The oxidation state of deeply subducted, altered oceanic crust: an experimental study and the evidence from natural samples
Abstract
Eclogitic xenoliths from kimberlites are occasionally
diamond-bearing, and are often interpreted as having an origin as
subducted oceanic crust. The existence of diamonds in these rocks
constrains equilibrium temperatures and pressures of some
eclogites to the upper mantle. However the additional critical
parameter controlling the stability of diamonds, oxygen fugacity
(fO₂), is poorly constrained in eclogitic assemblages.
A series of piston-cylinder experiments were conducted using
model carbonate and kyanite bearing eclogite assemblages to
determine the oxygen fugacity of the limiting reaction for
carbonate vs. graphite/diamond:
Dolomite + 2Coesite = Diopside + 2Graphite/Diamond + 2Oxygen
as a function of pressure (P=3.5-6 GPa) and temperature
(T=900-1300 degree C).
The oxygen fugacity in the experiments was determined using Fe-Ir
alloy ƒO₂ sensors and a newly developed Fe-Pd-based redox sensor
for high-pressure experiments. The experimental data allowed
calibration of two redox reactions (involving
garnet-clinopyroxene and garnet-kyanite) as oxybarometers to
determine ƒO₂ of eclogitic rocks. Both reactions can be used to
evaluate the ƒO₂ of UHP metamorphic eclogites and eclogite
xenoliths from kimberlites.
The accuracy of the calculated ƒO₂ is highly dependent on
precision of the garnet Fe³⁺/ΣFe measurements, which were
obtained using the flank method and the synchrotron based Fe
K-edge XANES method. Both reactions were calibrated and used to
estimate ƒO₂ of diamond, kyanite and coesite bearing eclogite
xenoliths from Udachnaya kimberlite pipe, Yakutia, Russia. The
relatively high ƒO₂ of diamond stability in eclogite relative to
peridotite at the upper mantle PT conditions may explain the
higher abundance of diamonds in eclogite xenoliths and constrains
the mechanism of transport of carbon to the deep mantle.
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