m-3.在城乡结合带,80%以上的多环芳烃存在于粒径<20μm的颗粒物中;在郊区,77%以上的多环芳烃存在于粒径<20μm的颗粒物中.比较不同环数的多环芳烃在不同粒径范围内大气颗粒物中的分配比例,发现随环数的减少其分配比例呈现归一化.不同粒径范围的颗粒物中苯并(a)芘均与总多环芳烃含量显著相关(p<0001).     

气相色谱-质谱联用测定土壤及底泥样品中的多环芳烃和硝基多环芳烃

采用气相色谱-质谱联用法测定了某化工厂火灾后周边土壤和底泥中的多环芳烃(PAHs)和硝基多环芳烃(Nitro-PAHs).结果表明,距离爆炸地点最近的几个采样点PAHs的含量均在16.61μg·g-1以上,其中厂东北采样点的PAHs总含量甚至高达417.4μg·g-1,污染最为严重;部分样品中检测到三环以下的硝基多环芳烃,三环以上的几乎均未检出.说明在燃烧爆炸过程中产生了多环芳烃,但没有显著产生高致癌性、致突变性的硝基多环芳烃.     

GC-MS/MS法定量分析大气PM2.5中6种硝基多环芳烃

本文建立了三重四极杆气质联用仪GCMS-TQ8040测定大气中6种硝基多环芳烃(NPAHs)含量的分析方法.采用正己烷∶丙酮=1∶1(V∶V)对大气采样滤膜样品进行萃取,萃取液定量浓缩后直接进GC-MS/MS分析.通过串联质谱的MRM方式,有效降低基质干扰.在1—100μg·L-1的浓度范围内,6种硝基多环芳烃的线性相关系数均在为0.999以上,对1.0和2.0μg·L-1的标准溶液连续8针进样,峰面积RSD%在9%以下.在1 ng的加标含量条件下,加标回收率在69%—85%之间;6种NPAHs的最低检出限均在0.3μg·L-1以下,可满足大气中硝基多环芳烃的科研和监测分析要求.     

城市回用水中多环芳烃致癌风险评价

为评价人群暴露于城市回用水中16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)对于人体健康的潜在风险,采用气相色谱-质谱(GC-MS)联用的分析化学方法对不同季节回用水中16种PAHs进行定量分析;在此基础上采用美国国家科学院和国家研究委员会提出的环境健康风险评价方法,分析不同回用条件下具有中国水体基质特色的城市回用水中PAHs健康风险.结果显示,回用水样中16种PAHs的总浓度为1 422.85 ng·L-1,污水处理厂二级出水水样16种PAHs的总浓度为1 791.77 ng ·L-1,经过处理后回用水中PAHs含量有所降低.风险评价分析结果显示,回用水在城市绿化、农业灌溉和景观娱乐3种不同回用途径下多环芳烃的致癌风险分别为788×10-8、2.77×10-6、3.04×10-6,总致癌风险为5.89×10-6.以上结果可以得出,回用水在城市绿化、农田灌溉和景观娱乐接触过程中多环芳烃所增加的致癌风险很低,回用水中多环芳烃的健康风险处于可接受水平.     

太原市雨水中多环芳烃的污染特征

对太原市2012年3—10月雨水中16种溶解态多环芳烃(PAHs)的分布特征、沉降通量和来源进行了分析.结果表明,16种PAHs总的(∑16-PAHs)平均浓度为1081.2 ng·L-1(范围为316.8—6272.3 ng·L-1),以2—3环PAHs为主,占75.4%,4环和5—6环PAHs分别占18.2%和6.4%.∑16-PAHs浓度与温度(P<0.05)和电导率(P<0.01)呈显著正相关.同一场降雨不同阶段的∑16-PAHs浓度及其组成与降雨量有关.∑16-PAHs的全年平均沉降通量为481.5 ng·m-2·d-1,9月的沉降通量最高(2342.8 ng·m-2·d-1),其次是7月(1604.4 ng·m-2·d-1),10月的最低(83.3 ng·m-2·d-1),其中2—3环PAHs的沉降通量明显高于4环和5—6环PAHs,∑16-PAHs的月沉降通量与月平均降雨量(P<0.01)和降雨频次(P<0.05)呈显著正相关.利用特征比值法判断PAHs的主要来源是煤燃烧,同时也存在一定的石油燃烧源和少部分的石油源.     

使用安捷伦7000A三重串联四极杆GC/MS/MS系统测定大气颗粒物中的硝基多环芳烃

采用毛细管GC结合安捷伦7000A三重串联四极杆GC/MS(G7010AA)系统的多反应监测(MRM)模式分析了大气颗粒物中的硝基多环芳烃(nitro-PAHs).传统硝基多环芳烃的分析方法是在样品前处理之后,使用单四极杆GC/MS的选择离子监测SIM模式或者多维GC/MS,但基于MS/MS检测模式超强的选择性,可直接分析大气颗粒物的粗提物.实际样品中的硝基多环芳烃可以检测到pg·μL-1的级别,相对应于大气样品中pg·m-3级的含量.     

北京市冬季大气气溶胶中PAHs的污染特征

利用大流量颗粒物采样器采集了2005-2006年冬季北京市大气气溶胶中PM10和PM2.5样品,采用气相色谱/质谱技术对样品中的多环芳烃进行检测.结果表明:北京市冬季大气颗粒物PM10和PM2.5中PAHs总量分别为520.5±476.9ng·m-3和326.8±294.3ng·m-3,且大部分存在于细粒子中,4环以上的稠环芳烃占总浓度的87%.根据荧蒽/芘等比值指标判别,北京市冬季PAHs主要以燃煤排放为主,其次是石油燃烧交通排放.风速增大和太阳辐射曝辐量增强,都会降低颗粒物中多环芳烃浓度.     

珠江隧道多环芳烃的含量与分布特征

为研究机动车尾气排放多环芳烃的排放特征,以及其从源到汇的过程变化,该研究选取珠江隧道为研究区域,采集了2006年4月、7月和12月珠江隧道中气相和颗粒相样品,以及7月、12月份隧道附近的大气样品,并对样品中多环芳烃(PAHs)进行检测.结果表明,隧道中馪AHs范围为896.1 ng·m-3～4066.2 ng·m-3,气相中馪AHs远远高于颗粒相馪AHs.环境大气样品中馪AHs为207.9 ng·m-3～353.0 ng·m-3,远远低于隧道里馪AHs,其PAHs各组分的分布特征与隧道中样品相似,说明汽车尾气是广州市大气中PAHs的重要来源;最后通过隧道中与隧道口的馪AHs来计算汽车的排放因子,得出PAHs排放因子平均值为:2164.7 靏穔m-1妨,并且估算出2006年广州市全年汽车尾气排放出PAHs 82 t.     

GCMS-NCI法测定PM_(2.5)中6种硝基多环芳烃

本文建立了气相色谱质谱联用仪结合负化学电离源(GCMS-NCI)测定大气PM_(2.5)中6种硝基多环芳烃(NPAHs)含量的分析方法.大气采样滤膜经快速溶剂萃取仪在线萃取、浓缩后,直接进GCMS分析.在1—100μg·L~(-1)的浓度范围内,6种硝基多环芳烃的线性相关系数均在为0.998以上,对1.0μg·L~(-1)的标准溶液连续6针进样,峰面积RSD在9%以下.在1 ng的加标含量条件下,加标回收率在63%—76%之间;6种NPAHs的最低检出限均在0.06μg·L~(-1)以下,可满足大气中硝基多环芳烃的科研和监测分析要求,为建立大气PM_(2.5)中的硝基多环芳烃测定建立了一套快速简便、准确的定量分析方法.     

Polycyclic aromatic hydrocarbons in medicinal plants from Syria

The levels of 16 US Environmental Protection Agency polycyclic aromatic hydrocarbons (EPA PAHs) in 10 medicinal plants in different used parts of plant (leaves and flowers) have been determined. The analytical method consists of sample preparation by ultrasonic extraction with dichloromethane followed by silica gel clean-up. Subsequently, the analysis was carried out by reversed-phase high-performance liquid chromatography (HPLC) coupled to both ultraviolet and fluorescence detections in series to insure the detection of all 16 EPA PAHs. It was observed that the sum of the 16 PAHs (ΣPAHs) in the investigated medicinal plants ranged from 47 to 890 μg kg^–1 where the highest ΣPAHs was found in Sage plant sample. Light PAHs were dominants in all studied medicinal plants. The sum of eight genotoxic PAHs (ΣPAH8) have shown a better indicator of the degree of contamination with carcinogenic PAHs compared to benzo[a]pyrene in these products.     

杭州市郊区表层土壤中的多环芳烃

采集了杭州市郊区表层土壤中多环芳烃样品,用内标法和色谱-质谱技术对多环芳烃化合物进行定量分析.美国环保总署推荐优先控制的16种多环芳烃均被检出,多环芳烃单体的质量浓度在1.49～87.43 ng·g-1之间;其中萘、芴、苊等低分子量芳烃的质量浓度相对较低; 、茚并[1,2,3-cd]芘、苯并[ghi]苝等高分子量芳烃的质量浓度相对较高,苯并[ghi]苝的质量浓度最高.16种多环芳烃的质量总浓度超过荷兰政府规定无污染土壤PAHs值的10～40倍;与国内外其他地区相比较,多环芳烃污染处于中等水平.多环芳烃Ant/(Phe+Ant)、BaA/(Chr+BaA)、Flua/(Pyr+Flua)等参数表明,多环芳烃主要来源于燃烧源,且以机动车尾气为主;BeP/(BeP+BaP)比值偏高,可能与土壤中的多环芳烃主要来源于大气沉降有关.     

Polycyclic aromatic hydrocarbons in surface sediments held in experimental mesocosms

Sediment was collected from three locations along a pollution gradient in Narragansett Bay and transplanted to controlled mesocosms. Total hydrocarbons and eleven individual polycyclic aromatic hydrocarbons (PAHs) were measured in these sediments over a period of 394 days. Total hydrocarbon concentrations increased in the “relatively uncontaminated”; (Rhode Island Sound) sediment that was held in the mesocosms, but did not change in the two other sediments. The concentrations of four PAHs: naphthalene, 2‐methyl naphthalene, 1‐methyl naphthalene and biphenyl, decreased in the “contaminated”; (Providence River) sediment during the experiment and the calculated half‐lives for these compounds were 287, 353, 321 and 333 days, respectively.     

Biogeochemistry of aromatic hydrocarbons in the benthos of microcosms†

Investigations into the fate of petroleum compounds in the marine environment were carried out using experimental microcosms of two sizes and designs. Aromatic hydrocarbons or No. 2 fuel oil were spiked to the water of a 13 m³ continuous flow system and to a 2281 recycled flow system. The transport and alteration of this oil was traced in the sediment and benthic organisms (Glycera americana, Crepidula sp., and Nephtys incisa) of these microcosms. Measurable contamination was found in both sample types. The aromatic hydrocarbon distribution, including relative isomeric distribution (e.g., C₂‐phenanthrenes) was found to be different in sediment and in organisms from that which was originally introduced to the experimental microcosm. Differences in isomer distribution between Glycera and Crepidula were also detected. Based on the experimental data: molecular weight and specific isomeric form, biochemical processes, solubility, and particle adsorption/desorption influence the fate of petroleum compounds in benthic ecosystems.     

红树林生态系统多环芳烃的污染研究进展

多环芳烃（PAHs）是一类广泛存在于天然环境中的持久性有机污染物,对生态环境和人类健康造成严重的潜在威胁。文章介绍了红树林生态系统PAHs污染的研究现状;总结了红树林生态系统PAHs的污染分布及其来源,以及PAHs污染胁迫对红树植物生长的影响;评述了红树植物对PAHs的直接吸收、红树林湿地微生物对PAHs的降解等研究;最后,对红树林生态系统PAHs污染的研究趋势进行了分析和展望,提出了今后可能的研究方向,主要包括：（1）综合应用多学科交叉研究典型PAHs在红树林生态系统中的环境行为;（2）结合双光子激光共焦扫描显微技术等原位研究手段,开展红树植物对典型PAHs的吸收、存赋形态、转运等相关研究;（3）结合激光诱导时间分辨荧光光谱测定系统,实现对现场红树林生态系统中PAHs等有机污染物的原位检测。     

环境中的氧化多环芳烃综述

氧化多环芳烃(OPAHs)是芳环上具有至少一个羰基氧(C=O)的PAH衍生物,广泛存在于环境中.氧化多环芳烃主要通过含碳燃料的燃烧和PAHs的转化释放到环境中,且其较稳定难降解,因此OPAHs被称为生物和化学降解的"末端产物".目前,在多种动物组织样本中都可检测出OPAHs,并发现OPAHs可能比亲代PAHs具有更强的毒性.本文阐述了OPAHs的理化性质、来源、测定方法、环境分布、转运和转化、(生态)毒理学效应及其毒性作用机制,并对今后的研究方向进行了展望,进而为该类化合物的环境污染及生态风险评估提供相应参考.     

Polycyclic aromatic hydrocarbons in household dust near diesel transport routes

A river-dredging project has been undertaken in Nantou, Taiwan. A large number of diesel vehicles carrying gravel and sand shuttle back and forth on the main roads. Ten stations along major thoroughfares were selected as the exposure sites for testing, while a small village located about 9 km from a main traffic route was selected as the control site. Levels of household dust loading at the exposure sites (60.3 mg/m²) were significantly higher than those at the control site (38.2 mg/m²). The loading (μg/m²) of t-PAHs (total polycyclic aromatic hydrocarbons) in the household dust at the exposure sites was significantly higher (P < 0.05) than was the case at the control site. The diagnostic ratios of PAHs showed that diesel emissions were the dominant source of PAHs at the exposure sites. The lack of a significant correlation between the concentrations of Fe and t-PAHs suggested that the t-PAHs in household dust might come from diverse sources. However, a significant correlation (P = 0.003) between the concentrations of Mo and t-PAHs implied that the most of the t-PAHs in the household dust might have resulted from diesel emissions. The lifetime cancer risks of BaP_eq from household dust exposure were markedly higher than those resulting from inhalation exposure.     

Ecotoxicity of polycyclic aromatic hydrocarbons, aromatic amines, and nitroarenes through molecular properties

Air, marine, and terrestrial pollution are continuously critical issues to be solved in environmental sciences. Particularly with the recent disaster in the Mexico Gulf and the risk of oil spills from the continuous offshore drilling activities in the North Sea, ecotoxicological profiling requires great attention. Fjord ecosystems are particularly neglected marine ecosystems, which require better surveillance and ecotoxicological profiling. In this context, this study focuses on exploring three potential indicators for aquatic stress [polycyclic aromatic hydrocarbons (PAHs), aromatic amines (AAs), and nitroarenes (NAs)] by the study of their molecular and sub-molecular properties. The results show that the aromatic amine, 4-aminobiphenyl, gains a particularly reactive electronic potential, which can be summarized as a large change in LUMO+2 and HOMO?1 electron orbitals upon metabolic activation in the organism. This change in orbitals increases the overall electrostatic energy of the molecule, inducing a high affinity for DNA-adduct formation. Electronic analysis on nitroarenes shows in addition why 1,6-dinitropyrene is more stable than 1,8-dinitropyrene, and how the electrons favor nitrenium activation on the 6th and 8th carbon. Further analysis shows also that PAHs have a present correlation with hormonal similarity, and that their resemblance to estrogen can be correlated to mutagenicity, contributing to increased ecotoxicity. The electronic analysis of these three types of fossil pollutants shows how their toxicity is exerted from the electronic level and which structural features that determine the level of reactivity and toxicity. The summation of the background and electronic properties of these molecular toxins elucidates that PAHs, aromatic amines, and nitroarenes are all of equal importance as stress indicators for fjord systems, with particular emphasis on PAHs, which also exert hormonal structural similarities as a probable base of their carcinogenic mechanisms.     

Urban fractionation of polycyclic aromatic hydrocarbons from Dalian soils

This report evidences the fractionation of polycyclic aromatic hydrocarbons (PAHs) from urban to rural areas, and a higher contribution of coal and wood combustion in rural areas. PAHs are persistent semi-volatile organic pollutants in the environment. PAHs originate from the incompleted combustion of fossil fuel and biomass. Cities are usually considered as primary sources of PAHs. Due to different types and loads of fuel consumption in various functional areas of a city, the levels and composition profiles of PAHs are expected to be different. We, therefore, studied the mechanisms ruling PAH distributions in soils from a major Chinese city. Seventeen soil samples were collected in urban traffic areas, residential and park areas, suburban areas and rural areas of Dalian, northeastern China. PAHs were analyzed using a high-performance liquid chromatography. The composition profiles and seasonal variation of PAHs were investigated. Results show that the proportions of low-weight molecular PAHs to total PAHs increased with urban-suburban-rural gradient. This trend is explained by the “urban fractionation” of PAHs. Furthermore, the spring/autumn ratios of PAH concentrations were higher than 1. Specifically, the spring/autumn ratio was 1.79 for two ring PAHs, 1.42 for three ring PAHs, and lower than 1.20 for five and six ring PAHs. The spring/autumn ratios of phenanthrene were higher than 1 and increased with increasing distance from the urban areas. The results imply that the contribution of coal and wood combustion PAHs increases with the urban-suburban-rural gradient.