2008 journal article
Uncertainties in the oxygen isotopic composition of barium sulfate induced by coprecipitation of nitrate
RAPID COMMUNICATIONS IN MASS SPECTROMETRY, 22(19), 2971–2976.
AbstractCoprecipitation of nitrate and sulfate by barium has probably resulted in significant error in numerous studies dealing with the oxygen isotopic composition of natural sulfates using chemical/thermal conversion of BaSO4 and analysis by isotope ratio mass spectrometry. In solutions where NO/SO molar ratios are above 2 the amount of nitrate coprecipitated with BaSO4 reaches a maximum of approximately 7% and decreases roughly linearly as the molar ratio decreases. The fraction of coprecipitated nitrate appears to increase with decreasing pH and is also affected by the nature of the cations in the precipitating solution. The size of the oxygen isotope artifact in sulfate depends both on the amount of coprecipitated nitrate and the δ18O and Δ17O values of the nitrate, both of which can be highly variable. The oxygen isotopic composition of sulfate extracted from atmospheric aerosols or rain waters are probably severely biased because photochemical nitrate is usually also present and it is highly enriched in 18O (δ18O ∼50–90‰) and has a large mass‐independent isotopic composition (Δ17O ∼20–32‰). The sulfate δ18O error can be 2–5‰ with Δ17O artifacts reaching as high as 4.0‰. Copyright © 2008 John Wiley & Sons, Ltd.