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。     

Development of a thermal desorption method for the analysis of particle associated polycyclic aromatic hydrocarbons in ambient air

An investigation for the analysis of polycyclic aromatic hydrocarbons in airborne particulates using thermal desorption and gas chromatography-mass spectrometry is described. Samples are obtained from ambient air using fibreglass filters and the volatile material from the filter is thermally desorbed to gas chromatograph. A 30 meter capillary column is used to separate the hydrocarbons and eight polyaromatic hydrocarbons are used to test the method and recovery is >95%. The eight polycyclic aromatic hydrocarbons anthracene, phenanthrene, fluoranthrene, pyrene, benzo (a) anthracene, chrysene, benzo (a) pyrene and benzo (e) pyrene were the most abundant PAHs found in the samples of ambient air with current method at Uxbridge-London. Application of the measurement of polycyclic aromatic hydrocarbons in ambient air samples shows that the hydrocarbons trapped in the particle phase to a lesser degree at higher ambient temperature. In conclusion a method has been developed to transfer the PAHs in particle phase from a filter to GC-MS by thermal desorption. A standard mixture of PAHs, when absorbed onto the filter, did lead to strong analyte absorbent interactions by the high percent recovery of the sample.     

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.     

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.     

重工业区高脆弱岩溶含水层中多环芳烃污染的初步研究

以西南岩溶地区某市重工业区为研究对象,采集水文地质单元内地下水和土壤样品,利用气相色谱-质谱法（GC-MS)测试美国环保署16 种多环芳烃（PAHs）优控物。初步研究表明,研究区地下水16种PAHs均被检出,浓度为1 135.79～1 361.26 ng/L,以菲、蒽、萘、屈、芘为主;地下水处于中等污染程度,其中苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽4种浓度超过美国EPA2009《国家推荐的优先有毒污染物水质标准》标准;PAHs特征比值显示含水层中的PAHs来源于燃煤和炼焦污染源,与钢铁厂和化肥厂排放的特征有机污染物一致。研究区污染源下游大面积区域地下水已经受到PAHs污染,且出现排泄区PAHs浓度高于径流区的现象,岩溶含水层PAHs的污染主要受两方面影响:一是洼地、裂隙发育,断层破碎带和强风化白云岩等为PAHs在含水层中的运移提供了有利条件,同时污染源区内地下水大量开采加速了污染物向地下水的入渗;二是水电站建坝蓄水发电,江水水位抬高,河岸地下水排泄速度减慢,可能致使岩溶含水层中PAHs的自净能力减弱。生态风险评价显示地下水中菲、蒽、芘、苯并[a]蒽、苯并[b]荧蒽处于重污染风险,应采取措施降低污染风险。      

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。     

Brick kiln exhaust as a source of polycyclic aromatic hydrocarbons (PAHs) in the surrounding soil and plants: a case study from the city of Peshawar, Pakistan

The purpose of the present study was to investigate the effects of brick kiln exhaust on the quantity of polycyclic aromatic hydrocarbons in surrounding soils and plants. In Pakistan, a big problem is the rapid conglomeration of the brick kilns in out skirt of nearly all urban centers to cope with the rapid construction work in big cities. A huge amount of low-grade coal, rubber, tires is used in non-scientific manner. The study was conducted in the City of Peshawar the capital of Kyber Pakhtunkhwa where many brick kilns are located in the periurban areas. Soil and medicinal plants samples were collected from different locations around the bricks kiln and were analyzed for selected polycyclic aromatic hydrocarbons (PAHs), i.e., benzo(a)pyrene, anthracene, chrysene, flourene, flouranthene, phenanthrene, naphthalene, and acenapthylene. Quantitative and qualitative analysis was carried out by UV spectrophotometer and high-performance liquid chromatography. Benzo[a]pyren and Chrysene were found to be the most abundant compounds. The total load of PAHs in the central location was found to be 0.4014 mg/kg. General trend of PAHs distribution was such that the concentration of individual PAHs was found to increase with depth clearly indicating their absorption in the soil. PAHs concentration increased with the distance up to 300 m and then gradual decreased which showed their movement with the water and air. The PAHs load was found high in the leaves as compared to stem and roots. This high load in the aerial parts indicated their excretion route as well as air deposition.     

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.     

Pollution characteristics of polycyclic aromatic hydrocarbons （PAHs） in oily sludge from the Zhongyuan Oilfield and its peripheral soils

The purpose of this study is to determine the degree of contamination caused by polycyclic aromatic hydrocarbons (PAHs) in oily sludge and soils around it in the Zhongyuan Oilfield. The contents of polycyclic aromatic hydrocarbons in oily sludge samples were determined with HPLC. The contents of PAHs of oily sludge from three different oil production plants vary from high to low in the order of the Wenming oily sludge dumping site of No. 3 Oil Production Plant (3W)>the Mazhai oily sludge dumping site of No. 3 Oil Production Plant (3M)>the Wen’er oily sludge dumping site of No. 4 Oil Production Plant (4W). Naphthalene, acenaphthylene, acenaphthene, fluorine and phenanthrene are the major pollutants of PAHs in oily sludge. The contents of PAHs in soil samples around the oily sludge dumping sites vary widely from 434.49 to 2408.8 ng/g. Naphthalene, acenaphthene, fluorine, phenanthrene and pyrene are the characteristic factors of PAHs in soil samples of 3M and 3W, and naphthalene, acenaphthene, fluorine and phenanthrene are the characteristic factors of PAHs in soil samples of 4W. According to these data and the ratios of Fl/Py, PAHs in oily sludge samples come mainly from petrogenic sources, and soil samples are divided into petrogenic soil samples and mixed-source soil samples, and both petrogenic and pyrogenic soil samples in terms of the sources of PAHs. The classification by Nemero index P indicates that soils around the oily sludge dumping sites have been seriously polluted.     

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.     

柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征及其地质意义

多环芳烃(PAHs)是古环境、古野火以及古气候的重要地质记录,本文通过气相色谱质谱法(GC- MS)研究了柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征,检测出一系列二环至七环芳烃化合物,包括高等植物衍生多环芳烃(卡达烯、6- 异丙基- 1- 异己基- 2- 甲基萘、惹烯、西蒙内利烯以及二氢惹烯)和燃烧衍生多环芳烃(荧蒽、芘、苯并\[a\]蒽、、苯并荧蒽、苯并\[e\]芘、苯并\[a\]芘、茚并\[cd\]芘、苯并\[ghi\]苝和晕苯)等。这些多环芳烃的检出表明石门沟组煤沉积于具有显著陆源高等植物输入的微咸水湖沼环境,成熟度较低(平均随机反射率为056%)。石门沟组煤中高等植物衍生多环芳烃以极高的惹烯含量为特征,且存在较高丰度的西蒙内利烯和二氢惹烯,卡达烯丰度极低,反映出成煤期陆地植被类型以松柏类植物的针叶林为主,气候温暖湿润。同时,煤中丰富的燃烧衍生多环芳烃证实了柴达木盆地北缘中侏罗世存在广泛的陆地古野火,较高的大气氧气浓度(256%)可能是该时期野火频发的一个重要诱因。本次研究为柴达木盆地中侏罗世古野火事件的研究提供了重要的分子化石证据,也是对中侏罗世古环境和古气候研究的有益补充。     

Ambient distribution of particulate- and gas-phase <Emphasis Type="Italic">n</Emphasis>-alkanes and polycyclic aromatic hydrocarbons in the Tibetan Plateau

Attention has been paid for the levels, sources and health risks of atmospheric aliphatic and polycyclic aromatic hydrocarbons (n-alkanes and PAHs) in remote areas, however, few studies have focused on those in the Tibetan Plateau. In this study, 18 pairs of atmospheric samples were obtained during the period from August 2006 to July 2007 in Lhasa, the capital city of Tibet. Both gas-phase and particulate-phase n-alkanes and PAHs were measured. Concentrations of n-alkanes (gas + particulate phase, 99.1–480.9 ng/m³) and PAHs (gas + particulate phase, 11.4–72.5 ng/m³) in Lhasa are lower than those in many cities. The sources of n-alkanes related to biological and petroleum sources were 67 and 33%, respectively. According to the results of diagnostic ratios and principal component analysis, emission of traffic vehicles was one of the important PAH sources, and sources of benzo(a)pyrene was likely attributed to incense burning. Good simulations were obtained by traffic soot-based model for fluoranthene, pyrene and benzo(a)anthracene, while, wood soot-based model fitted the experimental results of benzo(a)pyrene better. This meant atmospheric fate of PAHs was mainly influenced by the adsorptive partitioning that occurred during traffic and incense burning procedures. In addition, the benzo[a]pyrene-equivalent carcinogenic power (BaPE) in the present study (0.1–1.6 ng/m³) is lower than those in other cities and also the air quality standard of China, suggesting that atmospheric PAHs caused low health risks.     

过硫酸钠修复土壤中多环芳烃的准确测定

多环芳烃(PAHs)是一类具有致癌、致突变、致畸的碳氢化合物,具有较高的辛醇-水分配系数,易被土壤颗粒吸附而影响环境和人体健康。过硫酸钠(Na₂S₂O₈)氧化法是近些年来国内外修复PAHs污染土壤较为常用的方法,但现阶段在测定修复后土壤中PAHs含量、进行土壤修复效果评估时亟待解决的问题是：经该方法修复的土壤,若土壤中残留有过硫酸钠,在样品前处理过程中由于提取温度较高,可能会进一步加速多环芳烃的氧化反应,从而影响土壤中PAHs的准确测定。本文建立了一种在修复后土壤中加入还原剂抗坏血酸,与残留的过硫酸钠反应生成脱氢抗坏血酸,采用索氏提取结合气相色谱-质谱法(GC-MS)同时测定土壤中16种PAHs的方法,PAHs加标回收率为76.2%～110.0%。而修复后土壤若不加还原剂直接进行索氏提取,用GC-MS测定,可能会使部分PAHs及替代物的测定不准确,PAHs加标回收率仅为6.0%～72.4%。通过对比分析表明,在样品提取前加入还原剂,可以有效地消除残留过硫酸钠的影响,提高测定修复后土壤中PAHs含量的准确性。     

Source identification of polycyclic aromatic hydrocarbons in sediments of a creek around a flow station

Sources of the sixteen polycyclic aromatic hydrocarbons (PAHs) in the United States Environmental Protection Agency priority pollutants list were determined in sediments of Kolo Creek using diagnostic ratios of parent PAHs[phenanthrene/phenanthrene + anthracene; fluoranthene/fluoranthene + pyrene; benz(a) anthracene/benz(a) anthracene + chrysene and indeno(1,2,3-d)pyrene/indeno(1,2,3-cd)pyrene + benzo(ghi)pyrelene]. The study was conducted over four seasons (dry, late dry, rainy and late rainy seasons). Applying cross plots of the diagnostic ratios revealed that PAHs in Kolo Creek sediment have pyrogenic origins except in the rainy season that had petrogenic origins. Comparison of diagnostic ratio values obtained from this study with literature values enabled the further classification into types of pyrogenic and/or petrogenic sources. While the pyrogenic sources of PAHs were mainly as a result of Grass/Wood combustion, the petrogenic PAHs were as result of drained diesel and lubricating oil. The predicted sources corresponded with the prevailing human activities in the vicinity, especially samples collected near a petrol station and an abattoir. This study further affirms the simplicity and accuracy of the use of diagnostic ratios for PAHs source prediction.     

Polycyclic aromatic hydrocarbons in the soils of technogenic landscapes

An integrated study of qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAH) in the atmospheric precipitation-soil-lysimetric water system of aerotechnogenic polluted landscapes was conducted using high-performance liquid chromatography in a gradient mode. Only low-molecular weight polyarenes (phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, and chrysene) were found in the atmospheric precipitation and lysimetric waters. The growth of PAHs in soils is provided by the input of phenanthrene, fluoranthene, and pyrene with atmospheric precipitation. The absence of heavy PAHs (benzfluoranthenes, benz(a)pyrene, dibenz(a,h)anthracene, benz(ghi) perylene, and indeno[1,2,3-cd]pyrene) in the atmospheric precipitation and their identification in soil give grounds to state that their accumulation was caused mainly by transformation of organic matter during pedogenesis. The technogenic impact was estimated and criterion of the degree of soil pollution by PAH was proposed.     

土壤pH值对土壤多环芳烃纵向迁移影响的模拟实验研究

影响土壤多环芳烃(PAHs)纵向迁移行为的环境因素很多。文章以氧化钙和冰乙酸改变采自徐州土壤的pH值水平,人工装填土柱进行纵向淋滤试验,研究pH值对土壤PAHs纵向迁移行为的影响。结果表明,土壤pH值的变化加强了PAHs在土柱中的纵向淋滤能力,表层土壤中的PAHs可迅速向底层转移;不同种类的PAHs淋滤特性表现不同,pH值增加更能增强低环PAHs的迁移淋滤能力,pH值降低则更能促进高环PAHs从土壤表层向深部迅速迁移。     

Application of multivariate spatial analysis in scale-based distribution and source study of PAHs in the topsoil: an example from Tianjin,China

Polycyclic aromatic hydrocarbons (PAHs) in soil originate from various sources under different spatial scales. Coregionalization analysis is more revealing than univariate geostatistical analysis. Scale-dependent spatial features of variables reflect different sources of spatial variability. In this study, 188 topsoil samples in the Tianjin area were collected. The contents of 16 PAHs and soil background properties were determined for all samples. A multivariate geostatistical approach was used for multi-scale spatial analysis for PAH compounds. Results show that coal combustion was the major source for the spatial distribution patterns of PAHs in the topsoil of the studied area. It worked mainly at the short-range scale (5–10 km). Significant spatial variation patterns were identified. In contrast, no significant spatial distribution trends at the nugget (0–5 km) or long-range scales (10–50 km) were seen. Long-range transport and site contamination of PAHs might not be key contributors in forming the distribution pattern of PAHs in the topsoil of Tianjin area.     

Accumulation of polycyclic aromatic hydrocarbons in hummocky tundra peatlands under climate change at high latitudes

The quantitative and qualitative compositions of polycyclic aromatic hydrocarbons (PAHs) were determined, and the vertical stratification of PAHs was characterized along profiles in hummocky tundra peatlands. In perennially frozen peat layers, PAHs occur in a conserved state and do not undergo transformation in contrast to seasonally thawed layers. Statistically significant correlations were detected between the mass fraction of 5–6-ring structures (especially, benzo[ghi]perylene), individual PAHs, and botanical composition of the peat at the thawing–freezing boundary; and profile relations for various combinations of PAHs were calculated. The radiocarbon and paleobotanical analysis of peatlands in combination with the obtained results can be used for assignment of initial vegetation to periods of peat formation in the Holocene and as markers of the response of the peatland permafrost to climate changes at high latitudes.     

快速溶剂萃取(S-916)/GC-MS法测定土壤中15种多环芳烃

本文建立了S-916快速溶剂萃取仪(Buchi瑞士)快速萃取-气相色谱-质谱仪(GC-MS联用测定土壤中15种多环芳烃(PAHs)含量的方法。土壤样品经正己烷、丙酮快速溶剂萃取,除水浓缩后,利用硅酸镁小柱进行净化,直接进GC-MS测定。结果表明,在5. 0～1000. 0μg/L浓度范围内,15种PAHs的相关系数均在0. 996以上,RF RSD<12%,加标回收率在80%～117%之间,15种PAHs的最低检出限均低于0. 40μg·kg^-1.该方法灵敏、快速、准确可靠,完全满足实验室对土壤中PAHs的检测要求,可为土壤中多环芳烃(PAHs)的污染情况提供快速检测依据。     

Distribution of polycyclic aromatic hydrocarbons in recent sediments of Sundarban mangrove wetland of India and Bangladesh: a comparative approach

The present work is the first attempt to compare the data of a comprehensive study of the origin and distribution of 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) in surface sediments (<63 μm) from 18 sampling stations, 9 from Sundarban of Bangladesh and 9 from Indian counterpart. Σ19PAHs concentration in sediments showed wide variations from 208.3 to 12,993.1 ng g^?1 dry weight in Indian Sundarban, whereas 208.4 to 4,687.9 ng g^?1 in the case of Bangladesh. Fluoranthene, pyrene, benzo(b)fluoranthene, benzo(a)pyrene and dibenzo(a,h)anthracene were predominant species for both the countries. The PAH diagnostic ratios indicated that the PAHs in sediments from both the countries were of mixed source of hydrocarbons of both petrogenic and pyrolytic origin. According to the numerical effect-based sediment quality guidelines, the levels of PAHs in the Sundarban wetland of Bangladesh and India should not exert adverse biological effects. The TEQ values calculated for samples from the Bangladesh and Indian Sundarban varied from 13.68 to 1,014.75 and 1.31 to 2,451 ng g^?1 d.w. with an average of 221.02 and 358.63 ng g^?1, respectively. The overall contamination status of PAH was higher in India than Bangladesh.