Abstract. The rate and mechanism of nitrate removal along and between groundwater flow paths were investigated using a series of well nests screened in an unconfined sand and gravel aquifer. Intensive agricultural activity in this area has resulted in nitrate concentrations in groundwater often exceeding drinking water standards. Both the extent and rate of denitrification varied depending on the groundwater flow path. While little or no denitrification occurred in much of the upland portions of the aquifer, a gradual redox gradient is observed as aerobic upland groundwater moves deeper in the aquifer. In contrast, a sharp shallow redox gradient is observed adjacent to a third-order stream as aerobic groundwater enters reduced sediments. An essentially complete loss of nitrate concurrent with increases in excess N 2 provide evidence that denitrification occurs as groundwater enters this zone. Electron and mass balance calculations suggest that iron sulfide (e.g., pyrite) oxidation is the primary source of electrons for denitrification. Denitrification rate estimates were based on mass balance calculations using nitrate and excess N 2 coupled with groundwater travel times. Travel times were determined using a groundwater flow model and were constrained by chlorofluorocarbon-based age dates. Denitrification rates were found to vary considerably between the two areas where denitrification occurs. Denitrification rates in the deep, upland portions of the aquifer were found to range from <0.01 to 0.14 mM of N per year; rates at the redoxcline along the shallow flow path range from 1.0 to 2.7 mM of N per year. Potential denitrification rates in groundwater adjacent to the stream may be much faster, with rates up to 140 mM per year based on an in situ experiment conducted in this zone.

[1] Seepage at the sediment-water interface in several lakes, a large river, and an estuary exhibits substantial temporal variability when measured with temporal resolution of 1 min or less. Already substantial seepage rates changed by 7% and 16% in response to relatively small rain events at two lakes in the northeastern USA, but did not change in response to two larger rain events at a lake in Minnesota. However, seepage at that same Minnesota lake changed by 10% each day in response to withdrawals from evapotranspiration. Seepage increased by more than an order of magnitude when a seiche occurred in the Great Salt Lake, Utah. Near the head of a fjord in Puget Sound, Washington, seepage in the intertidal zone varied greatly from À115 to þ217 cm d À1 in response to advancing and retreating tides when the time-averaged seepage was upward at þ43 cm d À1. At all locations, seepage variability increased by one to several orders of magnitude in response to wind and associated waves. Net seepage remained unchanged by wind unless wind also induced a lake seiche. These examples from sites distributed across a broad geographic region indicate that temporal variability in seepage in response to common hydrological events is much larger than previously realized. At most locations, seepage responded within minutes to changes in surface-water stage and within minutes to hours to groundwater recharge associated with rainfall. Likely implications of this dynamism include effects on water residence time, geochemical transformations, and ecological conditions at and near the sediment-water interface.Citation: Rosenberry, D. O., R. W. Sheibley, S. E. Cox, F. W. Simonds, and D. L. Naftz (2013), Temporal variability of exchange between groundwater and surface water based on high-frequency direct measurements of seepage at the sediment-water interface, Water Resour.

Reservoir sediments from Lake Roosevelt (WA, USA) that were contaminated with smelter waste discharged into the Columbia River (BC, Canada) were examined using three measures of elemental release reflecting varying degrees of physical mixing and time scales. Aqueous concentrations of Cd, Cu, Pb, and Zn in the interstitial water of reservoir sediments, in the gently stirred overlying waters of incubated sediment cores, and in supernatants of aggressively tumbled slurries of reservoir sediments generally were higher than the concentrations from a reference site. When compared to chronic water-quality criteria, all three measures of release suggest that slag-contaminated sediments near the U.S.-Canadian border are potentially toxic as a result of Cu release and Pb release in two of the three measures. All three measures of Cd release suggest potential toxicity for one site farther down the reservoir, probably contaminated as a result of transport and adsorption of Cd from smelter liquid waste. Releases of Zn and As did not appear to be potentially toxic. Carbonate geochemistry indirectly affects the potential toxicity by increasing water hardness.

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Inset 1: Retrieval of 40 centimeter sediment core including lacustrine and pre-reservoir soil sediments near Marcus, Washington.