Detailed chemical characterization of the composition and variability of soil gas at remediated residential heating oil discharges

Highlights: • Total petroleum hydrocarbons in soil gas at remediated home heating oil discharges are often at or near levels of concern. • Composition of total petroleum hydrocarbons is highly variable between sites. • Metrics to predict of subsurface weathering are not found to be effective descriptors of overall chemical composition. • Potential risk from total petroleum hydrocarbons usually exceeds that from resolved, known carcinogens. Underground storage tanks containing petroleum or other hazardous substances are used widely for residential storage of home heating oil. Spills and leaks of fuel from these tanks are common, and resulting subsurface petroleum vapors may pose health risks. However, understanding of this risk is limited by a lack of observational data on the chemical composition of vapors from discharged fuel. We present here the composition of soil gas sampled at 66 remediated residential sites of underground heating oil discharges throughout Virginia using a newly developed data analysis technique that allows characterization of hydrocarbons by carbon number and degree of unsaturation. Measured concentrations of total petroleum hydrocarbons exceeded 100,000 μg/m³ at 12 sites, but its composition varied widely between sites. Concentrations of hydrocarbons from chemical classes differing by more than a few carbon numbers or degrees of unsaturation are found to be poorly correlated. Furthermore, differences in composition are poorly described by metrics expected to indicate subsurface weathering (e.g., discharge year, or ratio of n-heptadecane to pristane). These results suggest that the composition and magnitude of residual contamination at remediated subsurface discharges is driven by rarely documented spill characteristics (e.g., age and composition of source material, discharge rate, etc.).