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This study evaluated between-sample memory in isotopic measurements of ϐ2H and ϐ18O in water samples by laser spectroscopy. Ten isotopically depleted water samples spanning a broad range of oxygen and hydrogen isotopic compositions were measured by three generations of offaxis integrated cavity output spectroscopy and cavity ringdown spectroscopy instruments. The analysis procedure encompassed small (less than 2‰ for ϐ2H and 1‰ for ϐ18O) and large (up to 201‰ for ϐ2H and 25‰ for ϐ18O) differences in isotopic compositions between adjacent sample vials. Samples were injected 18 times each, and the betweensample memory effect was quantified for each analysis run. Results showed that samples adversely affected by betweensample isotopic differences stabilised after seven–eight injections. The between-sample memory effect ranged from 14% and 9% for ϐ2H and ϐ18O measurements, respectively, but declined to negligible carryover (between 0.1% and 0.3% for both isotopes) when the first ten injections of each sample were discarded. The measurement variability (range and standard deviation) was strongly dependent on the isotopic difference between adjacent vials. Standard deviations were up to 7.5‰for ϐ2H and 0.54‰for ϐ18O when all injections were retained in the computation of the reportable ϐ-value, but a significant increase in measurement precision (standard deviation in the range 0.1 ‰–1.0‰ for ϐ2H and 0.05‰– 0.17‰for ϐ18O) was obtained when the first eight injections were discarded. In conclusion, this study provided a practical solution to mitigate between-sample memory effects in the isotopic analysis of water samples by laser spectroscopy.

hydrology and earth system sciences

Technical Note: Evaluation of between-sample memory effects in the analysis of δ&amp;lt;sup&amp;gt;2&amp;lt;/sup&amp;gt;H and δ&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O of water samples measured by laser spectroscopes