Groundwater-surface water interaction and its role on TCE groundwater plume attenuation

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Occurrence and attenuation of specific organic compounds in the groundwater plume at a former gasworks site

The changing contaminant pattern with travelled distance was investigated in the anaerobic groundwater plume downstream from an extended zone containing residual NAPL at a former gas manufacturing plant. With increasing distance, O- and N-heterocyclic aromatic compounds are enriched in the plume relative to the usually assessed coal tar constituents (poly- and monocyclic aromatic compounds). In a first approximation, the overall concentration decrease of the investigated compounds follows a first order overall decay. The half life distance in the plume downgradient from the source varied between 20 m for benzene and up to 167-303 m for alkyl-naphthalenes. Acenaphthene is degraded only within about 50 m downstream from the source area, then its concentration remains constant (ca. 180 microg/l) and far above the legal limit. Dimethyl-benzofurans were the most recalcitrant among all compounds which could be quantified with the analytical method available. The overall groundwater contamination in the plume is seriously underestimated if only BTEX and 16-EPA-PAHs are monitored.     

A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions

An investigation of a tetrachloroethene (PCE) groundwater plume originating at a dry cleaning facility on a sand aquifer and discharging to a river showed that the near-river zone strongly modified the distribution, concentration, and composition of the plume prior to discharging into the surface water. The plume, streambed concentration, and hydrogeology were extensively characterized using the Waterloo profiler, mini-profiler, conventional and driveable multilevel samplers (MLS), Ground Penetrating Radar (GPR) surveys, streambed temperature mapping (to identify discharge zones), drivepoint piezometers, and soil coring and testing. The plume observed in the shallow streambed deposits was significantly different from what would have been predicted based on the characteristics of the upgradient plume. Spatial and temporal variations in the plume entering the near-river zone contributed to the complex contaminant distribution observed in the streambed where concentrations varied by factors of 100 to 5000 over lateral distances of less than 1 to 3.5 m. Low hydraulic conductivity semi-confining deposits and geological heterogeneities at depth below the streambed controlled the pattern of groundwater discharge through the streambed and influenced where the plume discharged into the river (even causing the plume to spread out over the full width of the streambed at some locations). The most important effect of the near-river zone on the plume was the extensive anaerobic biodegradation that occurred in the top 2.5 m of the streambed, even though essentially no biodegradation of the PCE plume was observed in the upgradient aquifer. Approximately 54% of the area of the plume in the streambed consisted solely of PCE transformation products, primarily cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). High concentrations in the interstitial water of the streambed did not correspond to high groundwater-discharge zones, but instead occurred in low discharge zones and are likely sorbed or retarded remnants of past high-concentration plume discharges. The high-concentration areas (up to 5529 microg/l of total volatile organics) in the streambed are of ecological concern and represent potential adverse exposure locations for benthic and hyporheic zone aquatic life, but the effect of these exposures on the overall health of the river has yet to be determined. Even if the upgradient source of PCE is remediated and additional PCE is prevented from reaching the streambed, the high-concentration deposits in the streambed will likely take decades to hundreds of years to flush completely clean under natural conditions because these areas have low vertical groundwater flow velocities and high retardation factors. Despite high concentrations of contaminants in the streambed, PCE was detected in the surface water only rarely due to rapid dilution in the river and no cDCE or VC was detected. Neither the sampling of surface water nor the sampling of the groundwater from the aquifer immediately adjacent to the river gave an accurate indication of the high concentrations of PCE biodegradation products present in the streambed. Sampling of the interstitial water of the shallow streambed deposits is necessary to accurately characterize the nature of plumes discharging to rivers.     

Field studies of a power plant plume in the arid southwestern United States

A study is presented of the physics and chemistry relevant to the visual impact of the plume from an electric power generating plant located in the Mojave Desert. The amount of light absorption by particles in the plume did not differ significantly from that by particles in the ambient air. While sulfate and nitrate occasionally contributed substantially to the total particle mass in the plume, generally they contributed < 10% to that mass, with the contribution of sulfate substantially greater than that of nitrate. Mean rates of gas-to-particle conversion in the plume were ∼ 0.6% h⁻¹ for sulfate and ∼ 0.08% h⁻¹ for nitrate. Light scattering by the plume was more dependent on the total mass of particles in the sub-μm size range than on sulfate mass alone. At a wavelength of 550 nm, NO₂ absorption frequently contributed about equally with light scattering particles to the optical depth of the plume.     

A Passive Flux Denuder for Evaluating Emissions of Ammonia at a Dairy Farm

Abstract

Passive samplers have been shown to be an inexpensive alternative to direct sampling. Diffusion denuders have been developed to measure the concentration of species such as ammonia (NH₃), which is in equilibrium with particulate ammonium nitrate. Conventional denuder sampling that inherently requires air pumps and, therefore, electrical power. To estimate emissions of NH₃ from a fugitive source would require an array of active samplers and meteorological measurements to estimate the flux. A recently developed fabric denuder was configured in an open tube to passively sample NH₃ flux. Passive and active samplers were collocated at a dairy farm at the California State University, Fresno, Agricultural Research Facility. During this comparison study, NH₃ flux measurements were made at the dairy farm lagoon before and after the lagoon underwent acidification. Comparisons were made of the flux measurements obtained directly from the passive flux denuder and those calculated from an active filter pack sampler and wind velocity. The results show significant correlation between the two methods, although a correction factor needed to be applied to directly compare the two techniques. This passive sampling approach significantly reduces the cost and complexity of sampling and has the potential to economically develop a larger inventory base for ambient NH₃ emissions.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

A controlled field experiment on groundwater contamination by a multicomponent DNAPL: creation of the emplaced-source and overview of dissolved plume development

A unique field experiment has been undertaken at the CFB Borden research site to investigate the development of dissolved chlorinated solvent plumes from a residual dense non-aqueous phase liquid (DNAPL) source. The "emplaced-source" tracer test methodology involved a controlled emplacement of a block-shaped source of sand containing chlorinated solvents below the water table. The gradual dissolution of this residual DNAPL solvent source under natural aquifer conditions caused dissolved solvent plumes of trichloromethane (TCM), trichloroethene (TCE) and perchloroethene (PCE) to continuously develop down gradient. Source dissolution and 3-D plume development were successfully monitored via 173 multilevel samplers over a 475-day tracer test period prior to site remediation research being initiated. Detailed groundwater level and hydraulic conductivity data were collected. Development of plumes with concentrations spanning 1-700,000 micrograms/1 is described and key processes controlling their migration identified. Plumes were observed to be narrow due to the weakness of transverse dispersion processes and long due to advection and significant longitudinal dispersion, very limited sorptive retardation and negligible, if any, attenuation due to biodegradation or abiotic reaction. TCM was shown to be essentially conservative, TCE very nearly conservative and PCE, consistent with its greater hydrophobicity, more retarded yet having a greater mobility than observed in previous Borden field tests. The absence of biodegradation was ascribed to the prevailing aerobic conditions and lack of any additional biodegradable carbon substrates. The transient groundwater flow regime caused significant transverse lateral plume movement, plume asymmetry and was likely responsible for most of the, albeit limited, transverse horizontal plume spreading. In agreement with the widespread incidence of extensive TCE and PCE plumes throughout the industrialized world, the experiment indicates such solvent plumes are likely to be highly mobile and persistent, at least in aquifers that are aerobic and have low sorption potential (low foc content).     

Pilot-scale demonstration of a two-stage methanotrophic bioreactor for biodegradation of trichloroethylene in groundwater

A two-stage methanotrophic bioreactor system was developed for remediation of water contaminated with TCE and other chlorinated, volatile, aliphatic hydrocarbons. The first stage of the reactor was a suspended-growth culture vessel using a bubbleless methane-transfer device. The second stage was a plug-flow bioreactor supplied with contaminated groundwater and cell suspension from the culture vessel. The test objectives were to determine the applicability of microbial culture conditions reported in the literature for continuous, pilot-scale TCE treatment; the technical feasibility of plug-flow bioreactor design for treatment of TCE; and the projected economic competitiveness of the technology considering the cost of methane for growth of methanotrophs. The methanotrophic organism used in the study was Methylosinus trichosporium OB3b. Information on system operation was obtained in bench tests prior to conducting the pilot tests. In bench- and pilot-scale tests, variability in the degree of TCE degradation and difficulty in maintaining the microbial culture activity led to short periods of satisfactory biotreatment. Further development of the microbial culture system will be required for long-term operation. During transient periods of high TCE degradation activity, the bioreactor concept proved feasible by exhibiting both a high degree of TCE biodegradation (typically about 90% at influent TCE concentrations of 0.5-4 ppm) and a close approximation to first-order reactor kinetics throughout the length of the reactor. Actual methane usage in the pilot-scale reactor resulted in projected methane costs of $0.33 per 1000 gallons of water treated. This cost theoretically would be reduced by system modifications. The theoretical minimum methane cost was approximately $0.05 per 1000 gallons.     

Development and evaluation of the PRIME plume rise and building downwash model

A new Gaussian dispersion model, the Plume Rise Model Enhancements (PRIME), has been developed for plume rise and building downwash. PRIME considers the position of the stack relative to the building, streamline deflection near the building, and vertical wind speed shear and velocity deficit effects on plume rise. Within the wake created by a sharp-edged, rectangular building, PRIME explicitly calculates fields of turbulence intensity, wind speed, and streamline slope, which gradually decay to ambient values downwind of the building. The plume trajectory within these modified fields is estimated using a numerical plume rise model. A probability density function and an eddy diffusivity scheme are used for dispersion in the wake. A cavity module calculates the fraction of plume mass captured by and recirculated within the near wake. The captured plume is re-emitted to the far wake as a volume source and added to the uncaptured primary plume contribution to obtain the far wake concentrations. The modeling procedures currently recommended by the U.S. Environmental Protection Agency (EPA), using SCREEN and the Industrial Source Complex model (ISC), do not include these features. PRIME also avoids the discontinuities resulting from the different downwash modules within the current models and the reported overpredictions during light-wind speed, stable conditions. PRIME is intended for use in regulatory models. It was evaluated using data from a power plant measurement program, a tracer field study for a combustion turbine, and several wind-tunnel studies. PRIME performed as well as or better than ISC/SCREEN for nearly all of the comparisons.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

某矿区土壤和地下水重金属污染调查与评价

为了解湘南某矿区土壤和地下水重金属污染状况,对该矿区东河流域附近重金属污染源进行了调查,同时,对地下水和土壤样品进行了采样分析,结果表明：（1）该矿区东河流域附近的主要污染源有18个,其中有色金属选厂、尾矿库、采矿场和冶炼厂是排放重金属较多的污染源;（2）20个采样点中土壤重金属Pb、Cd、Zn、As和Hg大部分超过国家土壤环境质量标准（GB15618-1995）,综合污染指数P综〉1,该矿区主要的重金属污染元素为Cd、As和Hg,且土壤中Cd、Zn和As的含量两两之间存在着极显著的正线性相关关系;（3）重金属元素在土壤中的纵向迁移不明显,该矿区附近20个采样点的地下水并未受到污染,综合污染指数P综〈1。20个采样点地下水Pb、Cd、Zn、As、Hg浓度均能达到地下水质量标准（GB／T14848．9）中的Ⅲ类标准。     

Field demonstration of the combined effects of absorption and evapotranspiration on septic system drainfield capacity.

Drainfields for disposal of septic tank effluents are typically designed by considering the loss of water by either upward evapotranspiration into the atmosphere or lateral and downward absorption into the adjacent soil. While this approach is appropriate for evapotranspiration systems, absorption systems allow water loss by both mechanisms. It was proposed that, in areas where high evapotranspiration rates coincide with permeable soils, drainfield sizes could be substantially reduced by accounting for both mechanisms. A two-year field demonstration was conducted to determine appropriate design criteria for areas typical of the Texas High Plains. The study consisted of evaluating the long-term acceptance rates for three different drainfield configurations: evapotranspiration only, absorption only, and combined conditions. A second field demonstration repeated the experiments for additional observation of the combined evapotranspiration and absorption and achieved similar results as the first study. The field tests indicated that the current design loading criteria may be increased by at least a factor of two for the Texas High Plains region and other Texas areas with similar soil composition and evapotranspiration rates, while still retaining a factor of safety of two.     

纳米零价铁对衰减停滞期氯代烃污染地下水的实地修复

在处于衰减停滞期的氯代烃污染场地,进行了液相纳米零价铁(nZVI)的现场制备,并针对目标含水层完成了nZVI的2次原位注入.监测结果表明,nZVI的原位注入可有效削减高浓度的氯乙烯(VC)且减缓其向下游的迁移.在第2次注入nZVI后期,在距注入井lm的上游和下游监测井中,氯代乙烯整体呈现降低的趋势;而上游监测井中的氯代...     

基于支持向量机的地下水质量综合评价

提出基于支持向量机（SVM）机器学习算法的地下水质量评价模型。首先给出了训练样本生成和数据规范化处理的具体方法,然后采用支持向量机的多分类算法构建模型,并使用k折交叉核实方法对参数进行验证优化。最后通过实证分析,并与单因子指数法、模糊综合评价法和BP神经网络法的评价结果对比分析可知,该方法简便易行,评价结果客观且准确度较高,具有很强的实用性。     

Migration and natural fate of a coal tar creosote plume: 1. Overview and plume development

A volume of sand containing coal tar creosote was emplaced below the water table at CFB Borden to investigate natural attenuation processes for complex biodegradable mixtures. Coal tar creosote is a mixture of more than 200 polycyclic aromatic hydrocarbons, heterocyclic compounds and phenolic compounds. A representative group of seven compounds was selected for detailed study: phenol, m-xylene, naphthalene, phenanthrene, 1-methylnaphthalene, dibenzofuran and carbazole. Movement of groundwater through the source led to the development of a dissolved organic plume, which was studied over a 4-year period. Qualitative plume observations and mass balance calculations indicated two key conclusions: (1) compounds from the same source can display distinctly different patterns of plume development and (2) mass transformation was a major influence on plume behaviour for all observed compounds.     

Biogeochemistry and isotope geochemistry of a landfill leachate plume

The biogeochemical processes were identified which improved the leachate composition in the flow direction of a landfill leachate plume (Banisveld, The Netherlands). Groundwater observation wells were placed at specific locations after delineating the leachate plume using geophysical tests to map subsurface conductivity. Redox processes were determined using the distribution of solid and soluble redox species, hydrogen concentrations, concentration of dissolved gases (N(2), Ar, and CH(4)), and stable isotopes (delta15N-NO(3), delta34S-SO(4), delta13C-CH(4), delta2H-CH(4), and delta13C of dissolved organic and inorganic carbon (DOC and DIC, respectively)). The combined application of these techniques improved the redox interpretation considerably. Dissolved organic carbon (DOC) decreased downstream in association with increasing delta13C-DOC values confirming the occurrence of degradation. Degradation of DOC was coupled to iron reduction inside the plume, while denitrification could be an important redox process at the top fringe of the plume. Stable carbon and hydrogen isotope signatures of methane indicated that methane was formed inside the landfill and not in the plume. Total gas pressure exceeded hydrostatic pressure in the plume, and methane seems subject to degassing. Quantitative proof for DOC degradation under iron-reducing conditions could only be obtained if the geochemical processes cation exchange and precipitation of carbonate minerals (siderite and calcite) were considered and incorporated in an inverse geochemical model of the plume. Simulation of delta13C-DIC confirmed that precipitation of carbonate minerals happened.     

Hydraulic constraints on the performance of a groundwater denitrification wall for nitrate removal from shallow groundwater

Denitrification walls are a practical approach for decreasing non-point source pollution of surface waters. They are constructed by digging a trench perpendicular to groundwater flow and mixing the aquifer material with organic matter, such as sawdust, which acts as a carbon source to stimulate denitrification. For efficient functioning, walls need to be permeable to groundwater flow. We examined the functioning of a denitrification wall constructed in an aquifer consisting of coarse sands. Wells were monitored for changes in nitrate concentration as groundwater passed through the wall and soil samples were taken to measure microbial parameters inside the wall. Nitrate concentrations upstream of the wall ranged from 21 to 39 g N m(-3), in the wall from 0 to 2 g N m(-3) and downstream from 19 to 44 g N m(-3). An initial groundwater flow investigation using a salt tracer dilution technique showed that the flow through the wall was less than 4% of the flow occurring in the aquifer. Natural gradient tracer tests using bromide and Rhodamine-WT confirmed groundwater bypass under the wall. Hydraulic conductivity of 0.48 m day(-1) was measured inside the wall, whereas the surrounding aquifer had a hydraulic conductivity of 65.4 m day(-1). This indicated that during construction of the wall, hydraulic conductivity of the aquifer had been greatly reduced, so that most of the groundwater flowed under rather than through the wall. Denitrification rates measured in the center of the wall ranged from 0.020 to 0.13 g N m(-3) day(-1), which did not account for the rates of nitrate removal (0.16-0.29 g N m(-3) day(-1)) calculated from monitoring of groundwater nitrate concentrations. This suggested that the rate of denitrification was greater at the upstream face of the wall than in its center where it was limited by low nitrate concentrations. While denitrification walls can be an inexpensive tool for removing nitrate from groundwater, they may not be suitable in aquifers with coarse textured subsoils where simple inexpensive construction techniques result in major decreases in hydraulic conductivity.