岩溶地下河系统石灰石对BTEX的吸附动力学和热力学

石油类单环芳香烃BTEX是岩溶地下水中常见的有机污染物,但有关BTEX与石灰石的吸附研究报道很少。文中利用静态吸附实验,研究了桂林寨底地下河系统石灰石含水介质对汽油组分BTEX化合物的吸附动力学和吸附热力学。结果表明：（1）石灰石含水介质对BTEX具有明显的吸附性,BTEX实验吸附容量介于0.004~0.061 mg/g,大小顺序为甲苯>苯>间对二甲苯>邻二甲苯>乙苯,其动力学过程适合用假二级动力学模型描述,表明乙苯和二甲苯的吸附速率明显高于甲苯和苯,模型预测的BTEX吸附容量介于0.005~0.067 mg/g,大小顺序与实验结果一致。（2）BTEX在石灰石含水介质中的吸附热力学符合Freundlich模型及其特例Linear模型,Freundlich常数介于0.076 4~0.189 3［mg/g］［L/mg］1/n,1/n介于0.943 4~0.970 1,BTEX分配系数为0.002 3~0.021 2 L/g。BTEX吸附能力顺序为间对二甲苯>乙苯>邻二甲苯>甲苯>苯。然而,石灰石与BTEX之间的吸附等温线不适合用Langmuir模型描述。这项研究能够为深入探讨BTEX在西南岩溶地下水中的迁移与归宿机制提供科学依据。     

汽油污染含水层中芳香烃的自然去除与生物降解特征

石油烃污染地下水是一个普遍而严重的环境问题.用砂卵石、中粗砂、细砂、粉砂和粘土等在实验室内按照自然界沉积物层序制作了一个含水层物理模型,具有给水、排水、监测、抽提、淋滤与注入等功能.利用该模型开展石油烃污染地下水的特征研究结果表明,苯、甲苯、乙苯和二甲苯(benzene,toluene,ethylbenzene,xylene;BTEX)各溶解组分能够被自然去除,其中甲苯自然衰减的速率系数为0.057 5～0.150 4 d-1,二甲苯为0.068 3～0.104 6 d,乙苯大约为0.047 8 d,苯为O.017 8～0.040 6 d.甲苯与二甲苯容易被去除,然而苯的去除则需要较长的时间.作为BTEX去除反应的电子受体,溶解氧、硝酸盐在需氧或厌氧条件下具有优先利用的机会,而硫酸盐则缺乏优先利用的机会.BTEX溶解组分浓度的降低,加上电子受体浓度的降低,可以表明含水层存在需氧条件与硝酸盐还原条件下的内在生物降解作用.其意义在于通过增加含水层中电子受体的浓度,将有助于内在生物降解能力的增强,从而能够提高含水层中污染物去除的效果.     

地下水石油烃生物降解作用研究

在对某石油污染场地地质、水文地质条件、污染源污染方式调查基础上,根据地下水样测试结果,分析了地下水石油烃污染分布特征、污染晕中指示生物降解作用的电子受体、代谢产物以及重要地球化学参数的变化规律,通过计算矿物饱和指数和采用含水层介质X射线矿物衍射方法研究了污染晕中矿物沉淀反应,计算了含水层的氧化容量。结果表明：由于SO42-背景浓度值较高,硫酸盐还原是污染场地地下水石油烃生物降解的优势反应;菱铁矿、黄铁矿和FeS的沉淀反应是HS-、Fe2＋浓度异常的原因;SO42-的氧化容量在含水层中的氧化容量（OXC）所占比例最大,可进一步推断硫酸盐还原反应是引起污染场地地下水石油烃生物降解的优势反应。     

某石油类污染场地地下水石油烃生物降解的地球化学证据

生物降解地下水石油烃会改变地下水环境的水化学组成,因此可以通过分析污染晕中电子受体、生物降解代谢产物以及重要的地球化学参数量值变化获得生物降解的地球化学证据。本次在对某石油污染场地地质、水文地质条件、污染源污染方式调查基础上,根据地下水样测试结果,详细分析了地下水石油烃污染分布特征、污染晕中指示生物降解作用的电子受体、代谢产物以及重要地球化学参数的空间变化规律,研究结果表明:污染场地内存在氧还原、硝酸盐还原、硫酸盐还原等生物降解作用,其中硫酸盐还原是污染场地地下水石油烃生物降解的优势反应; 在沿地下水流向上,TPH浓度、HCO₃^-浓度和碱度逐渐降低,Eh、电子受体(DO、NO₃^-、SO₄^2-)浓度逐渐升高; 在垂直于地下水流向上,从中心向两侧各组分也呈相似的变化规律。     

岩溶裂隙含水层中石油类有机物的自然衰减机制

石油类有机物污染是地下水环境领域亟须解决的关键课题.本次研究耦合数值模拟和水文地球化学技术模拟岩溶裂隙含水层中石油类有机物的自然衰减过程并定量计算其自然衰减机制.基于BIOSCREEN模型的模拟计算可知,近30年对流、弥散、稀释等物理过程和生物降解过程对石油类有机物衰减贡献率的平均值分别为31.53%和68.47%,生物降解作用是岩溶裂隙含水层自然修复能力的主要机制.利用质量守恒定律分析水化学（HCO₃-、NO₃-）和同位素（δ15N_NO3、δ18O_NO3和δ13C_DIC）之间的相关关系可知石油类有机物生物降解贡献地下水HCO₃-的平均值为33.93%;石油类有机物生物降解消耗主要电子受体NO₃-贡献地下水δ13C_DIC的百分率为30.77%且其占总生物降解的90.69%.      

石油类污染场地的自然衰减作用

在野外石油类污染场地地质、水文地质调查的基础上,对场地地下水中总石油烃的吸附、生物降解等自然衰减作用进行研究。开展了砂质粉土、粉砂、细砂等场地包气带、含水层介质对总石油烃的吸附动力学实验、等温吸附实验、不同矿化度吸附实验、生物降解实验和挥发实验等。实验结果显示,砂质粉土、粉砂、细砂的吸附平衡时间分别为4、7和10 h;通过计算确定了每种介质对总石油烃的等温吸附模型。矿化度对介质吸附总石油烃能力的影响表现为,矿化度越高吸附量越高。生物降解实验结果表明,在场地水土条件下,降解能力最强,且降解符合一级衰减动力学方程。研究表明,地下水受到污染后,吸附、降解、挥发等自然衰减作用对地下水石油类污染物的去除具有非常重要的作用。     

岩溶裂隙水动态系统的门限自回归模型分析

以淄河北部岩溶裂隙水系统为例,运用门限自回归模型分析方法,在模拟分析岩溶裂隙水动态系统特征的基础上,探讨北方岩溶区不同类型含水岩溶裂隙介质系统的岩溶发育规律和含水特征。      

反硝化增强去除乙醇对多孔介质渗透性的影响

随着乙醇混合汽油的不断推广应用,乙醇将成为地下水中与苯、甲苯、乙苯及二甲苯的同分异构体（BTEX）共存的一种新型污染物。通过4 个含水砂柱实验,研究了乙醇存在及其强化去除对含水介质渗透性能的影响。结果表明：在有限溶解氧与反硝化增强修复条件下,乙醇去除率达92% 以上;生物过程对介质渗透能力影响程度随乙醇初始浓度、消耗速率与补充频率而变化：乙醇初始浓度接近1 000 mg/L 和3 000 mg/L 时,乙醇消耗快,补充频率高,渗透系数下降总体上有连续性,最大下降幅度达一个数量级（×10-1 cm/s）;乙醇初始浓度达到5 000 mg/L 时,渗透性下降显著,可下降两个数量级,但乙酸的积累可影响生物活性,并使得渗透性变化出现反复;当不含乙醇时,汽油溶解组分对介质渗透性能的影响相对不明显。     

广西北山岩溶水系统地球化学的研究

研究岩溶水系统的含水介质特征是进行岩溶水文地质勘探工作的一项任务,本文从地球化学角度出发,利用北山矿区出露的泉水及大量的水文地质钻孔,通过地下水化学场在时间空间上的变化,研究了岩溶含水层的含水介质特征。 文中主要讨论了不同类型的地下水化学组成的季节变化,以及地下水矿化度在垂向上的变化,还讨论了利用碳酸盐平衡原理,通过矿物饱和指数（SIC,SID）与CO2分压（Pco2） 关系区分管道流及扩散流等。最后还提出了利用氚（3H）来区分含水介质类型的可能性。      

中国北方岩溶含水介质研究

岩溶含水介质是决定岩溶水文地质系统功能的最基本要素,是水文地质工作者长期关注的问题之一。本文把碳酸盐岩岩石学的现代理论同岩溶学、洞穴学、构造地质学与水文地质学密切结合起来,对碳酸盐岩骨架、岩溶含水空间的微观和宏观介质特征进行了深入的研究,把中国北方岩溶含水介质概化为五种类型。      

Interaction of dissolution,sorption and biodegradation on transport of BTEX in a saturated groundwater system: Numerical modeling and spatial moment analysis

Interaction of various physical, chemical and biological transport processes plays an important role in deciding the fate and migration of contaminants in groundwater systems. In this study, a numerical investigation on the interaction of various transport processes of BTEX in a saturated groundwater system is carried out. In addition, the multi-component dissolution from a residual BTEX source under unsteady flow conditions is incorporated in the modeling framework. The model considers Benzene, Toluene, Ethyl Benzene and Xylene dissolving from the residual BTEX source zone to undergo sorption and aerobic biodegradation within the groundwater aquifer. Spatial concentration profiles of dissolved BTEX components under the interaction of various sorption and biodegradation conditions have been studied. Subsequently, a spatial moment analysis is carried out to analyze the effect of interaction of various transport processes on the total dissolved mass and the mobility of dissolved BTEX components. Results from the present numerical study suggest that the interaction of dissolution, sorption and biodegradation significantly influence the spatial distribution of dissolved BTEX components within the saturated groundwater system. Mobility of dissolved BTEX components is also found to be affected by the interaction of these transport processes.     

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.     

淄博地下水中生物降解作用的水化学判别

环境调查研究表明,大武地下水水源地上游邻近的石化厂区出现严重的地下管道石油污染物持续泄漏现象。堠皋－柳杭地段地下水环境在成为集中污染地段的同时,水文地球化学环境也发生了迥然的变化：地下水中电子接受体溶解氧,ＮＯ３＾－末检出,ＳＯ４＾２－呈低值分布。这与地下水中存在微生物降解烃污染物的作用有关。其作用类型包括需氧降解,脱硝降解,脱硫降解以及有Ｆｅ＾３＋参与的降解作用。然而由于该地段需氧降解、脱硝降解、脱硫降懈以及有F3+参与的降解作用。然而由于废地段需氧降解、脱硝降懈难以进行,导致了生物降解污染物的速度降低 其研究意义是提高地下水中电子接受体的浓度．增强微生物的活性,以促进生物降解速度,将有利于含水层中这类污染物的清除。     

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。     

Fate and transport of ethanol-blended dissolved BTEX hydrocarbons: a quantitative tracing study of a sand tank experiment

To estimate the behavior of ethanol-blended dissolved BTEX hydrocarbons in groundwater, a quantitative tracing study instead of qualitative analysis was carried out by using a large sand tank, into which 2-L solution including bromide, ethanol and dissolved BTEX was injected under a controlled hydraulic condition. Mean residence time (MRT), pore volume swept by solute (V _p), retardation coefficient (R) and biodegradation rate constant (k) of injected solutes were estimated. Compared with bromide that was used as a conservative tracer, ethanol and BTEX had shorter MRT and smaller V _p with the sequence of EtOH < T < E < m/p-X < o-X < B < Br. Biodegradation was confirmed as evidenced by the consumptions of dissolved oxygen (DO), nitrate and sulfate, and the production of acetate. The sequence of k as EtOH > T > E > m/p-X > o-X > B was just opposite to the sequences of MRT and V _p. The relationship among above sequences implies that MRT and V _p can be used as indicators to assess in situ biodegradability of a solute. Biodegradation of a reactive solute can make its MRT shortened and V _p shrunk. In addition, the sorption of ethanol could be neglected (R = 1.0), whereas BTEX compounds were adsorbed (R = 1.04–1.15). It should be noted that biodegradation of a solute can affect the estimation of its retardation coefficient. To our knowledge, this paper provides an available route to quantitatively estimate biodegradability of a solute in groundwater.     

Field investigation of the natural attenuation and intrinsic biodegradation rates at an underground storage tank site

 Contamination of groundwater by petroleum-hydrocarbons is a widespread environmental problem. Natural attenuation is a passive remedial approach to degrade and dissipate contaminants in soil and groundwater. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is accomplished using the differences in total contaminant mass flux across two cross sections of the contaminant plume. The mass flux calculation shows that up to 88% of the dissolved BTEX (benzene, toluene, ethylbenzene, and xylene isomers) removal was observed by natural attenuation processes. The efficiency of intrinsic biodegradation was evaluated by the in situ tracer method. A first-order decay model was applied for the natural attenuation and intrinsic biodegradation rate calculation. Results reveal that intrinsic biodegradation process was the major cause of the BTEX reduction among the natural attenuation mechanisms, and iron reduction was the dominant biodegradation pattern within the plume. Approximately 87% of the BTEX removal was caused by intrinsic biodegradation processes. The calculated BTEX natural attenuation and intrinsic biodegradation rates were 0.24 and 0.16% l/day, respectively. Results suggest that natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the efficiency of the natural attenuation. Received: 6 December 1999 · Accepted: 11 July 2000     

High-resolution monitoring of biogeochemical gradients in a tar oil-contaminated aquifer

The detailed understanding of in situ biodegradation of petroleum hydrocarbons in porous aquifers requires knowledge on biogeochemical gradients, the distribution of individual redox species and microorganisms. The generally limited spatial resolution of conventional monitoring wells, however, hampers appropriate characterization of small-scale gradients and thus localization of the relevant processes. Groundwater sampling across a BTEX plume in a sandy aquifer by means of a novel high-resolution multi-level well (HR-MLW) is presented here. The presence of distinct and steep biogeochemical gradients is demonstrated in the centimeter and decimeter scale, which could not be resolved with a conventional multi-level well. The thin BTEX plume with a vertical extension of only 80 cm exhibited a decline of contaminant concentrations by two orders of magnitude within a few centimeters in the upper and lower fringe zone. The small-scale distribution of sulfate, sulfide and Fe(II) in relation to the contaminants and elevated δ³⁴S and δ¹⁸O values of groundwater sulfate strongly indicated sulfate and iron reduction to be the dominant redox processes involved in biodegradation. High microbial activities and biomass especially at the plume fringes and the slope of chemical gradients supported the concept that the latter are regulated by microbial processes and transverse dispersion, i.e. vertical mixing of electron donors and acceptors. Transverse dispersion therefore was suggested to be a driving factor controlling biodegradation in porous aquifers, but not exclusively limiting natural attenuation processes at this site. Broad overlapping zones of electron donors and electron acceptors point towards additional factors limiting anaerobic biodegradation in situ. The identification of small-scale gradients substantially contributed to a better understanding of biodegradation processes and hence is a prerequisite for the development of reliable predictive mathematical models and future remediation strategies.     

乙醇对过硫酸盐氧化地下水中苯系物的影响

过硫酸盐已经被广泛用于土壤和地下水有机污染物的原位化学氧化修复。随着乙醇汽油的推广,乙醇汽油引起的地下水污染问题越来越严重,因此有必要去除该类污染物。前人研究乙醇汽油污染修复多数停留在自然修复技术,为了进一步探究去除地下水中乙醇汽油更为有效的技术手段,深入了解乙醇对降解苯系物（BTEX）存在的潜在风险,需要研究使用新的修复方法。文章通过批实验探索了过硫酸盐氧化法对乙醇汽油污染地下水的修复效果,以及Fe2+活化和过硫酸盐添加方式变化对乙醇汽油中苯系物（BTEX）和乙醇的去除影响。结果表明:活化后的过硫酸盐能够有效去除地下水中的BTEX,但会抑制BTEX的生物降解作用;当有乙醇存在时,过硫酸盐能够优先氧化BTEX,其去除速率明显高于乙醇,这与单纯生物降解作用相反。在过硫酸盐投注总量一定时,分批添加更有利于BTEX的去除,但对乙醇去除没有明显促进作用。该研究为过硫酸盐原位化学氧化技术在地下水乙醇汽油污染修复中的应用提供了重要参考。     

四氯乙烯在不同地下水环境的生物共代谢降解

四氯乙烯是地下水中常见的污染物,采用生物方法进行处理的优点是可以实现无害化、无二次污染、处理成本低。四氯乙烯只能在厌氧条件下发生还原脱氯,目前对产甲烷环境下四氯乙烯的降解研究较多,而对较弱还原环境,如反硝化、铁锰还原和硫酸盐还原环境下四氯乙烯的脱氯行为研究甚少。本文采用批实验,研究了在不同地下水环境,包括反硝化、铁还原、硫酸盐还原、混合电子受体和天然地下水环境下四氯乙烯的脱氯性能。结果表明,铁还原环境的四氯乙烯脱氯效果最好,天然地下水环境次之,四氯乙烯的去除率分别达到91.34%和84.71%,四氯乙烯很快转化为三氯乙烯,并可以进一步转化为二氯乙烯,四氯乙烯的降解符合准一级反应动力学方程。在反硝化、硫酸盐还原、混合电子受体环境,四氯乙烯的去除以挥发为主,降解只占很小的比例,且最终的降解产物只有三氯乙烯。地下水中三价铁的存在,对于四氯乙烯脱氯起促进作用;而当地下水中硝酸盐和硫酸盐的浓度较高时,四氯乙烯脱氯受到抑制。