Storms dominate solute export budgets from catchments and drive hydrogeochemical changes in the near-stream environment. We captured near-stream hydrogeochemical dynamics during an intense storm (Hurricane Sandy, October 2012), by instrumenting a riparian-hyporheic zone transect of White Clay Creek in the Christina River Basin Critical Zone Observatory with pressure transducers, redox probes, and pore water samplers. In the floodplain aquifer, preferential vertical flow paths such as macropores facilitated rapid infiltration early in the storm. Water table rose quickly and promoted continuous groundwater discharge to the stream. Floodplain-hillslope topography controlled poststorm aquifer drainage rates, as the broad, western floodplain aquifer drained more slowly than the narrow, eastern floodplain aquifer adjacent to a steep hillslope. These changes in groundwater flow drove heterogeneous geochemical responses in the floodplain aquifer and hyporheic zone. Vertical infiltration in the floodplain and hyporheic exchange in the streambed increased DOC and oxygen delivery to microbially active sediments, which may have enhanced respiration. Resulting geochemical perturbations persisted from days to weeks after the storm. Our observations suggest that groundwater-borne solute delivery to streams during storms depends on unique interactions of vertical infiltration along preferential pathways, perturbations to groundwater geochemistry, and topographically controlled drainage rates.

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

Shallow stratigraphic features, such as infilled paleovalleys, modify fresh groundwater discharge to coastal waters and fluxes of saltwater and nutrients across the sediment-water interface. We quantify the spatial distribution of shallow surface water-groundwater exchange and nitrogen fluxes near a paleovalley in Indian River Bay, Delaware, using a hand resistivity probe, conventional seepage meters, and pore-water samples. In the interfluve (region outside the paleovalley) most nitrate-rich fresh groundwater discharges rapidly near the coast with little mixing of saline pore water, and nitrogen transport is largely conservative. In the peat-filled paleovalley, fresh groundwater discharge is negligible, and saltwater exchange is deep (,1 m). Long pore-water residence times and abundant sulfate and organic matter promote sulfate reduction and ammonium production in shallow sediment. Reducing, iron-rich fresh groundwater beneath paleovalley peat discharges diffusely around paleovalley margins offshore. In this zone of diffuse fresh groundwater discharge, saltwater exchange and dispersion are enhanced, ammonium is produced in shallow sediments, and fluxes of ammonium to surface water are large. By modifying patterns of groundwater discharge and the nature of saltwater exchange in shallow sediments, paleovalleys and other stratigraphic features influence the geochemistry of discharging groundwater. Redox reactions near the sediment-water interface affect rates and patterns of geochemical fluxes to coastal surface waters. For example, at this site, more than 99% of the groundwater-borne nitrate flux to the Delaware Inland Bays occurs within the interfluve portion of the coastline, and more than 50% of the ammonium flux occurs at the paleovalley margin.

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