Nitrogenous discharges to the eastern Gulf of Finland, the Baltic Sea: Elemental flows, stable isotope signatures, and their estuarine modification

We studied the nutrient input to the Gulf of Finland via River Neva, the largest river discharging freshwater to the Baltic Sea, and characterised the isotopic signatures (¹⁵N, ¹⁸O, ¹³C) in dissolved and particulate substances (NO₃⁻, PON, POC, DIC) in the River Neva over two seasonal cycles, as well as in samples from St. Petersburg wastewater treatment plants (NO₃⁻, NH₄⁺, PON, POC). These riverine and municipal discharges account for 40% of terrestrial inorganic N loading to the Gulf of Finland, representing annually 7% of the total nitrogen pool in the water mass of the whole Gulf. To describe and evaluate the modification of these isotopic signals along a Gulf of Finland transect towards the Baltic Proper, two cruises were arranged, one in late spring after the annual maximum in River Neva runoff, and one in autumn, in the late phase of the annual growth season.River Neva nitrate signatures of ¹⁵N and ¹⁸O indicated major agricultural fertilizer origin of nitrogen, and the isotopic composition was clearly lighter (δ¹⁵N-NO₃⁻ mean of 2.4‰ air) than previously measured from more southern rivers discharging into the Baltic Sea. Because of the light composition of the River Neva N source, close to the ¹⁵N signatures of the open Gulf, as well as of the efficient depletion of the inorganic load already in the innermost estuary, straightforward end-member tracer analysis of the transport of N in the basin is problematic. St. Petersburg wastewater ammonium showed, however, high δ¹⁵N values (ca. 13‰), which gives a first estimate of 5.8‰ for δ¹⁵N of the easternmost estuarine total inorganic N source. The available sediment data from the basin (δ¹⁵N 6 to 8‰) somewhat exceeds the average source signature. This emphasizes the significance of biological transformation processes, most importantly assimilation of inorganic nitrogen, food web interactions and denitrification, which all involve isotopic fractionation, for the mass balance models describing the dynamics of the sources and sinks of the N cycle of the basin.     

Distributions of oxygen and carbon stable isotopes and CFC-12 in the water masses of the Southern Ocean at 30°E from South Africa to Antarctica: results of the CIVA1 cruise

This study presents oceanic distributions of stable isotopes (δ¹⁸O of water and δ¹³C of ΣCO₂) and CFC-12 from samples collected during the CIVA1 cruise (February/March 1993), across the Southern Ocean, along a meridian section at 30°E, from South Africa (44°S) to Antarctica (70°S). The isotopic measurements show important variations between the subantarctic surface waters with low δ¹⁸O–high δ¹³C values and the antarctic surface waters with very low δ¹⁸O–low δ¹³C values. The surface distributions of δ¹³C values follow the major frontal oceanic structures; the vertical distribution shows the progressive upwelling from the subantarctic zone to the antarctic divergence of ¹³C-depleted CO₂ derived from remineralization of organic matter. Along the Antarctic continental shelf, between 2500 and 4000 m, a core of water with δ¹⁸O values close to −0.1‰ is associated with a relative maximum in CFC-12 concentration, although this core is not detected by its temperature and salinity parameters. This water mass, which corresponds to recently formed deep water, may originate from the eastward extension of the Weddell gyre or from bottom waters coming from the East and formed near Prydz Bay.     

Seasonal productivity dynamics in the pelagic central Benguela System inferred from the flux of carbonate and silicate organisms

Flux of bulk components, carbonate- and silicate-bearing skeleton organisms, and the δ¹⁵N-isotopic signal were investigated on a 1-year time-series sediment trap deployed at the pelagic NU mooring site (Namibia Upwelling, ca. 29°S, 13°E) in the central Benguela System. The flux of bulk components mostly shows bimodal seasonality with major peaks in austral summer and winter, and moderate to low export in austral fall and spring. The calcium carbonate fraction dominates the export of particulates throughout the year, followed by lithogenic and biogenic opal. Planktonic foraminifera and coccolithophorids are major components of the carbonate fraction, while diatoms clearly dominate the biogenic opal fraction. Bulk δ¹⁵N isotopic composition of particulate matter is positively correlated with the total mass flux during summer and fall, while negatively correlated during winter and spring. Seasonal changes in the intensity of the main oceanographic processes affecting the NU site are inferred from variations in bulk component flux, and in the flux and diversity patterns of individual species or group of species. Influence from the Namaqua (Hondeklip) upwelling cell through offshore migration of chlorophyll filaments is stronger in summer, while the winter flux maximum seems to reflect mainly in situ production, with less influence from the coastal and shelf upwelling areas. On a yearly basis, dominant microorganisms correspond well with the flora and fauna of tropical/subtropical waters, with minor contribution of near-shore organisms. The simultaneous occurrence of species with different ecological affinities mirrors the fact that the mooring site was located in a transitional region with large hydrographic variability over short-time intervals.     

The biogeochemical cycling of methane in Ria de Vigo, NW Spain: Sediment processing and sea–air exchange

Methane (CH₄) concentrations were measured in the water column, in sediment porewaters, and in atmospheric air, in the Ría de Vigo, NW Spain, during both the onset (April 2003) and at the end of (September 2004) seasonal upwelling. In addition, CH₄ concentration and stable isotopic signatures (δ¹³CH₄) were measured in porewaters, and sediment methanogenesis and aerobic oxidation of CH₄ were determined in sediment incubations. Surface water column CH₄ (2 m depth) was in the range 3–180 nmol l^− 1 (110–8500% saturation) and followed a generally landward increase but with localised maxima in both the inner and middle Ría. These maxima were consistent with CH₄ inputs from underlying porewaters in which CH₄ concentrations were up to 3 orders of magnitude higher (maximum 350 μmol l^− 1). Surface water CH₄ concentrations were approximately three times higher in September than in April, consistent with a significant benthic CH₄ flux driven by enhanced sediment methanogenesis following the summer productivity maximum. CH₄ and δ¹³CH₄ in sediment porewaters and in incubated sediment slurries (20 °C) revealed significant sediment CH₄ oxidation, with an apparent isotopic fractionation factor (r_c) of  1.004. Using turbulent diffusion models of air–sea exchange we estimate an annual emission of atmospheric CH₄ from the Ría de Vigo of 18–44 × 10⁶ g (1.1–2.7 × 10⁶ mol). This estimate is approximately 1–2 orders of magnitude lower than a previous estimate based on a bubble transport model.     

Seasonal variability of sediment trap collections in the Northeast Water Polynya. Part 2. Biochemical and microscopic composition of sedimenting matter

The annual pattern of vertical particle flux in the Northeast Water (NEW) Polynya was recorded from August 1992 to July 1993 by means of moored time-series sediment traps. A distinct seasonal pattern in sedimentation was observed, with highest flux rates during August–October 1992. During this time 40–70% of the annual total sedimented matter (dry weight, DW) and the components, carbonate, particulate organic carbon and nitrogen (POC and PON), particulate biogenic silica (bPSi) and biogenic matter were recorded: 9.83, 2.04, 1.03, 0.69, 0.14 and 5.55 g m⁻², respectively. Microscopic analysis of the particles revealed that diatoms contributed about 10% of the POC flux, but up to 40% of the POC flux originated from the houses and faeces of appendicularians during the period of highest flux rates. In contrast, faecal pellets were only a minor component of sedimenting POC after the opening of the polynya in June 1993. During this period a sedimentation event of Melosira arctica dominated the microscopically recognizable fraction of the POC. Following the low winter values a significant deviation in POC flux in March documented an early onset of plankton growth and a rapid response to the formation of a winter polynya paralleled by a local change in ice conditions. This was supported by the stable nitrogen isotope signature of the sedimented matter, also indicating an early onset of plankton production in the NEW Polynya. However, the overall amplitude of the Δ¹⁵N signal in the sinking particles showed only small variations (<4‰) and was significantly below the amplitude observed in sedimented material from the Northern North Atlantic ( 8‰). The composition of the sedimented matter, comprising mainly fast sinking particles (appendicularian houses, faecal peliets and Melosira aggregates) lead us to conclude that sedimentation in the NEW Polynya was spatially heterogeneous.     

Biogeochemistry of sulfur in a sediment core from the west-central Baltic Sea: Evidence from stable isotopes and pyrite textures

The biogeochemistry of the sulfur cycle in a ca. 5-m-long sediment core from the eastern slope (221 m water depth) of the Landsort Deep in the west-central Baltic Sea was investigated by analyzing the solid phase records of sulfur isotopes and pyrite textures, besides selected main and minor elements. The sediments were deposited during post-glacial history of the Baltic Sea when the basin experienced alteration of brackish (Yoldia Sea, Littorina Sea) and freshwater (Baltic Ice Lake, Ancylus Lake) conditions. The stable isotopic composition of total sulfur was analyzed as a function of depth. In selected samples pyrite (FeS₂), greigite (Fe₃S₄), and barite (BaSO₄) fractions were separated for isotope analyses. Pyrite textures were analyzed by SEM and optical microscopy.Microbial reactions associated with the oxidation of organic matter resulted in assemblages of authigenic sulfide minerals which for the post-Ancylus Lake brackish water environment are dominated by pyrite and for freshwater environments by Fe-monosulfides. The sulfur isotopic composition of the brackish water Littorina Sea sediments (δ³⁴S between −40 and −27‰ vs. V-CDT) is believed to be determined by cellular sulfate reduction rates and reactions involving intermediate sulfur species. The availability of reactive iron and decomposable organic matter as well as sedimentation rate and the chemocline position are important variables upon the δ³⁴S values of sulfides in brackish water environment. The syn-depositional abundance of sulfur and organic matter, and transport of dissolved sulfur species vs. rates of microbial reactions determine δ³⁴S in the freshwater sediments. The upper part of the Ancylus Lake sediments is sulfidized by downward diffusing H₂S and/or sulfate from overlying brackish water sediments. Minor concretionary barite formation in the freshwater sediments is most likely due to the reaction of pore water sulfate diffusing downward from brackish water sediments with barium desorbed from freshwater sediments. The size distribution of pyrite framboids in the brackish sediments indicates that the formation mainly occurred from anoxic pore waters, although some pyrite formation in an anoxic water column cannot be excluded.     

A numerical investigation of phytoplankton and Pseudocalanus elongatus dynamics in the spring bloom time in the Gda sk Gulf

A nutrient–phytoplankton–zooplankton–detritus (1D-NPZD) ‘phytoplankton {Phyt} and Pseudocalanus elongatus {Zoop} dynamics in the spring bloom time in the Gda sk Gulf. The 1D-NPZD model consists of three coupled, partial second-order differential equations of the diffusion type for phytoplankton {Phyt}, zooplankton {Zoop}, nutrients {Nutr} and one ordinary first-order differential equation for benthic detritus pool {Detr}, together with initial and boundary conditions. In this model, the {Zoop} is presented by only one species of copepod (P. elongatus) and {Zoop} is composed of six cohorts of copepods with weights (W_i) and numbers (Z_i); where . The calculations were made for 90 days (March, April, May) for two stations at Gda sk Gulf with a vertical space step of 0.5m and a time step of 900 s. The flow field and water temperature used as the inputs in the biological model 1D-NPZD were reproduced by the prognostic numerical simulation technique using hydrographic climatological data. The results of the numerical investigations described here were compared with the mean observed values of surface chlorophyll-a and depth integrated P. elongatus biomass for 10 years, 1980–1990. The slight differences between the calculated and mean observed values of surface chlorophyll-a and zooplankton biomass are ca. 10–60 mg C m⁻³ and ca. 5–23 mg C m⁻², respectively, depending on the location of the hydrographic station. The 1D-NPZD model with a high-resolution zooplankton module for P. elongatus can be used to describe the temporal patterns for phytoplankton biomass and P. elongatus in the centre of the Gda sk Gulf.     

Siliceous plankton dominate primary and new productivity during the onset of El Niño conditions in the Santa Barbara Basin, California

The potential for carbon export and the role of siliceous plankton in the cycling of C and N was assessed in natural plankton assemblages in the Santa Barbara Basin, California, by examining uptake rates of inorganic carbon, nitrate and silicic acid. In April–August 1997, the concentrations of chlorophyll a, particulate organic carbon, particulate organic nitrogen and biogenic silica were measured twice monthly, and results revealed the occurrence of at least three blooms, the largest in June. Particulate elemental ratios of C, N and Si were similar to ratios of nutrient-replete diatoms, suggesting that they dominated this bloom. Mean integrated rates of carbon, nitrate and silicon uptake during the 4-month study period are similar to other productive coastal and upwelling regions (103, 8.3 and 13 mmol m⁻² day⁻¹, respectively). New production rates were twice as high as previously reported in this region and indicate that high rates of new production along eastern boundary currents are not confined to the major coastal upwelling regions. C/NO₃⁻, Si/NO₃⁻ and Si/C uptake ratios varied widely, and mean integrated ratios were 14±5.4, 1.6±1.0 and 0.12±0.07 (S.D.), respectively. That mean C/NO₃⁻ uptake ratio corresponds to an f-ratio of about 0.5 indicating a large potential for particulate export. Based on the average Si/NO₃⁻ and Si/C uptake ratios, diatoms could perform all of the primary production and nitrate uptake that occurred during the study; these rates also suggest that export is controlled by diatoms in this system. The mean Si/C biomass ratio was lower than the mean Si/C uptake ratio, consistent with the preferential export of Si relative to C observed in sediment traps in the basin. The study took place during a period of surface-water warming, with nitrate and silicic acid concentrations decreasing throughout the onset of the 1997–1998 El Niño conditions. Although diatoms contributed less to particulate biomass during the low nutrient conditions, high f-ratios (0.33–0.66) were maintained.     

Habitat characteristics as determinant of the structure and spatial distribution of epibenthic and demersal communities of Le Danois Bank (Cantabrian Sea, N. Spain)

The purpose of this paper is to detect and describe general trends in the spatial distribution of epibenthic and demersal communities of Le Danois Bank (El Cachucho) in relation to the environmental variables that characterize their habitat by means of multivariate ordination. Data were derived from two multidisciplinary surveys carried out in October 2003 and April 2004 included in the ECOMARG project. The surveys were focused on the study of the physical scenario, including both geological (seabed characterization from bathymetry and backscatter data) and hydrographic features, and the different compartments of the benthic fauna (endobenthic, epibenthic, suprabenthic and demersal communities). For the present study, epibenthos and demersal species were sampled using two different gears, a 3.5 m beam trawl and a Porcupine 39/52 type baca otter trawl respectively. The total species richness combining both samplers ascended to 221, including 71 species of fishes, 65 crustaceans, 35 molluscs, 29 echinoderms, 10 cnidarians and 5 sponges.Multivariate methods were used for the study of the characteristics of communities and habitats. Hierarchical cluster analysis was applied to calculate and visualize similarities between samples in terms of species composition. To assess the amount of variation of faunal densities related to a set of eight environmental variables, a redundancy analysis (RDA) was used. The set of environmental variables used were: depth, near-bottom temperature and salinity, sedimentary typology (dry weight percentages of coarse sands, medium and fine sands, silt and organic matter) and seafloor reflectivity. Using the spatial distribution of the ranges of depth and seafloor reflectivity that characterize the habitats of the faunal assemblages we defined the spatial distribution of the different communities.The multivariate analysis of 18 beam-trawl samples and 15 otter trawl samples showed the existence of 4 main assemblages associated with the more characteristic habitats of the area. The Callogorgia–Chimaera community live mainly in the areas at the top of the Bank (425–550 m depth), where the sediment coverage is lower and there exists a high presence of rocky outcrops. The Gryphus–Galeus community were found in the areas at the top of the Bank covered by medium and fine sand sediments with low organic matter content. The Phormosoma–Trachyrincus community live on the sedimentary terraces that characterize the Bank break (550–800 m) and the Pheronema–Deania community occupy all the deeper (800–1050 m) sedimentary grounds of the inner basin.     

Turbulence in coastal fronts near the mouths of Block Island and Long Island Sounds

Measurements of turbulence were performed in four frontal locations near the mouths of Block Island Sound (BIS) and Long Island Sound (LIS). These measurements extend from the offshore front associated with BIS and Mid-Atlantic Bight Shelf water, to the onshore fronts near the Montauk Point (MK) headland, and the Connecticut River plume front. The latter feature is closely associated with the major fresh water input to LIS. Turbulent kinetic energy (TKE) dissipation rate, ε, was obtained using shear probes mounted on an autonomous underwater vehicle. Offshore, the BIS estuarine outflow front showed, during spring season and ebb tide, maximum TKE dissipation rate, ε, estimates of order 10^− 5 W/kg, with background values of order 10^− 6 to 10^− 9 W/kg. Edwards et al. [Edwards, C.A., Fake, T.A., and Bogden, P.S., 2004a. Spring–summer frontogenesis at the mouth of Block Island Sound: 1. A numerical investigation into tidal and buoyancy-forced motion. Journal of Geophysical Research 109 (C12021), doi:10.1029/2003JC002132.] model this front as the boundary of a tidally driven, baroclinically adjusted BIS flow around the MK headland eddy. At the entrance to BIS, near MK, two additional fronts are observed, one of which was over sand waves. For the headland site front east of MK, without sand waves, during ebb tide, ε estimates of 10^− 5 to 10^− 6 W/kg were observed. The model shows that this front is at the northern end of an anti-cyclonic headland eddy, and within a region of strong tidal mixing. For the headland site front further northeast over sand waves, maximum ε estimates were of order 10^− 4 W/kg within a background of order 10^− 7–10^− 6 W/kg. From the model, this front is at the northeastern edge of the anti-cyclonic headland eddy and within the tidal mixing zone. For the Connecticut River plume front, a surface trapped plume, during ebb tide, maximum ε estimates of 10^− 5 W/kg were obtained, within a background of 10^− 6 to 10^− 8 W/kg. Of all four fronts, the river plume front has the largest finescale mean-square shear, S² ~ 0.15 s^− 2. All of the frontal locations had local values of the buoyancy Reynolds number indicating strong isotropic turbulence at the dissipation scales. Local values of the Froude number indicated shear instability in all of the fronts.     

Environmental changes and the responses of the ecosystems of the Yellow Sea during 1976–2000

The changes in the environmental features of the Yellow Sea during the last 25 years of the 20th century were studied using a set of seasonally monitored data along a transect (at 36°N) maintained by the State Oceanic Administration of China. The data included the ocean temperature (T), salinity (S) and biogenic elements, such as dissolved oxygen (DO), phosphorus (PO₄-P), silicon (SiO₃-Si) and dissolved inorganic nitrogen (DIN).The seasonal (summer and winter) values and the annual mean of these elements showed significant changes during the monitored period. Time series of T, S, DIN and N:P ratios exhibited positive trends, while those of DO, P and Si exhibited negative trends. During this period, the annual mean of T and DIN in the Yellow Sea increased by 1.7 °C and 2.95 μmol L⁻¹, respectively, while those of DO, P and Si decreased by 59.1, 0.1 and 3.93 μmol L⁻¹, respectively. In the 1980s, particularly in between 1985 and 1989, concentrations of P and Si dropped to near the ecological threshold for growth of diatoms. The N:P ratio increased from 4 in 1984 to over 16 in 2000. The climate trend coefficients, R_xt, for these time series are all above 0.43 with significance levels of 95%, except for salinity. The increases in T were consistent with the recent climate warming in northern China and the adjacent seas, i.e. the Bohai Sea and the East China Sea. The reduction of DO was probably attributable to the increase in T and decrease in primary production in these regions. The positive trend of DIN was mainly attributable to precipitation and partly to Changjiang River discharge. The negative concentration trends of P and Si were due to the decreases in their concentrations in seawater that flowed to the Yellow Sea from the Bohai Sea. As a result, N:P ratios greatly increased in the seawater of the Yellow Sea.Moreover, some important responses of the Yellow Sea ecosystems to the changes in physical variables and chemical biogenic elements were obviously displayed. These responses include strengthening nutrient limitation, decreasing chlorophyll a, primary production and phytoplankton abundance, succession of dominant phytoplankton species from diatoms to non-diatoms, changes in fish community structure and species diversity.     

Role of filtering and biodeposition by Adamussium colbecki in circulation of organic matter in Terra Nova Bay (Ross Sea, Antarctica)

At Terra Nova Bay, the scallop Adamussium colbecki (Smith, 1902) characterises the soft and hard bottoms from 20 to 80 m depth, constituting large beds and reaching high values of density (50–60 individuals/m²) and biomass (120 g/m² DW soft tissues). To assess its role in the organic matter recycling in the coastal ecosystem, its filtering and biodeposition rates were evaluated in laboratory experiments during the austral summer 1993/94. Filtration rates, measured in a flow-through system, were calculated from the difference in particulate organic carbon (POC), nitrogen (PON) and chlorophyll-a (Chl-a) concentration in inflow and outflow water. Experiments were performed using natural sea water with POC, PON and Chl-a concentrations of about 450 μg/l, 90 μg/l and 2 μg/l, respectively. The biodeposition rate and the biochemical composition of the biodeposits were studied in order to detect how the organic matter is transformed through feeding activity of A. colbecki. At +1°C temperature, the average filtering rate was about 1 l h⁻¹ g⁻¹ (DW soft tissues) in specimens ranging in body mass from 2 to 3 g (DW soft tissues) and 6–7 cm long. The biodeposition rate in 3–8 cm long specimens, ranging from 0.4 to 5.7 g (DW soft tissues), was about 5.65 mg DW/g DW/day, leading to an estimate of Corg flux, through biodeposition by A. colbecki, of about 21 mg C m⁻² day⁻¹ at in situ conditions. Comparison between the biochemical composition of seston and biodeposits shows a decrease of the labile compounds, of the Chl-a/phaeopigments ratio in the biodeposits. The recorded C/N ratio decrease suggests a microbial colonisation in the biodeposits. This study suggests that Adamussium colbecki plays an important role in coupling the material fluxes from the water column to the sea bed, processing about 14% of total Carbon flux from the water column to the sediments, with an assimilation efficiency of 36%.     

Seasonality of picophytoplankton chlorophyll a and biomass in the central Cantabrian Sea, southern Bay of Biscay

Seasonal changes in the abundance and biomass of cyanobacteria (Synechococcus and Prochlorococcus) and picoeukaryotes were studied by flow cytometry in the upper layers of the central Cantabrian Sea continental shelf, from April 2002 to April 2006. The study area displayed the typical hydrographic conditions of temperate coastal zones. A marked seasonality of the relative contribution of prokaryotes and eukaryotes was found. While cyanobacteria were generally more abundant for most of the year (up to 2.4 10⁵ cells mL^− 1), picoeukaryotes dominated the community (up to 10⁴ cells mL^− 1) from February to May. The disappearance of Prochlorococcus from spring through summer is likely related to shifts in the prevailing current regime. The maximum total abundance of picophytoplankton was consistently found in late summer–early autumn. Mean photic-layer picoplanktonic chlorophyll a ranged from 0.06 to 0.53 µg L^− 1 with a relatively high mean contribution to total values (33 ± 2% SE), showing maxima around autumn and minima in spring. Biomass (range 0.58–40.16 mg C m^− 3) was generally dominated by picoeukaryotes (mean ± SE, 4.28 ± 0.27 mg C m^− 3) with an average contribution of cyanobacteria of 30 ± 2%. Different seasonality of pigment and biomass values resulted in a clear temporal pattern of picophytoplanktonic carbon to chlorophyll a ratio, which ranged from 10 (winter) to 140 (summer). This study highlights the important contribution of picoplanktonic chlorophyll a and carbon biomass in this coastal ecosystem.     

Seasonal study of dissolved CH4, CO2 and N2O in a shallow tidal system of the bay of Cádiz (SW Spain)

During 2004, 10 samplings were performed in order to measure dissolved methane (CH₄), carbon dioxide (CO₂) and nitrous oxide (N₂O) in the surface waters of Río San Pedro, a tidal creek in the salt marsh area of the Bay of Cádiz (SW Spain). The inner partvs of the creek is affected by the inputs coming from an intensive fish farm and the drainage of an extensive salt marsh area.Dissolved CH₄, CO₂ and N₂O concentrations ranged from 11 to 88 nM, 36 to 108 μM and 14 to 50 nM, respectively. Surface waters were in all cases oversaturated with respect to the atmosphere, reaching values of up to 5000% for CH₄, 1240% for CO₂ and 840% for N₂O. Dissolved CH₄, CO₂ and N₂O showed a significant tidal and seasonal variability. Over a tidal cycle, concentrations were always highest during low tide, which points to the influence of the inputs from the fish farm effluent and the drainage of the adjacent salt marsh area, as well as in situ production within the system. Dissolved CH₄, CO₂ and N₂O seasonal patterns were similar and showed maximum concentrations in summer conditions. Using four different parameterizations to calculate the gas transfer coefficients [Liss, P.S. and Merlivat, L., 1986. Air-sea exchange rates: introduction and synthesis. In P. Buat-Ménard (Ed.), The Role of Air-Sea Exchanges in Geochemical Cycling. Reidel, Dordrecht, The Netherlands, p. 113–127.; Clark, J.F., Schlosser, P., Simpson, H.J., Stute, M., Wanninkhof, R., and Ho, D.T., 1995. Relationship between gas transfer velocities and wind speeds in the tidal Hudson River determined by the dual tracer technique. In: B. Jähne and E. Monahan (Eds.), Air-Water Gas Transfer: AEON Verlag and Studio, Hanau, Germany, pp. 785–800.; Carini, S., Weston, N., Hopkinson, G., Tucker, J., Giblin, A. and Vallino, J., 1996. Gas exchanges rates in the Parker River estuary, Massachusetts. Biol. Bull., 191: 333–334.; Kremer, J.N., Reischauer, A. and D'Avanzo, C., 2003. Estuary-specific variation in the air-water gas exchange coefficient for oxygen. Estuaries, 26: 829–836.], the averaged air–water fluxes of CH₄, CO₂ and N₂O from the creek to the atmosphere ranged between 34 and 150 μmol CH₄ m^− 2 day^− 1, 73 and 177 mmol CO₂ m^− 2 day^− 1 and 24 and 62 μmol N₂O m⁻² day⁻¹, respectively.     

The Dead Sea hydrography from 1992 to 2000

The modern hydrological regime of the Dead Sea is strongly affected by anthropogenic activity. The natural fresh water budget has changed mainly due to the drastic reduction of runoff. Since 1977, the surface level of the Dead Sea has been lowered by an average rate of about 60 cm/year and for the period from 1998 to 2000, the lowering rate has reached about 100 cm/year. As a result of the runoff reduction, the upper layer salinity of the Dead Sea has increased and the gravitational stability of the water body was diminished. Eventually, during the winter of 1978–1979, the lake waters overturned, bringing to an end the long-term stable meromictic¹ hydrological regime. The lake entered a new phase in which its hydrological regime switches between holomictic and meromictic regimes, depending on the size of the runoff into the lake (i.e. the amount of precipitation in the lake's watershed). The first holomictic period, 1979–1980, lasted for 2 months only. It was succeeded by a 4-year meromictic period (1980–1983). The second holomictic period lasted for 9 years (1983–1991). The rainy winter of 1991–1992 resulted in an almost 2-m sea level rise. The upper layer with a relatively low salinity was restored and a new meromictic period persisted for 4 years, until winter 1995–1996. During the last meromictic period, the hydrological regime of the Dead Sea was characterized by following long-term trends: the depth of the summer thermocline increased from 12–15 to 25–30 m; the quasi-salinity of the upper layer, initially of about 164 kg/m³, increased rapidly at a rate of about 16–18 kg/m³/year; the quasi-salinity of the deep water, initially of about 235 kg/m³, decreased slowly at a rate of about 0.08–0.10 kg/m³/year (for the sake of comparison, a quasi salinity of 235 kg/m³ is the equivalent of 280‰ “usual” salinity); and the winter minimal temperature of the upper layer, initially of about 16 °C, increased rapidly at a rate of about 2 °C/year. In November 1995, the latest meromictic period of the Dead Sea came to an end. During the present holomictic period, 1996–2000, the hydrological regime of the Dead Sea is also characterized by long-term trends: the quasi-salinity of the entire Dead Sea increased at a rate of about 0.5 kg/m³/year, with practically no decrease during the winters; the temperature of the deep water mass increased with a rate of about 0.25 °C/year; and the period of vertical convection of the entire water column, initially about 3 months, increased at a rate of about 1 week/year. Moreover, we observed that the temperature and salinity of the bottom layer in the deepest part of the Dead Sea raised by about 0.5–0.6 °C and 0.15–0.25 kg/m³ during each holomictic summer.     

A novel method for estimating vertical eddy diffusivities using diurnal signals with application to western Long Island Sound

We present an approach that allows the estimation of vertical eddy diffusivity coefficients from buoy measurements made at two or more depths. By measuring the attenuation and phase lag of a scalar signal generated periodically at the surface as it propagates downwards, the vertical eddy diffusivity coefficients can be calculated as K_v = ωΔz²/2ln²(α₂/α₁), where α₂/α₁ is the ratio of the real amplitudes at frequency ω at the two depths separated by Δz = z₂ − z₁; as K_V = ωΔz²/2φ², where φ is the phase lag at the frequency ω; or as K_v = iωΔz²/ln²(U₂/U₁), where U₂/U₁ is the ratio of the complex signal amplitudes at the two depths. The method requires that horizontal fluxes be small at the ω frequency and that the signal-to-noise ratios at the two depths allow the determination of the amplitude and phase of ω.Application of this method to summertime 2004 western Long Island Sound oxygen and temperature buoy measurements at two depths provides a time-series of two-day average vertical eddy diffusivity estimates. Using these eddy diffusivities in conjunction with measured vertical concentration gradients, we obtain a time-series of vertical transport rates for oxygen and heat and estimate mean downward fluxes for June and July as 150–260 mMol m^− 2 day^− 1 and 100–400 W m^− 2 respectively. These estimates are of a similar magnitude to sub-pycnocline O₂ and heat demands of 240 ± 200 mMol m^− 2 day^− 1 and 180 ± 60 W m^− 2 that we infer from simple budgets, implying that vertical transport is significant to both budgets.The eddy coefficients obtained from the independent O₂ and temperature measurements have a 68% correlation, and the O₂ flux estimates show a correlation of 41% to measured rates of change in bottom dissolved oxygen levels. Our results indicate that extended time-series of eddy diffusivity coefficients can be obtained from in situ buoy measurements and the method shows promise as a way to constrain the vertical transport variability in budgets of dissolved materials in estuaries.     

The structure of dissipation in the western Irish Sea front

We report on an intensive campaign in the summer of 2006 to observe turbulent energy dissipation in the vicinity of a tidal mixing front which separates well mixed and seasonally stratified regimes in the western Irish Sea. The rate of turbulent dissipation ε was observed on a section across the front by a combination of vertical profiles with the FLY dissipation profiler and horizontal profiles by shear sensors mounted on an AUV (Autosub). Mean flow conditions and stratification were obtained from a bed mounted ADCP and a vertical chain of thermistors on a mooring. During an Autosub mission of 60 h, the vehicle, moving at a speed of ~ 1.2 m s^− 1, completed 10 useable frontal crossings between end points which were allowed to move with the mean flow. The results were combined with parallel measurements of the vertical profile of ε which were made using FLY for periods of up to 13 h at positions along the Autosub track. The two data sets, which show a satisfactory degree of consistency, were combined to elucidate the space–time variation of dissipation in the frontal zone. Using harmonic analysis, the spatial structure of dissipation was separated from the strong time dependent signal at the M₄ tidal frequency to yield a picture of the cross-frontal distribution of energy dissipation. A complementary picture of the frontal velocity field was obtained from a moored ADCP and estimates of the mean velocity derived from the thermal wind using the observed density distribution. which indicated the presence of a strong (0.2 m s^− 1) jet-like flow in the high gradient region of the front. Under neap tidal conditions, mean dissipation varied across the section by 3 orders of magnitude exceeding 10^− 2 W m^− 3 near the seabed in the mixed regime and decreasing to 10^− 5 W m^− 3. in the strongly stratified interior regime. The spatial pattern of dissipation is consistent in general form with the predictions of models of tidal mixing and does not reflect any strong influence by the frontal jet.     

Influence of the Mackenzie River plume on the sinking export of particulate material on the shelf

We examined the influence of the Mackenzie River plume on sinking fluxes of particulate organic and inorganic material on the Mackenzie Shelf, Canadian Arctic. Short-term particle interceptor traps were deployed under the halocline at 3 stations across the shelf during fall 2002 and at 3 stations along the shelf edge during summer 2004. During the two sampling periods, the horizontal patterns in sinking fluxes of particulate organic carbon (POC) and chlorophyll a (chl a) paralleled those in chl a biomass within the plume. Highest sinking fluxes of particulate organic material occurred at stations strongly influenced by the river plume (maximum POC sinking fluxes at 25 m of 98 mg C m^− 2 d^− 1 and 197 mg C m^− 2 d^− 1 in 2002 and 2004, respectively). The biogeochemical composition of the sinking material varied seasonally with phytoplankton and fecal pellets contributing considerably to the sinking flux in summer, while amorphous detritus dominated in the fall. Also, the sinking phytoplankton assemblage showed a seasonal succession from a dominance of diatoms in summer to flagellates and dinoflagellates in the fall. The presence of the freshwater diatom Eunotia sp. in the sinking assemblage directly underneath the river plume indicates the contribution of a phytoplankton community carried by the plume to the sinking export of organic material. Yet, increasing chl a and BioSi sinking fluxes with depth indicated an export of phytoplankton from the water column below the river plume during summer and fall. Grazing activity, mostly by copepods, and to a lesser extent by appendicularians, appeared to occur in a well-defined stratum underneath the river plume, particularly during summer. These results show that the Mackenzie River influences the magnitude and composition of the sinking material on the shelf in summer and fall, but does not constitute the only source of material sinking to depth at stations influenced by the river plume.     

Distribution of phytoplankton in the southern Black Sea in summer 1996, spring and autumn 1998

The species composition, abundance, and biomass of micro- (>15 μm) and nano- (<15 μm) phytoplankton were studied along the southern Black Sea during June–July 1996 and March–April and September 1998. A total of 150 species were identified, 50% of them being dinoflagellates. The average total phytoplankton abundance changed from 77×10³ cells l⁻¹ in spring to 110×10³ cells l⁻¹ in autumn and biomass from 250 μg l⁻¹ in summer to 1370 μg l⁻¹ in spring. Based on the extensive sampling grid from June–July 1996, phytoplankton seemed to have a rather homogeneous biomass distribution in the southern Black Sea. In all periods, the coccolithophorid Emiliania huxleyi was the most abundant species, its contribution to the total abundance ranging from 73% in autumn to 43% in spring. However, in terms of biomass, diatoms made up the bulk of phytoplankton in spring (97%, majority being Proboscia alata) and autumn (73%, majority being Pseudosolenia calcar-avis), and dinoflagellates in summer (74%, Gymnodinium sp.). There was a remarkable similarity in the dominant species between the western and eastern regions of the southern Black Sea, indicating transport of phytoplankton within the basin.     

Air–sea CO2 fluxes in the Caribbean Sea from 2002–2004

Air–sea fluxes in the Caribbean Sea are presented based on measurements of partial pressure of CO₂ in surface seawater, pCO_2sw, from an automated system onboard the cruise ship Explorer of the Seas for 2002 through 2004. The pCO_2sw values are used to develop algorithms of pCO_2sw based on sea surface temperature (SST) and position. The algorithms are applied to assimilated SST data and remotely sensed winds on a 1° by 1° grid to estimate the fluxes on weekly timescales in the region. The positive relationship between pCO_2sw and SST is lower than the isochemical trend suggesting counteracting effects from biological processes. The relationship varies systematically with location with a stronger dependence further south. Furthermore, the southern area shows significantly lower pCO_2sw in the fall compared to the spring at the same SST, which is attributed to differences in salinity. The annual algorithms for the entire region show a slight trend between 2002 and 2004 suggesting an increase of pCO_2sw over time. This is in accord with the increasing pCO_2sw due the invasion of anthropogenic CO₂. The annual fluxes of CO₂ yield a net invasion of CO₂ to the ocean that ranges from − 0.04 to − 1.2 mol m^− 2 year^− 1 over the 3 years. There is a seasonal reversal in the direction of the flux with CO₂ entering into the ocean during the winter and an evasion during the summer. Year-to-year differences in flux are primarily caused by temperature anomalies in the late winter and spring period resulting in changes in invasion during these seasons. An analysis of pCO_2sw before and after hurricane Frances (September 4–6, 2004), and wind records during the storm suggest a large local enhancement of the flux but minimal influence on annual fluxes in the region.