Tracers Of Submarine Groundwater Discharge Research Articles

Modeling time series radon inventory and constraints on the submarine groundwater discharge mass balance of a well-mixed, highly dynamic estuary

Although often diffuse and over-shadowed by surface-water inputs, submarine groundwater discharge (SGD) represents a significant source of freshwater and solutes to many sensitive marine environments. Radon (222Rn) is an effective naturally occurring tracer of SGD due to its non-reactive nature and dominant terrestrial source. However, limited continuous measurements and poor constraints on temporal 222Rn variability in shallow-turbulent estuaries introduce large uncertainties to SGD rate estimation. We hypothesize that nonlinear regression analysis (e.g., generalized additive model [GAM]) and machine learning (ML) algorithms could explain radon trends and resolve limitations of the traditionally used mass balance for estimating SGD in shallow and vertically mixed estuaries, thus enabling preliminary insights related to wind-driven mixing losses using sporadic groundwater tracer measurements and publicly available hydroclimatic parameters. Cross-correlation functions and a generalized additive model [GAM] were employed to quantify atmospheric and hydrologic controls and predict, respectively, 222Rn inventory variability modulated by windspeed and direction. Two ML models, neural network (deep-learning neural network [DNN]) and decision tree (random forest [RF]) based models, were trained on an intermittent 24-month 222Rn (n = 10,660, 30 min interval) dataset (2019–2021) collected from a well-mixed northwestern Gulf of Mexico estuary (Corpus Christi Bay, Texas) with publicly available inputs (e.g., windspeed/direction, tide levels, water temperature, creek discharge and barometric pressure, n = 35,088). Both ML models can predict observed radon concentrations with r2 > 0.90, however, only the RF model is able to predict within the observed range of the 222Rn magnitude dataset and finds the relevant hydroclimatic parameters (e.g., streamflow and wind direction) highly responsible for the seasonal and daily variability in the inventory, respectively. The DNN model can more closely predict extremely high inventories, but it overpredicts lows, resulting in numerous negative values, which suggests that large data gaps in the groundwater tracer cause overfitting and underperformance of this model in a wind-mixed estuary. Using the GAM predicted 222Rn dependency on wind direction and speed, the adjusted mass balance reduces overestimation of wind-mixing losses and results in overall lower fluxes. This research provides new opportunities to: 1) predict radon inventories in regions with large temporal data gaps using only publicly available hydroclimatic parameters and 2) better constrain SGD estimates in windy coastal areas, allowing for insights that can be used to plan field excursions and management strategies for coastal water and solute budgets.

Open-Source Code for Radium-Derived Ocean-Groundwater Modeling: Project Open RaDOM

Radium has been commonly used as a tracer of submarine groundwater discharge to the ocean and embankments, as radium activities are commonly input into box models to calculate a groundwater flux. Similarly, isotopes of radium (Ra224, Ra223, Ra226, Ra228) have been used to calculate water mass ages, which have been used as a proxy for residence times. Less commonly, radium and other tracers have been utilized in mixing models to determine the relative contribution of groundwater to a marine system. In the literature, all of these methods have almost exclusively been solved using analytical methods prone to large errors and other issues. Project Open RaDOM, introduced here, is a collection of open-source R scripts that numerically solve for groundwater flux, residence time, and relative contribution of groundwater to coastal systems. Solving these models numerically allows for over-constrained systems to increase their accuracy and force real solutions. The scripts are written in a way to make them user-friendly, even to scientists unfamiliar with R. This communication includes a description of the scripts in Project Open RaDOM, a discussion of examples in the literature, and case studies of the scripts using previously published data.

Submarine Groundwater Discharge (SGD) to Coastal Waters of Saipan (Commonwealth of the Northern Mariana Islands, USA): Implications for Nitrogen Sources, Transport and Ecological Effects

Seagrass meadows and coral reefs along the coast of Saipan, a US commonwealth in the Northern Pacific, have been declining since the 1940s, possibly due to nutrient loading. This study investigated whether submarine groundwater discharge (SGD) contributes to nutrient loading and supports primary production on Saipan’s coast. SGD can be an important source of freshwater, nutrients, and other pollutants to coastal waters, especially in oceanic islands without well-developed stream systems. Ra and Rn isotopes were used as natural tracers of SGD. Nitrate, phosphate, and ammonium concentrations, ancillary water quality parameters, δ15N and δ18O of dissolved nitrate, and δ15N of primary producer tissue were measured. Our results pointed to discharge of low-salinity groundwater containing elevated concentrations of sewage-derived N at specific locations along Saipan’s coast. High SGD areas had lower salinity and pH, higher dissolved inorganic nitrogen concentrations, and elevated primary producer δ15N, indicative of sewage nitrogen inputs. We estimated that SGD could support 730–6400 and 3000–15,000 mol C d−1 of primary production in Tanapag and Garapan Lagoons, respectively, or up to approximately 60% of primary production in Garapan Lagoon. Efforts to improve water quality, reduce nutrient loading, and preserve coastal ecosystems must account for groundwater, since our results demonstrate that it is an important pathway of nitrogen delivery.

Radium Mass Balance Sensitivity Analysis for Submarine Groundwater Discharge Estimation in Semi-Enclosed Basins: The Case Study of Long Island Sound

Estimation of submarine groundwater discharge (SGD) to semi-enclosed basins by Ra isotope mass balance is herein assessed. We evaluate 224Ra, 226Ra and 228Ra distributions in surface and bottom waters of Long Island Sound (CT-NY, USA) collected during spring 2009 and summer 2010. Surface water and bottom water Ra activities display an apparent seasonality, with greater activities during the summer. Long-lived Ra isotope mass balances are highly sensitive to boundary fluxes (water flux and Ra activity). Variation (50%) in the 224Ra, 226Ra and 228Ra offshore seawater activity results in a 63 – 74% change in the basin-wide 226Ra SGD flux and a 58 – 60% change in the 228Ra SGD flux, but only a 4 – 9% change in the 224Ra SGD flux. This highlights the need to accurately constrain long-lived Ra activities in the inflowing and outflowing water, as well as water fluxes across boundaries. Short-lived Ra isotope mass balances are sensitive to internal Ra fluxes, including desorption from resuspended particles and inputs from sediment diffusion and bioturbation. A 50% increase in the sediment diffusive flux of 224Ra, 226Ra and 228Ra results in a ~30% decrease in the 224Ra SGD flux, but only a ~6 – 10% decrease in the 226Ra and 228Ra SGD flux. When boundary mixing is uncertain, 224Ra is the preferred tracer of SGD if sediment contributions are adequately constrained. When boundary mixing is well-constrained, 226Ra and 228Ra are the preferred tracers of SGD, as sediment contributions become less important. A three-dimensional numerical model is used to constrain boundary mixing in Long Island Sound, with mean SGD fluxes of 1.2 ± 0.9 *1013 L y-1 during spring 2009 and 3.3 ± 0.7 *1013 L y-1 during summer 2010. The SGD flux to Long Island Sound during summer 2010 was one order of magnitude greater than the freshwater inflow from the Connecticut River. The maximum marine SGD-driven N flux is 14 ± 11 *108 mol N y-1 and rivals the N load of the Connecticut River.

Hydrogeological processes and near shore spatial variability of radium and radon isotopes for the characterization of submarine groundwater discharge

Inadequate characterization of variability in natural tracers of submarine groundwater discharge (SGD) introduces large errors into tracer-derived SGD estimates. To address this gap, we investigated spatial variability in the natural SGD tracers 223Ra, 224Ra, 226Ra, 228Ra and 222Rn using a high-density array of piezometers and seepage meters over a nearshore area where discharging groundwater transitioned from fresh to saline. Seepage meters and piezometers were used to sample groundwater and to quantify fluxes and salinity. A series of spatial patterns was distinguished beyond the normal salinity impact on Ra activity. The discharge in the interface between saltwater and freshwater was characterized by higher activities of the longer-lived isotopes (226Ra and 228Ra), while areas dominated by benthic exchange had higher activities of the shorter-lived isotopes (223Ra and 224Ra). Spatial differences in Ra activities were associated with variation in salinity and residence time in the aquifer and were indicative of underlying hydrogeological processes. At the freshwater-saltwater interface, fresh discharge is driven by terrestrial hydraulic gradients and saline discharge is driven by density gradients; both result in long residence times in the aquifer. Benthic exchange of saltwater has shorter residence times, much less than required to enrich long-lived isotopes and reach secular equilibrium. The highest activities of 222Rn were detected in the fresh discharge zone, and the lowest activities in areas dominated by benthic exchange. Direct sampling at discharge points allowed comparison between groundwater collected from inland wells and the water discharging to the bay, and indicated significant differences in the activities despite the short distance from wells to the discharge area. Substantial spatial variability in Ra and Rn was observed on the meter scale, with trends that reflected groundwater origin and residence time. Inadequate characterization of variability, trends, and fluxes introduces large errors into tracer-derived estimates of submarine groundwater discharge. Thus, the study of submarine groundwater discharge with radioactive tracers requires adequate hydrogeological knowledge to identify processes that have strong impacts on Ra and Rn activities and associated fluxes to the ocean.

Cross‐Shelf Transport of Submarine Groundwater Discharge Tracers: A Sensitivity Analysis

AbstractThe coastal mass balance for environmental tracers can be used to evaluate submarine groundwater discharge (SGD) and is often estimated using advective‐dispersive cross‐shelf transport models. Here we evaluate the sensitivity of different types of SGD tracers to key variables in this transport model under a wide range of environmental conditions. Salinity and long‐lived radionuclides (here represented by 226Ra; half‐life = 1,600 years) were transported by a combination of advection and dispersion under the scenarios considered, but short‐lived radionuclides (here represented by 224Ra; half‐life = 3.66 days) were mostly dispersed unless the offshore coefficient of solute dispersivity (Kx) was very low (<1 m2/s). Sensitivity to variations in key transport variables was further evaluated by reinterpreting the cross‐shelf trends in Ra activity in the semiarid Gulf St Vincent of South Australia (GSV). In GSV, the trends in most Ra isotopes (223Ra, 228Ra, and 226Ra) in seawater could be explained similarly by a large number of parameter combinations, implying these tracers would provide highly uncertain SGD estimates in this environment. However, the range of possible parameter combinations was relatively smaller for 224Ra, suggesting that SGD estimates derived from this tracer would be most reliable for GSV. In both the sensitivity analysis and the reevaluation of the GSV data, Kx was the most sensitive parameter in the transport equation. Because Kx is an empirical parameter potentially encompassing different dispersion processes in time and space (tidal currents, storms, etc.), it is likely to be tracer, time, and site specific.

Fluxes of dissolved organic carbon and nutrients via submarine groundwater discharge into subtropical Sansha Bay, China

To evaluate the role that submarine groundwater discharge (SGD) plays in the carbon and nutrient budgets in subtropical Sansha Bay, southeastern China, radium isotopes were used as SGD tracers and investigated in the bay and surrounding groundwater. In general, the activity of radium isotopes (223,224,226,228Ra) decreased from the bay head to the outlet that connects with the East China Sea. Based on the ratio of 224Ra and 228Ra, the water age was estimated to be 5.49 ± 3.64 and 1.50 ± 0.83 days in winter and summer, respectively. A three end-member mixing model and a box model were set up based on the mass balance of 226Ra and salinity to quantify SGD. The flux of SGD was calculated to be 9.33 ± 8.17 × 105 m3 d−1 (3.8 ± 3.4 × 10−3 m3 m−2 d−1) in winter and 4.89 ± 3.35 × 106 m3 d−1 (2.0 ± 1.4 × 10−2 m3 m−2 d−1) in summer, which were at least a few times less than the concomitant river discharge into the bay. In groundwater, an enrichment of dissolved inorganic nitrogen, phosphorus, and organic carbon was associated with relatively high activities of 226Ra. The SGD-associated nutrient flux was 1.99 ± 1.74–95.0 ± 83.2 μmol m−2 d−1 in winter and 0–0.89 ± 0.55 mmol m−2 d−1 in summer of phosphate, 6.76 ± 5.92–7.21 ± 6.32 mmol m−2 d−1 in winter and 66.2 ± 40.8–93.6 ± 57.7 mmol m−2 d−1 in summer of dissolved inorganic nitrogen, and 1.20 ± 1.05–1.74 ± 1.52 mmol m−2 d−1 in winter and 5.93 ± 4.06–8.22 ± 5.63 mmol m−2 d−1 in summer of silicate. The flux of dissolved organic carbon via SGD was 0.17 ± 0.15–0.33 ± 0.29 mmol m−2 d−1 in winter and 1.31 ± 0.81–2.94 ± 1.81 mmol m−2 d−1 in summer. The flux of N carried by SGD into Sansha Bay was comparable to the estuarine flux in winter, while was an order of magnitude greater than the estuarine flux in summer. The minimum flux of silicate via SGD was about half as much as the estuarine flux in summer, while was an order of magnitude smaller than the estuarine flux in winter. The minimum SGD-associated P flux was at least two orders of magnitude smaller than the estuarine flux in both seasons. Therefore, SGD on embayment scale is an important pathway for nitrogen from land to sea. These great SGD-associated nutrient fluxes may contribute to eutrophication and hypoxia in such stratified embayment.

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in the patagonian coastal zone (Argentina): an initial assessment

Submarine groundwater discharge (SGD) is herein recognized as a significant pathway of material transport from land to the coastal SW Atlantic Ocean and thus, it can be a relevant factor affecting the marine biogeochemical cycles in the region. This paper focuses on the initial measurements of 226Ra, 228Ra and 222Rn made in Patagonia’s coastal zone of Chubut and Santa Cruz provinces (42°S–48°S, Argentina). 226Ra activity ranged from 2.9 to 73.5 dpm 100 L−1, and 228Ra activity ranged from 11.9 to 311.0 dpm 100 L−1 in groundwater wells. The radium activities found in Patagonia’s marine coastal regions and adjacent shelf indicate significant enrichment throughout the coastal waters. Groundwater samples presented the largest 222Rn activity and ranged from 2.66 to 1083 dpm L−1. Conversely, in the coastal marine environment, the 222Rn activity ranged from 1.03 to 6.23 dpm L−1. The Patagonian coastal aquifer showed a larger enrichment in 228Ra than in 226Ra, which is a typical feature for sites where SGD is dominant, probably playing a significant role in the biogeochemistry of these coastal waters.

Significance of Submarine Groundwater Discharge in Nutrient Budgets in Tropical Sanya Bay, China

To quantify the contribution of submarine groundwater discharge (SGD) to the nutrient budget in tropical embayments, naturally occurring radium isotopes (223Ra, 224Ra, 226Ra, and 228Ra) were investigated as SGD tracers in Sanya Bay, China. Higher activities of radium were present along the north coast and near the Sanya River estuary. Using the activity ratio of 224Ra/228Ra, the apparent water age in Sanya Bay was estimated to be 0–13.2 days, with an average of 7.2 ± 3.2 days. Based on the mass balance of 226Ra and 228Ra, SGD was calculated to be 2.79 ± 1.39–5.07 ± 2.67 × 106 m3 d−1 (or 4.3 ± 2.1–7.8 ± 4.1 cm d−1). SGD associated dissolved inorganic nutrient fluxes into Sanya Bay were estimated to be 3.94 ± 2.00–7.15 ± 3.85 × 105 mol d−1 for oxidized inorganic nitrogen, 4.64 ± 2.74–8.42 ± 5.19 × 103 mol d−1 for phosphate, and 6.63 ± 3.29–12.0 ± 6.34 × 105 mol d−1 for silicate. The estuarine nutrient flux from the Sanya River was a few times smaller than the phosphate flux via SGD and at least an order of magnitude smaller than the oxidized inorganic nitrogen and silicate fluxes carried by SGD. SGD was also more important than atmospheric deposition and nitrogen fixation in the nutrient budget. Our results demonstrate that SGD compensated for at least 15% phosphate, 90% oxidized inorganic nitrogen, and 60% silicate of the nutrients sink in Sanya Bay.

Constraining the temporal variations of Ra isotopes and Rn in the groundwater end-member: Implications for derived SGD estimates

Submarine groundwater discharge (SGD) has been recognized as an important supplier of chemical compounds to the ocean that may influence coastal geochemical cycles. Radium isotopes (223Ra, 224Ra, 226Ra,228Ra) and radon (222Rn) have been widely applied as tracers of SGD. Their application requires the appropriate characterization of both the concentrations of tracers in the discharging groundwater and their distribution in the coastal water column. This study evaluates the temporal evolution of Ra isotopes and 222Rn concentrations in a dynamic subterranean estuary of a microtidal Mediterranean coastal aquifer that experiences large displacements of the fresh-saltwater interface as a necessary initial step in evaluating the influence of SGD in coastal waters. We show that changes in groundwater salinities due to the seaward displacement of the fresh-saltwater interface produced large variations in Ra activities in groundwater (by a factor of ~19, ~14, ~6, and ~11 for 223Ra, 224Ra, 226Ra and 228Ra, respectively), most importantly during rainfall events. In contrast, the 222Rn activities in groundwater oscillated only by a factor of 3 during these rainy periods. The large temporal variability in Ra activities hampers the characterization of the SGD end-member when using Ra isotopes as tracers, and thus presents a challenge for obtaining accurate SGD estimates. This study emphasizes the need to understand the hydrodynamics of coastal aquifers to appropriately constrain the Ra isotopes and 222Rn concentrations in groundwater and when applying both tracers in dynamic microtidal coastal systems.

Determining groundwater Ra end‐member values for the estimation of the magnitude of submarine groundwater discharge using Ra isotope tracers

AbstractRadium isotopes (228Ra and 226Ra) are excellent tracers of submarine groundwater discharge (SGD). To estimate SGD magnitudes, information on the end‐member values of Ra concentrations in groundwater is critical; however, the distribution characteristics of Ra in coastal aquifers are poorly understood. In this study, we show that Ra concentrations in coastal groundwater are primarily dependent on salinity based on the data (n > 500) obtained from global coastal aquifers, although previous end‐member calculations averaged all Ra concentrations without considering salinity. If we assume that SGD is composed mainly of seawater infiltrating the aquifer, previous estimates of SGD for the Atlantic Ocean and the global ocean were overestimated twofold to threefold. This may be similar for other applications using different Ra isotopes. Our study highlights that the end‐members of Ra isotopes in groundwater should be carefully considered when estimating SGD using Ra isotope mass balances in the ocean.

Fluorescent dissolved organic matter as a multivariate biogeochemical tracer of submarine groundwater discharge in coral reef ecosystems

In Hawaiʻi and other Pacific high islands submarine groundwater discharge (SGD) can be a significant and continuous source of solutes to nearshore reefs and may play a key role in the structure and function of benthic coral and algal communities. Identifying SGD sources and linking them to reef biogeochemistry is technically challenging. Here we analyzed spectra of fluorescent dissolved organic matter (fDOM) in coral reefs in the context of a suite of biogeochemical parameters along gradients of SGD to characterize fDOM composition and evaluate the utility of fDOM signatures in tracking groundwater dispersal and transformation. We spatially mapped water column chemistry in Maunalua Bay, Oʻahu, Hawaiʻi by collecting 24 water samples in grids at each of two ~0.15km2 regions during both high and low tides over a two-day period. We observed clear horizontal gradients in the majority of 15 measured parameters, including inorganic and organic solutes and organic particles that tracked concentrations of conservative SGD tracers (radon, salinity and silicate). Multivariate scanning excitation–emission fluorometry successfully differentiated two distinct groundwater sources and delineated regions of SGD dispersion in each reef from the surrounding water column samples without detectable groundwater. Groundwater was consistently depleted in DOC and enriched in nutrients; although the two SGD sources varied widely in fDOM quantity and fluorophore proportions, indices of humification were consistently elevated in SGD at both sites. Our results provide a robust spectral characterization of fDOM in SGD-influenced coral reefs and indicate the potential for this rapid and cost-effective measurement technique to be useful in tracking SGD dispersal in nearshore ecosystems.

Development of a sparging chamber for field radon analysis

Radon-222 has become a widely used tracer of submarine groundwater discharge. However, remote field studies are often limited by the need to pump water to a spray chamber which degasses dissolved radon for subsequent analysis in the gaseous phase. We develop here a new method of degassing dissolved 222Rn, utilizing a stream of bubbles driven by the internal air pump of a commercial radon analyzer to achieve air:water partitioning equilibrium, eliminating the need to pump water. This system utilizes a sparging chamber, comprised of a slotted vertically-oriented pipe with bubbles produced in the bottom. A non-slotted section of the pipe at the top of the chamber forms a sealed headspace, allowing air to be circulated in a closed loop between the sparging chamber and a radon-in-air monitor. We found that such a sparging chamber needs to allow bubbles to rise through at least 45 cm of water column to function at equal efficiency as the standard protocol of the spray chamber. Under our optimized configuration, the sparging chamber operates as efficiently as the standard protocol at measuring dissolved 222Rn activities when encountering increasing 222Rn activities, and offers even greater gas exchange efficiency when dissolved 222Rn activities decrease. The sparging chamber offers a more field-friendly alternative to measuring 222Rn activities, as it eliminates the need to maintain a submersible pump throughout the measurement and it offers increased temporal resolution when variable 222Rn activities are expected.

Submarine groundwater discharge: Natural radioactivity accumulation in a wetland ecosystem

Submarine groundwater discharge (SGD) has attracted the interest from the scientific community over the past decade for its impact on biogeochemical cycles of coastal ecosystems and/or management of water resources. SGD is associated with a flow of natural radionuclides (Ra isotopes and 222Rn), which are often used as SGD tracers that can significantly increase the natural background radiation. Although in many circumstances the discharge is produced directly to the sea and therefore the increase of natural radioactivity levels can generally be considered negligible due to a dilution processes, the discharge into coastal wetlands (marshes, coastal lagoons or ponds), with somewhat restricted exchange with the open sea, may require a detailed study of the distribution of natural radionuclides and their effects on the coastal ecosystem. The Peníscola marsh is a Mediterranean coastal wetland where such studies may be of special interest because it is fed exclusively by groundwater, mainly discharging from a deep aquifer with high natural radioactivity content.In the Peníscola marsh, brackish groundwater discharging through the wetland sediments is enriched in radionuclides to maximum values of 2.8 and 616kBqm−3 of 226Ra and 222Rn, respectively. These high dissolved concentrations result in high levels of 222Rn in air (up to 36Bqm−3) and 210Pb and 210Po dissolved in water (20 and 5.7Bqm−3, respectively). These elevated levels of natural radionuclides in the Peníscola marsh are also responsible of the significant increase in 210Po and 210Pb contents in both fish and plants.

Controls on solid-solution partitioning of radium in saturated marine sands

Solid-solution partitioning of Ra determines the dissolved Ra composition of porewater in marine sands. Therefore, sorption controls also influence the endmember concentration of Ra in submarine groundwater discharge (SGD). Ra is widely used as a tracer of SGD, and constraining sorption controls in permeable sands is necessary to evaluate spatial and temporal variation in Ra groundwater activities. This work presents Ra distribution coefficients measured in seawater (salinity 35) for some common solid sorbents as well as different solution compositions relevant to permeable marine sands and the subterranean estuary. There was a strong correlation of Ra distribution coefficient (Kd=solid-phase Ra/solution Ra) with surface area for size-fractionated sediments (log Kd (L/g)=0.77 [log S.A. (m2/g)]+0.73; r2=0.76). Ra sorption showed no direct relationship with solid-phase Fe or Mn content of the sands, although removal of visible surficial oxide coatings with dilute acid reduced Kd by a factor of 2 to 3. Synthetic Fe-oxides showed nearly two orders of magnitude difference in Ra sorption. Ferrihydrite had the highest Ra sorption coefficient at 1535±410Lkg−1, followed by lepidocrocite (174±21Lkg−1), hematite (75±17Lkg−1), and goethite (20±8Lkg−1). A marked increase in Ra adsorption was observed with increasing pH, with the sorption edge of natural sands falling within the pH range of 5–8. The extent of Ra sorption at a given pH varied among different substrates. No effect of dissolved Fe was observed on Ra partitioning. A large increase in Ra Kd was evident with increasing Ba concentration when seawater contained sulfate, opposite the effect that would be expected for sorption competition. No effect of Ba concentration was observed when sulfate was excluded from the ASW, indicating that barite precipitation caused the Kd increase. There was no clear effect of temperature on Ra sorption between 2 and 60°C. Results of this study show that minor solid-phase components increase the Ra sorption capacity of bulk sands and buffer the dissolved Ra concentration (i.e., the SGD endmember). Solution controls on Ra sorption have the potential to greatly alter the Ra composition of discharging groundwater. Given that high-salinity, high-pH conditions probably prevail in porewater below the sediment–water interface, the actual SGD Ra endmember may be less variable than suggested by compilations that include groundwater from deep and fresh groundwater.

An evaluation of the efficacy of radium isotopes as tracers of submarine groundwater discharge to southern Rhode Island's coastal ponds

Submarine groundwater discharge (SGD) represents a significant flux of water and chemical constituents to coastal regions. Because 226Ra and 228Ra are highly concentrated in groundwater relative to surface water, and their signal is well-integrated throughout coastal surface waters, these isotopes have been increasingly utilized to quantify SGD over the past several decades. In this study, a combined radium and salt balance is used to yield estimates of fresh and saline SGD to four of Rhode Island's coastal ponds (Winnapaug, Quonochontaug, Ninigret, and Point Judith Ponds). Fresh SGD rates determined for each pond range between 0 and 17Lm−2d−1. These values largely fall in line with previous estimates made using hydrologic models. The uncertainty of saline SGD estimates for each pond is high; minimum and maximum saline SGD estimates differ by as much as three orders of magnitude. These results echo the discrepancy between two previous radium-based studies from this location. The variability of dissolved radium in the Rhode Island coastal aquifer plays a large role in the uncertainty of these saline SGD estimates. Groundwater dissolved radium activity is dependent upon many different factors, including groundwater salinity and redox conditions, sediment thorium and radium activities, and the amount of time to which the sediment has been exposed to saline groundwater. Due to the heterogeneous nature of glacial outwash sediments, none of these parameters are likely consistent throughout the aquifer in this location. Groundwater 226Ra and 228Ra activities in the coastal ponds vary significantly both laterally and with sediment depth. For example, groundwater samples collected in Ninigret Pond separated by a vertical distance of only 5cm differ by as much as 3×103dpm100L−1 for both 226Ra and 228Ra. The results from this study indicate that a single groundwater sample or suite of samples may not accurately reflect the average radium activity of the groundwater actually discharging into each pond. Targeted sampling in areas where SGD is qualitatively observed can potentially remedy this problem.

New perspectives on radium behavior within a subterranean estuary

Over the past decade, radium isotopes have been frequently applied as tracers of submarine groundwater discharge (SGD). The unique radium signature of SGD is acquired within the subterranean estuary, a mixing zone between fresh groundwater and seawater in coastal aquifers, yet little is known about what controls Ra cycling in this system. The focus of this study was to examine controls on sediment and groundwater radium activities within permeable aquifer sands (Waquoit Bay, MA, USA) through a combination of field and laboratory studies. In the field, a series of sediment cores and corresponding groundwater profiles were collected for analysis of the four radium isotopes, as well as dissolved and sediment associated manganese, iron, and barium. We found that in addition to greater desorption at increasing salinity, radium was also closely tied to manganese and iron redox cycling within these sediments. A series of laboratory adsorption/desorption experiments helped elucidate the importance of 1) contact time between sediment and water, 2) salinity of water in contact with sediment, 3) redox conditions of water in contact with sediment, and 4) the chemical characteristics of sediment on radium adsorption/desorption. We found that these reactions are rapid (on the order of hours), desorption increases with increasing salinity and decreasing pH, and the presence of Fe and Mn (hydr)oxides on the sediment inhibit the release of radium. These sediments have a large capacity to sorb radium from fresh water. Combined with these experimental results, we present evidence from time series groundwater sampling that within this subterranean estuary there are cyclic periods of Ra accumulation and release controlled by changing salinity and redox conditions.

Radon and radium isotopes as tracers of submarine groundwater discharge – Results from the Ubatuba, Brazil SGD assessment intercomparison

We determined groundwater flow rates shortly after the wet season into an embayment near Ubatuba, Brazil as part of an international intercomparison experiment for submarine groundwater discharge (SGD) assessment techniques. Our estimated rates were determined by the combined use of continuous radon measurements and assessment of radium isotope patterns. The spatial distribution of the short-lived radium isotopes ( 223Ra and 224Ra) provided the means for independent evaluations of radon losses by mixing and atmospheric evasion. We were thus able to construct a well-constrained mass balance for radon that included a groundwater flux term. Our results showed that the groundwater discharge into this embayment from the fractured crystalline rock aquifer is not steady-state but varies with tidal modulation and rain-induced forcing. Tidally modulated and rain-induced flow rates were comparable during this period. The SGD rates estimated from radon ranged from 1 cm/day to 29 cm/day (cm 3/cm 2 day) with a mean and standard deviation of 13 ± 6 cm/day. These estimates were mostly similar to a dye-dilution automatic seepage meter (15 ± 19 cm/day) and were within the broad ranges estimated by manual and continuous heat seepage meters but lower than indicated by an artificial tracer test performed nearshore.

부산 남동지역 연안 대수층내 지하수의 지화학적 특성과 유출

We measured the salinity, pH, and concentrations of and nutrients in groundwater in the southeastern coastal aquifer off Busan from March to September 2005 to evaluate its submarine discharge and geochemical characteristics. Salinity in coastal groundwater increased sharply at 20 m depth and exceeded 25 ppt below 40 m during the study period, indicating that a strong transition zone between fresh groundwater and seawater developed between 20 and 40 m depths. Fresh groundwater in the upper layer of this transition zone was characterized by high pH, , dissolved inorganic nitrogen (DIN), and dissolved inorganic phosphorus (DIP) and low dissolved inorganic silicate (DSi) relative to seawater in the lower layer. In addition, the vertical profiles of the , DIN, and DIP concentrations imply that a strong advective groundwater flow occurs along the interface of fresh groundwater and seawater near 20 m depth. The geochemical constituents in coastal groundwater also showed strong seasonal variation, with the highest concentrations in summer (June 2005) due to the changes of groundwater recharge and sea level. This implies that the input of terrestrial chemical species into the coastal ocean through submarine groundwater discharge (SGD) could change seasonally. To ascertain the seasonal variation of SGD and SGD-driven chemical species fluxes, and associated ecological responses in the coastal ocean, more extensive studies are necessary using various SGD tracers or seepage meters in the future.

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in Tampa Bay, Florida

A suite of naturally occurring radionuclides in the U/Th decay series ( 222Rn, 223 , 224 , 226 , 228Ra) were studied during wet and dry conditions in Tampa Bay, Florida, to evaluate their utility as groundwater discharge tracers, both within the bay proper and within the Alafia River/estuary — a prominent free-flowing river that empties into the bay. In Tampa Bay, almost 30% of the combined riverine inputs still remain ungauged. Consequently, groundwater/surface water (hyporheic) exchange in the discharging coastal rivers, as well as submarine groundwater discharge (SGD) within the bay, are still unresolved components of this system's water and material budgets. Based on known inputs and sinks, there exists an excess of 226Ra in the water column of Tampa Bay, which can be evaluated in terms of a submarine groundwater contribution to the bay proper. Submarine groundwater discharge rates calculated using a mass balance of excess 226Ra ranged from 2.2 to 14.5 L m − 2 day − 1 , depending on whether the estuarine residence time was calculated using 224Ra/xs 228Ra isotope ratios, or whether a long term, averaged model-derived estuarine residence time was used. When extrapolated to the total shoreline length of the bay, such SGD rates ranged from 1.6 to 10.3 m 3 m − 1 day − 1 . Activities of 222Rn were also elevated in surface water and shallow groundwater of the bay, as well as in the Alafia River estuary, where upstream activities as high as 250 dpm L − 1 indicate enhanced groundwater/surface water exchange, facilitated by an active spring vent. From average nutrient concentrations of 39 shallow, brackish, groundwater samples, rates of nutrient loading into Tampa Bay by SGD rates were estimated, and these ranged from 0.2 to 1.4 × 10 5 mol day − 1 (PO 4 3−), 0.9–6.2 × 10 5 mol day − 1 (SiO 4 −), 0.7–5.0 × 10 5 mol day − 1 (dissolved organic nitrogen, DON), and 0.2–1.4 × 10 6 mol day − 1 (total dissolved nitrogen, TDN). Such nutrient loading estimates, when compared to average river discharge estimates (e.g., TDN = 6.9 × 10 5 mol day − 1 ), suggest that SGD-derived nutrient fluxes to Tampa Bay are indeed important components to the overall nutrient economy of these coastal waters.