TIMS measurements of Ra and Ra in the Gulf of Lion, an attempt to quantify submarine groundwater discharge

Submarine groundwater discharge (SGD) is now recognized as an important pathway for water and chemical species fluxes to the coastal ocean. In order to determinate SGD to the Gulf of Lion (France), we measured the activities of ²²⁶Ra and ²²⁸Ra by thermal ionization mass spectrometry (TIMS) in coastal waters and in the deep aquifer waters of the Rhone deltaic plain after pre-concentration of radium by MnO₂. Compared to conventional counting techniques, TIMS requires lower quantities of water for the analyses, and leads to higher analytical precision. Radium isotopes were thus measured on 0.25–2 L water samples containing as little as 20 fg of ²²⁶Ra and 0.2–0.4 fg of ²²⁸Ra with precision equal to 2%. We demonstrate that coastal surface waters samples are enriched in ²²⁶Ra and ²²⁸Ra compared to the samples further offshore. The high precision radium measurements display a small but significant ²²⁶Ra and ²²⁸Ra enrichment within a strip of circa 30 km from the coast. Radium activities decrease beyond this region, entrained in the northern current along the shelf break or controlled by eddy diffusion. The radium excess in the first 30 km cannot be accounted for by the river nor by the early diagenesis. The primary source of the radium enrichment must therefore be ascribed to the discharge of submarine groundwater. Using a mass-balance model, we estimated the advective fluxes of ²²⁶Ra and ²²⁸Ra through SGD to be 5.2 × 10¹⁰ and 21 × 10¹⁰ dpm/d respectively. The ²²⁶Ra activities measured in the groundwater from the Rhone deltaic plain aquifer are comparable to those from other coastal groundwater studies throughout the world. By contrast, ²²⁸Ra activities are higher by up to one order of magnitude. Taking those groundwater radium activities as typical of the submarine groundwater end-member, a minimum volume of 0.24–4.5 × 10¹⁰ l/d is required to support the excess radium isotopes on the inner shelf. This has to be compared with the average rivers water runoff of 15.4 × 10¹⁰ l/d during the study period (1.6 to 29% of the river flow).     

Submarine groundwater discharge to Great South Bay, NY, estimated using Ra isotopes

There is increasing evidence that submarine groundwater discharge (SGD) in many areas represents a major source of dissolved chemical constituents to the coastal ocean. In Great South Bay, NY, previous studies have shown that the discharge of nutrients with SGD may cause harmful algal blooms. This study estimates SGD to Great South Bay during August 2006 by performing a mass balance for each of the dissolved Ra isotopes (²²⁴Ra, ²²³Ra, ²²⁸Ra, ²²⁶Ra). The budget indicates a major unknown source (between 30 and 60% of the total input) of Ra to the bay. This imbalance can be resolved by a flux of Ra-enriched groundwater on the order of 3.5–4.5 × 10⁹ L d^− 1, depending on the Ra isotope. The Ra-estimated SGD rates compare well with those previously estimated by models of flow that decreases exponentially away from shore. Compared to previous reports of fresh groundwater discharge to the bay, the Ra-estimated discharge must comprise approximately 90% recirculated seawater. The good agreement between Ra- and model-estimated flow rates indicates that the primary SGD endmember may be best sampled at shallow depths in the sediments a short distance bayward of the low tide line.     

Submarine groundwater discharge and nutrient addition to the coastal zone and coral reefs of leeward Hawai'i

Multiple tracers of groundwater input (salinity, Si, ²²³Ra, ²²⁴Ra, and ²²⁶Ra) were used together to determine the magnitude, character (meteoric versus seawater), and nutrient contribution associated with submarine groundwater discharge across the leeward shores of the Hawai'ian Islands Maui, Moloka'i, and Hawai'i. Tracer abundances were elevated in the unconfined coastal aquifer and the nearshore zone, decreasing to low levels offshore, indicative of groundwater discharge (near-fresh, brackish, or saline) at all locations. At several sites, we detected evidence of fresh and saline SGD occurring simultaneously. Conservative estimates of SGD fluxes ranged widely, from 0.02–0.65 m³ m^− 2 d^− 1at the various sites. Groundwater nutrient fluxes of 0.04–40 mmol N m^− 2 d^− 1 and 0.01–1.6 mmol P m^− 2 d^− 1 represent a major source of new nutrients to coastal ecosystems along these coasts. Nutrient additions were typically greatest at locations with a substantial meteoric component in groundwater, but the recirculation of seawater through the aquifer may provide a means of transferring terrestrially-derived nutrients to the coastal zone at several sites.     

Radium tracing of submarine groundwater discharge (SGD) and associated nutrient fluxes in a highly-permeable bed coastal zone, Korea

In order to estimate submarine groundwater discharge (SGD) and SGD-driven nutrient fluxes, we measured the concentrations of nutrients, ²²⁴Ra, and ²²⁶Ra in seawater, river water, and coastal groundwater of Yeongil Bay (in the southeastern coast of Korea) in August 2004 and February 2005. The bottom sediments over the shallow areas of this bay are composed mainly of coarse sands. Large excess concentrations of ²²⁴Ra, ²²⁶Ra, and Si supplied from SGD were observed in August 2004, while these excess concentrations were not apparent in February 2005. Based on the mass balance for ²²⁴Ra, ²²⁶Ra, and Si, which showed conservative mixing behavior in seawater, SGD was estimated to be approximately 6 × 10⁶ m³ day^− 1 (seepage rate = 0.2 m day^− 1) in shallow areas (< 9 m water depth) in August 2004, which is much higher than the SGD level typically found in other coastal regions worldwide. During the summer period, SGD-driven nutrients in this bay contributed approximately 98%, 12%, and 76% of the total inputs for dissolved inorganic nitrogen (DIN), phosphorus (DIP), and silicate (DSi), respectively. Our study implies that the ecosystem in this highly permeable bed coastal zone is influenced strongly by SGD during summer, while such influences are negligible in winter.     

Estimating submarine groundwater discharge around Isola La Cura, northern Venice Lagoon (Italy), by using the radium quartet

The four naturally-occurring radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra and ²²⁸Ra) were used to estimate the submarine groundwater discharge (SGD) in the Isola La Cura marsh area in the northern Venice Lagoon (Italy). By determining the radium contributors to the study area (river, coastal ocean and sediments) the radium excess in the lagoon water was quantified through a mass balance model. This radium excess is attributed to a submarine groundwater discharge source and represents the most important input of radium. Possible endmembers were considered from analysis of groundwater samples (subtidal and marsh piezometers, marsh wells and seepage meters) that were enriched in Ra by one to two orders of magnitude relative to surface waters. In particular, a permeable layer at 80 cm depth in the surrounding marsh is considered to be representative of the most likely SGD source, although similar radium activities were measured in other subtidal porewater samples collected in the Isola La Cura area. The estimated SGD flux to the study area ranged from 1 · 10⁹ to 6 · 10⁹ L·d^− 1, the same order of magnitude as the overall riverine input to the lagoon (3 · 10⁹ L·d^− 1). A major fraction of this SGD flux is likely recirculated seawater, as evidenced by the endmember salinity. The water residence time of 2 days was estimated by both using the shortest-lived radium isotope and estimating the volume of water exchanged between the lagoon and the open sea during a tidal cycle (tidal prism approach). This SGD flux could be used to estimate the input of other chemical species (metals, nutrients, etc.) via SGD which might affect the Venice Lagoon ecosystem.     

苏北浅滩海底地下水排放及其对海域营养盐通量的贡献

海底地下水排放(SGD)是近海海域的一个重要的营养盐来源。本研究借助多种天然镭同位素对春季苏北浅滩海域的SGD及其携带入海的营养盐通量进行量化评估。研究发现:苏北浅滩海域的~(224)Ra、~(223)Ra和~(226)Ra等镭同位素的浓度水平较高,呈现近岸高、远岸低的分布趋势;根据~(224)Ra/~(226)Ra的"表观年龄模型"估算的水龄的分布情况推断,春季该海域表层水体主体流向为东北向,流速约为0.1m/s,这与前人物理海洋数值模拟结果一致;最终利用226Ra质量平衡模型发现海域的SGD通量为(46±29)cm/d,由其携带入海的溶解态无机氮、磷、硅营养盐(DIN、 DIP、 DSi)等的通量分别为(2.6±3.1)×1~09、(3.0±2.5)×10~6和(5.5±4.2)×10~8mol/d。     

Isotopic,trace element and nutrient characterization of coastal waters from Ubatuba inner shelf area,south-eastern Brazil

Stable isotopes, tritium, radium isotopes, radon, trace elements and nutrients data were collected during two sampling campaigns in the Ubatuba coastal area (south-eastern Brazil) with the aim of investigating submarine groundwater discharge (SGD) in the region. The isotopic composition (δD, δ¹⁸O, ³H) of submarine waters was characterised by significant variability and heavy isotope enrichment. The stable isotopes and tritium data showed good separation of groundwater and seawater groups. The contribution of groundwater in submarine waters varied from a few % to 17%. Spatial distribution of ²²²Rn activity concentration in surface seawater revealed changes between 50 and 200 Bq m⁻³ which were in opposite relationship with observed salinities. Time series measurements of ²²²Rn activity concentration in Flamengo Bay (from 1 to 5 kBq m⁻³), obtained by in situ underwater gamma-spectrometry showed a negative correlation between the ²²²Rn activity concentration and tide/salinity. This may be caused by sea level changes as tide effects induce variations of hydraulic gradients, which increase ²²²Rn concentration during lower sea level, and opposite, during high tides where the ²²²Rn activity concentration is smaller. The estimated SGD fluxes varied during 22–26 November between 8 and 40 cm d⁻¹, with an average value of 21 cm d⁻¹ (the unit is cm³/cm² per day). The radium isotopes and nutrient data showed scattered distributions with offshore distance and salinity, which implies that in a complex coast with many small bays and islands, the area has been influenced by local currents and groundwater–seawater mixing. SGD in the Ubatuba area is fed by coastal contaminated groundwater and re-circulated seawater (with small admixtures of groundwater), which claims for potential environmental concern with implications on the management of freshwater resources in the region.     

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (²²²Rn, ^{223,224,226,228}Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5 mg L^− 1) close to zero salinity and increased several-fold ( 18 mg L^− 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet.Surface water-column ²²²Rn activities were most elevated (> 28 dpm L^− 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (^{223,224,226,228}Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess ²²⁶Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 × 10⁵ m³ d^− 1 (20–74 L m^− 2 d^− 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH₄⁺ and PO₄^− 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5 μmol m^− 2 d^− 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates.     

海底地下水排放对典型红树林蓝碳收支的影响

海底地下水排放(Submarine Groundwater Discharge,SGD)是陆海相互作用的重要表现形式之一,其携带的物质对近岸海域生源要素的收支有重要影响。本文利用222Rn示踪技术估算了我国典型红树林海湾—广西珍珠湾在2019年枯季(1月)SGD携带的碳通量。调查发现,地下水中222Rn活度、溶解无机碳(DIC)和溶解有机碳(DOC)的平均浓度均高于河水和湾内表层海水。利用222Rn质量平衡模型估算得到珍珠湾SGD速率为(0.36±0.36) m/d,SGD输入到珍珠湾的DIC和DOC通量分别为(2.41±2.63)×107 mol/d和(1.96±2.20)×106 mol/d。珍珠湾溶解碳的源汇收支表明,SGD携带的DIC和DOC分别占珍珠湾总DIC和总DOC来源的91%和89%。因此,SGD携带的DIC和DOC是珍珠湾DIC和DOC的主要来源,是海岸带蓝碳收支和生物地球化学循环过程中的重要组成。     

Seasonal changes in submarine groundwater discharge to coastal salt ponds estimated using Ra and Ra as tracers

Submarine groundwater discharge (SGD) to coastal southern Rhode Island was estimated from measurements of the naturally-occurring radioisotopes ²²⁶Ra (t_1/2 = 1600 y) and ²²⁸Ra (t_1/2 = 5.75 y). Surface water and porewater samples were collected quarterly in Winnapaug, Quonochontaug, Ninigret, Green Hill, and Pt. Judith–Potter Ponds, as well as nearly monthly in the surface water of Rhode Island Sound, from January 2002 to August 2003; additional porewater samples were collected in August 2005. Surface water activities ranged from 12–83 dpm 100 L^− 1 (60 dpm = 1 Bq) and 21–256 dpm 100 L^− 1 for ²²⁶Ra and ²²⁸Ra, respectively. Porewater ²²⁶Ra activities ranged from 16–736 dpm 100 L^− 1 (2002–2003) and 95–815 dpm 100 L^− 1 (2005), while porewater ²²⁸Ra activities ranged from 23–1265 dpm 100 L^− 1. Combining these data with a simple box model provided average ²²⁶Ra-based submarine groundwater fluxes ranging from 11–159 L m^− 2 d^− 1 and average ²²⁸Ra-derived fluxes of 15–259 L m^− 2 d^− 1. Seasonal changes in Ra-derived SGD were apparent in all ponds as well as between ponds, with SGD values of 30–472 L m^− 2 d^− 1 (Winnapaug Pond), 6–20 L m^− 2 d^− 1 (Quonochontaug Pond), 36–273 L m^− 2 d^− 1 (Ninigret Pond), 29–76 L m^− 2 d^− 1 (Green Hill Pond), and 19–83 L m^− 2 d^− 1 (Pt. Judith–Potter Pond). These Ra-derived fluxes are up to two orders of magnitude higher than results predicted by a numerical model of groundwater flow, estimates of aquifer recharge for the study period, and values published in previous Ra-based SGD studies in Rhode Island. This disparity may result from differences in the type of flow (recirculated seawater versus fresh groundwater) determined using each technique, as well as variability in porewater Ra activity.     

228Ra, 226Ra, 224Ra and 223Ra in potential sources and sinks of land-derived material in the German Bight of the North Sea: implications for the use of radium as a tracer

Activities of the naturally occurring radium nuclides ²²⁸Ra, ²²⁶Ra, ²²⁴Ra and ²²³Ra were determined in waters of the open German Bight and adjacent nearshore areas in the North Sea, in order to explore the potential use of radium isotopes as natural tracers of land–ocean interaction in an environment characterised by extensive tidal flats, as well as riverine and groundwater influx. Data collected at various tidal phases from the Weser Estuary (²²⁸Ra: 46.3 ± 4.6; ²²⁶Ra: 17.1 ± 1.1; ²²⁴Ra: 26.1 ± 8.2 to 36.5 ± 6.1; ²²³Ra: 1.8 ± 0.1 to 4.0 ± 0.4), tidal flats near Sahlenburg (²²⁸Ra: 39.3 ± 3.8 to 46.0 ± 4.5; ²²⁶Ra: 15.5 ± 1.5 to 16.5 ± 1.7; ²²⁴Ra: 34.3 ± 2.2 to 85.3 ± 6.3; ²²³Ra: 3.6 ± 0.5 to 8.0 ± 1.2), freshwater seeps on tidal flats near Sahlenburg (²²⁸Ra: 42.1 ± 4.1; ²²⁶Ra: 21.3 ± 2.2; ²²⁴Ra: 5.1 ± 0.9; ²²³Ra: 2.6 ± 1.3) and also in permanently inundated parts of the North Sea (²²⁸Ra: 23.0 ± 2.3 to 28.2 ± 2.8; ²²⁶Ra: 8.2 ± 0.8 to 11.8 ± 1.2; ²²⁴Ra: 3.1 ± 1.0 to 10.1 ± 0.9; ²²³Ra: 0.1 ± 0.02 to 0.9 ± 0.05; units: disintegrations per minute per 100 kg water sample) reveal that, except for the fresh groundwater, the potential end-members of nearshore water mass mixing have quite similar radium signatures, excluding a simple discrimination between the sources. However, the decreasing activities of the short-lived ²²⁴Ra and ²²³Ra isotopes recorded towards the island of Helgoland in the central German Bight show a potential to constrain fluxes of land-derived material to the open North Sea. The largest source for all radium isotopes is generally found on the vast tidal flats and in the Weser Estuary. Future work could meaningfully combine this so-called radium quartet approach with investigations of radon activity. Indeed, preliminary data from a tidal flat site with fresh groundwater seepage reveal a ²²²Rn signal that is clearly lower in seawater.     

Radium mass-balance in Jamaica Bay, NY: Evidence for a substantial flux of submarine groundwater

A mass balance for the naturally-occurring radium isotopes (²²⁴Ra, ²²³Ra, ²²⁸Ra, and ²²⁶Ra) in Jamaica Bay, NY, was conducted by directly estimating the individual Ra contributions of wastewater discharge, diffusion from fine-grained subtidal sediments, water percolation through marshes, desorption from resuspended particles, and water exchange at the inlet. The mass balance revealed a major unknown source term accounting for 19–71% of the total Ra input, which could only be resolved by invoking a source from submarine groundwater. Shallow (< 2 m depth) groundwater from permeable sediments in Jamaica Bay was brackish and enriched in Ra relative to surface bay waters by over two orders of magnitude. To balance Ra fluxes, a submarine groundwater input of 0.8 × 10⁹–9.0 × 10⁹ L d^− 1 was required. This flux was similar for all four isotopes, with individual estimates varying by less than a factor of 2. Our calculated groundwater flux was 6- to 70-fold higher than the fresh groundwater discharge to the bay estimated by hydrological methods, but closely matched direct flow rates measured with seepage meters. This suggests that a substantial portion of the discharge consisted of recirculated seawater. The magnitude of submarine groundwater discharge varied seasonally, in the order: summer > autumn > spring. Chemical analyses suggest that the recirculated seawater component of submarine groundwater delivers as much dissolved nitrogen to the bay as the fresh groundwater flux.     

Characterizing sources of groundwater to a tropical coastal lagoon in a karstic area using radium isotopes and water chemistry

Radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and water chemistry were used to identify two chemically distinct sources of submarine groundwater discharge (SGD) in Celestún Lagoon, Yucatán, Mexico. Low salinity groundwater discharging from springs within the lagoon has previously been identified and extensively sampled for nutrient concentrations. However, a second type of groundwater discharging into the lagoon was detected during this study using radium isotope activity measurements. This second type of groundwater is characterized by moderate salinities (within the range of lagoon salinities) and very elevated radium activities in comparison to the low salinity groundwater, mixed lagoon water, and seawater. Further analysis showed that the two types of groundwater also have distinct chloride, strontium, and sulfate ratios, along with slightly different nutrient concentrations. Groundwater discharge occurs through large and small springs scattered throughout the lagoon, and both types of groundwater were detected discharging from one of the larger springs. The relative proportions of low salinity groundwater and brackish high radium groundwater varied over the tidal cycle. In order to better understand the relative contributions of each type of groundwater to the lagoon, a three end-member mixing model based on the distinct chemical and isotopic compositions of both types of groundwater and of seawater was used to estimate the distribution of each water type throughout the lagoon in different seasons. This study suggests that substantial groundwater discharge to the lagoon can occur during both dry and rainy seasons. The presence of two groundwater sources has implications for monitoring and protection of the Celestún Lagoon Biosphere Reserve, since the two sources may have different susceptibilities to anthropogenic contamination depending on their respective recharge area and recharge rates.     

基于223Ra和224Ra的桑沟湾海底地下水排放通量

海底地下水排放（SGD）是陆地向海洋输送水量和营养物质的重要通道之一,对沿海物质通量及其生物地球化学循环有重要的影响,对生态环境起着不可忽视的作用。本文运用天然放射性同位素223Ra和224Ra示踪估算了我国北方典型养殖基地桑沟湾的海底地下水排放通量。结果表明,海底地下水样尤其是间隙水中Ra活度[224Ra=（968±31）dpm/（100 L）,223Ra=（31.4±4.9）dpm/（100 L）,n=9]远高于表层海水[224Ra=（38.7±2.0）dpm/（100 L）,223Ra=（1.70±0.50）dpm/（100 L）, n=21]。假设稳态条件下,考虑Ra的各源、汇项,利用Ra平衡模型,估算出桑沟湾SGD排放通量为（0.23~1.03）×107 m3/d。潮周期内的观测结果显示,涨潮时,水力梯度较小,SGD排放变弱,落潮时,水力梯度较大,导致了相对较多的SGD排放。在一个潮周期间,基于223Ra和224Ra得到的SGD排放通量平均为0.39×107 m3/d。潮汐动力下的SGD排放平均占总SGD排放的61%,因此桑沟湾沿岸的地下水排放主要受潮汐动力的影响,并对海水组成及海陆间物质交换有显著贡献。     

Submarine groundwater discharge: A large, previously unrecognized source of dissolved iron to the South Atlantic Ocean

This paper reports the initial results of a study of groundwater and coastal waters of southern Brazil adjacent to a 240 km barrier spit separating the Patos Lagoon, the largest coastal lagoon in South America, from the South Atlantic Ocean. The objective of this research is to assess the chemical alteration of freshwater and freshwater–seawater mixtures advecting through coastal permeable sands, and the influence of the submarine discharge of these fluids (SGD) on the chemistry of coastal waters. Here we focus on dissolved iron in this system and use radium isotopic tracers to quantify SGD and cross-shelf fluxes. Iron concentrations in groundwaters vary between 0.6 and 180 μM. The influence of the submarine discharge of these fluids into the surf zone produces dissolved Fe concentrations as high as several micromolar in coastal surface waters. The offshore gradient of dissolved Fe, coupled with results for Ra isotopes, is used to quantify the SGD flux of dissolved Fe from this coastline. We estimate the SGD flux to be 2 × 10⁶ mol day^− 1 and the cross-shelf flux to be 3.2 × 10⁵ mol day^− 1. This latter flux is equal to about 10% of the soluble atmospheric Fe flux to the entire South Atlantic Ocean. We speculate on the importance of this previously unrecognized iron input to regional ocean production and on the potential significance of this source to understanding variations in glacial–interglacial ocean production.     

Extended time series measurements of submarine groundwater discharge tracers (222Rn and CH4) at a coastal site in Florida

We report the results of an experiment in which we measured ²²²Rn (15,000 observations), CH₄ (40,000 observations), and associated variables in seawater nearly continuously at a coastal site in the Gulf of Mexico for almost two years. Significant correlations between ²²²Rn and CH₄ imply that they are derived from a common source, most likely groundwater. However, we were unable to explain the overall tracer variability as a single function of groundwater table height, temperature, tidal range, and wind speed, indicating multiple, overlapping controls on SGD dynamics at this site. Methane and radon concentrations may vary 2-fold in a given well in the subterranean estuary over tidal time scales, demonstrating the complexity of determining SGD endmember concentrations and suggesting that unaccounted for temporal changes in groundwater may explain some of the patterns observed in seawater. Surprisingly, the variability of ²²²Rn and CH₄ in seawater over short (e.g., hourly) time scales was generally comparable to or even more pronounced than fluctuations over much longer (e.g., monthly) scales. While high tracer concentrations usually occurred during low tide and low tracer concentrations during high tide, this pattern was occasionally inverted or absent indicating that no single model can be used to describe the entire data set. We also describe a sequence of events in which SGD tracers were depleted in coastal waters during storms and regenerated afterwards. We found no increase in radon activities immediately after the largest storm (75 mm rainfall) perhaps because of the short residence times of groundwater in contrast to the ingrowth time of radon. Marine controls appeared to be the most important SGD drivers with only minor influence relating to the shallow and deep aquifers. This implies that seasonal investigations of SGD tracers in the coastal ocean may be masked by short-term variability.     

Comparison of techniques for pre-concentrating radium from seawater

In the framework of the KEOPS project (KErguelen: compared study of the Ocean and the Plateau in Surface water), we aimed to provide information on the water mass pathways and vertical mixing on the Kerguelen Plateau, Southern Ocean, based on ²²⁸Ra profiles. Because ²²⁸Ra activities are extremely low in this area (~ 0.1 dpm/100 kg or ~ 2.10^− 18 g kg^− 1), the filtration of large volumes of seawater was required in order to be able to detect it with minimal uncertainty. This challenging study was an opportunity for us to test and compare methods aimed at removing efficiently radium isotopes from seawater. We used Mn-fiber that retains radium and that allows the measurement of all four radium isotopes (²²⁶Ra, ²²⁸Ra, ²²³Ra, ²²⁴Ra). First, we used Niskin bottles or the ship's seawater intake to collect large volumes of seawater that were passed onto Mn-fiber in the laboratory. Second, we filled cartridges with Mn-fiber that we placed in tandem on in situ pumps. Finally, we fixed nylon nets filled with Mn-fiber on the frame of in situ pumps to allow the passive filtration of seawater during the pump deployment.Yields of radium fixation on the cartridges filled with Mn-fiber and placed on in situ pumps are ca. 30% when combining the two cartridges. Because large volumes of seawater can be filtered with these pumps, this yields to effective volumes of 177–280 kg (that is, higher than that recovered from fourteen 12-l Niskin bottles). Finally, the effective volume of seawater that passed through Mn-fiber placed in nylon nets and deployed during 4 h ranged between 125 and 364 kg. Consequently, the two techniques that separate Ra isotopes in situ are good alternatives for pre-concentrating radium from seawater. They can save ship-time by avoiding repeated CTD casts to obtain the large volumes of seawater. This is especially true when in situ pumps are deployed to collect suspended particles. However, both methods only provide ²²⁸Ra/²²⁶Ra ratios. The determination of the ²²⁸Ra specific activity is obtained by multiplying this ratio by the ²²⁶Ra activity measured in a discrete sample collected at the same water depth.     

Determination of residence time and mixing processes of the Ubatuba,Brazil, inner shelf waters using natural Ra isotopes

Coastal waters contain elevated dissolved activities of short-lived radium isotopes, ²²³Ra and ²²⁴Ra, having half-lives of 11.4 and 3.66 days, respectively. The input of these isotopes near the coast must be balanced by decay and mixing into the open ocean, where excess activities are zero. Since the decay rate is known, in the ideal case the mixing rate may be determined from the offshore distribution of these isotopes. This study found that samples collected in June 2000 followed the expected exponential decrease with distance offshore. We assign a dispersion coefficient of 28–39 m² s⁻¹ for this study. During January 2002 and November 2003, there was not a consistent decrease of activity with distance offshore. This is likely due to the ruggedness of the coastline, where many bays and small islands interrupt simple mixing patterns. To estimate exchange rates during 2002 and 2003, we used a model based on the decrease in the ²²⁴Ra/²²³Ra activity ratio (AR) with time for samples isolated from fresh inputs of Ra. This model yielded residence times of 1–2 weeks for samples collected within 20 km of the coast. We used this residence time to calculate the flux of ²²⁸Ra (half-life = 5.7 years) to the study area necessary to maintain the enrichment relative to ocean water. This enrichment is a factor of ten greater than the flux of ²²⁸Ra expected from submarine groundwater discharge (SGD) occurring within 50 m of shore.     

Estimating submarine groundwater discharge at a subtropical river estuary along the Beibu Gulf,China

In certain regions,submarine groundwater discharge(SGD) into the ocean plays a significant role in coastal material fluxes and their biogeochemical cycle;therefore,the impact of SGD on the ecosystem cannot be ignored.In this study,SGD was estimated using naturally occurring radium isotopes(~(223)Ra and ~(224)Ra) in a subtropical estuary along the Beibu Gulf,China.The results showed that the Ra activities of submarine groundwater were approximately 10 times higher than those of surface water.By assuming a steady state and using an Ra mass balance model,the SGD flux in May 2018 was estimated to be 5.98×10~6 m~3/d and 3.60×10~6 m~3/d based on ~(224)Ra and ~(223)Ra,respectively.At the same time,the activities of Ra isotopes fluctuated within a tidal cycle;that is,a lower activity was observed at high tide and a higher activity was seen at low tide.Based on these variations,the average tidal pumping fluxes of SGD were 1.15×10~6 m~3/d and 2.44×10~6 m~3/d with ~(224)Ra and ~(223)Ra,respectively.Tidaldriven SGD accounts for 24%-51% of the total SGD.Therefore,tidal pumping is an important driving force of the SGD in the Dafengjiang River(DFJR) Estuary.Furthermore,the SGD of the DFJR Estuary in the coastal zone contributes significantly to the seawater composition of the Beibu Gulf and the material exchange between land and sea.     

白令海峡水团来源的镭同位素示踪

对白令海峡64.3°N纬向断面镭同位素的研究表明,水体中226Ra比活度、228Ra比活度和228Ra/226Ra)A.R.存在明显的纬向变化,反映出太平洋与北冰洋水体交换的多种路径.根据温度、盐度和镭同位素的水平与垂直分布,太平洋水进入北冰洋的路径可能主要有3支,分别为白令海峡西侧的阿拉德水、白令海峡东侧的阿拉斯加沿...