The CISE-LOCEAN sea water isotopic database (1998–2021)

The characteristics of the CISE-LOCEAN sea water isotope data set (δ18O, δ2H, later designed as δD) are presented. This data set covers the time period from 1998 to 2021 and currently includes close to 8000 data entries, all with δ18O, three quarters of them also with δD, associated with a time and space stamp and usually a salinity measurement. Until 2010, samples were analysed by isotopic ratio mass spectrometry, and since then mostly by cavity ring-down spectroscopy (CRDS). Instrumental uncertainty on individual data in this dataset is usually with a standard deviation as low as 0.03 / 0.15 ‰ for δ18O and δD. An additional uncertainty is related to uncertain isotopic composition of the in-house standards that are used to convert daily data into the VSMOW scale. Different comparisons suggest that since 2010 the latter have remained within at most 0.03 / 0.20 ‰ for δ18O and δD. Therefore, combining the two suggests a standard deviation of at most 0.05 / 0.25 ‰ for δ18O / δD. Finally, for some samples, we find that there has been evaporation during collection and storage, requiring adjustment of the isotopic data produced by CRDS, based on d-excess. This adds an uncertainty on the adjusted data of roughly 0.05 / 0.10 ‰ on δ18O and δD. This issue of conservation of samples is certainly a strong source of quality loss for parts of the database, and ‘small’ effects may have remained undetected. The internal consistency of the database can be tested for subsets of the dataset, when time series can be obtained (such as in the southern Indian Ocean or North Atlantic subpolar gyre). These comparisons suggest that the overall uncertainty of the spatially (for a cruise) or temporally (over a year) averaged data is on the order of or less than 0.03 / 0.15 ‰ for δ18O / δD. On the other hand, 17 comparisons with duplicate sea water data analysed in other laboratories or with other data sets in deep regions suggest a larger scatter. When averaging the 17 comparisons done for δ18O, we find a difference close to the adjustment applied at LOCEAN to convert salty water data from the activity to the concentration scale. Such a difference is expected, but the scatter found suggests that care is needed when merging datasets from different laboratories. Examples of time series in the surface North Atlantic subpolar gyre illustrate the temporal changes in water isotope composition that can be detected with a carefully validated dataset.