Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Dissolved silica budget for the Baltic Sea

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

Total particulate and organic fluxes in anoxic Framvaren waters

Cylindrical sediment traps were deployed at various depths in the anoxic water of Framvaren for two periods of one year (1981–1982 and 1983–1984). The traps were emptied three times during 1981–1982 and five times during 1983–1984. The vertical fluxes of total suspended material, organic carbon and nitrogen were calculated on a daily and annual basis. The average annual sediment flux 20 m above the bottom was approximately 60 g m⁻² y⁻¹ and the flux of organic carbon was 20 g m⁻² y⁻¹. On the basis of an average C/N ratio of 8 and a constant carbon flux below a depth of 20 m, it is concluded that little mineralization of the organic matter takes place in the anoxic water column. Assuming a primary production of the order to 50–100 g m⁻² y⁻¹, 22–24% of that reaches the anoxic water masses. Further breakdown of organic matter takes place in the surface sediments.     

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

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

Indication of thiols in black sea deep water

Potentiometric titrations of deep Black Sea water give reasonably precise values of sulphide in the concentration range 30–300 μmol l⁻¹ and a strong indication of thiols in the concentration range 10–30 μmol l⁻¹. Organic analysis of Black Sea water should therefore include the search for compounds containing SH groups. A simple stoichiometric model indicates that sulphur-containing proteins might be the main source of thiols after hydrolysis and deamination. The alkalinity and total sulphide are simply related by A_t = 3287 ± 30 + (3.84 ± 0.10) [H₂ S]_t μmol kg⁻¹. The slope of 3.84 instead of the stoichiometric slope of 2.31 indicates a lack of reduced sulphate in the form of hydrogen sulphide.     

Some physicochemical features of a meromictic Lake Suigetsu

Physicochemical features of a typically meromictic lake, Lake Suigetsu, are studied. Vertical distributions of temperature and chlorinity show that the lake is well stratified, and no marked mixing occurs between the upper fresh water and lower salt water. In the chemocline, the vertical gradient of density is large, and the vertical eddy diffusion coefficient is as low as 1.5 × 10^–2 cm² sec.^–1 Dissolved oxygen is saturated in the surface portion of the upper water, and then rapidly decreases with depth towards the chemocline, where sulfide first appears and increases towards the bottom. In the chemocline oxygen consumption is prominent process reaching 290 mg 0₂/m²/day. The oxidation of sulfide, supplied from the underlying water layer, is the main factor causing the oxygen consumption in the chemocline.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

Precipitation of authigenic uranium in suboxic continental margin sediments from the Okinawa Trough

Concentrations of U and Th isotopes in Okinawa Trough and East China Sea sediment cores were determined by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) to investigate the behavior of redox sensitive uranium in suboxic hemipelagic sediments and determine their significance in oceanic uranium balance. ²³⁸U concentrations and ²³⁸U/²³²Th activity ratios in the East China Sea sediments showed no remarkable variation with depth. However, ²³⁸U and ²³⁸U/²³²Th ratios in the Okinawa Trough sediments were low in the surface oxidizing layer but increased where the suboxic condition was encountered. The distribution profiles of ²³⁰Th and ²³²Th concentrations were relatively constant with depth in both the Okinawa Trough and East China Sea sediment cores. These results suggested that there has been post-depositional precipitation of authigenic uranium within the suboxic Okinawa Trough sediment column. The post-depositional precipitation rates of authigenic uranium were estimated to be 47 ± 5 to >62 ± 8 ng cm⁻² yr⁻¹; these rates were comparable to those previously reported for several anoxic sediments. A mechanism controlling precipitation of uranium may be the downward diffusion of uranium U(VI), reduction to U(IV) and finally precipitation onto the solid phase. The accumulation rate of uranium for the Okinawa Trough sediments was approximately eight times higher than the world average rate reported for suboxic sediments. This removal of uranium in the oceanic budget increases the importance of the suboxic sediment sink.     

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

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

The benthic silica cycle in the Northeast Atlantic: annual mass balance, seasonality, and importance of non-steady-state processes for the early diagenesis of biogenic opal in deep-sea sediments

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 μM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment–water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment–water interface and the annual DSi efflux was close to 0.057 mol Si m⁻² yr⁻¹. Biogenic silica accumulation was close to 0.008 mol Si m⁻² yr⁻¹ and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si m⁻² yr⁻¹. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si m⁻² yr⁻¹). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.     

Iodine chemistry in deep anoxic basins and overlying waters of the Mediterranean Sea

Iodate (IO₃⁻) is the predominant dissolved species of iodine in the oxygenated waters of the Mediterranean Sea. Iodide (I⁻) is present in significant quantities (up to 65 nM) in oxygenated waters in the photic zone and near the interface above the anoxic and saline Bannock Basin. Lesser quantities of I⁻ (< 10 nM) are found throughout the rest of the oxic water column. An additional unidentified dissolved iodine species is present immediately above the anoxic interface.Total dissolved iodine (ΣI) increases dramatically across the seawater/brine interface. Part of this increase is undoubtedly the result of the dissolution of iodine-rich evaporites during formation of the brine bodies at the Tyro and Bannock Basins. The vertical distribution of ΣI and other dissolved chemical species (particularly PO₄³⁻) in the Bannock Basin brine, however, suggests an additional, present-day, diagenetic source of dissolved iodine to the brine. Based on the increase in the concentration of the most soluble major ions across the seawater/brine interface, 5–7 μM of the 11.5-μM increase in ΣI concentration must be attributed to diagenesis.     

Distribution and Seasonal Variability of Organic Matter in a Small Eutrophicated Salt Lake

Distribution and seasonal variability of dissolved organic carbon (DOC) and surface active substances (SAS) were studied along the depth profile (15 m) in a small eutrophicated and periodically anoxic sea lake (Rogoznica Lake, Eastern Adriatic coast) in 1996 and 1997. The range of DOC concentrations was characteristic for productive coastal marine ecosystems (60% of samples in the range of 1–2 mg l⁻¹and 40% between 2 and 3 mg l⁻¹). Distribution of SAS concentrations was uniform and shifted toward higher concentrations in comparison to other coastal areas in the Adriatic Sea. Eutrophication in the lake is generated by nutrient recycling under anaerobic conditions. Systematically higher concentrations of chlorophyll a, DOC and SAS were determined at the chemocline in the bottom layer (10–12 m) than in the upper water layer (0·5–2 m). Seasonal variability of organic matter was discussed regarding distributions of microphytoplankton (cells >20 μm) and photosynthetic pigments as well as oxygen and salinity changes along the depth profile. The dissolved oxygen saturation reaching up to 300% in the water layer between 8 m and 10 m depths in May and June 1996, was correlated with enhanced concentrations of phytoplankton biomass (reflected as chl a and b, fucoxanthin, peridinin, zeaxanthin) and increased concentrations of DOC and SAS.     

Flux of nutrients in the Gulf of California: Geostrophic approach

Continental margins exert a strong influence on global biogeochemical cycles; however there have been relatively few attempts to quantify either the magnitude or nature of temporal variability in material fluxes. At present here are no reports on nutrient fluxes at the mouth of the Gulf of California (GC) so further information is needed to provide estimated values from direct measurements. From 1995–1999 during five cruises covering all seasons, seawater samples were collected and measured the nutrient content from the surface to the bottom (some deeper than 2500 m) from a repeated hydrographic sections at the mouth of the GC. This chemical and physical database is unique because it covers an area with important biogeochemical signs, which has been detected as one of the highest in primary productivity of the world oceans. These sections are perpendicular to the coastlines of the Mexican states of Baja California Sur (BCS) and Sinaloa. In this section, the most dynamic area was the surface waters in February 1999 with strong geostrophic currents and temperatures of 20 ± 1.5 °C; salinity 35.091 ± 0.156; pH 8.16 ± 0.13; phosphate 0.85 ± 0.42 μM, nitrate + nitrite 2.35 ± 2.94 μM, and ammonia 2.00 ± 1.25 μM (average ± standard deviation).Geostrophic velocities were computed from high-resolution CTD sections across the entrance to the GC. During winter and spring, the outflow occurred near BCS and the inflow occurred either through the center of the section and/or along the Sinaloa coast. Both inflow and outflow cores were 45 km wide and extended deeper than 700 m. Summer and fall showed a complex pattern, alternating cores of inflow and outflow but with inflow along Sinaloa on all cruises. The maximum flow into the Gulf occurs during May in the center of the section while outflow was concentrated along BCS. Mascarenhas et al. [Mascarenhas, A., Castro, R., Collins, C.A., Durazo, R., 2004. Seasonal variation of geostrophic velocity and heat flux at the entrance to the Gulf of California, Mexico. Journal Geophysical Research, 2124.] calculated the section mean geostrophic velocity that was composed of two alternating cores of inflow and outflow. The two cores that were adjacent to either coast were broader and contained the highest inflow (0.40 m s^− 1) and outflow (− 0.25 m s^− 1) velocities, supporting the general idea of inflow along the Sinaloa and an outflow along BCS.The highest nutrient fluxes occur during El Niño conditions in November 1997 with outflows as high as 54.5 Tg yr^− 1 for Phosphate, 43.0 Tg yr^− 1 for Nitrate and 31.7 Tg yr^− 1 for Ammonia, this values were at least three times higher than in February 1999.     

Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

Changes in sediment processes across the western Irish Sea front

Sediment characteristics, sediment respiration (oxygen uptake and sulphate reduction) and sediment–water nutrient exchange, in conjunction with water column structure and phytoplankton biomass were measured at five stations across the western Irish Sea front in August 2000. The transition from thermally stratified (surface to bottom temperature difference of 2.3 °C) to isothermal water (14.3 °C) occurred over a distance of 13 km. The influence of the front on phytoplankton biomass was limited to a small region of elevated near surface chlorophyll (2.23 mg m⁻³; 50% > biomass in mixed waters). The front clearly marked the boundary between depositional sediments (silt/clays) with elevated sediment pigment levels (≈60 mg m⁻²) on the western side, to pigment impoverished (<5 mg m⁻²) sand, through to coarse sand and shell fragments on the eastern side. Maximal rates of sedimentary respiration on the western stratified side of the front e.g. oxygen uptake S2 (852 μmol O₂ m⁻² h⁻¹) and sulphate reduction at S1 (149 μmol SO₄²⁻ m⁻² h⁻¹), coupled to significant efflux of nitrate and silicate at the western stations indicate closer benthic–pelagic coupling in the western Irish Sea. Whether this simply reflects the input of phytodetritus from the overlying water column or entrapment and settlement of pelagic production from other regions of the Irish Sea cannot yet be resolved.     

Vertical profiles of nitrous oxide and dissolved oxygen in marine sediments

The whole core squeezing method was used to simultaneously obtain profiles of nitrous oxide (N₂O), nitrogenous nutrients, and dissolved oxygen in sediments of Koaziro Bay, Japan (coastal water), the East China Sea (marginal sea), and the central Pacific Ocean (open ocean). In the spring of Koaziro Bay, subsurface peaks of interstitial N₂O (0.5–3.5 cm depth) were observed, at which concentrations were higher than in the overlying water. This was also true for nitrate (NO₃⁻) and nitrite (NO₂⁻) profiles, suggesting that the transport of oxic overlying water to the depth through faunal burrows induced in situ N₂O production depending on nitrification. In the summer of Koaziro Bay, sediment concentrations of N₂O, NO₃⁻ and NO₂⁻ were lower than in the overlying water. In most East China Sea sediments, both N₂O and NO₃⁻ decreased sharply in the top 0.5–2 cm oxic layer (oxygen: 15–130 μM), which may have indicated N₂O and NO₃⁻ consumption by denitrification at anoxic microsites. N₂O peaks at subsurface depth (0.5–6.5 cm) implied in situ production of N₂O and/or its supply from the overlying water through faunal burrows. However, the occurrence of the latter process was not confirmed by the profiles of other constituents. In the central Pacific Ocean, the accumulation of N₂O and NO₃⁻ in the sediments likely resulted from nitrification. Nitrous oxide fluxes from the sediments, calculated using its gradient at the sediment–water interface and the molecular diffusion coefficient, were −45 to 6.9 nmolN m⁻² h⁻¹ in Koaziro Bay in the spring, −29 to −21 nmolN m⁻² h⁻¹ in the summer, −46 to 37 nmolN m⁻² h⁻¹ in the East China Sea, 0.17 to 0.23 nmolN m⁻² h⁻¹ in the equatorial Pacific, and <±0.2 nmolN m⁻² h⁻¹ in the subtropical North Pacific, respectively.     

Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of Mariager Fjord (Denmark)

Major electron donors (H₂S, NH₄⁺, Mn²⁺, Fe²⁺) and acceptors (O₂, NO₃⁻, Mn(IV), Fe(III)), process rates (³⁵SO₄²⁻ reduction, dark ¹⁴CO₂ fixation) and vertical fluxes were investigated to quantify the dominant biogeochemical processes at the chemocline of a shallow brackish fjord. Under steady-state conditions, the upward fluxes of reductants and downward fluxes of oxidants in the water column were balanced. However, changes in the hydrographical conditions caused a transient nonsteady-state at the chemocline and had a great impact on process rates and the distribution of chemical species. Maxima of S⁰ (17.8 μmol l⁻¹), thiosulfate (5.2 μmol l⁻¹) and sulfite (1.1 μmol l⁻¹) occurred at the chemocline, but were hardly detectable in the sulfidic deep water. The distribution of S⁰ suggested that the high concentration of S⁰ was (a) more likely due to a low turnover than a high formation rate and (b) was only transient, caused by chemocline perturbations. Kinetic calculations of chemical sulfide oxidation based on actual conditions in the chemocline revealed that under steady-state conditions with a narrow chemocline and low reactant concentrations, biological sulfide oxidation may account for more than 88% of the total sulfide oxidation. Under nonsteady-state conditions, where oxic and sulfidic water masses were recently mixed, resulting in an expanded chemocline, the proportion of chemical sulfide oxidation increased. The sulfide oxidation rate determined by incubation experiments was 0.216 μmol l⁻¹ min⁻¹, one of the highest reported for stratified basins and about 15 times faster than the initial rate for chemical oxidation. The conclusion of primarily biological sulfide oxidation was consistent with the observation of high rates of dark ¹⁴CO₂ fixation (10.4 mmol m⁻² day⁻¹) in the lower part of the chemocline. However, rates of dark ¹⁴CO₂ fixation were too high to be explained only by lithoautotrophic processes. CO₂ fixation by growing populations of heterotrophic microorganisms may have additionally contributed to the observed rates.     

Determination of the reduced sulfur species in the anoxic zone of the Black Sea: A comparison of the spectrophotometry and iodometry techniques

The report presents the results of the studies of the reduced sulfur species in the water of the anoxic zone of the Black Sea. The content of hydrogen sulfide was determined by means of spectrophotometry using dilution with oxygen-free distilled water. The detection limit of the H₂S amounted to 0.3 μM with the method’s precision below 3%. The accuracy of the spectrophotometric determination was verified by iodometry after the fixation of the hydrogen sulfide in zinc acetate under the distillation with argon from the acidified seawater sample.     

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

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

The production of biogenic silica in the Weddell and Scotia Seas

During the EPOS leg 2 cruise (European Polarstern Study, November 1988–January 1989), the production rate of biogenic silica in the euphotic zone was measured by the ³⁰Si method at stations in the Scotia and Weddell Seas.The highest integrated production rates were observed in the Scotia Sea (range: 11.2–20.6 mmol Si m⁻² day⁻¹), the marginal ice zone of the Weddell Sea exhibiting somewhat lower values (range: 6.0–20.0 mmol Si m⁻²day⁻¹).Our results demonstrate that as far as biogenic silica production is concerned the marginal ice zone of the Weddell Sea is considerably less productive than that of the Ross Sea. Our results also indicate that the water of the Antarctic Circumpolar Current (ACC) could be more productive in late spring and early summer than at the beginning of spring. Possible reasons for the differences among the three subsystems (Ross Sea, Weddell Sea and ACC) are discussed.