Submarine Groundwater Discharge Estimates Using Radium Isotopes and Related Nutrient Inputs into Tauranga Harbour (New Zealand)

Land-based pollutants such as fertilizers and wastewater can infiltrate into aquifers and discharge into surrounding coastal water bodies as submarine groundwater discharge (SGD). Oceanic islands, with a large coast length to land area ratio, may be hot spots of SGD into the global ocean. Although SGD may be a major pathway of dissolved nutrients, carbon and metals to coastal waters, studies have been limited due to the difficulties in measuring this often diffuse process. This study used radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra) to investigate SGD and the associated fluxes of nutrients into Tauranga Harbour, New Zealand. We calculated the apparent water mass ages of the harbour to be between ~4.1 and 7.8 days, which was similar to a previous numerical model of ~2–8 days. A ²²⁶Ra mass balance was constructed to quantify SGD fluxes at the harbour scale. A minimum SGD flux rate of 0.53 cm day^?1 was calculated by using the maximum groundwater end-member value from 22 sample sites. However, using the geometric mean from these samples as a representative end-member, a final value of 2.83 cm day^?1 or a flux of 3.09 × 10⁶ m³ day^?1 was calculated. These values were between ~1 and 2.8 times greater than all the major river and creeks discharging into the harbour during the sampling period. Due to the higher observed nutrient concentrations in groundwater, the SGD-derived dissolved inorganic nitrogen (DIN), dissolved organic nitrogen (DON) and total dissolved phosphorus (TDP) fluxes were calculated to be 1.07, 0.87 and 0.05 mmol m² day^?1, respectively. These SGD inputs were ~5 times (for nitrogen) and ~8 times (for phosphorus) greater than the input from surrounding rivers and streams. The average N:P ratio in groundwater samples was 36:1 (which was greatly in excess of the Redfield ratio of 16). The harbour water had a N:P ratio of ~17:1. A positive relationship between radium isotopes and N:P ratios in the harbour further supported the hypothesis that SGD can have major implications for primary production, including recurrent algal bloom events which occur in the harbour. We suggest SGD as a major driver of nutrient dynamics in Tauranga Harbour and potentially other similar coastal lagoon systems and estuaries on oceanic islands.     

Application of226Ra,228Ra,223Ra, and224Ra in coastal waters to assessing coastal mixing rates and groundwater discharge to oceans

The fate of dissolved material delivered to the coastal ocean depends on its reactivity and the rate at which it is mixed offshore. To measure the rate of exchange of coastal waters, we employ two short-lived radium isotopes,²²³Ra and²²⁴Ra. Along the coast of South Carolina, shore-perpendicular profiles of²²³Ra and²²⁴Ra in surface waters show consistent gradients which may be modeled to yield eddy diffusion coefficients of 350–540 m²s⁻¹. Coupling the exchange rate with offshore concentration gradients yields estimates of offshore fluxes of dissolved materials. For systems in steady state, the offshore fluxes must be balanced by new inputs from rivers, groundwater, sewers or other sources. Two tracers that show promise in evaluating groundwater input are barium and²²⁶Ra. These tracers have high relative concentrations in the fluids and low-reactivity in the coastal ocean. Applying the eddy diffusion coefficients to the offshore gradient of²²⁶Ra concentration provides an estimate of the offshore flux of²²⁶Ra. Measuring the concentrations of²²⁶Ra in subsurface fluids provides an estimate of the fluid flux necessary to provide the²²⁶Ra. These estimates indicate that the volume of groundwater required to support these fluxes is of the order of 40% of the surface water flow.     

Submarine groundwater discharge in a subsiding coastal lowland: A Ra and Rn investigation in the Southern Venice lagoon

Several recent studies have suggested that submarine groundwater discharge (SGD) occurs in the Venice lagoon with discharge rates on the same order or larger than the surface runoff, as demonstrated previously in several other coastal zones around the world. Here, the first set of ²²²Rn data, along with new ²²⁶Ra data are reported, in order to investigate the occurrence and magnitude of SGD specifically in the southern basin of the lagoon. The independent connection with the Adriatic Sea (at the Chioggia inlet), in addition to the relative isolation of the water body from the main lagoon, make this area an interesting case study. There is probably only minimal fresh groundwater flux to the lagoon because the surrounding aquifer is subsiding and mainly has a lower hydraulic head than seawater.The data show that the Ra and Rn activities are in slight excess in the lagoon compared to the open sea, with values on the same order as those observed in the northern and central basins. Taking into account the water exchange rate between the lagoon and adjacent seawater provided by previous hydrodynamic numerical modelling, it is shown that this excess cannot be supported at steady state by only riverine input and by diffusive release from the sediment interstitial water. High activities observed in groundwater samples collected from 16 piezometers tapping into the shallow aquifer over the coastal lowland substantiate that the excess radioactivity in the lagoon may indeed be due to the advection of groundwater directly into the lagoon bottom water through the sediment interface. However, the data show that the groundwater composition is extremely heterogeneous, with high Ra activities concentrated within a narrow coastal strip where the contact between fresh and saline water takes place, while Rn strongly decreases when approaching the lagoon shore across the 20 km coastal plain. Assuming that the average groundwater activities measured in the coastal strip are representative of the SGD composition, a SGD flux of 7.7 ± 3.5 × 10⁵ and 2.5 ± 2 × 10⁶ m³/d is calculated using a ²²⁶Ra and ²²²Rn budget, respectively, (i.e. about 1-3 times the surface runoff), substantially lower than in previous studies. The influence of all assumptions on SGD estimates (groundwater heterogeneity, diffusive sediment flux, one-box versus multi-boxes model calculations) is discussed, and a sensitivity analysis of the influence of imperfect exchange and mixing at the lagoon outlets that affects the lagoon composition is provided. Finally, the results confirm that the SGD flux, calculated with these assumptions, is largely (∼80%) composed of saline lagoon water circulating through the sediment under the lagoon margin, and that the fresh water discharge associated with SGD is at most a minor term in the lagoon hydrologic balance.     

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.     

用镭同位素评价海水滞留时间及海底地下水排泄

海底地下水排泄(submarine groundwater discharge, SGD)难以直接测量, 镭同位素和氡-222等天然示踪剂使得间接评价SGD通量成为可能.为了评价五缘湾的水体滞留时间和SGD通量, 实测了湾内海水、湾外海水和地下水中224Ra和226Ra的活度, 利用224Ra和226Ra半衰期的差异, 采用224Ra与226Ra的活度比值计算湾内水团的年龄和平均滞留时间, 利用224Ra和226Ra的质量平衡模型计算SGD通量.五缘湾13个站位的水团年龄在0.6~2.4 d之间, 湾顶水团年龄相对较大, 平均海水滞留时间1.4 d.地下水输入五缘湾的224Ra和226Ra通量分别为5.17×106 Bq/d和5.28×106 Bq/d, 将该通量用地下水端元的活度转换成为SGD通量分别是0.21 m3/m2/d(224Ra平衡模型)和0.23 m3/m2/d(226Ra平衡模型), 两种模型的结果较接近, 其平均值0.22 m3/m2/d可作为五缘湾的海底地下水排泄通量.      

A multi-method approach for groundwater resource assessment in coastal carbonate (karst) aquifers: the case study of Sierra Almijara (southern Spain)

Understanding the transference of water resources within hydrogeological systems, particularly in coastal aquifers, in which groundwater discharge may occur through multiple pathways (through springs, into rivers and streams, towards the sea, etc.), is crucial for sustainable groundwater use. This research aims to demonstrate the usefulness of the application of conventional recharge assessment methods coupled to isotopic techniques for accurately quantifying the hydrogeological balance and submarine groundwater discharge (SGD) from coastal carbonate aquifers. Sierra Almijara (Southern Spain), a carbonate aquifer formed of Triassic marbles, is considered as representative of Mediterranean coastal karst formations. The use of a multi-method approach has permitted the computation of a wide range of groundwater infiltration rates (17–60%) by means of direct application of hydrometeorological methods (Thornthwaite and Kessler) and spatially distributed information (modified APLIS method). A spatially weighted recharge rate of 42% results from the most coherent information on physiographic and hydrogeological characteristics of the studied system. Natural aquifer discharge and groundwater abstraction have been volumetrically quantified, based on flow and water-level data, while the relevance of SGD was estimated from the spatial analysis of salinity, ²²²Rn and the short-lived radium isotope ²²⁴Ra in coastal seawater. The total mean aquifer discharge (44.9–45.9 hm³ year^?1) is in agreement with the average recharged groundwater (44.7 hm³ year^?1), given that the system is volumetrically equilibrated during the study period. Besides the groundwater resources assessment, the methodological aspects of this research may be interesting for groundwater management and protection strategies in coastal areas, particularly karst environments.     

Temporal Changes in Seawater Carbonate Chemistry and Carbon Export from a Southern California Estuary

Estuaries are important subcomponents of the coastal ocean, but knowledge about the temporal and spatial variability of their carbonate chemistry, as well as their contribution to coastal and global carbon fluxes, are limited. In the present study, we measured the temporal and spatial variability of biogeochemical parameters in a saltmarsh estuary in Southern California, the San Dieguito Lagoon (SDL). We also estimated the flux of dissolved inorganic carbon (DIC) and total organic carbon (TOC) to the adjacent coastal ocean over diel and seasonal timescales. The combined net flux of DIC and TOC (F_DIC?+?TOC) to the ocean during outgoing tides ranged from ??1.8±0.5?×?10³ to 9.5±0.7?×?10³?mol C h^?1 during baseline conditions. Based on these fluxes, a rough estimate of the net annual export of DIC and TOC totaled 10±4?×?10⁶?mol C year^?1. Following a major rain event (36 mm rain in 3 days), F_DIC?+?TOC increased and reached values as high as 29.0 ±?0.7?×?10³?mol C h^?1. Assuming a hypothetical scenario of three similar storm events in a year, our annual net flux estimate more than doubled to 25 ±?4?×?10⁶?mol C year^?1. These findings highlight the importance of assessing coastal carbon fluxes on different timescales and incorporating event scale variations in these assessments. Furthermore, for most of the observations elevated levels of total alkalinity (TA) and pH were observed at the estuary mouth relative to the coastal ocean. This suggests that SDL partly buffers against acidification of adjacent coastal surface waters, although the spatial extent of this buffering is likely small.     

镭同位素示踪隆教湾的海底地下水排泄

福建省漳州市隆教湾海水中镭同位素的研究,目的是评价海底地下水排泄量。在2007年6月的航次中,垂直于岸线的9km剖面上布置15个站位,每个站位用潜水泵采集表层海水样60L于塑料桶中。水样运回实验室后,立即用装有锰纤维的PVC管以虹吸的方式富集水样中的镭同位素,水通过PVC管的流速小于300ml/min。224Ra活度用连续射气法测定,测完224Ra后密封7d以上,然后用直接射气法测定226Ra活度。224Ra和226Ra活度都呈现自岸向海逐渐降低的规律,表明扩散控制镭同位素的分布,由224Ra获得68.83km2d-1的扩散系数,同时226Ra形成-0.963dpm100l-1km-1的活度梯度。用扩散系数和活度梯度建立的226Ra的离岸通量为6.62×1011dpmkm-2d-1,这个通量一定是得到SGD输入的镭支持,从而获得隆教湾的海底地下水排泄量是3.03×109m3km-2d-1。该排泄量包括陆源地下淡水排泄量和再循环海水排泄量,绝大部分可能是再循环海水,有待进一步研究。     

Radium geochemistry of ground waters in Paleozoic carbonate aquifers,midcontinent, USA

The purpose of this study was to elucidate the processes controlling the distribution and behavior of the longer-lived Ra isotopes in continuous Paleozoic carbonate aquifers of parts of Missouri, Kansas, and Oklahoma. Activities of (²²⁸Ra) and (²²⁶Ra) were analyzed in fresh and saline ground waters, brines, and rocks. The fluids have a wide salinity range (200–250,000 mg l⁻¹ total dissolved solids). The (²²⁶Ra) activity ranges from 0.66–7660 dpm kg⁻¹ and correlates with salinity and other alkaline earth element (Ca, Sr, and Ba) concentrations. The range of (²²⁸Ra:²²⁶Ra) ratios in the fluids (0.06–1.48) is similar to that in the aquifer rocks (0.21–1.53). The relatively low mean fluid (²²⁸Ra:²²⁶Ra) ratio (0.30) reflects the low Th:U ratio of the predominant carbonate aquifer rock. Radium occurs mostly (≥77%) as Ra²⁺ species in the fluids. Salinity-dependent sorption–desorption processes (with log K values from 10⁰–10⁴ and negatively correlated with salinity), involving Th-enriched surface coatings on aquifer flow channels, can explain the rapid solid–fluid transfer of Ra isotopes in the system and the correlation of Ra with salinity.     

Assessment of Submarine Groundwater Discharge (SGD) as a Source of Dissolved Radium and Nutrients to Moorea (French Polynesia) Coastal Waters

Previous work has documented large fluxes of freshwater and nutrients from submarine groundwater discharge (SGD) into the coastal waters of a few volcanic oceanic islands. However, on the majority of such islands, including Moorea (French Polynesia), SGD has not been studied. In this study, we used radium (Ra) isotopes and salinity to investigate SGD and associated nutrient inputs at five coastal sites and Paopao Bay on the north shore of Moorea. Ra activities were highest in coastal groundwater, intermediate in coastal ocean surface water, and lowest in offshore surface water, indicating that high-Ra groundwater was discharging into the coastal ocean. On average, groundwater nitrate and nitrite (N + N), phosphate, ammonium, and silica concentrations were 12, 21, 29, and 33 times greater, respectively, than those in coastal ocean surface water, suggesting that groundwater discharge could be an important source of nutrients to the coastal ocean. Ra and salinity mass balances indicated that most or all SGD at these sites was saline and likely originated from a deeper, unsampled layer of Ra-enriched recirculated seawater. This high-salinity SGD may be less affected by terrestrial nutrient sources, such as fertilizer, sewage, and animal waste, compared to meteoric groundwater; however, nutrient-salinity trends indicate it may still have much higher concentrations of nitrate and phosphate than coastal receiving waters. Coastal ocean nutrient concentrations were virtually identical to those measured offshore, suggesting that nutrient subsidies from SGD are efficiently utilized.     

Detecting Freshwater Inputs via Groundwater Discharge to Marina Lagoon, Mediterranean Coast, Egypt

Much work in recent years has reported on the role of submarine groundwater discharge (SGD) on coastal biogeochemistry, but most of those studies have focused on temperate or tropical climates where year-round rainfall recharges surficial aquifers. The aim of this work, however, was to examine SGD behaviors in an arid setting??Marina Lagoon on the Egyptian Mediterranean coast. SGD was estimated via radon surveys and time-series measurements in lagoon waters during two campaigns (wet season in March 2009 and dry season in July 2010). Relatively higher values of radon were detected in March (maximum >30?dpm/L) compared to July (up to 16?dpm/L), which would indicate either enhanced input rates, or lower mixing/atmospheric losses during the wet season. Lower salinity waters within Marina Lagoon were characterized by higher radon and higher concentrations of dissolved inorganic nitrogen (DIN) and silica (DISi), characteristic of groundwater inputs. Based on lagoon and groundwater radon measurements and an advection-diffusion model, SGD average rates between 0.83 to 2.4?×?10⁸?L/day were estimated for both surveys. Since no seasonal pattern was detected, we suspect that either (1) SGD is derived from a regional aquifer not influenced by recharge from local rainfall or (2) local water use for irrigation and domestic purposes artificially recharges the surficial aquifer in the dry summer (tourist) months, which compensates for the lack of rainfall occurring at that time.     

Submarine and intertidal groundwater discharge through a complex multi-level karst conduit aquifer

The quantification of submarine and intertidal groundwater discharge (SiGD) or purely submarine groundwater discharge (SGD) from coastal karst aquifers presents a major challenge, as neither is directly measurable. In addition, the expected heterogeneity and intrinsic structure of such karst aquifers must be considered when quantifying SGD or SiGD. This study applies a set of methods for the coastal karst aquifer of Bell Harbour in western Ireland, using long-term onshore and offshore time series from a high-resolution monitoring network, to link catchment groundwater flow dynamics to groundwater discharge as SiGD. The SiGD is estimated using the “pollution flushing model”, i.e. a mass-balance approach, while catchment dynamics are quantified using borehole hydrograph analysis, single-borehole dilution tests, a water balance calculation, and cross-correlation analysis. The results of these analyses are then synthesised, describing a multi-level conduit-dominated coastal aquifer with a highly fluctuating overflow regime draining as SiGD, which is in part highly correlated with the overall piezometric level in the aquifer. This concept was simulated using a hydraulic pipe network model built in InfoWorks ICM [Integrated Catchment Modeling]^® version 7.0 software (Innovyze). The model is capable of representing the overall highly variable discharge dynamics, predicting SiGD from the catchment to range from almost 0 to 4.3 m³/s. The study emphasises the need for long-term monitoring as the basis for any discharge studies of coastal karst aquifers. It further highlights the fact that multiple discharge locations may drain the aquifer, and therefore must be taken into consideration in the assessment of coastal karst aquifers.     

Analytical descriptions of subaqueous groundwater seepage

Direct measurements of groundwater seepage show the importance of subaqueous discharges as sources of fresh water and of dissolved chemicals to lakes and the coastal ocean. The rate of seepage decreases rapidly offshore; an analytical solution was developed that describes the discharge as Ki(In(coth πxk/4l))/k where i is the hydraulic gradient, K is the vertical hydraulic conductivity,l is the aquifer thickness, x is the distance from the shoreline, and k² is K divided by the horizontal hydraulic conductivity. In addition to variations due to the inhomogeneities in the aquifer, seepage into the coastal ocean involves some recirculation of the salt water. In Great South Bay, New York measured fluxes were as great as 150 I m^?2 d^?1. The discharge near the shore was typically 50 I m^?2 d^?1, decreasing to 30 1 m^?2 d^?1 at a distance of 100 m offshore. Secondary convection due to an unstable density structure at the sediment-water interface may also be superimposed on the seepage distribution. Fingers of salt should be capable of carrying marine water many decimenters downward against the fresh groundwater advection. As a result, care must be exercised in interpreting direct measures of seepage flux to recognize the contribution of recirculated seawater.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

The effect of groundwater seepage on nutrient delivery and seagrass distribution in the northeastern Gulf of Mexico

A hypothesis was tested to determine if a relationship exists between rates of submarine groundwater discharge and the distribution of seagrass beds in the coastal, nearshore northeastern Gulf of Mexico. As determined by nonparametric statistics, four of seven seagrass beds in the northeastern Gulf of Mexico had significantly greater submarine groundwater discharge compared with adjacent sandy areas, but the remainder exhibited the opposite relationship. We were thus unable to verify if a relationship exists between submarine groundwater discharge and the distribution of seagrass beds in the nearshore sites selected. A second objective of this study was to determine the amount of nitrogen and phosphorus delivered to nearshore areas by submarine groundwater discharge. We considered new nutrient inputs to be delivered to surface waters by the upward flux of fresh water. This upward flux of water encounters saline porewaters in the surficial sediments and these porewaters contain recycled nutrients; actual nutrient flux from the sediment to overlying waters includes both new and recycled nutrients. New inputs of nitrogen to overlying surface waters for one 10-km section of coastline, calculated by multiplying groundwater nutrient concentrations from freshwater wells by measured seepage rates, were on the order of 1,100±190 mol N d⁻¹. New and recycled nitrogen fluxes, calculated by multiplying surficial porewater concentrations by measured seepage rates, yielded fluxes of 3,600 ±1,000 mol N d⁻¹. Soluble reactive phosphate values were 150±40 mol P d⁻¹ using freshwater well concentrations and 130±3.0 mol P d⁻¹ using porewater concentrations. These values are comparable to the average nutrient delivery of a small, local river.     

Submarine groundwater discharge enhances primary productivity in the Yellow Sea,China:Insight from the separation of fresh and recirculated components

Submarine groundwater discharge(SGD)is being increasingly recognized as a significant source of nutri-ent into coastal waters,and generally comprises two components:submarine fresh groundwater dis-charge(SFGD)and recirculated saline groundwater discharge(RSGD).The separate evaluation of SFGD and RSGD is extremely limited as compared to the conventional estimation of total SGD and associated nutrient fluxes,especially in marginal-scale regions.In this study,new high-resolution radium isotopes data in seawater and coastal groundwater enabled an estimation of SGD flux in a typical marginal sea of the Yellow Sea.By establishing 226Ra and 228Ra mass balance models,we obtained the SGD-derived radium fluxes,and then estimated the SFGD and RSGD fluxes through a two end-member model.The results showed that the total SGD flux into the Yellow Sea was equivalent to approximately 6.6 times the total freshwater discharge of surrounding rivers,and the SFGD flux accounted for only 5.2％-8.8％of the total SGD.Considering the nutrient concentrations in coastal fresh and saline groundwater,we obtained the dissolved inorganic nutrient fluxes(mmol m-2 yr-1)to be 52-353 for nitrogen(DIN),0.21-1.4 for phosphorus(DIP),34-226 for silicon(DSi)via SFGD,and 69-262 for DIN,1.0-3.9 for DIP,70-368 for DSi via RSGD,with the sum of nutrient fluxes equaling to(1.8-9.3)-fold,(1.3-5.6)-fold and(2.0-9.5)-fold of the riverine inputs.Compared to the conventional estimation of the total SGD flux,the nutrient fluxes derived from the separation of SFGD and RSGD were(1.6-2.1),(1.6-1.8)and(4.0-4.9)times lower for DIN,DIP and DSi,respectively,indicating that the estimates by separating SFGD and RSGD could be conservative and representative results of the Yellow Sea.Furthermore,we suggested that SGD played an important role in nutrient sources among all the traditional nutrient inputs sources,providing 15％-48％,33％-68％and 14％-43％of the total DIN,DIP and DSi input fluxes into the Yellow Sea,and the high nutrient stoichiometric ratios(i.e.,DIN/DIP)in SGD probably contributed to the increasing ratios in the Yellow Sea.In addition delivering large amounts of nutrient into the Yellow Sea,SGD would create primary productivity of 10-49,1.6-6.8 and 8.8-42 g C m-2 yr-1 based on N,P and Si,which were equivalent to 5.2％-27％,0.9％-3.7％and 4.7％-23％of the total primary productivity,respectively.In par-ticular,the SFGD-derived DIN flux can be converted to primary productivity of 4.2-28 g C m-2 yr-1 thus demonstrating the disproportionately large role of SFGD in ecological environment of the Yellow Sea rel-ative to its flux.Therefore,we conclude that SGD,particularly SFGD,plays an important role as a nutrient source for the Yellow Sea,and not only affects nutrient budgets and structures but also enhances the pri-mary productivity.     

Geochemical and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

Variations of Hydrodynamics and Submarine Groundwater Discharge in the Yellow River Estuary Under the Influence of the Water-Sediment Regulation Scheme

The “Water-Sediment Regulation Scheme” (WSRS) is critically important to the hydrologic evaluation of the Yellow River estuary since a huge pulse of water and sediment are delivered into the sea during a short period. We used the natural geochemical tracers radium (²²³Ra, ²²⁴Ra, ²²⁶Ra) and radon (²²²Rn) isotopes as well as other hydrological parameters to investigate the mixing variations and submarine groundwater discharge (SGD) in the Yellow River estuary under the influence of the 2013 WSRS. Dramatically elevated radium and radon isotopic activities were observed during this WSRS compared with activities measured during a non-WSRS period. Radium “water ages” indicated that the offshore transport rate nearly tripled when the river discharge increased from 400 to 3400 m³/s. We calculated the SGD flux in the Yellow River estuary based on a radium mass balance model as well as radium and radon time-series models. The SGD flux was estimated at 0.02~0.20 m/day during a non-WSRS period and 0.67~1.22 m/day during the 2013 WSRS period. The results also indicate that large river discharge tends to lead more intense SGD along the river channel direction with a large amount of fresh SGD.     

Trace element cycling in a subterranean estuary: Part 2. Geochemistry of the pore water

Submarine groundwater discharge (SGD) is an important source of dissolved elements to the ocean, yet little is known regarding the chemical reactions that control their flux from sandy coastal aquifers. The net flux of elements from SGD to the coastal ocean is dependent on biogeochemical reactions in the groundwater-seawater mixing zone, recently termed the “subterranean estuary.” This paper is the second in a two part series on the biogeochemistry of the Waquoit Bay coastal aquifer/subterranean estuary. The first paper addressed the biogeochemistry of Fe, Mn, P, Ba, U, and Th from the perspective of the sediment composition of cores Charette et al. [Charette, M.A., Sholkovitz, E.R., Hansell, C.M., 2005. Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments. Geochim. Cosmochim. Acta, 69, 2095-2109]. This paper uses pore water data from the subterranean estuary, along with Bay surface water data, to establish a more detailed view into the estuarine chemistry and the chemical diagenesis of Fe, Mn, U, Ba and Sr in coastal aquifers. Nine high-resolution pore water (groundwater) profiles were collected from the head of the Bay during July 2002. There were non-conservative additions of both Ba and Sr in the salinity transition zone of the subterranean estuary. However, the extent of Sr release was significantly less than that of its alkaline earth neighbor Ba. Pore water Ba concentrations approached 3000 nM compared with 25-50 nM in the surface waters of the Bay; the pore water Sr-salinity distribution suggests a 26% elevation in the amount of Sr added to the subterranean estuary. The release of dissolved Ba to the mixing zone of surface estuaries is frequently attributed to an ion-exchange process whereby seawater cations react with Ba from river suspended clay mineral particles at low to intermediate salinity. Results presented here suggest that reductive dissolution of Mn oxides, in conjunction with changes in salinity, may also be an important process in maintaining high concentrations of Ba in the pore water of subterranean estuaries. In contrast, pore water U was significantly depleted in the subterranean estuary, a result of SGD-driven circulation of seawater through reducing permeable sediments. This finding is supported by surface water concentrations of U in the Bay, which were significantly depleted in U compared with adjacent coastal waters. Using a global estimate of SGD, we calculate U removal in subterranean estuaries at 20 × 10⁶ mol U y⁻¹, which is the same order of magnitude as the other major U sinks for the ocean. Our results suggest a need to revisit and reevaluate the oceanic budgets for elements that are likely influenced by SGD-associated processes.     

Sorption of radium-226 from oil-production brine by sediments and soils

The sorption of²²⁶Ra from oil-production brine by soils and sediments was investigated. Sorption was rapid, and the percentage sorbed increased with brine dilution. Greatest removals of²²⁶Ra from sediments in the laboratory occurred with alkaline DTPA, HCl, and BaCl₂, with lesser removals using CaCl₂ and NaCl solutions. Digestion of sediments with NaOCl indicates that most of the native and sorbed²²⁶Ra is associated with the mineral rather than organic fraction of the sediments. Correlation analysis based on 14 soils indicates that the retention of²²⁶Ra may involve precipitation reactions associated with sulfate-bearing minerals, as well as ion-exchange reactions with the clay mineral fractions of surficial earth materials. Oceanographer, Naval Ocean Research and Development Activity, Code 334; NSTL Station, Mississippi 39529 NORDA Contribution #83:334:01.