Comparison of nonideal sorption formulations in modeling the transport of phthalate esters through packed soil columns

Abstract

Sorption of dimethyl phthalate (DMP), diethyl phthalate (DEP) and dipropyl phthalate (DPP) to two soil materials that vary in organic matter content was investigated using miscible displacement experiments under saturated flow conditions. Generated breakthrough curves (BTCs) were inversely simulated using linear, equilibrium sorption (LE), nonlinear, equilibrium sorption (NL), linear, first-order nonequilibrium sorption (LFO), linear, radial diffusion (LRD), and nonlinear, first-order nonequilibrium sorption (NFO) models. The Akaike information criterion was utilized to determine the preferred model. The LE model could not adequately describe phthalate ester (PE) BTCs in higher organic matter soil or for more hydrophobic PEs. The LFO and LRD models adequately described the BTCs but a slight improvement in curve-fitting was gained in some cases when the NFO model was used. However, none of the models could properly describe the desorptive tail of DPP for the high organic matter soil. Transport of DPP through this soil was adequately predicted when degradation or sorption hysteresis was considered. Using the optimized parameter values along with values reported by others it was shown that the organic carbon distribution coefficient (K(oc)) of PEs correlates well with the octanol/water partition coefficient (K(ow)). Also, a strong relationship was found between the first-order sorption rate coefficient normalized to injection pulse size and compound residence time. A similar trend of timescale dependence was found for the rate parameter in the radial diffusion model. Results also revealed that the fraction of instantaneous sorption sites is dependent on K(ow) and appears to decrease with the increase in the sorption rate parameter.