Composition and crystal parameters of carbonate-apatites from animal teeth and bones and from phosphate rocks of the ocean bottom

Samples of recent to Miocene fish and marine mammal bones from the bottom of the Atlantic and Pacific Oceans and Miocene Maikop deposits (Transcaspian region) are studied by X-ray diffraction technique combined with chemical and energy-dispersive analyses. Changes of lattice parameters and chemical composition of bioapatite during fossilization and diagenesis suggest that development of skeletal apatite proceeds from dahllite-type hydroxyapatite to francolite-type carbonate-fluorapatite. It is assumed that jump-type transition from dahllite to francolite during initial fossilization reflects replacement of biogeochemical reactions in living organisms, which are subject to nonlinear laws of nonequilibrium thermodynamics, by physicochemical processes according to the linear equilibrium thermodynamics.

Chemical and mineral compositions of basalts and volcanic glasses from DSDP Sites 65-483 and 65-485

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO*/MgO ratio (0.95 with total Fe as FeO), and Mg# (100 Mg/Mg + Fe" = 70), sample 483-17-2-(78-83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a La/Sm_cn (chondrite-normalized) = 0.36, and Eu/Sm_cn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (Eu/Sm_cn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78-83) to form the least differentiated sample with Mg# = 63. The La/Sm_cn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher La/Sm_cn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower La/Sm_cn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78-83) is required.

Petrographic description and mineral composition of ODP Site 161-975 sediments

Ocean Drilling Program Site 975 is located near the base of the Menorca Rise in the South Balearic Basin of the western Mediterranean Sea. Coring at this site penetrated the Pliocene/Miocene boundary and recovered a sequence of sediments that represent the final stages of salt deposition and the transition from evaporitic to open marine conditions at the end of the Miocene (Messinian). Detailed petrographic observations and bulk mineralogical analyses by X-ray diffraction form the basis for preliminary interpretations of depositional environments for this section. Gypsum is thought to have been deposited in an evaporating basin below wave base. Cycles consisting of a clay layer overlain by gypsiferous chalk, laminated gypsum, and finally pinch-and-swell gypsum suggest upsection increases in salinity. The gypsum section is overlain by two exotic sand layers thought to mark events of fresher water (marine or meteoric) inflow to the basin. Gypsum deposition terminated and was replaced by inorganic precipitation of micritic calcite with periodic, variable dilution by fine-grained terrigenous sediment. The micritic sediments have fine, slightly wavy, laminations indicating either an algal/microbial mat origin, or varve-like fluctuations in deposition, perhaps in a deep basin. The Pliocene/Miocene boundary falls within an interval of banded micritic silty clays that reflect the final environmental fluctuations during the transition to the open marine conditions of the Pliocene.

Abundance and chemical and mineral compositions of nodules from the Pacific Ocean

The monograph highlights extensive materials collected during expeditions of P.P. Shirshov Institute of Oceanology. We consider facial conditions of nodule formation, regularities of their distribution, stratigraphic position, petrography, mineral composition, textures, geochemistry of nodules and hosting sediments. Origin of iron-manganese nodules in the Pacific Ocean is considered as well.

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.