Designing working standards for stable H, C, and O isotope measurements in CO and H O.

Rationale: We address here the selection, preparation, calibration, storage, and use of carbonate and water working standards (WSs) for stable H, C, and O isotope measurements requiring the best possible precision and accuracy vs international reference materials (iRMs). This may be of interest for laboratories working intensively in the domains of the carbon and water cycles and of paleoclimate.

Methods: Defining a WS for stable C and O isotope studies requires combining mineralogical, physical, chemical (low Mg- and trace-carbonate), and isotopic measurements to select a carbonate fit for purpose; for water, two distinct deionized or distilled waters, with high and low δ H and δ O values, respectively, are normally used. In both cases, a strict protocol must be followed to properly qualify the WS vs the current international isotopic scales, and much attention must be paid to calculating rigorous estimates of final uncertainties on these scales.

Results: Two specific protocols for the selection of carbonate and water WSs are detailed. Equations for a proper estimate of uncertainties are proposed.

Conclusions: The selection of WSs involves a preselection of potentially suitable materials based on initial estimates of their mineralogical, chemical, and isotopic properties and long-term stability, based on literature or previous measurements. Their precise characterization vs international isotopic scales requires a thorough analytical work in a correct sequence. When properly carried out, the proposed protocols should permit WSs to be obtained, defined vs the VSMOW and VPDB scales, with uncertainties comparable with those achieved for the characterization of iRMs.