苯污染地下水系统更硝化菌分布及其净化过程

生物降解作用是地下水系统有机污染物自然衰减过程中最重要的破坏性衰减机制。在分析中，以我国某受苯污染水源地的地下水系统为对象，研究了该地下水中反硝化菌的分布，筛选出2株土著反硝化菌，通过生物降解实验证明其具有降解苯的能力，同时结合水源地历年的水质监测数据，首次从地球化学及生物学2个方面说明了该地下水中存在反硝化菌对苯的生物净化作用，为进一步研究该地下水中苯自然衰减规律奠定基础。     

石油烃在不同土壤中的气相自然衰减规律

挥发性有机物(VOCs)在包气带中的迁移扩散是土壤和地下水中可挥发污染物自然衰减的重要机制,也与蒸气入侵暴露和风险评估密切相关。采用微宇宙实验对12种挥发性石油烃(正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、环庚烷、环辛烷、苯、甲苯、乙苯、对二甲苯)在4种土壤(黑土、黄土、红土、石英砂)中的气相自然衰减机制和气态生物降解动力学规律进行了研究。结果表明,正构烷烃、环烷烃和苯系物蒸气在4种土壤中的气相自然衰减去除率都遵循黑土>黄土>红土>石英砂的规律;黑土中生物降解对污染物去除率的贡献高于黄土,而红土和石英砂中的生物降解速率极低;4种苯系物的自然衰减和生物降解潜力远高于正构烷烃和环烷烃;苯系物气相生物降解速率排序为：甲苯>苯>乙苯>对二甲苯。本研究结果可为蒸气入侵定量风险评估和石油污染场地自然衰减速率定量评估提供参考。     

地下水中药物及个人护理品类污染研究进展

针对地下水中药物及个人护理品(PPCPs)类污染展开综述,介绍了PPCPs类污染物的定义、分类、危害及其在地下水中来源、分布和自然衰减机制,分析并总结目前关于地下水中PPCPs类污染研究存在的问题,据此展望了研究发展方向,提出未来应以地下水特征为研究基础、建立完善的地下水PPCPs类污染环境风险评价体系、推进PPCPs作为地下水示踪剂等研究建议。     

焦化纳滤浓水的生物脱氮及其微生物菌群结构分析

针对焦化纳滤浓水中高总氮的问题,采用序批式反应器(SBR)对纳滤浓水进行了生物脱氮实验,并对其反硝化脱氮效果和反应器中微生物菌群特征开展了研究。结果表明,在SBR系统稳定运行期间,总氮和硝态氮的平均去除率分别为58.2%和93.8%,出水中硝态氮平均浓度为2.0 mg·L~(-1)。微生物菌群结构分析表明:变形菌门和拟杆菌门为纳滤浓水反硝化过程中的核心菌门,相对丰度之和为90.0%～96.0%;反硝化功能基因定量检测表明,在纳滤浓水反硝化过程中,亚硝酸盐还原酶nirS的拷贝数高于亚硝酸盐还原酶nirK约1～2个数量级,这说明nirS在亚硝酸转化为一氧化氮过程中起到了重要作用。SBR工艺处理焦化纳滤浓水具有良好的效果,为解决高盐水生物脱氮提供了新的途径。     

pH对氢自养型反硝化菌反硝化性能的影响

采用模拟硝酸盐污染地下水(简称模拟水)驯化培养氢自养型反硝化菌,建立了定量分析氢自养型反硝化菌生物量的方法,研究了pH对氢自养型反硝化菌反硝化性能的影响。结果表明,每单位OD600相当于水样中氢自养型反硝化菌的生物量为491.75mg/L。当初始pH在6.7以下或9.2以上时,氢自养型反硝化菌生物活性会受到抑制,而初始pH为7.2、7.7、8.2和8.7时,反硝化进行12h后模拟水中的总氮去除率分别为99.7%、99.6%、96.6%和83.5%。经过12h的反硝化模拟水的pH增加0.1～0.9,硬度降低10.01～48.05mg/L;初始pH为6.7～8.7的模拟水在反硝化进行12h后生物量增加5.68～6.03mg/L,初始pH为7.7的模拟水反硝化速率最高,达0.041mg/h。     

反硝化聚磷一体化设备中的聚磷菌

研究了新型生物脱氮除磷新工艺反硝化聚磷一体化设备中反硝化厌氧池活性污泥的兼性厌氧微生物组成，数量及其在该除磷系统中功能，结果表明，稳定运行期反硝化厌氧池内活性污泥混合液的兼性厌氧微生物总数大大多于启动期，稳定期和启动期分离的兼性厌氧微生物有假单胞菌属，副球菌属和肠杆菌科，通过对三种纯菌株进行吸放磷研究，三种菌都有不同程度的聚磷功能，说明反硝化菌也具有聚磷作用。     

地下水中BTEX的原位生物修复研究进展

BTEX是苯、甲苯、乙苯和二甲苯的统称,存在于原油和石油产品中,其作为化工原料,广泛应用于农药、塑料及合成纤维等制造业.BTEX已成为地下水中普遍存在的污染物,自然衰减或生物修复工程已成功应用于地下水中BTEX的去除.自然衰减受BTEX污染的地下水具有良好的效果,但相比之下,生物修复工程更快、更有效.综述了在好氧和厌氧条件下,地下水中BTEX原位生物修复过程的微生物降解机制.     

电化学强化脱氮中反硝化菌对活性炭纤维电极电化学反应影响初步研究

研究固定反硝化菌活性炭纤维电极的阴极极化行为及其硝酸盐氮脱除率,考察了活性炭纤维电极电化学强化脱氮系统中生物过程对电化学过程的影响。实验表明,反硝化过程影响电极电化学反应,参数表观交换电流密度可用来表征体系反硝化菌的反硝化能力,新定义了生物效益量,其变化率与硝酸盐氮脱除率相关性良好。     

可生物降解塑料与沸石载体体系对硝酸盐氮污染地下水的生物修复研究

生物反硝化是修复地下水硝酸盐氮污染的一种有效途径。为进一步确定异养反硝化碳源与载体投加量的配比,取用污水处理厂活性污泥为微生物来源,以可生物降解塑料为新型固相碳源,沸石为微生物载体,设计了9组固相碳源与载体不同配比的柱实验,旨在遴选出可生物降解塑料和沸石的最优配比。同时考察在最优配比时,不同进水硝酸盐氮浓度下的硝酸盐氮去除率、填料降解率、生物膜附着量、生物膜附着效率、反硝化效率等反应特性。结果表明,可生物降解塑料∶沸石(质量比)=2∶1为最优配比。在最优配比下,进水硝酸盐氮质量浓度为40~100mg/L时,异养反硝化对硝酸盐氮具有很好的去除效果(最终去除率均在99%以上),且能够保持较高的反硝化效率,同时载体负载微生物的性能稳定。     

固定化氧化还原介体加速亚硝酸盐生物反硝化作用

考察了利用循环伏安法所制备的固定化氧化还原介体(AQS/PPy/ACF)加速亚硝酸盐生物反硝化的特性,及其降解过程中pH和氧化还原电位(ORP)的变化特征。结果表明,AQS/PPy/ACF可显著地加速亚硝酸盐的生物降解;在不考虑各因子间交互作用的条件下,AQS/PPy/ACF加速亚硝酸盐降解的最佳条件为温度35℃,pH=8和碳氮比为6;AQS/PPy/ACF加速亚硝酸盐生物反硝化过程中pH的变化趋势与传统的亚硝酸盐生物反硝化过程中pH的变化趋势相似;AQS/PPy/ACF的加入可使亚硝酸盐生物反硝化过程中的ORP降低约45 mV;AQS/PPy/ACF具有较好的催化稳定性。本研究可为亚硝酸盐的生物降解提供新的技术途径,并为该技术的实际应用提供理论基础。     

Comprehensive Environmental Investigation at Former Industrial/Petroleum Underground Storage Tank Sites in Long Beach,CA: A Forensic Perspective

Two industrial sites were investigated based on years of available hydrogeologic information and monitoring data for soil and groundwater. Collected data were forensically evaluated using age-dating and fingerprinting methods. The previous business uses of the project sites were as a gas station, laundry/dry-cleaning service, and car wash with petroleum underground storage tanks (USTs). As a result, these sites were exposed to a number of toxic contaminants at relatively high concentrations. Source control was necessary for successful remediation and the ultimate removal of the remaining compounds from these industrial sites. Although contaminated soil around the source was excavated during the remedial action and the high concentrations of contaminants were reduced, typical groundwater contaminants such as petroleum hydrocarbons as gasoline (TPH-G), benzene, toluene, ethylbenzene, xylenes (BTEX), and oxygenates including methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-butyl alcohol (TBA) were persistently found at the studied sites around the source points. The plume and concentration of contaminants had changed their shapes and strength for all monitoring periods. Thus, additional source control seems to be a requirement for the complete removal of source contamination, which must be ascertained with groundwater and soil monitoring on a regular time base. For the study sites, monitored natural attenuation was relatively feasible for the long-term plan; however, it did not offer a perfect remediation solution for an ultimate goal because of residual toxic compounds that might have affected the surrounding residential areas at higher concentrations than their health limits. Therefore, as a remediation strategy, the combination of clean-up technology and natural attenuation with monitoring activities are more highly recommended than either clean-up or natural attenuation used separately.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Partitioning microbial respiration between jet fuel and native organic matter in an organic-rich long time-contaminated aquifer

The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.     

A field comparison of BTEX mass flow rates based on integral pumping tests and point scale measurements

Measuring contaminant flow rates at control cross sections is the most accurate method to evaluate natural attenuation processes in the saturated subsurface. In most instances, point scale measurement is the method of choice due to practical reasons and cost factors. However, at many field sites, the monitoring network is too sparse for a reliable estimation of contaminant and groundwater flow rates. Therefore, integral pumping tests have been developed as an alternative. In this study, we compare mass flow rates obtained by integral pumping test results and point scale data. We compare results of both methods with regard to uncertainties due to estimation errors and mass flow estimations based on two different point scale networks. The differences between benzene and groundwater flow rate estimates resulting from point scale samples and integral pumping tests were 6.44% and 6.97%, respectively, demonstrating the applicability of both methods at the site. Point scale-based data, especially with use of cost efficient Direct-Push technique, can be applied to show the contaminant distribution at a site and may be followed by a denser point scale network or an integral method. Nevertheless, a combination of both methods decreases uncertainties.     

Assessing benzene-induced toxicity on wild type Euglena gracilis Z and its mutant strain SMZ

Benzene is a representative member of volatile organic compounds and has been widely used as an industrial solvent. Groundwater contamination of benzene may pose risks to human health and ecosystems. Detection of benzene in the groundwater using chemical analysis is expensive and time consuming. In addition, biological responses to environmental exposures are uninformative using such analysis. Therefore, the aim of this study was to employ a microorganism, Euglena gracilis (E. gracilis) as a putative model to monitor the contamination of benzene in groundwater. To this end, we examined the wild type of E. gracilis Z and its mutant form, SMZ in their growth rate, morphology, chlorophyll content, formation of reactive oxygen species (ROS) and DNA damage in response to benzene exposure. The results showed that benzene inhibited cell growth in a dose response manner up to 48 h of exposure. SMZ showed a greater sensitivity compared to Z in response to benzene exposure. The difference was more evident at lower concentrations of benzene (0.005–5 μM) where growth inhibition occurred in SMZ but not in Z cells. We found that benzene induced morphological changes, formation of lipofuscin, and decreased chlorophyll content in Z strain in a dose response manner. No significant differences were found between the two strains in ROS formation and DNA damage by benzene at concentrations affecting cell growth. Based on these results, we conclude that E. gracilis cells were sensitive to benzene-induced toxicities for certain endpoints such as cell growth rate, morphological change, depletion of chlorophyll. Therefore, it is a potentially suitable model for monitoring the contamination of benzene and its effects in the groundwater.     

Natural attenuation of trichloroethylene in fractured shale bedrock

This paper describes one of the first well-documented field examples of natural attenuation of trichloroethylene (TCE) in groundwater in a fractured shale bedrock. The study was carried out adjacent to a former waste burial site in Waste Area Grouping 5 (WAG5) on the Oak Ridge Reservation, Oak Ridge, TN. A contaminant plume containing TCE and its daughter products were detected downgradient from the buried waste pits, with most of the contamination occurring in the upper 6 m of the bedrock. The monitoring well array consists of a 35-m-long transect of multilevel sampling wells, situated along a line between the waste pits and a seep which discharges into a small stream. Concentrations of volatile organic carbons (VOCs) were highest in the waste trenches and decreased with distance downgradient towards the seep. Sampling wells indicated the presence of overlapping plumes of TCE, cis-dichloroethylene (cDCE), vinyl chloride (VC), ethylene, ethane, and methane, with the daughter products extending further downgradient than the parent (TCE). This type of distribution suggests anaerobic biodegradation. Measurements of redox potential at the site indicated that iron-reduction, sulfate reduction, and potentially methanogensis were occurring and are conducive to dechlorination of TCE. Bacteria enrichment of groundwater samples revealed the presence of methanotrophs, methanogens, iron-reducing bacteria and sulfate-reducing bacteria, all of which have previously been implicated in anaerobic biodegradation of TCE. 16S rDNA sequence from DNA extracted from two wells were similar to sequences of organisms previously implicated in the anaerobic biodegradation of chlorinated solvents. The combined data strongly suggest that anaerobic biodegradation of the highly chlorinated compounds is occurring. Aerobic biodegradation may also be occurring in oxygenated zones, including near a seep where groundwater exits the site, or in the upper bedrock during seasonal fluctuations in water table elevation and oxygen levels.     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.     

Accumulation of nitrite in denitrifying barriers when phosphate is limiting

Permeable in situ denitrifying barriers can remove nitrate from groundwater. Barriers may be constructed by filling an excavated area with a porous mixture of sand, fine gravel, and substrate or by the injection of a nonaqueous phase substrate into an aquifer. The substrate stimulates the development of a denitrifying microbial community by providing an electron donor. The objective of this study was to determine the ability of denitrifying barriers to function under low-phosphate conditions. Sand columns injected with a soybean oil emulsion were used as laboratory models of denitrifying barriers. When a natural groundwater containing 17 mg l(-1) nitrate-N and 0.009 mg l(-1) phosphate-P was pumped through the columns, only a small amount of nitrate was removed from the water and, in some effluent fractions, 52% to 88% of the influent nitrate had converted to nitrite. Nitrite also accumulated when the phosphate concentration of the groundwater was increased to 0.040 or 0.080 mg l(-1) phosphate-P. Only when a 0.160 mg l(-1) phosphate-P supplement was added to the groundwater was there a loss of nitrate without a large accumulation of nitrite. The addition of solid calcium phosphate or rock phosphate to the sand columns was found to provide adequate phosphate for denitrification in short-term studies. These studies point out the need to ensure that adequate phosphate is present in denitrifying barriers especially when such barriers are used beneath phosphate-binding soils.