Using Comprehensive Two-Dimensional Gas Chromatography Retention Indices To Estimate Environmental Partitioning Properties for a Complete Set of Diesel Fuel Hydrocarbons

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Abstract
Comprehensive two-dimensional gas chromatography (GC×GC) provides nearly complete composition data for some complex mixtures such as petroleum hydrocarbons. However, the potential wealth of physical property information contained in the corresponding two-dimensional chromatograms is largely untapped. We developed a simple but robust method to estimate GC×GC retention indices for diesel-range hydrocarbons. By exploiting n-alkanes as reference solutes in both dimensions, calculated retention indices were insensitive to uncertainty in the enthalpy of gas−stationary-phase transfer for a suite of representative diesel components. We used the resulting two-dimensional retention indices to estimate the liquid vapor pressures, aqueous solubilities, air−water partition coefficients, octanol−water partition coefficients, and vaporization enthalpies of a nearly complete set of diesel fuel hydrocarbons. Partitioning properties were typically estimated within a factor of 2; this is not as accurate as some previous estimation or measurement methods. However, these relationships may allow powerful and incisive analysis of phase-transfer processes affecting petroleum hydrocarbon mixtures in the environment. For example, GC×GC retention data might be used to quantitatively deconvolve the effects of water washing and evaporation on environmentally released diesel fuels.