Quantifying climate change impacts on future water resources and salinity transport in a high semi-arid watershed.

High salinity mobilization and movement from salt-laden deposits in semi-arid landscapes impair soils and water resources worldwide. Semi-arid regions worldwide are expected to experience rising temperatures and lower precipitation, impacting water supply and spatio-temporal patterns of salinity loads and affecting downstream water quality. This study quantifies the impact of future climate on hydrologic fluxes and salt loads in the Gunnison River Watershed (GRW) (14,608 km2), Colorado, using the APEX-MODFLOW-Salt hydro-chemical watershed model and three different CMIP5 climate models projection downscaled by Multivariate Adaptive Constructed Analogs (MACA) for the period 2020-2099. The APEX-MODFLOW-Salt model accounts for the reactive transport of major salt ions (SO42-, Cl-, CO32-, HCO3-, Ca2+, Na+, Mg2+, and K+) to streams via surface runoff, rainfall erosional runoff, soil lateral flow, quick return flow and groundwater-stream exchange. Model results are analyzed for spatial and temporal trends in water yield and salt loading pathways. Although streamflow is primarily derived from surface runoff (65%), the predominant source of salt loads is the aquifer (73%) due to elevated concentrations of groundwater salt. Annual salt loading from the watershed is 582 Mkg, approximately 10% of the salt load in the Colorado River measured at Lee's Ferry, AZ. For future climate scenarios, annual salt loads from the watershed increased between 4.1% and 9.6% from the historical period due to increased salt loading from groundwater and quick return flow. From the results, applying the APEX-MODFLOW-Salt model with downscaled future climate forcings can be a helpful modeling framework for investigating hydrology and salt mobilization, transport, and export in historical and predictive settings for salt-affected watersheds.

The impact of extensive agricultural water drainage on the hydrology of the Kleine Nete watershed, Belgium.

Agricultural water drainage can significantly lower groundwater levels and affect catchment hydrology. Therefore, building models with and without these features can indicate an adverse impact on the geohydrological process. Therefore, the standalone Soil Water Assessment Tool (SWAT+) model was initially developed to simulate streamflow at the Kleine Nete catchment outlet. Next, a physically based and spatially distributed groundwater module (gwflow) was integrated into the SWAT+ model and calibrated for stream discharge at the catchment outlet. Finally, the same model was calibrated for both streamflow and groundwater heads. These final model parameters are used to investigate the basin-wide hydrologic fluxes with and without including agricultural drainage systems in the model scheme. The result suggested that the standalone SWAT+ model poorly represented the stream discharge and attained low NSE values of 0.18 and 0.37 during the calibration and validation periods, respectively. Integrating the gwflow module to SWAT+ improved the model representation of stream discharge (NSE = 0.91 and 0.65 for calibration and validation periods, respectively) and groundwater heads. However, calibrating the model for only streamflow resulted in a high root mean square error (above 1 m) for groundwater head, and the seasonality is not captured. On the other hand, calibrating the coupled model for streamflow and hydraulic head reduced the root mean square error (below 0.5 m) and captured the seasonality of groundwater level fluctuations. Finally, drainage application resulted in a 50 % (from 33.04 mm to 16.59 mm) reduction in groundwater saturation excess flow and an 18.4 mm increment in drainage water to streams. To conclude, the new SWAT+gwflow model is more appropriate than the standalone SWAT+ model for the case study. Furthermore, calibrating the SWAT+gwflow model for streamflow and groundwater head has improved the model simulation, with implications for general coupled models where representing surface and groundwater in the calibration strategy is beneficial.

Quantifying the impact of climate extremes on salt mobilization and loading in non-developed, high-desert landscapes using SWAT.

Excess salt loading from watershed landscapes into river systems acts as a chemical stressor in water bodies and can have significant impacts on downstream water quality. High salinity threatens sustainable crop production globally and is especially prevalent in semi-arid and arid regions. However, relatively little research has been conducted to evaluate salt movement and loadings in natural, high-desert catchments in the face of climate change and extreme climate events. In this study, we use the watershed model SWAT and a newly developed salinity module to simulate the mass transport of 8 major salt ions, SO42-, Cl-, CO32-, HCO3-, Ca2+, Na+, Mg2+, and K+, in the soil-aquifer-stream system of the Purgatoire River Watershed (PRW) (Colorado, USA, 8935 km2) via major hydrologic pathways (surface runoff, percolation, recharge, soil lateral flow, groundwater upflux, groundwater discharge) and quantify changes in predicted salt loads with possible future increasing storm intensity. The PRW is susceptible to high salt transport due to high topographic slopes, dry climatic conditions, and sparse vegetation, and loads to the Arkansas River, a major source of irrigation water in the Arkansas River Basin. From study results we conclude that 99% of salt in the Purgatoire River originates from subsurface water pathways (soil lateral flow, groundwater flow), composed primarily of SO42-, Ca2+, and HCO3-. If intensity of large storms increases by 5% and 35%, the total salt mass exported from the watershed increases by 12% and 73%, respectively, indicating large influxes of legacy salt from the soil-aquifer system. For baseline and storm intensity scenarios, the PRW contributes significant salt loads to agricultural regions via the Arkansas River, highlighting the need for basin-wide salt management strategies to include upland desert regions. We expect these results, and associated consequences for salt management, to be similar for other upland desert catchments worldwide.

Evaluating the contribution of subsurface drainage to watershed water yield using SWAT+ with groundwater modeling.

Drainage outflow from artificial subsurface drains can be a significant contributor to watershed water yield in many humid regions of the world. Although many studies have undertaken to simulate hydrologic processes in drained watersheds, there is a need for a study that first, uses physically based spatially distributed modeling for both surface and subsurface processes; and second, quantifies the effect of surface and subsurface parameters on watershed drainage outflow. This study presents a modified version of the SWAT+ watershed model to address these objectives. The SWAT+ model includes the gwflow module, a new spatially distributed groundwater routine for calculating groundwater storage, groundwater head, and groundwater fluxes throughout the watershed using a grid cell approach, modified in this study to simulate the removal of groundwater by subsurface drains. The modeling approach is applied to the South Fork Watershed (583 km2), located in Iowa, USA, where most fields are drained artificially. The model is tested against measured streamflow, groundwater head at monitoring wells, and drainage outflow from a monitored subbasin. Sensitivity analysis is then applied to determine the land surface, subsurface, and drainage parameters that control subsurface drainage. Simulated drainage flow fractions (fraction of streamflow that originates from subsurface drainage) range from 0.37 to 0.54 during 2001-2012, with lower fractions occurring during years of high rainfall due to the increased volumes of surface runoff. Subsurface drainage comprises the vast majority of baseflow. Results indicate surface runoff and soil percolation parameters have the strongest effect on watershed-wide subsurface drainage rather than aquifer and drain properties, pointing to a holistic watershed approach to manage subsurface drainage. The modeling code presented herein can be used to simulate significant hydrologic fluxes in artificially drained watersheds worldwide.

Investigating the controlling factors on salinity in soil, groundwater, and river water in a semi-arid agricultural watershed using SWAT-Salt.

Soil salinity can have a significant impact on crop yield, particularly in arid and semi-arid irrigated watersheds wherein irrigation and inadequate drainage often combine to increase salt ion concentrations in soil water. To control salinity, the principal step is to identify the key environmental and hydrologic factors that govern the fate and transport of salts in these irrigated areas. To accomplish this objective, global sensitivity analysis is applied to the newly developed SWAT-Salt model, which simulates the reactive transport of 8 major salt ions (SO4, Ca, Mg, Na, K, Cl, CO3, and HCO3) in major hydrologic pathways in a watershed system. The model is applied to a saline 1118 km2 irrigated stream-aquifer system located within the Lower Arkansas River Valley in southeastern Colorado, USA. Multiple parameters including plant growth factors, stream channel factors, evaporation factors, surface runoff factors, and the initial mass concentrations of salt minerals MgSO4, MgCO3, CaSO4, CaCO3, and NaCl in the soils and in the aquifer are investigated for control on salinity in groundwater, soils, and streams. The Morris screening method is used to identify the most sensitive factors, followed by the Sobol' variance-based method to provide a final ranking and to identify interactions between factors. Results show that salt ion concentration in soils and groundwater is controlled principally by hydrologic factors (evaporation, groundwater discharge and upflux, and surface runoff factors) as well as the initial amounts of salt minerals in soils. Salt concentration in the Arkansas River is governed by similar factors, likely due to salt ion mass in the streams controlled by surface runoff and groundwater discharge from the aquifer. Results can be used in decision making regarding the most impactful land and water management strategies for controlling salinity transport and build-up in soils, both for this watershed and other similar semi-arid salinity-impacted watersheds.

Appraising climate change impacts on future water resources and agricultural productivity in agro-urban river basins.

Climate change can have an adverse effect on agricultural productivity and water availability in semi-arid regions, as changes in surface water availability lead to groundwater depletion and resultant losses in crop yield. These inter-relationships necessitate an integrated management approach for surface water, groundwater, and crop yield as a holistic system. This study quantifies the future availability of surface water and groundwater and associated crop production in a large semi-arid agro-urban river basin in which agricultural irrigation is a leader consumer of water. The region of study is the South Platte River Basin (72,000 km2), Colorado, USA. The coupled SWAT-MODFLOW modeling code is used as the hydrologic simulator and forced with five different CMIP5 climate models downscaled by Multivariate Adaptive Constructed Analogs (MACA), each for two climate scenarios, RCP4.5, and RCP8.5, for 1980-2100. The hydrologic model accounts for surface runoff, soil lateral flow, groundwater flow, groundwater-surface water interactions, irrigation from surface water and groundwater, and crop yield on a per-field basis. In all climate models and emission scenarios, an increase of 3 to 5 °C in annual average temperature is projected. Whereas, variation in the projected precipitation depends on topography and distances from mountains. Based on the results of this study, the worst-case climate model in the basin is IPSL-CM5A-MR-8.5. Under this climate scenario, for a 1 °C increase in temperature and the 1.3% reduction in annual precipitation, the basin will experience an 8.5% decrease in stream discharge, 2-5% decline in groundwater storage, and 11% reduction in crop yield. These results indicate the significant effect of climate change on water and food resources of a large river basin, pointing to the need for immediate implementation of conservation practices.

Using nutrient transport data to characterize and identify the presence of surface inlets in regions with subsurface drainage.

Surface inlets route ponded surface water into subsurface drainage networks and are prevalent throughout North America. Despite serving as a nutrient loss pathway, contributing to downstream water quality degradation, surface inlets are thought to be underreported in drainage studies within the literature. Previous studies have demonstrated the footprint that surface inlets have on nutrient transport and drainage effluent but are site specific and focused on individual events. Moreover, although their ubiquitous presence is assumed, no regional surface inlet database exists. To this end, a structured review was undertaken with two goals. First, the MANAGE Drain Load database, consisting of nearly 1,500 site-years of drainage and nutrient data, was analyzed to determine distinctions between areas with and without surface inlets. The median annual total phosphorus (TP) load was greater at site-years with surface inlets (0.40 kg ha-1 ) than site-years without (0.21 kg ha-1 ). The opposite emerged for dissolved nitrogen (DN) loads as site-years with surface inlet had a smaller median annual load (3.3 kg ha-1 ) than site-years without (23.0 kg ha-1 ). This relationship is attributed to immobile TP being transported primarily through overland flow and routed to subsurface drains via surface inlets and to relatively more mobile DN being subsurface driven, bypassed in settings with surface inlets. No statistical differences were found in annual drainage or ratios of particulate P to TP between site-years with and without surface inlets. Second, a logistic regression model was developed that predicts the presence of surface inlets within MANAGE. Eighteen percent of site-years and 21% of sites were predicted to have surface inlets.

Assessing controls on selenium fate and transport in watersheds using the SWAT model.

Selenium toxicity in groundwater and surface water in many regions globally has resulted in toxicity in the food chain thus harming terrestrial and aquatic animals. Here we assess the environmental controls on selenium fate and transport in soils, groundwater, and rivers at the watershed scale using the SWAT watershed simulation model. We modify the SWAT modeling code to simulate selenium fate and transport in surface runoff, lateral flow, soil percolation, groundwater flow, streamflow, and irrigation water within a watershed subject to oxidation-reduction reactions. This modified SWAT model is applied to an irrigated watershed with selenium problems in the Arkansas River Valley, Colorado. The model is calibrated and tested using observed groundwater and surface water selenium data in different locations of the study area, whereupon global sensitivity analysis is performed to assess controls on selenium fate and transport in soil water, groundwater and streams. The impacts of reaction rates of selenate, selenite, oxygen and nitrate along with 14 hydrologic parameters are assessed. For the baseline model, selenium loading to streams during growing season is mostly via groundwater discharge (365 kg/ha; 85% of total), followed by surface runoff (14%), and soil lateral flow (1%), which are about 4-fold the loading that occurs during non-growing season. Results from the sensitivity analysis indicate that hydrologic factors (timing of recharge, soil hydraulic conductivity, and groundwater storage thresholds) are the principal controls on selenium content in soils, groundwater, and stream water, followed by the first-order reaction rates of selenate and selenite, amount of selenium-bearing shale in the aquifer, and sulfur to selenium ratio in the shale material. These results suggest that selenium mitigation procedures should focus on water management practices rather than influencing microbial redox reactions. Overall, the SWAT-Se model introduced here can be used to assess Se contamination and mitigation practices in watersheds worldwide.

Quantifying the effects of climate change on hydrological regime and stream biota in a groundwater-dominated catchment: A modelling approach combining SWAT-MODFLOW with flow-biota empirical models.

Climate change may affect stream ecosystems through flow regime alterations, which can be particularly complex in streams with a significant groundwater contribution. To quantify the impacts of climate change on hydrological regime and subsequently the stream biota, we linked SWAT-MODFLOW (A model coupling the Soil and Water Assessment Tool and the Modular Finite-difference Flow Model) with flow-biota empirical models that included indices for three key biological taxonomic identities (fish, macroinvertebrates and macrophytes) and applied the model-complex to a groundwater-dominated catchment in Denmark. Effects of predicted climate change towards the end of this century relative to the reference period (1996-2005) were tested with two contrasting climate change scenarios of different greenhouse gas emissions (Representative Concentration Pathway 2.6 (RCP 2.6) and RCP 8.5) and analysed for all subbasins grouped into streams of three size classes. The total water yield in the catchment did not change significantly (-1 ± 4 (SD) mm yr-1) from the baseline in the RCP2.6 scenario, while it increased by 9 ± 11 mm yr-1 in the RCP8.5 scenario. The three stream size classes underwent different alterations in flow regime and also demonstrated different biotic responses to climate change. All large and some small streams were impacted most heavily by the climate change, where fish and macrophyte indices decreased up to 14.4% and 11.2%, respectively, whereas these indices increased by up to 14.4% and 6.0%, respectively, in the medium and some small streams. The climate change effects were, as expected, larger in the RCP8.5 scenario than in the RCP2.6 scenario. Our study is the first to quantify the impacts of streamflow alterations induced by climate change on stream biota beyond specific species.

Assessing the impacts of groundwater abstractions on flow regime and stream biota: Combining SWAT-MODFLOW with flow-biota empirical models.

Assessing the impacts of groundwater abstractions on stream ecosystems is crucial for developing water planning and regulations in lowland areas that are highly dependent on groundwater, such as Denmark. To assess the effects of groundwater abstractions on flow regime and stream biota in a lowland groundwater-dominant catchment, we combined the SWAT-MODFLOW model with flow-biota empirical models including indices for three key biological taxonomic identities (fish, macroinvertebrates, and macrophytes). We assessed the effects of the current level of abstractions and also ran a scenario for assessing the effect of extreme groundwater abstractions (pumping rates of the drinking water wells were increased by 20 times in one subbasin of the catchment). Three subbasin outlets representing stream segments of different sizes were used for this evaluation. Current groundwater abstraction level had only minor impacts on the flow regime and stream biotic indices at the three subbasin outlets. The extreme abstractions, however, led to significant impacts on the small stream but had comparatively minor effects on the larger streams. The fish index responded most negatively to the groundwater abstractions, followed by the macrophyte index, decreasing, respectively, by 23.5% and 11.2% in the small stream in the extreme groundwater abstraction scenario. No apparent impact was found on macroinvertebrates in any of the three subbasin outlets. We conclude that this novel approach of a combined modelling system is a useful tool to quantitatively assess the effects of groundwater abstractions on stream biota and thereby support water planning and regulations related to groundwater abstractions. We highlight the need for developing improved biotic models that target specifically small headwater streams, which are often most affected by water abstraction.

Stream-aquifer and in-stream processes affecting nitrogen along a major river and contributing tributary.

This study assesses the spatio-temporal patterns of water and nutrient mass exchange in a stream-riparian system of a major river and a contributing tributary in an irrigated semi-arid region. Field monitoring is performed along reaches of the Arkansas River (4.7km) and Timpas Creek (2.0km) in southeastern Colorado during the 2014 growing season, with water quantity and water quality data collected using a network of in-stream sampling sites and groundwater monitoring wells. Mass balance approaches were used to identify temporal and spatial trends in flow, nitrogen (N), and salinity in stream-aquifer exchange. In the Arkansas River, percent decrease of N concentration along the study reach averaged 36% over the period, with results from a stochastic mass balance simulation indicating a 90% probability that 44% to 50% of NO3-N mass in the study reach (109-124kg/day/km) was removed by in-stream processes between 1 September and 8 November. Results suggest that contact with organic-rich river bed sediments has a strong impact on N removal. A greater decrease in concentrations of NO3-N along the reach during the low flow period suggests the effect of both in-stream processes and dilution by inflowing groundwater that undergoes denitrification as it flows through the riparian and hyporheic zones into the river. In contrast, N concentration decreases in the smaller Timpas Creek were negligible. Results for the Arkansas River also are in contrast with other large agriculturally-influenced rivers, which have not exhibited capacity to remove N at significant rates. Results provide important insights across spatial and temporal scales and point to the need for investigating nutrient dynamics in large streams draining agriculturally-dominated watersheds.

Assessing the effectiveness of land and water management practices on nonpoint source nitrate levels in an alluvial stream-aquifer system.

The search for ways to allay subsurface nitrate pollution and loading to streams over broad regional landscapes is taken up using a calibrated groundwater model supported by extensive field data. Major processes of transport and chemical reaction are considered in the irrigated vadose zone and the underlying alluvial aquifer in interaction with Colorado's Lower Arkansas River and its tributaries. Simulation of a variety of best management practices reveals that there is potential to lower regional nitrate concentrations in groundwater by up to about 40% and mass loading to the river network by up to 70% over a four-decade span. Over the 27BMP scenarios considered in this study, the most effective singular measures are reduction of fertilizer application and sealing of irrigation canals, while combinations of reduced fertilizer application, reduced irrigation application, canal sealing, and enhanced riparian buffer zones are predicted to have the greatest overall impact. Intermittent fallowing of 25% of the land to lease irrigation water also is found to be promising, resulting in a forecasted decrease of about 15% in nitrate groundwater loading to streams. Due to the strong similarity between the study region and other irrigated, fertilized alluvial river valley stream-aquifer systems worldwide, results of this study are expected to be broadly applicable.

Effects of marine overwash for atoll aquifers: environmental and human factors.

Inundation of atoll islands by marine overwash is a serious threat to fresh groundwater, which can be a critical emergency water resource after artificial storage or other water resource infrastructure has been exhausted or destroyed. In contrast to drought, which slowly exhausts water supplies and often can be forecasted in time, overwash can occur with little warning and can ruin both rain catchment storage and groundwater reserves. In this study, a SUTRA-based model is applied to estimate how groundwater contamination by overwash and subsequent recovery of fresh groundwater are influenced by geologic factors (aquifer hydraulic conductivity, dispersivity, and the presence or absence of a reef flat plate), the seasonal timing of the event (wet vs. dry), and the presence of hand-dug wells that penetrate the reef flat plate. Actual tidal and rainfall data from regions in the western Pacific are applied to simulated 30-month recovery periods for hypothetical islands with properties and conditions characteristic of the western Pacific. For all scenarios, results indicate that 12 to 16 months are required to achieve 60% recovery of fresh groundwater. However, the time required to restore useful quantities of groundwater to acceptable salt concentration at depths typical of hand-dug wells is only 3 to 6 months. Of particular interest is the influence of the reef flat plate, which acts as a barrier to infiltrating seawater, thus preserving a pocket of confined freshwater during an overwash event and the recovery, which could probably be utilized if the necessary tools and equipment are on hand.

The role of interior watershed processes in improving parameter estimation and performance of watershed models.

Watershed models typically are evaluated solely through comparison of in-stream water and nutrient fluxes with measured data using established performance criteria, whereas processes and responses within the interior of the watershed that govern these global fluxes often are neglected. Due to the large number of parameters at the disposal of these models, circumstances may arise in which excellent global results are achieved using inaccurate magnitudes of these "intra-watershed" responses. When used for scenario analysis, a given model hence may inaccurately predict the global, in-stream effect of implementing land-use practices at the interior of the watershed. In this study, data regarding internal watershed behavior are used to constrain parameter estimation to maintain realistic intra-watershed responses while also matching available in-stream monitoring data. The methodology is demonstrated for the Eagle Creek Watershed in central Indiana. Streamflow and nitrate (NO) loading are used as global in-stream comparisons, with two process responses, the annual mass of denitrification and the ratio of NO losses from subsurface and surface flow, used to constrain parameter estimation. Results show that imposing these constraints not only yields realistic internal watershed behavior but also provides good in-stream comparisons. Results further demonstrate that in the absence of incorporating intra-watershed constraints, evaluation of nutrient abatement strategies could be misleading, even though typical performance criteria are satisfied. Incorporating intra-watershed responses yields a watershed model that more accurately represents the observed behavior of the system and hence a tool that can be used with confidence in scenario evaluation.

Simulating variably-saturated reactive transport of selenium and nitrogen in agricultural groundwater systems.

Selenium (Se) contamination in environmental systems has become a major issue in many regions world-wide during the previous decades, with both elevated and deficient Se concentrations in groundwater, surface water, soils and associated cultivated crops reported. To provide a tool that can assess baseline conditions and explore remediation strategies, this paper presents a numerical model capable of simulating the reactive transport of Se species in large-scale variably-saturated groundwater systems influenced by agricultural practices. Developed by incorporating a Se reaction module into the multi-species, variably-saturated reactive transport model UZF-RT3D, model features include near-surface Se cycling due to agricultural practices, oxidation-reduction reactions, and the inclusion of a nitrogen (N) cycle and reaction module due to the dependence of Se transformation and speciation on the presence of nitrate (NO3). Although the primary motivation is applying the model to large-scale systems, this paper presents applications to agricultural soil profile systems to corroborate the near-surface module processes that are vital in estimating mass loadings to the saturated zone in large-scale fate and transport studies. The first application jointly tests the Se and N modules for corn test plots receiving varying loadings of fertilizer, whereas the second application tests the N module for fertilized and unfertilized test plots. Results indicate that the model is successful in reproducing observed measurements of Se and NO3 concentrations, particularly in lower soil layers and hence in regards to leaching. For the first application, the Ensemble Kalman Filter (EnKF) is used to condition model parameters, demonstrating the usefulness of the EnKF in real-world reactive transport systems.

Modeling variably saturated subsurface solute transport with MODFLOW-UZF and MT3DMS.

The MT3DMS groundwater solute transport model was modified to simulate solute transport in the unsaturated zone by incorporating the unsaturated-zone flow (UZF1) package developed for MODFLOW. The modified MT3DMS code uses a volume-averaged approach in which Lagrangian-based UZF1 fluid fluxes and storage changes are mapped onto a fixed grid. Referred to as UZF-MT3DMS, the linked model was tested against published benchmarks solved analytically as well as against other published codes, most frequently the U.S. Geological Survey's Variably-Saturated Two-Dimensional Flow and Transport Model. Results from a suite of test cases demonstrate that the modified code accurately simulates solute advection, dispersion, and reaction in the unsaturated zone. Two- and three-dimensional simulations also were investigated to ensure unsaturated-saturated zone interaction was simulated correctly. Because the UZF1 solution is analytical, large-scale flow and transport investigations can be performed free from the computational and data burdens required by numerical solutions to Richards' equation. Results demonstrate that significant simulation runtime savings can be achieved with UZF-MT3DMS, an important development when hundreds or thousands of model runs are required during parameter estimation and uncertainty analysis. Three-dimensional variably saturated flow and transport simulations revealed UZF-MT3DMS to have runtimes that are less than one tenth of the time required by models that rely on Richards' equation. Given its accuracy and efficiency, and the wide-spread use of both MODFLOW and MT3DMS, the added capability of unsaturated-zone transport in this familiar modeling framework stands to benefit a broad user-ship.

Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D.

A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

The influence of nitrate on selenium in irrigated agricultural groundwater systems.

Selenium (Se) contamination of groundwater is an environmental concern especially in areas where aquifer systems are underlain by Se-bearing geologic formations such as marine shale. This study examined the influence of nitrate (NO3) on Se species in irrigated soil and groundwater systems and presents results from field and laboratory studies that further clarify this influence. Inhibition of selenate (SeO4) reduction in the presence of NO3 and the oxidation of reduced Se from shale by autotrophic denitrification were investigated. Groundwater sampling from piezometers near an alluvium-shale interface suggests that SeO4 present in the groundwater was due in part to autotrophic denitrification. Laboratory shale oxidation batch studies indicate that autotrophic denitrification is a major driver in the release of SeO4 and sulfate. Similar findings occurred for a shale oxidation flow-through column study, with 70 and 31% more reduced Se and S mass, respectively, removed from the shale material in the presence of NO3 than in its absence. A final laboratory flow-through column test was performed with shallow soil samples to assess the inhibition of SeO4 reduction in the presence of NO3, with results suggesting that a concentration of NO3 of approximately 5 mg L or greater will diminish the reduction of SeO4. The inclusion of the fate and transport of NO3 and dissolved oxygen is imperative when studying or simulating the fate and transport of Se species in soil and groundwater systems.

Assessing selenium contamination in the irrigated stream-aquifer system of the Arkansas River, Colorado.

Prudent interventions for reducing selenium (Se) in groundwater and streams within an irrigated river valley must be guided by a sound understanding of current field conditions. An emerging picture of the nature of Se contamination within the Lower Arkansas River Valley in Colorado is provided by data from a large number of groundwater and surface water sampling locations within two study regions along the river. Measurements show that dissolved Se concentrations in the river are about double the current Colorado Department of Public Health and Environment (CDPHE) chronic standard of 4.6 microg L(-1) for aquatic habitat in the upstream region and exceed the standard by a factor of 2 to 4 in the downstream region. Groundwater concentrations average about 57.7 microg L(-1) upstream and 33.0 microg L(-1) downstream, indicating a large subsurface source for irrigation-induced dissolution and mobilization of Se loads to the river and its tributaries. Inverse correlation was found between Se concentration and the distance to the closest identified shale in the direction upstream along the principal groundwater flow gradient. The data also exhibited, among other relationships, a moderate to strong correlation between dissolved Se and total dissolved solids in groundwater and surface water, a strong correlation with uranium in groundwater, and power relationships with nitrate in groundwater. The relationship to nitrate, derived primarily from N fertilizers, reveals the degree to which dissolved Se depends on oxidation and inhibited reduction due to denitrification and suggests that there are prospects for reducing dissolved Se through nitrate control. Current and future results from these ongoing studies will help provide a foundation for modeling and for the discovery of best management practices (BMPs) in irrigated agriculture that can diminish Se contamination.