长江三角洲典型地区农田土壤多环芳烃分布特征与源解析

采集了长江三角洲地区苏州市的96个和嘉兴市的324个农田土壤样品,较为系统地分析了土壤中15种优控多环芳烃组成及含量,并运用比值法和主成分分析法判断了土壤中多环芳烃的来源。结果显示,苏州和嘉兴农田土壤中15种多环芳烃的总量范围分别为45.4~3 703μg kg-1和9.0~2 421μg kg-1,其平均值分别为312.5μg kg-1和152.4μg kg-1。苏州农田土壤苯并[a]芘含量平均值达21.4μg kg-1,超过了前苏联制定的土壤苯并[a]芘最高允许值(20.0μg kg-1)。苏州农田土壤中多环芳烃的含量从南部的吴江到北部的相城呈不断增加的趋势。嘉兴农田土壤多环芳烃含量远低于苏州,而在嘉兴毗邻吴江和上海的嘉善县土壤中多环芳烃含量较高。菲、荧蒽、苯并[b]荧蒽、芘、茚并[1,2,3-cd]芘是苏州土壤中多环芳烃的主要成分,而嘉兴土壤中多环芳烃的主要成分为菲、荧蒽、苯并[b]荧蒽、芘、屈。两个地区农田土壤多环芳烃的来源较为相似,主要为生物质和煤的燃烧以及石油源。     

混合菌降解土壤中多环芳烃的试验研究

PAHs生物降解程度受多种因素影响。通过筛选驯化PAHs降解菌,研究混合菌对土壤中菲、芘、苯并（a）蒽、苯并（b）荧蒽、苯并（k）荧蒽、茚并（1,2,3-cd）芘的生物降解性能,并考察污染时间对土壤中PAHs降解效果的影响。结果表明,筛选的混合菌具有很强的PAHs降解能力,缩短了PAHs生物降解的半衰期,且PAHs起始降解速率较快,之后趋于平缓。27d内土壤中的菲、芘、苯并（a）蒽、苯并（b）荧蒽、苯并（k）荧蒽、茚并（1,2,3-cd）芘的平均降解率分别为98.14%、89.97%、88.47%、63.55%、65.24%、60.49%,其中菲在5d之内的降解率高于93%。污染210d的土壤中各PAHs的起始降解速率高于污染50d的土壤,因此污染时间越长,PAHs生物降解的停滞期越短。     

产漆酶真菌筛选及其对PAHs污染土壤修复的初步研究

真菌漆酶可以高效转化多环芳烃(PAHs),因此,产漆酶真菌在PAHs污染土壤修复中极具应用前景。根据漆酶可将愈创木酚氧化为红色物质的特性,成功从土壤中筛选出一株能够分泌漆酶的真菌菌株F-1,初步鉴定该菌为疣孢漆斑菌(Myrothecium verrucaria)。通过Plackett-Burman试验对菌株F-1的产酶能力进行了分析,发现特定培养条件组合可将其酶活提高近300倍,达5628 U L-1,表明F-1的漆酶活性受到环境条件的显著影响。应用菌株F-1对PAHs污染土壤进行了初步修复研究,结果表明,接种F-1对菲、荧蒽、芘、苯并(a)蒽、屈、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,h)蒽、苯并(g,h,i)苝、茚苯(1,2,3-cd)芘等11种PAHs均有不同程度的降解,提示产漆酶真菌在PAHs污染土壤修复中的应用潜力。     

东莞市土壤中多环芳烃的含量、代表物及其来源

2002年10~12月采集东莞市各地土壤样品64个,采用气相色谱-质谱仪对土壤中的16种优先控制的多环芳烃(PAHs)进行分析。结果显示,东莞市土壤中16种PAHs平均含量413μg/kg,含量较高的几种组分分别是菲、萤蒽、屈、苯并[b]萤蒽、芘。与PAHs总含量相关性较好的7种组分分别为屈、苯并[a]蒽、苯并[b]萤蒽、苯并[k]萤蒽、苯并[a]芘、茚并[1,2,3]芘、二苯并[a,h]蒽;所有相关系数R2均超过0.9000,可作为东莞市土壤中PAHs的代表物。北部平原水乡的PAHs污染明显高于南部丘陵山区、水乡上游保护区以及中部过渡带。化石燃料高温燃烧产物的大气沉降为东莞市土壤中PAHs的主要来源。东莞市农业土壤中PAHs含量显著低于天津市受污染严重的农业土壤。     

某氮肥厂场地土壤PAHs污染特征研究

采用现场采样及室内测试方法对广州某氮肥厂原料车间和油库区土壤中16种优控多环芳烃（PAHs）的含量进行调查研究,分析了EPAHs含量及其组成特征和垂直分布特征,并在此基础上进行了源解析。结果表明,分析样品中∑PAHs范围在10-7795μg·kg,原料车间土壤中的∑PAHs小于油库区土壤中的,菲、芘、荧蒽、并（b）荧蒽、苯并（a）芘为主要污染物;油库土壤0-40cm的样品中16种PAHs均有检出,∑PAHs和单体分布基本一致;原料车间土壤∑PAHs和单体浓度随着地面深度的增加而减少。通过对单组分比值（菲／蒽,荧蒽／芘）的分析可以看出油库区土壤中PAHs来源于石油和燃烧源,而原料车间污染源主要为燃烧源。     

江苏省典型生态示范区土壤中多环芳烃的含量与风险评价

采集了江苏省某典型生态示范区内58个监测单元的土壤样品,并对样品中的多环芳烃(PAHs)进行了定量分析。结果表明,生态示范区土壤中的PAHs平均含量较低,但不同土壤样品之间PAHs的变异系数较大,以二苯[a,h]并蒽、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽为主要组成成分。从8个生态类型区分析,工矿企业搬迁区PAHs含量最高,达49.196μg/kg,其次是化工区周边,农业科技园土壤中的PAHs含量最低。工业区的PAHs多来源于石油输入,而以农业为主的生产基地、科技园等,PAHs主要来源于化石燃料的不完全燃烧。生态风险评价结果显示生态示范区内的PAHs处于较低毒性水平,尚未对生物造成不利的影响。     

活性炭对土壤中多环芳烃生物有效性的影响

多环芳烃(PAHs)是土壤中污染较为严重的一类持久性有机污染物，对农产品安全和人体健康构成严重威胁。本研究在某场地采集不同土层土壤，通过室内培养实验，研究添加5%活性炭对土壤中PAHs残留的影响，并利用羟丙基-β-环糊精提取方法评价土壤中PAHs生物有效性的动态变化，以期为治理石油泄露等突发性环境污染事件造成的土壤PAHs污染提供修复技术参考。结果表明，在8个月内，添加活性炭组土壤中菲、芘的残留量显著高于对照组，苯并[b]荧蒽的残留量显著低于对照组，苯并[ghi]芘残留量在两处理组之间无显著差异。在第1个月时，活性炭组土壤中菲、芘、苯并[b]荧蒽生物有效性较对照组分别降低了35.06%、37.73%、39.60%，苯并[ghi]芘生物有效性仅降低了1.37%。随着时间延长活性炭对土壤中PAHs生物有效性的阻控效果呈减弱趋势。因此，土壤添加5%活性炭能够有效降低PAHs生物有效性，减少其环境风险，并且在添加活性炭1个月内阻控效果最佳。     

土壤中多环芳烃和氨基甲酸酯等农药分析

应用超高效液相色谱和质谱串联技术对吉林省中部地区土壤中多环芳烃及氨基甲酸酯农药类成分进行含量测定分析。以超声波提取作为提取方法,以在线固相萃取作为纯化方法,以超高效色谱-三重四级杆质谱作为分析方法,共分离检测出12个多环芳烃类化合物,分别为:萘、苊、苊烯、氟、菲、蒽、芘、苯并[a]蒽、屈、苯并[a]芘、二苯并[a,h]蒽和茚并[1,2,3-cd]芘。11个氨基甲酸酯及其它类农药,分别为:灭多威,多菌灵,甲萘威,克百威,啶虫脒,涕灭威亚砜,涕灭威砜,苯醚甲环唑,阿维菌素,灭幼脲和氟虫腈。利用超声波提取和在线固相萃取法可以有效地提取纯化土壤中多环芳烃和氨基甲酸酯类农药。超高效液相色谱和质谱联用技术可以有效地分析食品中多环芳烃和有机氯农药类成分。     

蚯蚓和丛枝菌根真菌对南瓜修复多环芳烃污染土壤的影响

在温室盆栽实验条件下,研究接种AM(arbuscular mycorrhiza)真菌、蚯蚓(Eisenia fetida)对南瓜(Cucurbita moschata)修复3环以上多环芳烃(PAHs)污染农田土壤的影响,试验设置单接AM真菌、单接蚯蚓、双接AM真菌和蚯蚓、不接种的对照共4个处理,播种10周后收获。结果表明,接种AM真菌和蚯蚓促进AM真菌侵染南瓜,增加南瓜生物量;显著提高南瓜修复土壤中Phe(菲)、An(t蒽)、Py(r芘)、BkF(苯并(k)荧蒽)、BaP(苯并(a)芘)、BPe(r苯并(g,h,i)苝)等PAHs污染物的效率,促进南瓜高效地吸收3~5环PAHs,尤其是AM真菌和蚯蚓共同接种条件下对南瓜修复土壤效果最优;AM真菌利于南瓜转移根系吸收的高浓度PAHs化合物至地上部,降低PAHs对根系的胁迫,增强南瓜在高浓度PAHs污染土壤中存活,有利于南瓜应用于高浓度PAHs污染土壤的高效修复;蚯蚓对南瓜地下部吸持3~5环高分子量的PAHs化合物有积极作用。因此,选用的AM真菌和蚯蚓在土壤中具有协同作用,促进南瓜高效修复PAHs污染土壤。     

小麦秸秆生物炭对石油烃污染土壤的修复作用

以小麦秸秆为原材料,在300℃下缺氧裂解3、6、8 h制备生物炭,比较了3种生物炭的产率、pH值、灰分以及C、H、N元素含量,表征了300℃、6 h生物炭的表面形态,并用其作为修复材料,对大港油田的石油污染土壤进行修复。结果表明,随裂解时间的延长,生物炭产率下降,pH值升高,灰分含量增加,H/C值下降,但产率、pH值、灰分和H/C值都是从3 h到6 h差异显著,6 h到8 h差异不显著。C元素含量先升高后下降。石油污染土壤经生物炭修复14 d和28d后,总石油烃降解率分别为45.48%和46.88%,均显著高于对照组。修复14 d后土壤中的萘、苊、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、茚并[1,2,3-cd]芘也都有不同程度的下降,其中苯并[a]芘含量下降幅度达98.18%,其他几种PAH的降解率也都高于对照组,28 d后这些PAH的含量又有上升趋势。这说明小麦秸秆裂解时间对生物炭的性质有影响;300℃、6h生物炭可以用来修复石油污染的土壤。     

Rapid, semimicro method for determination of polycyclic aromatic hydrocarbons in shellfish by automated gel permeation/liquid chromatography

A simple, rapid, easily automated method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) in shellfish such as American lobster (Homarus americanus) and blue mussel (Mytilus edulis). PAHs are extracted from small amounts (1-8 g) of tissue by saponification in 1N ethanolic potassium hydroxide followed by partitioning into 2,2,4-trimethylpentane. This solution is evaporated just to dryness by rotary evaporation and the residue is dissolved in cyclohexane-dichloromethane (1 + 1) for gel permeation chromatography (GPC) on Bio-Beads SX-3. The GPC procedure is ideal as a screening method in the range 25-18 000 ng PAHs/g tissue. If individual PAH measurements are required, the appropriate GPC fraction is collected and PAHs are separated by reverse phase liquid chromatography (LC) with fluorometric detection. Individual PAHs at concentrations as low as 0.25-10 ng/g can be determined. Recoveries of added fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene were quantitative, with relative standard deviations ranging from 0.0 to 16.9%.     

Formation of polycyclic aromatic hydrocarbons in northern and middle taiga soils

An integrated study of the qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric precipitation-soil-lysimetric water system was performed using high performance liquid chromatography. It was shown that the accumulation of low-molecular PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, and chrysene) in soils is due to the transformation of organic matter and the regional transport and deposition of PAHs with atmospheric precipitation on the underlying surface. High-molecular polyarenes (benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene) mainly result from the decomposition of soil organic matter.     

Characterization and Sources of PAHs and Potentially Toxic Metals in Urban Environments of Sevilla (Southern Spain)

The purpose of this study was to determine the degree of PAH contamination and the association of PAHs with metals in urban soil samples from Sevilla (Spain). Fifteen polycyclic aromatic hydrocarbons-PAHs (naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-c,d]pyrene) and seven metals (Cd, Cr, Cu, Mn, Ni, Pb, Zn) have been evaluated in representative urban soil samples. Forty-one top soils (0–10 cm) under different land use (garden, roadside, riverbank and agricultural allotment) were selected. PAHs from soil samples were extracted by sonication using dichloromethane. The simultaneous quantification of 15 different PAH compounds were carried out by HPLC using multiple wavelength shift in the fluorescence detector. For qualitative analysis a photo diode-array detector was used. Metal (pseudo-total) analysis was carried out by digestion of the soils with aqua regia in microwave oven. The mean concentration of each PAH in urban soils of Sevilla showed a wide range, they are not considered highly contaminated. The results of the sum of 15 PAHs in Sevilla soils are in the range 89.5–4004.2 μg kg^?1, but there seems not to be a correlation between the concentration of PAHs and the land use. Of the 15 PAHs examined, phenanthrene, fluoranthene and pyrene were present at the highest concentrations, being the sum of these PAHs about 40% of the total content. Although metal content were not especially high in most soils, there are significant hints of moderate pollution in some particular spots. Such spots are mainly related with some gardens within the historic quarters of the city. The associations among metals and PAHs content in the soil samples was checked by principal components analysis (PCA). The largest values both for ‘urban’ metals (Pb, Cu and Zn) and for PAHs were mainly found in sites close to the historic quarters of the city in which a heavy traffic of motor vehicles is suffered from years.     

苏南地区农田表层土壤中多环芳烃和酞酸酯的污染特征及来源

采用气相色谱质谱（GC-MS）法测定了苏南地区13个农田表层土壤样品中的多环芳烃（PAHs）和酞酸酯（PAEs）污染物,分析比较了不同区域农田表层土壤,尤其是来自钢铁企业周边的表层土壤中PAHs和PAEs的污染特征及其来源。结果表明,苏南地区农田土壤中总PAHs和总PAEs的浓度分别在147～40300μg·kg-1和0.575～762μg·kg-1之间,其中钢铁厂周边的平均浓度分别为6130μg·kg-1和47.4μg·kg-1。土壤样品中苯并（a）芘的浓度与总PAHs的浓度显著相关,高分子量PAHs在钢铁厂周边表土中含量较高,钢铁冶炼焦化和烧结等工序是其污染来源。酞酸正丁酯（DBP）和酞酸乙基己基酯是苏南地区农田土壤中含量最高的两种PAEs类物质,钢铁厂周边有较高的DBP检出可能与炼钢、冷轧和炼铁等工序有关。本研究将为经济高速发展地区农田土壤环境质量评价、农产品安全生产及土壤污染防治对策的制定提供科学依据。     

Rapid magnetic solid-phase extraction based on magnetic multiwalled carbon nanotubes for the determination of polycyclic aromatic hydrocarbons in edible oils

In this study, magnetic multiwalled carbon nanotubes were fabricated by a simple method and applied to magnetic solid-phase extraction (MSPE) of eight heavy molecular weight polycyclic aromatic hydrocarbons (PAHs) including chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene from edible oil samples. Several parameters affecting the extraction efficiency were investigated, including the type and volume of desorption solvent, extraction and desorption time, washing solution and the amount of sorbent. Under the optimized conditions, a simple and effective method for the determination of PAHs in edible oils was developed by coupling with gas chromatography-mass spectrometry (GC-MS). The whole pretreatment process was rapid, and it can be accomplished within 10 min. The limits of quantitation for the target PAHs were found to be 0.34-2.9 ng/g. The recoveries in oil sample were in the range 87.8-122.3% with the RSDs less than 6.8% (intraday) and 9.6% (interday). This method was successfully applied to the analysis of PAHs in seven kinds of edible oils from local markets.     

土壤中多环芳烃的分布特征及其来源分析

利用气相色谱法分析了南充市10个不同功能区表层土壤中美国环保署规定的16种优控多环芳烃（PAHs）的含量和组分特征,运用同分异构体比率揭示了其污染来源。研究表明,该区土壤中PAHs的含量在9.1～2269.1μg·kg-1之间,而且工业区的残留量大于农业区和居民区的残留量。按PAHs的环数来分,在工业污染区PAHs的含量总的趋势是四环〉二环〉三环〉五环〉六环;农业和居民区二环〉三环〉五环〉四环〉六环。该污染状况与国内外相关研究比较,处于中等污染水平。煤、木材和化石的燃烧是该地区土壤中PAHs污染的主要来源,苯并（a）蒽和菲是主要的超标化合物。     

Polycyclic aromatic hydrocarbons in marine organisms from the Gulf of Naples, Tyrrhenian Sea

Polycyclic aromatic hydrocarbons (PAHs) were determined by an HPLC method with fluorescence detection in bivalves (Mitylus galloprovincialis), cephalopods (Todarodes sagittatus), crustaceans (Aristeus antennatus), and fish (Mullus surmeletus, Scomber scombrus, Micromesistius poutassou, and Merluccius merluccius) caught in the Gulf of Naples (Tyrrhenian Sea, Italy). Anthracene, fluoranthene, pyrene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, and benzo(k)fluoranthene were detected, at different concentrations, in all of the examined marine organisms, whereas benzo(a)pyrene, dibenz(a,h)anthracene, benzo(g,h,i)perylene, and indeno(1,2,3-cd)pyrene were found only in Mediterranean mussels. Of mussels collected in winter 71.43% exceeded the maximum residual levels (MRL) fixed for the benzo(a)pyrene in European Regulation 208/2005/EC, whereas all samples collected in summer reported values lower than this limit. In comparison to the other marine organisms, the mussels showed the highest PAH concentrations (p < 0.01). Fish showed total PAH levels lower than those of cephalopods and, in particular, European hake showed the lowest values (6.06 ng/g of fresh weight).     

Particle-associated Polycyclic Aromatic Hydrocarbons in the Atmosphere of Hong Kong

Polycyclic aromatic hydrocarbons (PAHs) in total suspended particulates (TSP) collected at six rural and urban stations in Hong Kong from 1993–1995 using high volume air samplers were identified using GC-MS (gas chromatography-mass spectrometry). The results showed that the PAHs exhibited distinct spatial and seasonal variability. The total PAH content (ΣPAH) in the samples ranged from 0.41 to 48 ng m^-3. The unsubstituted analogs are the characteristic products of high temperature combustion processes. The highest average ΣPAH was measured at the street-level station in Mong Kok indicating that vehicles were high PAHs contributors. The rural station at Hok Tsui exhibited the lowest PAH level, however; influences of city plumes could be seen when northerly or northeasterly winds prevailed in the winter. All stations experienced the highest loading of PAHs in autumn and the lowest in summer; the former was 2.8 times greater than the latter. This seasonal variability is due to the Asian monsoon system, precipitation, micrometeorology, and the rate of photodegradation. In summer, Hong Kong experiences relatively clean oceanic air and high rates of precipitation and photodegradation, while upon the onset of the winter monsoon, local air mass is replaced by polluted air streams from the Asian continent. Benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(e)pyrene, indeno(1,2,3-cd)pyrene and benzo(ghi)perylene were the dominant species in the samples. The PAH distribution patterns at different stations were similar within each season. However, seasonal variations existed. For example, phenanthrene contributed up to 14% of the total PAH in summer, while the dominance of benzo(b)fluoranthene, benzo(k)fluoranthene was more significant in autumn and winter.