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.     

Fluxes and sources of suspended organic matter in an estuarine turbidity maximum region during low discharge conditions

Water column concentrations of total suspended solids (TSS), particulate organic carbon (POC) and particulate nitrogen (PN) were measured at three different depths in four different locations bracketing the estuarine turbidity maximum (ETM) along the main channel of a temperate riverine estuary (Winyah Bay, South Carolina, USA). Measurements were carried out over full tidal cycle (over 24 h). Salinity, temperature, current magnitude and direction were also monitored at the same time throughout the water column. Tidally averaged net fluxes of salt, TSS, POC and PN were calculated by combining the current measurements with the concentration data. Under the extreme low river discharge conditions that characterized the study period, net landward fluxes of salt were measured in the lower part of the study area, suggesting that the landward transport through the main channel of the estuary was probably balanced by export out through the sides. In contrast, the net fluxes of salt in the upper reaches of the study area were near zero, indicating a closed salt balance in this part of the estuary. In contrast to salt, the net fluxes of TSS, POC and PN in the deeper parts of the water column were consistently landward at all four sites in Winyah Bay indicating the non-conservative behavior of particulate components and their active transport up the estuary in the region around the ETM.The carbon contents (%POC), carbon:nitrogen ratios (org[C:N]a) and stable carbon isotopic compositions (δ¹³C_POC) of the suspended particles varied significantly with depth, location and tidal stage. Tidally averaged compositions showed a significant increase up the estuary in the %POC and org[C:N]a values of suspended particles consistent with the preferential landward transport of carbon-rich particles with higher vascular plant debris content. The combination of tidal resuspension and flood-dominated flow appeared to be responsible for the hydrodynamic sorting of particles along the estuary that resulted in denser, organic-poor particles being transported landward less efficiently. The elemental and isotopic compositions indicated that vascular C₃ plants and estuarine algae were the major sources of the particulate organic matter of all the samples, without any significant contributions from salt marsh C₄ vegetation (Spartina alterniflora) and/or marine phytoplankton.     

Dispersal and deposition of suspended sediment on the shelf off the Tagus and Sado estuaries, S.W. Portugal

The Portuguese margin in front of the Tagus and Sado rivers is characterized by a narrow shelf incised by numerous canyons and by a large mud deposit. The two estuaries that feed this continental margin have distinct impact. The suspended particulate matter concentration values in the mouth of the Tagus are four times higher than in the Sado. During the summer the surface nepheloid layer is always larger than during the winter when it is restricted near the mouth of the estuary. This nepheloid layer may reach 30 km in length extending westward. The bottom nepheloid layer usually shows higher nephelometer values, and has a typical distribution: it is usually diverted southward in the direction of the Lisbon Submarine Canyon. We estimate the amount of suspended matter being discharged annually from the Tagus estuary to be between 0.4 and 1×10⁶ t. The area covered by fine deposits is about 560 km². Hence the thickness of sediments deposited annually should be between 0.07 and 0.18 cm. The sedimentation rates calculated from the ²¹⁰Pb excess vary between 0.16 and 2.13 cm y⁻¹ which correspond to the maximum rate. For a layer of 1 cm thick, 81,000 t of particulate organic carbon (POC) should be trapped. That would represent, with a minimum sedimentation rate between 0.07 and 0.18 cm y⁻¹, an entrapment of 6000–15,000 t POC y⁻¹. The trace metals content of box core samples clearly shows the anthropogenic impact in the uppermost level (5 cm thick) in the Tagus estuary and in all the sedimentary deposits (15 cm thick) on the shelf muddy area. Despite the narrowness of the shelf, a significant part of continental fluxes fails to reach the deep ocean.     

Short-lived thorium isotopes (Th, Th) as indicators of POC export and particle cycling in the Ross Sea, Southern Ocean

Repeated measurements of depth profiles of ²³⁴Th (dissolved, 1–70 and >70 μm particulate) at three stations (Orca, Minke, Sei) in the Ross Sea have been used to estimate the export of Th and particulate organic carbon (POC) from the euphotic zone. Sampling was carried out on three JGOFS cruises covering the period from October 1996 (austral early spring) to April 1997 (austral fall). Deficiencies of ²³⁴Th relative to its parent ²³⁸U in the upper 100 m are small during the early spring cruise, increase to maximum values during the summer, and decrease over the course of the fall. Application of a non-steady-state model to the ²³⁴Th data shows that the flux of Th from the euphotic zone occurs principally during the summer cruise and in the interval between summer and fall. Station Minke in the southwestern Ross Sea appears to sustain significant ²³⁴Th removal for a longer period than is evident at Orca or Sei. Particulate ²³⁴Th activities and POC are greater in the 1–70 μm size fraction, except late in the summer cruise, when the >70 μm POC fraction exceeds that of the 1–70 μm fraction. The POC/²³⁴Th ratio in the >70 μm fraction exceeds that in the 1–70 μm fraction, likely due in part to the greater availability of surface sites for Th adsorption in the latter. Particulate ²³⁴Th fluxes are converted to POC fluxes by multiplying by the POC/²³⁴Th ratio of the >70 μm fraction (assumed to be representative of sinking particles). POC fluxes calculated from a steady-state Th scavenging model range from 7 to 91 mmol C m⁻² d⁻¹ during late January–early February, with the greatest flux observed at station Minke late in the cruise. Fluxes estimated with a non-steady-state Th model are 85 mmol C m⁻² d⁻¹ at Minke (1/13–2/1/97) and 50 mmol C m⁻² d⁻¹ at Orca (1/19–2/1/97). The decline in POC inventories (0–100 m) is most rapid in the southern Ross Sea during the austral summer cruise (Smith et al., 2000. The seasonal cycle of phytoplankton biomass and primary productivity in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3119–3140. Gardner et al., 2000. Seasonal patterns of water column particulate organic carbon and fluxes in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3423–3449), and the ²³⁴Th-derived POC fluxes indicate that the sinking flux of POC is 30–50% of the POC decrease, depending on whether steady-state or non-steady-state Th fluxes are used. Rate constants for particle POC aggregation and disaggregation rates are calculated at station Orca by coupling particulate ²³⁴Th data with ²²⁸Th data on the same samples. Late in the early spring cruise, as well as during the summer cruise, POC aggregation rates are highest in near-surface waters and decrease with depth. POC disaggregation rates during the same time generally increase to a maximum and are low at depth (>200 m). Subsurface aggregation rates increase to high values late in the summer, while disaggregation rates decrease. This trend helps explain higher values of POC in the >70 m fraction relative to the 1–70 m fraction late in the summer cruise. Increases in disaggregation rate below 100 m transfer POC from the large to small size fraction and may attenuate the flux of POC sinking out of the euphotic zone.     

Upper ocean export of particulate organic carbon and biogenic silica in the Southern Ocean along 170°W

Upper-ocean fluxes of particulate organic carbon (POC) and biogenic silica (bSi) are calculated from four US JGOFS cruises along 170°W using a thorium-234 based approach. Both POC and bSi fluxes exhibit large variability vs. latitude during the seasonal progression of diatom dominated blooms. POC fluxes at 100 m of up to 50 mmol C m⁻² d⁻¹ are found late in the bloom, and farthest south near the Ross Sea Gyre. Biogenic Si fluxes also peak late in the bloom as high as 15 mmol Si m⁻² d⁻¹, but this flux peak occurs at a different latitude, just south of the Antarctic Polar Front (APF), which is centered around 60°S along this cruise track. The ratios of both POC and bSi export relative to their production rates are large, suggesting an efficient biological pump at these latitudes. The highest relative bSi/POC flux ratios at 100 m are found just south of the APF, coincident with a bSi/POC flux peak seen in 1000 m traps during this same program by Deep-Sea Research II (Honjo et al., Deep-Sea Research II 47, 3521–3548). These data suggest that efficient export at these latitudes can support the high accumulation rates of bSi found in the sediments under and south of the APF, despite the generally low biomass and productivity levels in this region.     

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.     

Sorption model for dissolved and particulate aluminium in the Conway estuary, UK

Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, K_d, which varies from 0.67 × 10⁵ to 3.38 × 10⁶ ml g⁻¹ for suspended particle concentrations of 2–64 mg l⁻¹. The K_d values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for K_d values of 10⁵, 10⁶ and 10⁷ ml g⁻¹ with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with K_d value 10⁷ ml g⁻¹ and C₀ values 16 × 10⁻⁶ mg ml⁻¹ and 92 × 10⁻⁶ mg ml⁻¹. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.     

Isotopic and biochemical composition of particulate organic matter in a shallow water estuary (Great Ouse, North Sea, England)

The biogeochemistry of particulate organic matter was studied in the Great Ouse estuary draining to the North Sea embayement known as the Wash from March 1990 to January 1991. Eleven locations were sampled monthly on a 50 km transect across the shallow estuary from the tidal weir to the middle of the Wash. Particulate organic carbon (POC) and total carbohydrate, protein and lipid analyses were combined with the determination of stable carbon isotopes. δ¹³C often increased from −30‰ in the river to −22‰ in the tidal freshwater reach. The mixing zone between fresh and marine tidal waters displayed only a slight increase in δ¹³C to −19‰. The change in δ¹³C values in the freshwater tidal reach demonstrated that mixing of riverborne and marine suspended POC was not the only process affecting the carbon stable isotope composition. Complementary sources, interfering considerably with the two end-member sources, may be identified as autocthonous primary production and resuspension of sediment that may be transported upstream. The respective importance of these sources is subject to seasonal variation. From March to August, high concentrations in carbohydrate and protein through the whole estuary indicate that despite turbidity significant primary production occurred. The proportional importance of the uncharacterized fraction of POC, which is considered as complex organic matter, was high from September to January and low from March to August. During most of the year, the biochemical compositions of particulate organic matter in the turbidity maximum and the rest of the estuary were similar. This contradicted the principle that owing to the long residence times of particles degradation processes largely dominate the production processes within the turbidity maximum. The occurence of significant in situ production in such shallow water estuaries may partially compensate for the degradation of suspended particulate organics, resulting in a complex relationship between the biogeochemical cycling and the fate of nutrients.     

Nutrients (organic C, P, N, Si) in the eutrophic River Loire (France) and its estuary

The Loire estuary has been surveyed from 1982 to 1985 by 13 isochronous longitudinal profiles realized at low tide. Nutrient (SiO₂, NO₃⁻, NH₄⁺, PO³⁻₄, particulate organic carbon or POC) patterns are very variable depending on the season, the estuarine section [river, upper-inner estuary, upstream of the fresh-water-saline-water interphase FSI, the lower-inner estuary characterized by the high turbidity zone (HTZ), the outer estuary] and the river discharge. Biological processes are dominant. In the eutrophied River Loire (summer pigment > 100 μg l⁻¹), the high algal productivity (algal POC > 3 mg l⁻¹) results in severe depletion of SiO₂, PO₄³⁻, NO₃⁻. The enormous biomass (55 000 ton algal POC/year) is degraded in the HTZ where bacterial activity is intense. As a result, there is generally a regeneration of dissolved SiO₂ and PO₄³⁻, a marked NH₄⁺ maximum, while NO₃⁻ is conservative or depleted when the HTZ is nearly anoxic. Other processes can be considered including pollution from fertilizer plans (PO₄³⁻, NH₄⁺) and from a hydrothermal power plant (NH₄⁺). In the less turbid outer estuary, nutrients are generally conservative. Major variations of concentrations are observed in the lowest chlorinity section (Cl⁻ < 1 g kg⁻) and also upstream the FSI, defined here as a 100% increase in Cl⁻. Nutrient inputs to the ocean are not significantly modified for SiO₂ and NO₂⁻, but are increased by 70% and 180% for PO₄³⁻ and NH₄⁺ and depleted by 60% for POC. Odd hydrological events, especially some floods, may perturbate or even mask the usual seasonal pattern observed in profiles.     

Dissolved Cd behaviour in some selected french and chinese estuaries. Consequences on Cd supply to the ocean

Few data on dissolved trace metals in rivers and estuaries are presently available. This paper is an attempt to provide additional data on dissolved concentrations obtained in polluted and so-called unpolluted river estuarine systems. Data for two major French rivers (Gironde, Rhône) have been compared with the Chinese Yellow River (Huanghe) and Yangtze River (Changjiang). Dissolved Cd concentrations have been measured by differential pulse anodic stripping voltammetry. Average concentrations range from 15 ng kg⁻¹ to 50 ng kg⁻¹ (0.13–0.45 nmol kg⁻¹) in the French rivers and are below 4 ng kg⁻¹ (0.040 nmol kg⁻¹) in the Chinese rivers.In all the estuaries studied the dissolved Cd concentrations depict a systematic bulge in the mixing zone which is attributed largely to remobilization processes from particulate matter when the chlorinity increases. Other parameters that may also play a significant role for remobilization are discussed. The processes concerned lead us to reassess the net Cd river input to the oceans, and this should be taken into account for a more precise evaluation of the residence time of oceanic Cd.     

Particle–water interactions of 2,2′,5,5′-tetrachlorobiphenyl under simulated estuarine conditions

A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, K_D, decreased from about 120×10³ to 10×10³ ml g⁻¹, and from about 150×10³ to 20×10³ ml g⁻¹, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l⁻¹. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds.     

Dissolved uranium, vanadium and molybdenum behaviours during contrasting freshwater discharges in the Gironde Estuary (SW France)

Understanding trace metal behaviour in estuarine environments requires sampling strategies and analytical methods adapted to strong physical and geochemical gradients. In this study, we present a specific sampling strategy covering a wide range of hydrological conditions during nine cruises in 2003–2007 to characterise the behaviour of three dissolved metals (uranium, vanadium and molybdenum) in surface and bottom water along the salinity gradient of the highly turbid macrotidal Gironde Estuary using a solid–liquid extraction. Uranium behaved conservatively whatever the water discharges observed. The slight dissolved U depletion compared to the theoretical dilution line between the fluvial and marine end-members occasionally observed in the low salinity range (0–3) was attributed to the mixing of different water bodies of the Gironde tributaries. In contrast, dissolved V behaviour was largely influenced by the hydrological conditions, showing increasingly pronounced addition with decreasing freshwater discharges, (i.e. increasing residence times of water and particles in the estuary). This addition of dissolved V in the low- to mid-salinity range was attributed to desorption processes observed in the Maximum Turbidity Zone (MTZ). The distribution of dissolved Mo concentrations along the salinity gradient was highly variable. Apparent conservative, and non-conservative behaviours were observed and were related to the concomitance of desorption from SPM, inputs from sediments for additive distribution and biological uptake and removal into sediments for subtractive distribution. Based on the whole database (2003–2007), annual net fluxes to the coastal ocean were estimated for dissolved U (15.5–16.6 t yr⁻¹) and V (31.3–36.7 t yr⁻¹).     

Was a carbon balance measured in the equatorial Pacific during JGOFS?

The likelihood that the carbon fluxes measured as part of the US-JGOFS field program in the equatorial Pacific ocean (EgPac) during 1992 yielded a balanced carbon budget for the surface ocean was determined. The major carbon fluxes incorporated into a surface carbon budget were: new production, particulate organic carbon (POC) and dissolved organic carbon (DOC) export, CaC0₃ export, C0₂ gas evasion, dissolved inorganic carbon (DIC) supply, and the time rate of charge. The ratio of the measured concentration gradients of DOC and DIC provided a constraint on the ratio of POC/DOC export. Uncertainties of ±30–50% for individual carbon flux measurements reduce the likelihood that a carbon balance can be measured during a JGOFS process-type study. As a benchmark, carbon fluxes were prescribed to yield a hypothetical surface carbon budget that was, on average, balanced. Given the typical errors in the individual carbon fluxes, however, there was only about a 30% chance that this hypothetical budget could be measured to be balanced to ±50%. Using this benchmark, it was determined that there was a 95 % chance that the carbon flux measurements yielded a surface DIC budget balanced (to ±50%) during El Nino conditions in boreal spring 1992, when the total organic carbon export rate was - 5 mmol C m-2 day- 1 and the POC export was 3 mmol C m⁻² day⁻¹. In boreal fall 1992, during cold period conditions, there was a 70% chance that the surface carbon DIC budget was balanced when the total organic carbon export rate was 20 mmol C m⁻² day⁻¹ and export was -13 mmol C m-2 day-'. The DOC to DIC concentration gradient ratio of - -0.15, measured in depth profiles down to 100m and in surface waters, was used as an important constraint that most (> 70%) of the organic carbon exported from the euphotic zone was POC rather than DOC. If a balanced surface DIC budget was used to test the compatibility of individual carbon fluxes measured during EgPac, then a three- to four-fold increase in total and particulate organic carbon export between spring and fall is indicated. This increase was not reflected in the POC loss rates measured by drifting sediment trap collections or estimated by²³⁴Th deficiencies coupled with the C/Th measured on suspended particles.     

Vertical flux of biogenic matter during a Lagrangian study off the NW Spanish continental margin

Lagrangian experiments with short-term, drifting sediment traps were conducted during a cruise on RRS Charles Darwin to the NW coast of Spain to study the vertical flux and composition of settling biogenic matter. The cruise was split into two legs corresponding to (i) a period of increased production following an upwelling event on the continental shelf (3–10 August 1998) and (ii) an evolution of a cold water filament originating from the upwelled water off the shelf (14–19 August). The export of particulate organic carbon (POC) from the upper layer (0–60m) on the shelf was 90–240mgC.m⁻².d⁻¹ and off the shelf was 60–180mgC.m⁻².d⁻¹. Off shelf the POC flux at 200m was 50–60mg.m⁻².d⁻¹. A modest sedimentation of diatoms (15–30mgC.m⁻².d⁻¹) after the upwelling was associated with increased vertical flux of chlorophyll a (1.8–2.1mg.m⁻².d⁻¹) and a decrease of the POC:PON molar ratio of the settled material from 9 to 6.4. Most of the pico-, nano-, and microplankton in the settled material were flagellates; diatoms were significant during the on shelf and dinoflagellates during the off shelf leg. Off shelf, the exponential attenuation of POC flux indicated a strong retention capacity of the plankton community between 40 and 75m. POC:PON ratio of the settled particulate matter decreased with depth and the relative portion of flagellates increased, suggesting a novel, flagellate and aggregate mediated particulate flux in these waters. Export of POC from the euphotic layer comprised 14–26% of the integrated primary production per day during the on shelf leg and 25–42% during the off shelf leg, which characterises the importance of sedimentation in the organic carbon budget of these waters.     

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.     

Modulation of the particulate organic carbon flux to the ocean by a macrotidal estuary: Evidence from measurements of carbon isotopes in organic matter from the Gironde system

The isotopic composition of the organic carbon of the suspended particulate matter in the Gironde estuary and the Biscay shelf has been measured on a seasonal basis from 1977 to 1982. The δ¹³C values show a progressive change along the estuary and permit an estimate of the proportion of terrestrial carbon in each sample. It is estimated from these data that up to 80% of the continental POC is mineralized in the estuary and 3–16% of the riverborne flux is exported to the shelf.     

Cadmium in Mytilus spp.: Worldwide survey and relationship between seawater and mussel content

A worldwide literature survey of data on cadmium concentration in the soft tissue of the mussel, Mytilus spp., from 591 stations is presented. These stations are from 13 regions. Geometric means for the regions vary from 0·6 to 3·3 μg g⁻¹ (dry weight) for the Barents Sea and the Northeastern Pacific coast, respectively.The averages of seven of these regions, for which reliable cadmium concentrations in seawater were available, were used to calculate a relationship between cadmium concentrations in seawater and mussel soft tissue. The relationship was highly significant: (Cd) mussel (μg g⁻¹, dry weight) = 0·074 (Cd) water (ng litre⁻¹) + 0·39 (P ≤ 0·0005).This model has been successfully applied in the context of the contamination of the Gironde estuary (France). It can also be used to define a water quality criterion for mussel maturing parks consistent with the quality criterion defined for shellfish for human consumption.     

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (δ¹³C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. δ¹³C values of both POC (−23.8‰ to −26.8‰) and DOC (−25.0‰ to −29.0‰) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in δ¹³C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-δ¹³C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-δ¹³C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10–30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted.     

Study of fluoride in polluted and unpolluted estuarine environments

Mindhola River estuary, which receives industrial waste containing high concentrations of fluoride, and Purna River estuary, which is free from fluoride contamination, have been investigated. While fluoride behaved conservatively in Purna River estuary, significant deviation from the theoretical dilution line (TDL) in the chlorinity range 0·5–8‰ was observed in Mindhola River estuary due to the externally added fluoride which largely remained in solution. The excess of fluroide over the theoretically calculated value was at a maximum around a chlorinity of 3‰. High natural fluoride content of the river waters resulted in F/Cl ratios exceeding 300 × 10⁻⁵ at low chlorinities. The ratio decreased rapidly with increasing chlorinity and the value near to that of seawater was observed at chlorinities above 14‰.     

Biological organic carbon export estimated from the annual carbon budget observed in the surface waters of the western subarctic and subtropical North Pacific Ocean from 2004 to 2013

The annual flux of biologically produced organic carbon from surface waters is equivalent to annual net community production (NCP) at a steady state and equals the export of particulate and dissolved organic carbon (POC and DOC, respectively) to the ocean interior. NCP was estimated from carbon budgets of salinity-normalized dissolved inorganic carbon (nDIC) inventories at two time-series stations in the western subarctic (K2) and subtropical (S1) North Pacific Ocean. By using quasi-monthly biogeochemical observations from 2004 to 2013, monthly mean nDIC inventories were integrated from the surface to the annual maximum mixed layer depth and corrected for changes due to net air–sea CO₂ exchange, net CaCO₃ production, vertical diffusion from the upper thermocline, and horizontal advection. The annual organic carbon flux at K2 (1.49 ± 0.42 mol m^?2 year^?1) was lower than S1 (2.81 ± 0.53 mol m^?2 year^?1) (p < 0.001 based on t test). These fluxes consist of three components: vertically exported POC fluxes (K2: 1.43 mol m^?2 year^?1; S1: 2.49 mol m^?2 year^?1), vertical diffusive DOC fluxes (K2: 0.03 mol m^?2 year^?1; S1: 0.25 mol m^?2 year^?1), and suspended POC fluxes (K2: 0.03 mol m^?2 year^?1; S1: 0.07 mol m^?2 year^?1). The estimated POC export flux at K2 was comparable to the sum of the POC flux observed with drifting sediment traps and active carbon flux exported by migrating zooplankton. The export fluxes at both stations were higher than those reported at other time-series sites (ALOHA, the Bermuda Atlantic Time-series Study, and Ocean Station Papa).