Intramolecular carbon isotopic analysis of acetic acid by direct injection of aqueous solution

We report an improved method for determining the intramolecular carbon isotopic composition of acetate using direct injection of aqueous samples. The system builds upon prior work that established pyrolytic conditions for online analysis and represents a significant advance in that it requires minimal preparation for samples containing as little as 1 mM sodium acetate in aqueous solution. The technique is applicable for analysis of oilfield brines, culture samples, biological samples and natural porewaters. We demonstrate its accuracy by use of a stable isotope dilution series. We also show that addition of a base and cryogenic preconcentration may induce an isotopic effect on the carboxyl carbon. This isotopic fractionation does not appear to extend to the measured methyl carbon isotope value although it can significantly alter the measured isotopic composition of the whole molecule. Our preconcentration experiments demonstrate that the method is suitable for carbon isotopic measurements of acetate methyl carbon in natural samples at concentrations as low as 90 μM, considerably broadening potential applications.