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.     

太湖胥口湾表层水和沉积物中多环芳烃的浓度水平及生态风险

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是环境中普遍存在的稠环类化合物,由于其对人体健康和生态环境产生较大危害,美国环保局将16种PAHs列为优先控制的污染物。PAHs也是太湖流域的主要污染物之一。作为华东地区的重要水系和水源地,研究太湖环境质量的变化对改善太湖流域水生生态系统和提高沿岸居民身体健康具有重要意义。论文研究了太湖胥口湾水域表层水和沉积物的PAHs。结果显示,表层水和沉积物的PAHs总浓度分别为7.2~83 ng·L~(-1)和66~620ng·g~(-1)干重;年均值为29 ng·L~(-1)和218 ng·g~(-1)干重;年均毒性当量浓度为2.4 ng·L~(-1)和28 ng·g~(-1)干重。沉积物中的主要污染物为荧蒽、芘和,影响毒性当量浓度的主要是苯并(a)芘和二苯并(a,h)蒽。4环PAHs在沉积物中占主要,其浓度百分比为44%~48%,而5环PAHs则占毒性当量总浓度的90%以上,说明其危害主要来自5环PAHs。PAHs特征化合物比值分析表明,胥口湾沉积物中PAHs主要来源于煤和木材燃烧,表层水大部分为燃烧和石油的混合来源。污染水平的时空变化特点为丰水期(8月)表层水PAHs浓度偏高,沉积物偏低。湖区和湖岸的PAHs浓度只在丰水期有显著差异,表层水PAHs浓度湖区高于湖岸,沉积物相反;其他时期湖区和湖岸PAHs浓度无显著差异。根据加拿大沉积物环境质量标准,胥口湾整体生态风险水平较低。从时空分布特征来看,个别生态风险较高的点主要分布在湖岸,5月平水期可能是沉积物中PAHs生态风险较高的频发期。     

墨水河表层沉积物中多环芳烃(PAHs)的分布特征、来源解析及生态风险评价

本文运用GC-MS测定了墨水河表层沉积物中16种优控多环芳烃(PAHs)浓度,采用多种数据分析技术解析了PAHs的来源.结果表明,苊烯、苊、蒽和苯并(a)蒽在部分样品中未检出,其余12种在所有样品中均有检出,16种PAHs总浓度为196.51—8549.33 ng·g~(-1),平均浓度为3320.03 ng·g~(-1).沉积物中PAHs的环数分布以高环为主,运用轻重比、分子比值和主成分分析-多元线性回归模型(PCA-MLR)等3种方法,共同确定PAHs的主要来源分别为混合源(煤炭、生物质和汽油燃烧源)、柴油燃烧源和石油源,这3种来源对总PAHs的贡献分别为59.8%、26.0%和14.2%.效应区间低/中值法(ERL/ERM)对PAHs生态风险分析表明,芴、菲、苯并(a)蒽、、苯并(b)荧蒽、苯并(k)荧蒽和苯并(a)芘在墨水河中下游偶尔会产生负面生态风险,二苯并(a,h)蒽存在经常产生负面生态效应的可能;平均效应区间中值商法(M-ERM-Q)分析表明,墨水河上游和入海口处PAHs的综合生态风险较低,而中下游站位则具有中低风险.     

上海市大气颗粒物中多环芳烃的季节变化特征和致癌风险评价

对上海市城区和郊区采集的64个总悬浮颗粒物(TSP)样品进行GC/MS分析,结果表明:全年PAHs浓度范围为2.25-221.6ng·m~(-3),并呈现明显的秋、冬季节高而夏季低的变化特征,且PAHs年平均值郊区稍微高于城区.多环芳烃中苯并(b k)荧蒽、茚并(1,2,3-cd)芘、晕苯等化合物相对含量较高,四环以上的组分全年平均含量在90%以上.采用苯并(a)芘和苯并(a)芘等效质量浓度(BaPE)对上海市大气颗粒物中的PAHs进行致癌风险评价,BaP年均值在城区和郊区分别为2.57ng·m~(-3)和2.86ng·m~(-3),秋季BaP年均值超过了居民区标准限值(5.0ng·m~(-3)).BaPE在城区和郊区的年均浓度分别为5.82ng·m~(-3)和7.24ng·m~(-3),秋季污染最为严重.     

呼和浩特市冬季PM_(10)中多环芳烃的污染特征及来源解析

2013年12月在呼和浩特市主城区9个环境空气监测点位同步采集PM_(10)样品,对PM_(10)浓度和16种多环芳烃的浓度、污染特征进行了分析,使用特征比值和主成分分析对多环芳烃来源进行了解析.9个监测点位的PM_(10)浓度介于23.5—322μg·m-3之间,16种多环芳烃总量介于5.34—850 ng·m-3之间.荧蒽、芘、苯并[a]蒽、、苯并[b]荧蒽、苯并[a]芘、苯并[g,h,i]苝和茚并[1,2,3-cd]芘等多环芳烃单体浓度较高,这8种多环芳烃占多环芳烃总浓度的80.4%.主成分分析所获得污染源结果和特征比值法定性判断出的污染源结果一致,燃烧源、机动车尾气源和石油源为主要污染源,分别贡献61.3%、16.0%和10.4%.     

我国10城市冬季大气颗粒物中多环芳烃污染及呼吸暴露风险评价

大气中颗粒物和多环芳烃对环境与人体健康危害较大,已引起社会各界的广泛关注。以我国10个城市2013年12月和2014年1月大气中空气动力学直径小于10μm的颗粒物(PM10)为研究对象,采用硅胶-氧化铝层析柱净化分离、气质联用仪分析的方法测定了27种多环芳烃(PAHs)的浓度水平,分析其谱分布及空间分布,并通过呼吸暴露途径估算了癌症病发增量(ILCRs)和人群归因危险度百分比(PAF)。结果表明,27种物质的总浓度为13.72~2 002 ng·m-3;在10个城市中晋中总浓度最高,厦门最低。PAHs空间污染水平呈现北方高于南方、东部沿海城市浓度相对较低的趋势。温度与总浓度有相关性。在27种PAHs中,占主导地位的单体为荧蒽(FLA,7.56%~19.8%),芘(PYR,6.72%~13.8%),艹屈(CHR,12.8%~19.6%)和苯并(k)荧蒽(Bk F,8.59%~15.5%),4者占到多环芳烃总浓度的42.1%~64.3%。根据研究区域苯并[a]芘(Ba P)人口加权浓度估算ILCRs范围为8.94×10-6~4.77×10-4,据此计算的PAFs为0.487%~13.2%,均值为3.44%,高于全国平均水平1.6%。上述研究结果为大气颗粒物中PAHs的研究提供重要的数据基础。     

北京地区表层土壤中多环芳烃的分布特征及污染源分析

根据北京地区不同环境功能区62个样品的分析结果,讨论了研究区表层土壤中多环芳烃的分布特征及污染源类型。结果表明：（1）研究区表层土壤中检测到的多环芳烃主要包括萘、苊、菲、惹烯、三芴、荧蒽、芘、、苯并蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[e]芘、苯并[a]芘、苝、二苯并[a,h]蒽、茚并[1,2,3–cd]芘、苯并[g,h,i]苝及其同系物;（2）不同环境功能区表层土壤中多环芳烃的组成及质量分数均存在一定的差别,16种优先控制的多环芳烃质量分数为175.1~10 344 ng.g-1,其中城市中心区表层土壤中多环芳烃的质量分数最高,交通干线附近、工矿企业附近表层土壤中PAHs的质量分数较高,林地、果园和农田表层土壤中PAHs的质量分数较低;（3）表层土壤中PAHs既有来源于石油源,也有来源于化石燃料燃烧产物的,但不同功能区二者贡献存在差别,其中农业用地（林地、果园、农田）中PAHs主要来源于石油源（或部分来源于土壤母岩中的有机质）,城区、交通干线附近及工矿企业附近表层土壤中PAHs污染源以化石燃料燃烧产物输入为主。     

新疆准东煤矿开采区域中多环芳烃的污染特征分析

本文采集并分析了新疆准东煤矿开采区域6个采样点的降尘、土壤和植物的样品,对样品中16种多环芳烃(PAHs)的含量进行了分析,结果显示,降尘中∑PAHs在1.07—8.34 mg·kg~(-1)间;土壤中(除1#点位)∑PAHs在0.134—1.06 mg·kg~(-1)间;植物中(除1#点位)∑PAHs在0.163—1.54 mg·kg~(-1)间.降尘中高含量PAHs主要为苯并[b]荧蒽、菲和萘;土壤中高含量PAHs主要为菲、荧蒽和蒽;植物中高含量PAHs主要为萘、菲和芴.降尘、土壤及植物中PAHs均显示出富三环的特征;研究区域土壤中PAHs的苯并(a)芘等效毒性当量结果显示,研究区域土壤中PAHs的污染存在一定的潜在风险.     

高铁酸钾降解荧蒽和苯并[a]芘的偏振荧光光谱研究

考察了高铁酸钾对荧蒽和苯并[a]芘两种PAHs(多环芳烃)的降解反应过程,并应用偏振荧光光谱技术研究了荧蒽和苯并[a]芘两种PAHsr降解体系反应过程及其差别的识别,着重探讨了两种PAHs降解体系反应过程中的多种荧光波长模式与偏振度、三维荧光(EEM)与偏振三维荧光(PEEM)变化规律,最后由时间扫描荧光模式直接获得反应动力学拟合方程式.实验结果表明,各荧光识别模式一致地显示出高铁酸钾对荧蒽和苯并[a]芘的显著性降解作用及其对应的各荧光强度变化规律,即反应时间大于40 s后,两种PAHs(多环芳烃)的降解反应均不明显,且降解过程中均无新的荧光发色团结构生成.在高铁酸钾与荧蒽/苯并[a]芘摩尔比为1∶1、1∶4、4∶1的各降解体系的反应过程均符合一级反应动力学规律.荧蒽降解曲线的线性关系更高,苯并芘降解速率更快,多种荧光光谱相结合能够实现对PAHs的降解过程的便捷而有效的追踪,其揭示的结果与分子机理一致,即苯并[a]芘分子较荧蒽分子具有更大的π电子密度,因而在Fe(Ⅵ)夺电子过程中,更易于失去电子而被Fe(Ⅵ)氧化降解.     

钢铁工业区周边农业土壤中多环芳烃(PAHs)残留及评价

对某大型矿业企业周边农业土壤中多环芳烃(PAHs)残留量进行了调查。结果表明,PAHs总残留量范围为312. 2~27 580. 9ng·g-1,且以4环以上多环芳烃组分为主。所有土样中均检出PAHs,单一污染物以芘、艹屈、荧蒽、苯并[a]芘、蒽、菲、苯并[a]蒽、苯并[k]荧蒽、茚并[1,2,3 cd]芘、苯并[g,h,i]苝为主。PAHs残留量与有机质含量相关性较好。不同样区土壤PAHs残留量受常年风向影响明显。以加拿大农业区域土壤PAHs的治理标准值为指标,用内梅罗综合指数法进行评价表明,研究区农业土壤达重污染水平的占37%,中度污染的占19%,轻污染的占25%,另有13%的采样点污染程度处于警戒限,仅有6%的采样点尚处于安全级。     

Occurrence and particle-size distributions of polycyclic aromatic hydrocarbons in the ambient air of coking plant

The purpose of this study was to characterize the occurrence and size distributions of ten species of polycyclic aromatic hydrocarbons (PAHs) in the ambient air of coking plants. Particulate-matter samples of four size fractions, including ≤2.1, 2.1–4.2, 4.2–10.2, and ≥10.2 μm, were collected using a Staplex234 cascade impactor during August 2009 at two coking plants in Shanxi, China. The PAHs were analyzed by a gas chromatograph equipped with a mass-selective detector. The concentrations of total particulate-matter PAHs were 1,412.7 and 2,241.1 ng/m³ for plants I and II, and the distributions showed a peak within the 0.1–2.1 μm size range for plant I and the 0.1–4.2 μm for plant II. The size distributions of individual PAHs (except fluoranthene) exhibited a considerable peak within the 0.1–2.1 μm size range in coking plant I, which can be explained by the gas–particle partition mechanism. The ambient air of the coking plant was heavily polluted by PAHs associated with fine particles (≤2.1 μm), and benzo[b]fluoranthene made the largest contribution to total PAHs. The exposure levels of coking-plant workers to PAHs associated with fine particles were higher than to PAHs associated with coarse particles. Benzo[b]fluoranthene, benzo[a]pyrene, and dibenzo[a,h]anthracene should be the primary pollutants monitored in the coking plant. This research constitutes a significant contribution to assessing the exposure risk of coking-plant workers and providing basic data for PAH standards for ambient air in coking plants.     

典型污水处理厂对多环芳烃及其衍生物的去除及再生水健康风险研究

多环芳烃(PAHs)在水环境中可以通过化学或微生物作用转化成其衍生物(SPAHs),而SPAHs可能具有更强的毒性和"三致性"从而危害人体健康。为探明污水厂中PAHs和SPAHs的存在性及不同二级处理和再生水处理工艺对它们的去除效果,对北京及广东共4座污水处理厂中PAHs及SPAHs进行了检测,同时对再生水进行了健康风险评价。结果显示:从进水浓度来看,4座污水处理厂中,低环芳烃浓度(191.8~394.2 ng·L~(-1))明显高于高环芳烃(89.3~108.2 ng·L~(-1));SPAHs中氧取代物(OPAHs)总浓度(253.8~322.2 ng·L~(-1))高于甲基取代物(MPAHs,44.3~220.4 ng·L~(-1))。不同二级处理工艺对PAHs的去除率为43.7%~58.2%,对SPAHs的去除率为45.8%~52.1%。不同再生水处理工艺对PAHs和SPAHs去除率差别较大,PAHs的去除率范围为1.8%~41.1%,SPAHs的去除率范围在2.35%~25.9%。结果表明,目标物的去除以生物降解为主,此外,吸附在固体颗粒上,随颗粒沉淀去除也是主要途径之一。通过对污水厂再生水的风险评价,苯并[a]芘(BaP)和二苯并[a,h]蒽(DBA)2种强致癌物TEQ浓度均高于1,其致癌风险较大,安全性有待提高。     

Distribution,source apportionment and health risk assessment of polycyclic aromatic hydrocarbons (PAHs) in intertidal sediment of Asaluyeh,Persian Gulf

Surface sediment samples were collected from intertidal zone of Asaluyeh, Persian Gulf, to investigate distribution, sources and health risk of sixteen polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 1.8 to 81.2 μg kg^?1 dry weight, which can be categorized as low level of pollution. Qualitative and quantitative assessments showed that PAHs originated from both petrogenic and pyrogenic sources with slight pyrogenic dominance. Source apportionment using principal component analysis indicated that the main sources of PAHs were fossil fuel combustion (33.59%), traffic-related PAHs (32.77%), biomass and coal combustion (18.54%) and petrogenic PAHs (9.31%). According to the results from the sediment quality guidelines, mean effects range-median quotient (M-ERM-Q) and benzo[a]pyrene toxic equivalents (BaP_eq), low negative ecological risks related to PAH compounds would occur in the intertidal zone of Asaluyeh. The total benzo[a]pyrene (BaP) toxic equivalent quotient (TEQ^carc) for carcinogenic compounds ranged from 0.01 to 7 μg kg^?1-BaP_eq, indicating low carcinogenic risk. The human health risk assessment of PAH compounds via ingestion and dermal pathways suggests low and moderate potential risk to human health, respectively.     

Spatial distribution and temporal trends of polycyclic aromatic hydrocarbons (PAHs) in water and sediment from Songhua River, China

The spatial and temporal distributions of polycyclic aromatic hydrocarbons (PAHs) in the Songhua River, Harbin, China, were investigated. Seventy-seven samples, 42 water and 35 sediment samples, were collected in April and October of 2007 and January of 2008. The concentrations of total PAHs in water ranged from 163.54 to 2,746.25 ng/L with the average value of 934.62 ng/L, which were predominated by 2- and 3-ring PAHs. The concentrations of total 16 PAHs in sediment ranged from 68.25 to 654.15 ng/g dw with the average value of 234.15 ng/g dw, which were predominated by 4-, 5- and 6-ring PAHs. Statistical analysis of the PAH concentrations shown that the highest concentrations of the total PAHs were found during rainy season (October of 2007) and the lowest during snowy season (January of 2008). Ratios of specific PAH compounds, including fluoranthene/(fluoranthene + pyrene) (Flu/(Flu + Pyr)) and phenanthrene/(phenanthrene + anthracene) (An/(Ant + PhA)), were calculated to evaluate the possible sources of PAH contaminations. These ratios reflected pyrolytic inputs of PAHs in Songhua River water and a mixed pattern of pyrolytic and petrogenic inputs of PAHs in the Songhua River sediments. Ecotoxicological risk levels calculated for PAHs suggested that there were individual PAHs, which can less frequently cause biological impairment in some samples, but no samples had constituents that may frequently cause biological impairment. Total toxic benzo[a]pyrene equivalent of ΣcPAHs varied from 10.03 to 29.7 ng/g dw and from 0.36 to 1.92 ng/g dw for total toxic tetrachlorodibenzo-p-dioxin equivalent. The level of PAHs indicated a low toxicological risk to this area.     

Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.     

基于统计方法的辽东湾沉积物中多环芳烃来源特征分析

为研究辽东湾表层沉积物中多环芳烃(PAHs)的来源特征,2014年5月采集了20个辽东湾海域表层沉积物样品,并利用气相色谱质谱联用仪对优先控制的16种PAHs进行测定,采用聚类分析、主成分分析-多元线性回归分析、异构体比值3种统计方法对辽东湾表层沉积物中PAHs来源特征进行了研究。结果表明,辽东湾表层沉积物中PAHs含量范围88.5~199.3 ng·g-1,平均值为(126.3±35.3)ng·g-1,其中,萘、菲和荧蒽是PAHs优势组分。通过统计分析结果表明,辽东湾北部表层沉积物中PAHs含量低于西南部,沉积物中PAHs的来源包括石油燃烧来源、煤炭、木材等生物质燃烧来源和石油来源,其中燃烧来源是主要来源,煤炭、木材等生物质燃烧来源占49.9%,石油燃烧来源和石油来源占50.1%。     

徐州市区大气颗粒物中多环芳烃的污染特征

采用高效液相色谱技术（HPLC）对徐州市大气颗粒物中优控的16种多环芳烃（PAHs）进行定量研究。结果表明：萘、芴、苊等低分子量芳烃的含量相对较低;苯并（g,h,i）苝、茚并（1,2,3-cd）芘、苯并（k）荧蒽、苯并（a）芘等高分子量芳烃的含量相对较高;含量最高的单体为荧蒽,占待检的16种PAHs的19%以上。不同环数多环芳烃含量大小顺序为：4环〉5环〉6环〉3环〉2环。可吸入颗粒物（PM10）中苯并（a）芘和∑PAHs在不同功能区的分布特征大体上一致,并呈现一定规律性：交通干线区〉工业区〉风景文化区〉居民区〉新城区。由此可以初步认为徐州市区PM10中的PAHs主要来源于燃煤和汽车尾气。     

珠江水体表层沉积物中PAHs的含量与来源研究

沿珠江白鹅潭水域及大学城官州河流域设立6个采样点,利用沉积物捕获器收集沉积物。参照美国EPA8000系列方法及质量保证和质量控制,对各采样点表层沉积物中16种多环芳烃（polycyclic aromatic hydrocarbons,PAHs）进行分析,以阐明珠江广州河段表层沉积物中PAHs的含量和分布特征,并结合特征化合物指数对其来源作初步探讨。珠江广州河段表层沉积物中PAHs总量介于4 787.5～8 665 ng·g^-1,平均值为7 078 ng·g^-1,黄沙码头河涌出口沉积物中总量为最高（8 665 ng·g^-1）,芳村码头为最低（4 787.5 ng·g^-1）。16种多环芳烃中菲、荧蒽、芘含量较高,分别占PAHs总量的16.11%、14.47%和17.77%。特征化合物荧蒽/202比值均小于0.5,茚并[1,2,3-cd]芘/276比值均大于0.2,表明珠江广州段表层沉积物中PAHs主要来源于化石燃料的不完全燃烧。