Composition of phosphorites from continental margins, seamounts, and islands

Behavior of molybdenum and manganese is studied in phosphorite samples from shelves, seamounts, and islands of the ocean. In shelf phosphorites molybdenum and manganese contents are 2-128 and 12-1915 ppm, respectively, while the Mo/Mn ratio varies from 0.004 to 4.5. Phosphorites from ocean seamounts impregnated with ferromanganese oxyhydroxides contain 0.84-14.5 ppm Mo and 0.1-17% Mn. The Mo/Mn ratio varies within 0.0008-0.004. Phosphate bearing ferromanganese crusts overlying seamount phosphorites contain 54-798 ppm Mo and 10-20% Mn; the Mo/Mn ratio varies within 0.002-0.005. Corresponding values for most island phosphorites are 0.44-11.2 ppm, 27-287 ppm, and 0.008-0.20. Phosphorites from reduced environment are characterized by relative enrichment in Mo and depletion in Mn, whereas the Mo/Mn ratio reaches maximum values. The ratio decreases with transition to suboxic and oxic conditions. Molybdenum content in recent shelf sediments is commonly higher than that in authigenic phosphorites from these sediments. Recent phosphorite nodules from the Namibian shelf become depleted in Mo and Mn during their lithification, but Pliocene-Pleistocene nodules of similar composition and origin from the same region are enriched in Mo and characterized by variable Mn content. Higher Mo contents in phosphate bearing ferromanganese crusts result from coprecipitation of Mo and Mn from seawater. Unweathered phosphorites on continents and phosphorites from ocean shelves are largely enriched in Mo with the Mo/Mn ratio varying from 0.01 to 1.0. This is an evidence of their formation in reduced conditions.

Minerals, geochemistry and x-ray power characteristics at DSDP Sites 54-424, 60-458 and 60-459

Secondary minerals filling veins and vesicles in volcanic basement at Deep Sea Drilling Project Sites 458 and 459 indicate that there were two stages of alteration at each site: an early oxidative, probably hydrothermal, stage and a later, low-temperature, less oxidative stage, probably contemporaneous with faulting in the tectonically active Mariana forearc region. The initial stage is most evident in Hole 459B, where low-Al, high Fe smectites and iron hydroxides formed in vesicles in pillow basalts and low-Al palygorskite formed in fractures. Iron hydroxides and celadonite formed in massive basalts next to quartz-oligoclase micrographic intergrowths. Palygorskite was found in only one sample near the top of basement in Hole 458, but it too is associated with iron hydroxides. Palygorskite has previously been reported only in marine sediments in DSDP and other occurrences. It evidently formed here as a precipitate from fluids in which Si, Mg, Fe, and even some Al were concentrated. Experimental data suggest that the solutions probably had high pH and somewhat elevated temperatures. The compositions of associated smectites resemble those in hydrothermal sediments and in basalts at the Galapagos mounds geothermal field. The second stage of alteration was large-scale replacement of basalt by dioctahedral, trioctahedral, or mixed-layer clays and phillipsite along zones of intense fracturing, especially near the bottom of Holes 458 and 459B. The basalts are commonly slickensided, and there are recemented microfault offsets in overlying sediments. Native copper occurs in one core of Hole 458, but associated smectites are dominantly dioctahedral, unlike Hole 459B, where they are mainly trioctahedral, indicating nonoxidative alteration. The alteration in both holes is more intense than at most DSDP ocean crust sites and may have been augmented by water derived from subducting ocean crust beneath the fore-arc region.