Catchment-scale quantification of hyporheic denitrification using an isotopic and solute flux approach.

A dual-isotope and solute flux mass-balance was used to elucidate the processes that lead to attenuation of nitrogen contamination in an agriculturally impacted river. The River Wensum drains a lowland catchment with an area of 570 km² in East Anglia, eastern England. Analysis of nitrate concentration, δ¹5N(NO3) and δ¹8O(NO3) of samples from the River Wensum collected from upstream locations to the catchment outlet through all seasons and flow conditions showed a consistent pattern of increasing isotope values with decreasing nitrate concentrations downstream. δ¹5N(NO3) and δ¹8O(NO3) of catchment surface water and groundwater samples revealed a dominant influence from microbially cycled and nitrified source-nitrogen, which results in high nitrate concentrations in Chalk groundwater and upstream in the River Wensum. Denitrification of Chalk groundwater-baseflow in the hyporheic zone results in the downstream trend observed in the river. Hyporheic denitrification is estimated to remove 931 kg/day of nitrate-nitrogen by the catchment outlet, representing 31% of the potential riverine nitrate load. The use of dual-isotope and solute flux modeling at the catchment scale is a novel application to quantify denitrification within the river valley, demonstrating the importance of hyporheic zone processes in attenuating the impacts of anthropogenic contamination of hydrologic systems.

Noble gas excess air applied to distinguish groundwater recharge conditions.

The application of geochemical tracers in groundwater studies can provide valuable insights into the rates and sources of groundwater recharge, residence times, and flow dynamics that are of significant value in the management of this important natural resource. This paper demonstrates the application of noble gas excess air to distinguish groundwater bodies with different recharge histories in a layered sandstone aquifer system in the east of England. The sampled groundwaters are all supersaturated with respect to neon, indicating the presence of excess air. The lowest excess air concentrations occur where the aquifer is unconfined (deltaNe, the proportion of neon in excess of saturation, = 12-26%) and recharge occurs directly to the outcrop. Groundwater in the confined part of the aquifer can be divided into two hydrochemical types based upon the dissolved ion chemistry: Type 1 groundwaters contain more excess air (deltaNe = 115-120%) than Type 2(deltaNe = 22-62%). The difference in excess air concentrations confirms that groundwater enters the confined aquifer along two discrete pathways. Furthermore, excess neon concentrations predicted from the magnitude of annual water table fluctuation observed in the different recharge areas are in good agreement with those measured in the corresponding groundwaters. We therefore recommend that excess air may be usefully employed as a direct indicator of the volume of long-term net annual groundwater recharge.

A dual isotope approach to identify denitrification in groundwater at a river-bank infiltration site.

The identification of denitrification in the Torgau sand and gravel aquifer, Germany, was carried out by a dual isotope method of measuring both the delta 15N and delta 18O in NO3-. Samples were prepared by an anion exchange resin method (Silva et al., J. Hydrol. 228 (2000) 22) with a modification to the AgNO3-drying process from a freeze-drying to an oven-drying method. The occurrence of denitrification in the aquifer was confirmed by comparing the reduction of dissolved oxygen, dissolved organic carbon and NO3- concentrations with the dual isotope signatures. High nitrate concentrations were associated with low delta 15N and delta 18O values, and vice versa. The denitrification accords with a Rayleigh equation with calculated enrichment factors of epsilon = -13.62@1000 for delta 15N and epsilon = -9.80@1000 for delta 18O. The slope of the straight-line relationship between the delta 15N and delta 18O data demonstrated that the enrichment of the heavy nitrogen isotope was higher by a factor of 1.3 compared with the heavy oxygen isotope. It is concluded that the identification of this factor is a useful means for confirming denitrification in future groundwater studies.