In order to preserve groundwater resources from contamination by volatile organic compounds and to clean up sites contaminated with the compounds, we should understand fate and transport of contaminants in the subsurface systems and physicochemical processes involving remediation technologies. To enhance our understanding, numerical studies were performed on the following topics: (i) multiphase flow and contaminant transport in subsurface environments; (ii) biological transformations of contaminants; (iii) in-situ air sparging (IAS); and, thermal-enhanced venting (TEV). Among VOCs, trichloroethylene (TCE) is one of the most-frequently-detected chemicals in the contaminated groundwater. TCE and its daughter products (cis-1,2-dichloroethylene (cDCE) and vinyl chloride (VC)) are chosen as target contaminants. Density-driven advection of gas phase is generated by the increase in gas density due to vaporization of high-molecular weight contaminants such as TCE in the unsaturated zone. The effect of the density-driven advection on fate and transport of TCE was investigated under several environmental conditions involving infiltration and permeability. Biological transformations of contaminants can generate byproducts, which may become new toxic contaminants in subsurface systems. Sequential biotransformations of TCE, cDCE, and VC are considered herein. Under different reaction rates for two bioreaction kinetics, temporal and spatial concentration profiles of the contaminants were examined to evaluate the effect of biotransformations on multispecies transport. IAS injects clean air into the subsurface below the groundwater table to remediate contaminated groundwater. The movement of gas and the groundwater as a multiphase flow in the saturated zone and the removal of TCE by IAS application were analyzed. Each fluid flow under IAS was examined in terms of saturation levels and fluid velocity profiles in a three-dimensional domain. Several scenarios for IAS systems were simulated to evaluate remedial performance of the systems. TEV was simulated to investigate its efficiency on the removal of a nonaqueous phase liquid in the unsaturated zone under different operational conditions. For numerical studies herein, the governing equations for multiphase flow, multispecies transport, and heat energy in porous media were developed and solved using Galerkin finite element method. A three-dimensional numerical model, called TechFlowMP model, has been developed.