In this laboratory study, the changes in gas-exposed perchloroethene (PCE) saturation in sand during a PCE removal process were measured using gaseous tracers. The flux of fresh air through a glass column packed with PCEcontaminated, partially water-saturated sand drove the removal of PCE from the column. During the removal of PCE, methane, n-pentane, difluoromethane and chloroform were used as the non-reactive, PCE-partitioning, water-partitioning, and PCE and water-partitioning tracers, respectively. N-pentane was used to detect the PCE fraction exposed to the mobile gas. At water saturation of 0.11, only 65% of the PCE was found to be exposed to the mobile gas prior to the removal of PCE, as calculated from the n-pentane retardation factor. More PCE than that detected by n-pentane was depleted from the column due to volatilization through the aqueous phase. However, the ratio of gas-exposed to total PCE decreased on the removal of PCE, implying gas-exposed PCE was preferentially removed by vaporization. These results suggest that the water-insoluble, PCE-partitioning tracer (n-pentane in this study), along with other tracers, can be used to investigate the changes in fluid (including nonaqueous phase liquid) saturation and the removal mechanism during the remediation process.