Christopher T. Green

Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

[1] Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2 threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

Limited Occurrence of Denitrification in Four Shallow Aquifers in Agricultural Areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N(2) from denitrification increases with age. Stable isotopes and excess N(2) imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 micromol N L(-1)d(-1), comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Nitrogen fluxes through unsaturated zones in five agricultural settings across the United States

The main physical and chemical controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Indiana, Maryland, Nebraska, and Washington from 2004 to 2005. Sites included irrigated and nonirrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 1 to 22 m. Chemical analyses of water from lysimeters and shallow wells indicate that advective transport of nitrate is the dominant process affecting the flux of N below the root zone. Vertical profiles of (i) nitrogen species, (ii) stable isotopes of nitrogen and oxygen, and (iii) oxygen, N, and argon in unsaturated zone air and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. As a result, physical factors, such as N application rate, water inputs, and evapotranspiration, control the differences in concentrations among the sites. Concentrations of N in shallow lysimeters exhibit seasonal variation, whereas concentrations in lysimeters deeper than a few meters are relatively stable. Based on concentration and recharge estimates, fluxes of N through the deep unsaturated zone range from 7 to 99 kg ha(-1) yr(-1). Vertical fluxes of N in ground water are lower due to spatial and historical changes in N inputs. High N fluxes are associated with coarse sediments and high N application rates.

Predicting Unsaturated Zone Nitrogen Mass Balances in Agricultural Settings of the United States

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond [Prunus dulcis (Mill.) D.A. Webb] orchard and cornfield (Zea mays L.) in the lower Merced River study basin, California; and corn-soybean [Glycine max (L.) Merr.] rotations in study basins at Maple Creek, Nebraska, and at Morgan Creek, Maryland. We used inverse modeling with a new version of the Root Zone Water Quality Model (RZWQM2) to estimate soil hydraulic and nitrogen transformation parameters throughout the unsaturated zone; previous versions were limited to 3-m depth and relied on manual calibration. The overall goal of the modeling was to derive unsaturated zone N mass balances for the four sites. RZWQM2 showed promise for deeper simulation profiles. Relative root mean square error (RRMSE) values for predicted and observed nitrate concentrations in lysimeters were 0.40 and 0.52 for California (6.5 m depth) and Nebraska (10 m), respectively, and index of agreement (d) values were 0.60 and 0.71 (d varies between 0 and 1, with higher values indicating better agreement). For the shallow simulation profile (1 m) in Maryland, RRMSE and d for nitrate were 0.22 and 0.86, respectively. Except for Nebraska, predictions of average nitrate concentration at the bottom of the simulation profile agreed reasonably well with measured concentrations in monitoring wells. The largest additions of N were predicted to come from inorganic fertilizer (153-195 kg N ha(-1) yr(-1) in California) and N fixation (99 and 131 kg N ha(-1) yr(-1) in Maryland and Nebraska, respectively). Predicted N losses occurred primarily through plant uptake (144-237 kg N ha(-1) yr(-1)) and deep seepage out of the profile (56-102 kg N ha(-1) yr(-1)). Large reservoirs of organic N (up to 17,500 kg N ha(-1) m(-1) at Nebraska) were predicted to reside in the unsaturated zone, which has implications for potential future transfer of nitrate to groundwater.

Accuracy of travel time distribution (TTD) models as affected by TTD complexity, observation errors, and model and tracer selection

Analytical models of the travel time distribution (TTD) from a source area to a sample location are often used to estimate groundwater ages and solute concentration trends. The accuracies of these models are not well known for geologically complex aquifers. In this study, synthetic data sets were used to quantify the accuracy of four analytical TTD models as affected by TTD complexity, observation errors, model selection, and tracer selection. Synthetic TTDs and tracer data were generated from existing numerical models with complex hydrofacies distributions for 1 public-supply well and 14 monitoring wells in the Central Valley, California. Analytical TTD models were calibrated to synthetic tracer data, and prediction errors were determined for estimates of TTDs and conservative tracer ( NO3−) concentrations. Analytical models included a new, scale-dependent dispersivity model (SDM) for two-dimensional transport from the water table to a well and three other established analytical models. The relative influence of the error sources (TTD complexity, observation error, model selection, and tracer selection) depended on the type of prediction. Geological complexity gave rise to complex TTDs in monitoring wells that strongly affected errors of the estimated TTDs. However, prediction errors for NO3− and median age depended more on tracer concentration errors. The SDM tended to give the most accurate estimates of the vertical velocity and other predictions, although TTD model selection had minor effects overall. Adding tracers improved predictions if the new tracers had different input histories. Studies using TTD models should focus on the factors that most strongly affect the desired predictions.

Decadal surface water quality trends under variable climate, land use, and hydrogeochemical setting in Iowa, USA

Understanding how nitrogen fluxes respond to changes in agriculture and climate is important for improving water quality. In the midwestern United States, expansion of corn cropping for ethanol production led to increasing N application rates in the 2000s during a period of extreme variability of annual precipitation. To examine the effects of these changes, surface water quality was analyzed in 10 major Iowa Rivers. Several decades of concentration and flow data were analyzed with a statistical method that provides internally consistent estimates of the concentration history and reveals flow-normalized trends that are independent of year-to-year streamflow variations. Flow-normalized concentrations of nitrate+nitrite-N decreased from 2000 to 2012 in all basins. To evaluate effects of annual discharge and N loading on these trends, multiple conceptual models were developed and calibrated to flow-weighted annual concentrations. The recent declining concentration trends can be attributed to both very high and very low discharge in the 2000s and to the long (e.g., 8 year) subsurface residence times in some basins. Dilution of N and depletion of stored N occurs in years with high discharge. Reduced N transport and increased N storage occurs in low-discharge years. Central Iowa basins showed the greatest reduction in flow-normalized concentrations, likely because of smaller storage volumes and shorter residence times. Effects of land-use changes on the water quality of major Iowa Rivers may not be noticeable for years or decades in peripheral basins of Iowa, and may be obscured in the central basins where extreme flows strongly affect annual concentration trends.

Simulating water-quality trends in public-supply wells in transient flow systems

Models need not be complex to be useful. An existing groundwater-flow model of Salt Lake Valley, Utah, was adapted for use with convolution-based advective particle tracking to explain broad spatial trends in dissolved solids. This model supports the hypothesis that water produced from wells is increasingly younger with higher proportions of surface sources as pumping changes in the basin over time. At individual wells, however, predicting specific water-quality changes remains challenging. The influence of pumping-induced transient groundwater flow on changes in mean age and source areas is significant. Mean age and source areas were mapped across the model domain to extend the results from observation wells to the entire aquifer to see where changes in concentrations of dissolved solids are expected to occur. The timing of these changes depends on accurate estimates of groundwater velocity. Calibration to tritium concentrations was used to estimate effective porosity and improve correlation between source area changes, age changes, and measured dissolved solids trends. Uncertainty in the model is due in part to spatial and temporal variations in tracer inputs, estimated tracer transport parameters, and in pumping stresses at sampling points. For tracers such as tritium, the presence of two-limbed input curves can be problematic because a single concentration can be associated with multiple disparate travel times. These shortcomings can be ameliorated by adding hydrologic and geologic detail to the model and by adding additional calibration data. However, the Salt Lake Valley model is useful even without such small-scale detail.

Multimodel analysis of anisotropic diffusive tracer‐gas transport in a deep arid unsaturated zone

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Lattice-Boltzmann simulation of coalescence-driven island coarsening

A two-dimensional lattice-Boltzmann model (LBM) with fluid-fluid interactions was used to simulate first-order phase separation in a thin fluid film. The intermediate asymptotic time dependence of the mean island size, island number concentration, and polydispersity were determined and compared with the predictions of the distribution-kinetics model. The comparison revealed that the combined effects of growth, coalescence, and Ostwald ripening control the phase transition process in the LBM simulations. However, the overall process is dominated by coalescence, which is independent of island mass. As the phase transition advances, the mean island size increases, the number of islands decrease, and the polydispersity approaches unity, which conforms to the predictions of the distribution-kinetics model. The effects of the domain size on the intermediate asymptotic island size distribution, scaling form of the island size distribution, and the crossover to the long-term asymptotic behavior were elucidated.

Bounded fractional diffusion in geological media: Definition and Lagrangian approximation

Spatiotemporal Fractional-Derivative Models (FDMs) have been increasingly used to simulate non-Fickian diffusion, but methods have not been available to define boundary conditions for FDMs in bounded domains. This study defines boundary conditions and then develops a Lagrangian solver to approximate bounded, one-dimensional fractional diffusion. Both the zero-value and non-zero-value Dirichlet, Neumann, and mixed Robin boundary conditions are defined, where the sign of Riemann-Liouville fractional derivative (capturing non-zero-value spatial-nonlocal boundary conditions with directional super-diffusion) remains consistent with the sign of the fractional-diffusive flux term in the FDMs. New Lagrangian schemes are then proposed to track solute particles moving in bounded domains, where the solutions are checked against analytical or Eularian solutions available for simplified FDMs. Numerical experiments show that the particle-tracking algorithm for non-Fickian diffusion differs from Fickian diffusion in relocating the particle position around the reflective boundary, likely due to the nonlocal and non-symmetric fractional diffusion. For a non-zero-value Neumann or Robin boundary, a source cell with a reflective face can be applied to define the release rate of random-walking particles at the specified flux boundary. Mathematical definitions of physically meaningful nonlocal boundaries combined with bounded Lagrangian solvers in this study may provide the only viable techniques at present to quantify the impact of boundaries on anomalous diffusion, expanding the applicability of FDMs from infinite domains to those with any size and boundary conditions. This article is protected by copyright. All rights reserved.