Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Vertical distribution of particulate manganese and iron in the Beppu Bay

Around the thermocline, difference in the depth of the maximum concentration between particulate manganese and iron was observed above the basin located at the south-western corner of the Beppu Bay, along with the remarkable difference in pH and Eh.     

Possibilities of the photoluminescence method for determining the oxygen concentration in the redox zone of the Black Sea in comparison with other methods

Different methods of measuring low oxygen concentrations were compared in July 2008 in the Black Sea: the conventional Winkler method, electrochemical sensors (membrane and membrane-free), and two modifications of photoluminescence sensors. The membrane-free sensor used in the Black Sea since 1999 and the domestic photoluminescence sensor showed the best results: agreement of data, possibility of fine oxygen distribution resolution, and absence of the oxygen and hydrogen sulfide coexistence layer. The latter has good technical characteristics: high oxygen sensitivity and complete inertness to hydrogen sulfide, possibility of calibration in a gaseous environment, and a relatively low time constant (5–6 s). An equation was suggested for dynamic correction of data in the testing mode, which eliminates hysteresis of data on probe descent and ascent to a significant degree. It was shown that the oxygen concentration above the hydrogen sulfide layer in the subreductive zone of the Black Sea did not exceed 0.02 μM.     

南海越南上升流区沉积物中溶解氧、锰和铁的垂直分布特征

2007年夏季航次对南海越南上升流区的三个站位进行现场采样,利用微电极技术测定了沉积物间隙水中的溶解氧(DO溶解氧分子)、锰(Mn2+)、铁(Fe2+)的浓度和氧化还原电位,估算了DO的通量、消耗速率和有机碳的消耗速率.在沉积物间隙水中DO浓度随深度的增加而迅速降低,渗透深度为9-48mm.在沉积物深处还检测到Mn2+和Fe2+.采用元素分析仪测定了沉积物中总有机碳(TOC)含量和总氮(TN)含量,三个站位沉积物中的TOC含量为0.7%-1.03%,TN含量为0.052%-0.10%,C/N为10.5-16.0.从C/N可以看出,该研究区域沉积物中的有机物有部分来源于陆源输入,其中一个站位位于湄公河冲淡水区域,其C/N最大.从氧化还原电位来看,三个站位的沉积环境都属于还原性环境.此研究首次测量了南海越南上升流区沉积物的氧化还原化学成分,对于认识该海区海底生物地球化学具有重要意义.     

A sulfur budget for the Black Sea anoxic zone

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

Reactive iron in Black Sea Sediments: implications for iron cycling

The distribution of reactive iron in sediments of the northwestern shelf, the shelf edge and the abyssal part of the Black Sea has been studied. In the euxinic Black Sea, iron sulfides (pyrite and iron monosulfide) are formed in the upper part of the anoxic water column and sink to the deep-sea floor where they are buried in the sediment. This flux of iron sulfides from the water column is reflected in enhanced concentrations of highly reactive iron and a high degree of pyritization (0.57–0.80) for the deep-water sediments of the Black Sea. The iron enrichment of deep-water sediments is balanced by a loss of highly reactive iron from the oxic continental shelf. Calculations from a numerical diagenetic model and reported in situ flux measurements indicate that the dissolved iron flux out of the shelf sediments is more than sufficient to balance the enrichment in reactive iron in deep-sea sediments, and that the majority of the dissolved iron efflux is redeposited on the continental shelf. This iron mobilization mechanism likely operates in most shelf areas, but its net effect becomes only apparent when reactive iron is trapped in sulfidic water bodies as iron sulfides or when iron is incompletely oxidized in low oxygen zones of the ocean and transported over long distances.     

Modeling Black Sea circulation with high resolution in the coastal zone

We present a numerical model of Black Sea circulation based on primitive equations with improved spatial resolution in the coastal zone. The model equations are formulated in a two-pole orthogonal coordinate system with arbitrary locations of the poles and a vertical σ coordinate. Increased horizontal resolution is gained by displacing the pole into the vicinity of the separated subdomain. The problem is solved over a grid with a variable step. The northern coordinate pole is displaced to the vicinity of Gelendzhik; the grid step varies from 150 m in the coastal zone to 4.6 km in the main basin. We simulated the fields of currents, sea level, temperature, and salinity under the given atmospheric forcing in 2007. The model is capable of reproducing the large-scale Black Sea circulation and submesoscale variations in the coastal currents.     

Subsatellite polygon for studying hydrophysical processes in the Black Sea shelf-slope zone

The first data on the creation of the subsatellite polygon on the Black Sea shelf and continental slope in the Gelendzhik area (designed in order to permanently monitor the state of the aquatic environment and biota) and the plans for maintaining and developing this polygon are presented. The autonomous measuring systems of the polygon in the composition of bottom stations with acoustic Doppler current profilers (ADCP), Aqualog robotic profilers, and thermo-chains on moored buoy stations should make it possible to regularly obtain hydrophysical, hydrochemical, and bio-optical data with a high spatial-time resolution and transmit these data to the coastal center on a real-time basis. These field data should be used to study the characteristics and formation mechanisms of the marine environment and biota variability, as well as the water-exchange processes in the shelf-deep basin system, ocean-atmosphere coupling, and many other processes. These data are used to calibrate the satellite measurements and verify the water circulation numerical simulation. It is assumed to use these data in order to warn about the hazardous natural phenomena and control the marine environment state and its variation under the action of anthropogenic and natural factors, including climatic trends. It is planned to use the polygon subsatellite monitoring methods and equipment in other coastal areas, including other Black Sea sectors, in order to create a unified system for monitoring the Black Sea shelf-slope zone.     

Fluxes of iron and manganese across the sediment–water interface under various redox conditions

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.     

Mathematical model for the ecosystem of the Black Sea hydrogen sulphide zone

A model for the ecosystem of the Black Sea hydrogen sulphide zone is suggested which incorporates seven components, namely, the concentrations of hydrogen sulphide, oxygen, dead organic matter, thiosulphates, molecular sulphur, and the biomass of sulphate-reducing and thiobacteria. With the minor terms neglected in the equations governing the system under consideration, the latter was divided into subsystems which allow an approximate calculation of the model components' vertical stationary profiles. The derived components' profiles agree qualitatively with available observations.Translated by V. Puchkin.     

Long-Term Variability of the Dissolved Oxygen Content and Water Temperatures in the Upper Layer of the Black Sea

Oceanology - Based on the archival oceanographic databank of the Institute of Natural and Technical Systems, the annual and interannual variability was analyzed for the dissolved oxygen content and...     

Numerical analysis of the mesoscale features of circulation in the Black Sea coastal zone

The results of simulating the hydrophysical fields of the Black Sea with a resolution of 1.64 × 1.64 km for January–September 2006 with the use of real atmospheric forcing are analyzed. Both vertical turbulent momentum exchange and vertical turbulent heat and salt diffusions are parameterized using the Mellor-Yamada level 2.5 scheme. The results of this numerical experiment are compared with similar data obtained with a horizontal resolution of 5 km. The features of the meso- and submesoscale dynamics of waters in individual sea regions are given. Possible physical mechanisms of forming meso- and submesoscale vortices are studied on the basis of energy analysis. It is shown that, in the absence of significant wind forcing, the main contribution to kinetic energy is made by the buoyancy force and wind-field inhomogeneities result in significant variations in both total vertical viscosity and total vertical diffusion.     

Dissolved uranium in the Baltic Sea

Filtered water from the Baltic Sea was analysed for uranium concentration and ²³⁴U/²³⁸U activity ratio with alpha-ray spectrometry. The uranium concentration shows a strong correlation to salinity, the correlation coefficient being close to 0.98. Consequently, the uranium concentration increases from 0.15 μg kg⁻¹ in the northern part, dominated by fresh water, to above 1.0 μg kg⁻¹ in the Belt Sea. However, the data also show that dissolved uranium is not strictly conservative in the Baltic. In deeper intermittently anoxic basins of the Baltic Proper, the element is removed from the water phase and incorporated into the sediment. This is most evident in the Gotland Deep, which has been anoxic below 200 m depth since 1979.     

Dissolved and particulate tin in North Atlantic seawater

A study of tin concentrations in the North Atlantic Ocean has revealed concentrations much lower than previously reported. Concentrations of dissolved tin in surface water are in the range of non-detectable (< 1.5 pM) to 16 pM. Almost all depth profiles have maxima in tin concentrations from 50 to 200 m depth. These maxima can be as high as 16 pM. In most depth profiles, dissolved tin is at or below detection limits at depths exceeding 1000 m.     

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.     

Variability of the oxygen deficit near the H2S zone in the Black Sea

Historical oceanographic databases are statistically treated to obtain the mean multi-annual oxygen deficit distributions in the 70–90 m layer for the four seasons of the year. Generalization of the results from 1596 measurements has shown that the oxygen deficit is maintained only at one 1°×1° square at a level of 70–90%. This fact is accounted for by the rise of waters in the cyclonic gyre area. Conversely, small oxygen deficit values in the coastal areas are related to the sinking of water, this being consistent with the pattern of vertical circulation in the sea.Translated by V. Puchkin.     

Dissolved microelements (heavy metals) in the near-Danube part of the Black Sea in the autumn of 1997

We analyse the distribution of the dissolved forms of cadmium, lead, cobalt, copper, and manganese in the near-Danube part of the Black Sea and in a section made at 45° 10′N in the autumn of 1997. It is shown that the discharge of rivers results in the appearance of significant amounts of cadmium, lead, cobalt, copper, and manganese in the near-Danube region. Copper is the most labile element in this collection of metals. Its behaviour is correlated with the vital activity of diatomic algae. The distribution of dissolved manganese in the near-bottom region is correlated with the distribution of O₂. Indeed, the elevated concentrations of manganese are observed in the regions with low concentrations of oxygen. Translated by Peter V. Malyshev and Dmitry V. Malyshev     

Dissolved and particulate organic carbon and nitrogen in the Northwestern Mediterranean

The distribution of dissolved organic carbon (DOC) and nitrogen (DON) and particulate organic carbon (POC) and nitrogen (PON) was studied on a transect perpendicular to the Catalan coast in the NW Mediterranean in June 1995. The transect covered a hydrographically diverse zone, including coastal waters and two frontal structures (the Catalan and the Balear fronts). The cruise was conducted during the stratified period, characterized by inorganic nutrient depletion in the photic zone and a well established deep chlorophyll a maximum. DOC concentrations were measured using a high-temperature catalytic oxidation method, and DON was determined directly, with an update of the Kjeldahl method, after removal of inorganic nitrogen.The ranges of DOC and DON concentrations were 44–95 μM-C and 2.8–6.2 μM-N. The particulate organic matter ranged between 0.9 and 14.9 μM-C and from 0.1 to 1.7 μM-N. The DOC : DON molar ratio averaged 15.5±0.4, and the mean POC : PON ratio was 8.6±0.6. The distribution of dissolved organic matter (DOM) was inverse to that of the salinity. The highest concentrations of DOM were found in coastal waters and in the stations affected by the Catalan front, located at the continental shelf break.It was estimated that recalcitrant DOM constituted 67% of the DOM pool in the upper 50 m. The data suggest that accumulation of DOC due to the decoupling of production and consumption may occur in the NW Mediterranean during stratification and that the organic matter exported from the photic layer is dominated by C-rich material.