O. Yu. Bogdanova

Transformations of ore minerals in genetically different oceanic ferromanganese rocks

Results of thermic transformations of ore minerals from genetically different oceanic ferromanganese rocks in the course of their heating up to 1000°C are considered. Manganese minerals with various types of crystalline lattice have different grades of thermic stability. Layered manganese minerals (buserite I, asbolane-buserite, and birnessite) are stable up to 120–150°C; asbolane up to 180°C, vernadite, up to ∼500°C; todorokite and pyrolusite (minerals of the tunnel group), up to 600 and 670°C, respectively. Sorbed cations of heavy metals govern the transformation temperature and mineral composition of products of the calcination of ferromanganese rocks. Study of birnessite and todorokite demonstrated that genesis of ferromanganese rocks do not affect thermic properties of minerals in them.

Mineralogical and geochemical features of authigenic carbonates on seepings and hydrothermal fields (By the examples of the Black Sea reefs and the mounds of the lost city field)

Two genetically different types of authigenic carbonate mounds are studied: those within an active hydrothermal field related to serpentinite protrusions in the zone of intersection of a transform fracture zone and the Mid-Atlantic Ridge, and those in an active field of methane seepings in the Dnieper canyon of the Black sea. The general geochemical conditions under which authigenic carbonate formation occurs in the two fields considered were found. They include the presence of reduced H2S, H2, and CH4 gases at the absence of free oxygen; the high alkalinity of the waters participating in the carbonate formation; the similarity of the textural and structural features of authigenic aragonite, which represents the initial mineral of the carbonate matter of the mounds; the paragenesis of aragonite with sulfide minerals; and the close relation of carbonate mounds with communities of sulfate-reducing and methane-oxidizing microorganisms. A new mechanism of formation of hydrothermal authigenic carbonates is suggested; it implies their microbial sulfate reduction over the hydrogen of the fluid in the subsurface zone (biosphere) of mixing between the hydrothermal solution and the adjacent seawater.

Structure and Composition of Ferromanganese-Phosphate Nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied using transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese hydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. The hydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Relative to sediments, concentrations of Mn, As, and Mo increase 12–18 times, while concentrations of Fe, P, Ni, and Co increase 5–7 times during the nodule formation.

Authigenic carbonates in methane seeps from the Norwegian sea: Mineralogy, geochemistry, and genesis

Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active CH4bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanetrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (δ13Cav =−28.9%0) of carbon dioxide produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (δ18Oav = 5%0) in carbonates is inherited from seawater sulfate. A rapid sulfate reduction (up to 12 mg S dm−3 day−1) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this, carbonates can only be formed in surface sediments near the water-bottom interface. Authigenic carbonates occurring within sediments occur do notin situ. Salinity, as well as CO32−/Ca and Mg/Ca ratios, correspond to the field of nonmagnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. The radiocarbon age of carbonates is about 10000 yr.

Sorption of Heavy Metal Cations by Low-Temperature Deposits of Pacific Hydrothermal Fields

Cation exchange reactions with participation of heavy metals Mn, Co, Ni, Cu, Zn, Cd, Ba, and Pb were studed in oceanic low-temperature hydrothermal deposits of various mineral compositions and in hydrogenic Fe-Mn crusts. Individual minerals and their assemblages differ significantly in absorptive capacity, which increases in the following order: hematite ≪ Si-protoferrihydrite < protoferrihydrite < geothite < nontronite ≪ Fe-vernadite + Mn-feroxyhyte < Fe-free vernadite < bernessite + Fe-free vernadite < bernessite; i.e., it successively increases from the mineral with a coordination type of lattice to minerals with a layer-type structure. The exchange complex of all minerals includes Na+, K+, Ca2+, and Mg2+, i.e., the main cations of seawater. In Mn minerals, Mn2+ is the main exchange component. The contribution of all the mentioned cations to the exchange capacity of minerals is as high as 90–98%. The highest absorptive capacity among the examined low-temperature oceanic deposits is characteristic of hydrothermal Mn minerals. Their capacity exceeds substantially that of hydrothermal oxides, hydroxides, Fe-aluminosilicates, and hydrogenic Fe-Mn minerals. The absorptive capacity of all examined Mn minerals relative to heavy metals increases in the same order: Ni < Zn < Cd < Mn < Co < Pb < Cu.

Layered Hydrous Manganese Dioxide Saturated with Alkaline-Earth Cations: Synthesis and Sorption Properties

Layered compounds based on hydrous manganese dioxides (hereafter, Mn-phases) saturated with alkaline-earth cations were synthesized at 3–6°C. These phases are analogues of manganese minerals from oceanic iron-manganese sediments (vernadite, birnessite, buserite-I, an asbolan-like phase, and a hybrid phase). All the Mn-phases, as a rule, had poorly ordered structures. The sorption properties of these phases were studied with respect to alkali-metal cations (Na+, K+), an s-metal cation (Ba2+), a p-metal cation (Pb2+), and d-metal cations (Mn2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+). The exchange capacities of the Mn-phases were 0.45–1.06 mg-equiv/g for the alkali cations and 0.94–5.78 mg-equiv/g for the other cations. The phase composition of the Mn-phase did not affect the alkali cation sorption but affected the divalent cation sorption. The divalent cation exchange capacity increased from well-ordered birnessite to poorly ordered vernadite.

Manganese carbonates in the upper quaternary sediments of the Deryugin basin (Sea of Okhotsk)

The mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core obtained from the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are first identified in the Sea of Okhotsk. Manganese carbonates in the Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.

Iron and Manganese Minerals in Suspended Matter from the Barents Sea

The mineralogy of suspended matter from surface and bottom waters is studied at two sites in the Barents Sea. Along with terrigenous minerals, the suspended matter samples contain authigenic mineral phases of iron and manganese oxyhydroxides. Mn-feroxyhite, Fe-vernadite, goethite, and proto-ferrihydrite were identified in samples from surface waters, whereas birnessite and nonferruginous vernadite were registered in samples from bottom waters. The formation of suspended manganese minerals in bottom waters is explained by an additional Mn supply from underlying reduced sediments during their early diagenesis and oxygen depletion in the near-bottom nepheloid layer. Bacteria are supposed to take part in the authigenic mineral formation.

Sulfides in Phosphorites of Africain Island: Morphological Peculiarities and Origin

The investigation of phosphorites from Africain Island situated in the Indian Ocean revealed that they contain iron sulfides in the form of framboids consisting of separate crystallites, as well as fine-dispersed colloidal particles of micrometer and submicrometer size. Crystallites consist of pyrite, whereas colloidal matter consists of troilite, which is initially formed as hydrogel inside voids. During the subsequent interaction of gelatinous troilite with sulfur, pyrite crystals are formed. The growth of crystals inside a 10987ted microvoid space in the rock leads to their dense hexagonal and tetragonal packing.