Geochemistry of a Tertiary sedimentary phosphate deposit: Baja California Sur, Mexico

The San Gregorio Formation in Baja California Sur, a phosphate-enriched sedimentary unit of late Oligocene to early Miocene age, has been analyzed in two areas (La Purisima and San Hilario) for its chemical composition (major oxides, Cu, Cd, Cr, Co, V, and rare-earth elements - REE) and isotopic composition (??18O and ??13C). A detrital and a marine component were determined from major oxides. The detrital component consists of an unaltered volcanic-ash fraction and a terrigenous clay-silt fraction. The marine component, which accumulated initially as biogenic and hydrogenous material, is now present as opal-A, opal-CT, CaCO3, organic matter, and an authigenic phosphate fraction, mostly pelletal and composed of the carbonate-fluorapatite mineral francolite. The minor elements have been partitioned into these components by assuming a constant composition for the two detrital fractions. The composition of the marine component of minor elements can then be interpreted by assuming that the stoichiometry of the original accumulating organic matter was equal to that of modern plankton. The Cu and Cd contents in the marine component of all rocks require that the seawater-derived fractions of these two metals were supplied to the seafloor solely by organic matter. Enrichments of Cr and V at both sites required an additional marine input. On the basis of their geochemistry in the modern ocean, Cr and V could have precipitated, or been adsorbed, onto settling particles from an O2 minimum zone in which the O2 content was low enough to promote denitrification rather than oxygen respiration. An enrichment of the REE, now within the apatite fraction, resulted from their adsorption onto particulates also in the O2 minimum zone and to the dissolution and alteration of biogenic phases (predominantly silica) within the sediment. Co and Fe2O3 show no enrichment above a detrital contribution. The ??18O-values of apatites from the La Purisima site are heavier than those of apatites from the San Hilario site, whereas the ??13C-values show the opposite trend. One possible interpretation of these variations is that ??18O reflects seawater values and ??13C sediment pore water values. This interpretation suggests that upwelling rates and primary productivity within the water column were greater at La Purisima, an interpretation that is corroborated by a greater abundance of apatite measured in outcrop at La Purisima. The Ce anomalies of the phosphate-enriched samples also differ between the two sites, indicating that they also recorded water masses, similar to the ??18O-values. ?? 1991.