Water-Enhanced Flux Changes under Dynamic Temperatures in the Vertical Vapor-Phase Diffusive Transport of Volatile Organic Compounds in Near-Surface Soil Environments

The quantitative understanding of the transport behavior of volatile organic compounds (VOCs) in near-surface soils is highly important in light of the potential impacts of soil VOC emissions on the air quality and climate. Previous studies have suggested that temperature changes affect the transport behavior; however, the effects are not well understood. Indeed, much larger changes in the VOC flux under in situ dynamic temperatures than those expected from the temperature dependence of the diffusion coefficients of VOCs in the air have been suggested but rarely investigated experimentally. Here, we present the results of a set of experiments on the upward vertical vapor-phase diffusive transport of benzene and trichloroethylene (TCE) in sandy soils with water contents ranging from an air-dried value to 10 wt% during sinusoidal temperature variation between 20 and 30 °C. In all experiments, the flux from the soil surface was correlated with the temperature, as expected. However, the changes in flux under wet conditions were unexpectedly large and increased with increasing water content; they were also larger for TCE, the volatility of which depended more strongly on the temperature. Additionally, the larger flux changes were accompanied by a recently discovered water-induced inverse correlation between temperature and flux into the overlying soil. These results demonstrated that the flux changes of VOCs under dynamic temperatures could be increased by volatilization-dissolution interactions of VOCs with water. Future extensive studies on this newly discovered phenomenon would contribute to a better understanding of the impacts of soil VOC emissions on the air quality and climate.