(Table 1) Chemical compositions of iron-manganese phosphate crusts, phosphorites, volcanic products, and phosphate limestones from ocean seamounts

New data on phosphorites of Atlantic seamounts are presented and used in combination with published data to analyze sources of phosphorus in them.

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.

(Table 4) Estimated surface water phosphate concentrations for the past 200 kyr at the location of sediment core GeoB1016-3

We compared ocean atlas values of surface water [PO4]3- and [CO2(aq)] against the carbon isotopic fractionation (ep) of alkenones obtained from surface sediments of the South Atlantic and the central Pacific (Pacific data are from Pagani et al. 2002, doi:10.1029/2002PA000756). We observed a positive correlation between ep and 1/[CO2(aq)], which is opposite of what would be expected if the concentration of CO2(aq) were the major factor controlling the carbon isotopic fractionation of C37:2 alkenones. Instead, we found inverse relationships between ep and [PO4]3- for the two ocean basins (for the Atlantic, ep = -4.6*[PO4]3- + 15.1, R = 0.76; for the Pacific, ep = -4.1*[PO4]3- + 13.7, R = 0.64), suggesting that ep is predominantly controlled by growth rate, which in turn is related to nutrient concentration. The similarity of the slopes implies that a general relationship between both parameters may exist. Using the relationship obtained from the South Atlantic, we estimated surface water nutrient concentrations for the past 200,000 years from a deep-sea sediment core recovered off Angola. Low ep values, indicating high nutrient concentrations, coincide with high contents of total organic carbon and C37 alkenones, low surface water temperatures, and decreased bulk d15N values, suggesting an increased upwelling of nutrient-rich cool subsurface waters as the main cause for the observed ep decrease.

Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

Chemical composition in phosphate materials from the ocean floor

Content, distribution patterns, and speciation of Cl in phosphorites and bone phosphate from the ocean floor, as well as in a set of samples from the land are studied. Total Cl content varies from 0.05 to 4.25% in phosphorites and from 2.48 to 2.75% in recent phosphate-bearing sediments. Recent phosphorites are enriched in Cl relative to ancient ones. Bound Cl content (not extractable by washing), which increases with lithification, varies from 0.17 to 0.60% in ocean and land phosphorites and from 0.02% to 1.30% in bone phosphate. Na content in most samples is higher relative to Na of NaCl due to its incorporation into the crystal lattice of apatite. However, the opposite relationship is observed in some samples indicating partial Cl incorporation into the anion complex of phosphate. Behavior of Cl in phosphorites from the present-day ocean floor is controlled by early diagenetic processes, whereas the role of weathering, catagenesis, and hydrogeological factors may be crucial for phosphorites on continents.