Abstract
Assessing petroleum biodegradation rates is an important part of predicting natural attenuation in subsurface sediments. Monitoring carbon dioxide (CO2) and methane (CH4) produced in situ, and their radiocarbon 14C), stable carbon (13C) and deuterium (D). signature provide a novel method to assess anaerobic microbial processes. Our objectives were to: (1) estimate the rate of anaerobic petroleum hydrocarbon (PH) mineralization by monitoring the production of soil gas CH4 and CO2 in the vadose zone of low-permeability sediment, (2) evaluate the dominant microbial processes using δ13C and δD, and (3) determine the proportion of CH4 and CO2 attributable to anaerobic mineralization of PH using 14C analysis. Argon was sparged into the subsurface to dilute existing CO2 and CH4 concentrations. Vadose zone CO2, CH4, oxygen, total combustible hydrocarbons, and argon concentrations were measured for 75 days. CO2 and CH4 samples were collected on day 86 and analyzed for 14C, δ13C, and δD. Based on CH4 soil gas production, the anaerobic biodegradation rate was estimated between 0.017 to 0.055 mg/kg soil-d. CH4 14C (2.6 pMC), δ13C (-45.64‰), and δD (-316‰) values indicated that fermentation of PH was the sale source of CH4 in the vadose zone. CO2 14C (62 pMC) indicated that approximately 47% of the total CO2 was from PH mineralization and 53% from plant root respiration. Although low-permeability sediment increases the difficulty of completely replacing in situ soil gas and assuring anaerobic conditions, this novel respiration method distinguished between anaerobic processes responsible for PH degradation.