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。     

多环芳烃长期污染土壤的微生物强化修复初步研究

本研究通过室内模拟试验,以急性毒性较强的菲(Phe)和遗传毒性较强的苯并[a]芘(B[a]P)为代表性多环芳烃(PAHs)污染物,以不同C源、通气状况和水分条件为调控因子,对PAHs长期污染土壤的土著微生物强化修复进行初步研究。结果表明,搅动处理使污染土壤中Phe和B[a]P的降解率分别达59.44%和26.14%,而淹水处理使两者降解率分别达46.48%和13.27%。添加C源(淀粉和葡萄糖)处理提高了土壤中PAHs的降解率,且随着C源的施用量而增加。同时也发现污染土壤中PAHs降解菌和微生物总量呈正相关,并随着PAHs降解菌数量的增加,土壤中PAHs降解率也随之提高。可见,土壤中PAHs降解速率主要决定于PAHs的降解菌数量。     

多环芳烃微生物降解机理研究进展

主要阐述了微生物降解PAHs的机理,比较了典型微生物种类芽孢杆菌(Bacillus)和分支杆菌(M.vanbaalenii PYR-1)对同种PAHs菲的代谢过程不同之处,并分析了分支杆菌(M.vanbaalenii PYR-1)对菲和芘的代谢机理,指出微生物氧化降解PAHs主要从其K区和湾区开始,而K区氧化是有毒PAHs降解的主要可能途径,资料显示真菌比细菌对苯并[a]芘的降解能力更强,同时给出了微生物代谢菲、芘和苯并[a]芘的降解图,以便做进一步研究。     

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。     

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。     

溶解性富里酸对土壤中多环芳烃迁移的影响

多数多环芳烃（PAHs）因其水溶性低,且易被土壤有机质固持,曾经被认为其迁移能力十分微弱。但土壤中溶解性有机质可能影响PAHs的溶解、吸附等环境过程,进而影响其迁移性。本文旨在研究富里酸提取的溶解性有机质（FDOM）对PAHs在土－水间迁移的影响及其可能机制。溶液化学稳定性研究结果显示,FDOM在溶液pH 2.0～7.0、CaCl₂浓度0～1 500 mmol L^-1范围内均能保持较好的分散性,未发生絮凝沉淀。室内土柱淋溶试验结果表明,FDOM在土壤中具有较强的迁移能力,在FDOM持续淋溶条件下,菲、芘以及苯并[a]芘在淋出液中的浓度明显提高,并有少量二苯并[a, h]蒽淋出。FDOM淋溶处理的土柱表层土壤中菲、芘、苯并[a]芘和二苯并[a, h]蒽的淋失率分别为92.06%、92.07%、84.52%和23.27%,显著高于对照组（p<0.05）。以上研究结果表明,FDOM可作为载体提高PAHs在土壤中的迁移性,增加PAHs向深层土壤和地下水迁移的可能性。     

微生物与有机肥混合剂修复石油污染土壤的研究

采用含有4种菌的菌剂与多种有机肥联合修复石油污染土壤,通过盆栽实验对不同浓度菌剂处理土壤中的石油烃降解率、16种多环芳烃（PAHs）浓度、脱氢酶活性、pH、阳离子交换量和微生物多样性等变化进行了研究。结果表明,腐植酸、诺沃肥和生物有机钙等有机肥和菌剂（4%处理）的加入使土壤盐碱环境得到明显改善,土壤pH稳定于6.9,阳离子交换量为201.94cmol·kg-1;对比4个不同浓度菌剂处理的效果,4%菌剂处理与有机肥联合作用修复效果最显著,石油烃降解率可达到73%,大部分所测PAHs浓度显著降低,其中萘、蒽、苯并（a）芘和苯并（g,h,i）芘降解率分别达到了65.5%、57.7%、74.7%和55.5%,土壤微生物数量增加,多样性更为丰富。     

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。     

低分子量有机酸作用下土壤中菲和芘的残留及形态

采用微宇宙试验方法,以菲和芘为多环芳烃(PAHs)代表物,研究了几种低分子量有机酸作用下黄棕壤中菲和芘的残留和形态。结果表明,老化60 d后土壤中菲和芘的残留含量明显减少;不施加有机酸的对照土壤中,菲和芘的残留含量为10.13和29.18 mg kg-1,去除率为87.33%和63.50%。与对照相比,供试浓度(0～64 mg kg-1)范围内,柠檬酸、草酸、酒石酸等3种低分子量有机酸作用下土壤中PAHs残留含量提高,去除率减小,表明供试条件下有机酸抑制土壤中菲和芘的降解;进一步分析发现,少量(≤4 mg kg-1)的有机酸即可对PAHs降解产生高的抑制效果。微生物降解在PAHs的去除中起重要作用,且芘比菲更抗微生物降解。供试条件下,可脱附态和有机溶剂提取态是土壤中菲和芘存在的主要形态,而结合态残留占总残留的比例很小(<8.5%)。3种有机酸均提高了土壤中可脱附态和有机溶剂提取态菲和芘的残留含量,施加有机酸使土壤中菲和芘的可脱附态含量较对照分别提高了46.67%～749.1%和1.83%～80.20%,有机溶剂提取态则提高了8.73%～375.2%和22.63%～114.3%;低分子量有机酸作用下结合态的菲和芘含量仍很小。     

Polycyclic aromatic hydrocarbon profile analysis of high-protein foods, oils, and fats by gas chromatography.

A method is described for the determination of polycyclic aromatic hydrocarbons (PAHs) with 3-7 rings in (I) meat, poultry, fish, and yeast; and (II) oils and fats. The extraction of PAHs from group I is incomplete, and, therefore, group I samples must be dissolved homogeneously by saponification in 2N methanolic potassium hydroxide. The PAHs are concentrated by liquid-liquid extraction (methanol-water-cyclohexane, N,N - dimethylformamide - water-cyclohexane) and by column chromatography on Sephadex LH 20. The PAHs are separated by high-performance gas-liquid chromatography (GLC) with columns containing 5% OV-101 on Gas-Chrom Q and estimated by integration of the flame ionization detector signals in relation to an internal standard (3,6-dimethylphenanthrene and/or benzo(b)chrysene). The sensitivity is significantly higher than that obtained with ultraviolet spectroscopic methods. The reproducibility and margin of error were tested with meat samples fortified with 11 PAHs and with samples of sunflower oil. The method was further applied to meat, smoked fish, yeast, and unrefined sunflower oil. All samples investigated contained more than 100 PAHs (characterized by mass spectrometry) of which only the main components were determined: phenanthrene, anthracene, fluorene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene + benzo (j)fluoranthene + benzo(k) fluoranthene, benzo(e)pyrene, benzo(a)pyrene, perylene, dibenz(a,j)anthracene, dibenz(a,h)anthracene + indeno(1,2,3,-cd)pyrene, benzo(ghi)perylene, anthanthrene, and coronene. In contrast to other methods, the GLC profile analysis allows the recording of known and unknown PAH peaks simultaneously and also allows a compilation of all PAHs.     

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.     

Particle Phase Concentrations of Polycyclic Aromatic Hydrocarbons in the Atmospheric Environment of Jinámar,Gran Canaria

Airborne concentrations of 8 polycyclic aromatic hydrocarbons (PAHs): fluoranthene, Flt, Pyrene, Pyr, benzo(a)anthracene, BaA, chrysene, Chr, benzo(b)fluoranthene + benzo(k)fluoranthene,B(b + k)F, benzo(a)pyrene, BaP and benzo(g,h,i)perylene, B(ghi)P,were measured in Jinámar, a small town on the island of Gran Canaria (Spain) during a 12 month period (January 1995–December 1995). Concentrations ranged between 0.613 ng m^-3 for B(ghi)P and 0.040 and 0.046 ng m^-3 for pyrene and chrysene. Except for BaA all PAHs occurred at lower concentrations at temperatures below 20 °C. Relative humidity seems to influence concentrations of pyrene, chrysene, benzo(b + k)fluoranthene and benzo(a)pyrene, also affecting the latter ina different way to the other three hydrocarbons cited.     

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.     

Polycyclic aromatic hydrocarbons in spanish olive oils: relationship between benzo(a)pyrene and total polycyclic aromatic hydrocarbon content

Samples of Spanish virgin olive oils (VOOs) from different categories, origins, varieties, and commercial brands were analyzed by HPLC with a programmable fluorescence detector to determine the content of nine heavy polycyclic aromatic hydrocarbons (PAHs): benzo(a)anthracene, chrysene, benzo(e)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perilene, and indeno(1,2,3-c,d)pyrene. Samples of olive pomace and crude olive pomace oils were also investigated. Benzo(a)pyrene concentrations were below the allowed limit in the European Union (2 microg/kg) in 97% of the VOO samples. Only those samples coming from contaminated olive fruits or obtained in oil mills with highly polluted environments exceeded this value. High correlation coefficients (<0.99) were obtained between the contents of benzo(a)pyrene and the sum of the nine PAHs for all of the analyzed categories, suggesting that benzo(a)pyrene could be used as a marker of the content of these nine PAHs in olive oils.     

湿热灭菌和氯化汞灭菌对双液相体系中PAHs降解的影响

A two-liquid-phase(TLP) soil slurry system was employed to quantify the efficiencies of autoclaving and mercuric chloride sterilization in the dissipation of polycyclic aromatic hydrocarbons(PAHs).The fates of 11 PAHs(naphthalene,fluorene,phenanthrene,anthracene,fluoranthene,pyrene,benzo(a)anthracene,benzo(a)pyrene,benzo(b)fluoranthene,benzo(k)fluoranthene,dibenzo(a,h)anthracene) were recorded over 113 days of incubation.No microorganisms were detected in the HgCl 2-sterilized soil slurries during the whole incubation period,indicating very effective sterilization.However,about 2%-36% losses of PAHs were observed in the HgCl 2 sterilized slurry.In contrast to the HgCl 2-sterilized soil slurry,some microorganisms survived in the autoclaved soil slurries.Moreover,significant biodegradation of 6 PAHs(naphthalene,fluorene,phenanthrene,anthracene,fluoranthene and pyrene) was observed in the autoclaved soil slurries.This indicated that biodegradation results of PAHs in the soil slurries,calculated on basis of the autoclaved control,would be underestimated.It could be concluded that the sterilization efficiency and effectiveness of HgCl 2 on soil slurry was much higher than those of autoclaving at 121℃ for 45 min.     

Input and behavior of polycyclic aromatic hydrocarbons in arable,fallow, and forest soils of the taiga zone (Tver oblast)

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65–70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[a]pyrene, and (4) anthracene and benzo[ghi]pyrene.     

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).     

Chemometric Study of the Ex Situ Underground Coal Gasification Wastewater Experimental Data

The main goal of the study was the analysis of the parameters of wastewater generated during the ex situ underground coal gasification (UCG) experiments on lignite from Belchatow, and hard coal from Ziemowit and Bobrek coal mines, simulated in the ex situ reactor. The UCG wastewater may pose a potential threat to the groundwater since it contains high concentrations of inorganic (i.e., ammonia nitrogen, nitrites, chlorides, free and bound cyanides, sulfates and trace elements: As, B, Cr, Zn, Al, Cd, Co, Mn, Cu, Mo, Ni, Pb, Hg, Se, Ti, Fe) and organic (i.e., phenolics, benzene and their alkyl derivatives, and polycyclic aromatic hydrocarbons) contaminants. The principal component analysis and hierarchical clustering analysis enabled to effectively explore the similarities and dissimilarities between the samples generated in lignite and hard coal oxygen gasification process in terms of the amounts and concentrations of particular components. The total amount of wastewater produced in lignite gasification process was higher than the amount generated in hard coal gasification experiments. The lignite gasification wastewater was also characterized by the highest contents of acenaphthene, phenanthrene, anthracene, fluoranthene, and pyrene, whereas hard coal gasification wastewater was characterized by relatively higher concentrations of nitrites, As, Cr, Cu, benzene, toluene, xylene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene.