深圳茅洲河表层沉积物卤代多环芳烃污染研究

利用GC-MS方法分析了卤代多环芳烃(halogenated polycyclic aromatic hydrocarbons,HPAHs)在深圳茅洲河流域表层沉积物中的含量水平以及空间分布特征.所关注的3种氯代多环芳烃(chlorinated polycyclic aromatic hydrocarbons,ClPAHs)和6种溴代多环芳烃(brominated polycyclic aromatic hydrocarbons,BrPAHs)的含量范围分别是3.00～301 ng.g-1和7.52～285ng.g-1.表层沉积物中HPAHs的主要污染来源包括垃圾焚烧、化石燃料的燃烧、汽车尾气以及农作物秸秆焚烧,它们所占的比例分别是40%、20.5%、11.9%和11.7%.此外,表层沉积物中ClPAHs和BrPAHs的毒性当量(toxic equivalency quotients,TEQs)范围分别是7.95～38.1 pg.g-1和38.1～105 pg.g-1.研究发现,HPAHs的含量与采样点周边土地利用类型有关.随着工业用地密度的增大,表层沉积物中HPAHs的含量呈现出一个先增后减的趋势;而表层沉积物中HPAHs的含量与农业用地密度呈反比关系.     

岩溶地下河流域水中多环芳烃污染特征及生态风险评价

利用气相色谱-质谱联用仪(GC/MS)测定了老龙洞地下河流域水中16种优控多环芳烃(polycyclic aromatic hydrocarbons,PAHs)含量,研究了流域内PAHs组成、污染水平,并对其进行了生态风险评价.结果表明,老龙洞地下河水中ΣPAHs含量变化范围为81.5~8 019 ng·L-1,表层岩溶泉ΣPAHs含量为288.7~15200 ng·L-1,地表水ΣPAHs含量为128.4~2 442 ng·L-1;受黄桷垭镇污水的影响,地下河水相对于地下水补给来源的落水洞和地表水含量较高.流域内水中PAHs均以低环为主,尤其是3环占主导.受污水、季节的影响及PAHs物理化学性质的差异,水中PAHs月变化呈现不同的变化特征.地表水、落水洞污水排放对地下河PAHs来源起重要作用.流域内水中PAHs以低环污染为特征,所有检测到的PAH化合物处于中等污染和重污染风险.     

基于Web of Science的环境科学领域多环芳烃研究动态

多环芳烃是一类普遍存在于环境中的有机污染物。由于其难降解危害性大等特点,近年来受到越来越多的关注。为深入了解环境中多环芳烃研究的全球状况和前沿动态,比较客观地反映相关国家在该领域的科学能力和科学影响,采用ISI Web of Knowledge的Web of Science引文数据库,选用普通检索方式,以polycyclic aromatic hydrocarbon*或PAH or PAHs作为检索主题词,对1962-2014年之间该库收录的相关文献进行了计量分析。结果表明,美国发文量居榜首,占全部发文量的28.06%;发文机构中,中国科学研究院位列第一;主要的发文期刊有《Environmental Science and Technology》、《Chemosphere》及《Environmental Toxicology and Chemistry》。此外,通过对近5 a关键词的分析,指出了环境领域多环芳烃研究的热点方向。     

Exposure measurement, risk assessment and source identification for exposure of traffic assistants to particle-bound PAHs in Tianjin, China

To investigate the levels of exposure to particulate-bound polycyclic aromatic hydrocarbon(PAH) and to estimate the risk these levels pose to traffic assistants(TAs) in Tianjin(a megacity in North China), a measurement campaign(33 all-day exposure samples, 25 occupational-exposure samples and 10 indoor samples) was conducted to characterize the TAs' exposure to PAHs, assess the cancer risk and identify the potential sources of exposure. The average total exposure concentration of 14 PAHs was approximately 2871 ± 928 ng/m3(on-duty), and 1622 ± 457 ng/m3(all-day). The indoor PAHs level was 1257 ± 107 ng/m3. After 8000 Monte Carlo simulations, the cancer risk resulting from exposure to PAHs was found to be approximately 1.05 × 10-4. A multivariate analysis was applied to identify the potential sources, and the results showed that, in addition to vehicle exhaust, coal combustion and cooking fumes were also another two important contributors to personal PAH exposure. The diagnostic ratios of PAH compounds agree with the source apportionment results derived from principal component analysis.     

典型工业区土壤多环芳烃污染特征及影响因素

为完善我国典型工业区土壤多环芳烃(polycyclic aromatic hydrocarbons,PAHs)污染特征数据库,系统采集了成都市4个典型石油加工类工业区表层土壤样品,采用高效液相色谱法分析16种美国环保署优先控制PAHs的含量和组分特征.结果表明,4个工业区表层土壤(0～30 cm)中多环芳烃总含量范围为191. 2～1 604. 2μg·kg-1,平均含量(583. 6±365. 6)μg·kg-1;各工业区土壤PAHs均主要以中环PAHs和高环PAHs为主,各单体PAHs中以菲、芘、荧蒽和苯并[b]荧蒽为主要特征因子,且均存在潜在的污染风险.同时,采用数理统计方法分析土壤有机质及土壤颗粒粒径与PAHs含量的相关性,并揭示土壤PAHs赋存影响因素.结果表明,在土壤污染含量较高地块,土壤有机质是PAHs较好的吸附剂,能够在一定程度上预测土壤PAHs的迁移转化行为及土壤生态风险(PAHs致癌性);与有机质相比,土壤粒径与PAHs的相关性较低,总体表现为砂粒与PAHs含量无显著相关性,粉粒与之弱正相关,黏粒与之弱负相关.通过本研究,为此类区域的土壤修复实践或学术研究提供依据.     

新乡市机动车排放对道路灰尘中重金属与多环芳烃污染的影响

以新乡市主要道路的地表灰尘为样本,采用电感耦合等离子体质谱仪和气相色谱质谱联用仪分别测定所含5种重金属(Cd、Pb、Cr、Cu和Zn)和15种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)的含量,并探究了机动车排放对其污染特征的影响.结果显示,重金属和PAHs的含量范围分别为2. 58～1 560 mg·kg~(-1)和ND～1. 30 mg·kg~(-1),其含量总体上随灰尘粒径减小而增高.组成上,重金属以Zn为主,PAHs主要以高环为优势组分.空间分布上,重金属和PAHs含量存在差异:人民路、小店工业园区和水泥厂附近道路灰尘中的重金属总含量最高,而PAHs含量的高值出现在人民路、高速上口和107国道的灰尘中.Pearson相关分析表明,5种重金属与15种PAHs间基本不存在正相关关系.通过聚类分析和因子分析发现,新乡市道路灰尘中的重金属基本不受机动车排放影响,而PAHs受机动车排放影响较大.     

广西水生蔬菜土壤多环芳烃污染特征

为研究水生蔬菜土壤中多环芳烃(PAHs)的污染水平,以广西水生蔬菜和相邻地块陆生蔬菜土壤作为研究对象,采集表层土壤,比较16种PAHs的污染特征,分析PAHs主要来源,评价潜在的生态风险。结果表明,研究区内水生蔬菜土壤中5、6环PAHs和7种致癌性PAHs的含量显著地高于陆生蔬菜土壤,2,3环PAHs的含量低于陆生蔬菜土壤,4环PAHs的含量没有显著差异;水生蔬菜和陆生蔬菜土壤中7种致癌性芳烃∑7cPAHs的平均贡献率分别为49. 03%和37. 61%,大部分样点属于重度污染水平;三种水生蔬菜土壤PAHs的污染模式相似,以4,5环PAHs为主,其次为2,3环PAHs,6环PAHs的含量最低。通过同分异构体比值法和主要成分分析法分析,发现土壤PAHs的主要来源为机动车尾气排放和生物质不完全燃烧。水生蔬菜土壤PAHs的苯并(a)芘总毒性当量为174. 59μg/kg,显著高于陆生蔬菜土壤的105. 54μg/kg,二者均低于加拿大土壤质量指标600μg/kg,但潜在的生态风险不可忽视。     

青岛市城郊蔬菜中多环芳烃污染特征和健康风险评估

2016年5月在青岛市城郊的蔬菜基地采集表层土壤和蔬菜的可食部位,采用高效液相色谱紫外/荧光检测器串联方法对美国环保署优先控制的16种多环芳烃(PAHs)进行检测,分析了土壤和蔬菜中PAHs的含量、组成及两者含量间的关系,并评价了蔬菜中PAHs的健康风险.结果表明,土壤中16种PAHs的总含量(∑16PAH)范围为277.0~1548.1μg·kg~(-1),主要呈现PAHs轻、中度污染.蔬菜中∑16PAH的平均含量为222.6μg·kg~(-1),叶菜类、瓜果类和根茎类蔬菜中∑16PAH含量没有显著性差异.3类蔬菜中PAHs的组成均是以3环PAHs为主,比例达到51.4%~56.2%,但根茎类蔬菜中致癌PAHs所占比例高于叶菜类和瓜果类.叶菜类蔬菜中PAHs含量与土壤中PAHs含量具有显著的正相关关系(r=0.434,p0.05).蔬菜中PAHs的毒性主要来自于7种致癌PAHs,成年人通过摄食蔬菜产生的日平均PAHs暴露量高于其他人群,青岛市城郊部分品种蔬菜中的PAHs对人群存在潜在的致癌风险.     

岩溶地下河流域表层土壤多环芳烃污染特征及来源分析

采集重庆南山老龙洞地下河流域农田土壤(0～20 cm),利用气相色谱-质谱联用仪(GC/MC)测定了土壤样品中16种优控多环芳烃(polycyclic aromatic hydrocarbons,PAHs)含量,分析其含量和组成,污染水平及污染来源.结果表明,流域内不同地点表层土壤16种PAHs总量变化范围为277～3301 ng·g-1,平均值为752.6 ng·g-1±635.5 ng·g-1,所有样品均遭受污染,其中57%为轻污染,29%为污染土壤,而14%为重污染.多环芳烃的组成以2～3环为主,占总量的28.72%～72.68%,平均值为48.20%;4环和5～6环含量分别为7.77%和34.03%.土壤PAHs含量与有机质(SOM)含量显著相关,而与pH值相关性不强.比值法和主成分分析(PCA)表明,流域内土壤主要来自交通排放与煤炭、石油及生物质燃烧的混合源以及石油源.     

种植油麦菜评价多环芳烃污染土壤的农用风险

污染土壤引起的农产品安全问题已不容忽视.为了探讨多环芳烃(polycyclic aromatic hydrocarbons,PAHs)污染土壤农用的安全性,本文通过盆栽实验方法,以某焦化企业周边长期受PAHs污染的农田土壤为研究对象,以广泛种植的油麦菜(Lactuca sativa L.)为农产品代表,利用超声振荡提取和气相色谱-质谱联用仪(GC-MS)分析方法,解析样品中优先控制的16种PAHs的含量,揭示土壤-油麦菜体系中PAHs的迁移转化与富集特征,评估其潜在风险.结果表明,油麦菜地上部分(YS)PAHs的含量(Σ16PAHs)大于地下部分(GS),YS中3～5环PAHs相对含量高,GS中4～6环PAHs含量高. YS对不同PAHs的富集系数均大于GS,YS中蒽(Ant)的富集系数最大(2. 41),荧蒽(Fla)最小(0. 458),GS中苯并[a]芘(Bap)最大(0. 862),Fla最小(0. 130). 16种PAHs从GS到YS的转运系数均大于1. 00.关联性分析表明GS与初始土壤(SS) PAHs拟合优度中等(R~2=0. 71),YS与SS的PAHs拟合优度最大(R~2=1. 0),YS和GS的PAHs拟合优度最小(R~2=0. 39). YS和GS的健康风险值分别是国家食品标准Bap最大风险控制值的11. 8和12. 7倍.表明油麦菜食用的潜在风险较高,焦化企业周边污染土壤农用的安全问题不容忽视.     

燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃的赋存特征和毒性风险

研究了燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃（HPAHs）的赋存特征、生成机制和毒性效应.结果表明,燃煤电厂和垃圾电厂飞灰中氯代PAHs （Cl-PAHs）的含量为1.06~1.67 ng·g^-1和2.76 ng·g^-1,溴代PAHs （Br-PAHs）的含量为26.4~44.2 ng·g^-1和6.31 ng·g^-1;垃圾电厂飞灰中Cl-PAHs的含量明显高于燃煤电厂,主要是因为生活垃圾中含有大量的聚氯乙烯为代表的塑料.来自煤粉炉的飞灰中Br-PAHs和Cl-PAHs的含量明显低于循环流化床燃煤飞灰,主要是因为煤粉炉具有更高的燃烧温度和燃烧效率.燃煤电厂飞灰中主要为7-BrBaA和9-ClPhe;垃圾电厂除尘器飞灰中Br-PAHs主要为9-BrPhe和2-ClAnt.7-BrBaA和9,10-Br₂Ant在燃煤电厂除尘器飞灰的含量远高于其在底灰和脱硫石膏的含量,但摩尔质量相对较小的2-BrFle在飞灰、底灰和脱硫石膏中的含量相近.垃圾电厂除尘器飞灰经过半干法脱酸后Br-PAHs的含量减少50%以上,但是经过螯合剂稳固化作用之后飞灰中Br-PAHs的含量明显升高.Pearson相关分析结果表明,燃煤电厂不同燃烧产物的HPAHs生成机制相同,而垃圾焚烧电厂不同产物中HPAHs具有不同的生成机制,飞灰螯合化过程导致HPAHs的二次生成.垃圾电厂除尘器飞灰中HPAHs的TEQs值（10.0×10^-3 ng·g^-1）与燃煤电厂相近（8.87×10^-3~15.0×10^-3 ng·g^-1）.对于垃圾电厂不同燃烧产物,脱酸工艺能够显著去除7-BrBaA从而降低飞灰的TEQ值,而飞灰螯合化后TEQ值达到螯合前的5.4倍.燃煤电厂的飞灰因年产量较大,且总HPAHs的TEQs值相对较高,对其处理和资源化利用应考虑HPAHs带来的生态风险.     

Comparison of polycyclic aromatic hydrocarbon pollution in Chinese and Japanese residential air

Comparative studies on polycyclic aromatic hydrocarbon (PAH) pollution in residential air of Hangzhou (China) and Shizuoka (Japan) were conducted in summer (August, 2006) and winter (January, 2007). Total concentrations of 8 PAHs ranged from 7.1 to 320 ng/m³ and 0.15 to 35 ng/m³ in residential air of Hangzhou and Shizuoka, respectively. Air PAH concentrations in smoking houses were higher than that in nonsmoking houses. In nonsmoking houses, mothball emission and cooking practice were the emission sources of 2- and 3-ring PAHs in Hangzhou, respectively. The 2- and 3-ring PAHs were from use of insect repellent, kerosene heating and outdoor environment in nonsmoking houses in Shizuoka. The 5- and 6-ring PAHs in residential air were mainly from outdoor environment in both cities. Toxicity potencies of PAHs in residential air of Hangzhou were much higher than that in Shizuoka.     

Experiments and modelling of phenanthrene biodegradation in the aqueous phase by a mixed culture

Pollution by polycyclic aromatic hydrocarbons（PAHs） is widespread due to tmsuitable disposal of industrial waste. They are mostly defined as priority pollutants by environmental protection authorities worldwide. Phenanthrene, a typical PAH, was selected as the target in this paper. The PAH-degrading mixed culture, named ZM, was collected from a petroleum contaminated river bed. This culture was injected into phenanthrene solutions at different concentrations to quantify the biodegradation process. Results show near-complete removal of phenanthrene in three days of biodegradation if the initial phenanthrene concentration is low. When the initial concentration is high, the removal rate is increased but 20%-40% of the phenanthrene remains at the end of the experiment. The biomass shows a peak on the third day due to the combined effects of microbial growth and decay. Another peak is evident for cases with a high initial concentration, possibly due to production of an intermediate metabolite. The pH generally decreased during biodegradation because of the production of organic acid. Two phenomenological models were designed to simulate the phenanthrene biodegradation and biomass growth. A relatively simple model that does not consider the intermediate metabolite and its inhibition of phenanthrene biodegradation cannot fit the observed data. A modified Monod model that considered an intermediate metabolite （organic acid） and its inhibiting reversal effect reasonably depicts the experimental results.     

百色市工业区表层土壤中多环芳烃污染特征及来源分析

为完善我国实地的不同的PAHs污染特征数据库,系统采集了百色市5个工业区表层土壤样品,利用HPLC分析了16种US EPA 优控PAHs的含量和组分特征,运用同分异构体比率法和主成分因子载荷法揭示其污染来源.结果表明,工业区土壤中PAHs总含量范围在18.7~6437μg/kg之间,电厂2土壤中PAHs平均含量最高,达1923.4μg/kg.与国内外相关研究比较,处于中高等污染水平.5个工业区表层土壤样品中PAHs的残留大小顺序为:电厂2>电厂1>炼油厂>润滑油厂>水泥厂;电厂2、电厂1、炼油厂和润滑油厂4个工业区土壤中PAHs污染以4环为主,毒性较高的4环和5环PAHs均高于其他环数PAHs;水泥厂附近土壤中PAHs污染以2、3环为主.研究区域内土壤中Baa、Bkf、Chr和Fla等单体超标严重.工业区土壤中PAHs污染主要来自于燃烧源、石油源及石油源和燃烧源的混合源,燃烧源贡献最大(占45.0%),石油源和燃烧源混合贡献率为36.8%,而石油源所占比例相对较小(占18.2%).     

Polycyclic aromatic hydrocarbons (PAHs) in a sediment core from Lake Taihu and their associations with sedimentary organic matter

Sediment core is the recorder of polycyclic aromatic hydrocarbon (PAH) pollutions and the associated sedimentary organic matter (SOM), acting as crucial supports for pollution control and environmental management. Here, the sedimentary records of PAHs and SOM in the past century in Lake Taihu, China, were reconstructed from a 50-cm sediment core. On the one hand, the presence of PAHs ranged from 8.99 to 199.2 ng/g. Vertically, PAHs declined with the depth increased, and the sedimentation history of PAHs was divided into two stages with a discontinuity at 20 cm depth. In composition, PAHs in the sediment core were dominated by three-ring PAHs (44.6% ± 9.1%, mean ± standard deviation), and were followed by four-ring (27.0% ± 3.3%), and five-ring (12.1% ± 4.0%) PAHs. In toxicity assessment, the sedimentary records of benzo[a]pyrene-based toxic equivalency were well described by an exponential model with R-square of 0.95, and the environmental background toxic value was identified as 1.62 ng/g. On the other hand, different components of SOM were successfully identified by n-alkane markers (p < 0.01) and the variations of SOM were well explained (84.6%). A discontinuity of SOM was recognized at 22 cm depth. Association study showed that the sedimentary PAHs were associated with both anthropogenic and biogenic SOM (p < 0.05) with explained variances for most individual PAHs of 60%. It indicated the vertical distributions of PAHs were driven by sedimentary SOM. Therefore, environmental processes such as biogenic factors should attract more attentions as well as PAH emissions to reduce the impacts of PAHs.     

Polycyclic aromatic hydrocarbons in soils of Beijing and Tianjin region： Vertical distribution, correlation with TOC and transport mechanism

The contents and distribution of 20 polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic hydrocarbons (HAHs) were investigated in 16 soil profiles of Beijing and Tianjin region. Transport of high molecular weight PAHs (HMWPAHs) and the correlation between total organic carbon (TOC) and their concentrations were also discussed. The results indicated that highly contaminated sites were located at urban or wastewater irrigation areas and pollutants mainly accumulated in topsoil (< 40 cm), with a sharp content decrease at the vertical boundary of 30–40 cm. Total PAHs/HAHs concentrations in soils from Tianjin were markedly greater than those from Beijing. Even the contents at bottoms of soil profiles in Tianjin were higher than those in topsoils of Beijing soil profile. HMWPAHs dominated the PAH profiles, exhibiting a uniform distribution of pyrogenic origin between topsoils and deep layers. Furthermore, the percentages of HMWPAHs remained relative constant with the depth of soil profiles, which were consistent with the distribution of particulate matter-associated PAHs in the local atmospheric environments. Therefore, HMWPAHs transport with particulates might be the predominant source found in soil profiles.     

化工区土壤中多环芳烃的污染特征及其来源分析

系统采集了天津滨海新区3个化工区28个表层土壤样品,利用GC/MS分析了16种US EPA优控多环芳烃(PAHs)的含量和组分特征,运用环数比值法和主成分因子载荷法揭示了其污染来源.结果表明,化工区土壤中PAHs最高含量达5 991.7　ng·g^-1(塘沽化工区),平均含量1 18５.０　ng·g^-1,与国内外相关研究比较,处于中高等污染水平,工业污染排放已明显影响到周边环境中PAHs的残留,且塘沽化工区＞汉沽化工区＞大港采油区;塘沽和汉沽2个化工区土壤中毒性较高的4环和5环PAHs均高于其他环数PAHs,大港采油区3环所占比例明显占主导;土壤有机碳(TOC)和PAHs之间存在显著相关关系(n=28,R²=0.847,p＜0.01),TOC是影响研究区域PAHs在土壤中分配的一个重要因素;煤燃烧的排放是化工区土壤中PAHs污染的主要来源,石油类挥发或泄漏对大港采油区影响显著.     

莱州湾大气颗粒相中多环芳烃及其衍生物的赋存特征

多环芳烃作为一类典型的持久性有毒物质,一直是环境领域关注的热点和重点,有关多环芳烃衍生物的报道,尤其是有关大气中烷基和硝基多环芳烃的研究报道仍非常缺乏。本研究选取莱州湾刁龙嘴为采集区域,对大气颗粒相样品中16种母体多环芳烃（PAHs）、12种烷基多环芳烃（A–PAHs）和25种硝基多环芳烃（N–PAHs）进行分析。结果表明,16种母体多环芳烃（Σ₁₆PAHs）的浓度范围为517.2 ~ 64124.8 pg/m3;12种烷基化多环芳烃（Σ₁₂A–PAHs）的浓度范围为273.6 ~ 5897.3 pg/m3;25种硝基化多环芳烃（Σ₂₅N–PAHs）的浓度范围为113.5 ~ 1032.3 pg/m3。3种类型多环芳烃的浓度和污染模式均表现出明显的季节变化特征,其中,夏季,2环、3环的PAHs、A–PAHs和N–PAHs比例相对较高,而冬季4环及以上单体的比例偏高。PAHs的特征比值表明,莱州湾刁龙嘴地区PAHs的来源主要以柴油、煤及生物质燃烧为主。Σ₁₆PAHs、Σ₁₂A–PAHs和Σ₂₅N–PAHs与温度均呈现出显著的负相关性（R2 = 0.94,p < 0.01;R2 = 0.61, p < 0.01;R2 = 0.74,p < 0.01）,说明温度是影响颗粒相吸附芳烃类物质的一个主要因素。此外,三者之间Pearson相关关系表明,PAHs及其衍生物表现出相同的污染来源和相似的环境行为。