Determining the O/O ratio of water using a water-CO2 equilibration method: Application to glacial-interglacial changes in O-excess from the Dome Fuji ice core, Antarctica |
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| Authors: | Ryu Uemura Osamu Abe |
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| Institution: | a National Institute of Polar Research, Research Organization of Information and Systems, 10-3, Midoricho, Tachikawa, Tokyo 190-8518, Japan
b Graduate School of Environmental Studies, Nagoya University, Nagoya, Japan |
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| Abstract: | Recent studies show that oxygen three isotope measurement (16O, 17O, and 18O) of water provides additional information for investigating the hydrological cycle and paleoclimate. For determining the 18O/16O value of water, a conventional CO2-water equilibration method involves measurement of the ratios of CO2 isotopologues which were equilibrated with water. However, this long-established technique was not intended to measure the 17O/16O ratio, primarily because the historic ion correction scheme does not allow for possible deviations from a fixed (and mass-dependent) relationship between 17O/16O and 18O/16O isotope ratios. Here, we propose an improved method for obtaining the 17O/16O isotope ratio of fresh water by the equilibration method and measurement of the 45/44 CO2 ion abundance ratio. Equations which we formulated for 17O/16O measurement have two features: first, instead of absolute isotope ratio (R), all equations are formulated in δ values, measured by isotope ratio mass spectrometry. Second, we include two “assigned” δ values of water standards in the equations, because the δ18O are commonly measured against two working standards to normalize the span of the δ scale. This approach clarifies that the contribution from 17O (12C16O17O+) to the molecular ion current at mass-to-charge ratio m/z 45 signal depends not on the absolute 13C/12C ratio, but on the relative δ13C differences between the working standards and the sample. The pH value of water affects δ17O estimation because δ13C of CO2 was changed in the water-CO2 system. We reevaluated this effect using a set of equations, which explicitly includes CO2 partial pressure effect on pH value. Our new estimation of pH effect is significantly smaller than previously reported value, but it does not alter the main conclusions in the previous study. The method was verified by δ17O measurements of an international standard reference water (GISP) provided by the IAEA. We applied the method to investigate 17O-excess of the ice core drilled at the Dome Fuji station, Antarctica. A total of 1320 samples from a 130 m section around Marine Isotope Stage 9.3 (∼330,000 years before present) were measured. The error of a measurement for δ17O is 0.175‰ and that of 17O-excess is 184 per meg. Although these analytical uncertainties hampered accurate estimation of the changes in 17O-excess, the averaged data indicate that 17O-excess around MIS 9.3 was higher than during the subsequent glacial period. This approach can be applied only to fresh water samples, and additional improvements will be needed to measure samples which contains significant amount of carbonate minerals. |
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