Rare earth element geochemistry of Central Pacific ferromanganese encrustations

Abstract

Analyses have been made of the REE contents of a suite of hydrogenous δMnO 2-rich ferromanganese encrustations obtained from a variety of depths (1000–4700 m) on the Line Islands Archipelago. The crusts form a coherent sample group, the REE contents of which are distinctly higher than those of diagenetic nodules. Crusts from 1 to 2 km depth exhibit higher Mn/Fe ratios and are approximately 50% REE depleted with respect to crusts below ∼ 2 km. Furthermore, the shale-normalised patterns of the REE fall into the same depth-related categories. Crusts from depths greater than 2000–2500 m exhibit slight heavy REE depletion relative to intermediate REE whilst crusts from above that level exhibit more fractionated, heavy-REE-enriched patterns. To explain these depth-related processes, it is proposed that Mn and Fe oxides exhibit distinct behaviour with respect to REE scavenging. Between ∼ 1 and 2 km, higher Mn/Fe ratios in the crusts are considered to be caused by an enhanced supply of Mn 2+ —by diffusion and advection from nearshore sediments—which is adsorbed by and occludes existing oxide flocs. At these depths, oxides therefore tend to exhibit predominantly Mn oxide adsorptive properties. Consideration of the REE patterns shows that Fe oxides must be enriched overall in REE relative to Mn oxides and exhibit a flat shale-normalised REE pattern, whilst Mn oxide exhibits a heavy-REE-enriched pattern. Comparison of dissolved REE depth profiles with the crust data enables a qualitative appraisal of the application of scavenging models to the oxide-REE system. The data are not simply described by either equilibrium or irreversible adsorption models alone. It is concluded that whilst oxides may play a general role in creating the LREE depleted seawater pattern, they have little effect on individual vertical profiles, except close to points where fresh oxides precipitate.