Enrichments of Platinum-group Elements in Hydrogenous, Diagenetic and Hydrothermal Marine Manganese and Iron Deposits

摘要

Twenty-seven marine Mn and Fe deposits chosen for their diverse origins have been analyzed for five platinum-group elements (PGE). The PGE display their highest concentrations in hydrogenous Mn crusts and nodules, lesser concentrations in diagenetic nodules and two to three orders of magnitude lower concentrations in hydrothermal Mn and Fe crusts. This difference of behavior reflects the well-known fractionation of Mn and Fe from the other transition elements, rare earth elements (REE) and PGE in hydrothermal Mn and Fe crusts. Pt, Ru, Rh, and Ir show a close geochemical coherence in these deposits and are differentiated from Pd which shows a negative anomaly with respect to the other PGE in hydrogenous and diagenetic Mn deposits. Pd is less depleted than the other PGE and the Pd anomaly much less pronounced in the hydrothermal Mn and Fe crusts relative to the hydrogenous and diagenetic Mn deposits.Stability field diagrams show no evidence for the oxidation of Pt to the tetravalent state in seawater as suggested by some authors. Rather, Pt appears to be present in seawater as Pt(OH)_2~0. Adsorption of Pt(OH)_2~0 onto the surface of Mn and Fe oxyhydroxide minerals may explain the enrichment of Pt in marine Mn deposits. However, Pt metal is the thermodynamically stable solid phase of Pt under seawater conditions and reduction of Pt(OH)_2~0 to Pt metal, particularly in the vicinity of the oxygen minimum zone, is possible, although the high Ce/La ratios of the Co-rich Mn crusts do not support this hypothesis. Pt, Ru, Rh, and Ir display their maximum concentrations in the Co-rich Mn crusts. This may reflect, among other things, the low growth rates of these deposits. The stability field diagram of Pd shows that Pd is undersaturated in seawater and occurs in seawater dominantly as PdCl_4~(2-) and anionic mixed-hydroxide-chloride complexes. This would explain the anomalous position of Pd among the PGE with respect to its uptake into marine Mn deposits. A study of inter-element associations indicates that the incorporation of the PGE from meteoritic dust plays only a minor role in the uptake of these elements into marine Mn deposits. The PGE remain the most poorly studied group of elements in marine Mn deposits. The data presented here emphasize the need for the establishment of a more comprehensive database of the PGE in marine Mn deposits in order to understand more fully their uptake into marine Mn deposits and their pathways through the oceans.