The impact of various mixtures of CO2, H2O, H-2, and CH4 upon Fe, Ni, Co, W
. Ge, P, and Mo partitioning between silicate and metal alloy liquids was e
valuated experimentally at 1400 degrees C and 10 kb in graphite. The effect
s observed are consistent with the control expected from redox-driven trans
fer between metal and silicate liquids. Oxidation moves these metals to the
silicate liquid. Oxidizing C-O-H or C-O vapors generated by decomposition
of either brucite or magnesite or both have a stronger, opposite effect on
element distribution than the reducing C-H vapors generated by anthracene d
ecomposition. Special effects associated with particular volatile and sider
ophile elements were largely unobserved. Individual C-O-H species involved
in the redox equilibria are not so important as their redox effect, except
for phosphorous which responds differently to CO2- and H2O-inspired vapors.
An analysis of the redox effects of several M/MOy, equilibria confirm the
presence of large departures from ideality in the solutions involved.
Oxidants might be quite potent in remediating some of the excesses in the s
iderophile element chemistry of the mantle. Because little special effect f
or any volatile species is observed, siderophile elements should respond in
a coherent manner regardless of which volatile species is the immediate ca
use of the redox transfer. In consequence, oxidizing the system with any of
the plausible volatile agents we have investigated to make Ni or Ge or Mo
less siderophile than they are in the absence of volatile elements will als
o make Fe, Co, W, and P too lithophile to be consistent with their observed
abundances in the mantle. The observed Fe abundances in the mantle put lim
its on redox ability to explain the excesses of other siderophile elements.
Furthermore it is unlikely that redox effects can be fine tuned to give ch
ondritic relative abundance values in the mantle as needed. Nevertheless, t
he possible effects of redox equilibria have long been known to be commensu
rate in importance with pressure and temperature effects upon siderophile e
lement distribution and should continue to be considered in any analysis of
core formation. Copyright (C) 1999 Elsevier Science Ltd.