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.

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[1] In [2003][2004][2005], systematic studies in four contrasting hydrogeologic settings were undertaken to improve understanding of source and transport controls on nitrate movement to public supply wells (PSW) in principal aquifers of the United States. Chemical, isotopic, and age tracer data show that agricultural fertilizers and urban septic leachate were the primary sources of large nitrate concentrations in PSW capture zones at Modesto, California (Central Valley aquifer system) and York, Nebraska (High Plains aquifer). Urban septic leachate and fertilizer (possibly nonfarm) were the primary sources of large nitrate concentrations in PSW capture zones at Woodbury, Connecticut (glacial aquifer system), and Tampa, Florida (Floridan aquifer system), respectively. Nitrate fluxes to the water table were larger in agricultural settings than urban settings, indicating that it would be beneficial to reduce PSW capture zone areas in agricultural regions. Mixing calculations indicate that about 50 to 85% of the nitrate in water from the PSW could be from those modern anthropogenic sources, with the remainder coming from sources in old (>50 years) recharge or sources in young recharge in undisturbed settings such as forests. Excess N 2 concentrations and age tracers showed that denitrification at Modesto occurred gradually (first-order rate constant of 0.02/a) in a thick reaction zone following a $30-year lag time after recharge. Denitrification generally was not an important nitrate sink at Woodbury. At York and Tampa, denitrification occurred rapidly (0.5 to 6/a) in thin reaction zones in fine-grained sediments that separated the anoxic PSW producing zones from overlying oxic, highnitrate ground water. Particle tracking showed that a major pathway by which anthropogenic nitrate reached the York and Tampa PSW was by movement through long well screens crossing multiple hydrogeologic units (York) and by movement through karst features (Tampa), processes which reduced ground water residence times in the denitrifying zones. These results illustrate how PSW vulnerability to nitrate contamination depends on complex variations and interactions between contaminant sources, reaction rates, transit times, mixing, and perturbation of ground water flow in contrasting hydrogeologic settings.

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Groundwater age is an important indicator of groundwater susceptibility to anthropogenic contamination and a key input to statistical models for forecasting water quality. Numerical models can provide estimates of groundwater age, enabling interpretation of measured age tracers. However, to extend to national‐scale groundwater systems where numerical models are not routinely available, a more efficient metamodeling approach can provide a less precise but widely applicable estimate of groundwater age, trained to make forecasts based on predictor variables that can be measured independent of numerical models. We trained gradient‐boosted regression tree statistical metamodels to MODFLOW/MODPATH‐derived groundwater age estimates in five inset models in the Lake Michigan Basin, USA. Using high‐throughput computing, we explored an exhaustive range of tuning parameters and tested metamodels through cross validation, a 20% holdout, and a round robin approach among the five inset models withholding each inset model from training and testing on the held‐out inset model. Forecast skill—measured by Nash Sutcliffe efficiency—was high for age‐related responses in the 20% hold‐out case (ranging from 0.73 to 0.84). The round robin analysis provided the opportunity to explore extending to unmodeled areas and a greater range of skill indicated the need to evaluate when it is appropriate to apply a metamodel from one region to another. We further explored the ramifications of metamodel simplification achieved through removing predictor variables based on their estimated importance. We found that similar metamodel performance was achievable with a fraction of the candidate set of predictor variables with well construction variables being most important.

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