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。     

Evaluation of petroleum hydrocarbon biodegradation in shallow groundwater by hydrogeochemical indicators and C, S-isotopes

Biodegradation is one of the main natural attenuation processes in groundwater contaminated with petroleum hydrocarbons. In this work, preliminary studies have been carried out by analyzing the concentrations of total petroleum hydrocarbons (TPH), dissolved inorganic carbon (DIC), dominant terminal electron accepters or donors, as well as δ ¹³C_DIC and δ ³⁴S_SO4, to reveal the biodegradation mechanism of petroleum hydrocarbons in a contaminated site. The results show that along groundwater flow in the central line of the plume, the concentrations of electron acceptors, pH, and E _h increased but TPH and DIC decreased. The δ ¹³C_DIC values of the contaminated groundwater were in the range of ?14.02 to ?22.28 ‰_PDB and ?7.71 to 8.36 ‰_PDB, which reflected a significant depletion and enrichment of ¹³C, respectively. The increase of DIC is believed to result from the non-methanogenic and methanogenic biodegradation of petroleum hydrocarbon in groundwater. Meanwhile, from the contaminated source to the downgradient of the plume, the ³⁴S in the contaminated groundwater became more depleted. The Rayleigh model calculation confirmed the occurrence of bacterial sulfate reduction as a biodegradation pathway of the petroleum hydrocarbon in the contaminated aquifers. It was concluded that stable isotope measurements, combined with other biogeochemical measurements, can be a useful tool to prove the occurrence of the biodegradation process and to identify the dominant terminal electron-accepting process in contaminated aquifers.     

Contamination,risk, and heterogeneity: on the effectiveness of aquifer remediation

The effectiveness of aquifer remediation is typically expressed in terms of a reduction in contaminant concentrations relative to a regulated maximum contaminant level (MCL), and is usually confirmed by sparse monitoring data and/or simple model calculations. Here, the effectiveness of remediation is re-examined from a more thorough risk-based perspective that goes beyond the traditional MCL concept. A methodology is employed to evaluate the health risk to individuals exposed to contaminated household water that is produced from groundwater. This approach explicitly accounts for differences in risk arising from variability in individual physiology and water use, the uncertainty in estimating chemical carcinogenesis for different individuals, and the uncertainties and variability in contaminant concentrations within groundwater as affected by transport through heterogeneous geologic media. A hypothetical contamination scenario is developed as a case study in a saturated, alluvial aquifer underlying an actual Superfund site. A baseline (unremediated) human exposure and health risk scenario, as induced by contaminated groundwater pumped from this site, is predicted and compared with a similar estimate based upon pump-and-treat exposure intervention. The predicted reduction in risk in the remediation scenario is not an equitable one—that is, it is not uniform to all individuals within a population and varies according to the level of uncertainty in prediction. The importance of understanding the detailed hydrogeologic connections that are established in the heterogeneous geologic regime between the contaminated source, municipal receptors, and remediation wells, and its relationship to this uncertainty is demonstrated. Using two alternative pumping rates, we develop cost-benefit curves based upon reduced exposure and risk to different individuals within the population, under the presence of uncertainty.     

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%.      

Evaluation of remedial alternatives for a petroleum contaminated unconfined aquifer with fluctuating groundwater level

This study evaluated remedial alternatives for a petroleum-contaminated site where an unconfined aquifer composed of a sandy layer of about 3–3.5 m thickness is covered by alluvial deposits and reclaimed soil of about 1.5 m thickness. Precambrian gneiss, of low permeability, lies below the sandy layer. The shallow water table is about 3 m below the surface, but shows high fluctuations of up to 1.5 m in response to precipitation events. The unsaturated soil near the water table and the groundwater are highly contaminated with petroleum hydrocarbons, especially toluene, which have apparently leaked from storage tanks. Selection of the remedial alternatives required consideration of the relevant laws on soil and groundwater conservation in Korea, the results of risk analysis and the hydrogeological conditions. The contaminated area has been divided into zones in which different remediation goals are set based on risk analysis and the degree of natural attenuation. It is estimated that the clean-up goal can be achieved in two years by the combined use of a trench drain and well point pumping to collect the contaminated groundwater for treatment, and a dual air injection system for the contaminated soil.     

Site characterization and monitoring of natural attenuation indicator parameters in a fuel contaminated coastal aquifer: Karaduvar (Mersin,SE Turkey)

This paper presents results from a site characterization and monitoring study at Karaduvar area (Mersin, SE Turkey), where high concentrations of refined petroleum products have been detected in domestic and irrigation water wells. The saturated and unsaturated zones in the deltaic aquifer are contaminated by large quantities of gasoline and diesel range fuel hydrocarbons (GRHs and DRHs) released from diverse sources that include accidental spills, storage tank fires, pipeline breaks, deliberate discharge of waste petroleum products from slop tanks and illegal tanker truck washing facilities. At the site, due to the complex nature of the pollution sources, overlapping contaminant plumes exist and cover an area of about 0.5 km². In both polluted and unpolluted parts of the aquifer, monitoring of groundwater physicochemical parameters in a total of 55 sampling points was carried out between 2006 and 2007. The results show that the terminal electron acceptors (e.g. dissolved oxygen, nitrate, Mn(IV), Fe(III), sulfate) were reduced near the source area(s) indicating presence of actively operating biodegradation processes at the site. Close to the contaminant source area(s), conditions in the plume are highly anoxic and reducing; where high amounts of transformation products (e.g. bicarbonate, dissolved iron, and manganese) are present in solution. Additionally, at the site, excessive pumping, careless land use, and deliberate wastewater discharges significantly deteriorated the quality and quantity of groundwater. Excessive groundwater pumping for industrial and agricultural uses has resulted in substantial water level declines (2–3 m) near the coastal part where seawater intrusion threatens the groundwater resources.     

Crude oil in a shallow sand and gravel aquifer—II. Organic geochemistry

Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O₂ concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.     

Use of a forensic geochemical technique and a hydrogeological assessment to determine the source of petroleum hydrocarbon contamination at a foreshore site in Korea

Investigations undertaken in 2013 at a foreshore site that was historically used for ship repairs in Korea indicated that soil and groundwater were contaminated with petroleum hydrocarbons over an area of 10,000 m². Groundwater investigations and modelling were undertaken to determine the characteristics of aquifers beneath the site, including the direction and rate of groundwater flow and the extent of dispersion of total petroleum hydrocarbon contamination. To identify petroleum products residing in contaminated soils, the hump of an unresolved complex mixture on the baseline found in the data of gas chromatography was used as a new method. Based on objective facts obtained from basic investigation, the current state of contamination, and discrimination of oil species, the polluter as specified in the Korean Soil Environment Conservation Act was identified.     

华北煤田矿山开采导致含水层破坏风险评估:以淄博洪山煤矿为例

煤矿由建设到关闭后多年的生命过程都对含水层具有破坏作用,造成生态环境破坏、影响社会经济发展,其风险具有长期性.在华北煤田水文地质结构及矿山地质环境问题分析的基础上,总结了含水层破坏形式及其风险组成,提出了含水层破坏风险评估与管理的技术思路.利用淄博洪山煤矿从开采到关闭多年的试验和监测数据开展了实证研究.结果表明:（1）矿业活动对含水层破坏形式表现为含水层结构破坏、地下水流场变化和地下水污染3类,洪山煤矿奥灰水遭受破坏的可能性高,危险性低、中等和高的危险区面积分别为20.61、22.39、19.26 km2;（2）社会、经济和生态易损性由破坏性、脆弱性和可恢复性三项指标表达,洪山煤矿社会经济高度依赖奥灰水,其易损性高.（3）含水层破坏风险是可利用地下水资源量减少、生态环境恶化、社会经济负面影响及其长期效应的综合表达,洪山煤矿关闭后奥灰水遭受破坏的风险高.      

Controls on groundwater flow in the Bengal Basin of India and Bangladesh: regional modeling analysis

Groundwater for domestic and irrigation purposes is produced primarily from shallow parts of the Bengal Basin aquifer system (India and Bangladesh), which contains high concentrations of dissolved arsenic (exceeding worldwide drinking water standards), though deeper groundwater is generally low in arsenic. An essential first step for determining sustainable management of the deep groundwater resource is identification of hydrogeologic controls on flow and quantification of basin-scale groundwater flow patterns. Results from groundwater modeling, in which the Bengal Basin aquifer system is represented as a single aquifer with higher horizontal than vertical hydraulic conductivity, indicate that this anisotropy is the primary hydrogeologic control on the natural flowpath lengths. Despite extremely low hydraulic gradients due to minimal topographic relief, anisotropy implies large-scale (tens to hundreds of kilometers) flow at depth. Other hydrogeologic factors, including lateral and vertical changes in hydraulic conductivity, have minor effects on overall flow patterns. However, because natural hydraulic gradients are low, the impact of pumping on groundwater flow is overwhelming; modeling indicates that pumping has substantially changed the shallow groundwater budget and flowpaths from predevelopment conditions.     

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。     

Impact of intense exploitation on the groundwater balance and flow within Mullusi aquifer (arid zone, west Iraq)

The main results that derived from this study is the quantitative determination of subsurface water balance and the water loses along flow line during drought decade (before 2000–2009), with intense exploitation of groundwater from water wells. The hydrogeological data are presented as spatial distribution maps and three dimensional models. The results are correlated with the main hydrogeologic control points including (storage and transmissivity coefficients, groundwater depths, aquifers thickness, lateral extensions, well productivity) to determine the preferable hydrogeologic districts for development and exploitations, avoiding groundwater depletion as captured zone flow. Based on the isotope analysis of deuterium, oxygen-18, tritium, carbon-13, and carbon-14, the recharge of the aquifer is originated to direct infiltration of atmospheric water through exposure outcrops within Hauran catchments area. The isotope compositions also show that the groundwater is a mixture of an old groundwater with modern recharge in the areas adjacent to Rutba. The fact that the Mullusi aquifer is of major importance as the water supply of people in Rutba region, particularly, for increasing demand of water resources and sustainability assessment in the future, this study developed a reliable strategic suggested plan in groundwater supply, based on groundwater exploitation and amount of safe yield within Dhabaa basin.     

Characterization of salt-water intrusion in the lower Esino Valley, Italy using a three-dimensional numerical model

A seawater-intrusion study was conducted at an oil-refinery site located on the coast in the lower Esino Valley, Italy. A steady-state density-dependent flow model was used in order to understand the position of the freshwater/salt-water interface, as influenced by the hydrogeologic structure and the presence of industrial activities and a river. Collected data and model results showed that in a large part of the area, the salt-water interface is steep and can penetrate only a few meters inland. On the other hand, close to the river mouth, seawater represents the main saline source for the aquifer. The river, in connection with the sea, can enhance seawater encroachment into the coastal aquifer; a long-term survey of river level and chloride concentrations in groundwater is recommended to further improve the physical model and to obtain a better calibration. At the refinery site, two “secondary” sources of saline water were identified and were demonstrated to have had a great influence on the presence of brackish waters in the unconfined aquifer: leakage from the fire-extinguishing system (network of pipes containing seawater) and rough sea events. This confirmed that groundwater contamination by chloride can result from means other than seawater intrusion.     

典型石油烃组分在地下水中的自然衰减规律

为了解石油烃类污染物在地下水中的自然衰减规律,以苯、萘、菲作为目标污染物,采用实验场地4种天然砂土作为含水层介质进行了室内模拟实验。结果表明：在单组分和混合组分溶液中,苯、萘和菲在地下含水层介质中的自然衰减均符合一级动力学方程;在不同含水层介质中,苯和萘的衰减速率大小顺序为粉砂>中砂≈粗砂>砾砂,而菲的自然衰减速率大小顺序为粉砂≈中砂≈粗砂>砾砂;微生物降解在苯和萘的自然衰减中起重要作用,而固相吸附在菲的自然衰减中起重要作用。3种物质共存时,苯和萘的自然衰减加快,菲的自然衰减减慢。     

Variations in the environmental characteristics of groundwater slightly contaminated with petroleum: effects of enhanced bioremediation in northeast China

The objective of this paper was to investigate a petroleum-contaminated groundwater site in northeast China. Based on the monitoring and analysis of environmental characteristics of groundwater slightly contaminated with petroleum, microbes were added into the petroleum-contaminated groundwater via single-well and multiple-well models to enhance bioremediation. The effect of enhanced bioremediation was monitored and analyzed, and variations in the environmental characteristics of groundwater containing total petroleum hydrocarbons (TPH) were identified to provide a scientific basis for controlling and remediating petroleum-contaminated groundwater. Findings confirmed that this site was slightly contaminated and TPH levels exhibited a slight decreasing trend. After enhanced remediation, the microbial degradation effect was large, and the TPH concentration significantly reduced. In particular, near the wells treated by bioremediation, the amounts of electron acceptors, such as NO₃ ^?, Fe³⁺, and SO₄ ^2?, markedly decreased. The product of the microbial degradation process, HCO₃ ^?, gradually increased in the treated wells. Activities of the enzyme catechol 1, 2-dioxygenase decreased, while those of catalase increased. Reductions in pH, from 7.4 to 6.1, were recorded, and the groundwater environment became further deoxidized.     

Mixing of groundwaters with uncertain end-members: case study in the Tepalcingo-Axochiapan aquifer, Mexico

Groundwater geochemical data from the northern portion of the Tepalcingo-Axochiapan Valley, in the state of Morelos, Mexico, are analyzed to improve the conceptual hydrogeologic model of the region. The geochemical data suggest that the chemical composition of groundwater is the result of a mixing process between two end-members represented by groundwater from an upper aquifer composed of volcanic-sedimentary rocks and groundwater from a lower aquifer composed of carbonate rocks. Analysis of published data demonstrates that the chemical composition of at least one of the end-members varies significantly in time. Mixing ratios are computed, taking into account the uncertainty in identifying end-members and the time variability in their chemical composition, using published methods. Computed mixing ratios suggest there is a significant contribution from the lower aquifer to the water pumped by the wells in the area, which should be taken into account in the conceptual hydrogeologic model of the region.     

Characterization of regional land subsidence in Yangtze Delta, China: the example of Su-Xi-Chang area and the city of Shanghai

Su-Xi-Chang area and the city of Shanghai, located in the south of Yangtze Delta, China, has subsided due to groundwater overpumping. Because of the regional scale of the groundwater exploitation, cone of depression and land subsidence at present, Su-Xi-Chang area and Shanghai are treated as a single area for a land subsidence study, which could more clearly elaborate the relationships between the deformation features of hydrostratigraphic units and the different sites of the cone of depression. All hydrostratigraphic units in the study area were discussed throughout. Based on the field data, including data on compression of individual strata from groups of extensometers and groundwater levels from observation wells, the relationship between the deformation and the groundwater level was analyzed. The results indicate that the deformation features of the hydrogeologic units are greatly related to hydrogeologic properties and groundwater-level variations. An identical hydrogeologic unit may exhibit different deformation features in different locations such as along the periphery and in the center of the cone of depression. In addition, in the same location, a hydrogeologic unit also exhibits different features in different periods because of different groundwater level variations. The delay phenomenon of the sandy aquifer is not specific but occurs widely.     

某油田地下水污染特征及其机理分析

在对某油田石油类污染物分布特征研究的基础上,对其进入地下水的途径进行分析。研究表明,除石油类外,CODMn、Cl-、NO3-N和TDS具异常变化,这些异常变化已成为石油类污染的参考指标。含水层污染程度主要以严重污染和中度污染为主,下段含水层中的石油类污染物的浓度明显高于上段含水层。地下水遭受污染的途径类型分为地表渗透型和优势通道渗漏型,但地表渗透型污染对研究区地下水的威胁性相对来说较小。由构造活动、地下水开采引发的地裂缝形成的优势通道渗漏型污染是地下水污染的主要途径。     

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。     

Groundwater flow and capture zone analysis of the Central Passaic River Basin, New Jersey

Delineating capture zones of pumping wells is an important part of safe drinking water and well protection programs. Capture zones or contributing areas of a groundwater extraction well are the parts of the aquifer recharge areas from which the wells draw their water. Their extent and location depend on the hydrogeologic conditions such as groundwater recharge, pumping scenario and the aquifer properties such as hydraulic conductivity, porosity, heterogeneity of the medium and hydraulic gradient. Different methods of delineation can be used depending on the complexity of the hydrogeologic conditions. In this study, a 3-dimensional transient numerical MODFLOW model was developed for the Central Passaic River Basin (CPRB), and used with a MODPATH particle tracking code to determine 3-dimensional transient capture zones. Analytically calculated capture zones from previous studies at the site were compared with the new numerically simulated capture zones. The study results revealed that the analytical solution was more conservative, estimating larger capture zones than the numerical models. Of all the parameters that can impact the size, shape and location of a capture zone, the hydraulic conductivity is one of the most critical. Capture zones tend to be smaller in lower hydraulic conductivity areas.