Equilibrium ²H/¹H fractionations in organic molecules. II: Linear alkanes, alkenes, ketones, carboxylic acids, esters, alcohols and ethers

Equilibrium ²H/¹H fractionation factors (α_eq) for various H positions in alkanes, alkenes, ketones, carboxylic acids, esters, alcohols, and ethers were calculated between 0 and 100 °C using vibrational frequencies from ab initio QM calculations (B3LYP/6-311G**). Results were then corrected using a temperature-dependent linear calibration curve based on experimental data for H_α in ketones (Wang et al., 2009). The total uncertainty in reported α_eq values is estimated at 10-20‰. The effects of functional groups were found to increase the value of α_eq for H next to electron-donating groups, e.g. {single bond}OR, {single bond}OH or {single bond}O(C{double bond, long}O)R, and to decrease the value of α_eq for H next to electron-withdrawing groups, e.g. {single bond}(C{double bond, long}O)R or {single bond}(C{double bond, long}O)OR. Smaller but significant functional group effects are also observed for H_β and sometimes H_γ. By summing over individual H positions, we estimate the equilibrium fractionation relative to water to be -90‰ to -70‰ for n-alkanes and around -100‰ for pristane and phytane. The temperature dependence of these fractionations is very weak between 0 and 100 °C. Our estimates of α_eq agree well with field data for thermally mature hydrocarbons (δ²H values between -80‰ and -110‰ relative to water). Therefore the observed δ²H increase of individual hydrocarbons and the disappearance of the biosynthetic δ²H offset between n-alkyl and linear isoprenoid lipids during maturation of organic matter can be confidently attributed to H exchange towards an equilibrium state. Our results also indicate that many n-alkyl lipids are biosynthesized with δ²H values that are close to equilibrium with water. In these cases, constant down-core δ²H values for n-alkyl lipids cannot be reliably used to infer a lack of isotopic exchange.