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。     

生物表面活性剂强化微生物修复多环芳烃污染土壤的初探

通过温室盆栽实验,单独或联合接种多环芳烃专性降解菌(DB)和添加生物表面活性剂-鼠李糖脂(RH),研究了生物表面活性剂强化微生物修复多环芳烃(PAHs)长期污染土壤的效果。结果表明,添加RH和接种DB能明显促进土壤中PAHs总量和各组分PAHs的降解。经过90 d培养后,添加RH、DB和RH+DB处理的PAHs的降解率分别为21.3%、32.6%、36.0%,较对照分别提高了333.0%、563.3%、633.0%。此外,随着苯环数的增加,土壤中15种PAHs平均降解率逐渐降低。同时也发现DB、RH+DB处理土壤中脱氢酶活性、多酚氧化酶活性和PAHs降解菌数量显著高于CK、RH处理,但是CK与RH处理没有显著差异,说明DB、RH在促进土壤中PAHs的降解方面有不同的机制。     

多环芳烃污染土壤的微生物与植物联合修复研究进展

本文综述了多环芳烃(PAHs)污染土壤中微生物降解途径、机理及生物反应器的应用,并从植物修复角度,进一步阐述了与微生物联合作用促进污染土壤中PAHs降解的途径、机理及其应用。提出了利用微生物共代谢降解及其与植物联合修复PAHs污染土壤环境的生物修复技术未来研究课题。     

多环芳烃污染土壤的生物修复

综述了土壤环境中多环芳烃的来源、归宿、生物转化机理、影响因素及生物修复技术研究进展,提出了利用生物技术治理土壤环境中多环芳烃的思路及方法。     

土壤环境中多环芳烃的微生物降解及联合生物修复

研究土壤环境中持久性有机污染物的生物降解及其生物修复技术是当今国际环境修复科学技术前沿领域的重要课题。本文重点论述了土壤环境中持久性有机污染物多环芳烃的微生物降解机理及其在生物修复中的应用等,并结合当前研究进展,展望了基于多种修复措施相结合的多环芳烃污染土壤联合生物修复工程技术的开发与应用前景。     

多环芳烃污染土壤真菌修复进展

多环芳烃是一类具有致癌、致畸、致突变效应的化合物,主要通过生物质和化石燃料的不完全燃烧产生,过量的排放可能导致土壤污染。现有多环芳烃污染土壤的生物修复大多利用细菌的降解功能,真菌的修复潜力尚未被充分认识。真菌是土壤生态系统的重要组成部分,具有极高的多样性。多种真菌,主要是担子菌和子囊菌具有降解多环芳烃的能力,它们通过细胞内的细胞色素P450氧化酶、细胞外的木质素水解酶及胞外聚合物系统作用于多环芳烃;某些真菌与植物形成共生菌根,以协同方式实现污染物的降解。由于真菌降解多环芳烃的特点,其在减少土壤高环多环芳烃含量、降低多环芳烃毒性方面具有独特的优势。本文综合介绍了多环芳烃降解真菌的多样性和降解机制,对现有的真菌土壤修复技术进行了总结,针对目前真菌修复中存在的问题作了进一步讨论,并对真菌修复的未来发展趋势提出了展望。     

根系分泌物及其在修复多环芳烃污染土壤中的应用

修复被多环芳烃污染的土壤是目前环境和生态领域的一个前沿课题,植物修复是一种经济廉价、可操作性强、美化景观的绿色技术,而根系分泌物在植物修复污染土壤过程中有着重要的意义。总结了近年来国内外植物根系分泌物研究的主要成果,系统介绍了根系分泌物的定义、组成、影响因素及其收集和分离纯化方法,综述了近年来根系分泌物在植物修复技术中的应用情况,以期为进一步开展多环芳烃污染土壤植物修复研究提供实践参考和理论依据。     

土壤多环芳烃、重金属及其复合污染的植物修复研究进展

复合污染研究已成为环境科学发展的重要方向之一,重金属和多环芳烃是土壤环境中的重要污染物,开展两者复合污染研究,对于农业环境生态安全具有重要意义。本文结合前人的研究结果,通过分析多环芳烃污染土壤的植物修复和重金属污染土壤的植物修复的研究现状,来探讨植物对重金属和多环芳烃复合污染的修复研究进展,并从生态地理学的角度提出相应的研究趋势,提出植物修复需因地制宜的特性。     

几种豆科、禾本科植物对多环芳烃复合污染土壤的修复

通过盆栽试验,研究了几种豆科植物与禾本科植物对多环芳烃(PAHs)复合污染土壤的修复作用。结果显示,90天后8种植物对土壤中PAHs均有不同程度降解效果,其中紫花苜蓿和多年生黑麦草对土壤PAHs的去除率分别达48.4%、46.8%,且对3环PAHs去除较为彻底,对4环及4环以上的PAHs去除效果较差。8种供试植物对PAHs均有一定的吸收、富集与转运的能力,紫花苜蓿和多年生黑麦草对土壤PAHs的生物富集系数分别为0.096、0.085,其提取修复效率为0.017%和0.013%。可见,紫花苜蓿和多年生黑麦草具有较好的根际修复潜力。     

丛枝菌根作用下土壤中多环芳烃的残留及形态研究

采用盆栽试验方法,以苊为多环芳烃(PAHs)代表物,研究了丛枝菌根(AM)作用下土壤中 PAHs 的残留及形态.供试污染土壤中苊的起始浓度为 35.0 mg/kg.结果表明,AM作用下土壤中苊总残留量明显降低;接种摩西球囊霉菌Glomus mosseae或幼套球囊霉菌Glomus etunicatum后,供试两个污染土样中苊总残留降解率达32.7%～45.2%,比未接种对照高 6.8%～9.8%.有机溶剂提取态是土壤中苊残留的主要部分,AM 作用促进了苊各形态之间的转化;接种AM后土壤 1、2 中苊可脱附态和有机溶剂提取态残留量分别比对照降低了17.0%～37.8% 和 5.4%～26.6%,而结合态残留量比对照增加了12.2%～89.5%.AM 作用能降低土壤中苊可提取态残留含量;但培养55 天后土壤中仍有 65.7%～81.7% 苊属于可提取态残留,对生物有毒害风险.     

多环芳烃在土壤中的环境行为研究进展

综述了土壤环境中多环芳烃(PAHs)来源及其进入环境后的行为和归宿,并提出多环芳烃污染土壤的修复对策。     

Identifying sources of polycyclic aromatic hydrocarbons (PAHs) in soils: distinguishing point and non-point sources using an extended PAH spectrum and <Emphasis Type="Italic">n</Emphasis>-alkanes

Background, aim, and scope  Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants. They are formed during pyrogenic and diagenetic processes and are components of petrogenic materials such as oils and coals. To identify PAH sources, several studies have employed forensic methods, which may be costly to execute. Although a large number of possible forensic methods are available (e.g., total ion chromatograms, PAH ratios, PAH alkyl homologue series, isoalkanes and isoprenoids, steranes and terpanes, stable isotope ratios, n-alkanes), one has to decide which method is the appropriate cost effective screening approach. In this study, three approaches were tested and compared by measuring (1) an extended PAH spectrum (i.e., 45 instead of the common 16 EPA-PAHs), (2) PAH ratios and (3) n-alkanes to determine if point sources are distinguishable from non-point sources, and if an individual source can be distinguished from a multiple source contaminated site in the study area. In addition, the study evaluated whether these methods are sufficient for source identification of selected samples, and if they constitute a sound strategy for source identification prior to the selection of more cost intensive methods. Materials and methods  Eighteen samples with previously characterized PAH point sources (previously characterized point sources in the Mosel and Saar region) were analyzed. Additionally, three river bank soils of Mosel and Saar rivers with known non-point PAH sources were investigated. The point sources were two gasworks, a tar impregnation facility, a creosoted timber, an acid tar, a tank farm, and a diesel contaminated site. Non-point sources were hard coal particles and atmospheric inputs in river bank soils. All samples were extracted with hexane and acetone, analyzed with a gas chromatograph coupled to a mass spectrometer for PAH distribution patterns and ratios. n-Alkanes were measured by a gas chromatograph equipped with a flame ionization detector. Results  Samples collected from point sources and non-point sources were analyzed by the use of three forensic methods, i.e., PAH patterns of an extended PAH spectrum, PAH ratios and n-alkanes. Identification by PAH patterns alone was insufficient for the non-point sources and some point sources, since the n-alkanes must be measured, as well. The use of PAH ratios with only 16 EPA-PAHs is less indicative in determining multiple sources because source assignments (or categories) change depending on the ratio used. Discussion  This study showed that by employing an extended PAH spectrum it is possible to fingerprint and distinguish sources. The use of alkylated PAHs is essential for identifying petrogenic sources. It is insufficient to rely exclusively on either the common 16 EPA-PAHs or the ratios to the parent PAHs when identifying non-point sources. Source identification using PAH ratios is only reliable if both parent and alkylated PAHs are measured. n-Alkane analyses provide more detailed information about petrogenic sources by verifying the presence of oils, diesel, gasoline, or coal in non-point sources. Conclusions  The three methods tested were deemed sufficient to distinguish between point and non-point PAH sources in the samples investigated. The use of an extended PAH spectrum provides the first step toward identifying possible sources. It simplifies the decision whether additional forensic methods should be necessary for more detailed source identification. Recommendations and perspectives  The determination of PAH alkyl homologue series, biomarkers, and isotopes is often advised (Kaplan et al., Environ Forensics 2:231–248, 2001; Oros and Simoneit, Fuel 79:515–536, 2000; Wang and Fingas, Mar Pollut Bull 47:423–452, 2003). The methods involved are complex and often expensive. We recommend a relatively uncomplicated and cost-effective method (i.e., extended PAH spectrum) before further and more expensive forensic investigations are to be conducted. Additional research with an extended sample set should be carried out to validate these findings for other sources and sites. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

甜菜与牧草间作对多环芳烃污染土壤的修复作用

通过盆栽试验方法,选择经济作物甜菜和牧草类黑麦草、苏丹草、香根草为供试植物,研究了甜菜与3种牧草分别间作及各自单作对多环芳烃（PAHs）菲、荧蒽、芘和苯并[a]芘污染土壤修复作用。结果显示：经6个月连续两茬种植试验后,所有种植植物的处理中土壤PAHs的去除率均高于无植物种植组,间作种植土壤PAHs的去除率高于单作,黑麦草、苏丹草、香根草与甜菜间作对土壤PAHs的去除率分别达到84.85%、79.96%、84.11%;在土壤污染条件下,间作模式更有利于甜菜生长;种植植物增强了土壤中多酚氧化酶和过氧化氢酶的活性,间作模式下二者活性高于单作4.37%~43.07%,过氧化氢酶较多酚氧化酶对PAHs土壤污染更敏感,可作为关键酶用于评价土壤PAHs污染状况。在不影响农业生产的前提下,修复植物牧草和经济作物甜菜间作种植模式显著提高了土壤PAHs的降解率。     

Distribution of polycyclic aromatic hydrocarbons (PAHs) in floodplain soils of the Mosel and Saar River

Background, Aim and Scope  Polycyclic aromatic hydrocarbons (PAHs) have gained serious attention in the scientific community due to their persistence and toxic potential in the environment. PAHs may pose a risk to ecosystem health. Along the Mosel River/Germany, a tributary of the river Rhine, PAHs were found at significantly high concentrations (> 20 mg kg⁻¹, German national guideline value Z2, LAGA 1998). These high concentrations were detected during the construction of a storm water retention basin, in which the contaminated soils had to be removed and treated as hazardous waste. This resulted in higher construction costs for implementing flood prevention measures, but did not address the origin of these PAHs and its distribution along Mosel River. Hence, for future flood prevention projects, it is necessary to estimate the extent of PAH contamination along the Mosel River. The aim of the study is to determine the extent of PAH contamination in soils collected along Mosel and Saar River, and to obtain a first insight into the origin of the PAH contamination in this region. Materials and Methods  In total twenty seven sample sites were investigated. Forty two single samples were collected along a 167 km distance of Mosel River and six samples were collected along a 20 km distance of Saar River. Soil samples were collected at a depth of 0 to 2 m with a stainless steel corer (▫ 8 cm). Each 2 m sample was further separated into two sub-samples (0–1 m and 1–2 m). The sixteen EPA PAHs and three additional PAHs (1methylnaphthalene, 2methylnaphthalene and perylene) were analysed with gas chromatography mass spectrometry (GC-MS). For soil characterisation, total organic carbon (TOC), grain size, microscope and X-ray diffraction (XRD) analysis were performed. Results  Grain size for all soil samples was classified as a mixture of sand and silt. XRD analysis showed that all samples were dominated by quartz. Some clay minerals, such as illite and montmorillonite and feldspars, i.e. anorthoclase and orthoclase, were found in minor quantities. TOC ranged from 0.1% to 13%. Microscope analysis showed black coal particles in the majority of the soils collected from the Saar River and part of the Mosel River (downstream of the confluence of Saar and Mosel River). The black particles were not found further upstream along Mosel River. The sum of nineteen PAHs in the soil samples was up to 81 mg kg⁻¹ dry weight (dw). Most soil samples showed a relationship between the presence of coal particles and PAH concentrations. Discussion  Elevated PAH concentrations were found in all soil samples collected from Saar River and downstream Mosel River. Due to former coal mining activities in the Saarland, Germany, there is a strong evidence that the majority of the PAH contamination in the soils downstream Mosel River are linked to these mining activities. Upstream Mosel River coal particles were hardly found although PAH concentrations were high. Therefore another PAH source has to be responsible for these concentrations. PAH distribution patterns indicate a pyrogenic PAH input upstream Mosel River and a mixed input (petrogenic and pyrogenic) downstream Mosel River. Conclusions  Due to PAH distribution patterns, the contamination along the upstream of the Mosel River is probably linked to atmospheric depositions and other sources not linked to coal mining activities. Downstream Mosel River the PAH distribution patterns reflect former coal mining activities. We could corroborate for the first time that coal mining resulted in a serious problem of an extensive PAH contamination at Saar and Mosel River floodplain soils. Recommendations and Perspectives  Coal mining activities have a strong impact on the neighbouring regions (Johnson and Bustin 2006, Short et al. 1999, Stout et al. 2002). It is known that coals exhibit relative high PAH concentrations, especially in the low molecular weight PAHs (Chapman et al. 1996, Radke et al. 1990). However, PAHs in coals are hardly bioavailable (Chapman et al. 1996) and hence may have less adverse effects on exposed biota. They can act as sink for other hydrophobic contaminants. For the assessment of the environmental impact, a detailed study of the sorption and desorption behaviour of PAHs linked to coal particles should be carried out. ESS-Submission Editor: Dr. Ralph Portier (rportie@lsu.edu)     

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。     

多环芳烃在岩溶区上覆土壤中的垂直迁移及控制因素

选取典型表层岩溶泉域内的土壤剖面为研究对象,分析土壤样品的主要理化指标,并采用气相色谱-质谱联用仪对土壤中的多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)进行定量分析,研究16种PAHs在土壤剖面中的垂直迁移规律及控制因素。结果表明,所研究的5个土壤剖面中,16种PAHs均被检测出,其多环芳烃含量范围为161～3 285 ng g-1,平均值为987 ng g-1。兰花沟泉域水稻田和水房泉泉域土壤剖面中,PAHs的组成均以低环PAHs为主,后沟泉泉域土壤剖面中以高环PAHs为主,柏树湾泉域马尾松林地和兰花沟泉域马尾松林地土壤剖面中,0～2 cm表层土壤中以高环PAHs为主,2 cm以下土层中以低环PAHs为主。从剖面PAHs含量和组成变化可以判断,低环PAHs较易迁移,但在土层较薄的后沟泉泉域土壤剖面中,由于翻耕等人为的扰动,高环PAHs也较易迁移。5个剖面中,PAHs在水房泉泉域土壤剖面的迁移能力最强。由于岩溶区较薄的土壤层,使得PAHs较易迁移并污染表层岩溶泉水。对土壤理化性质和PAHs总量进行多元回归分析,表明土壤总有机碳(TOC)是控制后沟泉、兰花沟泉和柏树湾泉泉域土壤中PAHs迁移的主要因子,而在水房泉泉域土壤中,无主要影响因子。