农药企业搬迁土地多环芳烃的风险评价

以常州市某农药厂搬迁土地为研究对象,在监测分析土壤中16种多环芳烃（PAHs）的基础上,对该区域土壤进行健康风险和生态风险评价。结果表明,研究区域土壤中∑PAHs的含量范围为0～1.546mg·kg-1,优势化合物中萘、菲等低环化合物含量大于高环的荧蒽、苯并[k]荧蒽和芘等化合物,且土壤中PAHs可能来源于石油源。健康风险评价结果在可接受的10-6～10-4范围内,而生态风险评价表明,尽管研究区域土壤中的多环芳烃不存在严重的生态风险,但是化合物苊和芴含量超出了风险评价低值（ER-L和ISQV-L）,存在着对生物的潜在危害。     

火干扰后土壤多环芳烃时空分布特征

采集马尾松次生林的灰烬、0~3 cm和3~10 cm深度的土壤样品,研究了火干扰后多环芳烃的时空分布特征。结果表明:火干扰样地Ⅰ、Ⅱ、Ⅲ土壤的多环芳烃总浓度介于757.8~1718 ng g-1,平均浓度为74.2 ng g-1,是对照样地的10倍以上。火后1个月土壤多环芳烃成分以萘、荧蒽、芘、蒽、芴、菲、苊烯为主,火后6个月以菲、荧蒽、芘为主,火后12个月也以菲、荧蒽、芘为主;样地Ⅳ和Ⅴ0~3 cm土层各多环芳烃含量是3~10 cm土层的3~4倍,轻多环芳烃(含2~4环)的含量比重多环芳烃(含5~6环)高;火干扰后6和12个月,土壤多环芳烃总浓度下降显著(P0.05),含2~环的多环芳烃含量下降,含4~6环的多环芳烃比例增加;灰烬中轻多环芳烃含量比较高、重多环芳烃含量较少,灰烬中多环芳烃含量高于相应的土壤样本;多环芳烃总量和含2环或3环多环芳烃与土壤有机质及其他化学性质指标显著相关。     

北京东南郊再生水灌区土壤PAHs污染特征

采用Eijkelkamp土壤采样器对北京东南郊再生水灌区进行了3个钻孔剖面采样,同时采集了灌溉用水及地下水样品,并采用气相色谱-质谱联用仪对16种多环芳烃（PAHs）进行定量分析。结果表明,表层土壤中有14种PAHs检出,浓度在0.4-53.1 μg·kg-1之间,∑PAHs平均含量为206.7 μg·kg-1,达到了土壤污染临界值;表层以下PAHs的检出种类和含量显著减少,以中、低环的萘、菲、芴、荧蒽、芘为主,∑PAHs仅占表层的3.8%-12.0%,从剖面PAHs含量变化可以判断,低环PAHs较易迁移,迁移性强弱顺序为萘、芴〉菲〉芘、荧蒽;污灌区表土中PAHs组成与大气降尘接近,但与再生灌区有明显差异,这种差异主要由于灌溉用水不同所造成;再生水灌区表土以下土壤剖面检出的PAHs与再生水中的PAHs一致,说明再生水灌溉是导致土壤剖面PAHs污染的主要原因,同时地下水中检出的PAHs种类也与土壤剖面基本一致,但含量较高,可能是早期污水灌溉所造成。     

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。     

皂角苷增强洗脱复合污染土壤中多环芳烃和重金属的作用及机理

通过增溶实验和土壤洗脱实验,研究了一种生物表面活性剂——皂角苷（saponin）对多环芳烃-重金属复合污染土壤的洗脱作用及机理。结果表明,皂角苷对菲、芘等多环芳烃有极强的增溶作用,当皂角苷浓度为0.04%时,菲、芘在液相中的表观溶解度分别增大了约22倍和128倍,因而皂角苷能显著增强多环芳烃污染土壤中菲、芘的洗脱,洗脱效率最大分别可达84.1%和81.4%,增大了约2倍和17倍。皂角苷可与重金属离子形成水溶性的络合物,从而增强洗脱重金属污染土壤中的Zn^2＋和Cd^2＋,在皂角苷浓度为0.4%时,Zn^2＋、Cd^2＋的洗脱效率分别可达93.0%和79.4%,增大了约75倍和8倍。皂角苷可同时洗脱多环芳烃-重金属复合污染土壤中的菲、芘和Zn^2＋、Cd^2＋,洗脱效率分别达87.6%、83.5%和92.3%、78.6%,重金属的存在略增大了皂角苷对菲、芘等多环芳烃的洗脱效率,但多环芳烃对Zn^2＋、Cd^2＋的洗脱效率没有明显影响。皂角苷可同时增强洗脱复合污染土壤中的多环芳烃和重金属,从而为多环芳烃-重金属复合污染土壤的修复奠定基础。     

污泥中多环芳烃分析方法的综述

多环芳烃是列于美国EPA黑名单上的一组优先污染物,一般指2个或2个以上苯环以稠环形式相连的化合物,如萘、蒽、菲等,由于其特殊的结构,具有致癌、致畸、致突变作用,而且广泛的存在于环境当中,种类繁多且难降解,对人类的危害很大,所以对环境中多环芳烃的测定及分析引起人们的关注,分析测定环境中的多环芳烃越来越重要,本文对污泥中多环芳烃的分析测定方法进行了系统的综述     

南京有机污染风险区农田土壤多环芳烃污染状况研究

采集南京地区不同有机污染风险区农田表层土壤,用超快速液相色谱仪检测样品中15种EPA优控的多环芳烃(PAHs)含量。结果表明,被检农田土壤多环芳烃总量分布于306.0~1251.3μg kg~(-1)之间,均值682.0μg kg~(-1),四环以上高环多环芳烃占较大比例(80%)。根据欧洲土壤质量标准,所检土壤样本已达污染水平。不同风险污染区农田土壤PAHs的含量由高至低为:钢铁工业区、有机垃圾处理区、化工工业区及炼油工业区。钢铁工业区附近主要的污染物为荧蒽、芘、屈和苯并[a]蒽,分别占到污染物总量的16%、13%、10%和10%。采用荧蒽/(荧蒽+芘)与茚并[1,2,3-cd]芘/(茚并[1,2,3-cd]芘+苯并[g,h,i]苝)比值对各地污染物来源进行分析,结果发现调查区域的PAHs污染物以燃烧源为主,生物质燃料为主要污染物,部分地区同时有石油燃烧污染。     

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。     

北京市东南郊再生水灌区地下水多环芳烃污染风险评估

为研究污染物随再生水进入地下环境后其迁移衰减情况及对地下水的潜在危害性,以Multi-cell模型为基础,结合污染物质量守恒、在水土中吸附再分配、生物降解等机理,针对地下水污染风险评估构建了计算污染物随水在土壤剖面的垂向迁移衰减一维模型,并以北京通州大兴再生水灌区为研究区域,以再生水中持久性有机污染物多环芳烃萘和菲为研究对象,根据当地钻孔资料及灌溉水水质、地下水水质资料,应用该模型进行试算。结果表明,经过多年连续灌溉后,通州大兴大部分地区进入潜水含水层的萘、菲浓度较低,整体污染风险较低,仅在通州区潞城镇等个别地区萘、菲浓度较高,应引起重视;由于大兴区整体包气带较厚,其污染风险低于通州区。土壤粘土层是萘、菲积累的主要层位,其吸附容量远大于细砂等粗颗粒介质,在土壤表层低环多环芳烃迁移性更强。应用这一模型,能够较为宏观地掌握通州大兴再生水灌区不同区域地下水中多环芳烃萘和菲的污染风险差异。     

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。     

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.     

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。     

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.     

Batch Culture Enrichment of Indiginous Soil Microorganisms Capable of Catabolizing Creosote Components

Batch enrichment cultures for creosote catabolizing microorganisms was carried out using a creosote-contaminated soil as the inoculum. The flasks were separately spiked with phenol, o-cresol, m-cresol, p-cresol, naphthalene, anthracene, phenanthrene, pyrrole, fluorene, pyrene, fluoranthene, chrysene,benzo(a)pyrene and creosote (a complex mixture of about 400 compounds) in concentrations of 50, 100, 500, 1000, 5000, 10 000, 15 000, 20 000, 25 000 and 30 000 mg L^-1. The flasks were incubated on a rotary shaker in the dark at 30 °C. Samples for analysis were taken from the flasks every three days for three weeks. Counts of microorganisms were observed to be highest in most cases in 5000 mg L^-1 cultures. The pH values were observed to fluctuate between 5 and8 but this did not seem to affect the growth of the organisms except at 50 and 100 mg L^-1 in the phenolics and some polycyclic aromatic hydrocarbons (PAHs) were the decreases correlated with decreases in cell counts. The isolates in the first week were mainly of one morphological type in most cultures. In subsequent weeks, the populations became mixed. The higher molecular mass PAHs at higher concentration continued to support only a few types of organisms. Isolates included bacteria, actinomycetes and fungi. The phenolics and naphthalene were more readily removed (up to 100%) from the cultures. Other hydrocarbons removal were between 45 and 83% with the higher molecular mass compounds being most recalcitrant. The decreases in creosote concentration was similar to those in the phenolic compounds and the lower molecular mass compounds up to a concentration of 10 000mg L^-1. Decreases in creosote concentration started to decrease from a concentration of 15 000 mg L^-1 upward. Subsequent subculturing was observed to enhance the degradative capabilities of the isolates and the further removal of the higher molecular mass compounds. However, this enhanced degradation was much lower in creosote cultures than in the other cultures.     

Spectroscopic determination of poly-aromatic compounds in petroleum contaminated soils

The determination of poly-aromatic hydrocarbons (PAHs) in the soil is of interest because of their carcinogenic and mutagenic activity in biological systems. The present study deals with the rapid application of infrared, fluorescence, synchronous luminescence spectrometries and gas chromatography to detect organic pollutants and their quantity in the soil. Sohxlet extraction followed by column separation was used to isolate organic pollutants. Although several solvent mixtures were used as eluents for the column, the solvent mixture, hexane:dichloromethane (50:50) efficiently extracts the aromatic compounds. Total petroleum hydrocarbons (TPH) measured by IR were found at high concentrations (30810.0 ppm) in the contaminated soil compared with the reference soil (30.0 ppm). Furthermore, the fluorescence results reveal that almost one-fourth of the 30810.0 ppm are aromatic hydrocarbons. In addition, the presence of PAHs such as naphthalene, acenaphthene, fluorene, fluoranthene, phenanthrene, pyrene, benzo(a)pyrene, chrysene, and dibenzo(a,h)anthracene in the polluted soil was determined by using synchronous study.     

混合菌群强化去除泥浆体系中菲、芘的效果及影响因素

通过室内泥浆体系模拟试验,研究了混合微生物菌群(嗜热菌和多环芳烃特异性降解菌),在40℃条件下(两类微生物均能较快生长繁殖),对泥浆体系中代表性多环芳烃菲、芘的去除效果及其影响因素(水土比,葡萄糖、淀粉、水杨酸及其浓度)。结果表明:泥浆体系中混合微生物菌群对多环芳烃的去除效果显著(P0.01),单日菲去除率最大可达20.0%,芘达15.3%。随着反应进程的进行,菲和芘的去除率提高,去除速率则逐步降低,菲的半衰期1.8天小于芘4.9天,因此菲的去除较芘更快。试验得到该泥浆体系中混合微生物菌群去除多环芳烃最合适的水土比为2︰1,碳源为葡萄糖,浓度TOC_(葡萄糖):TOC_(PAHs)为2︰1。该研究结果可为泥浆体系中混合微生物菌群强化修复多环芳烃污染土壤的技术研发提供理论基础和技术支撑。     

Low‐molecular‐weight organic acids enhance desorption of polycyclic aromatic hydrocarbons from soil

The impact of low‐molecular‐weight organic acids (LMWOAs) on desorption of phenanthrene and pyrene as representative polycyclic aromatic hydrocarbons (PAHs) from a contaminated soil was investigated by using a laboratory batch experiment. Three LMWOAs were used in this study and were citric, oxalic and malic acids. The LMWOAs in aqueous solution promoted desorption of PAHs from soil significantly and demonstrated an increasing trend as the concentration of LMWOAs increased. When compared with desorption of phenanthrene and pyrene from soil to water, the addition of LMWOAs enhanced desorption of test PAHs by up to 285 and 299%, respectively. Among the three LMWOAs studied, citric acid demonstrated the greatest efficiency in promoting PAH desorption from soil. Solutions of LMWOA continuously promoted PAH removal from soil during the multiple cycles of desorption. Overall, the experimental results suggest that LMWOAs in aqueous solution could disrupt soil organic matter (SOM)–metal cation–mineral linkages in soils, resulting in the release of SOM from soil and simultaneous increase of dissolved organic carbon (DOC) in solution. The loss of SOM from soil and increase of DOC in solution are responsible for the enhanced PAH desorption from soil. The positive correlation between DOC in solution and desorbed PAHs from soil suggests that the loss of SOM from soil plays an important role in LMWOA‐enhanced desorption of PAHs from soil.