Chemical composition of ocean phosphorites and hosted sediments

The book provides an overview of recent data on processes of dispersion and concentration of phosphorus in marine sedimentation. Distribution, chemical and mineral compositions, structure and age of phosphorites occurring on the floor are described. Phosphorites are one of potential mineral resources of the World Ocean. A scheme of multistage-oceanic phosphorite formation is motivated. Modern and pre-Quaternary phosphorite formations in the ocean are paralleled.

(Table 1) Chemical composition of buried manganese noduls and host sediments of ODP Hole 138-854C

Two manganese (Mn) nodules were found in upper Miocene sediments in Hole 854C at a depth of 32.12 mbsf (Samples 138-854C-5H-1,0-2 cm, and -6H-1, 2-4 cm). In structure and composition, the lower nodule is similar to the Pleistocene surface nodules associated with radiolarian ooze from the Clarion-Clipperton Nodule Province. The upper nodule resembles those occurring on pelagic clay from the northern margin of that province.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.

Distribution of Florisphaera profunda and Helicosphaera carteri in down core and surface sediments

A detailed assessment of the respective roles of production, export, and subsequent preservation of organic carbon (Corg) in the eastern Mediterranean (EMED) sediments during the formation of sapropels remains elusive. Here we present new micropaleontological results for both surface samples taken at several locations in the EMED and last interglacial sapropel S5 from core LC21 in the southeastern Aegean Sea. A strong exponential anticorrelation between relative abundances of the lower photic zone coccolithophore Florisphaera profundain the surface sediments and modern concentrations of chlorophyll a (Chl-a) at the sea surface suggests thatF. profunda percentages can be used to track past productivity changes in the EMED. Prior to S5 deposition, an abrupt and large increase of F. profunda percentages in LC21 coincided (within the multidecadal resolution of the records) with the marked freshening of EMED surface waters. This suggests a strong coupling between freshwater-bound surface to intermediate water (density) stratification and enhanced upward advection of nutrients to the base of the photic zone, fuelling a productive deep chlorophyll maximum (DCM) underneath a nutrient-starved surface layer. Our findings imply that (at least) at the onset of sapropel formation physical and biogeochemical processes likely operated in tandem, enabling high Corg accumulation at the seafloor.

Chemical composition of phosphorites and host sediments

Paleotemperature curves were drawn from oxygen-isotope ratios in CaCO3 of planktonic foraminiferal tests and by the micropaleontological method using quantitative relationships of their species. Two series of curves yield similar results. These data confirm that isotope composition of oxygen reflects primarily temperature, and not isotope composition in ocean water. Temperature of the upper layer of ocean water increased from north to south both during the last two glaciations and in the interglacials. All three sediment cores collected from different latitudes show approximately the same amplitudes of fluctuation of mean annual temperature during times of their accumulation, as determined independently by different methods; these amplitudes are estimated as 5-7°C.

137Cs in waters and bottom sediments of the Sea of Japan in 2002 and 1994

During an expedition aboard R/V Pavel Gordienko (September, 2002) investigations in the Sea of Japan areas, where radioactive wastes were disposed by the former Soviet Union, were carried out in order to assess present level of radioactive contamination of marine environment. Concentration of I37Cs, radioecologically one of the most important radionuclides, in near-bottom sea water and bottom sediments were measured to be low, 2.8-17.2 Bq/m**3 and 3.2-27.2 Bq/kg dry weight, respectively, that did not differ significantly from levels elsewhere in the northwest Pacific Ocean arising from global fallout. Results of measurements were compared with results of the Joint Japanese- Korean -Russian expedition to the Sea of Japan in 1994.

Geochemical and optical study of organic matter in some Pleistocene and Pliocene sediments at DSDP Leg 64 Holes

Pleisto-Pliocene hemipelagic and diatomaceous mud was recovered from Deep Sea Drilling Project (DSDP) Sites 474 through 481 in the Gulf of California. The organic matter is mostly marine and mainly derived from diatomaceous protoplasm. We found some continental organic matter in sediments near the bottom basalts or near dolerites (Holes 474A and 478). The organic matter in most of the samples is in an early stage of evolution.

Methane in waters and bottom sediments of the North (Severnaya) Dvina mouth area in 2004-2006

The mouth area of the North (Severnaya) Dvina River is characterized by a high concentrations of methane in water (from 1.0 to 165.4 µl/l) and bottom sediments (from 14 to 65000 µl/kg), being quite comparable to productive mouth areas of rivers from the temperate zone. Maximum methane concentrations in water and sediments were registered in the delta in segments of channels and branches with low rates of tidal and runoff currents, where domestic and industrial wastewaters are supplied. In the riverine and marine water mixing zone with its upper boundary, locating far into the delta and moving depending on a phase of the tidal cycle, decrease of methane concentration with salinity increase was observed. The prevailing role in formation of the methane concentration level in water of the mouth area pertains to bottom sediments, which is indicated by close correlation between gas concentrations in these two media. Existence of periodicity in variations of methane concentration in river water downstream caused by tidal effects was found.

Composition and age of ores and bottom sediments accumulated within and near the Rainbow hydrothermal field

Results of direct geological and geochemical observations of the modern Rainbow hydrothermal field (Mid-Atlantic Ridge, 36°14'N; 33°54'W) carried out from the deep-sea manned Mir submersibles during Cruises 41 and 42 of the R/V Akademik Mstislav Keldysh in 1998-1999 and data of laboratory studies of collected samples are under consideration in the paper. The field lacks neovolcanic rocks and the axial part of the rift is filled in with a serpentinite protrusion. In this field there occur metalliferous sediments, as well as active and relict sulfide edifices composed of sulfide minerals; pyrrhotite, chalcopyrite, isocubanite, sphalerite, marcasite, pyrite, bornite, chalcosine, digenite, magnetite, anhydrite, rare troilite, wurtzite, millerite, and pentlandite have been determined. Sulfide ores are characterized by concentric-zoned textures. During in situ measurements during 35 minutes temperature of hydrothermal fluids was varying within a range from 250 to 350°C. Calculated chemical and isotopic composition of hydrothermal fluid shows elevated concentrations of Cl, Ni, Co, CH4, and H2. Values of d34S of H2S range from +2.4 to +3.1 per mil, of d13C of CH4 from -15.2 to -11.2 per mil, and d13C of CO2 from +1.0 to -4.0 per mil. Fluid inclusions are homogenized at temperatures from 140 to 360°C, whereas salinity of the fluid varies from 4.2 to 8.5 wt %. d34S values of sulfides range from +1.3 to +12.5 per mil. 3He/4He ratio in mineral-forming fluid contained in the fluid inclusions from sulfides of the Rainbow field varies from 0.00000374 to 0.0000101. It is shown that hydrothermal activity in the area continues approximately during 100 ka. It is assumed that the fluid and sulfide edifices contain components from the upper mantle. A hypothesis of phase separation of a supercritical fluid that results in formation of brines is proposed. Hydrothermal activity is related to the tectonic, not volcanic, phase of the Mid-Atlantic Ridge evolution.

Major and rare earth element contents and their speciations in ferruginous nodules and host sediments from the Barents Sea

Contents of Fe, Mn, Al, P, and rare earth elements (REE) in ferruginous nodules and host sediments of the eastern Barents Sea were studied. A direct Fe-P correlation in reactive components of the sediments and nodules was found. The nodules were shown to be formed through Fe(II) oxidation in the surface layer of sediments and cementation of terrigenous fraction of sediments by Fe(III) oxyhydroxides. The latter accumulate phosphorus due to processes of sorption - co-precipitation, by forming Fe(III) hydrophosphates. REE composition in the sediments and nodules normalized to NASC contents is characterized by increased proportion of light REE that may be caused by regional features of their sources. Due to significant share of terrigenous matter in the Fe nodules (up to 65% for Nd), REE composition of bulk samples is similar to that of host sediments. A negative cerium anomaly in composition of reactive REE may result from REE sorption from seawater. REE bulk composition of a ferruginous crust is closer to that of seawater than one of the ferruginous nodules from the sediments because of essentially lower content of diluent terrigenous matter.