Pure-phase transport and dissolution of TCE in sedimentary rock saprolite.

The objective of this study was to experimentally determine the influence of pore structure on the transport and dissolution of trichloroethylene (TCE) in clay-rich saprolite. In order to simulate a "spill," pure-phase TCE containing a water-insoluble fluorescent dye was injected into two heterogeneous 24-cm-diameter by 37-cm-long undisturbed columns of water-saturated saprolite. TCE entry occurred at capillary pressures of 2.7 and 4.0 kPa. Ten or 28 d after injection, the column was sliced horizontally into three sections and visually examined. The distribution of fluorescent dye indicated that pure-phase TCE migrated mainly through fractures in the shale saprolite and through fine root holes or other macropores in the limestone saprolite residuum. Analysis of saprolite subsamples indicated that TCE was present throughout much of the saprolite column but usually at concentrations less than the solubility of TCE. This spreading was caused by diffusion, which also contributed to the rapid dissolution of TCE in the fractures and macropores. Modeling was carried out using previously published dissolution and diffusion equations. The calculations confirm that rapid disappearance of immiscible TCE can occur in this type of material because of the small size of fracture or macropore openings and the high porosity of the fine-grained material. This study indicates that industrial solvents can readily enter fractures and macropores in otherwise very fine-grained subsoils and then rapidly dissolve and diffuse into the fine-pore structure, from which they may be very difficult to remove.

Reaction-based model describing competitive sorption and transport of Cd, Zn, and Ni in an acidic soil.

Predicting the mobility of heavy metals in soils requires models that accurately describe metal adsorption in the presence of competing cations. They should also be easily adjustable to specific soil materials and applicable in reactive transport codes. In this study, Cd adsorption to an acidic soil material was investigated over a wide concentration range (10(-8) to 10(-2) M CdCl2) in the presence of different background electrolytes (10(-4) to 10(-2) M CaCl2 or MgCl2 or 0.05 to 0.5 M NaCl). The adsorption experiments were conducted at pH values between 4.6 and 6.5 A reaction-based sorption model was developed using a combination of nonspecific cation exchange reactions and competitive sorption reactions to sites with high affinity for heavy metals. This combined cation exchange/specific sorption (CESS) model accurately described the entire Cd sorption data set. Coupled to a solute transport code, the model accurately predicted Cd breakthrough curves obtained in column transport experiments. The model was further extended to describe competitive sorption and transport of Cd, Zn, and Ni. At pH 4.6, both Zn and Ni exhibited similar sorption and transport behavior as observed for Cd. In all transport experiments conducted under acidic conditions, heavy metal adsorption was shown to be reversible and kinetic effects were negligible within time periods ranging from hours up to four weeks.