Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba.

Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.

Does submarine groundwater discharge contribute to summer hypoxia in the Changjiang (Yangtze) River Estuary?

The Changjiang (Yangtze) River Estuary (CJE) is one of the largest and most intense seasonal hypoxic zones in the world. Here we examine the possibility that submarine groundwater discharge (SGD) may contribute to the summer hypoxia. Spatial distributions of bottom water 222Rn suggest a hotspot discharge area in the northern section of the CJE. SGD fluxes were estimated based on a 222Rn mass balance model and were found to range from 0.002 ± 0.004 to 0.022 ± 0.011 m3/m2/day. Higher SGD fluxes were observed during summer hypoxia period. The well-developed overlap of the distribution patterns for SGD flux and dissolved oxygen (DO) implies that SGD could be an important contributor to summer hypoxia in the region off the CJE. We suggest that SGD contributes to the seasonal hypoxia either: (1) directly via discharge of anoxic groundwaters together with reducing substances; and/or (2) indirectly by delivering excess nutrients that stimulate primary productivity with consequent consumption of DO during organic matter decomposition.

Mercury flux from salt marsh sediments: Insights from a comparison between 224Ra/228Th disequilibrium and core incubation methods.

In aquatic environments, sediments are the main location of mercury methylation. Thus, accurate quantification of methylmercury (MeHg) fluxes at the sediment-water interface is vital to understanding the biogeochemical cycling of mercury, especially the toxic MeHg species, and their bioaccumulation. Traditional approaches, such as core incubations, are difficult to maintain at in-situ conditions during assays, leading to over/underestimation of benthic fluxes. Alternatively, the 224Ra/228Th disequilibrium method for tracing the transfer of dissolved substances across the sediment-water interface, has proven to be a reliable approach for quantifying benthic fluxes. In this study, the 224Ra/228Th disequilibrium and core incubation methods were compared to examine the benthic fluxes of both 224Ra and MeHg in salt marsh sediments of Barn Island, Connecticut, USA from May to August, 2016. The two methods were comparable for 224Ra but contradictory for MeHg. The radiotracer approach indicated that sediments were always the dominant source of both total mercury (THg) and MeHg. The core incubation method for MeHg produced similar results in May and August, but an opposite pattern in June and July, which suggested sediments were a sink of MeHg, contrary to the evidence of significant MeHg gradients between overlying water and porewater at the sediment-water interface. The potential reasons for such differences are discussed. Overall, we conclude that the 224Ra/228Th disequilibrium approach is preferred for estimating the benthic flux of MeHg and that sediment is indeed an important MeHg source in this marshland, and likely in other shallow coastal waters.

Increased fluxes of shelf-derived materials to the central Arctic Ocean.

Rising temperatures in the Arctic Ocean region are responsible for changes such as reduced ice cover, permafrost thawing, and increased river discharge, which, together, alter nutrient and carbon cycles over the vast Arctic continental shelf. We show that the concentration of radium-228, sourced to seawater through sediment-water exchange processes, has increased substantially in surface waters of the central Arctic Ocean over the past decade. A mass balance model for 228Ra suggests that this increase is due to an intensification of shelf-derived material inputs to the central basin, a source that would also carry elevated concentrations of dissolved organic carbon and nutrients. Therefore, we suggest that significant changes in the nutrient, carbon, and trace metal balances of the Arctic Ocean are underway, with the potential to affect biological productivity and species assemblages in Arctic surface waters.

Lingering radioactivity at the Bikini and Enewetak Atolls.

We made an assessment of the levels of radionuclides in the ocean waters, seafloor and groundwater at Bikini and Enewetak Atolls where the US conducted nuclear weapons tests in the 1940's and 50's. This included the first estimates of submarine groundwater discharge (SGD) derived from radium isotopes that can be used here to calculate radionuclide fluxes in to the lagoon waters. While there is significant variability between sites and sample types, levels of plutonium (239,240Pu) remain several orders of magnitude higher in lagoon seawater and sediments than what is found in rest of the world's oceans. In contrast, levels of cesium-137 (137Cs) while relatively elevated in brackish groundwater are only slightly higher in the lagoon water relative to North Pacific surface waters. Of special interest was the Runit dome, a nuclear waste repository created in the 1970's within the Enewetak Atoll. Low seawater ratios of 240Pu/239Pu suggest that this area is the source of about half of the Pu in the Enewetak lagoon water column, yet radium isotopes suggest that SGD from below the dome is not a significant Pu source. SGD fluxes of Pu and Cs at Bikini were also relatively low. Thus radioactivity associated with seafloor sediments remains the largest source and long term repository for radioactive contamination. Overall, Bikini and Enewetak Atolls are an ongoing source of Pu and Cs to the North Pacific, but at annual rates that are orders of magnitude smaller than delivered via close-in fallout to the same area.

Unexpected source of Fukushima-derived radiocesium to the coastal ocean of Japan.

There are 440 operational nuclear reactors in the world, with approximately one-half situated along the coastline. This includes the Fukushima Dai-ichi Nuclear Power Plant (FDNPP), which experienced multiple reactor meltdowns in March 2011 followed by the release of radioactivity to the marine environment. While surface inputs to the ocean via atmospheric deposition and rivers are usually well monitored after a nuclear accident, no study has focused on subterranean pathways. During our study period, we found the highest cesium-137 (137Cs) levels (up to 23,000 Bq⋅m-3) outside of the FDNPP site not in the ocean, rivers, or potable groundwater, but in groundwater beneath sand beaches over tens of kilometers away from the FDNPP. Here, we present evidence of a previously unknown, ongoing source of Fukushima-derived 137Cs to the coastal ocean. We postulate that these beach sands were contaminated in 2011 through wave- and tide-driven exchange and sorption of highly radioactive Cs from seawater. Subsequent desorption of 137Cs and fluid exchange from the beach sands was quantified using naturally occurring radium isotopes. This estimated ocean 137Cs source (0.6 TBq⋅y-1) is of similar magnitude as the ongoing releases of 137Cs from the FDNPP site for 2013-2016, as well as the input of Fukushima-derived dissolved 137Cs via rivers. Although this ongoing source is not at present a public health issue for Japan, the release of Cs of this type and scale needs to be considered in nuclear power plant monitoring and scenarios involving future accidents.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES.

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Hydrologic controls on nutrient cycling in an unconfined coastal aquifer.

Groundwater is an important pathway for terrestrially derived nutrients to enter the coastal ocean. In coastal aquifers, groundwater transits the subterranean estuary, a region of sharp gradients in redox conditions and the availability of reactants. In one such system (Waquoit Bay, MA, USA), we observed more than a doubling of the groundwater-associated nitrogen flux to surface water during the summer compared to winter due primarily to a reduction in nitrogen attenuation within the subterranean estuary. Because marine groundwater intrusion has been shown to increase during the summer, we calculate a greater contribution of recycled nutrients from the coastal ocean to the subterranean estuary. We posit that the longer residence times within the subterranean estuary during the winter, which would result from reduced marine groundwater circulation, allow oxygen depletion of the groundwater, creating a favorable environment for important nutrient transformations such as nitrification, denitrification, and anammox. The timing of nutrient delivery to the coastal ocean has important implications for coastal marine ecology including the potential development of harmful algal blooms.

Coupled radon, methane and nitrate sensors for large-scale assessment of groundwater discharge and non-point source pollution to coastal waters.

We constructed a survey system of radon/methane/nitrate/salinity to find sites of submarine groundwater discharge (SGD) and groundwater nitrate input. We deployed the system in Waquoit Bay and Boston Harbor, MA where we derived SGD rates using a mass balance of radon with methane serving as a fine resolution qualitative indicator of groundwater. In Waquoit Bay we identified several locations of enhanced groundwater discharge, out of which two (Childs and Quashnet Rivers) were studied in more detail. The Childs River was characterized by high nitrate input via groundwater discharge, while the Quashnet River SGD was notable but not a significant source of nitrate. Our radon survey of Boston Harbor revealed several sites with significant SGD, out of these Inner Harbor and parts of Dorchester Bay and Quincy Bay had groundwater fluxes accompanied by significant water column nitrogen concentrations. The survey system has proven effective in revealing areas of SGD and non-point source pollution.

Field, laboratory, and modeling study of reactive transport of groundwater arsenic in a coastal aquifer.

A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(III) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows toward the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80-90% Fe(III)) are 734 +/- 232 mg kg(-1) and sedimentary phosphate-extractable As (90-100% As(VI) are 316 +/- 111 microg kg(-1) and are linearly correlated. Batch adsorption of As(III) onto orange, brown, and gray sediments follows Langmuir isotherms and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site-specific isotherms should be established for Kd- or SCM-based models.

Southern Ocean deep-water carbon export enhanced by natural iron fertilization.

The addition of iron to high-nutrient, low-chlorophyll regions induces phytoplankton blooms that take up carbon. Carbon export from the surface layer and, in particular, the ability of the ocean and sediments to sequester carbon for many years remains, however, poorly quantified. Here we report data from the CROZEX experiment in the Southern Ocean, which was conducted to test the hypothesis that the observed north-south gradient in phytoplankton concentrations in the vicinity of the Crozet Islands is induced by natural iron fertilization that results in enhanced organic carbon flux to the deep ocean. We report annual particulate carbon fluxes out of the surface layer, at three kilometres below the ocean surface and to the ocean floor. We find that carbon fluxes from a highly productive, naturally iron-fertilized region of the sub-Antarctic Southern Ocean are two to three times larger than the carbon fluxes from an adjacent high-nutrient, low-chlorophyll area not fertilized by iron. Our findings support the hypothesis that increased iron supply to the glacial sub-Antarctic may have directly enhanced carbon export to the deep ocean. The CROZEX sequestration efficiency (the amount of carbon sequestered below the depth of winter mixing for a given iron supply) of 8,600 mol mol(-1) was 18 times greater than that of a phytoplankton bloom induced artificially by adding iron, but 77 times smaller than that of another bloom initiated, like CROZEX, by a natural supply of iron. Large losses of purposefully added iron can explain the lower efficiency of the induced bloom(6). The discrepancy between the blooms naturally supplied with iron may result in part from an underestimate of horizontal iron supply.

Has submarine groundwater discharge been overlooked as a source of mercury to coastal waters?

We measured the mercury (Hg) in groundwater, aquifer sediments, and surface water in Waquoit Bay (Massachusetts) and found that this toxic metal (range: <3.2-262 pM) was being released within the subterranean estuary, with similarly high levels (range: 18-256 pM) found in the surface waters of the bay. None of the dissolved species (DOC, chloride, and Fe) normally observed to influence Hg partitioning correlated well with the observed Hg concentrations. It was hypothesized that this was in part due to the variable loading in time and space of Hg onto the aquifer sands in combination with the seasonality of groundwater flow through the aquifer. Aquifer sediment samples from the study site ranged from <1 to 12.5 pmol of Hg/g of sediment, suggesting log Kd values on the order of 1. We hypothesize that this was due to the low organic carbon content typical of the aquifer sediments. Last, itwas estimated that submarine groundwater discharge supplied 0.47-1.9 nmol of Hg m(-2) day(-1) to the bay, which is an order of magnitude higher than the atmospheric deposition rate for the northeastern U.S.

Geochemical cycling of arsenic in a coastal aquifer.

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.

The effects of iron fertilization on carbon sequestration in the Southern Ocean.

An unresolved issue in ocean and climate sciences is whether changes to the surface ocean input of the micronutrient iron can alter the flux of carbon to the deep ocean. During the Southern Ocean Iron Experiment, we measured an increase in the flux of particulate carbon from the surface mixed layer, as well as changes in particle cycling below the iron-fertilized patch. The flux of carbon was similar in magnitude to that of natural blooms in the Southern Ocean and thus small relative to global carbon budgets and proposed geoengineering plans to sequester atmospheric carbon dioxide in the deep sea.