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 N2 from denitrification increases with age. Stable isotopes and excess N2 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 μmol N L−1d−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.

[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 O 2 reduction rate, denitrification rate, O 2 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 O 2 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.Citation: Green, C. T., J. K. Böhlke, B. A. Bekins, and S. P. Phillips (2010), Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer, Water Resour. Res., 46, W08525,

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[1] The impact of agricultural chemicals on groundwater quality depends on the interactions of biogeochemical and hydrologic factors. To identify key processes affecting distribution of agricultural nitrate in groundwater, a parsimonious transport model was applied at 14 sites across the U.S. À fronts at sites with denitrification rates <0.25 mg-N L À1 yr À1 . The steady state depth of NO 3 À depended to a similar degree on application rate, leaching fraction, recharge, and NO 3 À and O 2 reaction rates. Steady state total mass in each aquifer depended primarily on the N application rate. In addition to managing application rates at land surface, efficient water use may reduce the depth and mass of N in groundwater because lower recharge was associated with lower N fraction leached. Management actions to reduce N leaching could be targeted over aquifers with high-recharge and low-denitrification rates.

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.