某石化污染场地含水层自然降解BTEX能力评估

地下水污染问题是国家关注的重要环境问题之一,监测与评估含水层自然降解污染物能力是防治地下水污染的基本手段,也是国外地下水中修复技术研究热点课题。以华北平原某石油化工类场地为案例,通过调查场地水文地质条件、土壤及地下水污染现状,监测场地地下水中苯系物(BTEX)浓度及相关化学参数变化,运用微生物水文地球化学方法和水文地质方法,估算了该场地含水层自然降解苯系物量。这一研究成果为评估我国石油类场地地下水污染的自然修复能力提供了实证和基础数据。     

贵州主要碳酸盐岩含水层污染现状与特征

岩溶地区地下水环境脆弱,易受人类活动及区域环境变化影响.目前将岩溶水污染与污染点所在区域的地层岩性、水文地质条件等结合起来的研究较少.采用改进后的层级阶梯评价法开展贵州省区域地下水污染评价,并结合实地调查分析污染成因.结果显示二叠系栖霞-茅口组,三叠系下统嘉陵江组、夜郎组等,中统关岭组、杨柳井组等是全省污染程度最高的碳酸盐岩含水层,原因与含水层岩石类型和出露位置密切相关.含水层岩石类型与特点决定了含水介质组合类型、岩溶发育程度和污染途径污染距离,石灰岩地层天然防污能力差,以中远源径流型污染为主,白云岩地层天然防污能力较好,以近源入渗型污染为主.贵州产煤地层龙潭组上覆嘉陵江组、夜郎组,下伏栖霞-茅口组最易受煤矿开采及其化工影响,污染组分以铁、铝、锰为主;而三叠系碳酸盐岩分布区域与安顺、贵阳、遵义等大中型城市和磷化工、铝工业、锰系铁合金生产等工矿企业聚集区域重合度高,更容易受到生产生活影响,污染组分多为氨氮、重金属、耗氧量及有机污染组分.      

含水层中铁锰的地下去除方法

本文在分析大量文献的基础上,归纳并总结了国外目前正大力推广应用的含水层中铁锰地下去除方法——Vyredox 法的特点。并对该方法净化地下水的基本原理、使用条件及系统设置做了扼要说明,对运行中可能出现的问题,如堵塞及合理选择回灌周期等也做了进一步论述。最后以实例来证明该方法不愧为一种处理效果明显、易于管理的地下水除铁锰的新方法。对于地下水中铁含量不大干15mg/L,锰含量不大于4mg/L 的含水层,均可采用该方法在地下将铁锰含量降低到符合饮用水标准的程度。     

去除地下水芳香烃污染物:实验室含水层土柱研究

芳香烃污染地下水以其污染普遍、危害巨大、去除困难及治理费用昂贵而倍受各国环境学者及水文地质学者的关注。以苯及甲苯作为标示污染物,利用室内饱水含水层土柱,通过对污染带的模拟实验发现,苯和甲苯在反硝化条件下产生生物降解,二者的去除率分别大于７７％和８８％;反硝化条件下,苯和甲苯显示出降解性差异,甲苯更易于降解;硫酸还原作用可能是苯和甲苯被去除的另一机理,但实验结果显示,ＮＯ－３高时,对硫酸还原菌的生长具有抑制作用。     

含水层热量运移中自然热对流作用的数值模拟

较严密地推导了能够描述含水层热量运移中自然热对流作用的水流方程和热量运移方程,并在此基础上建立了一个三维非线性模型.根据模型的特点,提出综合采用Douglas Brian ADI差分法、特征线法返回技术及改进Picard迭代法求解,并给出了计算步骤.模型及数值方法用于模拟上海第二承压含水层中的一个群井储能试验.试验中的自然热对流作用得到了较好的体现,反映出模型合理可靠,方法有效,结果令人满意.     

离子类型对石油污染含水层中微生物去除苯的影响

近来利用微生物原位修复受石油污染的含水层已被广泛关注,然而地下水中含有许多离子成分,这些无机离子对微生物降解有机污染物的影响机制还不清楚。本文采用批量实验研究了淄博齐鲁石化污染地下水中常见的7种无机离子(NO3-、PO4 3-、SO4 2-、Cl-、Ca2+、Mg2+、Fe3+)对微生物生长及生物降解苯的影响规律,利用高通量测序技术进一步探究了苯降解菌的种群特征。结果表明：7种离子都存在一个最适宜微生物生长的离子浓度,低于或超过该浓度苯的去除率明显降低,其中NO3-、SO42-、Fe3+最适宜浓度为0. 4mmol/L,PO4 3-、Cl-、Ca2+、Mg2+最适宜浓度分别为0. 2mmol/L、0. 1mol/L、2. 5mmol/L、2mmol/L;从微生物含量及其变化幅度来看,地下水环境中的NO3-离子对微生物的生长及苯的去除影响最显著,其他离子的影响则较小,但微生物对Cl-的耐受浓度较高。高通量测序结果显示驯化出的苯降解菌主要属于脱硫弧菌属(Desulfovibrio sp)、脱硫芽胞弯曲菌属(Desulfosporosinus sp)、不动杆菌属(Acinetobacter sp)和假单胞菌属(Pseudomonas sp)中的菌株。研究结果可为石油污染地下水的原位生物修复提供一定的科学依据。     

石油碳氢化合物污染含水层的快速氧化还原进程

搜集的六年地下水化学数据显示，经过一段时间后。被石油类碳氢化合物污染的浅含水层的污染物的分布和氧化还原进程已发生了快速的变化。在1990年发生石油泄漏后不久，大量的苯存在于污染源地区，在受污染的地区，地下水中的溶解氧被消耗掉。截止到1994年，Fe(Ⅲ)和硫酸盐的减少是显著的晚期电子接收过程。非常有意义的是，1994年的溶解甲烷在测量下限以下。这暗示了缺乏有意义的甲烷群。然而，到1996年，含水层沉积物中固相Fe(Ⅲ)的氢氧化物的消耗和地下水中溶解硫酸盐的消耗导致了甲醇类的大量繁殖。在1996年—2000年期间，水化学数据显示甲醇类的新陈代谢更加普遍了，对沉积物的萃取物16s-rDNA进行分子分析，显示了更加多元化的甲醇类的存在，相对于污染羽中心的外面，它和水化学数据反映的变化是一致的。该快速氧化还原过程反映了几种因素，包括大量污染物，相对快速的地下水流动(0．3m／day)(1foot／day)和原始存在于含水层沉积物中的可由细菌引起减少的低浓度Fe(Ⅲ)氢氧化物(1umol／g)。这些结果表明，在一定水文条件下受石油碳氢化合物污染含水层中的氧化还原条件。在时间和空间上能快速发生变化，并且有效的固相Fe(Ⅲ)的氢氧化物影响了变化的速度。     

土耳其默辛地区非承压含水层中地下水重金属污染的监测

在本项研究中，利用光度测定法测定Mersin含水层地下水的重金属含量，确定默辛地区地下水污染的主控因素。利用Maplnfo GIS软件开展空间分析和集成，来绘制盆地饮用水水质图。根据重金属的光度分析可推断得出，在某些地区地下水中铁、镍、锰、销和铜的浓度过高，是地下水不适于饮用的根本原因。同样，电导率（EC）专题图表明，盆地内大多数地区地下水的含盐最过高。地下水中多种重金属的浓度过高是由工业活动、石油管道泄漏以及较高的含盐度（由海水入侵导致）引起的。     

污染土壤石油生物降解与调控效应研究

为考察修复过程中土壤石油降解效应,选用中国北方某油田区现场的原油污染土壤,进行了投加除油菌、调节氮磷营养含量和水分含量等强化措施的修复试验。经过180d修复,结果表明,土壤石油污染物去除率达70·6%,去除速率达0·15g·kg-1·d-1,与自然条件相比,石油污染物半衰期由929d减少为103d。饱和烃去除率占总石油去除的75%以上,主要为十八烷、二十七烷、二十九烷、三十一烷与三十四烷。初期投菌对石油污染土壤的生物修复具有快速启动作用,但后期多次投菌对生物修复的促进作用不明显。对氮磷营养水平的适当调节有利于生物修复进行,本试验中对除油菌生长和石油去除最有利的有效态碳氮比为C∶N=100∶1~50∶1。在石油去除过程中,土壤石油去除速率的变化与除油菌数量变化趋势基本一致,表明微生态环境调控对于污染土壤中的石油降解具有显著的促进作用。     

Fenton试剂快速氧化处理地下水中BTEX可行性研究

研究了Fenton试剂氧化处理地下水中苯、甲苯、乙苯和二甲苯(BTEX)的效果。结果表明Fenton试剂具有很好的氧化处理BTEX的能力;H2O2/BTEX(摩尔比)=5和10时,在H2O2/Fe(Ⅱ)(摩尔比)=4和8的情况下氧化去除效果最好,去除率能达到80%以上;H2O2/BTEX(摩尔比)=20时,氧化去除效果显著,此时H2O2/Fe(Ⅱ)摩尔比对处理效果影响较小,H2O2/Fe(Ⅱ)=10时最终去除效率均达到97%～100%;整个实验过程中体系处于强氧化环境,pH值由6～7迅速下降至3左右。     

Biodegradability of trimethylbenzene isomers under the strictly anaerobic conditions in groundwater contaminated by gasoline

Trimethylbenzene (TMB), as a constituent of gasoline, is often expected to be used as a conservative tracer in anaerobic BTEX-contaminated groundwater site to correct for attenuation due to dispersion, dilution and sorption along a flow path. To evaluate the suitability of using TMB as a tracer and to better understand biodegradability of TMB in contaminated groundwater by gasoline under anaerobic conditions, laboratory microcosms were conducted with mixed nitrate/iron/sulfate electron-acceptor amendments, using aquifer materials collected from Canadian Forces Base (CFB), Borden, Ontario, Canada. The results showed that under denitrifying conditions, biodegradation of 1,3,5-TMB, 1,2,4-TMB and 1,2,3-TMB were relatively slow and after 204 days of incubation approximately 27, 24, and 16% of the initial concentrations, respectively, were degraded in the microcosms. Under sulfate-reducing conditions, TMB isomers were recalcitrant. In contrast, significant biodegradation of TMB was observed under iron-reducing conditions. 1,3,5-TMB, 1,2,4-TMB and 1,2,3-TMB were degraded to 44, 47, and 24% of initial concentrations with first-order biodegradation rate constants of 0.003, 0.006 and 0.013 d⁻¹, respectively. This study indicates that TMB biodegradation is insignificant under nitrate and sulfate-reducing conditions but significant under iron-reducing conditions. Therefore, the use of TMB as a tracer for interpreting removal of other biodegradable gasoline constituents such as BTEX requires caution, especially in the presence of iron-reducing conditions.     

应用质量通量评估地下水中BTEX和乙醇的自然衰减

近年来,应用于修复石油烃污染地下水的监测自然衰减技术得到了广泛深入研究,同时质量通量方法已逐渐成为评 估地下水燃油污染场地自然衰减监测修复效能的重要手段。通过在室内砂槽中添加乙醇汽油组分,监测其自然衰减,利用 质量通量方法,得出了BTEX和乙醇的质量减少率、自然衰减速率常数K;结合非反应示踪剂溴离子,评价了BTEX和乙醇 自然衰减因素中吸附和微生物的联合降解效应。结果表明,自然衰减是地下水中燃油组分修复的重要机制,质量通量方法 是评估自然衰减的有效方法之一。BTEX和乙醇在自然衰减过程中被去除的比例分别为78.88%和98.71%,其中约98%的 BTEX 因吸附和生物降解联合作用被去除,接近100%的乙醇因内在生物降解作用被去除;BTEX 的自然衰减速率为 0.077d-1~0.167d-1,乙醇为0.353d-1,自然条件下乙醇比BTEX更容易衰减。     

Distribution characteristics and source of BTEX in groundwater in Guangzhou,Guangdong Province,P. R. China

In order to find out the distribution characteristics of BTEX in groundwater, which include Benzene, Toluene, Ethylbenzene, p-Xylene, m-Xylene, and o-Xylene, 82 groups of groundwater samples and 10 surface water samples collected from Guangzhou in Guangdong during 2005 to 2008 were tested by gas chromatography and mass spectrum(GC/MS). The result showed that the BTEX concentration in groundwater does not exceed the standard. The detection rate of BTEX is 14.63% in groundwater, and the total BTEX concentration is lower than 9.5 μg/L. Of 6 kinds of BTEX, toluene had the highest detection rate(12.20%) and detection value(9.5 μg/L), which was followed by Benzene, with the detection rate of 3.65%, and detection value of 4.9 μg/L respectively; most of samples with BTEX are distributed in Huangpu district, Baiyun district, Huadu district and other industrialized areas; this spatial distribution and urban distribution have obvious consistency. With economic development, plant expansion and population growth led to a large amount of waste water discharge, and infrastructure construction is lagging behind, indicating that rapid urbanization is a major driving force of BTEX in groundwater, and through the analysis of a typical area, it is found that benzene system surface water infiltration was an important source of BTEX in groundwater of Guangzhou.     

Correction: Feasibility of nitrate reduction combined with persulfate oxidation in the remediation of groundwater contaminated by gasoline

Hydrogeology Journal -     

Feasibility of nitrate reduction combined with persulfate oxidation in the remediation of groundwater contaminated by gasoline

Hydrogeology Journal - Enhanced bioremediation combined with in-situ chemical oxidation has the potential to remediate groundwater contaminated with organics. To explore the remediating effects of...     

Assessment of MTBE biodegradation in contaminated groundwater using C and C analysis: Field and laboratory microcosm studies

Radiolabelled assays and compound-specific stable isotope analysis (CSIA) were used to assess methyl tert-butyl ether (MTBE) biodegradation in an unleaded fuel plume in a UK chalk aquifer, both in the field and in laboratory microcosm experiments. The ¹⁴C-MTBE radiorespirometry studies demonstrated widespread potential for aerobic and anaerobic MTBE biodegradation in the aquifer. However, δ¹³C compositions of MTBE in groundwater samples from the plume showed no significant ¹³C enrichment that would indicate MTBE biodegradation at the field scale. Carbon isotope enrichment during MTBE biodegradation was assessed in the microcosms when dissolved O₂ was not limiting, compared with low in situ concentrations (2 mg/L) in the aquifer, and in the absence of O₂. The microcosm experiments showed ubiquitous potential for aerobic MTBE biodegradation in the aquifer within hundreds of days. Aerobic MTBE biodegradation in the microcosms produced an enrichment of 7‰ in the MTBE δ¹³C composition and an isotope enrichment factor (ε) of −1.53‰ when dissolved O₂ was not limiting. However, for the low dissolved O₂ concentration of up to 2 mg/L that characterizes most of the MTBE plume fringe, aerobic MTBE biodegradation produced an enrichment of 0.5-0.7‰, corresponding to an ε value of −0.22‰ to −0.24‰. No anaerobic MTBE biodegradation occurred under these experimental conditions. These results suggest the existence of a complex MTBE-biodegrading community in the aquifer, which may consist of different aerobic species competing for MTBE and dissolved O₂. Under low O₂ conditions, the lower fractionating species have been shown to govern overall MTBE C-isotope fractionation during biodegradation, confirming the results of previous laboratory experiments mixing pure cultures. This implies that significant aerobic MTBE biodegradation could occur under the low dissolved O₂ concentration that typifies the reactive fringe zone of MTBE plumes, without producing detectable changes in the MTBE δ¹³C composition. This observed insensitivity of C isotope enrichment to MTBE biodegradation could lead to significant underestimation of aerobic MTBE biodegradation at field scale, with an unnecessarily pessimistic performance assessment for natural attenuation. Site-specific C isotope enrichment factors are, therefore, required to reliably quantify MTBE biodegradation, which may limit CSIA as a tool for the in situ assessment of MTBE biodegradation in groundwater using only C isotopes.     

天津平原区加油站地下水石油烃污染特征及其生物降解机理研究

加油站地下水中石油烃污染是较为普遍的现象,本文对研究区位于不同水文地质条件的加油站地下水进行取样分析,分析加油站地下水中石油烃的污染特征和地下水化学类型特征,并运用因子分析、相关性分析和多元回归分析揭示加油站地下水中石油烃潜在的生物降解机制。研究结果表明,地下水化学类型主要可划分为Cl-Na型、HCO₃-Na型、HCO₃-Ca型和SO₄-Na型4类。加油站地下水中石油烃的检出率为85.71%,检出浓度为0.020.35 mg/L。因子分析结果表明影响地下水化学组成的因素主要以水-岩相互作用和石油烃的生物降解为主。TPH与地下水化学指标间的相关关系表明:TPH与K⁺、Na⁺、Cl^-、Mn、Mg²⁺、 {\mathrm{SO}}_4^{2-}呈现负相关的关系,与pH值、 {\mathrm{HCO}}_3^{-}、 {\mathrm{NO}}_3^{-}、 {\mathrm{NO}}_2^{-}、Ca²⁺、Fe不存在显著的相关关系。加油站地下水环境中可能存在嗜盐或耐盐微生物,导致随着盐度的升高,总石油烃(total petroleum hydrocarbon,TPH)生物降解率加快,TPH浓度呈现出降低的趋势。微生物利用电子受体( {\mathrm{SO}}_4^{2-}、Mn、 {\mathrm{NO}}_3^{-}、Fe)降解TPH的过程中,电子受体的贡献率为:铁还原(64.88%)>锰还原(24.86%)>硫酸根还原(5.78%)>硝酸盐还原(4.46%),即加油站地下水中铁锰还原菌的石油烃生物降解为优势反应。