Degradation of bis(2-ethylhexyl) phthalate constituents under methanogenic conditions

The degradation of bis(2-ethylhexyl) phthalate (DEHP) and its intermediary hydrolysis products 2-ethylhexanol (2-EH) and mono(2-ethylhexyl) phthalate (MEHP) was investigated in a methanogenic phthalic acid ester-degrading enrichment culture at 37°C. 2-Ethylhexanoic acid (2-EHA), a plausible degradation product of 2-EH, was also studied. The culture readily degraded 2-EH via 2-EHA to methane which was formed in stoichiometric amounts assuming complete degradation of 2-EH to methane and carbon dioxide. MEHP was degraded to stoichiometric amounts of methane with phthalic acid as a transient intermediate. DEHP remained unaffected throughout the experimental period (330 days).Abbreviations 2-EH 2-ethylhexyl alcohol - 2-EHA 2-ethylhexanoic acid - BBP butylbenzyl phthalate - Be-CoA benzoyl Coenzyme A - CoA Coenzyme A - DEHP bis(2-ethylhexyl) phthalate - MEHP mono(2-ethylhexyl) phthalate - MSW municipal solid waste - PA phthalic acid - PAE phthalic acid ester - TMS trimethylsilyl derivative     

电子垃圾拆解地区土壤和植物中邻苯二甲酸酯分布特征

近年来,电子垃圾不当拆解带来的环境问题引起国际社会的极大关注.本研究对浙江省台州市不同电子垃圾拆解地区土壤和植物样品中5种邻苯二甲酸酯类（PAEs）污染物进行了测定分析.结果表明：土壤（以干质量计）中PAEs类污染物的浓度为12.566~46.669 mg·kg^-1,其中邻苯二甲酸二异辛酯（DEHP）、邻苯二甲酸二丁酯（DBP）和邻苯二甲酸二乙酯（DEP）相对含量较高,约占PAEs总量的94%以上.拆解地区蚕豆（Vicia faba L.）中PAEs总量明显高于同地区其他植物,且土壤和所有植物体内PAEs浓度相关性均不显著(P>0.05).与美国国家环保局制定的土壤PAEs治理标准比较,台州电子垃圾拆解地区土壤PAEs污染较为严重.     

城市污泥中邻苯二甲酸酯(PAEs)的厌氧微生物降解

邻苯二甲酸酯(PAEs)是城市污泥中普遍存在的一类具有内分泌干扰性作用的有机污染物.研究污泥厌氧生物处理过程中PAEs的微生物降解对保障污泥农用的安全性十分必要.本文以污泥中两种主要的PAEs——邻苯二甲酸二丁酯(DBP)和邻苯二甲酸(2-乙基己)酯(DEHP)为研究对象,通过比较PAEs在污泥厌氧消化系统与发酵产氢系统中降解过程的差异及系统污泥特性的变化,分析不同污泥厌氧生物处理系统中影响PAEs降解的可能因素.结果表明: 在污泥厌氧发酵系统中,DBP在6 d内降解率达99.6%, DEHP在整个14 d的培养期间也降解了46.1%;在发酵产氢系统中,在14 d培养过程DBP的降解率仅为19.5%,DEHP则没有明显的降解.与厌氧消化系统相比,PAEs在发酵产氢系统中的降解受到明显抑制,这与发酵产氢过程中微生物量下降、革兰氏阳性菌/革兰氏阴性菌(G⁺/G^-)和真菌/细菌变小及挥发性脂肪酸(包括乙酸、丙酸及丁酸)浓度升高有关.     

5-Chloropicolinic acid is produced by specific degradation of 4-chlorobenzoic acid by Sphingomonas paucimobilis BPSI-3

We have previously shown that the bacterium Sphingomonas paucimobilis BPSI-3, isolated from PCB-contaminated soil, can degrade halogenated biphenyls, naphthalenes, catechols and benzoic acids. However, before such an organism can be used in bioremediation, it is important to characterise the degradation products and determine the degradation pathways to ensure that compounds more toxic or mobile than the original contaminants are not produced. In the degradation of 4-chlorobiphenyl, S. paucimobilis BPSI-3 produces a novel chlorinated picolinic acid. In this paper, we show that 4-chlorobenzoate is an intermediate in this degradation and, through ¹⁵N-labelling, that 5-chloropicolinate is the only nitrogenous metabolite isolated under the extraction conditions used. The position of the chlorine indicates that degradation of 4-chlorocatechol occurs exclusively via a 2,3-extradiol cleavage. These data allow us to postulate a more definitive catabolic pathway for the biodegradation of 4-chlorobiphenyl to 5-chloro-2-hydroxymuconic acid semialdehyde via 4-chlorobenzoate in S. paucimobilis BPSI-3. Received 19 April 1999/ Accepted in revised form 23 July 1999     

LEGUME-GRASS INTERCROPPING PHYTOREMEDIATION OF PHTHALIC ACID ESTERS IN SOIL NEAR AN ELECTRONIC WASTE RECYCLING SITE: A FIELD STUDY

A field experiment was conducted to study the phytoremediation of phthalic acid esters (PAEs) by legume (alfalfa, Medicago sativa L.)-grass (perennial ryegrass, Lolium perenne L. and tall fescue, Festuca arundinacea) intercropping in contaminated agricultural soil at one of the largest e-waste recycling sites in China. Two compounds, DEHP and DnBP, were present in the soil and in the shoots of the test plants at much higher concentrations than the other target PAEs studied. Over 80% of ‘total’ (i.e., all six) PAEs were removed from the soil across all treatments by the end of the experiment. Alfalfa in monoculture removed over 90% of PAEs and alfalfa in the intercrop of the three plant species contained the highest shoot concentration of total PAEs of about 4.7 mg kg^?1 DW (dry weight). Calculation of phytoextraction efficiency indicated that the most effective plant combinations in eliminating soil PAEs were the three-species intercrop (1.78%) and the alfalfa monocrop (1.41%). Phytoremediation with alfalfa was effective in both monoculture and intercropping. High bioconcentration factors (BCFs) indicated the occurrence of significant extraction of PAEs by plants from soil, suggesting that phytoremediation may have potential for the removal of PAEs from contaminated soils.     

农业土壤中邻苯二甲酸酯污染研究进展

由邻苯二甲酸酯(PAEs)引起的环境污染和食品安全问题已经引起全球性关注.我国既是邻苯二甲酸酯生产大国,又是消费大国,其环境污染问题不容忽视.本文综述了美国国家环保署所列出的6种优先控制PAEs污染物在我国农田土壤中的污染现状,分析了其来源,重点阐述了不同类型农作物对PAEs化合物的吸收累积特征及PAEs类污染物的生物毒害效应.我国多数地区农业土壤中PAEs的含量显著高于美国和欧洲等国家.大气沉降、农用薄膜、施用污泥和污水灌溉是我国农业土壤中PAEs的主要来源.不同作物对PAEs的吸收、累积和分配特征具有显著的差异性.PAEs不但影响土壤质量、作物生长和生理生化性质,而且具有生物累积效应.最后指出了当前研究中的不足及对今后研究的展望,建议扩大PAEs污染调查范围,深入揭示PAEs对农作物的毒害机理,重点研发PAEs污染土壤的原位修复技术.     

人工榆树林对温带草原植物多样性的影响

在样线和样方调查的基础上,研究了内蒙古四子王旗人工榆树林对温带草原物种多样性的影响.结果表明:榆树林对草原的物种多样性有明显影响.随榆树林树木密度的提高,林下草本植物的丰富度、均匀度和多样性等指数均呈降低趋势.靠近榆树林的草原群落的物种丰富度、均匀度和多样性等指数高于远离榆树林的草原群落.喜生于树林内部的草本植物有旱麦瓶,喜生于榆树林周边草原的草本植物有阿尔泰狗娃花、扁蓄豆、二裂委陵菜、赖草和糙隐子草等.可见,盲目排斥草原地区造林并非科学之举,应选择土壤水分相对丰富的地段营造适当规模的人工林,以促进草原地区的植物多样性保护.     

广州、深圳地区蔬菜生产基地土壤中邻苯二甲酸酯(PAEs)研究

对广州 (含增城、花都 )和深圳地区的 9个代表性蔬菜生产基地进行调查采样 ,利用超声波提取 -硅胶柱净化 -气相色谱 /质谱联机检测技术 (GC/ MS) ,分析了土壤中属于 U.S.EPA优控污染物的 6种邻苯二甲酸酯 (PAEs)化合物。结果表明 ,6种PAEs化合物总含量 (Σ PAEs)在 3.0 0～ 4 5 .6 7mg/ kg之间 ,其中 37%样品的Σ PAEs在 10～ 2 0 mg/ kg,2 2 %样品的Σ PAEs在2 0～ 30 m g/ kg。各蔬菜基地中以联兴基地的 Σ PAEs平均值最高 (35 .6 2 m g/ kg) ;广清基地的 Σ PAEs平均值最低 (10 .31m g/kg)。各 PAEs化合物中以 DEHP的含量最高 ,Dn BP次之 ,两者共占 Σ PAEs的 90 %以上。BBP、DEP、DMP和 Dn OP的含量均在 2 .0 mg/ kg以下。与美国土壤 PAEs控制标准相比 ,除了 Dn OP外 ,其余 5个化合物均不同程度超标 ,其中 DEP、Dn OP、DEHP超标较普遍且较严重。但所有 PAEs化合物的含量均低于美国土壤 PAEs治理标准。总体上看 ,上述蔬菜基地土壤中PAEs的含量较高 ,说明受到了不同程度的污染     

山东省花生主产区土壤和花生籽粒中邻苯二甲酸酯的分布特征

在山东省四大花生主产区采集耕层土壤(0～20 cm)和花生籽粒,应用气相色谱测定样品中美国国家环保署(EPA)优先控制的6种邻苯二甲酸酯(PAEs)化合物的含量.结果表明: 山东省花生主产区土壤中6种PAEs化合物累计(∑PAEs)含量范围为0.34～2.81 mg·kg^-1,平均含量为1.22 mg·kg^-1;四大花生主产区土壤∑PAEs含量为：鲁中南山区＞鲁西平原＞胶东半岛＞鲁北平原;与美国土壤PAEs控制标准相比,山东省四大花生主产区土壤中的邻苯二甲酸正二丁酯(DBP)超标严重.花生籽粒中∑PAEs含量范围为0.17～0.66 mg·kg^-1,平均含量为0.34 mg·kg^-1,低于美国和欧洲的建议指标,健康风险很小.邻苯二甲酸二(2-乙基己基)酯(DEHP)和DBP在土壤和花生籽粒中占∑PAEs的百分比、检出率均较高,是主要的污染物组分.覆膜种植模式下土壤和花生籽粒中的∑PAEs显著高于露地种植模式.花生籽粒和土壤中的∑PAEs、DBP及DEHP存在显著正相关性,Pearson相关系数分别为0.786、0.747和0.511.     

Biodegradation of Hopane Prevents Use as Conservative Biomarker During Bioremediation of PAHs in Petroleum Contaminated Soils

The pentacyclic triterpane C₃₀ 17α (H), 21β (H)-hopane, a biomarker commonly used in hydrocarbon bioremediation laboratory experiments and field studies, was found to be completely removed without the formation of the demethylated intermediate nor-hopane in a crude oil-contaminated soil undergoing slurry biotreatment, while PAHs such as benzo(e)pyrene were recalcitrant. The partial or complete biodegradation of hopane has also been previously reported in a few bioremediation studies and has been explored by petroleum geochemists in an effort to characterize crude oil deposits. It is currently not clear what conditions induce hopane biodegradation or biotransformation, although the use of microbial enrichment cultures appears to speed up the process. Considering that hopane is not necessarily conserved during a bioremediation study, the uncritical normalization of hydrocarbon concentrations using this biomarker can lead to incorrect estimates of biodegradation rates and extents. If hopane is found to be unstable in a particular case, other potential biomarkers such as pentahopane, oleanane, or vanadium may be used instead.     

Isolation of polyacrylamide-degrading microorganisms from soil

Two polyacrylamide-degrading bacterial strains, No. 2 and No. 11, were isolated from soil, and identified asBacillus sphaericus No. 2 andAcinetobacter sp. No. 11, respectively. Both strains grew on medium containing polyacrylamide as sole carbon and nitrogen sources.B. sphaericus No. 2 andA. sp. No. 11 reduced by 16% and 19% of the initial polyacrylamide concentration, respectively. Optimal pH and temperature in growth ofAcinetobacter sp. No. 11 were 8.0 and 37°C, respectively. After 14-day cultivation ofA. sp. No. 11, the average molecular weight of polyacrylamide has been shifted from 2.3×10⁶ to 0.5×10⁶.     

On-Site Treatment of Contaminated Soils: An Approach to Bioremediation of Weathered Petroleum Compounds

A bench-scale investigation was conducted prior to on-site bioremediation of 52,000 cubic yards of contaminated soil containing weathered, structurally complex petroleum compounds from an inactive oil refinery. Addition of bulking agents was required to improve soil physical properties. A supplemental study was also conducted to evaluate the effectiveness of bio-enhancement products. Loss of n-alkanes was rapid in soil mixtures containing a high nitrogen sludge compost, but very slow in mixtures containing wood products as bulking agents. By completion of the study at day 110, the isoprenoids pristane and phytane had nearly disappeared from mixtures containing sludge compost. Clearly, pristane and phytane are inadequate biomarkers when conditions favor an advanced stage of biodegradation. Nearly half the complex branched and cyclic alkanes in the unresolved complex mixture also degraded. After 70 days, depletion of dibenzo-thiophenes and phenan-threnes was 75 and 90%, respectively. The most stable PAHs within each group were the highly methylated homologues. Because of their complex structures, both steranes and hopanes were stable in all soil mixtures. Data were normalized to hopanes as a conserved internal standard or biomarker. Use of hopane-normalized data successfully eliminated much of the data variability and permitted a more accurate assessment of biodegradation. A relatively slow decline in total hydrocarbons occurred later in the study. This slowing tendency of microbial utilization is caused not only by substrate depletion, but also because remaining hydrocarbons are structurally more complex and persistent. Because of this, it is important to avoid using kinetic data from early stages of bioremediation to predict later hydrocarbon losses, such as the time required to attain a cleanup standard. In the supplemental study, an oleophilic fertilizer product accelerated hydrocarbon degradation when compared with a conventional fertilizer. This product will be tested in combination with organic bulking agents under field conditions to determine its cost effectiveness.     

柴油降解细菌的分离及其降解能力初探

从含油土壤中,筛选出能以0#柴油为惟一碳源的2株柴油降解菌,经鉴定分别为假单胞菌(Pseudomonoussp.)和芽孢杆菌(Bacillussp.)。通过其降解能力的测试,假单胞杆菌属细菌A8的降解能力较强;在含油浓度ρ=10g/L的摇瓶试验中,培养7d后其除油率分别为18%和31%。在含油浓度1%的土壤中,2株菌均能正常生长和繁殖,接种30d除油率分别为35%和48.3%。     

细菌对环境污染物的趋化性及其在生物修复中的作用

细菌对有机化合物的降解能力是一种利用碳源和能源的优势,这种能力可以用来设计安全、有效和无二次污染的污染物的生物修复系统。趋化性是细菌适应外界化学环境变化而作出的行为反应,是一种寻找碳源和能源的优势。细菌的趋化性能够增强细菌在自然环境中的降解污染物的效果,细菌的趋化性与降解性之间的关系研究已经成为热点。介绍了细菌的趋化性的基本概念和趋化信号转导的机制,重点讨论了细菌对环境污染化合物的趋化性,从基因水平揭示了趋化性与降解性之间的紧密联系,认为趋化性可以有效地促进降解性细菌对污染物的生物修复作用。     

微生物对拟除虫菊酯类农药残留的生物修复

拟除虫菊酯类农药是一类高效、广谱农药,且具有低毒性和能被生物降解之特性,但其残留却给人们的健康带来了巨大的威胁,如何有效地去除其残留成为摆在环境工作者面前的一项重大课题。以生物修复为理论基础的农药残留降解菌技术为解决这一难题带来了新思路,该方法操作简便、经济实用,在国内外均成为环境工作者的研究热点。     

Surfactant enhances biodegradation of hydrocarbons: Microcosm and field study

The purpose of the present study was to provide new methods that would increase the rates of biodegradation of petroleum hydrocarbons in soil, thus reducing the time required to achieve a satisfactory level of residual hydrocarbon in an ex situ bioremediation. Results of laboratory studies on several techniques were used to guide our implementation of these methods in controlled field studies. Soils contaminated with nonvolatile hydrocarbons were treated with various combinations of (1) an anionic surfactant guanidinium cocoate (CGS), (2) a consortium of hydrocarbon‐degrading microorganisms, (3) a slow‐release form of nitrogen:urea, and (4) the bulking agent vermiculite. Laboratory results describing the activity of CGS have been presented previously (Jain et al., 1992). The amount and rate of hydrocarbon loss in treated soil was compared with hydrocarbon lost in soil that received no amendment other than water (water only). We also used a sheen screen method (Nelson et al., 1995), to assess the effectiveness of our field application of microorganisms.     

Assessment of Anaerobic Biodegradation of Aromatic Hydrocarbons: The Impact of Molecular Biology Approaches

One of the most cost effective methods of pollution remediation is through natural attenuation where the resident microorganisms are responsible for the breakdown of pollutants (Dou et al. 2008). Other forms of bioremediation – such as analogue enrichment, composting and bio-venting – also use the microbes already present in a contaminated site to enhance the remediation process. In order for these approaches to be successful, in an industrial setting, some form of monitoring needs to take place enabling conclusions to be drawn about the degradation processes occurring. In this review we look at some key molecular biology techniques that have the potential to act as a monitoring tool for industries dealing with contaminated land.