A comparison of pre‐ and post‐remediation water quality,Mineral Creek,Colorado

Pre‐ and post‐remediation data sets are used herein to assess the effectiveness of remedial measures implemented in the headwaters of the Mineral Creek watershed, where contamination from hard rock mining has led to elevated metal concentrations and acidic pH. Collection of pre‐ and post‐remediation data sets generally followed the synoptic mass balance approach, in which numerous stream and inflow locations are sampled for the constituents of interest and estimates of streamflow are determined by tracer dilution. The comparison of pre‐ and post‐remediation data sets is confounded by hydrologic effects and the effects of temporal variation. Hydrologic effects arise due to the relatively wet conditions that preceded the collection of pre‐remediation data, and the relatively dry conditions associated with the post‐remediation data set. This difference leads to a dilution effect in the upper part of the study reach, where pre‐remediation concentrations were diluted by rainfall, and a source area effect in the lower part of the study reach, where a smaller portion of the watershed may have been contributing constituent mass during the drier post‐remediation period. A second confounding factor, temporal variability, violates the steady‐state assumption that underlies the synoptic mass balance approach, leading to false identification of constituent sources and sinks. Despite these complications, remedial actions completed in the Mineral Creek headwaters appear to have led to improvements in stream water quality, as post‐remediation profiles of instream load are consistently lower than the pre‐remediation profiles over the entire study reach for six of the eight constituents considered (aluminium, arsenic, cadmium, copper, iron, and zinc). Concentrations of aluminium, cadmium, copper, lead, and zinc remain above chronic aquatic‐life standards, however, and additional remedial actions may be needed. Future implementations of the synoptic mass balance approach should be preceded by an assessment of temporal variability, and modifications to the synoptic sampling protocol should be made if necessary. Published in 2009 by John Wiley & Sons, Ltd.     

Bioremediation in Fractured Rock: 1. Modeling to Inform Design,Monitoring, and Expectations

Field characterization of a trichloroethene (TCE) source area in fractured mudstones produced a detailed understanding of the geology, contaminant distribution in fractures and the rock matrix, and hydraulic and transport properties. Groundwater flow and chemical transport modeling that synthesized the field characterization information proved critical for designing bioremediation of the source area. The planned bioremediation involved injecting emulsified vegetable oil and bacteria to enhance the naturally occurring biodegradation of TCE. The flow and transport modeling showed that injection will spread amendments widely over a zone of lower‐permeability fractures, with long residence times expected because of small velocities after injection and sorption of emulsified vegetable oil onto solids. Amendments transported out of this zone will be diluted by groundwater flux from other areas, limiting bioremediation effectiveness downgradient. At nearby pumping wells, further dilution is expected to make bioremediation effects undetectable in the pumped water. The results emphasize that in fracture‐dominated flow regimes, the extent of injected amendments cannot be conceptualized using simple homogeneous models of groundwater flow commonly adopted to design injections in unconsolidated porous media (e.g., radial diverging or dipole flow regimes). Instead, it is important to synthesize site characterization information using a groundwater flow model that includes discrete features representing high‐ and low‐permeability fractures. This type of model accounts for the highly heterogeneous hydraulic conductivity and groundwater fluxes in fractured‐rock aquifers, and facilitates designing injection strategies that target specific volumes of the aquifer and maximize the distribution of amendments over these volumes.     

Analytical and Numerical Modeling of Solute Intrusion,Recovery, and Rebound in Fractured Bedrock

Contaminated groundwater in fractured bedrock can expose ecosystems to undesired levels of risk for extended periods due to prolonged back-diffusion from rock matrix to permeable fractures. Therefore, it is key to characterize the diffusive mass loading (intrusion) of contaminants into the rock matrix for successful management of contaminated bedrock sites. Even the most detailed site characterization techniques often fail to delineate contamination in rock matrix. This study presents a set of analytical solutions to estimate diffusive mass intrusion into matrix blocks, it is recovered by pumping and concentration rebound when pumping ceases. The analytical models were validated by comparing the results with (1) numerical model results using the same model parameters and (2) observed chloride mass recovery, rebound concentration, and concentration in pumped groundwater at a highly fractured bedrock site in Alberta, Canada. It is also demonstrated that the analytical solutions can be used to estimate the total mass stored in the fractured bedrock prior to any remediation thereby providing insights into site contamination history. The predictive results of the analytical models clearly show that successful remediation by pumping depends largely on diffusive intrusion period. The results of initial mass from the analytical model was used to successfully calibrate a three-dimensional discrete fracture network numerical model further highlighting the utility of the simple analytical solutions in supplementing the more detailed site numerical modeling. Overall, the study shows the utility of simple analytical methods to support long-term management of a contaminated fractured bedrock site including site investigations and complex numerical modeling.     

Passive Samplers for Monitoring VOCs in Groundwater and the Prospects Related to Mass Flux Measurements

Measurement and interpretation of mass fluxes in favor of concentrations is gaining more and more interest, especially within the framework of the characterization and management of large-scale volatile organic carbon (VOC) groundwater contamination (source zones and plumes). Traditional methods of estimating contaminant fluxes and discharges involve individual measurements/calculations of the Darcy water flux and the contaminant concentrations. However, taken into account the spatially and temporally varying hydrologic conditions in complex, heterogeneous aquifers, higher uncertainty arises from such indirect estimation of contaminant fluxes. Therefore, the potential use of passive sampling devices for the direct measurement of groundwater-related VOC mass fluxes is examined. A review of current passive samplers for the measurement of organic contaminants in water yielded the selection of 18 samplers that were screened for a number of criteria. These criteria are related to the possible application of the sampler for the measurement of VOC mass fluxes in groundwater. This screening study indicates that direct measurement of VOC mass fluxes in groundwater is possible with very few passive samplers. Currently, the passive flux meter (PFM) is the only passive sampler which has proven to effectively measure mass fluxes in near source groundwater. A passive sampler for mass flux measurement in plume zones with regard to long-term monitoring (several months to a year) still needs to be developed or optimized. A passive sampler for long-term monitoring of contaminant mass fluxes in groundwater would be of considerable value in the development of risk-based assessment and management of soil and groundwater pollutions.     

Improved Resolution of Ambient Flow through Fractured Rock with Temperature Logs

In contaminant hydrogeology, investigations at fractured rock sites are typically undertaken to improve understanding of the fracture networks and associated groundwater flow that govern past and/or future contaminant transport. Conventional hydrogeologic, geophysical, and hydrophysical techniques used to develop a conceptual model are often implemented in open boreholes under conditions of cross-connected flow. A new approach using high-resolution temperature (±0.001°C) profiles measured within static water columns of boreholes sealed using continuous, water-inflated, flexible liners (FLUTe™) identifies hydraulically active fractures under ambient (natural) groundwater flow conditions. The value of this approach is assessed by comparisons of temperature profiles from holes (100 to 200 m deep) with and without liners at four contaminated sites with distinctly different hydrogeologic conditions. The results from the lined holes consistently show many more hydraulically active fractures than the open-hole profiles, in which the influence of vertical flow through the borehole between a few fractures masks important intermediary flow zones. Temperature measurements in temporarily sealed boreholes not only improve the sensitivity and accuracy of identifying hydraulically active fractures under ambient conditions but also offer new insights regarding previously unresolvable flow distributions in fractured rock systems, while leaving the borehole available for other forms of testing and monitoring device installation.     

Machine Learning Predictions of pH in the Glacial Aquifer System,Northern USA

A boosted regression tree model was developed to predict pH conditions in three dimensions throughout the glacial aquifer system of the contiguous United States using pH measurements in samples from 18,386 wells and predictor variables that represent aspects of the hydrogeologic setting. Model results indicate that the carbonate content of soils and aquifer materials strongly controls pH and, when coupled with long flowpaths, results in the most alkaline conditions. Conversely, in areas where glacial sediments are thin and carbonate-poor, pH conditions remain acidic. At depths typical of drinking-water supplies, predicted pH >7.5—which is associated with arsenic mobilization—occurs more frequently than predicted pH <6—which is associated with water corrosivity and the mobilization of other trace elements. A novel aspect of this model was the inclusion of numerically based estimates of groundwater flow characteristics (age and flowpath length) as predictor variables. The sensitivity of pH predictions to these variables was consistent with hydrologic understanding of groundwater flow systems and the geochemical evolution of groundwater quality. The model was not developed to provide precise estimates of pH at any given location. Rather, it can be used to more generally identify areas where contaminants may be mobilized into groundwater and where corrosivity issues may be of concern to prioritize areas for future groundwater monitoring.     

Innovative Contaminant Mass Flux Monitoring in an Aquifer Subject to Tidal Effects

Exposure from groundwater contamination to aquatic receptors residing in receiving surface water is dependent upon the rate of contaminated groundwater discharge. Characterization of groundwater fluxes is challenging, especially in coastal environments where tidal fluctuations result in transient groundwater flows towards these receptors. This can also be further complicated by the high spatial heterogeneity of subsurface deposits enhanced by anthropogenic influences such as the mixing of natural sediments and backfill materials, the presence of subsurface built structures such as sheet pile walls or even occurrence of other sources of contaminant discharge. In this study, the finite volume point dilution method (FVPDM) was successfully used to characterize highly transient groundwater flows and contaminant mass fluxes within a coastal groundwater flow system influenced by marked tides. FVPDM tests were undertaken continuously for more than 48 h at six groundwater monitoring wells, in order to evaluate groundwater flow dynamics during several tide cycles. Contaminant concentrations were measured simultaneously which allowed calculating contaminant mass fluxes. The study highlighted the importance of the aquifer heterogeneity, with groundwater fluxes ranging from 10⁻⁷ to 10⁻³ m/s. Groundwater flux monitoring enabled a significant refinement of the conceptual site model, including the fact that inversion of groundwater fluxes was not observed at high tide. Results indicated that contaminant mass fluxes were particularly higher at a specific monitoring well, by more than three orders of magnitude, than at other wells of the investigated aquifer. This study provided crucial information for optimizing further field investigations and risk mitigation measures.     

Evaluation of Extensive Secondary Maximum Contaminant Level Exceedances Following Remediation by In Situ Chemical Oxidation

In situ chemical oxidation (ISCO) with activated persulfate is commonly used for the remediation of petroleum impacted soil and groundwater because of its proven efficiency and the perception that reaction end products are completely innocuous. While the reaction products are less hazardous compared to the contaminants being treated, they may inadvertently prolong site closure in areas that have adopted the U.S. Environmental Protection Agency (EPA) Secondary Maximum Contaminant Levels (SMCLs) as enforceable standards. This study examines the occurrence and persistence of iron, manganese, sulfate, sodium, and total dissolved solids (TDS) in groundwater following persulfate ISCO. The concentrations of these chemicals were observed remaining above their respective regulatory criteria almost 3 years following the chemical application. Background concentrations and mobilization due to the petroleum contamination and ISCO application are also evaluated. Baseline sampling revealed substantially higher iron and manganese concentrations inside the plume area compared to the upgradient and downgradient wells suggesting mobilization due to redox reactions occurring inside of the plume. Iron was not a component in the applied chemical formula, yet the iron concentration spiked by 366% in the key monitoring well during the first post-remediation monitoring event. Ionic interactions between the ISCO amendment and native soils are believed to be responsible for displacing significant quantities of iron from the soil. Sulfate, sodium, and TDS exceedances are primarily associated with decomposition products of the ISCO amendments. The iron, manganese, sulfate, sodium, and TDS concentrations are trending downward over time, but still exceed regulatory criteria or pre-ISCO concentrations.     

Plume Detachment and Recession Times in Fractured Rock

The influence of source zone concentration reduction on solute plume detachment and recession times in fractured rock was investigated using new semianalytical solutions to transient solute transport in the presence of advection, dispersion, sorption, matrix diffusion, and first-order decay. Novel aspects of these solutions are: (1) the source zone concentration behavior is simulated using a constant concentration with the option for either an instantaneous reduction to zero concentration or an exponentially decaying source zone concentration initiated at some time (t^*) after the source is introduced, and (2) different biodegradation rates in the fracture and rock matrix. These solutions were applied for sandstone bedrock and revealed that biodegradation in the matrix, not the fracture, may be the most significant attenuation mechanism and therefore may dictate remediation time scales. Also, instantaneous and complete source concentration reduction in aged plumes may not be beneficial with respect to plume response because back-diffusion can sustain plume migration for long periods of time. Moderate source zone concentration reduction has a similar impact on the rate of advance of the leading edge of the plume as aggressive concentration reduction. If the source zone concentration reduction half-life is less than the plume decay half-life, then volatile organic compound (VOC) mass sequestered in the rock matrix will ultimately dictate plume persistence and not the presence of the source zone.     

Groundwater remediation: the next 30 years

Groundwater remediation technologies are designed, installed, and operated based on the conceptual models of contaminant hydrogeology that are accepted at that time. However, conceptual models of remediation can change as new research, new technologies, and new performance data become available. Over the past few years, results from multiple-site remediation performance studies have shown that achieving drinking water standards (i.e., Maximum Contaminant Levels, MCLs) at contaminated groundwater sites is very difficult. Recent groundwater research has shown that the process of matrix diffusion is one key constraint. New developments, such as mass discharge, orders of magnitude (OoMs), and SMART objectives are now being discussed more frequently by the groundwater remediation community. In this paper, the authors provide their perspectives on the existing "reach MCLs" approach that has historically guided groundwater remediation projects, and advocate a new approach built around the concepts of OoMs and mass discharge.     

Shear dispersion in a fracture with porous walls

We present an analytical expression for the shear dispersion during solute transport in a coupled fracture–matrix system. The dispersion coefficient is obtained in a fracture with porous walls by taking into account an accurate boundary condition at the interface between the matrix and fracture, and the results were compared with those in a non-coupled system. The analysis presented identifies three regimes: diffusion-dominated, transition, and advection-dominated. The results showed that it is important to consider the exchange of solute between the fracture and matrix in development of the shear dispersion coefficient for the transition and advection-dominated regimes. The new dispersion coefficient is obtained by imposing the continuity of concentrations and mass fluxes along the porous walls. The resulting equivalent transport equation revealed that the effective velocity in a fracture increases while the dispersion coefficient decreases due to mass transfer between the matrix and fracture. A larger effective advection term leads to greater storage of mass in the matrix as compared with the classical double-porosity model with a non-coupled dispersion coefficient. The findings of this study can be used for modeling of tracer tests as well as fate, transport, and remediation of groundwater contaminants in fractured rocks.     

Groundwater contributions of flow and nitrogen in a headwater agricultural watershed

Nonpoint sources of nitrogen (N) and other nutrients are a major source of water pollution within the Chesapeake Bay watershed and other basins around the world. Human activities associated with agricultural practices can account for a large percentage of N loadings delivered to streams and rivers. This work aims to improve understanding of N transport from groundwater to surface waters, quantifying the principal hydrological processes driving water and N fluxes into and out of a headwater agricultural stream reach. The study site is a 175-m stream reach in a heavily cultivated 40-ha watershed in east-central Pennsylvania. This subwatershed is underlain by fractured shale bedrock, and receives most of its baseflow from groundwater, either by diffuse matrix discharge through the streambed or by localized discharge through riparian seeps. Samples of stream, seep, and shallow groundwater were collected approximately monthly under steady hydrologic conditions in 2017. Calculated matrix flow from hydraulic head and conductivity measurements paired with differential stream gauging was used to solve for the riparian seep flux using a mass balance approach. Riparian seep fluxes ranged from 45 to 217 m³/d, transporting 0.6–4.2 kg N d⁻¹ of nitrate-N from the fractured bedrock aquifer to the stream. Hydrochemical data suggest that the stream is mainly disconnected from the underlying aquifer and that seeps supply essentially all water and N to the system. Seeps are likely sourced with N in nearby agricultural fields and accelerated through the system with shorter residence times than shallow groundwater. Water isotope data reinforced this notion. This study underscores the importance of agriculture as a source of N to ground and surface waters. Identifying source areas that are causing groundwater enrichment of N and seep areas where N discharges to streams is beneficial for developing N pollution mitigation strategies and implementing management practices that aim to reduce nutrient loads to the Chesapeake Bay.     

Modelling of colloidal particle and heavy metal transfer behaviours during seawater intrusion and refreshing processes

The proper management of coastal aquifers commonly requires an understanding of regional mass flow and complete seawater–freshwater circulation. In this study, time series observations of seawater intrusion and refreshing were conducted using a column experiment based on natural flow conditions in coastal groundwater and a sampled medium from a coastal sandy aquifer without chemical treatment. Ranges of hydrodynamic and hydrochemical variables were tested and analysed. The results showed that the zeta potential of suspended colloids in aqueous solution in an aquifer polluted with 0.5 g/kg of heavy metals exhibited an isoelectric point for pH values ranging from 5.70 to 6.07 when freshwater or seawater completely occupied the aquifer pores, which is representative of natural hydrochemical conditions. In this scenario, a high background concentration of heavy metals induced colloidal immobilization. Otherwise, seawater–freshwater circulation enabled colloid mobilization due to ionic strength and pH fluctuations. The migration of multiple heavy metals occurred at a characteristic time of approximately 1 pore volume after each intrusion stage began and when the peak rate of colloid release was reached. At these times, the colloid behaviour determined the quantity and pathway of heavy metal transport. On the basis of the influences of seawater and freshwater interactions, the quantity of mobilized particles generally decreased and was uniformly distributed in each fraction due to particle loss and decreased porous connectivity. We speculate that the decrease in the total surface area of the migratory colloids may cause colloid‐associated heavy metal transport to decrease. The experimental results provide a useful basis for testing coastal groundwater flow and mass transport models because these phenomena require full characterization to precisely evaluate the associated fluxes from the field scale to the microscopic dimension.     

Pre‐drill Groundwater Geochemistry in the Karoo Basin,South Africa

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre‐development assessment of groundwater geochemistry in the critically water‐restricted Karoo Basin, South Africa. Twenty‐two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end‐members: a deep, saline groundwater with a sodium‐chloride composition, an old, deep freshwater with a sodium‐bicarbonate‐chloride composition and a shallow, calcium‐bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water‐rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium‐chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon‐rich saline waters to the surface. This pre‐drill evaluation indicates that the natural migration of methane‐ and salt‐rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.     

A Borehole Test for Chlorinated Solvent Diffusion and Degradation Rates in Sedimentary Rock

We present a new field measurement and numerical interpretation method (combined termed “test”) to parameterize the diffusion of trichloroethene (TCE) and its biodegradation products (DPs) from the matrix of sedimentary rock. The method uses a dual-packer system to interrogate a low-permeability section of the rock matrix adjacent to a previously contaminated borehole and uses the borehole monitoring history to establish the pretest condition. TCE and its DPs are removed from the groundwater between the packers at the onset of the testing. The parameters estimated by fitting a radial diffusion model to the concentration history and borehole concentration data, also termed back diffusion, are the tortuosity factor and sorption coefficients of TCE and DPs in the rock matrix and the TCE and DP biodegradation rate coefficients in the borehole. We demonstrate the equipment design and the interpretive method using a borehole accessing the gray mudstone at a TCE contaminated site in the Newark Basin. In this test, both nonreactive (bromide) and reactive (trichlorofluoroethene) tracers are used to constrain the estimated parameters; however, the bromide tracer was not needed to estimate the parameters in this test. The parameters estimated from the field test are consistent with values measured independently in laboratory experiments using field samples of similar lithology. From the interpretation, we compute the TCE and DP concentration distributions in the rock matrix prior to the test to illustrate how the results can be used to enhance understanding of contaminant distribution in the rock matrix.     

Monitoring Hydrogeologlcal Conditions in Fractured Rock at the Site of Canada's Underground Research Laboratory

Atomic Energy of Canada Limited is constructing an Underground Research Laboratory (URL) at a depth of 250m in a plutonic rock body near Lac du Bonnet, Manitoba. The facility is being constructed to carry out a variety of in situ geotechnical experiments as part of the Canadian Nuclear Fuel Waste Management Program. A unique feature of the URL, in comparison to other similar facilities such as the Stripa Mine in Sweden, is that it is to be constructed below the ground water table in a previously undisturbed plutonic rock body. One of the main research objectives of the project is to develop and validate comprehensive three-dimensional models of the hydrogeology of the rock mass encompassing the URL site. These models will be used, before excavation of the URL shaft begins, to predict the hydrogeological perturbation that will be created by the excavation of the shaft and the horizontal working levels below the ground water table. As a model-validation exercise, these drawdown predictions will be compared with actual hydrogeological perturbations that will be monitored at the study area over the next several years by an extensive network of instrumented boreholes. Measurements made in an array of boreholes extending to depths of 1,000m on the 4.8 km² study area have established that the permeability distribution in three major extensive subhorizontal fracture zones controls the movement of ground water within the rock mass. Several types of multiple-interval completion systems have been installed in the boreholes to monitor the three-dimensional, physico-chemical hydrogeological conditions within the fractured rock mass. These include conventional piezometer nests and water-table wells that have been installed in shallow holes (less than 30m deep), and multiple-packer/ multiple-standpipe piezometers and multiple-interval casing systems installed in deeper holes (30 to 1,000m deep). An automated, electronic, piezometric pressure-monitoring system has been designed to collect continuous measurements from 75 isolated hydrogeological monitoring positions within the rock mass. Another 200 positions are being monitored frequently using a variety of techniques. Piezometric data have been collected from this monitoring network to establish baseline conditions prior to any excavation into the rock mass. These data have also been used to determine the steady-state, three-dimensional ground water flow regimes that exist at the URL site under natural conditions.     

Numerical Modeling of Thermal Conductive Heating in Fractured Bedrock

Numerical modeling was employed to study the performance of thermal conductive heating (TCH) in fractured shale under a variety of hydrogeological conditions. Model results show that groundwater flow in fractures does not significantly affect the minimum treatment zone temperature, except near the beginning of heating or when groundwater influx is high. However, fracture and rock matrix properties can significantly influence the time necessary to remove all liquid water (i.e., reach superheated steam conditions) in the treatment area. Low matrix permeability, high matrix porosity, and wide fracture spacing can contribute to boiling point elevation in the rock matrix. Consequently, knowledge of these properties is important for the estimation of treatment times. Because of the variability in boiling point throughout a fractured rock treatment zone and the absence of a well-defined constant temperature boiling plateau in the rock matrix, it may be difficult to monitor the progress of thermal treatment using temperature measurements alone.     

Application of the geographical information systems approach to watershed mass balance studies

This study was undertaken to test the utility of a geographical information systems (GIS) approach to problems of watershed mass balance. This approach proved most useful in exploring the effects that watershed scale, lithology and land use have on chemical weathering rates, and in assessing whether mass balance calculations could be applied to large multilithological watersheds. Water quality data from 52 stations were retrieved from STORET and a complete GIS database consisting of the watershed divide, lithology and land use was compiled for each station. Water quality data were also obtained from 7 experimental watersheds to develop a methodology to estimate annual fluxes from incomplete data sets. The methodology consists of preparing a composite of daily flux data, calculating a best fit sinusoid and integrating the equation to obtain an annual flux. Comparison with annual fluxes calculated from high resolution data sets suggests that this method predicts fluxes within about 10% of the true annual flux. Annual magnesium fluxes (moles km⁻² yr⁻¹) were calculated for all stations and adjusted for fluxes from atmospheric deposition. Magnesium flux was found to be a strong function of the amount of carbonate in the watershed, and silica fluxes were found to increase with the fraction of sandstone present in the watershed. All fluxes were strongly influenced by mining practices, with magnesium fluxes from affected watersheds being 6–10 times higher than fluxes from comparable pristine watersheds. Mining practices enhance chemical weathering by increasing the surface area of unweathered rock to which water has access and by increasing acidity and rate of mineral weathering. Fluxes were also found to increase with watershed size. This scale dependence is most likely caused by the sensitivity of weathering fluxes to even minor quantities of carbonates, which are likely to be found in all lithologies at larger scales. Mass balances were carried out in watersheds where gauged sub-watersheds made up more than 95% of the area. The calculations show large magnesium flux and water balance discrepancies. These errors may be a result of significant groundwater inputs to streams between gauges. The results suggest that improvements in how we measure discharge and estimate fluxes may be required before we can apply mass balance techniques to larger scales. © 1997 John Wiley & Sons, Ltd.     

Benzene Dynamics and Biodegradation in Alluvial Aquifers Affected by River Fluctuations

The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on‐going under sulfate reducing conditions. Long‐term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO₄^2–) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2 m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels.     

引潮力作用下饱和地质岩体的力学响应

本文应用孔隙弹性理论,探讨了引潮力作用下饱和地质岩体的力学响应.首先通过引潮力作用下饱和岩体的自由能表达式,得到岩体孔压与应力、应力与应变之间的关系;然后从引潮力作用下饱和岩体的平衡微分方程出发,结合流-固耦合理论,分析了饱水岩体应变与引潮位之间的关系;最后推导出饱和岩体的两大力学物理量--孔压和潮汐应力(平均应力)与引潮位之间的物理关系.模型表明:饱和岩体孔压与引潮位成反比,平均潮汐应力与引潮位成正比;比例系数不仅与岩体骨架的Lame系数有关,而且与Biot模量有关.将模型应用于会理川-18井水位变化分析,估计出水位响应系数D,并以此为基础,求得岩体孔压、潮汐应力与引潮位的相关系数(A和C)及Skempton系数B.最后对比分析了耦合条件下与不考虑耦合时得到的各参数之间的差异,分析表明:对饱和地质岩体而言,应力、孔压对引潮力的响应是流-固耦合作用的产物;研究其力学响应时必须充分考虑耦合效应.模型的建立,为研究引潮力作用下井-承压含水层系统力学、水动力学、与地震有关的断层力学以及引潮力触发机制的定量研究提供了基础.