Online high‐precision δ2H and δ18O analysis in water by pyrolysis

Abstract

AbstractA method for online simultaneous δ2H and δ18O analysis in water by high‐temperature conversion is presented. Water is injected by using a syringe into a high‐temperature carbon reactor and converted into H2 and CO, which are separated by gas chromatography (GC) and carried by helium to the isotope ratio mass spectrometer for hydrogen and oxygen isotope analysis. A series of experiments was conducted to evaluate several issues such as sample size, temperature and memory effects. The δ2H and δ18O values in multiple water standards changed consistently as the reactor temperature increased from 1150 to 1480°C. The δ18O in water can be measured at a lower temperature (e.g. 1150°C) although the precision was relatively poor at temperatures <1300°C. Memory effects exist for δ2H and δ18O between two waters, and can be reduced (to <1%) with proper measures. The injection of different amounts of water may affect the isotope ratio results. For example, in contrast to small injections (100 nL or less) from small syringes (e.g. 1.2 µL), large injections (1 µL or more) from larger syringes (e.g. 10 µL) with dilution produced asymmetric peaks and shifts of isotope ratios, e.g. 4‰ for δ2H and 0.4‰ for δ18O, probably resulting from isotope fractionation during dilution via the ConFlo interface. This method can be used to analyze nanoliter samples of water (e.g. 30 nL) with good precision of 0.5‰ for δ2H and 0.1‰ for δ18O. This is important for geosciences; for instance, fluid inclusions in ancient minerals may be analyzed for δ2H and δ18O to help understand the formation environments. Copyright © 2009 John Wiley & Sons, Ltd.