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Qinghai Lake, the largest lake in China with a surface area of 4260 km2, lies in the northeastern Qinghai-Tibet Plateau (QTP) at a mean altitude of 3194 m above sea level. The lake has a water volume of 71.6 × 109 m3, a salinity ranges of 4.18 ± 0.14 ppt to 12.3 ± 0.14 ppt during sampling period which is about a half of typical seawater. The aquifer systems at the lake shoreline have obvious saline water and freshwater mixing zones with similar hydrogeological and biogeochemical settings to coastal aquifers. This study aims to estimate lacustrine groundwater discharge (LGD) and the associated chemical loadings to western Qinghai Lake. Naturally occurring radium isotopes (223Ra, 224Ra, 226Ra and 228Ra), nutrients, heavy metals and dissolved inorganic carbon (DIC) were systematically investigated in different water endmembers of western Qinghai Lake. LGD was estimated with radium inventory model and radium eddy diffusion model, leading to a LGD estimate of 7.67 × 106 m3 d−1 and 8.52 × 106 m3 d−1, respectively. The fresh groundwater discharge obtained based on regional water budget is about 5.97 × 106 m3 d−1 during sampling period, accounting for 73.74% (ranging from 53.22 to 80.43%) of total LGD. This study reveals that the fresh groundwater component is dominant in LGD of Qinghai Lake, which is quite different from most coastal scenarios. Furthermore, the chemical loadings derived from fresh-LGD and recirculated-LGD are evaluated. The preliminary results indicate that fresh-LGD is an important source of nutrient, barium, strontium, uranium, and DIC to the lake, and may significantly impact biogeochemical and ecological processes in the lake. This study presents the first LGD estimate in the largest QTP saline lake in China, and would be instructive to further similar studies in saline lakes in QTP and elsewhere in the world.

Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 125(5), (2020): e2019JC016007, doi:10.1029/2019JC016007.

Methane concentrations can be high in coastal groundwater, resulting in methane export driven by submarine groundwater discharge. However, the magnitude of this methane flux depends significantly on the rate of methanotrophy, the often overlooked process of microbial methane consumption that occurs within coastal aquifer sediments. Here we describe a zone of methanogenesis within the freshwater lens of a barrier island aquifer and investigate the methane source/sink behavior of the barrier island system as a whole. The median concentration of methane dissolved in fresh groundwater beneath the center of the island was 0.6 mM, supported by high rates of potential methanogenesis (22 mmol m−2 day−1). However, rates of microbial methane consumption were also elevated in surrounding sediments (18 mmol m−2 day−1). Groundwater flowing from the zone of methanogenesis to the point of discharge into the ocean had a long residence time within methanotrophic sediments (∼195 days) such that the majority of the methane produced within the barrier island aquifer was likely consumed there.

Processes leading to the development of coastal hypoxia are usually attributed to anthropogenic nutrient loading. We present new evidence documenting a natural process capable of producing large-scale water masses undersaturated with respect to dissolved oxygen, independent of human-caused nutrient loading and subsequent nutrient-enhanced productivity. Along the heavily developed coastline of Myrtle Beach, South Carolina, the offshore discharge of saline, anoxic groundwater generates undersaturated bottom water masses which can be advected into nearshore waters. Highly elevated radium isotope activities measured in low-oxygen bottom waters cannot be supported by any known terrestrial source. Rather, discharge of cold, anoxic, high-radium water from offshore carbonate aquifers is the likely source. Density stratification inhibits mixing of these discharged waters during inshore transport. During a low-oxygen event in August 2012, this restricted mixing is likely the mechanism for the observed oxygen deficit in bottom waters. This discovery suggests benthic layers undersaturated with respect to dissolved oxygen may be considerably more prevalent than currently recognized, particularly around the carbonate-platform of the US East Coast.

This study examined dissolved Mo and sedimentary Mo along with hydrochemical parameters in the western Taiwan Strait (WTS) in May and August 2012. The results demonstrate that dissolved Mo could be depleted of as high as 10–20 nM during our May sampling period when the nutrient-enriched Min-Zhe coastal current ceased and spring blooms developed. The negative correlation between Chl-a and dissolved Mo suggests the possible involvement of high algal productivity in removing dissolved Mo out of the water column. Specific oceanographic settings (little currents) permitted a high sedimentary enrichment of Mo (>6 µg/g Mo) within the highly productive waters outside the Jiulong River mouth. Possibly, the high algal productivities and consequent organic matter sinks provide a pathway of Mo burial from water columns into sediments. Dissolved Mo was relatively high in groundwater samples, but we observed that submarine groundwater discharges (SGDs) only contributed to a relatively small percentage of the total dissolved Mo pool in WTS. It is probably attributable to the immediate removal of SGD-released Mo ions via adsorption onto newly formed Mn oxides once exposed to oxygenated seawater, followed by an elevated sedimentary Mo accumulation near the SGDs (∼5 µg/g). In addition to metal oxide particle scavenging and sulfide precipitation, we estimated that biological uptake along with Mo adsorption onto organic matter carriers could finally provide more than 10% of the annual sedimentary Mo accumulation in WTS.

The shores of the Pearl River estuary are home to 35 million people. Their wastes are discharged into the large river delta-front estuary (LDE), one of the most highly polluted systems in the world. Here we construct a radium reactive transport model to estimate the terrestrial groundwater discharge (TGD) into the highly urbanized Pearl River LDE. We find the TGD comprises only approximately 0.9% in term of water discharge compared to the river discharge. The TGD in the Pearl River LDE delivers significant chemical fluxes to the coast, which are comparable to the fluvial loadings from Pearl River and other world major rivers. Of particular importance is the flux of ammonium because of its considerable role in Pearl River estuary eutrophication and hypoxia. Unlike the ammonium in many other aquifers, the ammonium in the Pearl River aquifer system is natural and originated from organic matter remineralization by sulfate reduction in the extremely reducing environment. The TGD derived NH4+ is as much as 5% of the upstream Pearl River fluvial loading and 42% of the anthropogenic inputs. This high groundwater NH4+ flux may greatly intensify the eutrophication, shift the trophic states, and lead to alarming hypoxia within the affected ecosystems in the Pearl River LDE. The large TGD derived chemical fluxes will lead to deterioration of water and will potentially affect human health.

Shelf inputs in the Arctic Ocean appear to be increasing, which could change the nutrient balance of the central basin., 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.

The first full transarctic section of 228Ra in surface waters measured during GEOTRACES cruises PS94 and HLY1502 (2015) shows a consistent distribution with maximum activities in the transpolar drift. Activities in the central Arctic have increased from 2007 through 2011 to 2015. The increased 228Ra input is attributed to stronger wave action on shelves resulting from a longer ice‐free season. A concomitant decrease in the 228Th/228Ra ratio likely results from more rapid transit of surface waters depleted in 228Th by scavenging over the shelf. The 228Ra activities observed in intermediate waters (

article i nfo The application of thorium-228 towardsunderstandingparticle dynamics intheopen ocean islimitedbecauseof its low natural abundanceinseawaterand associated sampling and analytical challenges.Here we describea fast and nondestructivemethod for measuringboth dissolved and particulate 228 Thactivities inthe openocean using Radium Delayed-Coincidence Counters (RaDeCC). Particulate and dissolved samples were collected from the

Actinium-227 (t 1/2 = 21.77 y) is produced by decay of protactinium-231 (t 1/2 = 32,760 y). Abyssal sediments are enriched in 231 Pa and thus provide a source of the more soluble 227 Ac to the deep-sea, where it can be used as a tracer of deep ocean diapycnal mixing. In this study, we examine the distribution of dissolved and particulate 227 Ac within a neutrally buoyant hydrothermal plume overlying the TAG vent field (26.14°N, 44.83°W, Mid-Atlantic Ridge) collected during the U.S. GEOTRACES North Atlantic Transect (2011). Elevated activities of both particulate and dissolved 227 Ac within the plume indicate that hydrothermal vents may be a previously unrecognized source of this isotope to the marine environment. We contend that vent fluids are the main source of the 227 Ac enrichment. Based on the activities of dissolved and particulate 227 Ac within the plume, a 3 He dilution model was used to derive a hydrothermal 227 Ac end-member activity of 1.5 × 10 4 –2.5 × 10 4 dpm m − 3 . Assuming that TAG is characteristic of all vents along the Mid-Atlantic Ridge, the hydrothermal source of 227 Ac to the deep Atlantic is estimated to be 1.9–5.8% of the flux from Atlantic sediments. Although this hydrothermal flux may not have a large impact on the total oceanic inventory of 227 Ac, it must be considered when using this isotope as a tracer of deep ocean mixing in areas where hydrothermal activity is present.

Radium isotopes are produced in sediments via the decay of thorium isotopes and are generally soluble in seawater. As such, isotopes of the radium quartet (224Ra, 223Ra, 228Ra, 226Ra) have been used as tracers of ocean boundary inputs and mixing processes. We measured radium isotopes on the US GEOTRACES North Atlantic cruises in 2010 and 2011, which crossed a number of key ocean boundary features including the Mediterranean outflow, the Mauritanian upwelling and oxygen minimum zones (OMZ) along western Africa, a hydrothermal plume over the mid-Atlantic Ridge (MAR), and the broad continental margin of the north-eastern United States. Radium isotope features at these locations are discussed in the context of their potential to quantify fluxes of trace elements and isotopes (TEIs) from common sources. Notable observations include: (1) a Mediterranean outflow spreading rate of 0.52–0.60 cm/s derived from 228Ra, (2) evidence of substantial sediment–water interaction in the benthic boundary layer along the OMZ, (3) decoupling between 223Ra and the other Ra isotope sources over the MAR, and (4) significant continental inputs (e.g. submarine groundwater discharge—SGD) in the western Atlantic. Lastly, 228Ra inventories have remained constant over the past 30 years, which suggests that SGD is steady-state for the North Atlantic on decadal time scales.

Radium isotopes ( 223 Ra, t 1/2 = 11.4 d; 224 Ra, t 1/2 = 3.66 d; 226 Ra, t 1/2 = 1600 y; and 228 Ra, t 1/2 = 5.75 y) are considered excellent tracers of groundwater movement and discharge in coastal systems. However, spatial and temporal variability in porewater radium activity have raised questions about the accuracy of these tracers. To better understand the factors affecting radium variability in coastal systems, measurements of porewater and surface water radium activity were made at an island in North Inlet Salt Marsh in Georgetown, South Carolina, from November 2009 to February 2011. Water salinity, temperature, pH, and redox potential were also recorded, and sediment samples were collected for analysis of bulk 228 Ra and 226 Ra activity. Hydraulic head observations during 2007–2008 from piezometers on the island were used to generate independent estimates of groundwater fluxes. Porewater radium activities decreased with depth below the marsh surface and increased with distance from the creek banks. Salinity measurements were lower and redox potential higher near the marsh creeks. The stratigraphy of the island is typical of intertidal wetlands in the southeastern U.S., with a mud layer overlying a confined sandy aquifer; the observed patterns in porewater radium, salinity, and redox potential were consistent with (1) shorter porewater residence times in the permeable sand aquifer than in the low-permeability mud, (2) differences in grain size between the mud and sand, and (3) greater tidal exchange near the creeks. Temporal variations in porewater radium activity were not associated with salinity, pH, and redox potential although temperature provided significant control (P 2 228 Ra and 226 Ra activity. Lower mean sea water levels resulted in greater calculated groundwater discharge and were also associated with lower average porewater 224 Ra and 223 Ra activity, in that groundwater discharge variations strongly affected short-lived radium activity at this site. The 228 Ra/ 226 Ra activity ratios in the surface water and porewater signified that the confined aquifer, rather than the surficial mud, was the primary source of radium to the surface water. Our results highlight the importance of understanding the hydrology of any coastal system when interpreting radium results. It is also essential to identify and measure the correct porewater end-member(s) (i.e. source aquifers) when calculating radium budgets.

Approximately 40% of the total global rate of nitrogen fixation is the result of human activities, and most of this anthropogenic nitrogen is used to fertilize agricultural fields. Approximately 23% of the applied agricultural nitrogen is delivered to the coastal zone, often reducing water quality and driving eutrophication. Nitrogen cycling in coastal sediments can mitigate eutrophication by removing bioavailable nitrogen. However, some of these processes generate nitrous oxide, a potent greenhouse gas, as a by-product. Here we report the discovery of a nitrous oxide production hot spot in shallow barrier island sands. Nitrous oxide concentrations, production and consumption rates, vertical diffusion fluxes, and flux to the atmosphere were measured across triplicate depth profiles. Using a mass balance approach, rates of net nitrous oxide production were estimated to be 40 µmol m−2 d−1. This production was driven by a hot spot of nitrate consumption that removed bioavailable nitrogen from the coastal environment at a rate of 10 mmol m−2 d−1, a rate that is comparable with the highest rates of denitrification reported for coastal sediments.

Numerous investigators have used the advection–diffusion equation and the distributions of the four isotopes of radium to model coastal mixing rates. However, there is a dichotomy in approach. Some models use the short-lived 224 Ra ( T 1/2 =3.7 days) and 223 Ra ( T 1/2 =11 days) to determine horizontal mixing coefficients and the long-lived 226 Ra ( T 1/2 =1600 years) and 228 Ra ( T 1/2 =5.75 years) to test for the effects of advection. Because the timescales of mixing in most coastal systems (10–80 km offshore) are on the order of months or less, radioactive decay and particle removal of the long-lived isotopes are neglected in these models. If the long-lived isotopes display a linear gradient with distance offshore, this is taken as evidence that conservative mixing rather than advection controls the radium distribution. In this case it is appropriate to neglect the advection term and calculate mixing rates based on the exponential decay of the short-lived isotopes. Other models assume that radioactive decay of all of the isotopes impacts their distribution offshore. These models set up equations that separate the effects of mixing from advection and attempt to force mixing rates derived from all of the Ra isotopes to match. There are several reasons these models are doomed to fail. First, 224 Ra and 223 Ra look at different scales of mixing-there is no reason they must give the same rate. Secondly, on the timescale of coastal mixing decay of 226 Ra and 228 Ra is essentially zero. Equations that include decay terms for 226 Ra and 228 Ra become unrealistic when we consider that the measurement error is considerably greater than decay. In fact particle removal of 226 Ra is more important than radioactive decay. Finally, these models require steady-state conditions on the timescales of the decay terms. In order to use such models, the source functions and distributions of 228 Ra and 226 Ra would have to be constant for several times their half lives, approximately 25 and 4000 years, respectively. Seasonal and annual variability in supply and mixing rearranges the distributions, violating the steady-state assumption. Thus, models utilizing 226 Ra and 228 Ra radioactive decay are useless in the coastal zone.

Submarine groundwater discharge (SGD) varies significantly across time scales ranging from hours to years, but studies that allow quantitative comparisons between different time scales are few. Most of these studies have focused on beach settings, where the combined variations in fresh and saline SGD can be difficult to interpret. We calculated variations in saline SGD based on a 1 year record of hydraulic head in a salt marsh, where we could isolate variations in saline, tidally driven SGD. Observed SGD varied by an order of magnitude over the course of the year. Groundwater discharge was proportional to tidal amplitude and varied by at least a factor of 2 between spring and neap tides. Monthly average SGD was inversely proportional to average sea level; it increased by nearly a factor of 2 as sea level declined by ∼50 cm from late summer to late winter. This variation was far larger than that predicted by analytic models, owing to the flat topography and inundation of the marsh platform. The effect of short-term (days) variations in sea level associated with wind events and storms was small in comparison. SGD is probably proportional to tidal amplitude in nearly all coastal settings, including beaches. Seasonal variations in sea level may not affect the volume of SGD as significantly in coastal settings where the slope of the intertidal zone is relatively constant, but such variations have the potential to strongly affect the composition of SGD.

Ecological zonation of salt marsh macrophytes is strongly influenced by hydrologic factors, but these factors are poorly understood. We examined groundwater flow patterns through surficial sediments in two saltmarshes in the southeastern United States to quantify hydrologic differences between distinct ecological zones. Both sites included tall- or medium-form Spartina alterniflora near the creek bank; short-form Spartina alterniflora in the mid-marsh; salt flats and Salicornia virginica in the high marsh; and Juncus roemarianus in brackish-to-fresh areas adjacent to uplands. Both sites had relatively small, sandy uplands and similar stratigraphy consisting of marsh muds overlying a deeper sand layer. We found significant hydrologic differences between the four ecological zones. In the zones colonized by S. alterniflora, the vertical flow direction oscillated with semi-diurnal tides. Net flow (14-day average) through the tall S. alterniflora zones was downward, whereas the short S. alterniflora zones included significant periods of net upward groundwater flow. An examination of tidal efficiency at these sites suggested that the net flow patterns rather than tidal damping controlled the width of the tall S. alterniflora zone. In contrast to the S. alterniflora zones, hypersaline zones populated by S. virginica were characterized by sustained periods (days) of continuous upward flow of saline water during neap tides. The fresher zone populated by J. roemarianus showed physical flow patterns that were similar to the hypersaline zones, but the upwelling porewaters were fresh rather than saline. These flow patterns were influenced by the hydrogeologic framework of the marshes, particularly differences in hydraulic head between the upland water table and the tidal creeks. We observed increases in hydraulic head of approximately 40 cm from the creek to the upland in the sand layers below both marshes, which is consistent with previous observations that sandy aquifers below fine-grained marsh soils act as conduits for flow from uplands to tidal creeks. This hydrologic framework supports relatively good drainage near the creek, increased waterlogging in the mid-marsh, and the development of hypersalinity adjacent to the freshwater upland. These hydrologic differences in turn support distinct ecological zones.

To evaluate geochemical impacts of the subterranean estuary (STE) on the Jiulong River estuary, China, we estimated seasonal fluxes of subterranean water discharge into the estuary based on the mass balance of radium isotopes and net subterranean export fluxes of dissolved inorganic C (DIC), N (DIN), Si (DSi), soluble reactive phosphorus (SRP), and total alkalinity (TA). Based on 226Ra data, the subterranean discharge (in 107 m3 d−1) was estimated to be 0.29–0.60 in the spring, 0.69–1.44 in the summer, 0.45–0.93 in the fall, and 0.26–0.54 in the winter. This was equivalent to 8–19% of the concomitant river discharge. The net spatially integrated material fluxes from the STE into the estuary were equivalent up to 45–110% of the concomitant riverine fluxes for DIC and TA, around 14–32% for DSi and 7–19% for DIN, and negligible for SRP. Paradoxically, the mixing lines along the salinity gradient revealed no apparent additions of these species. These additions are not revealed because the STE is a relatively small spatially-averaged source (at most 11% of the total input at steady state) that spreads throughout the estuary as a non-point source in contrast to the major point sources of the river and the ocean for the estuary and a true open ocean endmember is likely lacking. Greater water flushing in the summer might dilute the STE effect on the mixing lines even more. The great spatial variation in salinity in the estuary introduced the major uncertainty in our estimates of the flushing time, which further affected the estimate of the subterranean discharge and associated material fluxes. Additionally, the great spatial variation in the STE endmember caused the relatively large ranges in these flux estimates. Despite apparent conservative mixing of DIC, DIN, and DSi in estuaries, net subterranean exports must be taken into account in evaluating geochemical impacts of estuarine exports on shelf waters.

We collected samples from January 2010 to December 2011 to determine the concentrations and fluxes of uranium in the Changjiang (Yangtze) and Huanghe (Yellow) Rivers in China. The dissolved U concentrations (DUC) were measured by inductively coupled plasma mass spectrometry (ICP-MS) at the freshwater end members of the Changjiang and Huanghe Rivers. The DUCs ranged from 1.32 to 4.06 nmol/L and 13.85 to 29.99 nmol/L in the Changjiang and Huanghe Rivers, respectively. The temporal variations of DUC followed the seasonal change, with high values in the two rivers occurring during the dry seasons and low values during the flood seasons. A strong negative correlation was observed between DUC and discharge in the Changjiang River (R2 = 0.69), but a weak correlation (R2 = 0.35) was found in the Huanghe River. The correlations between the major ions and the U in the rivers indicated that the primary source of uranium was from the weathering of carbonate and evaporite in the Changjiang Basin. The weathering of evaporite-bearing sequences and the erosion of loess dominated the U sources of the Huanghe River. Carbonate ligands in the dry season and phosphate ligands in the wet season were the primary factors controlling the accumulation and transportation of dissolved uranium in the Changjiang River. The soils of the Huanghe Basin contained five times more leachable uranium compared to the soils of the Changjiang Basin, which may explain the high DUC in the Huanghe River. The weighted-mean-concentrations of uranium were 2.78 nmol/L in the Changjiang River and 22.07 nmol/L in the Huanghe River. This lead to annual dissolved U fluxes (DUF) of 2.3 × 106 mol/yr in the Changjiang River and 4.1 × 105 mol/yr in the Huanghe River. The sum of the U fluxes in the two rivers represented 11.9% of the global U riverine flux into the sea comparing with 2.5% of the global runoff into the sea. The 234U/238U activity ratio of the Huanghe River had higher values (1.455–1.418) compared to the Changjiang River (1.424–1.374) from the dry season to the wet season, respectively.

We discovered a hotspot of elevated nitrate concentration (median = 431 μM) in shallow beach pore water that extended across the entire length of two barrier islands in the southeastern United States of America. We investigated this feature by surveying groundwater geochemistry, measuring fluctuations in in situ dissolved oxygen (DO) concentrations, modeling groundwater flow, and quantifying nitrification rates. Nitrification of groundwater ammonium was the only possible nitrate source, with a measured potential rate of 0.84 μmol m−2 h−1. However, the observed nitrate concentrations were far in excess of the predicted maximum achievable by aerobic nitrification assuming a 2 : 1 ratio of O : N and around 200 μM DO in air-saturated seawater. Groundwater DO concentrations within the hotspot (65 cm depth) were consistently 20–50 μM. The nitrate hotspot was located at the top of the water table beneath dry, undersaturated sand that allowed the penetration of air and the dissolution of excess oxygen into the pore fluids. The total dissolved nitrogen concentration of the hotspot was higher than anywhere else on the island, indicating nitrogen accumulation within the hotspot, most likely via ammonium adsorption. Vertical dispersion was the dominant pathway for nitrate loss from the hotspot. This nitrate was consumed in underlying anoxic sand, coupling microbial pathways of nitrogen oxidation and reduction and removing bioavailable nitrogen from the beach ecosystem.

Along the continental margins, rivers and submarine groundwater supply nutrients, trace elements, and radionuclides to the coastal ocean, supporting coastal ecosystems and, increasingly, causing harmful algal blooms and eutrophication. While the global magnitude of gauged riverine water discharge is well known, the magnitude of submarine groundwater discharge (SGD) is poorly constrained. Using an inverse model combined with a global compilation of 228Ra observations, we show that the SGD integrated over the Atlantic and Indo-Pacific Oceans between 60°S and 70°N is (12 ± 3) × 1013 m3 yr−1, which is 3 to 4 times greater than the freshwater fluxes into the oceans by rivers. Unlike the rivers, where more than half of the total flux is discharged into the Atlantic, about 70% of SGD flows into the Indo-Pacific Oceans. We suggest that SGD is the dominant pathway for dissolved terrestrial materials to the global ocean, and this necessitates revisions for the budgets of chemical elements including carbon.

Chemistry of Southern Brazilian Continental Shelf (SBS) waters, between 28.5°S and 34°S, is evaluated in relation to the mixing of thermohaline defined water masses and concomitant water column processes. Data on inorganic nutrient and trace metal (Ba, Cd, Co, Cu, Fe, Mn, U, V and Zn) concentrations and radium isotopic activities from previous reports and recent analyses are presented and discussed with the aim of providing a state of knowledge on processes governing their sources, distribution, transport and fate on the SBS. Nutrients concentrations/distributions on the shelf are controlled mainly by Tropical Water/Subtropical Shelf Water, seasonally modified as a result of summer upwelling in the northern shelf region, and by Plata Plume Water, which is seasonally modified by discharges of submarine groundwater (SGD), the Patos Lagoon and by the greater northern penetration of the Rio de la Plata plume during winter. Radium-226 activity varies little across the shelf. Radium-228 activity, associated dominantly with SGD, decreases conservatively, with respect to salinity, across shelf transects, converging on a typical ocean endmember activity. The low salinity endmember activity, however, depends on the location of the shelf transect controlled by the variability of coastal SGD. Because SGD is so important to the coastal shelf region, 228 Ra activity appears to provide a better tracer of water mass interactions than thermohaline characteristics. Using metal– 228 Ra relationships, sources, transport and fate of trace metals are better constrained enabling the following conclusion: The major source of dissolved Co, Mn and Fe to the shelf is SGD, along the coastal Holocene barrier system, followed by removal as coastal water mixes across the shelf. Cu and Si concentrations are explained as conservative mixtures of three endmembers: SGD, surface freshwater discharge and oceanic. Cd and Zn are largely explained similarly. Vanadium is enriched in coastal waters during the summer presumably due to seasonal remobilization from sediments but exhibits conservative mixing behavior across the shelf. Barium behavior is the most unexpected and is speculated to be the result of biochemical removal in highly productive coastal waters followed by release from decaying phytoplankton detritus as it is advected across the shelf.

Multiple techniques, including thermal infrared aerial remote sensing, geophysical and geological data, geochemical characterization and radium isotopes, were used to evaluate the role of groundwater as a source of dissolved nutrients, carbon, and trace gases to the Okatee River estuary, South Carolina. Thermal infrared aerial remote sensing surveys illustrated the presence of multiple submarine groundwater discharge sites in Okatee headwaters. Significant relationships were observed between groundwater geochemical constituents and 226 Ra activity in groundwater with higher 226 Ra activity correlated to higher concentrations of organics, dissolved inorganic carbon, nutrients, and trace gases to the Okatee system. A system-level radium mass balance confirmed a substantial submarine groundwater discharge contribution of these constituents to the Okatee River. Diffusive benthic flux measurements and potential denitrification rate assays tracked the fate of constituents in creek bank sediments. Diffusive benthic fluxes were substantially lower than calculated radium-based submarine groundwater discharge inputs, showing that advection of groundwater-derived nutrients dominated fluxes in the system. While a considerable potential for denitrification in tidal creek bank sediments was noted, in situ denitrification rates were nitrate-limited, making intertidal sediments an inefficient nitrogen sink in this system. Groundwater geochemical data indicated significant differences in groundwater chemical composition and radium activity ratios between the eastern and western sides of the river; these likely arose from the distinct hydrological regimes observed in each area. Groundwater from the western side of the Okatee headwaters was characterized by higher concentrations of dissolved organic and inorganic carbon, dissolved organic nitrogen, inorganic nutrients and reduced metabolites and trace gases, i.e. methane and nitrous oxide, than groundwater from the eastern side. Differences in microbial sulfate reduction, organic matter supply, and/or groundwater residence time likely contributed to this pattern. The contrasting features of the east and west sub-marsh zones highlight the need for multiple techniques for characterization of submarine groundwater discharge sources and the impact of biogeochemical processes on the delivery of nutrients and carbon to coastal areas via submarine groundwater discharge.

US National Science Foundation [OCE-0926559, OCE-1231211]; National Basic Research Program ("973" Program) of China [2009CB421203]; Natural Science Foundation of China (NSFC) [41076041]; National Natural Science Foundation of China [41121091]

State Key Laboratory of Estuarine and Coastal Re-search of China [SKLEC-2012KYYW05, 2011KYYW04]; 111 project [B08022]

Large amounts of fission products were released from the Fukushima nuclear accident after a devastating earthquake and subsequent tsunami hit the northeast coast of Japan on 11 March 2011. The radioactive mass was sent high into the atmosphere by hydrogen explosions and fires in the reactor buildings at Fukushima Daiichi Nuclear Power Plant and spread all over the world. A relatively complete detection of both gaseous and particulate fission products was conducted during 15 March and 30 May 2011 at Orangeburg, South Carolina, located along the southeast coast of the United States, 11,000 km from the accident site. The histograms of gaseous and particulate radionuclides were obtained, and the major radioactivity plateaus were found between 18 March and 7 April 2011. The maximum levels of particulate and gaseous 131I were 1.0 ± 0.1 and 5.0 ± 0.4 mBq m-3, respectively. The maximum radioactivities of 134Cs and 137Cs were 10 times less than that of the particulate 131I. The average activity ratio of 134Cs to 137Cs was determined as 0.98 ± 0.26 throughout the observation. It was found that the plateaus and spikes in the histogram curves corresponded to the nuclear release events at Fukushima Daiichi. The arrival times of the particulate and gaseous nuclear fallout were determined to be 8 and 10 d, respectively. The deposition rates of gaseous and particulate iodine and the mass transfer between the two phases were discussed based on the radioactivity ratios of the fission products. By comparing with the radionuclide effluent concentrations issued in NRC 10 CFR 20, it was concluded that the Fukushima fallout presented negligible radiation risk to the public at Orangeburg as well as in the southeastern coastal region of the U.S.

[1] The timescale of transport processes in estuarine and coastal regions can be evaluated using natural radionuclides with different half-lives. The distribution patterns of 7Be, 210Pb, and 234Th in the water column from April to July 2008 were used to calculate the removal and residence times in the Changjiang Estuary. The results showed that the maximum particulate activities of 7Be, 210Pb, and 234Th were observed approximately 150 km downstream (the turbidity maximum zone) of the freshwater end-number. The mean distribution coefficients (Kd, cm3 g−1) of the high suspended particulate matter (SPM) group are higher than those of the lower-SPM group for 7Be and 210Pb; for 234Th, the reverse is true. Based on a material balance in two-dimensional models of 7Be, 210Pb, and 234Th in the Changjiang River mouth, the removal times of these nuclides were approximately 0.66–12, 1.6–21, and 1.2–5.4 days, respectively. The residence times increased toward the seaward side. In the coastal region, the removal times of 7Be, 210Pb, and 234Th calculated by material balance in one-dimensional models were approximately 1.1–26, 1.2–27, and 0.70–23 days, respectively. Moreover, an enhanced resuspension process not only controlled the partitioning of 7Be, 210Pb, and 234Th between the particulate and dissolved phases, but also, this process may play a dominant role in controlling the dynamic behavior of SPM in the water column compared with the advection input/output fluxes of the SPM in the river mouth areas. The removal and the resuspension fluxes were comparable in the estuary. Meanwhile, old composition (whose deposition into the seabed for a long time is enough for 7Be to decay completely) occupied only a small part in the resuspended sediment during resuspension process.

Submarine groundwater discharge (SGD) with inputs of nutrients in certain regions may play a significant role in controlling water quality in the coastal regions. In this paper, we have determined four naturally occurring radium isotope (223Ra, 224Ra, 226Ra and 228Ra) activities and nutrient concentrations in surface water, coastal groundwater and river water in the mixing zone of Laoye Lagoon to estimate the fluxes of SGD by several models. The activities of the four radium isotopes of ground water were considerably greater than those in surface water samples. Using a 224Ra/228Ra activity ratio (AR) model, we estimated the average lagoon water age to be 3.2 days, which was comparable with the flushing time of 4.0 days. Based on the excess radium isotopes and the water age of the lagoon, the estimated fluxes of SGD (in 106 m3/d) ranged from 2.64 to 5.32 with an average of 4.11. Moreover, we used Si balance to evaluate the flux of SGD (4.8 × 106 m3/d) which was close to the result calculated by radium. The SGD-derived nutrient fluxes (in mol/d) were DIN = 1.7 × 105, PO43 − = 5.2 × 102, and SiO3 = 5.3 × 104. Furthermore, we applied the biogeochemical budget approach using SiO3 as a tracer to evaluate the impact of SGD. The differences between the results estimated by radium and SiO3 may indicate different pathways for the input of nutrients.

Radium-226 and 228 Ra activities were determined in water samples from within and adjacent to Sepetiba Bay, Rio de Janeiro State (Brazil) in 1998, 2005 and 2007. Surface waters in Sepetiba Bay were substantially higher in 226 Ra and 228 Ra compared to ocean end member samples. Using the residence time of water in the bay we calculated the flux required to maintain the observed enrichment over the ocean end members. We then applied a radium mass balance to estimate the volume of submarine groundwater discharge (SGD) into the bay. The estimates of SGD into Sepetiba Bay (in 10 10 L day −1 ) were 2.56, 3.75, and 1.0, respectively for 1998, 2005, and 2007. These estimates are equivalent to approximately 1% of the total volume of the bay each day or 50 L m −2 day −1 . It is likely that a substantial portion of the SGD in Sepetiba Bay consists of infiltrated seawater. This large flux of SGD has the potential to supply substantial quantities of nutrients, carbon and metals into coastal waters. The SGD found here is greater than what is typically found in SGD studies along the eastern United States and areas with similar geologic characteristics. Considering there are many coastal areas around the world like Sepetiba Bay, this could revise upward the already important contribution of SGD to coastal as well as oceanic budgets.

A new approach for quantifying radium isotopes in seawater was developed in advance of the international GEOTRACES program, which has the goal of identifying processes and quantifying fluxes that control the distribution of trace elements and isotopes (TEIs) in the ocean. High-resolution water column samples were collected via a commercially available in situ pump modified to accept multiple filter media including a manganese-oxide (MnO2) impregnated acrylic cartridge for extracting dissolved radionuclides from seawater. The modifications mitigated prefilter clogging and allowed for up to 1,800 L filtrations in 4 h of pumping. Different MnO2 cartridge preparation methods were investigated to achieve maximum radium (Ra) extraction efficiency under high sample flow rates. Full-ocean depth profiles were measured for short-lived radium isotopes (223Ra and 224Ra) in shipboard laboratories using a delayed coincidence alpha scintillation counter (RaDeCC). Samples were reanalyzed 4 weeks and 2 months after collection for 228Th and 227Ac to correct for supported 224Ra and 223Ra, respectively. Finally, the cartridges were measured on a gamma-ray spectrometer for the long-lived radium isotopes (226Ra and 228Ra). Parallel 20 L samples at each pumping depth were collected from Niskin bottles and analyzed via alpha scintillation for 226Ra to determine radium extraction efficiencies for the cartridges. These modified methods will allow for increased sample throughput, and hence higher spatial resolution for radium isotopes in the ocean. Such resolution will greatly improve the determination of oceanic vertical and horizontal mixing rates over small and large scales, which in turn can be used to calculate fluxes of TEIs into the ocean.

The Black Sea is the world's largest anoxic-sulfidic marine basin and has unique sedimentation conditions. Recent studies suggested that mass accumulation rates (MAR) in this environment have increased in the past century when compared to the last 2000 years (Unit 1 period). In this paper we test this hypothesis with new MAR data and further explore the relationship between the depositional pattern and pyrite-sulfur isotopic signature. Based on 15 cores sampled in 2001 and 2003, our dataset comprises radioactive isotopes (Pb-210, Ra-226, Cs-137 Cs-137) and sulfur stable isotopes (delta S-34(VCDT)) along with organic, inorganic carbon and pyrite-sulfur. We calculated MARs using Pb-210 profiles and/or Chernobyl-derived Cs-137 horizon buried in the sediment column. Our turbidite-free deep basin sediment MARs (61 to 76 g m(-2) yr(-1)) agreed with the previous results (50-100 g m(-2) yr(-1)) and confirm the view that MARs of the deep Black Sea basin have been increasing. A unique feature of our dataset was the presence of Chernobyl-derived radionuclides below up to 20 cm thick turbidite layers (deposited between 1986 and 2003), which enabled us to compute MARS for these coring locations. MARs were 1120 +/- 103 and 5230 +/- 125 g m(-2) yr(-1) for the last two decades in two turbidite-impacted western central basin cores, 20-100 times the long-term rates of the deep basin. This fast depositional pattern was reflected in the geochemical and isotopic data as well. Turbidites had isotopically heavier pyrite-sulfur compared to the Unit 1-type water column formed pyrite. This is probably because the turbidites originated from slope and transported slope pyrite isotopic signature to the deep basin. Diagenetic effects within the turbidite can make pyrite-sulfur even heavier. These tightly linked results demonstrate the importance of turbidites in recent sedimentation of the Black Sea. (C) 2012 Elsevier Ltd. All rights reserved.

National Basic Research Program ("973" Program) of China [2009CB421203]; Natural Science Foundation of China (NSFC) [41076041]; funds for creative research groups of the National Natural Science Foundation of China [41121091]

In anticipation of the international GEOTRACES program, which will study the global marine biogeochemistry of trace elements and isotopes, we conducted a multi-lab intercomparison for radium isotopes. The intercomparison was in two parts involving the distribution of: (1) samples collected from four marine environments (open ocean, continental slope, shelf, and estuary) and (2) a suite of four reference materials prepared with isotopic standards (circulated to participants as 'unknowns'). Most labs performed well with Ra-228 and Ra-224 determination, however, there were a number of participants that reported Ra-226, Ra-223, and Th-228 (supported Ra-224) well outside the 95% confidence interval. Many outliers were suspected to be a result of poorly calibrated detectors, though other method specific factors likely played a role (e. g., detector leakage, insufficient equilibration). Most methods for radium analysis in seawater involve a MnO2 fiber column preconcentration step; as such, we evaluated the extraction efficiency of this procedure and found that it ranged from an average of 87% to 94% for the four stations. Hence, nonquantitative radium recovery from seawater samples may also have played a role in lab-to-lab variability.

This paper reports the initial result of the flux of submarine groundwater discharge (SGD) into the Changjiang effluent plume (CEP). A radium mass balance model and a 224Ra/223Ra activity ratio (AR) apparent age model were applied to estimate the residence time of water above the pycnocline in the CEP. These two approaches gave similar results, yielding residence times of 5.4 d and 7.0 d, respectively, in the inner and outer plume zones. The nonconservative inventory of 226Ra was established in the CEP, and converted to a 226Ra flux by dividing by the water residence time and assuming steady state conditions. After subtracting the desorption of 226Ra from suspended sediment and the diffusion from the bottom sediment, the 226Ra flux from SGD was converted to a total SGD flux by dividing by the measured activity of 226Ra in local groundwater. The SGD flux in the CEP is estimated to be 0.2–1.0×109 m3 d−1, which is equivalent to 6–30% of the Changjiang water discharge during flood season. This large flux indicates that SGD may be another important nutrient source to the East China Sea.

International audience; Submarine groundwater discharge (SGD) into a shallow lagoon on the west coast of Mauritius Island (Flic-en-Flac) was investigated using radioactive ((3)H, (222)Rn, (223)Ra, (224)Ra, (226)Ra, (228)Ra) and stable ((2)H, (18)O) isotopes and nutrients. SGD intercomparison exercises were carried out to validate the various approaches used to measure SGD including radium and radon measurements, seepage rate measurements using manual and automated meters, sediment bulk conductivity and salinity surveys. SGD measurements using benthic chambers placed on the floor of the Flic-en-Flac Lagoon showed discharge rates up to 500 cm/day. Large variability in SGD was observed over distances of a few meters, which were attributed to different geomorphological features. Deployments of automated seepage meters captured the spatial and temporal variability of SGD with a mean seepage rate of 10 cm/day. The stable isotopic composition of submarine waters was characterized by significant variability and heavy isotope enrichment and was used to predict the contribution of fresh terrestrially derived groundwater to SGD (range from a few % to almost 100%). The integrated SGD flux, estimated from seepage meters placed parallel to the shoreline, was 35 m(3)/m day, which was in reasonable agreement with results obtained from a hydrologic water balance calculation (26 m(3)/m day). SGD calculated from the radon inventory method using in situ radon measurements were between 5 and 56 m(3)/m per day. Low concentrations of radium isotopes observed in the lagoon water reflected the low abundance of U and Th in the basalt that makes up the island. High SGD rates contribute to high nutrients loading to the lagoon, potentially leading to eutrophication. Each of the applied methods yielded unique information about the character and magnitude of SGD. The results of the intercomparison studies have resulted a better understanding of groundwater-seawater interactions in coastal regions. Such information is an important pre-requisite for the protection and management of coastal freshwater resources.

A decade of studies of metal and nutrient inputs to the back-barrier area of Spiekeroog Island, NW German Wadden Sea, have concluded that pore water discharge provides a significant source of the enrichments of many components measured in the tidal channels during low tide. In this paper we add studies of radium isotopes to help quantify fluxes into and out of this system. Activities of radium isotopes in surface water from tidal channels in the back-barrier area exhibit pronounced changes in concert with the tide, with highest activities occurring near low tide. Other dissolved components: silica, total alkalinity (TA), manganese, and dissolved organic carbon (DOC) exhibit similar changes, with patterns matching the Ra isotopes. Uranium follows a reverse pattern with highest concentrations at high tide. Here we use radium isotope measurements in water column and pore water samples to estimate the fluxes of pore waters that enter the tidal channels during low tide. Using a flushing time of 4 days and the average activities of 224Ra, 223Ra, and 228Ra measured in the back-barrier surface and pore waters, we construct a balance of these isotopes, which is sustained by a deep pore water flux of (2–4) × 108 L per tidal cycle. This flux transports Ra and the other enriched components to the tidal channels and causes the observed low tide enrichments. An independent estimate of pore water recharge is based on the depletion of U in the tidal channels. The U-based recharge is about two times greater than the Ra-based discharge; however, other sinks of U could reduce the recharge estimate. The pore waters have wide ranges of enrichment in silica, alkalinity, manganese, DOC, and depletion of U with depth. We estimate concentrations of these components in pore water from the depth expected to contribute the majority of the pore water flux, 3.5 m, to determine fluxes of these components to the tidal channels. Samples from this depth have minimum concentrations of silica, alkalinity, manganese, and DOC. We also estimate the exports of these components (and import of U) due to mixing based on average measured concentrations in the tidal creeks and the 4-day flushing time. A comparison of these estimates reveals that the exports (negative in the case of U) equal or exceed the pore water fluxes. By using values slightly higher than the minimum concentrations at 3.5 m to calculate inputs, the two estimates could be forced to match. We conclude that pore water drainage is the major factor regulating fluxes of Ra isotopes, silica, alkalinity, manganese, DOC, and uranium in this system.

The nutrient concentrations and stoichiometry in a coastal bay/estuary are strongly influenced by the direct riverine discharge and the submarine groundwater discharge (SGD). To estimate the fluxes of submarine groundwater discharge into the Bamen Bay (BB) and the Wanquan River Estuary (WQ) of eastern Hainan Island, China, the naturally occurring radium isotope (226Ra) was measured in water samples collected in the bay/estuary in August 2007 and 2008. Based on the distribution of 226Ra in the surface water, a 3-end-member mixing model was used to estimate the relative contributions of the sources to these systems. Flushing times of 3.9 ± 2.7 and 12.9 ± 9.3 days were estimated for the BB and WQ, respectively, to calculate the radium fluxes for each system. Based on the radium fluxes from groundwater discharge and the Ra isotopic compositions in the groundwater samples, the estimated SGD fluxes were 3.4 ± 5.0 m3 s−1 in the BB and 0.08 ± 0.08 m3 s−1 in the WQ, or 16% and 0.06%, respectively, of the local river discharge. Using this information, the nutrient fluxes from the submarine groundwater discharge seeping into the BB and WQ regions were estimated. In comparison with the nutrient fluxes from the local rivers, the SGD-derived nutrient fluxes played a vital role in controlling the nutrient budgets and stoichiometry in the study area, especially in the BB.