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Abstract: Terrestrial groundwater travels through subterranean estuaries before reaching the sea. Groundwater‐derived nutrients drive coastal water quality, primary production, and eutrophication. We determined how dissolved inorganic nitrogen (DIN), dissolved inorganic phosphorus (DIP), and dissolved organic nitrogen (DON) are transformed within subterranean estuaries and estimated submarine groundwater discharge (SGD) nutrient loads compiling > 10,000 groundwater samples from 216 sites worldwide. Nutrients exhibited complex, nonconservative behavior in subterranean estuaries. Fresh groundwater DIN and DIP are usually produced, and DON is consumed during transport. Median total SGD (saline and fresh) fluxes globally were 5.4, 2.6, and 0.18 Tmol yr−1 for DIN, DON, and DIP, respectively. Despite large natural variability, total SGD fluxes likely exceed global riverine nutrient export. Fresh SGD is a small source of new nutrients, but saline SGD is an important source of mostly recycled nutrients. Nutrients exported via SGD via subterranean estuaries are critical to coastal biogeochemistry and a significant nutrient source to the oceans.

Driven by the need for integrated management of groundwater (GW) and surface water (SW), quantification of GW–SW interactions and associated contaminant transport has become increasingly important. This is due to their substantial impact on water quantity and quality. In this review, we provide an overview of the methods developed over the past several decades to investigate GW–SW interactions. These methods include geophysical, hydrometric, and tracer techniques, as well as various modeling approaches. Different methods reveal valuable information on GW–SW interactions at different scales with their respective advantages and limitations. Interpreting data from these techniques can be challenging due to factors like scale effects, heterogeneous hydrogeological conditions, sediment variability, and complex spatiotemporal connections between GW and SW. To facilitate the selection of appropriate methods for specific sites, we discuss the strengths, weaknesses, and challenges of each technique, and we offer perspectives on knowledge gaps in the current science. [ABSTRACT FROM AUTHOR]

Riverbed microbial communities play an oversized role in many watershed ecosystem functions, including the processing of organic carbon, cycling of nitrogen, and alterations to metal mobility. The structure and activity of microbial assemblages depend in part on geochemical conditions set by river-groundwater exchange or hyporheic exchange. To assess how seasonal changes in river-groundwater mixing affect these populations in a snowmelt-dominated fluvial system, vertical sediment and pore water profiles were sampled at three time points at one location in the hyporheic zone of the Colorado River and analyzed by using geochemical measurements, 16S rRNA gene sequencing, and ecological modeling. Oxic river water penetrated deepest into the subsurface during peak river discharge, while under base flow conditions, anoxic groundwater dominated shallower depths. Over a 70 cm thick interval, riverbed sediments were therefore exposed to seasonally fluctuating redox conditions and hosted microbial populations statistically different from those at both shallower and deeper locations. Additionally, microbial populations within this zone were shown to be the most dynamic across sampling time points, underlining the critical role that hyporheic mixing plays in constraining microbial abundances. Given such mixing effects, we anticipate that future changes in river discharge in mountainous, semiarid western U.S. watersheds may affect microbial community structure and function in riverbed environments, with potential implications for biogeochemical processes in riparian regions.

Understanding fate and transport processes for per‐ and poly‐fluoroalkyl substances (PFAS) is critical for managing impacted sites. “PFAS Salting Out” in groundwater, defined herein, is an understudied process where PFAS in fresh groundwater mixes with saline groundwater near marine shorelines, which increases sorption of PFAS to aquifer solids. While sorption reduces PFAS mass discharge to marine surface water, the fraction that sorbs to beach sediments may be mobilized under future salinity changes. The objective of this study was to conceptually explore the potential for PFAS Salting Out in sandy beach environments and to perform a preliminary broad‐scale characterization of sandy shoreline areas in the continental U.S. While no site‐specific PFAS data were collected, our conceptual approach involved developing a multivariate regression model that assessed how tidal amplitude and freshwater submarine groundwater discharge affect the mixing of fresh and saline groundwater in sandy coastal aquifers. We then applied this model to 143 U.S. shoreline areas with sandy beaches (21% of total beaches in the USA), indirectly mapping potential salinity increases in shallow freshwater PFAS plumes as low (<10 ppt), medium (10–20 ppt), or high (>20 ppt) along groundwater flow paths before reaching the ocean. Higher potential salinity increases were observed in West Coast bays and the North Atlantic coastline, due to the combination of moderate to large tides and large fresh groundwater discharge rates, while lower increases occurred along the Gulf of Mexico and the southern Florida Atlantic coast. The salinity increases were used to estimate potential perfluorooctane sulfonic acid (PFOS) sorption in groundwater due to salting out processes. Low‐category shorelines may see a 1‐ to 2.5‐fold increase in sorption of PFOS, medium‐category a 2.0‐ to 6.4‐fold increase, and high‐category a 3.8‐ to 25‐fold increase in PFOS sorption. The analysis presented provides a first critical step in developing a large‐scale approach to classify the PFAS Salting Out potential along shorelines and the limitations of the approach adopted highlights important areas for further research. [ABSTRACT FROM AUTHOR]

The flow of fresh groundwater to the ocean through the coast (fresh submarine groundwater discharge or fresh SGD) plays an important role in global biogeochemical cycles and coastal water quality. In addition to delivering dissolved elements from land to sea, fresh SGD forms a natural barrier against salinization of coastal aquifers. Here we estimate groundwater discharge rates through the near‐global coast (60°N to 60°S) at high resolution using a water budget approach. We find that tropical coasts export more than 56% of all fresh SGD, while midlatitude arid regions export only 10%. Fresh SGD rates from tectonically active margins (coastlines along tectonic plate boundaries) are also significantly greater than passive margins, where most field studies have been focused. Active margins combine rapid uplift and weathering with high rates of fresh SGD and may therefore host exceptionally large groundwater‐borne solute fluxes to the coast. Plain Language Summary: Fresh groundwater flows from land to sea through coastal rocks and sediment. While the amount of groundwater flow is small compared with rivers, it plays an important role in carrying dissolved chemicals like nutrients to sea, and it helps protect aquifers against salinization. We estimate groundwater flow through the near‐global coast. Tropical regions have more groundwater flow, while dry midlatitudes have less. Dry midlatitude regions are therefore more vulnerable to salinization, which is problematic because these regions are also more likely to depend on groundwater to meet their water needs. Additionally, mountainous coastlines along tectonic plate boundaries have relatively large rates of groundwater discharge and may be associated with higher dissolved chemical fluxes to the coast. Key Points: Almost half of fresh submarine groundwater discharge (SGD) enters the ocean at wet equatorial regionsHigh‐relief, tectonically active margins have higher ratios of fresh SGD to river dischargeTotal annual volume of fresh SGD is ~489 km3/year, or ~1% of river discharge [ABSTRACT FROM AUTHOR]

Rivers and their hyporheic zones play an important role in nutrient cycling. The fate of dissolved inorganic nitrogen is governed by reactions that occur in the water column and streambed sediments. Sediments are heterogeneous both in term of physical (e.g., hydraulic conductivity) and chemical (e.g., organic carbon content) properties, which influence water residence times and biogeochemical reactions. Yet few modeling studies have explored the effects of both physical and chemical heterogeneity on nutrient transport in the hyporheic zone. In this study, we simulated hyporheic exchange in physically and chemically heterogeneous sediments with binary distributions of sand and silt in a low‐gradient meandering river. We analyzed the impact of different silt/sand patterns on dissolved organic carbon, oxygen, nitrate, and ammonium. Our results show that streambeds with a higher volume proportion of silt exhibit lower hyporheic exchange rates but more efficient nitrate removal along flow paths compared to predominantly sandy streambeds. The implication is that hyporheic zones with a mixture of inorganic sands and organic silts have a high capacity to remove nitrate, despite their moderate permeabilities. Plain Language Summary: With the advent of intensive cultivation and livestock farms, nutrient contamination has increased in streams. Microbial communities in streambeds reduce nitrate, effectively removing it from streams. However, quantifying this removal is difficult because it is influenced by many spatially variable factors, among which sediment type plays an important role. Streambeds can contain both sandy and silty sediments distributed in complex patterns. The present study employs computer simulations to analyze how nitrate is removed in a mixture of different streambed sediments. Key Points: Role of physical and chemical heterogeneity of streambed sediments on denitrification is numerically investigatedSilt sediments promote denitrification since they experience longer residence times and are source of dissolved organic carbonStreambeds with mixture of sand and silt have high capacity to remove nitrate despite moderate permeabilities [ABSTRACT FROM AUTHOR]

Changes in streamflow and water table elevation influence oxidation–reduction (redox) conditions near river–aquifer interfaces, with potentially important consequences for solute fluxes and biogeochemical reaction rates. Although continuous measurements of groundwater chemistry can be arduous, in situ sensors reveal chemistry dynamics across a wide range of timescales. We monitored redox potential in an aquifer adjacent to a tidal river and used spectral and wavelet analyses to link redox responses to hydrologic perturbations within the bed and banks. Storms perturb redox potential within both the bed and banks over timescales of days to weeks. Tides drive semidiurnal oscillations in redox potential within the streambed that are absent in the banks. Wavelet analysis shows that tidal redox oscillations in the bed are greatest during late summer (wavelet magnitude of 5.62 mV) when river stage fluctuations are on the order of 70 cm and microbial activity is relatively high. Tidal redox oscillations diminish during the winter (wavelet magnitude of 2.73 mV) when river stage fluctuations are smaller (on the order of 50 cm) and microbial activity is presumably low. Although traditional geochemical observations are often limited to summer baseflow conditions, in situ redox sensing provides continuous, high‐resolution chemical characterization of the subsurface, revealing transport and reaction processes across spatial and temporal scales in aquifers. [ABSTRACT FROM AUTHOR]

In coastal rivers, tides can propagate for tens to hundreds of kilometres inland beyond the saltwater line. Yet the influence of tides on river-aquifer connectivity and solute transport in tidal freshwater zones (TFZs) is largely unknown. We estimate that along the TFZ of White Clay Creek (Delaware, USA), 11% of river water exchanges through tidal bank storage zones. Additional hyporheic processes such as flow through bedforms likely contribute even more exchange. The turnover length associated with tidal bank storage is 150 km, on the order of turnover lengths for all hyporheic exchange processes in non-tidal rivers of similar size. Based on measurements at a transect of piezometers located 17 km from the coast, tides exchange 0.36 m3 of water across the banks and 0.86 m3 across the bed per unit river length. Exchange fluxes range from −1.66 to 2.26 m day−1 across the bank and −0.84 to 1.88 m day−1 across the bed. During rising tide, river water infiltrates into the riparian aquifer, and the downstream transport rate in the channel is low. During falling tide, stored groundwater is released to the river, and the downstream transport rate in the channel increases. Tidal bank storage zones may remove nutrients or other contaminants from river water and attenuate nutrient loads to coasts. Alternating expansion and contraction of aerobic zones in the riparian aquifer likely influence contaminant removal along flow paths. A clear need exists to understand contaminant removal and other ecosystem services in TFZs and adopt best management practices to promote these ecosystem services. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]