Stable carbon isotopic characterization of hydrocarbons in contaminated soils

Effective management of risks at sites featuring refractory hydrocarbon wastes is often constrained by the limitations of conventional analytical methodologies. Stable carbon isotope analysis was therefore evaluated as an alternative means of characterizing the composition, source and weathering of hydrocarbon contaminants. Bulk δ13C of selected heavy oils (boiling range 50 to 500 C) of varying component class distribution decreased from -28.9 to -27.4 per-thousand as oil saturate class content decreased (from 70.6 to 31.7%w/w) and polar/asphaltene content increased (from 7.4 to 50.5%w/w). Class δ13C increased by up to 2.5 per-thousand as follows: saturates (ca. -29 per-thousand) < aromatics (∼ whole oil) < polars < asphaltenes (ca. -26 per-thousand). Thus, the prevalence of either saturates or polar/asphaltenes can be inferred from unusually low (for saturates) or high (for polar/asphaltenes) whole oil δ13C. Plots of oil δ13C vs. saturate and polar/asphaltene content confirmed this relationship, returning linear correlation coefficients (r2) of 0.93 and 0.99, respectively. Characteristic isotopic fingerprints of heavy oils, crude oils and acid tar wastes may also provide a valuable means of differentiating between possible source terms. Unweathered, 25%, 50% and 75% weathered reference oils were analyzed by compound specific isotope analysis (CSIA). n-Alkane (C13-C23) δ13C were often 1--2 per-thousand lower in the weathered samples (e.g., δ13C of C15 = -27.14 per-thousand (fresh), -26.86 per-thousand at 25%, -25.36 per-thousand at 50%, undetected at 75%). CSIA of established oil biomarkers, detected by GC/MS, facilitated the creation of a index for quantifying the extent of weathering undergone. Subsequent work investigating the effects of biotransformation on selected oil δ13C is underway