Rare earth and other chemical element contents and partitions in bottom sediments, micronodules, and nodules from the bioproductive zone of the Pacific Ocean

Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.

(Table 1) Redox potential and chemical element contents in CaCO3 and amorphous silica free matter in surface layer bottom sediments of the Pacific Ocean from Hawaiian Islands to Mexico coast

Distribution of Fe, Mn, P, Ti, Cu, Ni, Co, V, Cr, W, Mo, and As in the surface sediment layer on the section from the Hawaiian Islands to the coast of Mexico (Mexico section) is studied. Contents of all studied elements increase from biogenic-terrigenous sediments off the coast of Mexico to pelagic red clays of the Northeast Basin, and more sharply for mobile elements - Mn, Mo, Cu, Ni, Co, and As. In near Hawaii sediments rich in coarsely fragmented volcanic-terrigenous and pyroclastic material of basaltic composition with high contents of Ti, Fe, V, Cr, W, and P, contents of these elements increase sharply, and contents of Mn, Mo, Ni, Co, and Cu for the same reason decrease sharply in comparison with red clay. Abnormally high contents of Mn, Mo, Cu, Ni, Co, and As in the upper layer of hemipelagic and transition sediments of the Mexico section result from diagenetic redistribution and their accumulation on the surface. Processes of diagenetic redistribution in hemipelagic and transition sediment mass of the Mexico section are more rapid than in similar sediments of the Japan section due lower sedimentation rates and higher initial concentrations of Mn. Basic similarity of element distribution regularities in sediments of Japan and Mexico sections is shown.

Lead in bottom sediments, nodules, and sulfides from the Black Sea

A study of lead distribution in recent, ancient Black Sea and Neweuxinian bottom sediment shows similar vertical distributions of the element in the oxygen and hydrogen sulfide zones of the sea; i.e. hydrogen sulfide contamination does not affect lead contents in bottom sediments of the sea. Lead distribution in sediment mass of the Black Sea reflects dependence of accumulation of the element on the hydrodynamic regime of the sea and forms of its migration. It is noted that absence of lead accumulation in Black Sea nodules results from specific nodule formation and from geochemical activity of the element. A large role of diagenetic sulfide formation in lead geochemistry is shown. Degree of lead accumulation in iron sulfides depends on conditions of sedimentation and on physical and chemical parameters in the sea.

Contents of major components, U, and Th in bones and bone debris

Uranium and thorium contents, as well as their distribution patterns have been studied in biogenic phosphates from the Atlantic and Pacific Oceans. Differently lithified fish remains (bones, scales, teeth) and marine mammal bones (ribs, vertebras, earbones) collected from both reduced shelf sediments and oxidized pelagic ones have been analyzed. U content in the material varies from 0.7 to 700 ppm, and Th content - from <0.5 to 14 ppm. U/Th ratio varies from 0.16 to 400. Contents of both elements increase with lithification of biogenic phosphates. U concentration is more intense on shelves, whereas thorium concentration increases in pelagic areas. Partial positive correlation of U and Th with Fe and negative correlation of U with organic carbon are noted. The latter corresponds to higher lithification of biogenic phosphates. Calcium phosphate transformed from hydroxyapatite to fluorcarbonate-apatite is the main carrier of U, while transformed organic matter is a minor agent. Thorium is mainly bound with Fe.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Chemical composition of <0.001 mm grain size fraction from sedimentary rocks and bottom sediments of the Philippine Sea

Distriburtion and formation of clay minerals in different types of bottom sediments from the West Pacific are under consideration.

Sulfur compounds in bottom sediments and interstitial waters of the Pacific Ocean to the east of Japan

In near-shore Pacific bottom sediments to the east of Japan unusually high content of free H2S ocurs. H2S resulting from bacterial reduction of sulfates from interstitial waters has a number of derivatives; pyrite dominates among them. Contents of other derivatives of H2S: sulfide sulfur and organic sulfur do not exceed 0,01%, content of organic sulfur does not exceed 0.1%. Due to reduction content of sulfates can reduce to 0,03% S. Capacity of the process of sulfate reduction, estimated by sum of all reduced forms of S - derivatives of H2S, is a function of organic matter content in sediments. Ability of bottom sediments to accumulate free H2S depends on content of reactive forms of Fe. Spatial distribution of reduced forms of S in the studied sediments is considered.

Chemical composition of sepiolites and palygorskites from bottom sediments of the Eastern Indian

In fault zones of the East Indian Ridge and adjacent areas of ocean floor almost monomineral sepiolite- and palygorskite clays have been found. They have been studied by a complex of optical and physical methods. Formation of authigenic sepiolites and palygorskite had occurred under influence of Mg- and Si-rich hydrothermal solutions by metasomatic replacement of montmorillonite clays, or by precipitation from saturated solutions in cracks of various rocks.