Isotope dilution measurement of inorganic chromium(III) and total chromium in seawater

A reproducible, low-blank, isotope-dilution technique for the determination of inorganic Cr(III) and total dissolved chromium in seawater has been developed. Analysis of coastal water from Brittany, France, confirms that inorganic Cr(III) exists in excess of the thermodynamic equilibrium value calculated from the model of Elderfield (1970). A vertical profile of total chromium at 13°N on the East Pacific Rise confirms the general features of Cr behaviour: slight depletion at the surface (Cr = 2.0 nmol l⁻¹ compared to 2.6 nmol l⁻¹ below 1000 m) and bottom excess possibly due to Cr (III) release from sediments (up to 15.8 nmol l⁻¹). A maximum enrichment of six times the average seawater value is obtained in hydrothermal waters. The chromium content of metalliferous sediments is mainly due to scavenging from the water column; input of chromium into the ocean through hydrothermalism is negligible.     

Mercury levels in the dissolved and particulate fractions of the Tyrrhenian sea

Determination of the actual mercury concentration in Mediterranean basin seawater was achieved by means of an instrument based on fluorescence spectrometry developed for this purpose, during a field study aboard the oceanographic ship “L.F. Marsili”, between August 1980 and May 1982.Dissolved ·total’ and ·reactive’ mercury and mercury associated with particulate matter were determined on surface and subsurface waters in the Tyrrhenian Sea from La Spezia to Sicily.Concentrations in the range 1.4–19.7 ng l⁻¹ for ·total dissolved mercury’, 0.5–5.9 ng l⁻¹ for ·reactive dissolved mercury’ and 0.3–8.0 ng l⁻¹ for mercury associated with the particulate matter, were measured on surface and subsurface waters in the Tyrrhenian Sea from La Spezia to Sicily.Even if the mean value of the total mercury concentration (dissolved + particulate) was found to be about twice as high as those observed for the oceans, the difference does not seem to be as high as predicted by the model proposed by Buffoni and co-workers to explain the large difference of mercury levels between tunas caught, respectively, in the Mediterranean and in the Oceans.     

Temporal variability of dimethylsulfide and dimethylsulfoniopropionate in the Sargasso Sea

Vertical profiles of dimethylsulfide (DMS) and β-dimethylsulfoniopropionate, particulate (pDMSP) and dissolved (dDMSP), were measured biweekly in the upper 140 m of the Sargasso Sea (32°10′N, 64°30′W) during 1992 and 1993. DMS and pDMSP showed strong, but different, seasonal patterns; no distinct intra-annual pattern was observed for dDMSP. During winter, concentrations of DMS were generally less than 1 nmol l⁻¹ at all depths, dDMSP was less than 3 nmol l⁻¹ and pDMSP was less than 8 nmol l⁻¹. In spring, concentrations of both dDMSP and pDMSP rose, on a few occasions up to 20 nmol l⁻¹ in the dissolved pool and up to 27 nmol l⁻¹ in the particulate pool. These increases, due to blooms of DMSP-containing phytoplankton, resulted in only minor increases in DMS concentrations (up to 4 nmol l⁻¹). Throughout the summer, the concentrations of DMS continued to increase, reaching a maximum in August of 12 nmol l⁻¹ (at 30 m depth). There was no concomitant summer increase in dDMSP or pDMSP. The differences among the seasonal patterns of DMS, dDMSP, and pDMSP suggest that the physical and biological processes involved in the cycling of DMS change with the seasons. There is a correlation between the concentration of DMS and temperature in this data set, as required by some of the climate feedback models that have been suggested for DMS. A full understanding of the underlying processes controlling DMS is required to determine if the temperature-DMS pattern is of significance in the context of global climate change.     

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.     

A regeneration model to estimate addition fluxes and removal constants of trace metals in seawater

A model is presented for flux evaluation of trace metals in situ. For the practically feasible simplified model, mere estimation of metals in various dissolved states (e.g. Cr(III) and Cr(VI)) and in particulate phase, in a single vertical profile at least, together with temperature, salinity, O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, HPO₄²⁻ and H₄SiO₄ parameters enable evaluation of the amount of metal removed in situ, to a first approximation. From the evaluated net metal removed (M_R), estimation could be made for removal constants, i.e. removal times (t), residence times (τ) and removal rate constants (ψ), not only for the average ocean but also for the oxygen-minimum zone. Besides, M_R can be used to calculate t, τ and ψ of various species of the metal concerned, that are not yet available. The present model evaluates t, τ and ψ for total chromium from a single station, which are consistent with the reported values, and shows that chromium is removed with fast-settling particulate matter. This study also reveals that t, τ and ψ values of 0.001 years 7 years and 0.150 y⁻¹, respectively, for Cr(III) in the oxygen-minimum zone and 0.006 y, 211 y and 0.005 y⁻¹ in the marine environment, respectively.     

Manganese and iron distributions off central California influenced by upwelling and shelf width

In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L⁻¹ and dissolved manganese reached 25 nmol L⁻¹. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L⁻¹ and dissolved manganese concentrations were less than 5 nmol L⁻¹. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L⁻¹, and dissolvable iron concentrations of 12–20 nmol L⁻¹ in the upper 100 m in the north, compared to 3.5–2 nmol L⁻¹ Mn and 0.6 nmol L⁻¹ Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L⁻¹ dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L⁻¹ dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.     

Copper in the resurrection fjord, Alaska

Copper concentrations have been measured in more than 200 samples collected from an Alaskan fjord and continental shelf and slope regions in the northwestern Gulf of Alaska. Concentrations were lowest (2·1 nmol kg⁻¹) at depths of 400–1000 m in the continental slope waters of the Gulf of Alaska. Copper increased systematically with decreasing salinities shoreward to concentrations >30 nmol kg⁻¹ in fjord surface waters during summer months of high freshwater runoff. Copper concentrations increased with depth at an inner fjord station where deep basin waters have restricted circulation, and these data together with surface (<5 cm) pore water copper concentrations (mean=122 nmol kg⁻¹) about an order of magnitude higher than bottom water copper concentrations are indicative of a flux of copper across the sediment-seawater interface. This latter was estimated at 32±12 nmol cm⁻² annually, and represented less than 20% of the annual input to fjord surface water (228–411 nmol cm⁻²) added during summer months. Mass balances in bottom waters indicate a vigorous recycling of copper with a residence time estimated at 21±11 days. Most copper that is remobilized in surface sediments is returned to bottom waters and little (3%) is removed by subsequent diagenetic reaction in the buried sediments. However, an estimate of copper accumulating in anoxic fjord sediments was comparable with copper added to fjord surface waters suggesting that input-removal reactions rather than internal cycling controls copper geochemistry in this estuary.     

Distribution and transfer of trace elements in the Western Mediterranean

Results concerning the concentration of cadmium and lead in Mediterranean waters collected during the 2nd PHYCEMED cruise (Oct. 1983) are discussed. Sampling has been performed at seven stations in the Western Mediterranean Basin, two in the Strait of Gibraltar and the near Atlantic, two in the Sicily Strait and the Eastern Basin.In the Western Basin the observations are in fair agreement with those of PHYCEMED 1. Cadmium has a fairly homogeneous distribution vertically as well as from one station to another, with an average concentration of 8 ng l⁻¹; while lead shows a slight but continuous decrease in concentrations with depth (from at least 50 ng l⁻¹ in surface waters to 20 or 25 ng l⁻¹ at depth). On the other hand, at the basin boundaries, where waters from different origins are present, vertical distributions appear very different. On the basis of calculated water budgets it can be estimated that the Mediterranean Sea discharges about 200 t y⁻¹ of cadmium and about 250 t y⁻¹ of lead into the Atlantic Ocean while 1000 t y⁻¹ of lead are transferred from the Western to the Eastern Basin.     

Estimates of Energy Dissipation Rates in the Three-Dimensional Deep Ocean Internal Wave Field

Using the “Eikonal Approach” (Henyey et al., 1986), we estimate energy dissipation rates in the three-dimensional Garrett-Munk internal wave field. The total energy dissipation rate within the undisturbed GM internal wave field is found to be 4.34 × 10⁻⁹ W kg⁻¹. This corresponds to a diapycnal diffusivity of about 0.3 × 10⁻⁴ m²s⁻¹, which is less than the value 10⁻⁴ m²s⁻¹ required to sustain the global ocean overturning circulation. Only when the high vertical wavenumber, near-inertial current shear is enhanced can diapycnal diffusivity reach ∼10⁻⁴ m²s⁻¹. It follows that the energy supplied at low vertical wavenumbers and low frequencies is efficiently transferred to high vertical wavenumbers and near-inertial frequencies in the mixing hotspots in the real ocean.     

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.     

Thorium isotopes as tracers of particles dynamics and deep water circulation in the Indian sector of the Southern Ocean (ANTARES IV)

Dissolved and particulate samples were collected to study the distribution of thorium isotopes (²³⁴Th, ²³²Th and ²³⁰Th) in the water column of the Indian sector of the Southern Ocean (from 42°S to 47°S and from 60°E to 66°E, north of the Polar Front) during Austral summer 1999. Vertical profiles of excess ²³⁰Th (²³⁰Th_xs) increases linearly with depth in surface water (0–100 m) and a model was applied to estimate a residence time relative to the thorium scavenging (τ_scav). Low τ_scav in the Polar Front Zone (PFZ) are found, compared to those estimated in the Subtropical Front Zone (STZ). Changes in particle composition between the PFZ and STZ could influence the ²³⁰Th_xs scavenging efficiency and explain this difference. An innovative coupling between ²³⁴Th and ²³⁰Th_xs was then used to simultaneously constrain the settling velocities of small (0.6–60 μm) and large (above 60 μm) particles. Although the different hydrological and biogeochemical regimes visited during the ANTARES IV cruise did not explain the spatial variation of sinking velocity estimates, our results indicate that less particles may reach the seafloor north (60 ± 2 m d^− 1, station 8) than south of the Agulhas Return Current (119 ± 23 and 130 ± 5 m d^− 1 at stations 3 and 7, respectively). This information is essential for understanding particle transport and by extension, carbon export. In the deep water column, the ²³⁰Th_xs concentrations did not increase linearly with depth, probably due to lateral transport of North Atlantic Deep Water (NADW) from the Atlantic to the Indian sector, which renews the deep waters and decreases the ²³⁰Th_xs concentrations. A specific ²³⁰Th_xs transport model is applied in the deep water column and allows us to assess a “travel time” of NADW ranging from 2 to 15 years.     

Spatial patterns of primary production on the shelf, slope and basin of the Western Arctic in 2002

In the spring and summer of 2002 primary production in the Chukchi Sea was measured, using ¹⁴C uptake experiments. Our cruise track encompassed the shelf and continental slope area of the Chukchi and Beaufort Seas progressing into deep water over the Canada Basin. The study area experienced upwards of 90% ice cover during the spring, with ice retreating into the basin during the summer. Production in the spring was light-limited due to ice cover, with average euphotic zone production rates of <0.3 g C m⁻² d⁻¹. Values of 8 g C m⁻² d⁻¹ were observed in association with surface bloom conditions during the initial ice breakup. Considerable nutrient reduction in the surface waters took place between the spring and summer cruise, and although not observed, this was attributed to a spring bloom. Decreased ice cover and increased clarity of surface waters in the summer allowed greater light penetration. The highest rates of production during the second cruise were found at 25–30 m, coincident with the top of the nutricline. Daily euphotic zone productivity in the summer averaged 0.78 g C m⁻² d⁻¹ on the shelf and 0.32 g C m⁻² d⁻¹ on the edge of the Canada basin. These data provide an estimated annual production of 90 g C m⁻² yr⁻¹ in the study area.     

Trace metal distributions across the continental shelf near Otago Peninsula, New Zealand

The distributions of the trace metals iron (Fe), copper (Cu) and cadmium (Cd) along with hydrological parameters (salinity, temperature and reactive phosphate) across the New Zealand continental shelf near Otago Peninsula have been studied. This is a region in which the Subtropical Convergence (STC), a major oceanic front separating subtropical and subantarctic waters, is uniquely located close to land, permitting an examination of the influence of terrestrial sources of Fe and Cu on oceanic waters containing excess micronutrients. Acid-soluble (110 nmol kg⁻¹) and dissolved (6.3 nmol kg⁻¹) Fe concentrations were highest over the central shelf, and decreased rapidly across the mixing zone of the STC to about 5 nmol kg⁻¹ for both forms. The distribution of acid-soluble and dissolved Cu were similar to their counterparts for Fe. Depth-concentration profiles for acid-soluble Fe and Cu suggest resuspension of shelf sediments is the main source. The ratio of oxine-labile to acid-soluble Fe varied from 0.03 to 0.26, with the highest values found in the near surface waters. Oxine-labile Fe and Cu also decreased in concentration in a seawards direction, and with depth, indicating the influence of near surface processes on the reactivity of these elements. Cd concentrations across the continental shelf were very low (<200 pmol kg⁻¹) and exhibited no clear spatial trend and no correlation with phosphate. Comparison of the Cd/P ratio across the shelf indicated that the waters in this region were strongly depleted in Cd relative to P. Phosphate concentrations were lowest in neritic water and increased in the seawards direction because of mixing with nutrient-rich Subantarctic Surface Water.     

The behaviour of dissolved Cd, Co, Zn, and Pb in North Atlantic near-surface waters (30°N/60°W–60°N/2°W)

In September 1993 (M26) and June/July 1996 (M36), a total of 239 surface samples (7 m depth) were collected on two transects across the open Atlantic Ocean (224 samples) and northwest European shelf edge area. We present an overview of the horizontal variability of dissolved Cd, Co, Zn, and Pb in between the northwest and northeast Atlantic Ocean in relation to salinity and the nutrients. Our data show a preferential incorporation of Cd relative to P in the particulate material of the surface ocean when related to previously published parallel measurements on suspended particulate matter from the same cruise. There is a good agreement with results recently estimated from a model by Elderfield and Rickaby (Nature 405 (2000) 305), who predict for the North Atlantic Ocean a best fit for α_Cd/P=[Cd/P]_POM/[Cd/P]_SW of 2.5, whereas the approach of our transect shows a α_Cd/P value of 2.6. The Co concentrations of our transects varied from <5 to 131 pmol kg⁻¹, with the lowest values in the subtropical gyre. There were pronounced elevations in the low-salinity ranges of the northwest Atlantic and towards the European shelf. The Co data are decoupled from the Mn distribution and support the hypothesis of marginal inputs as the dominant source. Zinc varied from a minimum of <0.07 nmol kg⁻¹ to a maximum of 1.2 and 4.8 nmol kg⁻¹ in regions influenced by Labrador shelf or European coastal waters, respectively. In subtropical and northeast Atlantic waters, the average Zn concentration was 0.16 nmol kg⁻¹. Zinc concentrations at nearly three quarters of the stations between 40°N and 60°N were <0.1 nmol kg⁻¹. This suggests that biological factors control Zn concentrations in large areas of the North Atlantic surface waters. The Pb data indicated that significant differences in concentration between the northwest and northeast Atlantic surface waters presently (1996) do not exist for this metal. The transects in 1993 and 1996 exhibited Pb concentrations in the northeast Atlantic surface waters of 30 to 40 pmol kg⁻¹, about a fifth to a quarter of the concentrations observed in 1981. This decline is supported by our particle flux measurements in deep waters of the same region.     

Uncoupled distributions of transparent exopolymer particles (TEP) and dissolved carbohydrates in the Southern Ocean

Transparent exopolymer particles (TEP) are formed by the assembly of dissolved precursors, mainly mono and polysaccharides (DMCHO and DPCHO) that are released by microorganisms. Although TEP formation plays a significant role in carbon export to deep waters and can affect gas exchange at the sea surface, simultaneous measurements of TEP and their precursors in natural waters have been scantly reported. In this study, we described the spatial (vertical and regional) distribution of TEP, DMCHO and DPCHO in a region located around the Antarctic Peninsula, assessed their contribution to the total organic carbon pool, and explored their relationships with phytoplankton (with chlorophyll a (chl a) as a proxy) and bacteria. TEP concentration ranged from undetectable values to 48.9 µg XG eq L^− 1 with a mean value of 15.4 µg XG eq L^− 1 (11.6 µg TEP-C L^− 1). DMCHO and DPCHO showed average values of 4.3 µmol C L^− 1 and 8.6 µmol C L^− 1, respectively. We did not find simple relationships between the concentrations of TEP and dissolved carbohydrates, but a negative correlation between DMCHO and DPCHO was observed. Chl a was the best regressor of TEP concentration in waters within the upper mixed layer, while bacterial production was the best regressor of TEP concentration below the mixed layer, underlining the direct link between these particles and bacterial activity in deep waters.     

An analysis of bomb radiocarbon trends in the Pacific

The post-nuclear time-series curves of Δ¹⁴C from corals at different locations in the surface of the Pacific Ocean show a variation in the shape, amplitude and timing of the peak, with the subtropical records peaking first, followed by the western, and then eastern tropical records with lower maxima. This work takes an in-depth look at the processes that shape the time histories of Δ¹⁴C in surface waters at different locations in the Pacific. A one-dimensional (1-D) model is used to examine whether convection and diffusion can delay the peaking of the Δ¹⁴C time series. Using the three-dimensional (3-D) MIT general circulation model (GCM), the distribution and evolution of Δ¹⁴C is simulated “offline” from 1955 onwards at 1° resolution globally. The GCM is used to tease apart the contribution of various processes, viz. advection, air–sea flux, convection and diffusion, to altering the Δ¹⁴C content of surface waters at different locations in the Pacific. A time history of ¹⁴C column inventories from the model is constructed to examine the role of horizontal advection in supplying tropical locations with ¹⁴C much after the peak atmospheric flux. This model analysis supports the idea of ¹⁴C-rich waters from the subtropics being transported to the western tropics via the subsurface, and then being advected eastward in the equatorial undercurrent and upwelled in the east.     

Depth profiles of volatile iodine and bromine-containing halocarbons in coastal Antarctic waters

Measurements of bromoform (CHBr₃), diiodomethane (CH₂I₂), chloroiodomethane (CH₂ICl) and bromoiodomethane (CH₂IBr) were made in the water column (5–100 m depth) of the Southern Ocean within 0–40 km of the Antarctic sea ice during the ANTXX1/2 transect of the German R/V Polarstern, at five locations between 70–72°S and 9–11°W in the Antarctic spring/summer of 2003–2004. Some of the profiles exhibited a very pronounced layer of surface sea-ice meltwater, as evidenced by salinity minima and temperature maxima, along with surface maxima in concentrations of CHBr₃, CH₂I₂, CH₂ICl and CH₂IBr. These results are consistent with in situ surface halocarbon production by ice algae liberated from the sea ice, although production within the sea ice followed by transport cannot be entirely ruled out. Additional sub-surface maxima in halocarbons occurred between 20 and 80 m. At a station further from shore and not affected by surface sea-ice meltwater, surface concentrations of CH₂I₂ were decreased whereas CH₂ICl concentrations were increased compared to the stations influenced by meltwater, consistent with photochemical conversion of CH₂I₂ to CH₂ICl, perhaps during upward mixing from a layer at  70 m enhanced in iodocarbons. Mean surface (5–10 m) water concentrations of halocarbons in these coastal Antarctic waters were 57 pmol l^− 1 CHBr₃ (range 44–78 pmol l^− 1), 4.2 pmol l^− 1 CH₂I₂ (range 1.7–8.2 pmol l^− 1), 0.8 pmol l^− 1 CH₂IBr (range 0.2–1.4 pmol l^− 1), and 0.7 pmol l^− 1 CH₂ICl (range 0.2–2.4 pmol l^− 1). Concurrent measurements in air suggested a sea-air flux of bromoform near the Antarctic coast of between 1 and 100 (mean 32.3, median 10.4) nmol m^− 2 day^− 1 and saturation anomalies of 557–1082% (mean 783%, median 733%), similar in magnitude to global shelf values. In surface samples affected by meltwater, CH₂I₂ fluxes ranged from 0.02 to 6.1 nmol m^− 2 day^− 1, with mean and median values of 1.9 and 1.1 nmol m^− 2 day^− 1, respectively.     

Modelling of natural and synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches

In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et₄NI and NaCl (for fulvic acid 0.1 < I /mol L^− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) and anions (Cl⁻, SO₄²⁻) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.     

Hydrological heterogeneity, nutrient dynamics and water quality of a non-tidal lentic ecosystem (Lesina Lagoon, Italy)

The dynamics of the Lesina coastal lagoon (Italy) in terms of nutrients, phytoplankton and chemical–physical parameters were evaluated, together with their functional relationships with freshwater inputs, in order to identify ecosystem responses to changes in driving forces in a Mediterranean non-tidal lentic environment. Lesina Lagoon is a shallow coastal environment characterised by limited exchange with coastal waters, which favours enrichment of nutrients and organic matter and benthic fluxes within the system. Lagoon–sea exchanges are influenced by human management. There is a steep salinity gradient from East to West. High nitrogen and silica values were found close to freshwater inputs, indicating wastewater discharges and agricultural runoff, especially in winter. Dissolved oxygen was well below saturation (65%) near sewage and runoff inputs in the western part of the lagoon during summer. Classification in accordance with EEA (2001) guidelines suggests the system is of “poor” or “bad” quality in terms of nitrogen concentrations in the eastern zone during the winter rainy period. In terms of phosphate concentrations, the majority of the stations fall into the “good” category, with only two stations (close to the sewage and runoff inputs) classed as “bad”. In both cases, the raw nitrogen levels make the lagoon a P-limited system, especially in the eastern part. There was wide space–time variability in chlorophyll a concentrations, which ranged from 0.25 to 56 μg l⁻¹. No relationships between chlorophyll a and nutrients were found, suggesting that autotrophic biomass may be controlled by a large number of internal and external forcing factors driving eutrophication processes. Water quality for this type of environment depends heavily on pressure from human activities but also on the management of sewage treatment plants, agricultural practices and the channels connecting the lagoon with the sea.     

Spatio-temporal distribution of dissolved inorganic carbon and net community production in the Chukchi and Beaufort Seas

As part of the 2002 Western Arctic Shelf–Basin Interactions (SBI) project, spatio-temporal variability of dissolved inorganic carbon (DIC) was employed to determine rates of net community production (NCP) for the Chukchi and western Beaufort Sea shelf and slope, and Canada Basin of the Arctic Ocean. Seasonal and spatial distributions of DIC were characterized for all water masses (e.g., mixed layer, halocline waters, Atlantic layer, and deep Arctic Ocean) of the Chukchi Sea region during field investigations in spring (5 May–15 June 2002) and summer (15 July–25 August 2002). Between these periods, high rates of phytoplankton production resulted in large drawdown of inorganic nutrients and DIC in the Polar Mixed Layer (PML) and in the shallow depths of the Upper Halocline Layer (UHL). The highest rates of NCP (1000–2850 mg C m⁻² d⁻¹) occurred on the shelf in the Barrow Canyon region of the Chukchi Sea and east of Barrow in the western Beaufort Sea. A total NCP rate of 8.9–17.8×10¹² g for the growing season was estimated for the eastern Chukchi Sea shelf and slope region. Very low inorganic nutrient concentrations and low rates of NCP (<15–25 mg C m⁻² d⁻¹) estimated for the mixed layer of the adjacent Arctic Ocean basin indicate that this area is perennially oligotrophic.