Marine ecosystems are sensitive to inputs of chemicals from submarine groundwater discharge. Tidally influenced saltwater‐freshwater mixing zones in beach aquifers can host biogeochemical transformations that modify chemical loads prior to discharge. A numerical variable‐density groundwater flow and reactive transport model was used to evaluate the physical controls on reactivity for mixing‐dependent and mixing‐independent reactions in beach aquifers, represented as denitrification and sulfate reduction, respectively. A sensitivity analysis was performed across typical values of tidal amplitude, hydraulic conductivity, terrestrial freshwater flux, beach slope, dispersivity, and DOC reactivity. For the model setup and conditions tested, the simulations demonstrate that denitrification can remove up to 100% of terrestrially derived nitrate, and sulfate reduction can transform up to 8% of seawater‐derived sulfate prior to discharge. Tidally driven mixing between saltwater and freshwater promotes denitrification along the boundary of the intertidal saltwater circulation cell in pore water between 1 and 10 ppt. The denitrification zone occupies on average 49% of the mixing zone. Denitrification rates are highest on the landward side of the circulation cell and decrease along circulating flow paths. Reactivity for mixing‐dependent reactions increases with the size of the mixing zone and solute supply, while mixing‐independent reactivity is controlled primarily by solute supply. The results provide insights into the types of beaches most efficient in altering fluxes of chemicals prior to discharge and could be built upon to help engineer beaches to enhance reactivity. The findings have implications for management to protect coastal ecosystems and the estimation of chemical fluxes to the ocean.

Beach aquifers host a dynamic and reactive mixing zone between fresh and saline groundwater of contrasting origin and composition. Seawater, driven up the beachface by waves and tides, infiltrates into the aquifer and meets the seaward‐discharging fresh groundwater, creating and maintaining a reactive intertidal circulation cell. Within the cell, land‐derived nutrients delivered by fresh groundwater are transformed or attenuated. We investigated this process by collecting pore water samples from multilevel wells along a shore‐perpendicular transect on a beach near Cape Henlopen, Delaware, and analyzing solute and particulate concentrations. Pore water incubation experiments were conducted to determine rates of oxygen consumption and nitrogen gas production. A numerical model was employed to support field and laboratory interpretations. Results showed that chemically sensitive parameters such as pH and ORP diverged from salinity distribution patterns, indicating biogeochemical reactivity within the circulation cell. The highest respiration rates were found in the landward freshwater‐saltwater mixing zone, supported by high dissolved inorganic carbon. Chlorophyll a, a proxy for phytoplankton, and particulate carbon did not co‐occur with the highest respiration rates but were heterogeneously distributed in deeper and hypoxic areas of the cell. The highest rates of N₂ production were also found in the mixing zone coinciding with elevated O₂ consumption rates but closer to the lower discharge point. Model results were consistent with these observations, showing heightened denitrification in the mixing zone. The results of this work emphasize the relationship between the physical flow processes of the circulation cell and its biogeochemical reactivity and highlight the environmental significance of sandy beaches.

The mixing between fresh and saline groundwater in beach aquifers promotes biogeochemical transformations that affect nutrient fluxes to the coastal ocean. We performed variable-density groundwater flow and reactive transport simulations with geostatistical representations of sedimentary structure to understand the influence of heterogeneity on groundwater dynamics and denitrification in intertidal mixing zones. Ensemble-averaged simulation results show that heterogeneity can enhance mixing between fresh and saline groundwater and increase residence time, resulting in up to 80% higher nitrate removal relative to equivalent effective homogeneous aquifer sediment. Denitrification hotspots form in high permeability structures where DOC and nitrate are readily supplied by convergent flow. The results provide a physical explanation for the formation of denitrification hotspots observed in beach aquifers and illustrate for the first time the influence of sediment heterogeneity on rates and spatial patterns of biogeochemical processes in intertidal aquifers that are critical mediators of land-sea solute fluxes along world coastlines.

The intertidal zone of beach aquifers hosts biogeochemical transformations of terrestrially derived nutrients that are mediated by reactive organic carbon from seawater infiltration. While dissolved organic carbon is often assumed the sole reactive organic carbon component, advected and entrapped particulate organic carbon (POC) is also capable of supporting chemical reactions. Retarded advection of POC relative to groundwater flow forms pools of reactive carbon within beach sediments that support biogeochemical reactions as dissolved solutes move across them due to transient groundwater flow. In this work, we simulate the contribution of POC to beach reactions and identify parameters that control its relative contribution using a groundwater flow model (SEAWAT) and reactive transport model (PHT3D). Results show transient contributions of POC to denitrification, as the spatial extent of the saline circulation cell varies over time due to changing hydrologic factors. A decrease in POC retardation and an increase in tidal amplitude during POC deposition resulted in POC expansion, which increased the relative contributions of POC to beach reactivity. Decreased hydraulic conductivity and increased tidal amplitude post‐deposition decreased the utilization of POC for denitrification by allowing the oxic, saline water to completely encompass the pool of POC. Results highlight that POC is an intermittently utilized source of carbon that displays complex spatial relationships with groundwater flow conditions and overall beach biogeochemistry. This work demonstrates that POC may be a periodically important but overlooked contributor to biogeochemical reactions in carbon‐poor beach aquifers.

Future increases in the frequency of tidal flooding due to sea level rise (SLR) are likely to affect pore water salinities in coastal aquifers. In this study, we investigate the impact of increased tidal flooding frequency on salinity and flow dynamics in coastal aquifers using numerical variable‐density variably‐saturated groundwater flow and salt transport models. Short (sub‐daily) and long (decadal) period tides are combined with SLR projections to drive continuous 80‐year models of flow and salt transport. Results show that encroaching intertidal zones lead to both periodic and long‐term vertical salinization of the upper aquifer. Salinization of the upper aquifer due to tidal flooding forces the lower interface seaward, even under SLR. System dynamics are controlled by the interplay between SLR and long period tidal forcing associated with perigean spring tides and the 18.6‐year lunar nodal cycle. Periodic tidal flooding substantially enhances intertidal saltwater‐freshwater mixing, resulting in a 6‐ to 10‐fold expansion of the intertidal saltwater‐freshwater mixing area across SLR scenarios. The onset of the expansion coincides with extreme high water levels resulting from lunar nodal cycling of tidal constituent amplitudes. The findings are the first to demonstrate the combined effects of gradual SLR and short and long period tides on aquifer salinity distributions, and reveal competing influences of SLR on saltwater intrusion. The results are likely to have important implications for coastal ocean chemical fluxes and groundwater resources as tidal flooding intensifies worldwide.

Coastal aquifers are host to a range of biogeochemical reactions that alter groundwater‐derived nutrient, metal, and other chemical loads to coastal ecosystems. Temperature is a strong control on microbially mediated reactions; thus, chemical reactivity in coastal aquifers may vary spatially and temporally with changes to groundwater temperature. In this study, we investigated the influence of global groundwater and sea surface temperature controls and seasonal temperature variability on biogeochemical processing in coastal aquifers using variable‐density groundwater flow, heat transport, and reactive transport models. The coupled models showed that nitrate removal efficiency in coastal aquifers increased from 5% to 88% as fresh groundwater temperature increased from 5°C to 35°C, while ocean temperature had a negligible effect on removal efficiency. Transient simulations based on monthly groundwater and ocean temperature measurements showed that denitrification and ammonification hotspots migrated seaward seasonally within warm fresh groundwater masses. The reaction hotspots were separated by colder groundwater emplaced during winter months. The reaction hotspots and nitrate plumes oscillated vertically along horizontal flow paths due to buoyancy effects between warm and cold groundwater. Comparison between transient and temperature‐equivalent steady‐state models suggests that steady‐state models adequately capture mean annual NO₃⁻ removal, but neglect local reactive transience and changes to plume geometry. The sensitivity analysis provides a first‐order estimate of the reactive potential of coastal aquifers considering globally diverse thermal regimes. The findings have implications for regional‐scale estimates of groundwater nutrient fluxes and for predicting coastal aquifer reactivity in a warming climate.