Oxygen isotope analysis for silicate minerals using a high temperature
conversion/elemental analyzer-isotope ratio mass spectrometer
Abstract
RATIONALE: Oxygen isotope composition of silicates is an
important indicator of the formation environment and/or subsequent
geochemical processes of minerals. Compared to carbonate minerals and
organic matter, silicate is a less common target for oxygen isotope
measurements because of the need for specialized fluorination
instruments to break strong Si-O bonds. METHODS: We introduce a
simple method using a high temperature conversion elemental
analyzer-isotope ratio mass spectrometer (TC/EA-IRMS), which does not
require specialized instrumentation. Silicate powder with various
fluorine compounds and ratios of fluorine/oxygen were decomposed at
1450°C, and then, mass spectral characteristics, oxygen yields, and δ
18O values were compared. RESULTS: NaF and KF
were the most reactive fluorine sources, followed by
polytetrafluoroethylene, LiF, CaF 2, BaF
2, and AlF 3, with decreasing
reactivity. The F/O ratio affected the tailing of the CO peaks in the
mass spectrum. Higher F/O ratios show a more rapid regression to
background, resulting in higher reproducibility of oxygen yield and δ
18O. In addition to simply adding fluorides to the
sample, homogenization treatment also improved the reactivity. Activated
carbon catalyzed by nickel is a better carbon source than graphite in
terms of reactivity. The quartz and smectite with NaF added at an F/O
ratio of 6 provided 90.0–99.3% of oxygen yields, δ
18O values that deviated less than 1.2‰ from
literature values, and 0.18–0.29 ‰ of precision. CONCLUSIONS:
Although further investigation is required to verify its accuracy, the
potential of the TC/EA-IRMS method for silicates is demonstrated.
Because the hydrogen isotope composition can also be examined using the
same instrument, it is expected that this method can be applied to a
wider range of earth materials, including hydrous silicates such as clay
minerals.