Effects of nitrate and water on the oxygen isotopic analysis of barium sulfate precipitated from water samples.

BaSO(4) precipitated from mixed salt solutions by common techniques for SO(4) (2-) isotopic analysis may contain quantities of H(2)O and NO(3) (-) that introduce errors in O isotope measurements. Experiments with synthetic solutions indicate that delta(18)O values of CO produced by decomposition of precipitated BaSO(4) in a carbon reactor may be either too low or too high, depending on the relative concentrations of SO(4) (2-) and NO(3) (-) and the delta(18)O values of the H(2)O, NO(3) (-), and SO(4) (2-). Typical delta(18)O errors are of the order of 0.5 to 1 per thousand in many sample types, and can be larger in samples containing atmospheric NO(3) (-), which can cause similar errors in delta(17)O and Delta(17)O. These errors can be reduced by (1) ion chromatographic separation of SO(4) (2-) from NO(3) (-), (2) increasing the salinity of the solutions before precipitating BaSO(4) to minimize incorporation of H(2)O, (3) heating BaSO(4) under vacuum to remove H(2)O, (4) preparing isotopic reference materials as aqueous samples to mimic the conditions of the samples, and (5) adjusting measured delta(18)O values based on amounts and isotopic compositions of coexisting H(2)O and NO(3) (-). These procedures are demonstrated for SO(4) (2-) isotopic reference materials, synthetic solutions with isotopically known reagents, atmospheric deposition from Shenandoah National Park, Virginia, USA, and sulfate salt deposits from the Atacama Desert, Chile, and Mojave Desert, California, USA. These results have implications for the calibration and use of O isotope data in studies of SO(4) (2-) sources and reaction mechanisms.