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.

Phosphate d18O pore-water profiles of sediment core GeoB11807-2 and GeoB11804-4

Phosphorus cycling in the ocean is influenced by biological and geochemical processes that are reflected in the oxygen isotope signature of dissolved inorganic phosphate (Pi). Extending the Pi oxygen isotope record from the water column into the seabed is difficult due to low Pi concentrations and small amounts of marine porewaters available for analysis. We obtained porewater profiles of Pi oxygen isotopes using a refined protocol based on the original micro-extraction designed by Colman (2002). This refined and customized method allows the conversion of ultra-low quantities (0.5 - 1 µmol) of porewater Pi to silver phosphate (Ag3PO4) for routine analysis by mass spectrometry. A combination of magnesium hydroxide co-precipitation with ion exchange resin treatment steps is used to remove dissolved organic matter, anions, and cations from the sample before precipitating Ag3PO4. Samples as low as 200 µg were analyzed in a continuous flow isotope ratio mass spectrometer setup. Tests with external and laboratory internal standards validated the preservation of the original phosphate oxygen isotope signature (d18OP) during micro extraction. Porewater data on d18OP has been obtained from two sediment cores of the Moroccan margin. The d18OP values are in a range of +19.49 to +27.30 per mill. We apply a simple isotope mass balance model to disentangle processes contributing to benthic P cycling and find evidence for Pi regeneration outbalancing microbial demand in the upper sediment layers. This highlights the great potential of using d18OP to study microbial processes in the subseafloor and at the sediment water interface.

Composition of marine phosphorites and phosphate-bearing sediments

The book deals with behavior of phosphorus and its concentration in oceanic phosphorites. The major stages of marine geochemical cycle of phosphorus including its supply to sedimentary basins, precipitation from sea water, distribution and speciation in bottom sediments, diagenetic redistribution, and relation to other elements are under consideration. Formation of recent phosphorites as a culmination of phosphate accumulation in marine and oceanic sediments is examined. Distribution, structure, mineral and chemical compositions of major phosphorite deposits of various age on continental margins, as well as on submarine plateaus, uplifts and seamounts and some islands are described. A summary of trace element abundances in oceanic phosphorites is presented. Problems of phosphorite origin are discussed.