Abstract

The δD and δ18O values of water are key measurements in polar ice-core research, owing to their strong and well-understood relationship with local temperature. Deuterium excess, d, the deviation from the average linear relationship between δD and δ18O, is also commonly used to provide information about the oceanic moisture sources where polar precipitation originates. Measurements of δ17O and “17O excess” (Δ17O) are also of interest because of their potential to provide information complementary to d. Such measurements are challenging because of the greater precision required, particularly for Δ17O. Here, high-precision measurements are reported for δ17O, δ18O, and δD on a new ice core from the South Pole, using a continuous-flow measurement system coupled to two cavity ring-down laser spectroscopy instruments. Replicate measurements show that at 0.5 cm resolution, external precision is ∼0.2‰ for δ17O and δ18O, and ∼1‰ for δD. For Δ17O, achieving external precision of <0.01‰ requires depth averages of ∼50 cm. The resulting ∼54,000-year record of the complete oxygen and hydrogen isotope ratios from the South Pole ice core is discussed. The time series of Δ17O variations from the South Pole shows significant millennial-scale variability, and is correlated with the logarithmic formulation of deuterium excess (dln), but not the traditional linear formulation (d).

Highlights

  • Measurements of the isotopes of hydrogen and oxygen of water from ice cores provide important records of past climate (Dansgaard, 1964)

  • We describe the use of a continuous-flow analysis system to measure the complete set of water isotopologues on ice cores, yielding simultaneous measurements of δD, δ18O, and δ17O, as well as the “excess” parameters, d, dln, and δ17O and “17O excess” (Δ17O)

  • We show that, using laser spectroscopy, precise continuous-flow analysis (CFA) measurements of δ17O are as straightforward as the more conventional δD and δ18O

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Summary

Introduction

Measurements of the isotopes of hydrogen and oxygen of water from ice cores provide important records of past climate (Dansgaard, 1964). Both δD and δ18O have long been used as proxies for temperature (Jouzel et al, 1997). The relationship between δD and δ18O in precipitation is nearly linear, but deviations from the average global relationship, defined as the “deuterium excess”, provide valuable additional information (Merlivat and Jouzel, 1979). The deuterium excess is sensitive to kinetic fracationation processes that occur during evaporation when the air is undersaturated, and the combined use of δD and δ18O can be used to determine past temperature and humidity variations at the ocean surface (Johnsen et al, 1989; Petit et al, 1991; Vimeux et al, 2001; Jouzel et al, 2007; Markle et al, 2017)

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