title: δ18O anchoring to VPDB: calcite digestion with 18O-adjusted ortho-phosphoric acid.
abstract: For anchoring CO(2) isotopic measurements on the δ(18)O(VPD-CO2) scale, the primary reference material (NBS 19 calcite) needs to be digested using concentrated ortho-phosphoric acid. During this procedure, great care must be taken to ensure that the isotopic composition of the liberated gas is accurate. Apart from controlling the reaction temperature to ±0.1 °C, the potential for oxygen isotope exchange between the produced CO(2) and water must be kept to a minimum. The water is usually assumed to reside on the walls in the headspace of the reaction vessel. We demonstrate here that a large fraction of the exchange may also occur with water inside the acid. Our results indicate that both exchange reactions have a significant impact on the results and may have largely been responsible for scale inconsistencies between laboratories in the past. The extent of CO(2)/H(2)O oxygen exchange depends on the concentration (amount of free water) in the acid. For acids with a nominal H(3)PO(4) mass fraction of less than 102%, oxygen isotope exchange can create a substantial isotopic bias during high-precision measurements with the degree of the alteration being proportional to the effective isotopic contrast between the acid and the CO(2) released from the calcite. Water evaporating from the acid at 25 °C has a δ(18)O value of -34.5‰ relative to the isotopic composition of the whole acid. This large fractionation is likely to occur in two steps; by exchange with phosphate, water inside the acid is decreased in oxygen-18 relative to the bulk acid by ∼ -22‰. This water is then fractionated further during evaporation. Oxygen exchange with both water inside the acid and water condensate in the headspace can contribute to the measured isotopic signature depending on the experimental parameters. The system employed for this study has been specifically designed to minimize oxygen exchange with water. However, the amount of altered CO(2) for a 95% H(3)PO(4) at 25 °C still accounts for about 3% of the total CO(2) produced from a 40 mg calcite sample, resulting in a δ(18) O range of about 0.8‰ when varying the δ(18)O value of the acid by 25‰. Least biased results for NBS19-CO(2) were obtained for an acid with a δ(18)O value close to +23‰ vs. VSMOW. In contrast, commercial acids from several sources had an average δ(18)O value of +13‰, amounting to a 10‰ offset from the optimal value. This observation suggests that the well-known scale incompatibilities between laboratories could arise from this difference with measurements that may have suffered systematically from non-optimal acid-δ(18)O values, thus producing variable offsets, depending on the experimental details. As a remedy, we suggest that the δ(18)O of phosphoric acid reacted with calcites for establishing a δ(18)O scale anchor be adjusted, and this should reduce the variability of the δ(18)O of CO(2) evolved in acid digestion to less than ±0.05‰. The adjustment should be made by taking into account the difference in δ(18)O between the calcite-CO(2) and the acid, with a target difference of 16‰. With this strategy, agreement between δ(18)O scales based on water, atmospheric CO(2) , and carbonates as well as data compatibility between laboratories may be substantially improved.
authors.affiliation: MPI-BGC (Max-Planck-Institut für Biogeochemie), Postfach 10 01 64, D-07701 Jena, Germany.
authors.forename: Magnus
authors.initials: M
authors.lastname: Wendeberg
authors.forename: Jürgen M
authors.initials: JM
authors.lastname: Richter
authors.forename: Michael
authors.initials: M
authors.lastname: Rothe
authors.forename: Willi A
authors.initials: WA
authors.lastname: Brand
mesh_terms: D002119:Calcium Carbonate / Q000737:chemistry*; D002245:Carbon Dioxide; D002247:Carbon Isotopes / Q000737:chemistry*; D002255:Carbonic Acid; D013058:Mass Spectrometry; D008956:Models, Chemical; D010103:Oxygen Isotopes / Q000737:chemistry*; D010756:Phosphoric Acids / Q000737:chemistry*; D014867:Water
chemical_list: D002247:Carbon Isotopes; D010103:Oxygen Isotopes; D010756:Phosphoric Acids; D014867:Water; D002245:Carbon Dioxide; D002255:Carbonic Acid; C030242:phosphoric acid; D002119:Calcium Carbonate