Spatiotemporal variability in hydrochemistry of shallow groundwater in a small pre‐alpine catchment: The importance of landscape elements

Topography and landscape characteristics affect the storage and release of water and, thus, groundwater dynamics and chemistry. Quantification of catchment scale variability in groundwater chemistry and groundwater dynamics may therefore help to delineate different groundwater types and improve our understanding of which parts of the catchment contribute to streamflow. We sampled shallow groundwater from 34 to 47 wells and streamflow at seven locations in a 20‐ha steep mountainous catchment in the Swiss pre‐Alps, during nine baseflow snapshot campaigns. The spatial variability in electrical conductivity, stable water isotopic composition, and major and trace ion concentrations was large and for almost all parameters larger than the temporal variability. Concentrations of copper, zinc, and lead were highest at sites that were relatively dry, whereas concentrations of manganese and iron were highest at sites that had persistent shallow groundwater levels. The major cation and anion concentrations were only weakly correlated to individual topographic or hydrodynamic characteristics. However, we could distinguish four shallow groundwater types based on differences from the catchment average concentrations: riparian zone‐like groundwater, hillslopes and areas with small upslope contributing areas, deeper groundwater, and sites characterized by high magnesium and sulfate concentrations that likely reflect different bedrock material. Baseflow was not an equal mixture of the different groundwater types. For the majority of the campaigns, baseflow chemistry most strongly resembled riparian‐like groundwater for all but one subcatchment. However, the similarity to the hillslope‐type groundwater was larger shortly after snowmelt, reflecting differences in hydrologic connectivity. We expect that similar groundwater types can be found in other catchments with steep hillslopes and wet areas with shallow groundwater levels and recommend sampling of groundwater from all landscape elements to understand groundwater chemistry and groundwater contributions to streamflow.     

Lithological controls on biological activity and groundwater chemistry in Quaternary sediments

Depth profiles of solute chemistry and sulfate isotopic compositions are presented for groundwater and pore water in a sequence of Quaternary glacial outwash sediments. Sand units show evidence for hydraulic connection to the surface and thus modern sources of solutes. Finer‐grained sediments show a general pattern of increasing solute concentrations with depth, with sulfate derived from ancient rainwater and pyrite oxidation in the soil/drift. In these sediments sulfate has undergone bacterial sulfate reduction (BSR) to produce biogenic sulfide. In clay sediments, with d₁₀ ≤ 1·6 µm, high concentrations of sulfate and acetate now co‐exist, implying that BSR is inhibited. The correlation with smaller sediment grain size indicates that this is due to pore size exclusion of the sulfate reducing bacteria. Mechanical restriction of microbial function thus provides a fundamental limitation on microbial respiration in buried clay‐rich sediments, which acts as a control on the chemical evolution of their pore waters. Copyright © 2009 John Wiley & Sons, Ltd.     

Identification of Multiple Sources of Groundwater Contamination by Dual Isotopes

Chlorinated solvents are one of the most commonly detected groundwater contaminants in industrial areas. Identification of polluters and allocation of contaminant sources are important concerns in the evaluation of complex subsurface contamination with multiple sources. In recent years, compound‐specific isotope analyses (CSIA) have been employed to discriminate among different contaminant sources and to better understand the fate of contaminants in field‐site studies. In this study, the usefulness of dual isotopes (carbon and chlorine) was shown in assessments of groundwater contamination at an industrial complex in Wonju, Korea, where groundwater contamination with chlorinated solvents such as trichloroethene (TCE) and carbon tetrachloride (CT) was observed. In November 2009, the detected TCE concentrations at the study site ranged between nondetected and 10,066 µg/L, and the CT concentrations ranged between nondetected and 985 µg/L. In the upgradient area, TCE and CT metabolites were detected, whereas only TCE metabolites were detected in the downgradient area. The study revealed the presence of separate small but concentrated TCE pockets in the downgradient area, suggesting the possibility of multiple contaminant sources that created multiple comingling plumes. Furthermore, the variation of the isotopic (δ¹³C and δ³⁷Cl) TCE values between the upgradient and downgradient areas lends support to the idea of multiple contamination sources even in the presence of detectable biodegradation. This case study found it useful to apply a spatial distribution of contaminants coupled with their dual isotopic values for evaluation of the contaminated sites and identification of the presence of multiple sources in the study area.     

Isotopic Characterization of Sulfate in a Shallow Aquifer Impacted by Agricultural Fertilizer

The stable isotope ratios of groundwater sulfate (³⁴S/³²S, ¹⁸O/¹⁶O) are often used as tracers to help determine the origin of groundwater or groundwater contaminants. In agricultural watersheds, little is known about how the increased use of sulfur as a soil amendment to optimize crop production is affecting the isotopic composition of groundwater sulfate, especially in shallow aquifers. We investigated the isotopic composition of synthetic agricultural fertilizers and groundwater sulfate in an area of intensive agricultural activity, in Ontario, Canada. Groundwater samples from an unconfined surficial sand aquifer (Lake Algonquin Sand Aquifer) were analyzed from multi-level monitoring wells, riverbank seeps, and private domestic wells. Fertilizers used in the area were analyzed for sulfur/sulfate content and stable isotopic composition (δ¹⁸O and/or δ³⁴S). Fertilizers were isotopically distinct from geological sources of groundwater sulfate in the watershed and groundwater sulfate exhibited a wide range of δ³⁴S (−6.9 to +20.0‰) and δ¹⁸O (−5.0 to +13.7‰) values. Quantitative apportionment of sulfate sources based on stable isotope data alone was not possible, largely because two of the potential fertilizer sulfate sources had an isotopic composition on the mixing line between two natural geological sources of sulfate in the aquifer. This study demonstrates that, when sulfate isotope analysis is being used as a tracer or co-tracer of the origin of groundwater or of contaminants in groundwater, sulfate derived from synthetic fertilizer needs to be considered as a potential source, especially when other parameters such as nitrate independently indicate fertilizer impacts to groundwater quality.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Enhancing Microbial Sulfate Reduction of Hydrocarbons in Groundwater Using Permeable Filled Borings

At a service station closed in 1993, groundwater contained benzene that persisted above the cleanup goal of 1 mg/L in zones depleted of background sulfate. The benzene and other petroleum hydrocarbons (PHCs) were present as much as 36 feet (11 m) below the water table and therefore remediation of a thick saturated zone interval was required. Microcosms using site sediments demonstrated that anaerobic benzene biodegradation occurred only if sulfate was added, suggesting sulfate addition as a remediation approach. Twenty-four boreholes (9.1″ diameter and 56′ deep) were drilled around four monitoring wells, in which benzene concentrations exceeded 1 mg/L. The boreholes were backfilled with a mixture of gravel and 15,000 pounds of gypsum (which releases sulfate as it dissolves) to create “Permeable Filled Borings” (PFBs). Concurrently, nine high pressure injections (HPIs) of gypsum slurry were conducted in other site locations (312 pounds of gypsum total). PFBs were expected to release sulfate for up to 20 years, whereas HPIs were expected to produce a short-lived plume of sulfate. Concentrations of benzene and sulfate in groundwater were monitored over a 3-year period in six monitoring wells. In two wells near PFBs, benzene concentrations dropped below the cleanup goal by two to three orders of magnitude; in one well, sulfate concentrations exceeded 500 mg/L for the most recent 18 months. Benzene concentrations in two other PFB monitoring wells declined by a factor of 2 to 4, but remained above 1 mg/L, presumably due to high-dissolved PHC concentrations and possibly greater residual PHC mass in adjacent sediments, and therefore greater sulfate demand. However, hydrogen and sulfur isotopic enrichment in benzene and sulfate, respectively, confirmed biodegradation of benzene and stimulation of sulfate-reducing conditions. Thus, it is hypothesized that the PHC mass in adjacent sediments will decline over time, as will dissolved PHC concentrations, and eventually benzene concentrations will decrease below the cleanup goal. Benzene in two HPI monitoring wells was below the cleanup goal for all but one sampling event before HPIs were conducted and remained below the cleanup goal after HPIs; there was no stimulation of sulfate-reducing conditions. It is concluded that sulfate released from PFBs contributed to declining benzene concentrations.     

Hydrogeochemistry and its relation to groundwater level fluctuation in the Palar and Cheyyar river basins,southern India

An investigation was carried out to understand the role of water level fluctuation on major‐ion chemistry of groundwater in the Palar and Cheyyar river basins, southern India. As groundwater is the only major source of water for agricultural and drinking purposes in this area, it is important to know the effect of geological formations and agricultural activities on groundwater chemistry. Groundwater samples were collected once a month from 43 wells (641 samples in total), from January 1998 to June 1999, and analysed for major ions. The results indicate that the major‐ion chemistry of the groundwater varies with respect to space. Groundwater occurring near the River Palar has a high concentration of major ions except calcium, due to the absence of any recharge from the river, whereas lower concentrations of major ions were observed in the central part of the study area due to the recharge of fresh water from a number of surface reservoirs. The major‐ion chemistry of the study region is controlled by both mineral dissolution and anthropogenic activities. The relative contributions of mineral dissolution and anthropogenic contamination are estimated by a stoichiometric approach, which suggests that mineral dissolution is the dominant process in both the formations. The relation between water level fluctuations and major‐ion chemistry indicates that major‐ion chemistry is also greatly influenced by the water level fluctuations in different geological formations. Thus, the major‐ion chemistry of groundwater in this region is greatly influenced by mineral dissolution, anthropogenic activities and water level fluctuations in different geological formations. Copyright © 2006 John Wiley & Sons, Ltd.     

The role of perched aquifers in hydrological connectivity and biogeochemical processes in vernal pool landscapes,Central Valley,California

Relatively little is known about the role of perched aquifers in hydrological, biogeochemical, and biological processes of vernal pool landscapes. The objectives of this study are to introduce a perched aquifer concept for vernal pool formation and maintenance and to examine the resulting hydrological and biogeochemical phenomena in a representative catchment with three vernal pools connected to one another and to a seasonal stream by swales. A combined hydrometric and geochemical approach was used. Annual rainfall infiltrated but perched on a claypan/duripan, and this perched groundwater flowed downgradient toward the seasonal stream. The upper layer of soil above the claypan/duripan is ～0·6 m in thickness in the uplands and ～0·1 m in thickness in the vernal pools. Some groundwater flowed through the vernal pools when heads in the perched aquifer exceeded ～0·1 m above the claypan/duripan. Perched groundwater discharge accounted for 30–60% of the inflow to the vernal pools during and immediately following storm events. However, most perched groundwater flowed under or around the vernal pools or was recharged by annual rainfall downgradient of the vernal pools. Most of the perched groundwater was discharged to the outlet swale immediately upgradient of the seasonal stream, and most water discharging from the outlet swale to the seasonal stream was perched groundwater that had not flowed through the vernal pools. Therefore, nitrate‐nitrogen concentrations were lower (e.g. 0·17 to 0·39 mg l^?1) and dissolved organic carbon concentrations were higher (e.g. 5·97 to 3·24 mg l^?1) in vernal pool water than in outlet swale water discharging to the seasonal stream. Though the uplands, vernal pools, and seasonal stream are part of a single surface‐water and perched groundwater system, the vernal pools apparently play a limited role in controlling landscape‐scale water quality. Copyright © 2005 John Wiley & Sons, Ltd.     

Understanding the dynamics and contamination of an urban aquifer system using groundwater age (14C, 3H,CFCs) and chemistry

The quality of the groundwater supplying drinking water to the Guadalajara metropolitan area has deteriorated due to both endogenic and exogenic processes. Previous studies of this complex neotectonic volcanic environment suggest that the sources of contamination here are underground fluids derived from an active volcanic center and surface wastewater derived from regional land‐use intensification. This study uses isotopic, gaseous, and chemical signatures to more comprehensively characterize this groundwater flow and its contamination paths. Groundwater is mainly recharged at the La Primavera Caldera to the west and is discharged into the Santiago River to the east. The exception to this trend is the Toluquilla area, where groundwater most likely represents rainfall originating from outside the basin limits. Evaporation affects groundwater in these areas, especially waters that have been affected by recycling below urban areas in the Atejamac area and by intensive agricultural activity in the Toluquilla area. Additionally, we present evidence that groundwater flow through alluvial sediments and tuffs in deeper wells mixes with a lower aquifer unit in basaltic‐andesitic rocks, which are in contact with hydrothermal fluids. Groundwater ages range from postbomb in the western and northwestern regions of the study area (i.e., the Atemajac aquifer unit) to Late Pleistocene in the southern and southeastern regions (i.e., the Toluquilla aquifer unit). Recently recharged water records little mixing and is located mostly in or near the La Primavera volcanic system. As groundwater undergoes gravitational flow towards discharge areas, it mixes with older water components. Chloride and sodium concentrations above natural background levels are primarily related to volcanic activity, nitrate is associated with human activities, and sulfate originates from both anthropogenic sources and water–rock interactions. Nitrate originating from land‐use activities (such as sewers, septic tanks, landfills, and agricultural fields) that is introduced into the deeper part of the groundwater system is expected to travel with the groundwater to the discharge areas because oxidizing conditions will prevent microbial reduction. See Supplementary Information.     

Hydrochemical characteristics and groundwater evolution modeling in sedimentary rocks of the Tono mine,Japan

Based on geochemical data collected by Japan Nuclear Cycle Development Institute (JNC) in the Tono uranium mine, a conceptual groundwater evolution model developed by JNC is tested to evaluate whether equilibrium-based concepts of water–rock interaction are consistent with observed variations in the mineralogy and hydrochemistry of the Tono mine area. The chemical evolution of the groundwaters is modeled assuming local equilibrium for selected mineral–fluid reactions, taking into account the rainwater origin of these solutions. Results suggest that it is possible to interpret approximately the actual groundwater chemistry (i.e., pH, Eh, total dissolved concentrations of Si, Na, Ca, K, Al, carbonate and sulfate) if the following assumptions are adopted (a) CO₂ concentration in the gas phase contacting pore solutions in the overlying soil zone=10⁻¹ atm, and (b) minerals in the rock zone that control the solubility of respective elements in the groundwater include: chalcedony (Si), albite (Na), kaolinite (Al), calcite (Ca and carbonate), muscovite (K) and pyrite (Eh and sulfate). This result helps to build confidence in the use of simplified geochemical modeling techniques to develop an understanding of dominant geochemical reactions controlling groundwater chemistry in rocks similar to those that could be used for the geological disposal of radioactive wastes. It is noted, however, that the available field data may not be sufficient to adequately constrain parameters in the groundwater evolution model. In particular, more detailed information characterizing certain site properties are needed to improve the model. For this reason, a model that accounts for ion-exchange reactions among clay minerals, and which is based on the results of laboratory experiments, has also been evaluated in the present study. Further improvement of model considering ion-exchange reactions are needed in future, however.     

Comparison of Phytoscreening and Direct‐Push‐Based Site Investigation at a Rural Megasite Contaminated with Chlorinated Ethenes

The reliable characterization of subsurface contamination of spatially extended contaminated sites is a challenging task, especially with an unknown history of land use. Conventional technologies often fail due to temporal and financial constraints and thus hinder the redevelopment of abandoned areas in particular. Here we compare two site screening techniques that can be applied quickly at relatively low cost, namely Direct Push (DP)‐based groundwater sampling and tree core sampling. The effectiveness of both methods is compared for a rural megasite contaminated with chlorinated hydrocarbons. Unexpected pollution hot spots could be identified using both of these methods, while tree coring even enabled the delineation of the contaminant plume flowing into an adjacent wetland inaccessible for DP units. Both methods showed a good agreement in revealing the spatial pattern of the contamination. The correlation between groundwater concentrations and equivalent concentrations in wood was linear and highly significant for trichloroethene. Correlation was less obvious for its metabolite cis‐dichloroethene, but still significant. As outcome of our study we recommend tree coring and for initial screening in combination with a DP sampling to retrieve quantitative data on groundwater pollutants in order to assess the contamination situation of a non‐ or only partly investigated site. The subsequent placement of monitoring wells for long‐term monitoring of contamination levels is recommended. A combination of methods would achieve more relevant information at comparable or possibly even lower efforts in comparison to a conventional site investigation.     

Types and Usages of Drilling Fluids Utilized to Install Monitoring Wells Associated with Metals and Radionuclide Ground Water Studies

Evaluation for metal and radionuclide contamination associated with selected inactive uranium mill tailings repositories required the installation of monitoring wells in both shallow unconfined and deep artesian aquifer systems. To prevent ionic exchange between the dissolved cationic metals and the cations in bentonitic drilling fluids, organic-based fluids were used during the drilling and installation of monitoring wells. Experience gained at three western U.S. sites involving inactive uranium mill tailings indicates organic drilling fluids can be used to advance drill holes in soil materials ranging from saturated silts and fine sands to unsaturated gravels. However, it has been determined that certain types of these organic fluids can clog very narrow screen slots and remain present in well discharge, even after several hours of well cleaning. Certain types of organic drilling fluids appear to be preferable for these types of water chemistry studies.     

Contamination of groundwater under cultivated fields in an arid environment, central Arava Valley, Israel

The purpose of this study is to obtain a better understanding of groundwater contamination processes in an arid environment (precipitation of 50 mm/year) due to cultivation. Additional aims were to study the fate of N, K, and other ions along the whole hydrological system including the soil and vadose zone, and to compare groundwater in its natural state with contaminated groundwater (through the drilling of several wells).

A combination of physical, chemical, and isotopic analyses was used to describe the hydrogeological system and the recharge trends of water and salts to the aquifers. The results indicate that intensive irrigation and fertilization substantially affected the quantity and quality of groundwater recharge. Low irrigation efficiency of about 50% contributes approximately 3.5–4 million m³/year to the hydrological system, which corresponds to 0.65 m per year of recharge in the irrigated area, by far the most significant recharge mechanism.

Two main contamination processes were identified, both linked to human activity: (1) salinization due to circulation of dissolved salts in the irrigation water itself, mainly chloride, sulfate, sodium and calcium, and (2) direct input of nitrate and potassium mainly from fertilizers.

The nitrate concentrations in a local shallow groundwater lens range between 100 and 300 mg/l and in the upper sub-aquifer are over 50 mg/l. A major source of nitrate is fertilizer N in the excess irrigation water. The isotopic compositions of δ¹⁵N–NO₃ (range of 4.9–14.8‰) imply also possible contributions from nearby sewage ponds and/or manure. Other evidence of contamination of the local groundwater lens includes high concentrations of K (20–120 mg/l) and total organic carbon (about 10 mg/l).     

Land Application of Sulfate Salts for Enhanced Natural Attenuation of Benzene in Groundwater: A Case Study

Sulfate reducing conditions are widely observed in groundwater plumes associated with petroleum hydrocarbon releases. This leads to sulfate depletion in groundwater which can limit biodegradation of hydrocarbons (usually benzene, toluene, ethylbenzene, xylenes [BTEX] compounds) and can therefore result in extended timeframes to achieve groundwater cleanup objectives by monitored natural attenuation. Under these conditions, sulfate addition to the subsurface can potentially enhance BTEX biodegradation and facilitate enhanced natural attenuation. However, a delivery approach that enables effective contact with the hydrocarbons and is able to sustain elevated and uniform sulfate concentrations in groundwater remains a key challenge. In this case study, sulfate addition to a groundwater plume containing predominantly benzene by land application of agricultural gypsum and Epsom salt is described. Over 4 years of groundwater monitoring data from key wells subjected to pilot‐scale and site‐wide land application events are presented. These are compared to data from pilot testing employing liquid Epsom salt injections as an alternate sulfate delivery approach. Sulfate land application, sulfate retention within the vadose zone, and periodic infiltration following ongoing precipitation events resulted in elevated sulfate concentrations (>150 mg/L) in groundwater that were sustained over 12 months between application events and stimulated benzene biodegradation as indicated by declines in dissolved benzene concentration, and compound‐specific isotope analysis data for carbon in benzene. Long‐term groundwater benzene concentration reductions were achieved in spite of periodic rebounds resulting from water table fluctuations across the smear zone. Land application of gypsum is a potentially cost‐effective sulfate delivery approach at sites with open, unpaved surfaces, relatively permeable geology, and shallow hydrocarbon impacts. However, more research is needed to understand the fate and persistence of sulfate and to improve the likelihood of success and effectiveness of this delivery approach.     

Results of Seepage Meter and Mini-Piezometer Study, Lake Mead, Nevada

The seepage meter and the mini-piezometer were utilized in an attempt to evaluate ground-water reservoir interactions over a 12-month period at Echo Bay in Lake Mead. In conjunction with these techniques three standard piezometers, refraction seismic data, and water chemistry data were utilized to interpret seepage device results. During a four-month period, from December 1979 to March 1980, an 8 ft (2.5 m) rise in reservoir stage, the reservoir contributed water to Echo Wash bank storage at rates of up to 0.29 gpd/ft² (12 lpd/m²). Ground-water discharge occurred for the remainder of the project, during a stage decline from April 1980 to May 1980, a rise in June 1980, and leveling off and slight decline for the remainder of the year, July 1980 to December 1980. The maximum seepage meter ground-water discharge rate of 3.0 gpd/ft² (122 lpd/m²) was recorded in December 1980. Seepage meter water chemistry data for June were similar to Lake Mead water chemistry and were interpreted to be previously recharged Lake Mead water. September water chemistry data showed two possible components of ground-water discharge, a high SpC calcium sulfate Echo Wash ground water and a lower SpC Lake Mead recharged bank storage water. December ground-water chemistry data showed discharge to be a high SpC calcium sulfate water similar to Echo Wash ground-water quality which was apparently unaffected by Lake Mead inflow. Mini-piezometer data were collected at each seepage meter site. However, these data usually did not provide correlative results with seepage meter data probably because of suspended sediment in the piezometer water column and plugging of the perforated tip. Seepage meters were successfully utilized to characterize reservoir ground-water interaction in Echo Bay.     

Application of Direct Push Methods to Investigate Uranium Distribution in an Alluvial Aquifer

The U.S. EPA 2000 Radionuclide Rule established a maximum contaminant level (MCL) for uranium of 30 µg/L. Many small community water supplies are struggling to comply with this new regulation. At one such community, direct push (DP) methods were applied to obtain hydraulic profiling tool (HPT) logs and install small diameter wells in a section of alluvial deposits located along the Platte River. This work was conducted to evaluate potential sources of elevated uranium in the Clarks, Nebraska drinking water supply. HPT logs were used to understand the hydrostratigraphy of a portion of the aquifer and guide placement of small diameter wells at selected depth intervals. Low-flow sampling of the wells provided water quality parameters and samples for analysis to study the distribution of uranium and variations in aquifer chemistry. Contrary to expectations, the aquifer chemistry revealed that uranium was being mobilized under anoxic and reducing conditions. Review of the test well and new public water supply well construction details revealed that filter packs extended significantly above the screened intervals of the wells. These filter packs were providing a conduit for the movement of groundwater with elevated concentrations of uranium into the supply wells and the community drinking water supply. The methods applied and lessons learned here may be useful for the assessment of unconsolidated aquifers for uranium, arsenic, and many other drinking water supply contaminants.     

Estimating the Impact of Vadose Zone Sources on Groundwater to Support Performance Assessment of Soil Vapor Extraction

Soil vapor extraction (SVE) is a prevalent remediation remedy for volatile organic compound (VOC) contaminants in the vadose zone. To support selection of an appropriate condition at which SVE may be terminated for site closure or for transition to another remedy, an evaluation is needed to determine whether vadose zone VOC contamination has been diminished sufficiently to keep groundwater concentrations below threshold values. A conceptual model for this evaluation was developed for VOC fate and transport from a vadose zone source to groundwater when vapor‐phase diffusive transport is the dominant transport process. A numerical analysis showed that, for these conditions, the groundwater concentration is controlled by a limited set of parameters, including site‐specific dimensions, vadose zone properties, and source characteristics. On the basis of these findings, a procedure was then developed for estimating groundwater concentrations using results from the three‐dimensional multiphase transport simulations for a matrix of parameter value combinations and covering a range of potential site conditions. Interpolation and scaling processes are applied to estimate groundwater concentrations at compliance (monitoring) wells for specific site conditions of interest using the data from the simulation results. The interpolation and scaling methodology using these simulation results provides a far less computationally intensive alternative to site‐specific three‐dimensional multiphase site modeling, while still allowing for parameter sensitivity and uncertainty analyses. With iterative application, the approach can be used to consider the effect of a diminishing vadose zone source over time on future groundwater concentrations. This novel approach and related simulation results have been incorporated into a user‐friendly Microsoft® Excel®‐based spreadsheet tool entitled SVEET (Soil Vapor Extraction Endstate Tool), which has been made available to the public.     

Factors controlling seasonal groundwater and solute flux from snow‐dominated basins

Critical zone influences on hydrologic partitioning, subsurface flow paths and reactions along these flow paths dictate the timing and magnitude of groundwater and solute flux to streams. To isolate first‐order controls on seasonal streamflow generation within highly heterogeneous, snow‐dominated basins of the Colorado River, we employ a multivariate statistical approach of end‐member mixing analysis using a suite of daily chemical and isotopic observations. Mixing models are developed across 11 nested basins (0.4 to 85 km²) spanning a gradient of climatological, physical, and geological characteristics. Hydrograph separation using rain, snow, and groundwater as end‐members indicates that seasonal contributions of groundwater to streams is significant. Mean annual groundwater flux ranges from 12% to 33% whereas maximum groundwater contributions of 17% to 50% occur during baseflow. The direct relationship between snow water equivalent and groundwater flux to streams is scale dependent with a trend toward self‐similarity when basins exceed 5.5 km². We find groundwater recharge increases in basins of high relief and within the upper subalpine where maximum snow accumulation is coincident with reduced conifer cover and lower canopy densities. The mixing model developed for the furthest downstream site did not transfer to upstream basins. The resulting error in predicted stream concentrations points toward weathering reactions as a function of source rock and seasonal shifts in flow path. Additionally, the potential for microbial sulfate reduction in floodplain sediments along a low‐gradient, meandering portion of the river is sufficient to modify hillslope contributions and alter mixing ratios in the analysis. Soil flushing in response to snowmelt is not included as an end‐member but is identified as an important mechanism for release of solutes from these mountainous watersheds. End‐member mixing analysis used in combination with high‐frequency observations reveals important aspects of catchment hydrodynamics across scale.     

Effects of uranium mining discharges on water quality in the Puerco River basin,Arizona and New Mexico

Abstract

From 1967 until 1986, uranium mine dewatering increased dissolved gross alpha, gross beta, uranium and radium activities and dissolved selenium and molybdenum concentrations in the Puerco River as indicated by time trends, areal patterns involving distance from the mines and stream discharge. Additionally, increased dissolved uranium concentrations were identified in groundwater under the Puerco River from where mine discharges entered the river to approximately the Arizona-New Mexico State line about 65 km downstream. Total mass of uranium and gross alpha activity released to the Puerco River by mine dewatering were estimated as 560 Mg (560 × 10⁶ g) and 260 Ci, respectively. In comparison, a uranium mill tailings pond spill on 16 July 1979, released an estimated 1.5 Mg of uranium and 46 Ci of gross alpha activity. Mass balance calculations for alluvial ground water indicate that most of the uranium released did not remain in solution. Sorption of uranium on sediments and uptake of uranium by plants probably removed the uranium from solution.     

Conservative behavior of arsenic and other oxyanion-forming trace elements in an oxic groundwater flow system

Groundwater samples were collected along a flow path in a shallow, fractured tuffaceous aquifer from the Oasis Valley–Beatty Wash region of southern Nevada, USA, and analyzed for a number of oxyanion-forming trace elements including arsenic (As), antimony (Sb), selenium (Se), molybdenum (Mo), and tungsten (W). In addition, ancillary geochemical parameters, including pH, major solute compositions, dissolved silica, dissolved oxygen, and iron and manganese concentrations were quantified in the groundwaters. Arsenic concentrations range from 70 nmol/kg up to 316 nmol/kg in groundwaters of the Oasis Valley–Beatty Wash flow system, and generally exhibit increasing concentrations with flow down-gradient along the flow path. Antimony, W, and to a lesser extent, Mo, exhibit similar increasing concentration trends with flow down-gradient in the aquifer, albeit, at lower concentrations levels (e.g., mean ± SD for Sb, W, and Mo are 2.3 ± 0.9 nmol/kg, 7.4 ± 3.7 nmol/kg, and 101 ± 19 nmol/kg, respectively). Selenium concentration, which range between 4 and 11 nmol/kg, generally decrease in groundwaters with flow down-gradients in the Oasis Valley–Beatty Wash groundwater flow systems. Inverse modeling of groundwater chemistry evolution from the lower reaches of the Oasis Valley flow path using PHREEQC indicate that the groundwater composition is consistent with mixing of nearly equal proportions of groundwater from upper reaches of Oasis Valley and Beatty Wash groundwater, along with dissolution of volcanic glass, potassium feldspar, and gypsum, followed by calcite precipitation, and formation of secondary zeolites (analcime), clay minerals (Ca-montmorillonite), and cristobalite. The geochemical modeling indicates that the concentrations of As and the other oxyanion-forming trace elements are controlled by dissolution of volcanic glass, water–rock interaction with mineralized zones within the aquifer (i.e., sulfide oxidation), desorption from aquifer surface sites, and mixing of Oasis Valley and Beatty Wash groundwaters.