Water isotopic ratios from a continuously melted ice core sample

TL;DR

This paper introduces a novel on-line high-resolution isotopic analysis technique for ice core studies, combining a spectrometer with a continuous flow system to measure water isotopic ratios efficiently and accurately.

Contribution

The study presents a new integrated system for simultaneous δ18O and δD analysis of melted ice, achieving mass spectrometry comparable precision with reduced analysis time and power.

Findings

Achieved below 0.1 permil uncertainty for δ18O

Achieved below 0.5 permil uncertainty for δD

Demonstrated field application during NEEM ice core drilling

Abstract

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneous water isotopic analysis of $\delta^{18}$O and $\delta$D on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub ${\mu}$l amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a home made oven. A calibration procedure allows for proper reporting of the data on the VSMOW--SLAP scale. Application of spectral methods yields the combined uncertainty of the system at below 0.1 permil and 0.5 permil for $\delta^{18}$O and $\delta$D, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneous measurement of $\delta^{18}$O and $\delta$D, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.