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。     

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。     

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。     

不同类型生物炭理化特性及其对土壤持水性的影响

[目的]对比分析不同原料制备的生物炭的理化性质及其对土壤持水性的影响,为选择合适的生物炭改良和修复土壤提供理论依据。[方法]以鸡粪、浒苔及稻草为原料,分高、中、低3种不同温度制备生物炭,运用元素分析、盆栽培养等试验研究其特性。[结果]稻草中C,H及灰分的含量较高,鸡粪中N含量较高,浒苔中C含量低,O含量较高;而在制备的生物炭中,鸡粪基生物炭C和N含量较高,浒苔基生物C含量却比较低。另外,3种类型生物炭的H/C摩尔比值随着热解温度的升高而逐渐降低,C/N比随着热解温度的升高而增大。不同原料制备的生物炭pH值随着热解温度的升高而增大,pH值从6.82~8.35升高至9.33~10.29;3种类型的生物炭pH值随着灰分含量的增大而增大,但增长速率不同,稻草基生物炭浒苔基生物炭鸡粪基生物炭。并且,随着热解温度的升高,鸡粪、浒苔及稻草基生物炭引起土壤持水性逐渐增强。[结论]在土壤提供营养成分方面,鸡粪基生物炭显然更具优势,而且在促进土壤持水性方面,鸡粪生物炭也相对更强一些。     

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。     

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。     

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。     

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。     

黑麦草对土壤中苯并[a]芘动态变化的影响

本文通过盆栽试验初步研究了黑麦草 (LoliummultiflorumLam)对污染土壤中多环芳烃苯并 [a]芘动态变化的影响。盆栽试验设计 3种苯并 [a]芘处理浓度 ,分别为 1、10、10 0mgkg-1。将苗龄为 1周的黑麦草移植于受苯并 [a]芘污染的土壤中 ,同时设置有相同的苯并 [a]芘处理浓度但不种植物的对照试验。试验在2 0m3 的控温、控光的生长室内进行 ,土壤湿度维持在田间持水量的 6 0 %。通过 12 0d的温室盆栽试验 ,观察到土壤中苯并 [a]芘的可提取浓度随着时间逐渐减少 ,种植黑麦草加快了土壤中可提取态苯并 [a]芘浓度的下降。在 1、10、10 0mgkg-1苯并 [a]芘处理浓度下 ,黑麦草生长的土壤中苯并 [a]芘的减少率分别达 82 3%、74 0 %和 5 5 9%。结果还显示 ,随盆栽时间的延长 ,黑麦草根圈土壤中多酚氧化酶含量提高 ,这可能根圈土壤中可提取态苯并 [a]芘含量降低有关。黑麦草的地上部可以积累苯并 [a]芘 ,变幅在 0 0 6～ 3 6 0mgkg-1。初步认为 ,土壤具有缓解苯并 [a]芘污染的自然本能 ,促进黑麦草生长 ,增强土壤多酚氧化酶活性 ,可提高黑麦草对苯并 [a]芘污染土壤的修复能力。     

锯末对生物修复荧蒽和芘污染土壤的强化作用及影响因素

通过土壤微宇宙培养试验,研究了锯末尺寸、添加量和种类等因素对荧蒽特效降解菌MC(Mycobacterium flavescens)修复污染土壤(潮土、红壤、黑土、黄棕壤和水稻土)的效果.结果表明:锯末联合降解菌MC修复荧蒽污染的黄棕壤效果较好,优化条件下25 d荧蒽降解率为42.63％ ±1.05％;该联合修复对黑土和...     

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.     

皇竹草生物炭的结构特征及其对（）的吸附性能

以皇竹草茎秆为原料,在限氧控温（300、500、700℃）条件下制备生物炭,研究该生物炭的结构特征及其对Cr（Ⅵ）的吸附行为。结果发现,随着热解温度的升高,皇竹草生物炭的产率下降,而灰分、pH呈上升趋势;电镜扫描（SEM）观察可见不同热解温度下所制备的生物炭结构相似,均具多孔和管状结构,但在700℃条件下所制备的生物炭相对300℃下制备的生物炭孔壁变薄,且孔壁有附着物,切面有突起结构。三种温度下制备的皇竹草生物炭对溶液中的Cr（Ⅵ）都具有较好的吸附作用,且500、700℃下制备的生物炭比300℃下制备的生物炭具有更好的吸附效果。在0~1 h之间,三种热解温度下制备的生物炭对铬的吸附量均随着时间的延长而快速增加,当吸附至1h时,基本达到饱和状态,随后吸附量无明显变化。     

棉花、花生秸秆生物炭对棕壤中Cu(Ⅱ)运移的影响

[目的]分析棉花、花生生物炭基本理化性质,模拟自然条件下降雨对土壤中Cu(Ⅱ)淋失量的影响,探讨生物炭修复Cu(Ⅱ)污染棕壤的可行性。[方法]以棉花、花生秸秆为原料,采用限氧热解法分别在350,500,650℃下制备生物炭,将生物炭按1%的炭土干重比施入铜污染棕壤[Cu(Ⅱ)的浓度200mg/kg],通过室内土柱淋溶试验分析添加不同生物炭对土壤缓冲性能和吸附能力的影响。[结果]两类生物炭的H/C及O/C的比值随着温度的升高逐渐降低,而生物炭的BET比表面积则随着制备温度的升高而逐渐增大;添加生物炭的土壤淋溶液pH值显著高于空白处理,花生生物炭的效果更为显著;随着淋溶次数的增加,添加生物炭的土壤中Cu(Ⅱ)的淋失量明显低于空白处理;添加花生生物炭提高了土壤中Cu(Ⅱ)的专性吸附,以650℃最为显著。[结论]两种生物炭能明显提高土壤的缓冲性能和对重金属的吸持能力,其中以花生生物炭的效果更为明显。     

4种不同原料生物炭对镉污染土壤的钝化效果与稳定性比较

生物炭的性质与老化作用是影响生物炭钝化修复Cd污染土壤效果的重要因素。比较研究4种不同原料生物炭(污泥类、秸秆类、动禽粪便类和木本类)对Cd²⁺吸附作用和Cd污染土壤的钝化修复效果的差异。结果表明:施用生物炭显著提升土壤孔隙水pH(棕榈丝生物炭除外),降低孔隙水DOC和Cd浓度,从而减少水稻根系对孔隙水中Cd的吸收。同时,4种生物炭提高土壤pH,降低土壤有效态Cd、水稻根系和籽粒Cd含量。老化作用减弱稻秆生物炭的钝化效果,显著增强棕榈丝生物炭对土壤Cd的钝化作用,然而,老化作用对富含灰分的猪粪生物炭和污泥生物炭的影响较小。因此,选择生物炭钝化修复Cd污染稻田土壤时,必须考虑生物炭的原料及其老化作用。     

Studying the Effects of Two Various Methods of Composting on the Degradation Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in Sewage Sludge

The research comprised of studying the effect composting sewage sludge with sawdust and vermicomposting with earthworm Eisenia fetida has on the degradation of 16 polycyclic aromatic hydrocarbons (PAHs). Raw rural sewage sludge prior composting was more contaminated with PAHs than urban sewage sludge, in both cases exceeding EU cutoff limits of 6 mg/kg established for land application. Dibenzo[a,h]anthracene (DBahAnt), acenaphtylene (Acy) and indeno[1,2,3-c,d]pyrene (IPyr) were predominant in rural sewage sludge, whilst the urban sewage sludge contained the highest concentrations of benzo[b]fluoranthene (BbFl), benzo[k]fluoranthene (BkFl) and indeno[1,2,3-c,d]pyrene (IPyr). Thirty days of composting with sawdust has caused a significant reduction of 16 PAHs on average from 26.07 to 4.01 mg/kg (84.6%). During vermicomposting, total PAH concentration decreased on average from 15.5 to 2.37 mg/kg (84.7%). Vermicomposting caused full degradation of hydrocarbons containing 2 and 6 rings and significant reduction of PAHs with 3 aromatic rings (94.4%) as well as with 5 aromatic rings (83.2%). The lowest rate of degradation (64.4%) was observed for hydrocarbons with 4 aromatic rings such as fluoranthene, benzo(a)anthracene, chrysene and pyrene. On the other hand, the highest level of degradation was determined for PAHs with 2 rings (100%), 3 rings (88%) and 6 aromatic rings in the molecule (86.9%) after composting with sawdust. Acenaphthene and pyrene were found to be the most resistant to biodegradation during both composting methods.     

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%.     

Polycyclic aromatic hydrocarbons in soils of Vasilievsky Island (St. Petersburg)

The composition and accumulation patterns of priority polycyclic aromatic hydrocarbons (PAHs) in soils of Vasilievsky Island in Saint Petersburg were studied. Concentrations of benzo[a]pyrene were found to exceed maximum permissible concentrations in all the samples, and the maximum recorded concentration exceeded the MPC by 50 times. Concentrations of other PAHs also exceeded the background values. The main soil pollutants were found to be fluoranthene, pyrene, benzo[b]fluoranthene, benzo[a]pyrene, and benzo[g, h, i] perylene, the part of which in the total content of PAHs was 65–80%.     

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.