江汉平原四湖流域上区地下水中多环芳烃分布特征与源解析

初次对江汉平原四湖流域上区地下水中多环芳烃(PAHs)的分布特征和来源进行研究,选择湖北潜江长湖-汉江一带9个典型地下水采样点分枯水期和丰水期进行采样,并利用气相色谱与质谱联用仪对16种优控PAHs进行定量分析.结果表明,研究区枯水期和丰水期地下水中PAHs的浓度变化范围分别为62.74~224.63 ng·L-1和55.86~115.15 ng·L-1,总体水平表现出枯水期高于丰水期,且分布于滨湖区域和近岸带的地下水中PAHs浓度较高.这些PAHs输入途径比较复杂,经用主成分分析法分析其来源,大致可归结为燃烧源,部分采样点有石油或石油燃烧的污染.研究区域地下水中PAHs浓度与国内某些地区相比,显示出较低的污染水平,但就致癌性PAHs来看,枯水期具有致癌性PAHs的浓度范围在19.32~153.39 ng·L-1之间,丰水期在16.30~64.22 ng·L-1之间,均已远远超出地下水中PAHs所允许的致癌浓度范围,这必然会对当地人类身体健康构成威胁.     

三种农作物秸秆燃烧颗粒态多环芳烃排放特征

收集3种农作物秸秆玉米,水稻和小麦露天燃烧排放的颗粒物样品,并利用气相色谱-质谱(GC-MS)对样品中的34种多环芳烃(PAHs)进行分析,研究颗粒态PAHs的排放因子及可用于源解析的诊断参数.结果表明,3种秸秆燃烧总PAHs的排放因子为644.18~1798.13μg/kg;其中4环PAHs在秸秆燃烧样品中含量最高,约占38.8%~58.8%,6环PAHs所占比例相对较小,约占5.72%~15.17%.PAHs中部分单体具有相对较强致癌性,对环境和人体健康的影响不可忽视.首次检测分子量为300的高分子多环芳烃二苯并[a,e]荧蒽.在玉米、水稻和小麦秸秆燃烧排放颗粒物中的排放因子分别为6.70,2.77和2.92μg/kg.此外,研究发现BaP/BghiP, Phe/Phe+Ant和Flu/(Flu + Pyr)比值可以作为较好的区分秸秆燃烧与其他来源的诊断参数.     

上海市表层土壤中多环芳烃的分布特征与源解析

应用气相色谱-质谱联用仪(GC-MS)对上海市80个表层土壤样品中16种优控多环芳烃的浓度进行了测定,分析了上海市土壤中PAHs的含量分布特征,并利用同分异构体比值、主成分分析方法对表层土壤中的PAHs进行了源解析.结果表明,80个样点PAHs的含量在0.12~24.5μg/g之间,呈现出郊区>市区>农村的梯度变化,市区内不同功能区采样点呈现出交通区>文教区>公园绿地>商业区>住宅区的梯度变化. PAHs组成以4环和5环为主,平均含量分别占∑PAHs的49.2%和27.0%,其次为3环和6环,分别占∑PAHs的14.8%和6.6%,最低为2环PAHs,仅占2.4%,单体PAHs化合物以荧蒽、芘、苯并芘为主.源解析表明,表层土壤中PAHs的主要来源是燃烧源,主要是石油燃烧.     

Emission factors of polycyclic aromatic hydrocarbons from domestic coal combustion in China

Domestic coal stove is widely used in China, especially for countryside during heating period of winter, and polycyclic aromatic hydrocarbons （PAHs） are important in flue gas of the stove. By using dilution tunnel system, samples of both gaseous and particulate phases from domestic coal combustion were collected and 18 PAH species were analyzed by GC-MS. The average emission factors of total 18 PAH species was 171.73 mg/kg, ranging from 140.75 to 229.11 mg/kg for bituminous coals, while was 93.98 mg/kg, ranging from 58.48 to 129.47 mg/kg for anthracite coals. PAHs in gaseous phases occupied 95% of the total of PAHs emission of coal combustion. In particulate phase, 3-ring and 4- ring PAHs were the main components, accounting for 80% of the total particulate PAHs. The total toxicity potency evaluated by benzo[a]pyrene-equivalent carcinogenic power, sum of 7 carcinogenic PAH components and 2,3,7,8-tetrachlorodibenzodioxin had a similar tendency. And as a result, the toxic potential of bituminous coal was higher than that of anthracite coal. Efficient emission control should be conducted to reduce PAH emissions in order to protect ecosystem and human health.     

成都市冬季PM2.5中多环芳烃的源解析与毒性源解析

对成都市2010~2011年住宅区冬季PM2.5中16种多环芳烃(PAHs)进行了来源解析、毒性评估以及毒性源解析研究.结果表明,16种PAHs普遍检出,成都市冬季PM2.5中的ΣPAHs浓度范围为22.79~215.82ng/m3,平均浓度为71.38ng/m3.PAHs组分分析结果显示,低环(2~3环)PAHs含量较低,高环(4~6环)所占比例较大,其比例范围为75.95%~99.52%.利用EPA PMF5.0解析PAHs污染源类型,结果表明成都市冬季PM2.5中PAHs的主要来源是煤和木材燃烧源、柴油燃烧源和汽油燃烧源,其分担率分别是14.88%、31.34%和54.08%.等效因子(TEF)毒性评估表明,成都市冬季的TEQ均值为16.82ng/m3.此外,运用PMF-TEF耦合模型对PAHs进行了毒性源解析,结果表明煤和木材燃烧、柴油燃烧和汽油燃烧的毒性分担率分别是12.39%、24.78%、62.83%.     

珠江广州段沉积物中PAHs生态风险的蒙特卡洛模拟

以珠江广州段24个采样站位表层沉积物的实测16种多环芳烃(PAHs)浓度为基础资料,采用基于Logistic混沌迭代序列改进的蒙特卡洛算法对珠江广州段沉积物中PAHs的生态风险发生概率进行了定量分析.研究结果表明:PAHs风险排序从大到小依次是:菲>芘>荧蒽> >苯并[a]蒽>苯并[a]芘>二苯并[a,h]蒽.菲、芘和荧蒽引发水生生态风险概率较大,应重点关注.除菲外,其余6种PAHs暴露浓度对生态风险发生概率的贡献率均超过90%,可见PAHs在本区域环境中的风险大小主要取决于其暴露量.     

多环芳烃对卤虫无节幼体的光诱导毒性

以卤虫Ⅱ～Ⅲ龄无节幼体为实验材料,在实验室内研究4种多环芳烃的光诱导毒性,比较了在有紫外(UV)和无UV照射条件下多环芳烃对卤虫幼体的存活和几种生理生化指标的影响.结果表明:UV辐射(UVA:476 μw·cm-2;UVB:6.5 μW·cm-2)明显提高了菲、蒽、荧蒽和芘对卤虫幼体的毒性,其24 h LC50值分别是无UV照射条件下LC50值的1/139、1/182、1/102和1/88.UV照射诱导了荧蒽对卤虫幼体的氧化损伤,过氧化物酶(POD)对荧蒽的光诱导毒性较超氧化物歧化酶(SOD)敏感;卤虫幼体的丙二醛(MDA)和Na ·K -ATPase是衡量荧蒽光诱导毒性的较敏感参数.     

上海工业区玻璃表面多环芳烃分布特征与溯源

利用GC-MS对上海工业区玻璃表面16种优控多环芳烃(PAHs)进行了定量分析.结果表明,宝山工业区、吴泾化工区和金山化工区玻璃表面PAHs平均含量分别为10.66,16.48,31.94mg/m2,工业区附近对照点PAHs平均含量分别为2.7,8.86,4.18mg/m2.各采样点玻璃表面不同环数PAHs分布特征相似,以3环和4环PAHs为主,平均含量分别占∑16PAHs的25%和47%;其次为5环和6环PAHs,分别占∑16PAHs的14%和9%,最低为2环PAHs,仅占5%.单体PAH以Phe、Fluo、Py和Chry为主.源解析表明,玻璃表面PAHs主要来源于煤和焦炭燃烧,部分来源于石油燃烧.质量标准化毒性当量浓度范围在0.07~3.23mg/g之间,对毒性当量贡献最大的单体PAH分别是BaP,BbF,BkF,DahA.     

南水北调中线源头淹没区土壤中多环芳烃的赋存分布特征

研究了南水北调中线源头淹没区农田土壤中多环芳烃(PAHs)的分布特征与来源.采集了丹江口水库淅川淹没区(高程170 m以下)8个乡镇的18个农田土壤.以索氏提取法对样品处理后,采用GC/MS对土壤中美国EPA优先控制的16种PAHs进行了检测分析.结果表明,淹没区农田土壤中共有10种PAHs组分检测出,总残留量范围为5.29~173.11 ng·g^-1,平均值为41.89 ng·g^-1,具有致癌作用的组分苯并 蒽(Baa)、 (Chr)和苯并(b)荧蒽(Bbf)含量约占PAHs总残留量的2.4%.个别采样点的PAHs残留量高于荷兰政府规定的无污染土壤的PAHs值(干重:20~50 ng·g^-1),表明淹没区部分农田土壤已受到轻微的PAHs污染.通过使用PAHs环数相对丰度法和Phe/Ant、Fla/Pyr、Ant/(Ant+Phe)和Fla/(Fla+Pyr)等分子标志物指示法来解析PAHs来源,结果显示,淅川淹没区土壤中PAHs的来源主要是煤等化石燃料和草木等植物性燃料的燃烧,少量来源于汽车尾气的排放以及石油产品的泄漏.淹没区农田土壤中PAHs污染存在一定的生态风险,值得进一步关注.     

Influence of rice straw burning on the levels of polycyclic aromatic hydrocarbons in agricultural county of Taiwan

Atmospheric particulate and polycyclic aromatic hydrocarbons (PAHs) size distribution were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan during the rice straw burning and non-burning periods. The concentrations of total PAHs accounting for a roughly 58% (34%) increment in the concentrations of total PAHs due to rice-straw burning. Combustion-related PAHs during burning periods were 1.54–2.57 times higher than those during non-burning periods. The mass median diameter (MMD) of 0.88–1.21 m in the particulate phase suggested that rice-straw burning generated the increase in coarse particle number. Chemical mass balance (CMB) receptor model analyses showed that the primary pollution sources at the two sites were similar. However, ricestraw burning emission was specifically identified as a significant source of PAH during burning periods at the two sites. Open burning of rice straws was estimated to contribute approximately 6.3%–24.6% to total atmospheric PAHs at the two sites.     

多环芳烃(PAHs)在大气中的相分布

通过对广州市老城区空气中多环芳烃的研究表明 ,该区多环芳烃的污染相当严重 ,不同季节测定的多环芳烃总量差别不大 ,但颗粒相多环芳烃在春季占的比例 (44 8% )要高于夏季 (9 4 % ) .气相中主要以芴、菲、甲基菲、荧蒽、芘等低环数的多环芳烃为主 ,而高于四环的多环芳烃主要是分布在颗粒相中 ,苯并 (ghi)是最主要的颗粒相多环芳烃物质 .     

Investigation of polycyclic aromatic hydrocarbons from coal gasification

The hazardous organic pollutants generated from coal gasification, such as polycyclic aromatic hydrocarbons(PAHs), are highly mutagenic and carcinogenic. More researchers have paid particular attention to them. Using air and steam as gasification medium, the experiments of three kinds of coals were carried out in a bench-scale atmospheric fluidized bed gasifier. The contents of the 16 PAHs specified by US EPA in raw coal, slag, bag house coke, cyclone coke and gas were measured by HPLC to study the contents of PAHs in raw coal and the effects of the inherent characters of coals on the formation and release of PAHs in coal gasification. The experimental results showed that the distributions of PAHs in the gasified products are similar to raw coals and the total-PAHs content in coal gasification is higher than in raw coal(except Coal C). The totaI-PAHs contents increase and then decrease with the rise of fixed carbon and sulfur of coal while there has an opposite variation when volatile matters content increase. The quantities of PAHs reduce with the increase of ash content or the drop of heating value during coal gasification.     

南京大气气溶胶中多环芳烃源识别及污染评价

采用GC、GC-MS等方法,研究了南京市不同功能区夏、冬季大气气溶胶中多环芳烃(PAHs)的污染状况和污染来源,并对不同功能区的PAHs进行了污染评价.结果表明,南京市各功能区气溶胶中PAHs总量在19.73～497.40ng/m³之间,且冬季高于夏季,细颗粒中含量高于粗颗粒.通过一些特征标志PAHs的比值,可判断夏季各功能区的PAHs污染主要来自于汽车尾气(主要是柴油型)的排放,冬季则为汽车尾气和燃煤污染.采用苯并(a)芘(BaP)及苯并(a)芘等效致癌浓度(BaPE)来评价5个功能区气溶胶中PAHs的污染状况,夏季除交通干道超过国家标准(BaP,10ng/m³),居民区细颗粒中略超过居民区标准(BaP,5ng/m³)外,空气质量良好.而冬季各功能区PAHs基本上均严重超标.     

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%).     

河蚬对太湖梅梁湾沉积物多环芳烃的生物富集

以采自清洁水体的河蚬(Corbicula flumiaea)为实验生物,利用生物富集实验测试了河蚬对太湖梅梁湾水源地沉积物巾多环芳烃的乍物富集.研究结果表明:将河蚬暴露于多环芳烃污染程度不同的太湖梅梁湾沉积物中(PAHs总含量分别为991.4-1210.9 ng·g-1(以干重汁),平均为1 101.0 ng·g-1),暴露7d后各样点中河蚬对PAHs的富集量为233.5-342.6 ng·g-1,其中2、3、4环PAHs分别占总含量的23.5%±4.9%、26.2%±4.4%和46.6%±8.5%;含量最高的4种多环芳烃依次为芘、萘、菲和荧蒽,它们所占的比例分别为29.4%±8.2%、23.5%±4.9%、14.6%±6.1%和12.5%±3.6%.河蚬对多环芳烃的生物-沉积物生物富集因子(BSAF)为0.09-0.44.低分子鼍多环芳烃的BSAF要比高分子最多环芳烃的BSAF值高,其中芘、萘、菲和荧蒽的BSAF值分别为0.09±0.04、0.24±0.04、0.44±0.23和0.19±0.09.     

在线表征萘二次有机气溶胶硝基多环芳烃

硝基多环芳烃(NPAHs)广泛存在于大气气溶胶中,是棕色碳的重要组成部分.萘和其他多环芳烃是NPAHs的重要前体物.为研究NO₂对NPAHs形成的影响,本文利用气溶胶激光飞行时间质谱仪(ALTOFMS)在线测定不同NO₂浓度下萘光氧化形成的二次有机气溶胶(SOA)的NPAHs组分.实验结果表明,NO₂对NPAHs的产生和萘SOA的形成有促进作用.通过ALTOFMS在线检测、模糊C均值(FCM)聚类分析,结合离线电喷雾电离质谱验证,测得萘酚和羰基化合物是不存在NO₂时萘SOA粒子主要成分,而通过OH-萘加合物和萘酚硝化产生的硝基萘、二硝基萘、硝基萘酚和二硝基萘酚及其衍生物是NO₂存在时萘SOA粒子的主要组分.这为城市大气高浓度NO_x背景下,研究NPAHs的化学组分和形成机理提供了实验依据.     

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.     

金属离子对长期污染土壤中多环芳烃解吸的影响

研究了离子强度、不同金属离子对土壤中PAHs表观解吸水平的影响.根据Pearson原理计算了菲、荧蒽、芘和苯并[k]荧蒽等几种PAHs的碱性特征参数并据此分析了其酸碱性类型.结果表明:实验条件下,解吸液中离子强度并非影响土壤中PAHs解吸的控制要素;不同硬度酸性金属离子与PAHs之间的酸碱作用是影响土壤中PAHs解吸水平变化的关键.硬酸性金属离子Ba2+、Al3+、Ca2+对土壤中PAHs的解吸具有促进作用,软酸性离子Hg2+、Ag+则具有抑制作用,比较而言交界酸性金属离子Cu2+、Fe2+、Zn2+在提高土壤中PAHs解吸上作用更加明显.     

Emissions of parent, nitrated, and oxygenated polycyclic aromatic hydrocarbons from indoor corn straw burning in normal and controlled combustion conditions

Emission factors （EFs） of parent polycyclic aromatic hydrocarbons （pPAHs）, nitrated PAHs （nPAHs）, and oxygenated PAHs （oPAHs） were measured for indoor corn straw burned in a brick cooking stove under different burning conditions. The EFs of total 28 pPAHs, 6 nPAHs and 4 oPAHs were （7.9 ±3.4）, （6.5 ±1.6）×10^-3, and （6.1 ±1.4）×10^-1mg/kg, respectively. Fuel charge size had insignificant influence on the pollutant emissions. Measured EFs increased significantly in a fast burning due to the oxygen deficient atmosphere formed in the stove chamber. In both restricted and enhanced air supply conditions, the EFs of pPAHs, nPAHs and oPAHs were significantly higher than those measured in normal burning conditions. Though EFs varied among different burning conditions, the composition profiles and calculated isomer ratios were similar, without significant differences. The results from the stepwise regression model showed that fuel burning rate, air supply amount, and modified combustion efficiency were the three most significant influencing factors, explaining 72%-85% of the total variations.     

中国主要河流中多环芳烃生态风险的初步评价

以现有的中国主要河流中多环芳烃(PAHs)的浓度数据为基础,通过定义1个危害商,利用商值法筛选出菲、蒽、荧蒽、芘、苯并[a] 蒽、 和苯并[a]芘7种对水生生态具有潜在风险的PAHs.以河流水相中PAHs浓度数据为依据,结合毒性数据库中PAHs水相浓度对水生生物的毒性数据,用概率风险评价法分析了这7种PAHs对水生生物的生态风险.结果表明,7种筛选出的PAHs风险大小依次为：蒽>芘>苯并[a]蒽>荧蒽>苯并[a]芘>菲> .