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.     

西江水体中多环芳烃的分布特征及来源

为确定西江水体中多环芳烃(PAHs)的分布特征和来源,分别在洪水期(2003年8月)和枯水期(2003年11月)对西江水体进行了两次水柱采样,利用气相色谱-质谱(GC-MS)对样品中15种优控的PAHs进行定量分析,并运用分子比值法探寻多环芳烃的来源.结果表明,西江水体溶解相和颗粒相中PAHs的质量浓度分别为21.7～138 ng·L-1,和40.9～238 μg·kg-1.水体中PAHs的总质量浓度(溶解相及颗粒相),洪水季(43.9～116.9 ng·L-1)大于枯水季(25.2～34.1 ng·L-1).溶解相和颗粒相中PAHs质量浓度都表现相同的垂直变化即中层>下层>上层.从PAHs组成特点来看,溶解相以3环的PAHs为主,占总组分的80%;而颗粒相以3环、4环的PAHs为主,分别占总组分的48%和41%.西江水体PAHs的质量浓度,与欧洲其他一些低污染水域相比相对较高;而低于国内一些主要受污染河流.分子比值法表明,西江水体PAHs主要来源于高温燃烧排放.     

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.     

雾霾期北京大气中多环芳烃污染特征及暴露风险评估

雾霾对我国尤其是华北平原地区造成了极大的困扰,其发生常以颗粒物浓度急剧增长为特征,给人群健康带来了极大的风险。为进一步阐释雾霾的形成过程及其健康效应,在冬季雾霾期对北京城区大气颗粒态及气态中18种多环芳烃(PAHs)进行了连续测定,同步监测颗粒物、痕量气体污染物以及气象参数的变化,并对PAHs的浓度、组成、气粒分配等大气行为以及其与气象因素的作用机制进行了探讨。北京城区大气气相和颗粒物相中ΣPAHs浓度分别为585 ng·m~(-3)和705 ng·m~(-3)。雾霾发生时,PM_(2.5)浓度升高了3.6倍,PAHs浓度升高了2.6倍,18种PAHs同系物的浓度均随PM_(2.5)的浓度线性增加,其线性相关性受PAHs来源以及氧化活性的影响;夜间较重质量数的PAHs相对比例增加,主要受日间交通源以及夜间燃烧源贡献强度影响。受颗粒物组成以及湿度的影响,雾霾天气下PAHs颗粒相分配率降低。进一步评估了北京城区人群的PAHs吸入健康效应,冬季雾霾频繁发生下其对人群癌症风险为6.2×10~(-5)。     

山西晋中焦化基地多环芳烃排放对周边大田卷心菜的影响

饮食摄入是多环芳烃(PAHs)人体暴露的主要途径之一,探究PAHs污染对农产品安全和人体健康的影响具有重要意义。山西晋中拥有大型焦化企业,也是北方重要的大田蔬菜种植基地,当地PAHs污染的特征和影响具有相当的典型性。研究选取修文工业基地周边的大田蔬菜基地作为研究区域,分别采集大气(含气相和颗粒相)、菜地表土和卷心菜菜心样品,确定各类样品中母体PAHs的浓度水平、组成比例和分布特征。结果表明,蔬菜基地周边大气中母体PAHs的平均浓度为301 ng·m-3。大气母体PAHs主要存在于气相,低环(2~3环)组分占据优势。利用同分异构体特征比值和主成分分析对大气PAHs进行初步源解析,炼焦、燃煤和生物质燃烧、以及交通尾气排放是当地PAHs的主要排放源。菜地表土母体PAHs的中位数浓度为236ng·g-1,范围为130~703 ng·g-1,以中、高环(4~6环)组分为主,菜地表土母体PAHs浓度与土壤总有机碳(TOC)分数呈现显著正相关关系。当地大田种植卷心菜菜心的PAHs中位数浓度为12.9 ng·g-1,范围为0.9~47.6 ng·g-1,低环组分所占比例最大,其组分谱分布与大气相似。偏相关分析显示周边大气PAHs对卷心菜菜心PAHs的传输贡献要大于表土PAHs。     

我国主要市售香烟主流烟气中多环芳烃的分析

选取我国主要市售烤烟型和混合型两种类型卷烟共15种,采集自动吸烟机抽吸后主流烟气中的颗粒物,用GC/MS选择离子方式测定其中USEPA优先控制的16种多环芳烃(PAHs)的含量.结果表明:卷烟主流烟气中PAHs总量的范围为34.27-1603.75ng ·cig-1,且烤烟含量普遍高于混合型卷烟.主流烟气中轻组分PAHs为主,其中(2 3)环PAHs占总量的86%.苯并(a)芘浓度范围为0.79-17.88ng ·cig-1,与多环芳烃总量、致癌性多环芳烃总量、苯并(a)芘当量浓度呈现较好的正相关,因此,可以用苯并(a)芘作为主流烟气中PAHs的指标物.烤烟型卷烟中苯并(a)芘均高于混合型卷烟,但单位重量颗粒物中BaP在部分混合型卷烟中含量却高于烤烟型卷烟,可能是不同过滤嘴过滤效果不同所致.     

淮南燃煤电厂烟气中颗粒相和气相中多环芳烃的赋存特征

采集安徽省淮南市3个燃煤发电锅炉排放的气态和颗粒态样品,通过GC-MS测定美国环保局优控的16种多环芳烃(PAHs),并对其残留、赋存和分配特征进行了分析研究.结果表明,PM_(10)相和气相中PAHs的质量浓度范围分别为2.9—7.5μg·m~(-3)和6.0—15.1μg·m~(-3),PAHs的质量浓度明显受到锅炉类型、装机容量与燃烧条件的影响,静电除尘器(ESP)对气相PAHs清除效率较低;PM_(10)相中PAHs主要为中分子量4环和高分子量5环,分别占总PAHs的35.8%—49.3%和16.2%—27.3%,与PM_(10)相相比,气相PAHs主要分布为2—3环,而4—6环PAHs含量较少.脱硫装置有效地提高了高分子PAHs的去除率;PM_(10)相及气相中PAHs分布不均衡,吸收作用主导了PM_(10)相与气相之间的PAHs分配;PAHs单体显示出不同的主导分配机制,主要由于它们之间不同的化学亲和力和蒸气压所导致的.     

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.     

徐州市区不同季节大气TSP和PM10中PAHs污染特征及健康风险评估

于2009年2月-8月利用高效液相色谱法对徐州市区冬、春、夏3个季节大气TSP和PM10中16种多环芳烃进行分析,结果表明：大气TSP和PM10中∑PAHs不同季节分布规律均为：冬季〉春季〉夏季;冬季,荧蒽污染浓度最高;春季和夏季苯并（g,h,i）芘浓度最高;不同环数PAHs春季和年均值呈规律均为：6环〉4环〉5环〉3环〉2环;夏季为：6环〉5环〉4环〉3环〉2环;冬季为：4环〉5环〉6环〉3环〉2环;大气TSP中整体苯并（a）芘等效致癌毒性（BEQ）不同季节分布规律为：冬季（4.517ng/m3）〉夏季（1.602ng/m3）〉春季（1.413ng/m3）;PM10中整体BEQ不同季节分布规律为：冬季（3.706ng/m3）〉春季（1.504ng/m3）〉夏季（1.331ng/m3）;采暖期大气颗粒物中PAHs污染对人体健康危害风险相对较高。     

上海地区大气中二噁类分布特征的初步研究

为了研究上海地区大气中二噁英（PCDD/Fs）的污染水平、分布特征和相分配规律,分别选取了上海典型的工业区、居民区和郊区的采样点进行了大气样品的采集。通过对3个采样点的研究发现,上海地区的大气中二噁英的平均毒性当量浓度为0.201 pg/m^3,居民区最高,工业区其次,郊区最低。大气中二噁英排放的平均浓度属于典型的城市工业区水平。在常温下,大气中90%二噁英主要分布在颗粒物相中,从单体看,高氯代同系物主要分布在颗粒相中,而低氯代同系物则分布在气相当中。通过二噁英的气相/颗粒相分配系数Kp与蒸气压PL的关系式评价了污染物的气相/颗粒相分配行为。并应用Junge-Pankow模型预测了大气中的气相/颗粒相分配,通过与实测值的比较发现,上海地区大气中二噁英的气相/颗粒相分布十分接近于模型中的城市地区,郊区采样点和模型预测值最为吻合,工业区和居民区大气中的二噁英在颗粒物上的浓度则要高于模型预测值,对造成偏离的原因进行了分析,并对3个采样点周围的污染源进行了初步的探究。     

Pah characteristics in ambient air within a steel industrial complex

Ambient air samples at ten sites in an iron and steel industrial complex were collected from June to December for analyzing polycyclic aromatic hydrocarbons (PAHs). Sixteen species of PAH components in air samples were identified. The results indicate that both gaseous phase and particle‐bound PAHs at the top of the cokemaking plants are unusually high. The profiles of particle‐bound PAHs indicate that the predominant species at the top of, the coke oven batteries are those of high molecular weight components. The major components of particle‐bound PAHs at sampling sites near the fenceline, however, include the medium molecular weight components. The PAH profiles of air samples within the industrial complex show a strong similarity to those of cokemaking plant samples. The concentrations and the specific content of benzo(a)pyrene in the iron and steel industrial complex are higher than those values measured in urban area, petrochemical industry park, and open‐air burning 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.     

Investigation on sampling artifacts of particle associated PAHs using ozone denuder systems

Polycyclic aromatic hydrocarbons （PAHs） are complex organic compounds which are identified as significant carcinogenic to human health. PAHs （mainly in particle phase） are susceptible to atmospheric oxidant gases, especially ozone, nitrogen oxides （NOx）, hydroxyl radical （OH）, and could be degraded on filters during sampling process, leading to an underestimation of ambient PAH concentrations. The goal of this work was to investigate particle associated PAHs sampling artifacts caused by ozone in summer of Beijing. Comparative sampling systems were operated simultaneously during the whole campaign, one with activated carbon ozone denuder, the other being set as conventional sampling system. Activated carbon denuder was testified to be highly efficient to eliminate ozone from air stream. In general, nine particle-bound PAHs observed from conventional sampler were all lower than those from ozone denuder system. The total PAHs （particle phase） concentration was averagely underestimated by 35.9% in conventional sampling procedure. Benzo[a]pyrene （BaP） had the highest percentage of mass loss. founded to have influences Ambient temperature was on PAHs sampling artifacts. High temperature can increase loss of particle associated PAHs during sampling.     

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。     

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。     

某癌症高发区水中多环芳烃测定及其风险评价

在某癌症高发区选取5个镇中的10个村进行布点,分别在2010年6月和12月采集丰水期和枯水期水样,采用固相萃取与气相色谱-质谱联用方法对深层地下水、浅层地下水以及地表水中的多环芳烃（PAHs）进行测定.检测结果表明,深层地下水在丰、枯水期时PAHs总量分别为4058.29—9613.53 ng.L-1和72.78—809.00 ng.L-1.浅层地下水丰、枯水期PAHs总量分别为2205.84—24621.20 ng.L-1和82.88—601.95 ng.L-1.地表水丰、枯水期PAHs的总量分别为2747.44—33532.90 ng.L-1和127.78—321.04 ng.L-1.丰水期萘含量较高是造成PAHs总量在丰水期远高于枯水期的主要原因.10个水样中苯并（a）芘超标（GB5749—2006）,最大超标8.42倍.采用优化的USEPA风险评价模型,对PAHs进行人体健康风险评价,其致癌风险水平在2×10-8—1.28×10-5之间,部分水样致癌风险超过10-6的水质监控值.     

兰州地区苯并(a)芘的环境多介质迁移和归趋模拟

利用Level Ⅲ逸度模型模拟计算了稳态假设下苯并(a)芘在兰州地区大气、水体、土壤和沉积物中的相间迁移通量、浓度分布.结果表明:大气的平流输入和化石燃料燃烧是该区域苯并(a)芘的主要来源,土壤是其最大的储库,占总残留量的99.6%;在大气、水体、土壤和沉积物中的浓度分别为1.61×10-10 mol·m-3、9.39×10-7 mol·m-3、7.13×10-4 mol·m-3和9.17×10-5mol·m-3,模型计算浓度与同期实测浓度吻合较好,验证了模型的可靠性,并通过灵敏度分析,确定了模型的关键参数.     

Polycyclic aromatic hydrocarbons in soils around Guanting Reservoir,Beijing, China

The concentrations of 16 polycyclic aromatic hydrocarbons (∑ 16PAHs) were measured by gas chromatography equipped with a mass spectrometry detector (GC-MS) in 56 topsoil samples around Guanting Reservior (GTR), which is an important water source for Beijing. Low to medium levels of PAH contamination (mean=394.2±580.7 ng g^?1 dry weight (d.w.)) was evident throughout the region. In addition, localised areas of high PAH contamination near steel and cement factories were identified, with ∑ 16PAHs concentrations as high as 4110 ng/g, dry weight (d.w.). There was a significant positive correlation (r²=0.570, p<0.01) between total organic carbon content and ∑ 16PAHs concentrations. Phenanthrene was the predominant compound, accounting for 27.2% of the ∑ PAH concentration, followed by chrysene>pyrene>benzo[a]anthracene≈ benzo[b]fluoranthene≈ benzo[a]pyrene. Four-ring PAH homologues (39%) were dominant. The higher proportion of 4–6 ring homologues, molecular indices, and the spatial distribution of PAH indicated that industrial discharges, incineration of wastes and traffic discharges were the major sources of soil PAHs around the water reservoir.     

Occurrence of and risk posed by highly carcinogenic dibenzo[def,p]chrysene isomers in urban soil

Dibenzopyrene and its isomers are considered the most potent carcinogens of all polycyclic aromatic hydrocarbons tested to date. However, despite public concerns over their deleterious effects, they have not been extensively studied. The occurrence of four highly carcinogenic isomers of dibenzopyrene – dibenzo[def,p]chrysene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene in urban soil samples from Shanghai, China, have been determined in this study, as well as that of benzo[a]pyrene and coronene. A total of 14 peaks with ions at m/z 302 were detected by gas chromatography-mass spectrometry. Although the concentrations of benzo[a]pyrene and the sum of the 16 priority polycyclic aromatic hydrocarbons were greater than that of dibenzopyrene and its isomers, the carcinogenic potency of the latter was higher than that of benzo[a]pyrene. The results also indicate that the relative carcinogenic potency of the four dibenzopyrene isomers in the samples is higher than that of the 16 priority polycyclic aromatic hydrocarbons.     

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。