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.

Volatile organic compounds (VOCs) in contaminated soils have been investigated in near-surface environments to describe their transport behaviors and the resultant impacts of vapor intrusion into buildings. Prior studies have suggested that temperature changes significantly influence such transport behaviors in near-surface soils; however, the nature of these influences and their mechanisms have remained unclear. This is because an inverse correlation between the in situ temperature and VOC flux changes has been suggested but has not been experimentally investigated or demonstrated. Herein, we show the results of a set of experiments on the vertical and upward vapor-phase diffusive transport of benzene in sandy soils for different sand grain size and water content combinations under sinusoidal temperature changes between 20 and 30 °C. Under all experimental conditions, changes in the flux from the soil surface correlated with temperature changes, whereas changes in the flux into the overlying soil showed inverse correlations. Concurrent monitoring of the relative humidity revealed that an inverse correlation was exhibited in response to the condensation and volatilization of water. Moreover, the intensity of the inverse correlation was independent of grain size but was larger at higher water contents. Overall, water in soil may induce an inverse correlation.

Understanding the diffusive transport behavior of volatile organic compounds (VOCs) in near-surface soils is important because soil VOC emissions affect atmospheric conditions and climate. Previous studies have suggested that temperature changes affect the transport behavior; however, the effect of these changes are poorly understood. Indeed, under dynamic temperature conditions, the change in VOC flux is much larger than that expected from the temperature dependency of the diffusion coefficient of VOCs in air. However, the mechanism is not well understood, although water in soil has been considered to play an important role. Here, we present the results of experiments for the upward vertical vapor-phase diffusive transport of two VOCs (benzene and tetrachloroethylene) in sandy soil under sinusoidal temperature variations of 20–30 °C, as well as its numerical representation. The results clarify that the unexpectedly large changes in emission flux can occur as a result of changes in the VOC concentration gradient due to VOC release (volatilization) from/trapping (dissolution) into water, and that such flux changes may occur in various environments. This study suggests the importance of a global evaluation of soil VOC emissions by continuous measurements in various soil environments and/or predictions through numerical simulations with thorough consideration of the role of water in dynamic soil environments.

<p>Investigation of the transport behaviors of volatile organic compounds (VOCs) in contaminated soils has previously been conducted in various environments. Accordingly, the present study focuses on specific phenomena in the near-surface soil environment where dynamic temperature affects the diffusive flux of VOC vapor phase as previous studies have suggested that temperature variations significantly influence such transport behaviors near-surface soils, but the nature of those influences and their mechanisms have remained unclear because of unexpected correlation of flux with the temperature that impacts on VOC vapor transport. More specifically, current practices report on a set of experiments into the vertical and upward vapor phase diffusive transport of benzene and trichloroethylene (TCE) in sandy soils that were conducted in soil column with water content conditions of up to 10 wt% and sinusoidal temperature conditions ranging from 20 to 30°C. This studies experimentally investigated that in all conditions tested, the top (outlet) flux change correlated positively with temperature change, while the bottom (inlet) flux change showed negative correlations. These results are consistent with previous observations showing that, at relatively deeper locations, there is little correlation between near-surface vertical VOC flux and soil temperature levels, and that VOC concentrations can be independent of the soil temperature at those locations. The present study's results highlighted for the first time that the negative correlation impact of temperature on VOC transport may occur frequently at deeper locations of subsurface soil. This occurs because the VOC concentration gradient is reduced by VOC desorption and the evaporation of water containing VOCs that accompany increasing temperature levels. However, our results also show that such mechanisms have a positive impact on VOC emissions from the upper part of subsurface soils to the atmosphere that can act as a low concertation boundary.</p>