ABSTRACT
The oxidation state of eleven mantle-derived ilmenite-bearing
xenoliths from four different localities was studied using
O2-specific solid electrolytes. Repetitive calibrations of the
experimental apparatus with the iron-wustite (IW) buffer indicate
that the precision of the measured fO2's at 1312 ± 1 K is
2.37% (±0.01 log units). Results obtained with the IW and
Ni-NiO buffers agree with values reported by other investigators
(e.g., Darken and Burry, 1945; Kemori et al., 1979).
Experiments on blank systems (no sample) demonstrated that the
oxygen sensors that include Al203 elements (SIRO2) are reactive to
free oxygen. They also indicate that the fO2 of equilibration of
an Ar-filled SIRO2 sensor depends, among other factors, on the fO2
of the previous run.
Results from some natural samples indicate that: (a) the fO2
developed by the blank system can modify the composition of the
sample during the experiments; and (b) the criteria of stability
of the Emf with time, and thermal reproducibility of the measured
fO2's are not sufficient to demonstrate equilibrium. To circumvent
these problems, an experimental procedure was developed to reverse
and bracket the equilibrium fO2's.
Good agreement was obtained between electrochemically derived
fO2's on Mg-ilmenite-titanomagnetite intergrowths and values
calculated using the iron-titanium oxide
geothermometer-oxybarometer. However, the electrochemical
determinations are systematically about 0.6 log fO2-units more
oxidized. This bias may be ascribed to the effects of the
geikielite component of the iimenitess.
Auto-oxidation was observed in clinopyroxene-ilmenite
intergrowths. Whether this behavior is observed, however, depends
on the thermal treatment given to the sample during the
experiment.
All of the results are characterized by redox conditions at or
above the FMQ (or EMOG) buffer at one bar and are in agreement
with those of Haggerty and Tompkins (1983) and Arculus et al.
(1984) for similar samples. The measured intrinsic fO2's of a
homogeneous Mg-ilmenite from Monastery Mine, which showed good
reversibility and a continuous log fO2 - 1/T pattern from
800°C to 1150°C during slow heating, agree very well with
data obtained independently by McMahon (1984) using gas
equilibration techniques at 1 atm. The agreement indicates that
electrochemically derived fO2's are not high pressure relicts but
rather are equilibrium values at 1 atm.
Loureiro, D., 1986. Electrochemical determination of the oxygen
fugacity of mantle-derived ilmenite megacrysts. Unpublished PhD
dissertation, State University of New York at Albany. 375pp., +xvi
University at Albany Science Library call number: SCIENCE
MIC Film QE 40 Z899 1986 L68
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