Hydrogen isotopic fractionation of petroleum hydrocarbons during vaporization: implications for assessing artificial and natural remediation of petroleum contamination

Abstract

Compound-specific H isotope analysis has been used to monitor bioremediation of petroleum hydrocarbons. However, the success of this approach requires a full evaluation of the isotopic effects resulting from evaporation, because light petroleum hydrocarbons undergo both biodegradation and evaporation under natural conditions. The authors determined the H isotope fractionation of common volatile petroleum hydrocarbons, including the C 10–C 14 n-alkanes, MTBE ( tert-butyl methyl ether), and BTEX (benzene, toluene, ethylbenzene, p-xylene and o-xylene) during progressive vaporization under simulated experimental conditions. A decrease in δD values for n-alkanes of up to 33.3‰ and up to 44.5‰ for BTEX compounds when 99% of these substances had evaporated was observed. The results also show that H isotope fractionation increases with n-alkane chain length. Such fractionation patterns are interpreted in terms of competition between the decreased intermolecular binding energy in D-enriched species, and the isotope effect due to the mass difference. In contrast to hydrocarbons, methanol and ethanol show H isotopic enrichment during vaporization, indicating that H-bonding, when present in organic molecules, plays a controlling role on the vapor pressure of different isotope species.