Carbonate minerals provide a rich source of geochemical information because their delta C-13 and delta O-18 values provide information about surface and subsurface Earth processes. However, a significant problem is that the same delta O-18 value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the delta O-18 measurements are performed on CO2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO2 is isotopically fractionated (enriched in O-18) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and delta O-18 value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate delta O-18(VPDB) values on a scale normalized such that the delta O-18 value of SLAP reference water is -55.5 parts per thousand relative to VSMOW reference water. To enable researchers worldwide to publish the same delta O-18 value (within experimental uncertainty) for the same carbonate sample, we have re-evaluated reported acid fractionation factors for calcite at 25, 50, and 75 degrees C and propose a revised relation for the temperature dependence of oxygen isotopic acid fractionation factor, alpha CO2(ACID)-calcite, of 1000ln alpha(CO2(ACID)-calcite) = 3.48(10(3)/T) - 1.47 where T is temperature in kelvin. At 25 degrees C, alpha(CO2(ACID)-calcite) = 1.01025, the most commonly accepted value for this quantity. We propose a normalization protocol in which (1) the internationally distributed carbonate isotopic reference materials NBS 18 and NBS 19 are interspersed among carbonate samples analyzed by treatment with phosphoric acid, (2) the delta O-18 values of the calcite reference materials and the carbonate samples are calculated, respectively, by using the alpha(CO2(ACID)-calcite) relation above and oxygen-isotope acid fractionation factors appropriate for the sample mineralogy and reaction temperature, (3) the delta O-18 values of solid carbonate samples are determined on the VPDB scale (delta O-18(VPDB)) with IUPAC-recommended scale expansion such that the delta O-18 of SLAP reference water is -55.5 parts per thousand relative to VSMOW reference water by normalizing delta O-18 values of carbonate samples with 2014-IUPAC-recommended delta O-18 values of NBS 18 and NBS 19, and (4) delta O-18 values on the VPDB scale are converted to delta O-18 values on the VSMOW-SLAP scale by using IUPAC recommendations. To ease calculations in the protocol, a software application titled "Carbon and Oxygen Isotopic Normalization Tool for Carbonates" is available that relies upon IUPAC-recommended delta C-13 and delta O-18 values of carbonate isotopic reference materials (http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html). (C) 2015 Elsevier Ltd. All rights reserved.
