Subterranean Estuary Research Articles

Global Research Trends and Hotspots on Submarine Groundwater Discharge (SGD): A Bibliometric Analysis.

Submarine groundwater discharge (SGD), a major component of the hydrological cycle, has significant impacts on the sustainable development of the marine environment. This study aimed to examine the literature characteristics and research hotspots of SGD based on Web of Science’s citation database from 1998–2019. With systematic bibliometric analysis, insights were made into multiple aspects including research output, subject categories, journals, countries/territories, institutions, authors, and hotspots and research trends. Results showed that the current amount of publications on SGD has increased exponentially. The characteristics of multi-subject, active international and inter-institutional collaborations were identified. There were 11 core journals publishing the research on SGD, and the number of covered journals increased linearly from 1998. USA had distinct advantages in publication outputs and took the core position in international collaborations. At present, the research hotspots of SGD mainly include the following: dynamics process and estimation of SGD with hydrogeological methods, tracer techniques, geochemical process in subterranean estuary, and dissolved material inputs to coastal waters via SGD. Citation analysis implied much development space in carbon flux transported by SGD and the implement of head as groundwater tracer. These results provided an instructive perspective of the present situation and future research direction on SGD.

Carbon and phosphorus processing in a carbonate karst aquifer and delivery to the coastal ocean

In siliciclastic systems, submarine groundwater discharge (SGD) provides a fraction of freshwater and nutrients delivered to coastal waters, but in many carbonate karst terrains SGD represents the predominant source of terrestrial water and solutes. Water compositions may be modified by reactions in subterranean estuaries, altering chemical fluxes via SGD. In carbonate settings, feedbacks between organic carbon remineralization and calcium carbonate mineral (CaCO3) dissolution and precipitation may alter carbon dioxide (CO2) and phosphorus (P) concentrations and fluxes associated with SGD. To assess these effects, we sampled water from multiple submarine springs along the east coast of the Yucatan peninsula, as well as inland cenotes, and a coastal groundwater well. We measured ammonium (NH4), phosphate (PO4), major element, dissolved inorganic and organic carbon concentrations (DIC and DOC), fluorescent characteristics of colored dissolved organic matter (CDOM) and modeled calcite saturation indices (SIcal) and the partial pressure of dissolved CO2 (PCO2). These data indicate that reactions along a hypothetical flow path to the coast control the composition of terrestrial fresh water entering the subterranean estuary. Non-conservative mixing between brackish groundwater and lagoon water reflect changes to groundwater compositions within the subterranean estuary from CO2 produced during organic matter remineralization and CaCO3 dissolution. Although both organic matter remineralization and carbonate dissolution should liberate P, molar N:P ratios in spring discharge are higher than the Redfield Ratio of 16:1, suggesting sequestration of remineralized P through sorption to carbonate minerals within the STE. This result indicates that SGD, the primary source of water and nutrient to this coastal zone, results in P limitation in coastal water and is a source of CO2 despite buffering by CaCO3 dissolution. This result also emphasizes the importance of biogeochemical reactions within subterranean estuaries for estimates of SGD solute delivery to the oceans and impacts to the coastal carbon cycle.

Submarine Groundwater Discharge: Updates on Its Measurement Techniques, Geophysical Drivers, Magnitudes, and Effects

The number of studies concerning Submarine Groundwater Discharge (SGD) grew quickly as we entered the 21st century. Many hydrological and oceanographic processes that drive and influence SGD were identified and characterized during this period. These processes included tidal effects on SGD, water and solute fluxes, biogeochemical transformations through the subterranean estuary, and material transport via SGD from land to sea. Here we compile and summarize the significant progress in SGD assessment methodologies, considering both the terrestrial and marine driving forces, and local as well as global evaluations of groundwater discharge with an emphasis on investigations published over the past decade. Our treatment presents the state-of-the-art progress of SGD studies from geophysical, geochemical, bio-ecological, economic, and cultural perspectives. We identify and summarize remaining research questions, make recommendations for future research directions, and discuss potential future challenges, including impacts of climate change on SGD and improved estimates of the global magnitude of SGD.

Development of anchialine cave habitats and karst subterranean estuaries since the last ice age

Extinction models generally predict that coastal and neritic fauna benefit during sea-level rise (transgression), whereas sea-level retreat (regression) diminishes their suitable habitat area and promotes evolutionary bottlenecks. Sea-level change also impacts terrestrial island biogeography, but it remains a challenge to evidence how sea-level rise impacts aquatic island biogeography, especially in the subterranean realm. Karst subterranean estuaries (KSEs) occur globally on carbonate islands and platforms, and they are populated by globally-dispersed, ancient ecosystems (termed anchialine). Anchialine fauna currently exhibit a disjunct biogeography that cannot be completely explained by plate tectonic-imposed vicariance. Here we provide evidence that anchialine ecosystems can experience evolutionary bottlenecks caused by habitat reduction during transgression events. Marine-adapted anchialine fauna benefit from habitat expansion during transgressions, but fresh- and brackish-adapted fauna must emigrate, evolve to accommodate local habitat changes, or are regionally eliminated. Phanerozoic transgressions relative to long-term changes in subsidence and relief of regional lithology must be considered for explaining biogeography, evolution, local extirpation or complete extinction of anchialine fauna. Despite the omission of this entire category of environments and animals in climate change risk assessments, the results indicate that anchialine fauna on low-lying islands and platforms that depend upon meteoric groundwater are vulnerable to habitat changes caused by 21st century sea-level rise.

Bacterial and Archaeal Assemblages from Two Size Fractions in Submarine Groundwater Near an Industrial Zone

Nutrients and organic pollutants transported by submarine groundwater discharge (SGD) play a significant role in controlling water quality, and can lead to the concerned deleterious effects on marine ecosystems. Subterranean estuaries are complicated habitats of diverse microbial communities that mediate different biogeochemical processes. However, there is less information on how microorganisms mediate biogeochemical cycles in the submarine groundwater system. In this study, we investigated the changes in bacterial and archaeal assemblages from two size fractions (0.2–0.45 μm and >0.45 μm) in the submarine groundwater of Qinzhou Bay, China. Phylogenetic analysis showed that Bathyarchaeota was dominant in archaeal communities in the >0.45 μm size fraction, but was seldom in the 0.2–0.45 μm fraction. The co-occurrence of sequences belonging to Bathyarchaeota and Methanosaeta was found in the >0.45 μm size fraction. Since a gene encoding acetate kinase of Bathyarchaeota is involved in acetate production, and acetate is also a necessary growth factor for Methanosaeta, the acetate produced by Bathyarchaeota can provide food or energy sources for Methanosaeta in this very >0.45 μm size fraction. The most abundant bacterial sequences in the >0.45 μm size fraction was closely related to biomineral iron-oxidizing Gallionella spp., whereas the dominant bacterial sequences in the 0.2–0.45 μm fraction were affiliated with Limnohabitans spp., which can utilize dissolved organic matter as an important source of growth substrates. Notably, approximately 10% of the bacterial sequences in both of the two size fractions belonged to Novosphingobium spp., which plays an important role in the degradation of pollutants, especially aromatic compounds. Furthermore, the predictive functional profiling also revealed that the pathways involved in the degradation of aromatic compounds by both bacteria and archaea were identified. The presence of nutrients or pollutants in our study site provides different substrates for the growth of the specific microbial groups; in turn, these microbes may help to deplete pollutants to the ocean through submarine groundwater. We suggest that these specific microbial groups could be potential candidates for effective in situ bioremediation of groundwater ecosystems.

Inorganic and organic iron and copper species of the subterranean estuary: Origins and fate

Subterranean estuaries (STEs) are land-ocean interfaces where meteoric fresh groundwater mixes with intruding seawater in a coastal aquifer, before discharging into the adjacent water column. In contrast to surface estuaries, STEs have the potential to amplify concentrations of constituents such as copper (Cu) and iron (Fe) due to long residence times and reductive dissolution of mineral phases along the groundwater flowpaths. However, oxidative precipitation of Fe and Mn at the sediment-water interface may scavenge many constituents again before they reach the coastal water column. Hence, the geochemical impact of the suboxic to anoxic submarine groundwater discharge (SGD) on the oxygenated coastal ocean relies on the capability of constituents such as Cu and Fe to stay in solution across redox boundaries. Here, we propose that dissolved organic matter (DOM) in the STE plays a pivotal role in the speciation of Cu and Fe through (i) fueling reductive dissolution and (ii) providing ligands to form stable metal-DOM complexes, increasing their transfer from the STE into the coastal ocean. We investigated the concentrations and speciation of Cu and Fe, and DOM chemical characteristics, in two beach STEs of a barrier island. By combining well-established techniques with novel quantification and speciation approaches from both the inorganic and organic geochemical realm (size-fractionation filtration, ferrozine detection, voltammetry, sequential DOM extraction, and ultra-high resolution mass spectrometry) we characterized metal-DOM associations down to the molecular level. Overall, pore water from both STEs was enriched with Cu and Fe compared to seawater, which indicated transfer potential for both trace metals across the sediment-water interface. However, Fe gradients from pore water to surface were steeper than those for Cu, indicating a larger net transfer of the latter compared to the former. Our voltammetry data showed that Cu was exclusively organically bound in both STEs and the water column, mostly in soluble form (<20 nm). The majority of >60 newly identified Cu-containing complexes had primarily aliphatic character and N and S in their molecular formulae resembling labile marine DOM, while two Cu-DOM complexes had polyphenol (“humic-like”) molecular formulae indicative of terrestrial vascular plant-derived material. In contrast to Cu, the Fe pool consisted of either reduced, soluble (<20 nm), likely free Fe(II) in the anoxic STE, or of larger colloids (<200 nm and >20 nm) in the fresh groundwater and seawater endmembers, likely as Fe(III)(hydr)oxides stabilized by DOM. Furthermore, while Fe and humic-like DOM seemed to share common sources, all directly identified mobile Fe-DOM complexes appeared to have marine origins. Therefore, organic forms of Fe in the STE may primarily consist of immobile humic-Fe coagulates, partially mobile Fe-nanocolloids, and mobile, N-containing, marine aliphatic Fe-complexes. Our study indicates that aliphatic, N-containing ligands may play an important role in the organic complexation and stabilization of Fe and particularly Cu in the STE, and enable them to cross redox boundaries at the sediment-water interface.

Spatial and Temporal Patterns of Pore Water Chemistry in the Inter-Tidal Zone of a High Energy Beach

Submarine groundwater discharge (SGD) is a ubiquitous source of meteoric fresh groundwater and recirculating seawater to the coastal ocean. Due to the hidden distribution of SGD, as well as the hydraulic- and stratigraphy-driven spatial and temporal heterogeneities, one of the biggest challenges to date is the correct assessment of SGD-driven constituent fluxes. Here, we present results from a 3-dimensional seasonal sampling campaign of a shallow subterranean estuary in a high-energy, meso-tidal beach, Spiekeroog Island, Northern Germany. We determined beach topography and analyzed physico-chemical and biogeochemical parameters such as salinity, temperature, dissolved oxygen, Fe(II) and dissolved organic matter fluorescence (FDOM). Overall, the highest gradients in pore water chemistry were found in the cross-shore direction. In particular, a strong physico-chemical differentiation between the tidal high water and low water line was found and reflected relatively stable in- and exfiltrating conditions in these areas. Contrastingly, in between, the pore water compositions in the existing foreshore ridge and runnel system were very heterogeneous on a spatial and temporal scale. The reasons for this observation may be the strong morphological changes that occur throughout the entire year, which affect the exact locations and heights of the ridge and runnel structures and associated flow paths. Further, seasonal changes in temperature and inland hydraulic head, and the associated effect on microbial mediated redox reactions likely overprint these patterns. In the long-shore direction the pore water chemistry varied less than the along the cross-shore direction. Variation in long-shore direction was probably occurring due to topography changes of the ridge-runnel structure and a physical heterogeneity of the sediment, which produced non-uniform groundwater flow conditions. We conclude that on meso-tidal high energy beaches, the rapidly changing beach morphology produces zones with different approximations to steady-state conditions. Therefore, we suggest that zone-specific endmember sampling is the optimal strategy to reduce uncertainties of SGD-driven constituent fluxes.

Sources and sinks of CO2 and CH4 in siliciclastic subterranean estuaries

AbstractAnthropogenic production of greenhouse gases (GHGs) has intensified the need to constrain estimates of natural atmospheric sources from both terrestrial and marine systems. Estuaries are known sources of carbon dioxide (CO2) and methane (CH4); however, less is known about GHG dynamics in subterranean estuaries (STEs). We evaluate CO2 and CH4 dynamics in three proximal STEs bordering Indian River Lagoon, Florida, where groundwater flows through siliciclastic sediments with minor carbonate mineral contents. Although the three STEs have similar mineralogical and flow characteristics, CO2 and CH4 concentrations vary by orders of magnitude. Nonconservative mixing of both gases is observed, and CH4 is generally produced while CO2 is sequestered. The extent of methanogenesis is linked to the redox potential of inflowing groundwaters, as well as degree of CH4 oxidation, which results mostly from anaerobic oxidation of methane. Methane concentrations vary by orders of magnitude, and stable isotopic signatures suggest differences in the microbial production pathway between sites. CO2 is sequestered due to the production of alkalinity relative to dissolved inorganic carbon, which occurs both through rapid CaCO3 dissolution at the shoreline as low‐pH groundwater from the siliciclastic aquifer interacts with carbonate minerals in lagoon sediments, as well as redox reactions, particularly sulfate reduction and denitrification. These results demonstrate a high variability in CO2 and CH4 concentrations, and thus fluxes, even among geographically constrained and hydrogeologically similar STEs. Although STEs are sources of both CO2 and CH4 to surface waters, the variability of production and consumption complicates global estimates of GHG fluxes from STEs.

Organic matter quantity and quality across salinity gradients in conduit‐ vs. diffuse flow‐dominated subterranean estuaries

AbstractSubmarine groundwater discharge (SGD) is a source of water and bioreactive solutes to coastal zones but may be modified by organic matter (OM) remineralization dynamics within subterranean estuaries (STEs). We hypothesize that bioreactive solute fluxes should depend on water residence time in STEs, but links between OM transformations and residence time in STEs are poorly characterized. To test this hypothesis, we compare dissolved OM (DOM) quantity and quality in two hydrologically distinct STE systems: a reef lagoon on the east coast of the Yucatan Peninsula, Mexico, where semidiurnal mixing in submarine springs of a carbonate karst aquifer results in short residence times, and a barrier lagoon on the east coast of Florida, where slow flow through siliciclastic sediments results in long residence times. We measured dissolved organic carbon concentrations and characterized colored DOM (CDOM) with ultraviolet spectroscopy and fluorescence combined with Parallel Factor Analysis. Both sites exhibit similar shifts in OM quality with salinity and reflect a marine source of labile OM to the STEs. Nonconservative mixing and CDOM production occurs at all sites but the long water residence times in the siliciclastic STEs cause orders of magnitude greater production than the carbonate STE. Consistent CDOM production across sites with disparate characteristics indicates that STEs are common sources of CDOM to surface water. However, observed variation in the magnitudes of CDOM production indicates that estimating global, and even regional, solute fluxes associated with SGD will be complicated by hydrologic control on extents of OM remineralization.

Vertical Stratification of Sediment Microbial Communities Along Geochemical Gradients of a Subterranean Estuary Located at the Gloucester Beach of Virginia, United States.

Subterranean estuaries (STEs) have been recognized as important ecosystems for the exchange of materials between the land and sea, but the microbial players of biogeochemical processes have not been well examined. In this study, we investigated the bacterial and archaeal communities within 10 cm depth intervals of a permeable sediment core (100 cm in length) collected from a STE located at Gloucester Point (GP-STE), VA, United States. High throughput sequencing of 16S rRNA genes and subsequent bioinformatics analyses were conducted to examine the composition, diversity, and potential functions of the sediment communities. The community composition varied significantly from the surface to a depth of 100 cm with up to 13,000 operational taxonomic units (OTUs) based on 97% sequence identities. More than 95% of the sequences consisted of bacterial OTUs, while the relative abundances of archaea, dominated by Crenarchaea, gradually increased with sediment core depth. Along the redox gradients of GP-STE, differential distribution of ammonia- and methane-oxidizing, denitrifying, and sulfate reducing bacteria was observed as well as methanogenic archaea based on predicted microbial functions. The aerobic-anaerobic transition zone (AATZ) had the highest diversity and abundance of microorganisms, matching with the predicted functional diversity. This indicates the AATZ as a hotspot of biogeochemical processes of STEs. The physical and geochemical gradients in different depths have attributed to vertical stratification of microbial community composition and function in the GP-STE.

Effects of multi-constituent tides on a subterranean estuary

Subterranean estuary, as a saltwater-freshwater mixing zone in a coastal aquifer, is significantly affected by tides. While many studies have been conducted to examine the effects of tides on groundwater dynamics in subterranean estuaries in relation to submarine groundwater discharge and seawater intrusion, the focus of the investigation, particularly for those based on numerical modelling, has been on tides with few frequencies, e.g., monochromatic tide and spring-neap tides (bichromatic). In this study, we examine numerically effects of measured multi-constituent tides on a coastal unconfined aquifer. With the antecedent tidal conditions accounted for using the Gamma distribution function, we conducted regression analysis and quantified the effects of measured multi-constituent tides on coastal unconfined aquifers in a prolonged and cumulative fashion. The results showed that the response of submarine groundwater discharge to the tidal fluctuation is mostly instantaneous. The coastal aquifer behaved like a low-pass filter that smooths out high-frequency tidal signals and leaves behind low-frequency signals to affect upper saline plume and lower saltwater wedge. The upper saline plume and lower saltwater wedge were significantly affected by antecedent tidal conditions at monthly and yearly time scales, respectively. Sensitivity analysis showed that the low-pass filter capacity can be altered by soil hydraulic conductivity and beach slope. This study revealed the importance of antecedent tidal conditions for seawater intrusion and will help to improve our understanding of hydrological processes in natural coastal unconfined aquifers.

Hydrologic Controls of Methane Dynamics in Karst Subterranean Estuaries

AbstractKarst subterranean estuaries (KSEs) extend into carbonate platforms along 12% of all coastlines. A recent study has shown that microbial methane (CH4) consumption is an important component of the carbon cycle and food web dynamics within flooded caves that permeate KSEs. In this study, we obtained high‐resolution (~2.5‐day) temporal records of dissolved methane concentrations and its stable isotopic content (δ13C) to evaluate how regional meteorology and hydrology control methane dynamics in KSEs. Our records show that less methane was present in the anoxic fresh water during the wet season (4,361 ± 89 nM) than during the dry season (5,949 ± 132 nM), suggesting that the wet season hydrologic regime enhances mixing of methane and other constituents into the underlying brackish water. The δ13C of the methane (−38.1 ± 1.7‰) in the brackish water was consistently more 13C‐enriched than fresh water methane (−65.4 ± 0.4‰), implying persistent methane oxidation in the cave. Using a hydrologically based mass balance model, we calculate that methane consumption in the KSE was 21–28 mg CH4·m−2·year−1 during the 6‐month dry period, which equates to ~1.4 t of methane consumed within the 102‐ to 138‐km2 catchment basin for the cave. Unless wet season methane consumption is much greater, the magnitude of methane oxidized within KSEs is not likely to affect the global methane budget. However, our estimates constrain the contribution of a critical resource for this widely distributed subterranean ecosystem.

Dissolved silica in the subterranean estuary and the impact of submarine groundwater discharge on the global marine silica budget

Groundwater's role in the global marine budget of dissolved silica (DSi), an essential nutrient, is constrained using DSi groundwater concentrations from multiple endmember lithologies and a global terrestrial submarine groundwater discharge (SGD) model. We report new DSi concentrations in nine subterranean estuaries throughout the world, including Panama, Mauritius, Guam, Yucatan (Mexico), Chile, Argentina, Southwest Florida (USA), Long Island Sound (USA) and Waquoit Bay (USA). These new data are augmented with a literature survey of DSi endmember concentrations in the subterranean estuary to determine the global DSi endmember in SGD, classified by the regional lithology (carbonate, shale, sandstone, extrusive igneous, shield and “complex”). DSi fluxes to the ocean from terrestrial (fresh) SGD equal 0.7 ± 0.1 Tmol y−1, more than half of which enters the Pacific Ocean. Non-conservative DSi enrichment was observed in marine groundwaters circulated through extrusive igneous and complex lithology sediments for twenty different study sites. Dissolution rate calculations indicate that non-conservative DSi enrichments in marine groundwaters can be supported, in part, by lithogenic dissolution of the coastal sediment, rather than biogenic silica dissolution. We make preliminary estimates of DSi inputs via marine SGD in shallow coastal aquifers of ~3 Tmol y−1. Considering recent revisions to the marine silica budget (e.g., increased estimates of biogenic silica storage via reverse weathering reactions, increased estimates of standing stocks of biogenic silica, and changing estimates of silica burial efficiency), sources and sinks in the marine Si budget can be balanced when taking into account estimates of new DSi inputs from total SGD (terrestrial and marine flow paths). These findings impact the residence time of oceanic Si and mass balances of the stable Si isotopes, as well as associated silicate weathering products, including Li and Ge.

Coral geochemical record of submarine groundwater discharge back to 1870 in the northern South China Sea

The importance of submarine groundwater discharge (SGD) is becoming increasingly recognized because of its potential significance as a source of dissolved species. To explore the probable coral geochemical signal of SGD and verify the validity of potential reliable proxies, multiple geochemical proxies over the last 137 years were identified from a Porites coral near a subterranean estuary in the northern South China Sea, where the SGD was reported to be the predominant flux of terrestrial waters to the coastal ocean. Results indicated that the SGD in the coastal zone was the dominant source of trace elements, especially REE and Ba, due to the various dissolution reactions occurring during groundwater flow in the karst terrain. The time- and frequency-domain comparison between the coral geochemical proxy and the local/regional precipitation indicated that coral REE/Ca ratios are predominantly impacted by the SGD associated with local precipitation, while coral Ba/Ca ratios are also affected by the primary productivity and allochthonous seawater Ba from surrounding areas. The REE signal from coral allows us to reconstruct the coastal surface seawater REE concentrations and the SGD rates on the coast of Sanya during 1870–2006. In a novel approach to developing a proxy for historic SGD to coastal waters, this study provides evidence that the coral REE/Ca record from the karst coast with large SGD has potentials to be a promising paleohydrological indicator.

Seawater recirculation drives groundwater nutrient loading from a developed estuary shoreline with on-site wastewater treatment systems: Mobile Bay, USA

Previous studies have highlighted the influence of submarine groundwater discharge (SGD) on the environmental condition of coastal waters worldwide. Here, we focus on the quantity and quality of SGD from a developed estuarine shoreline in Mobile Bay to investigate the effects of residential development, specifically on-site wastewater treatment, on coastal water quality. A variety of techniques including a hydrologic balance, Darcy calculations, seepage meter observations, and coastal water radon-222 surveys were employed to quantify fresh and total components of SGD under varying hydrometeorological scenarios. Samples of groundwater from shallow wells, SGD from seepage meters, and surface water were analyzed for dissolved nutrients throughout the year to determine nutrient sources and loadings to the Bay. Comparisons of SGD yielded by Darcy’s calculations with seepage meter and radon-222 observations revealed that fresh, meteoric groundwater contributes only a minor fraction (~ 7%) of total SGD, thereby suggesting that seawater recirculation is the dominant mechanism driving SGD. Total dissolved nitrogen loading averaged 1960 mmol d−1 per m shoreline for the duration of the study; however, total dissolved nitrogen loading supported by the fresh, meteoric SGD component was only 11.2 mmol d−1 per m shoreline (less than 1% of the total loading), despite the presence of on-site wastewater treatment systems. These results demonstrate the importance of SGD as a source of nutrients to Mobile Bay and suggest that nutrient loading from regeneration and remineralization processes in the subterranean estuaries can exceed that of groundwater nutrient transport from developed watersheds.

Interactions between iron and organic carbon in a sandy beach subterranean estuary

Understanding the behavior of terrestrially derived dissolved organic carbon (DOC) through subterranean estuaries (STEs) is essential for determining the carbon budget in coastal waters. However, few studies exist on the interaction of organic carbon (OC) and iron (Fe) in these dynamic systems, where fresh groundwater mixes with recirculated seawater. Here, we focused on the origin and behavior of DOC, and we quantified the relative proportion of OC trapped by reactive Fe-hydroxides along a sandy beach STE. The δ13C-DOC signal in beach groundwater seems to respond rapidly to OC inputs. Our results show a terrestrial imprint from the aquifer matrix dominated by the degradation of particulate organic carbon (POC) issue from an old soil horizon composed of terrestrial plant detritus (14C dating ~800 to 700 years B.P) which is buried below the Holocene sand. Even though the system can be sporadically affected by massive inputs of marine OC, this transient marine imprint seems to be rapidly evacuated from the STE. As reported in soil and in marine mud, Fe–OC trapping occurs in the sandy sediment of the STE. At the groundwater–seawater interface, newly precipitated reactive Fe-hydroxides interact with and trap terrestrial OC independently of the DOC origin in beach groundwater. The molecular fractionation of DOC along the STE and preferential trapping of terrestrial compounds favor the in situ degradation and/or export of non-Fe-stabilized marine-derived molecules to coastal waters. These findings support the idea that the sandy beach STE acts as a transient sink for terrestrial OC at the land–sea interface and contributes to the regulation of marine vs. terrestrial carbon exports to coastal waters.

Influence of labile dissolved organic matter on nitrate reduction in a seepage face.

Seepage faces, the outer rim of subterranean estuaries, are an important reaction node for SGD-borne nitrate (NO3-) on a global scale. Labile dissolved organic matter (DOM) has been suggested to be a key factor constraining the NO3- removal rate in aquifer systems. To determine whether and to what extent the availability of labile DOM affects benthic NO3- reduction in seepage faces, a series of flow-through reactor (FTR) experiments with sandy sediment collected from a seepage face was conducted under oxic conditions. Experimental results revealed that the addition of labile DOM (glucose) to porewater did not trigger a significant enhancement in NO3- reduction rate. In contrast, the aerobic respiration was boosted from ca. 50 to 90μmoldm-3 sediment h-1 by glucose amendments, accounting for approximately 70% consumption of the labile DOM pool. This rapid consumption may increase the NO3- reducing capability within the sediment, but only indirectly. Together with fluorescent DOM (FDOM) analyses, it can be inferred that NO3- reducers tend to choose sediment organic matter the prime electron donor under the experimental conditions. As a result, enrichment of DOM in seepage faces, depending on composition, might only stimulate aerobic respiration and nitrification, thus promoting the increase of ensuing NO3- fluxes to adjacent coastal waters.

Temperature as a tracer of hydrological dynamics in an anchialine cave system with a submarine spring

Although temperature is a nonconservative tracer, it often provides useful information to understand hydrological processes. This study explores the potential of temperature to characterize the hydrological dynamics of a submarine spring and its coastal karst aquifer in Krka Estuary (Croatia). The estuary is well stratified and its water column has a clear thermocline. A network of loggers was designed to monitor the temperature along vertical profiles in the estuary and the coastal aquifer, taking advantage of an anchialine cave that enabled access to the subterranean estuary. The location of the thermocline in the groundwater, which defines the upper boundary of the saline intrusion, depends on (1) the recharge of the aquifer via infiltration of precipitation, (2) the evolution of the thermocline in the estuary, and (3) the tidal oscillations. The sources of water flowing though the anchialine cave were identified: brackish water from the estuary above the thermocline, saline water from the estuary below the thermocline, and freshwater from infiltrated precipitation. A conceptual model is described that characterizes the hydrological dynamics of this coastal aquifer and its interactions with the estuary. Thus, at least for some hydrological settings, temperature is a valid tracer to characterize the main hydrological processes. The measurement of temperature is inexpensive compared to other (conservative) tracers. Therefore, for those hydrological settings that have water masses with distinct temperatures, the use of temperature as a tracer to establish conceptual models of the hydrological dynamics is encouraged.

Flow and discharge of groundwater from a snowmelt-affected sandy beach

The study is based on a complex and unique data set of water stable isotopes (i.e., δ18O and δ2H), radon-222 activities (i.e., 222Rn) and groundwater levels to better understand the interaction of fresh groundwater and recirculated seawater in a snowmelt-affected subterranean estuary (STE) in a boreal region (Îles-de-la-Madeleine, Qc, Canada). By using a combination of hydrogeological and marine geochemical approaches, the objective was to analyze and quantify submarine groundwater discharge processes through a boreal beach after the snow melt period, in early June. The distribution of δ18O and δ2H in beach groundwater showed that inland fresh groundwater contributed between 97 and 30% of water masses presented within the STE. A time series of water table levels during the 16 days of the study indicated that tides propagated as a dynamic wave limiting the mass displacement of seawater within the STE. This up-and-down movement of the water table (∼10–30 cm) induced the vertical infiltration of seawater at the falling tide. At the front of the beach, a radon-based mass balance calculated with high-resolution 222Rn survey estimated total SGD of 3.1 m3/m/d at the discharge zone and a mean flow to 1.5 m3/m/d in the bay. The nearshore discharge agreed relatively well with Darcy fluxes calculated at the beach face. Fresh groundwater makes up more than 50% of the total discharge during the measuring campaign. These results indicate that beaches in boreal and cold regions could be important sources of freshwater originate and groundwater-borne solutes and contaminants to the marine environment after the snowmelt.

Methane- and dissolved organic carbon-fueled microbial loop supports a tropical subterranean estuary ecosystem

Subterranean estuaries extend inland into density-stratified coastal carbonate aquifers containing a surprising diversity of endemic animals (mostly crustaceans) within a highly oligotrophic habitat. How complex ecosystems (termed anchialine) thrive in this globally distributed, cryptic environment is poorly understood. Here, we demonstrate that a microbial loop shuttles methane and dissolved organic carbon (DOC) to higher trophic levels of the anchialine food web in the Yucatan Peninsula (Mexico). Methane and DOC production and consumption within the coastal groundwater correspond with a microbial community capable of methanotrophy, heterotrophy, and chemoautotrophy, based on characterization by 16S rRNA gene amplicon sequencing and respiratory quinone composition. Fatty acid and bulk stable carbon isotope values of cave-adapted shrimp suggest that carbon from methanotrophic bacteria comprises 21% of their diet, on average. These findings reveal a heretofore unrecognized subterranean methane sink and contribute to our understanding of the carbon cycle and ecosystem function of karst subterranean estuaries.