Improving estuarine net flux estimates for dissolved cadmium export at the annual timescale: Application to the Gironde Estuary

Dissolved Cd (Cd_D) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net Cd_D fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating Cd_D concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (Cd_D⁰), each representative of one distinct situation. The obtained Cd_D⁰ concentrations were relatively similar (201 ± 28 ng L⁻¹) when freshwater discharge Q was >500 m³ s⁻¹ (508 ≤ Q ≤ 2600 m³ s⁻¹), but were highly variable (340 ± 80 ng L⁻¹; 247–490 ng L⁻¹) for low discharge situations (169 ≤ Q ≤ 368 m³ s⁻¹). The respective daily Cd_D net fluxes were 5–39 kg day⁻¹, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual Cd_D net fluxes, we proposed an empirical model, using representative Cd_D⁰ values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable Cd_D net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a⁻¹ in 2005 and 6.0–7.2 t a⁻¹ in 2004, depending on freshwater discharge. Comparing Cd_D net fluxes with the incoming Cd_D fluxes suggested that the annual net Cd_D addition in the Gironde Estuary ranged from 3.5 to 6.7 t a⁻¹, without any clear temporal trend during the past seven years. The annual Cd_D net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual Cd_D net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.     

Relevance of peat draining rivers in central Sumatra for the riverine input of dissolved organic carbon into the ocean

Sources and discharges of dissolved organic carbon (DOC) from the central Sumatran river Siak were studied. DOC concentrations in the Siak ranged between 560 and 2594 μmol l⁻¹ and peak out after its confluence with the river Mandau. The Mandau drains part of the central Sumatran peatlands and can be characterized as a typical blackwater river due to its high DOC concentration, its dark brown-coloured, acidic water (pH 4.4–4.7) and its low concentration of total suspended matter (12–41 mg l⁻¹). The Mandau supplies about half of the DOC that enters the Siak Estuary where it mixes conservatively with ocean water. The DOC input from the Siak into the ocean was estimated to be 0.3 Tg C yr⁻¹. Extrapolated to entire Indonesia the data suggest a total Indonesian DOC export of 21 Tg yr⁻¹ representing 10% of the global riverine DOC input into the ocean.     

Concentrations of mercury in near shore surface waters of the bay of Biscay and in the Gironde Estuary

Total and reactive mercury concentrations have been measured on samples of surface water taken along the shores of the Bay of Biscay and in the Gironde Estuary. In the low turbid areas of the Bay of Biscay the average concentration of total mercury of unfiltered samples is 3.5 ± 0.7 (n = 15) and the reactive mercury 2.1 ± 0.7 (n = 12) pmol l⁻¹; the high levels, up to 27.6 (total mercury) and 4.6 (reactive mercury) pmol l⁻¹ are from the most turbid samples taken from the Marennes-Oléron basin. In the Gironde Estuary, the distribution of total dissolved mercury rises to a peak of concentration (38 pmol l⁻¹) within the high turbidity zone where the salinity is lower than 10‰. The possible origin of this pattern of distribution is discussed.     

Inputs of organic carbon from Ria de Aveiro coastal lagoon to the Atlantic Ocean

Land/ocean boundaries constitute complex systems with active physical and biogeochemical processes that affect the global carbon cycle. An example of such a system is the mesotidal lagoon named Ria de Aveiro (Portugal, 40°38′N, 08°45′W), which is connected to the Atlantic Ocean by a single channel, 350 m wide. The objective of this study was to estimate the seasonal and inter-tidal variability of organic carbon fluxes between the coastal lagoon and the Ocean, and to assess the contribution of the organic carbon fractions (i.e. dissolved organic carbon (DOC) and particulate organic carbon (POC)) to the export of organic carbon to the Ria de Aveiro plume zone. The organic carbon fractions fluxes were estimated as the product of the appropriate fractional organic carbon concentrations and the water fluxes calculated by a two-dimensional vertically integrated hydrodynamic model (2DH). Results showed that the higher exchanges of DOC and POC fractions at the system cross-section occurred during spring tides but only resulted in a net export of organic carbon in winter, totalling 85 t per tidal cycle. Derived from the winter and summer campaigns, the annual carbon mass balance estimated corresponded to a net export of organic carbon (7957 = 6585 t yr⁻¹ POC + 1372 t yr⁻¹ DOC). On the basis of the spring tidal drainage area, it corresponds to an annual flux of 79 g m⁻² of POC and 17 g m⁻² of DOC out of the estuary.     

Possible effects of climate change on estuarine nutrient fluxes: a case study in the highly nutrified Schelde estuary (Belgium, The Netherlands)

Global change models predict effects of climate change on hydrological regimes at the continental scale in Europe. The aim of this study was to gain a better understanding of the possible effect of changing external forcing conditions on the functioning of estuarine ecosystems. In densely populated areas, anthropogenic nutrient enrichment and consequent alteration of nutrient biogeochemical cycles have already had a big impact on these ecosystems. The average yearly discharge of the upper Schelde estuary increased nearly threefold over the period 1996–2000, from 28 m³ s⁻¹ in 1996 to 73 m³ s⁻¹ in 2000. The continuously rising discharge conditions over the five-year period were used as a reference situation for possible future effects of climate on ecological functioning through increase of discharge. At high discharges, nutrient (NH₄⁺, NO₃⁻, dissolved silica and PO₄³⁻) concentrations in the tidal fresh- and brackish water showed a decrease of up to 50% while total discharged nutrient loadings increased up to 100%. Opposite effects of increasing discharge on NH₄⁺, NO₃⁻ and dissolved silica concentrations in summer and winter, resulted in the flattening out of seasonal cycles for these nutrients. Under high discharge conditions, silica uptake by diatom communities was lowered. Dissolved silica loadings to the coastal area increased concurrently with total silica loadings upstream. Salt intrusion to the marine parts of the estuary decreased. This resulted in a downstream shift of the salinity gradient, with lower salinity observed near the mouth. As a result, TDIN, NO₃⁻ and dissolved silica concentrations doubled at the mouth of the estuary.     

Effect of salinity on heavy metal mobility and availability in intertidal sediments of the Scheldt estuary

The effect of the flood water salinity on the mobility of heavy metals was studied for intertidal sediments of the Scheldt estuary (Belgium). Soils and sediments of 4 sampling sites were flooded with water of different salinities (0.5, 2.5, and 5 g NaCl L⁻¹). Metal concentrations were monitored in pore water and surface water. To study the potential effects of flood water salinity on metal bioavailability, duckweed (Lemna minor) was grown in the surface water. The salinity was found to primarily enhance the mobility of Cd and its uptake by duckweed. Cadmium concentrations in pore water of soils and sediments and surrounding surface waters significantly exceeded sanitation thresholds and quality standards during flooding of initially oxidized sediments. Moreover, the effect was observed already at lower salinities of 0.5 g NaCl L⁻¹. This implies that risks related to Cd uptake by organisms and Cd leaching to ground water are relevant when constructing flooding areas in the brackish zones of estuaries. These risks can be reduced by inducing sulphide precipitation because Cd is then immobilised as sulphide and its mobility becomes independent of flood water salinity. This could be achieved by permanently flooding the polluted sediments, because sulphates are sufficiently available in the river water of the brackish part of the estuary.     

Carbon cycling in a high-arctic marine ecosystem – Young Sound, NE Greenland

Young Sound is a deep-sill fjord in NE Greenland (74°N). Sea ice usually begins to form in late September and gains a thickness of 1.5 m topped with 0–40 cm of snow before breaking up in mid-July the following year. Primary production starts in spring when sea ice algae begin to flourish at the ice–water interface. Most biomass accumulation occurs in the lower parts of the sea ice, but sea ice algae are observed throughout the sea ice matrix. However, sea ice algal primary production in the fjord is low and often contributes only a few percent of the annual phytoplankton production. Following the break-up of ice, the immediate increase in light penetration to the water column causes a steep increase in pelagic primary production. Usually, the bloom lasts until August–September when nutrients begin to limit production in surface waters and sea ice starts to form. The grazer community, dominated by copepods, soon takes advantage of the increased phytoplankton production, and on an annual basis their carbon demand (7–11 g C m⁻²) is similar to phytoplankton production (6–10 g C m⁻²). Furthermore, the carbon demand of pelagic bacteria amounts to 7–12 g C m⁻² yr⁻¹. Thus, the carbon demand of the heterotrophic plankton is approximately twice the estimated pelagic primary production, illustrating the importance of advected carbon from the Greenland Sea and from land in fuelling the ecosystem.In the shallow parts of the fjord (<40 m) benthic primary producers dominate primary production. As a minimum estimate, a total of 41 g C m⁻² yr⁻¹ is fixed by primary production, of which phytoplankton contributes 15%, sea ice algae <1%, benthic macrophytes 62% and benthic microphytes 22%. A high and diverse benthic infauna dominated by polychaetes and bivalves exists in these shallow-water sediments (<40 m), which are colonized by benthic primary producers and in direct contact with the pelagic phytoplankton bloom. The annual benthic mineralization is 32 g C m⁻² yr⁻¹ of which megafauna accounts for 17%. In deeper waters benthic mineralization is 40% lower than in shallow waters and megafauna, primarily brittle stars, accounts for 27% of the benthic mineralization. The carbon that escapes degradation is permanently accumulated in the sediment, and for the locality investigated a rate of 7 g C m⁻² yr⁻¹ was determined.A group of walruses (up to 50 adult males) feed in the area in shallow waters (<40 m) during the short, productive, ice-free period, and they have been shown to be able to consume <3% of the standing stock of bivalves (Hiatella arctica, Mya truncata and Serripes Groenlandicus), or half of the annual bivalve somatic production. Feeding at greater depths is negligible in comparison with their feeding in the bivalve-rich shallow waters.     

Dissolved silica budget for the Baltic Sea

A budget model covering the Baltic Sea was developed for the time period 1980–2000 to estimate water and dissolved silica (DSi) fluxes as well as internal DSi sinks/sources. The Baltic Sea was resolved by eight basins, where the largest basin — the Baltic Proper — was divided laterally into north/west and southern/east parts as well as vertically to take into account the existence of the permanent halocline. The basins demonstrated rather different patterns with regard to silica cycling. The Gulfs of Finland and Riga together with the northernmost basins, Bothnian Bay and Bothnian Sea, are distinguished by substantial specific rates of silica removal accounting for 1.6–4.9 g Si m^− 2 yr^− 1. Bearing in mind the large total primary production, the basins comprising the Baltic Proper with the specific removal rates 0.2 and 1.2 g Si m^− 2 yr^− 1, do not appear as regions with a high silica accumulation. The Arkona and the Kattegat mainly behave as regions of rapid through-flows. These results point out the northernmost Gulf of Bothnia, the Gulfs of Riga and Finland as areas with a larger share of biogenic silica accumulation than in the Baltic Proper. It is attributed to hydrographic and hydrochemical features. An estimate of diatom export production was made for the Baltic Proper showing that the diatom contribution accounts for 19–44% of the net export production.     

A sulfur budget for the Black Sea anoxic zone

A budget for the sulfur cycle in the Black Sea is proposed which incorporates specific biogeochemical process rates. The average sulfide production in the water column is estimated to be 30–50 Tg yr⁻¹, occurring essentially in the layer between 500 and 2000 m. About 3.2–5.2 Tg sulfide yr⁻¹ form during sulfate reduction in surface sediments of the anoxic zone. Total sulfur burial in anoxic sediments of 1 Tg yr⁻¹ consists of 10–70% (ca. 40–50% is the average) water column formed (syngenetic) component, the rest being diagenetic pyrite. As a maximum, between 3 and 5 Tg yr⁻¹ contribute sulfide to the bottom water or diffuse downward in the sediment. About 20–50 Tg yr⁻¹ sulfide is oxidized mostly at the chemocline and about 10–20% of this amount (4.4–9.2 Tg yr⁻¹) below the chemocline by the oxygen of the Lower Bosphorus Current. A model simulating the vertical distribution of sulfide in the Black Sea water column shows net consumption in the upper layers down to ca. 500 m, essentially due to oxidation at the chemocline, and net production down to the bottom. On the basis of the calculated budget anoxic conditions in the Black Sea are sustained by the balance between sulfide production in the anoxic water column and oxidation at the chemocline. On average the residence time of sulfide in the anoxic zone is about 90–150 yr, comparable to the water exchange time between oxic and anoxic zones. Hydrophysical control on the sulfur cycle appears to be the main factor regulating the extent of anoxic conditions in the Black Sea water column, rather than rates of biogeochemical processes.     

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959–1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990–1999 are about 34×10⁹ m³ year⁻¹ for river water, 3.24×10⁶ t year⁻¹ for suspended solids (TSS) and 9.88×10⁹ mol year⁻¹ for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110×10³ mol year⁻¹ of which 19.6×10³ mol year⁻¹ are transported in the dissolved and 90.8×10³ mol year⁻¹ in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻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.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

Isotopic fractionation of dissolved nitrate during denitrification in the eastern tropical north pacific ocean

The isotopic composition (δ¹⁵N) of dissolved nitrate was measured at five stations within the oxygen-deficient region of the eastern tropical North Pacific Ocean (ETNP) and at one station 900 km northeast of Hawaii, which was considered to be representative of all major water masses of the Pacific. At this last station, the δ¹⁵N composition of dissolved nitrate decreased systematically from about +6‰ at 400 m to approximately +5‰ at 5,000 m; these results are consistent with other estimates from the western Pacific.In contrast, vertical profiles of δ¹⁵N of dissolved nitrate from the ETNP showed marked departure from the above observed trend and correlated with losses of nitrate arising from denitrification. Instantaneous fractionation factors (α) were estimated, using the one dimensional vertical diffusion-advection model. These results suggest that ¹⁴NO₃⁻ is consumed 3–4% faster than ¹⁵NO₃⁻, significantly larger than fractionations (2%) observed under laboratory conditions.Maximum rates of denitrification at 100 m were also evaluated and ranged from 0.6 to 8 μg-at 1⁻¹ yr⁻¹ for the stations investigated. The above upper limit is probably excessive, but the average maximum for the four stations analyzed is estimated to be 3.5 μg-at NO₃⁻ 1⁻¹ yr⁻¹. These results compare favorably with suitably corrected oxygen utilization rates derived from electron transport activity measurements.     

Seasonal variability of leaf litter removal by crabs in a Kandelia candel mangrove forest in Jiulongjiang Estuary, China

The seasonal variability of leaf litter removal by crabs was observed from May 2006 to April 2007 in a Kandelia candel mangrove forest in Jiulongjiang Estuary, China. Daily average quantities of leaf fall ranged 0.85–3.86 gDW m⁻² d⁻¹, with high values in May, August, October and November. The whole-year's leaf fall was 6.48 t ha⁻¹ yr⁻¹ (1.81 gDW m⁻² d⁻¹). The standing stock of leaf litter on the forest floor was 7.78 gDW m⁻² averaged from the whole year's data, with the lowest value in December (1.23 gDW m⁻²) and the highest in April (16.18 gDW m⁻²). Annually averaged removal (consumption on mangrove floor + burial in burrows) rate of leaf litter by crabs was 0.59 gDW m⁻² d⁻¹. High seasonal variability was observed in the removal rates of leaf litter by crabs. Removal rates in the winter months (December, January and February) were 0.07–0.09 gDW m⁻² d⁻¹, much lower than those in other months with values of 0.59–1.18 gDW m⁻² d⁻¹. Annually averaged percentage of leaf fall removed by crabs was 33%, with the highest values in September (reached 76%) and the lowest values in winter months. Of leaf litter removed by crabs, a large proportion was buried by crabs, and only 12% was consumed by crabs on the forest floor. Leaf litter removal rate, consumption rate on the forest floor, percentages of leaf fall and standing stock removed on the forest floor were significantly positively correlated with air temperature, indicating that leaf removal ability by crabs was higher in warm months than in cold months.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

Particle fluxes to the interior of the Southern Ocean in the Western Pacific sector along 170°W

An array of five bottom-tethered moorings with 19 PARFLUX time-series sediment trap at three depths (1 and 2 km below the surface, and 0.7 km above the sea-floor) was deployed in the western Pacific sector of the Southern Ocean, along 170°W. The five stations were selected to sample settling particles in the main hydrological zones of the Southern Ocean. The sampling period spanned 425 days (November 28, 1996–January 23, 1998) and was divided into 13 or 21 synchronized time intervals. A total of 174 sequential samples were recovered and analyzed to estimate fluxes of total mass (TMF), organic carbon, carbonate, biogenic silica, and lithogenic particles. The fluxes of biogenic material were higher than anticipated, challenging the notion that the Southern Ocean is a low-productivity region. Organic carbon fluxes at 1 km depth within the Polar Frontal Zone and the Antarctic Zone were relatively uniform (1.7–2.3 g m⁻² yr⁻¹), and about twice the estimated ocean-wide average (ca. 1 g m⁻² yr⁻¹). Carbonate fluxes were also high and uniform between the Subantarctic Front and ca. 64°S (11–13 g m⁻² yr⁻¹). A large fraction of the carbonate flux in the Antarctic Zone was due to the presence of pteropod shells. Coccoliths were found only to the north of the Polar Front, and calcium carbonate became the dominant phase in the Subantarctic Zone. In contrast, carbonate particles were nearly absent near 64°S. Latitudinal variations in biogenic silica fluxes were substantial. The large opal flux (57 g m⁻² yr⁻¹) measured in the Antarctic Zone suggests that opal productivity in this region has been previously underestimated and helps to explain the high sedimentary opal accumulation often found south of the Polar Front. Unlike biogenic material, fluxes of lithogenic particles were among the lowest measured in the open-ocean (0.12–0.05 g m⁻² yr⁻¹), reflecting a very low dust input.     

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.     

Physical and biological characteristics of the pelagic system across Fram Strait to Kongsfjorden

The Fram Strait is very important with regard to heat and mass exchange in the Arctic Ocean, and the large quantities of heat carried north by the West Spitsbergen Current (WSC) influence the climate in the Arctic region as a whole. A large volume of water and ice is transported through Fram Strait, with net water transport of 1.7–3.2 Sv southward in the East Greenland Current and a volume ice flux in the range of 0.06–0.11 Sv. The mean annual ice flux is about 866,000 km² yr⁻¹. The Kongsfjorden–Krossfjorden fjord system on the coast of Spitsbergen, or at the eastern extreme of Fram Strait, is mainly affected by the northbound transport of water in the WSC. Mixing processes on the shelf result in Transformed Atlantic Water in the fjords, and the advection of Atlantic water also carries boreal fauna into the fjords. The phytoplankton production is about 80 g C m⁻² yr⁻¹ in Fram Strait, and has been estimated both below and above this for Kongsfjorden. The zooplankton fauna is diverse, but dominated in terms of biomass by calanoid copepods, particularly Calanus glacialis and C. finmarchicus. Other important copepods include C. hyperboreus, Metridia longa and the smaller, more numerous Pseudocalanus (P. minutus and P. acuspes), Microcalanus (M. pusillus and M. pygmaeus) and Oithona similis. The most important species of other taxa appear to be the amphipods Themisto libellula and T. abyssorum, the euphausiids Thysanoessa inermis and T. longicaudata and the chaetognaths Sagitta elegans and Eukrohnia hamata. A comparison between the open ocean of Fram Strait and the restricted fjord system of Kongsfjorden–Krossfjorden can be made within limitations. The same species tend to dominate, but the Fram Strait zooplankton fauna differs by the presence of meso- and bathypelagic copepods. The seasonal and inter-annual variation in zooplankton is described for Kongsfjorden based on the record during July 1996–2002. The ice macrofauna is much less diverse, consisting of a handful of amphipod species and the polar cod. The ice-associated biomass transport of ice-amphipods was calculated, based on the ice area transport, at about 3.55 × 10⁶ ton wet weight per year or about 4.2 × 10⁵ t C yr⁻¹. This represents a large energy input to the Greenland Sea, but also a drain on the core population residing in the multi-year pack ice (MYI) in the Arctic Ocean. A continuous habitat loss of MYI due to climate warming will likely reduce dramatically the sympagic food source. The pelagic and sympagic food web structures were revealed by stable isotopes. The carbon sources of particulate organic matter (POM), being Ice-POM and Pelagic-POM, revealed different isotopic signals in the organisms of the food web, and also provided information about the sympagic–pelagic and pelagic–benthic couplings. The marine food web and energy pathways were further determined by fatty acid trophic markers, which to a large extent supported the stable isotope picture of the marine food web, although some discrepancies were noted, particularly with regard to predator–prey relationships of ctenophores and pteropods.     

Nutrient budgets and trophic state in a hypersaline coastal lagoon: Lagoa de Araruama, Brazil

Lagoa de Araruama in the state of Rio de Janeiro, Brazil, is a hypersaline lagoon with salinity varying spatially from 45 to 56. We collected water samples during monthly cruises throughout the lagoon, and along the streams feeding the system, from April 1991 to March 1992. Nutrients and other water quality parameters exhibited great spatial and temporal variations. Mass balance calculations indicate large amounts of anthropogenic nutrient inputs. The data indicate that the lagoon currently is oligotrophic but is in a state of transition to become a mesotrophic system. Molar dissolved inorganic nitrogen:dissolved inorganic phosphorus (DIN/DIP) varied between 2.2:1 and 659:1 with a volume-weighted average of 22:1. The high DIN/DIP ratio contrasts with that found in nearby lagoons, suggesting that phytoplankton primary production is limited by phosphorus in Lagoa de Araruama. The major loss of DIP is apparently driven by biological assimilation and diagenic reactions in the sediments. Calculations indicate that the lagoon is slightly net autotrophic at +0.9 mol C m⁻² yr⁻¹. This suggests that the biomass of the primary producers is restricted by phosphorus availability. Phosphorus retention in the sediment and the hypersaline state of the lagoon prevent changes in autotrophic communities and the formation of eutrophic conditions.