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.     

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.     

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: 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.     

Submarine groundwater discharge of nutrients to the ocean along a coastal lagoon barrier, Southern Brazil

The Patos–Mirim Lagoon system along the southern coast of Brazil is linked to the coastal ocean by a narrow mouth and by groundwater transport through a Holocene barrier. Although other groundwater systems are apparently active in this region, the hydraulic head of the lagoon, the largest in South America, drives groundwater transport to the coast. Water levels in wells placed in the barrier respond to changing water level in the lagoon. The wells also provide a measure of the nutrient concentrations of groundwater flowing toward the ocean. Additionally, temporary well points were used to obtain nutrient samples in groundwater on the beach face of the barrier. These samples revealed a subterranean freshwater–seawater mixing zone over a ca. 240 km shoreline. Previously published results of radium isotopic analyses of groundwater and of surface water from cross-shelf transects were used to estimate a water flux of submarine groundwater discharge (SGD) to nearshore surface waters of 8.5 × 10⁷ m³/day. Using this SGD and the nutrient concentrations in different compartments, nutrient fluxes between groundwater and surface water were estimated. Fluxes were computed using both average and median reservoir (i.e. groundwater and surface water) nutrient concentrations. The SGD total dissolved inorganic nitrogen, phosphate and silicate fluxes (2.42, 0.52, 5.92 × 10⁶ mol day^− 1, respectively) may represent as much as 55% (total N) to 10% (Si) of the nutrient fluxes to the adjacent shelf environment. Assuming nitrogen limitation, SGD may be capable of supporting a production rate of ca. 3000 g C m² year^− 1in the nearshore surf zone in this region.     

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.     

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.     

Radium and radon radioisotopes in regional groundwater, intertidal groundwater, and seawater in the Adelaide Coastal Waters Study area: Implications for the evaluation of submarine groundwater discharge

The input of groundwater-borne nutrients to Adelaide's (South Australia) coastal zone is not well known but could contribute to the ongoing decline of seagrass in the area. As a component of the Adelaide Coastal Waters Study (ACWS), the potential for using the radium quartet (²²³Ra, ²²⁴Ra, ²²⁶Ra and ²²⁸Ra) and ²²²Rn to evaluate submarine groundwater discharge (SGD) was evaluated. Potential isotopic signatures for SGD were assessed by sampling groundwater from three regional aquifers potentially contributing SGD to the ACWS area. In addition, intertidal groundwater was sampled at two sand beach sites. In general, the regional groundwaters were enriched in long-lived Ra isotopes (²²⁶Ra and ²²⁸Ra) and in ²²²Rn relative to intertidal groundwater. Radium activity (but not ²²²Rn activity) was positively correlated to salinity in groundwater from one of the regional aquifers and in intertidal groundwater. Radium isotope ratios (²²³Ra/²²⁶Ra, ²²⁴Ra/²²⁶Ra and ²²⁸Ra/²²⁶Ra) were less variable than individual Ra isotope activities within potential SGD sources. Recirculated seawater (estimated from the intertidal groundwater samples with seawater-like salinities) also had distinctly higher Ra isotope ratios than the regional groundwaters. The activities for all radioisotopes were relatively low in seawater. The activity of the short-lived ²²³Ra and ²²⁴Ra were highest at the shoreline and declined exponentially with distance offshore. In contrast, ²²⁸Ra and ²²⁶Ra activities had a weak linear declining trend with distance offshore. Rn-222 activity was at or near background in all seawater samples. The pattern of enrichment in short-lived Ra isotopes and the lack of ²²²Rn in seawater suggest that seawater recirculation is the main contributor to SGD in the ACWS area. Preliminary modeling of the offshore flux of ²²⁸Ra and ²²⁶Ra suggest that the SGD flux to the ACWS area ranges between 0.2 and 3 · 10^− 3 m³ (m of shoreline)^− 1 s^− 1.     

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.     

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.     

Short-lived radium isotopes in the Hawaiian margin: Evidence for large fluid fluxes through the Puna Ridge

We measured significant activities of short-lived radium isotopes, ²²³Ra (half-life = 11 days) and ²²⁴Ra (half-life = 3.7 days), around the margins of the Hawaiian Islands to water depths of 3500 m. These measurements suggest fluid inputs from the basalt to the surrounding ocean. In general ²²³Ra activities were considerably greater than ²²⁴Ra in spite of the expected higher production rate of ²²⁴Ra activity in basalt. The ²²³Ra was not supported by dissolved ²²⁷Ac. The highest enrichments of ²²³Ra were measured over the Puna Ridge (2100 m depth) east of Hawaii. Here ²²³Ra activities reached 19 dpm/m³, similar to activities measured near sites of active submarine groundwater discharge in the South Atlantic Bight. To explain the high activities of ²²³Ra unaccompanied by ²²⁴Ra, we postulate that thermally-driven circulation of seawater through the Puna Ridge deposits ²³¹Pa on basalt surfaces. With time the ²³¹Pa produces ²²⁷Ac and ²²³Ra; and ²²³Ra desorbs into the circulating fluids. These fluids then transport ²²³Ra into the overlying ocean. Based on the inventory of ²²³Ra above the Puna Ridge, we estimate the flow of fluids through the ridge to be on the order of 20–60 cm³ cm^− 2 day^− 1. In less than 1000 years the incoming seawater could provide enough ²³¹Pa to basalt surfaces to balance the inventory of ²²³Ra above the ridge if only 8% of the ²²³Ra was transported to the overlying water. These observations on the flanks of a volcanically-active ocean island have significant implications for quantifying fluid fluxes from the flanks of the mid-ocean ridge system. By mapping ²²³Ra inventories in the ocean above ridge flanks and measuring the activity of ²²³Ra in the emerging fluids, the fluid flux can be obtained.     

Water mass ages of coastal ponds estimated using Ra and Ra as tracers

Measurements of the naturally occurring radioisotopes ²²³Ra (t_1/2 = 11.4 days) and ²²⁴Ra (t_1/2 = 3.66 days) in southern Rhode Island salt ponds were combined with a simple model to obtain independent estimates of the age of these coastal waters. 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, beginning January 2002 through August 2003. Surface water activities ranged from 1–78 dpm 100 L^− 1 and 5–885 dpm 100 L^− 1 for ²²³Ra and ²²⁴Ra, respectively. Porewater radium activities ranged from 3 to 715 dpm 100 L^− 1 for ²²³Ra, and 57–4926 dpm 100 L^− 1 for ²²⁴Ra. Results indicate seasonally varying water mass ages for Ninigret (5–12 days), Winnapaug (2–6 days) and Pt. Judith-Potter Ponds (1–9 days) and, in contrast, relatively constant ages for Green Hill (5–7 days) and Quonochontaug Ponds (3–6 days).     

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。     

Coincident application of a mass balance of radium and a hydrodynamic model for the seasonal quantification of groundwater flux into the Venice Lagoon, Italy

A mass balance of the naturally occurring short-lived radium isotopes (^223,224Ra) in the Venice Lagoon was conducted by an integrated approach combining the directly estimated individual Ra contributions and hydrodynamic model results. Hydrodynamic data allows for the calculation of the Ra mass balance in sub-sections of the Venice Lagoon (boxes), which are characterized by physically homogeneous properties, instead of investigating the entire lagoon. Utilizing this method, both the seasonal and the spatial variability of the submarine groundwater discharge in the Venice Lagoon have been estimated. Between 14–83 × 10⁹ L d^− 1 of water were calculated to flow across the sediment–sea interface, corresponding to 5–28 times the mean annual river input. The submarine groundwater discharge estimates were correlated with the residence time calculation to better understand spatial and seasonal variation.     

Elemental mercury concentrations and formation rates in the Scheldt estuary and the North Sea

Concentrations of Hg⁰ in surface waters and atmosphere of the Scheldt estuary and the North Sea are presented and their relationship with biological processes is discussed. Hg⁰ concentrations in the Scheldt estuary range from 0.1 to 0.38 pmol·l⁻¹ in the winter and from 0.24 to 0.65 pmol·l⁻¹ in the summer and show a positive relationship with phytoplankton pigments. In the North Sea Hg⁰ concentrations range from 0.06 to 0.8 pmol·l⁻¹ and are higher in coastal stations. Transfer velocities across the air–sea interface were calculated using a classical shear turbulence model. Volatilization fluxes of Hg⁰ were calculated for the Scheldt estuary and the North Sea. For the Scheldt estuary the fluxes range from 226–284 pmol·m⁻²·d⁻¹ in winter and 500–701 pmol·m⁻²·d⁻¹ in summer and for the North Sea the fluxes range from 59–1110 pmol·m⁻²·d⁻¹ for an average windspeed of 8.1 m·s⁻¹. These fluxes are comparable to the wet and dry depositional fluxes to the North Sea. Hg⁰ formation rates necessary to balance the volatilization fluxes vary from 0.2 to 4% d⁻¹.     

Rapid sediment accumulation and microbial mineralization in forests of the mangrove Kandelia candel in the Jiulongjiang Estuary, China

Rates of sediment accumulation and microbial mineralization were examined at three Kandelia candel forests spanning the intertidal zone along the south coastline of the heavily urbanized Jiulongljiang Estuary, Fujian Province, China. Mass sediment accumulation rates were rapid (range: 10–62 kg m⁻² y⁻¹) but decreased from the low- to the high-intertidal zone. High levels of radionuclides suggest that these sediments originate from erosion of agricultural soils within the catchment. Mineralization of sediment carbon and nitrogen was correspondingly rapid, with total rate of mineralization ranging from 135 to 191 mol C m⁻² y⁻¹ and 9 to 11 mol N m⁻² y⁻¹; rates were faster in summer than in autumn/winter. Rates of mineralization efficiency (70–93% for C; 69–92% for N) increased, as burial efficiency (7–30% for C; 8–31% for N) decreased, from the low-to the high-intertidal mangroves. Sulphate reduction was the dominant metabolic pathway to a depth of 1 m, with rates (19–281 mmol S m⁻² d⁻¹) exceeding those measured in other intertidal deposits. There is some evidence that Fe and Mn reduction-oxidation cycles are coupled to the activities of live roots within the 0–40 cm depth horizon. Oxic respiration accounted for 5–12% of total carbon mineralization. Methane flux was slow and highly variable when detectable (range: 5–66 μmol CH₄ m⁻² d⁻¹). Nitrous oxide flux was also highly variable, but within the range (1.6–106.5 μmol N₂O m⁻² d⁻¹) measured in other intertidal sediments. Rates of denitrification were rapid, ranging from 1106 to 3780 μmol N₂ m⁻² d⁻¹, and equating to 11–20% of total sediment nitrogen inputs. Denitrification was supported by rapid NH₄ release within surface deposits (range: 3.6–6.1 mmol m⁻² d⁻¹). Our results support the notion that mangrove forests are net accumulation sites for sediment and associated elements within estuaries, especially Kandelia candel forests receiving significant inputs as a direct result of intense human activity along the south China coast.     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.     

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.     

The European coastal zone: characterization and first assessment of ecosystem metabolism

The geomorphic, oceanographic, terrestrial and anthropogenic attributes of the European coastal zone are described and published data on ecosystem function (primary production and respiration) are reviewed. Four regions are considered: the Baltic Sea, Mediterranean Sea, Black Sea and the European Atlantic coast including the North Sea. The metabolic database (194 papers) suffers from a non-homogeneous geographical coverage with no usable data for the Black Sea which was therefore excluded from this part of our study. Pelagic gross primary production in European open shelves is, by far, the most documented parameter with an estimated mean of 41 mmol C m⁻² d⁻¹, the lowest value is reported in the Mediterranean Sea (21 mmol C m⁻² d⁻¹) and the highest one in the Atlantic/North Sea area (51 mmol C m⁻² d⁻¹). Microphytobenthic primary production, mostly measured in shallow areas, is extrapolated to the entire 0–200 m depth range. Its contribution to total primary production is low in all regions (mean: 1.5 mmol C m⁻² d⁻¹). Although macrophyte beds are very productive, a regional production estimate is not provided in this study because their geographical distribution along the European coastline remains unknown. Measurements of pelagic community respiration are clearly too sparse, especially below the euphotic zone, to yield an accurate picture of the fate of organic matter produced in the water column. With a mean value of 17 mmol C m⁻² d⁻¹, benthic community respiration consumes approximately 40% of the pelagic organic matter production. Estuaries generally exhibit high metabolic rates and a large range of variation in all parameters, except microphytobenthic primary production. Finally, the problem of eutrophication in Europe is discussed and the metabolic data obtained in the framework of the Land–Ocean Interactions in the Coastal Zone (LOICZ) project are compared with available direct measurements of net ecosystem production.     

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.