A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/ MS) to measure the delta(18)O and delta(17)O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degreesC, typically in 50 degreesC increments) under a flowing stream of helium carrier gas. The method has considerable advantages over others used for water analysis in that it is quick; requires only small samples, typically 1-50 mg of whole rock samples (corresponding to similar to0.2 mumol of H2O); and the reagent is easy and safe to handle. Reproducibility in isotope ratio measurement obtained from pyrolysis of samples of a terrestrial solid standard are delta(18)O +/- 0.54, delta(17)O +/- 0.33, and Delta(17)O +/- 0.10parts per thousand, 1sigma in all cases. The technique was developed primarily for the analysis of meteorites, and the efficiency of the method is illustrated herein by results from water standards, solid reference materials, and a sample of the Murchison CM2 meteorite.