北京通州某改造区土壤中PAHs的来源分析及风险评价

近些年,随着我国城市化进程不断加快,土壤中多环芳烃污染已经成为威胁土壤环境质量和人体健康的主要因素。文章采集了北京市通州某改造区15件表层土壤（0~20 cm）样品,利用GC-MS分析技术,研究了土壤中美国环境保护署（USEPA）优控的16种多环芳烃（PAHs）的含量及组分特征,根据多环芳烃的空间分布特征和特定成分之间的浓度比值结合多元统计法分析了其污染来源,初步评价了其污染水平,并进行健康风险评价。结果表明:表层土壤中16种多环芳烃含量范围为6.57~8 307.2 μg/kg,均值为1 004.08 μg/kg。多环芳烃组分特征及Fla与（Fla+Pyr）、BaA与(BaA+Chr)的相对质量比值特征显示改造区是燃煤和汽车尾气混合型来源;多元统计后发现石油烃类污染源和化石燃料燃烧源是两种主要成分。最后参照《污染场地风险评估技术导则（HJ 25.3—2014）》对土壤中PAHs进行了健康风险评价,除苯并（a）芘（BaP）致癌风险值略偏高不可接受外,其余致癌与非致癌风险值均可接受。     

Levels and sources of polycyclic aromatic hydrocarbons (PAHs) in selected irrigated urban agricultural soils in Accra, Ghana

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic pollutants in urban environments including urban soils. Elevated concentrations of PAHs in urban soils are caused by incomplete combustion of petroleum and coal. This study assesses 16 individual PAH compounds in a total of 112 surficial soil samples. The objective was to assess and compare the levels of contamination as well as examine the main sources of PAHs in four urban agricultural soils using molecular ratios of some specific hydrocarbons. The study showed that PAH levels in soil ranged from 1.23 ng/kg in soil collected from Dzorwulu to 2.95 ng/kg in soil collected from Ghana Broadcasting Cooperation (GBC) vegetable irrigation site. Of the total PAHs, the more water soluble PAHs (2–4 rings), which tend to be concentrated in the vapour phase were found to dominate the soils. The percentage dominance were Dzorwulu (52.8 %), Marine Drive (62.5 %), CSIR (53.2 %) and GBC (49.2 %). However, there were significant levels of the more carcinogenic PAHs (5–6 rings) present with percentages as 47.1, 37.5 46.8 and 50.8 % for Dzorwulu, Marine Drive, CSIR and GBC vegetable irrigation sites, respectively, and therefore, may impact negatively on public health. Based on the classification by the Institute of Soil Science and Plant Cultivation in Pulawy, Poland, urban soils in Accra could be classified as contaminated to different levels. Molecular ratios of Flu/pyr and PA/Ant were calculated to determine the main sources of PAHs. Results showed that PAHs could originate mainly from incomplete combustion of petroleum products, especially from atmospheric fallout from automobile exhausts. The study further showed that B(a)P concentration of 0.05 ng/kg in soil from GBC urban vegetable irrigation site requires immediate clean-up exercise and monitoring to mitigate human health impact.     

Survey of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons in Jiaxing city, China

Polycyclic aromatic hydrocarbon (PAH) and nitrated PAH (NPAH) products are toxic. Thus, determination of their concentrations is of great interest to researchers of soil and water pollution control. In this work, soil samples, surface water samples, and groundwater samples were collected, and the concentrations of 16 priority PAHs and 15 NPAHs were determined using an HPLC-ultraviolet detector. Results showed that the total PAH concentrations ranged within 489.69–1,670.11 ng/g (average = 905.89 ng/g) in soil samples, 4.00–23.4 μg/l (average = 9.84 μg/l) in surface water samples, and 2.14–22.3 μg/l (average = 8.37 μg/l) in groundwater samples. The NPAH concentrations were one to two orders of magnitude lower than the PAH concentrations and ranged within 22.72–128.70 ng/g (average = 63.88 ng/g) in soil samples. 2-Nitropyrene and 6-nitrochrysene were the most abundant compounds, accounting for about 14.3 and 26.5 %, respectively. Source analysis revealed that most PAHs originated from coal combustion around the study area, whereas NPAH studies suggested that the primary emission of gasoline engines and daytime OH reactions were the dominant sources of these compounds.     

Polycyclic aromatic hydrocarbon concentrations in urban soils representing different land use categories in Shanghai

An extensive soil survey was carried out in Shanghai to investigate the spatial distribution and possible sources of polycyclic aromatic hydrocarbons (PAHs) in urban soils. Soil samples were collected from highways, iron-smelting plants, steel-smelting plants, shipbuilding yards, coking plants, power plants, chemical plants, urban parks, university campuses and residential areas and were analyzed for 16 PAHs by gas chromatography with mass detection. High PAH concentrations were found in all locations investigated, with mean values of soil total PAH concentrations in the range 3,279–38,868 μg/kg DM, and the PAH concentrations were significantly influenced by soil organic matter content. Soil PAH profiles in all districts were dominated by PAHs with 4–6 rings. Principal components analysis and diagnostic ratios of PAHs indicate that they were mainly derived from coal combustion and petroleum but in soils from highways the PAHs were derived largely from vehicle exhaust emissions. The high concentrations of PAHs found indicate that many urban soils in Shanghai represent a potential hazard to public health.     

广州地区蔬菜生产基地有机污染物含量状况及分布

为了解广州地区蔬菜基地有机污染物的分布情况,选取了6个代表性基地进行调查采样,测试分析了表层土壤、蔬菜及灌溉水中15种邻苯二甲酸酯(PAEs)化合物、16种多环芳烃(PAHs)化合物和19种有机氯农药(OCPs)化合物的质量分数及质量浓度.结果表明:在15种PAEs化合物的总质量分数(w(ΣPAEs))中,土壤样品为158.0~4 321.0 ng/g,蔬菜样品为1 134.0~48 576.0 ng/g;水样中15种PAEs化合物的总质量浓度(ρ(ΣPAEs))为632.0~14 271.0 ng/L;就单个化合物而言,以DiBP、DBP、DEHP三种污染物为主,其三项之和占所有PAEs质量分数的97.5%~99.1%;在16种PAHs化合物的总质量分数(w(ΣPAHs))中,土壤样品为28.48~1 121.96 ng/g,蔬菜样品为238.09~1 000.61 ng/g;水样中16种PAHs化合物的总质量浓度(ρ(ΣPAHs))为338.21~1 239.78 ng/L;在19种OCPs化合物的总质量分数(w(ΣOCPs))中,土壤为0.04~71.28 ng/g,蔬菜为1.08~9.18 ng/g.总体上看,各基地土壤中DBP质量分数均超标,多环芳烃类在灵山、花东、黄埔菜地土壤中存在轻微污染,有机氯农药均未出现污染.     

Polycyclic aromatic hydrocarbons in Niger Delta soil: contamination sources and profiles

The distribution and sources of PAHs in soil as well as PAHs profiles have been investigated in areas with anthropogenic pollution in the Niger Delta (Nigeria) such as Warri and Ughelli. PAHs were identified in 21 soil samples (0–10cm upper layer) collected in May, 2003. The typical total PAHs level in Niger Delta soil ranged from 182 ± 112 - to - 433 ±256 íg/kg dw. PAH concentrations in soil samples from Warri Refinery, Tanker Loading point and Ugboko via Rapele oil field were quite high ( the mean ÓPAH concentrations were 433, 402 and 384 íg/kg dry weight respectively). The dominant PAHs in soil samples were pyrene, naphthalene and benzo[k]fluoranthene. The soil total PAHs (PAH_tot.) concentration, normalized to organic carbon content (OC), ranged from 11.4 to 47.2 mg PAH_tot. /kg OC; and showed that organic matter of the soil samples from Quality Control Centre, Ugelli West is highly contaminated with PAHs and had a value of 47.2 ± 31.2 mg PAH_tot./kg OC. Two and three ring aromatic hydrocarbons predominated in soil samples from Ughelli West, Tanker Loading point and Delta Steel Company, which is indicative of petrogenic origin.     

北京密云房山地区土壤中多环芳烃的组成与分布特征

选择北京城近郊房山与密云地区的土壤进行了多环芳烃的定量分析，同时探讨了多环芳烃在土壤中的分布特征与来源。研究结果显示：密云、房山两地土壤中多环芳烃的含量值具有明显差异，提示了两地工业活动影响强度的不同；各采样区土壤中多环芳烃总量的平均值在45．98～388．23ng／g变化，根据多环芳烃的特征参数可以推测研究区土壤中的多环芳烃主要来自于化石燃料的不完全燃烧。     

The polycyclic aromatic hydrocarbon concentrations in soils in the Region of Valasske Mezirici, the Czech Republic

The polycyclic aromatic hydrocarbon (PAH) contamination of urban, agricultural and forest soil samples was investigated from samples obtained in the surroundings of Valasske Mezirici. Valasske Mezirici is a town located in the north-east mountainous part of the Czech Republic, where a coal tar refinery is situated. 16 PAHs listed in the US EPA were investigated. Organic oxidizable carbon was also observed in the forest soils. The PAH concentrations ranged from 0.86-10.84 (with one anomalous value of 35.14) and 7.66-79.39 mg/kg dm in the urban/agricultural and forest soils, respectively. While the PAH levels in the urban/agricultural soils are within the range typically found in industrialized areas, the forest soils showed elevated PAH concentrations compared to other forest soils in Western and Northern Europe. The PAH concentrations and their molecular distribution ratios were studied as functions of the sample location and the meteorological history. The soils from localities at higher altitudes above sea level have the highest PAH concentrations, and the PAH concentrations decrease with increasing distance from the town.     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

Assessment of organic pollutants (PAH and PCB) in surface water: sediments and shallow groundwater of Grombalia watershed in northeast of Tunisia

Toxic organic compounds in wastewater are serious threats for both human and environment healthy states. This study investigates the potential sources of surface water, sediment and groundwater pollution by polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyl (PCBs) as discharged by wastewater into the River of Oued El bey in northeastern Tunisia. Analysis indicates that the concentration of PAHs and PCBs are high in wastewater and vary from 0.37 to 0.83 mg/L and from 0.28 and 1.18 mg/L, respectively. The spatial distribution of PAHs and PCB in surface water showed a variation between 0.37 to 9.91 mg/L and between 0.1 to 0.47 mg/L, respectively. However, the quality of surface water is changed after wastewater evacuation at Oued Tahouna. The determination of PAH and PCB pollutants in groundwater shows a great interest in the development of water resources. The Concentration of these pollutants varying from 0.0204 to 1.93 mg/L and from 0.0052 to 0.196 mg/L, respectively. For PAH, analysis reveals also that naphtelene, fluorene, anthracene and chrysene are the most detected PAHs compounds in water and sediment samples while benzo[b]fluoranthene and benzo[a]pyrene are less present and in trace level. Higher concentrations of PAHs and PCBs are found in samples taken close to industrial areas of Bouargoub and Soliman, and wastewater discharge locations in Soliman. Analysis of the spatial distribution of PAHs and PCBs clearly link their higher concentration in water and sediments to wastewater and manufacturing discharges in the study area. In surface sediment, the organic pollutants are present. The cluster analysis for organic pollutants in different state and different matrix highlight a relationship between the wastewater evacuation and the water qualities which confirmed the direct response of the pollution sources on the surface water and groundwater organic pollution quality.     

环境中的多环芳烃及其生物恢复技术

多环芳烃是一大类广泛存在于环境中的有机污染物。天然燃烧、火山爆发、矿物资料及其它有机物的不完全燃料和热解产生的PAH进入大气中，气态沉降、城市地表径流、城市污水、废水及油的溢涵和渗漏等是PAH进行地表水的主要途径，大气中PAH的干、湿沉降，污水灌溉，地面及地下储油装置的渗漏，地面固体废物堆的淋滤等是土壤中PAH的主要来源，沉积物和土壤是PAH的主要环境归宿。生物恢复是一种处理有机污染的新方法。     

Polycyclic aromatic hydrocarbons (PAHs) in particle-size fractions of urban topsoils

Polycyclic aromatic hydrocarbons’ (PAHs) concentrations in bulk samples are commonly used to assess contamination but PAHs are unevenly distributed among particle-size fractions. Seventeen urban surface soil samples from the city of Xuzhou, China, were collected and then fractionated into five size fractions (2,000–300, 300–150, 150–75, 75–28, and <28 μm). The concentrations of 12 US EPA PAHs were measured using gas chromatograph/mass spectrometry in various fractions, and the bulk soil samples and distribution patterns of PAHs in different particle-size fractions were investigated. The mean concentration of total PAHs in bulk soil samples was 1,879 ng/g. The median concentrations for all individual PAH were higher for the 75–2,000 μm fraction than for the <75 μm fraction. The distribution factors for various PAHs in <28 μm soil fraction were closely correlated (r = ?0.661, p < 0.019) to bulk soil fugacity capacity. The values of PAH isomer indicated that traffic emissions might be the major origin of PAHs in Xuzhou surface soils. Spearman correlation analysis was performed and the result suggested that soil organic carbon might be a factor controlling the concentrations of PAHs in soils.     

湖州市不同土地利用类型土壤中多环芳烃的分布及来源

建立了原子发射光谱法测定独居石矿物中钇组稀土元素的分析方法。在260.00~360.00 nm波段内,选择不受干扰的分析谱线,用炭粉作缓冲剂,钪作内标元素,样品不需要化学处理,不需分离,可直接采用原子发射光谱法测定钇组稀土元素。方法相对标准偏差(RSD,n=12)为1.6%~6.2%,相对误差RE<±12.0%,方法简单、快速、可行。     

水体悬浮颗粒物的扫描电镜与X射线能谱显微分析

通过对湖州地区74个土壤样品多环芳烃含量的测定,分析了湖州市不同土地利用类型土壤中多环芳烃(PAHs)的含量特征及污染水平。结果表明,湖州地区PAHs各组分的含量均有检出,各种土地利用类型表层土壤均受到一定程度的PAHs污染,但均小于荷兰土壤修复标准;湖州市区耕地中PAHs的含量最高;从PAHs低环/高环比值小于1以及芘/苯并(a)芘比值小于2,反映了湖州地区土壤中PAHs主要是由燃煤和生活污染产生的。     

Compositional fractionation of polyaromatic hydrocarbons in the karst soils, South China

This study aims to explore the condensation and fractionation trends of persistent organic pollutants (POPs) in the karst soils. The tiankeng is a karst surface expression that can act as a focal point for introduction of contaminants to a karst aquifer, which may serve both as condenser for vapor phase POPs and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs in soils from the upper rim and floor of tiankeng is of interest in understanding the role of tiankeng in the long-distance transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in the surface soils from the upper rim and floor of Dashiwei tiankeng in Southern China were analyzed. The total PAH concentrations in soils were 23.40–190 ng g⁻¹, with phenanthrene being the most abundant. The distribution patterns of PAH compounds in the soil samples matched well with their properties. It indicated the heavy PAHs were susceptible to retention by the floor soils of tiankeng than light PAHs. A plot of Cfloor/Crim against PAH molecular weight gave a good positive relationship in the molecular weight range of 152–276. It is suggested that the floor soils can be focal points of more concentrated PAH and deserve attention. The concentrations of total PAHs in the floor soils (43.40–190 ng g⁻¹, mean 87.76 ng g⁻¹) were higher than those in the upper rim (23.40–88.94 ng g⁻¹, mean 57.74 ng g⁻¹). In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation is proposed as the major mechanism for the compositional fractionation of PAHs in the soils from the upper rim and floor of tiankeng.     

Characterization and source apportionment of polycyclic aromatic hydrocarbons (PAHs) in sediments in the Yellow River Estuary, China

Concentrations and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated in surface sediments of the Yellow River Estuary (YRE). The isobath-parallel tidal and residual currents play important roles in the variation of PAH distribution, such that the contamination level of PAHs in fine-grained sediments is significantly higher than in the relatively coarse grain size sediments. Both diagnostic ratios and principal component analysis (PCA) with multivariate linear regression (MLR) were used to apportion sources of PAHs. The results revealed that pyrogenic sources are important sources of PAHs. Further analysis indicated that the contributions of coal combustion, traffic-related pollution and mixed sources (spills of oil products and vegetation combustion) were 35, 29 and 36 %, respectively, using PCA/MLR. Pyrogenic sources (coal combustion and traffic-related pollution) contribute 64 % of anthropogenic PAHs in sediments, which indicates that energy consumption could be a predominant factor in PAH pollution of YRE. Acenaphthylene and acenaphthene are the two main species of PAHs with more ecotoxicological concern in YRE.     

Polycyclic aromatic hydrocarbons in surface sediments of Laizhou Bay,Bohai Sea,China

Concentration, distribution, and sources of 16 polycyclic aromatic hydrocarbons (PAHs) were investigated in surface sediments of Laizhou Bay, China. Total PAH concentrations ranged from 97.2 to 204.8 ng/g, with a mean of 148.4 ng/g. High concentrations of PAHs were found in the fine-grained sediments on both sides of the Yellow River estuary (YRE). In contrast, low levels of PAHs were observed in relatively coarse grain sediments, suggesting hydrodynamics influence the accumulation of sedimentary PAHs. The YRE and its adjacent area is the main sink for Yellow River-derived PAHs. Both PAH isomer ratios and principal component analysis (PCA) with multivariate linear regression (MLR) were applied to apportion sources of PAHs. Results indicated that both pyrogenic and petrogenic PAH sources were important. Further PCA/MLR analysis showed that the contributions of coal combustion, petroleum combustion and a combined source of spilled oil and biomass burning were 41, 15 and 44%, respectively. From an ecotoxicological viewpoint, the studied area appears to have low levels of PAH pollution.     

Polycyclic aromatic hydrocarbons in sediments from the Pearl river and estuary,China: spatial and temporal distribution and sources

Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Pearl river and estuary, China, to investigate the spatial and temporal variability of anthropogenic pollutants. The sediments from the sampling stations at the Guangzhou channel have the highest concentrations of PAHs, owing to contributions from the large amount of urban/industrial discharges from the city of Guangzhou. The significant decrease of PAHs concentrations in sediments from the Shiziyang channel is mainly attributed to the increasing degradation and desorption of low molecular weight PAHs and alkyl PAHs, and the dilution by less contaminated water and particles from the East river. The PAH contaminants were concentrated on the western side in the Lingding bay of the Pearl river estuary because of the hydrodynamic and sedimentation conditions. Based on the characteristics of the parent compound distributions (PCDs) and the alkyl homologue distributions (AHDs) of PAHs, the potential source of PAHs in sediments from each sampling station was identified. Results indicated that the pyrogenic (combustion) source, characterized by the abundance of parent PAHs, were predominant in the heavily contaminated station (ZB01) near the aging industrial area, and the petrogenic (petroleum- derived) PAHs were more abundant in the stations (ZB02, ZB03) adjacent to the petrochemical plant and shipping harbor. Sediments from Lingding bay show variable distributions of PAH composition and variety in the proportion of combustion and petrogenic sources for the PAHs in different stations. Perylene, a naturally derived PAH, was found to be highly abundant in less contaminated stations. Analysis of the dated sediments (²¹⁰Pb) indicates that higher PAH concentrations occurred in the sediments deposited after 1980, and higher fluxes of PAHs discharged to the Pearl river are found after 1990.     

Soil contamination by polycyclic aromatic hydrocarbons at natural recreational areas in Delaware,USA

As a US east coast state with a major income from outdoor recreation and tourism, Delaware highly values its environmental quality and natural resources. However, no results on polycyclic aromatic hydrocarbons (PAHs) contamination in soil at natural recreational areas (NRAs) in the state have been reported. In this study soil samples from seven state parks, two city parks, two state forests, and two national wildlife refuges in Delaware were analyzed for the concentrations of 12 selected PAHs. Results indicated that the median concentration of total PAHs in urban, suburban, and rural NRAs was 1,159, 138, and 130 μg/kg, respectively. Based on the classification proposed by Maliszewska-Kordybach, soil PAH contamination level at almost all sampling sites in urban NRAs was classified as contaminated or heavily contaminated, while that at sampling sites in suburban and rural NRAs was classified as not or weakly contaminated. Principal component analysis showed that all these areas share the same independent variable, which may be composed of one or more contribution sources. Pyrogenic processes were inferred to be the major source of soil PAH contamination in Delaware NRAs. Individual PAH concentration at all sampling sites were observed below the limit of Canadian Quality Guidelines except for site F3, where the concentration of benzo[b]flouranthene, benzo[k]flouranthene, and benzo[a]pyrene was found to exceed the limit by 88.3, 125, and 281 %, respectively. Further investigation on PAH contamination and possible remediation in area F are recommended.     

Black carbon in soils from different land use areas of Shanghai,China: Level,sources and relationship with polycyclic aromatic hydrocarbons

Black carbon (BC) in soils plays a key role of carrying hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs). However, little is known about the spatial distribution, sources of BC and its relationship with PAHs in urban soils. We studied BC, total organic carbon (TOC) and PAHs concurrently in 77 soils collected from downtown area, suburban and rural area and industrial area of Shanghai, China. BC was determined by both chemical oxidation (dichromate oxidation, BC_Cr) and chemo-thermal oxidation (CTO-375, BC_CTO). BC sources were identified qualitatively by BC/TOC concentration ratios and BC-cogenerated high molecular weight (HMW) PAH isomer ratios and quantitatively by principal component analysis followed by multiple linear regression (PCA-MLR). Results showed that BC_Cr concentration (4.65 g/kg on average) was significantly higher than BC_CTO (1.91 g/kg on average) in Shanghai soils. BC_Cr concentrations in industrial area were significantly higher than those in other two. Stronger correlation was found between PAHs and TOC, BC_Cr than that between PAHs and BC_CTO, which indicates the possibility of PAHs being carried by charcoal and other organic matters thus negating its exclusive dependence on soot. Charcoal was therefore suggested to be taken into account in studies of BC and its sorption of PAHs. BC/TOC ratios showed a mixed source of biomass burning and fossil fuel combustion. PCA scores of BC-cogenerated HMW PAHs isomer ratios in potential sources and soil samples clearly demonstrated that sources of BC in urban soils may fall into two categories: coal and biomass combustion, and traffic (oil combustion and tire wear). PCA-MLR of HMW PAHs concentrations in soil samples indicated that coal and oil combustion had the largest contribution to BC in urban soils while tire wear and biomass combustion were important in downtown and rural area, respectively, which indicated they were main sources of HMW PAHs and presumably of BC.