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DGT (diffusive gradients in thin films) was used to measure the distribution and rates of exchange of Zn, Cd, and Ni between solid phase and solution in five different soils. Soil texture ranged from sandy loam to clay, pH ranged from 4.9 to 7.1, and organic carbon content ranged from 0.8% to 5.8%. DGT devices continuously remove metal to a Chelex gel layer after passage through a well-defined diffusion layer. The magnitude of the induced remobilization flux from the solid phase is related to the pool size of labile metal and the exchange kinetics between dissolved and sorbed metal. DGT devices were deployed over a series of times (4 h to 3 weeks), and the DIFS model (DGT induced fluxes in soils) was used to derive distribution coefficients for labile metal (Kdl) and the rate at which the soil system can supply metal from solid phase to solution, expressed as a response time. Response times for Zn and Cd were short generally (<8 min). They were so short in some soils (<1 min) that no distinction could be made between supply of metal being controlled by diffusion or the rate of release. Generally longer response times for Ni (5-20 min) were consistent with its slow desorption. The major factor influencing Kdl for Zn and Cd was pH, but association with humic substances in the solid phase also appeared to be important. The systematic decline, with increasing pH, in both the pool size of Ni available to the DGT device and the rate constant for its release is consistent with a part of the soil Ni pool being unavailable within a time scale of 1-20 min. This kinetic limitation is likely to limit the availability of Ni to plants.

Abstract:We examined the influence of river stage on subsurface hydrology and pore water chemistry within the hyporheic zone of a groundwater-fed river during the summer baseflow period of 2011. We found river stage and geomorphologic environment to control chemical patterns in the hyporheic zone. At a high river stage, the flux of upwelling water in the shallow sediments (>20 cm) decreased at sample sites in the upper section of our study reach and increased substantially at sites in the lower section. This differential response is attributed to the contrasting geomorphology of these subreaches that affects the rate of the rise and fall of a river stage relative to the subsurface head. At sites where streamward vertical flux decreased, concentration profiles of a conservative environmental tracer suggest surface water infiltration into the riverbed below depths recorded at a low river stage. An increase in vertical flux at sites in the lower subreach is attributed to the movement of lateral subsurface waters originating from the adjacent floodplain. This lateral-moving water preserved or decreased the vertical extent of the hyporheic mixing zone observed at a low river stage. Downwelling surface water appeared to be responsible for elevated dissolved organic carbon (DOC) and manganese (Mn) concentrations in shallow sediments (0-20 cm); however, lateral subsurface flows were probably important for elevated concentrations of these solutes at deeper levels. Results suggest that DOC delivered to hyporheic sediments during a high river stage from surface water and lateral subsurface sources could enhance heterotrophic microbial activities.

Abstract:The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse-scale (5-10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine-scale (<1 cm) biogeochemical patterns, especially in near-surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO 3 À . In this study, we utilised diffusive equilibrium in thin-films samplers to capture high resolution (cm-scale) vertical concentration profiles of NO 3 À , SO 4 2À , Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub-reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin-films samplers indicate considerable cmscale variability in NO 3 À (4.4 ± 2.9 mg N/L), SO 4 2À (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface-subsurface water mixing in the shallow sediments of our sub-reach under baseflow conditions. The significance of this is that upwelling NO 3 À -rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub-reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper-seated groundwater fluxes and hydro-stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub-reach.