The area under study covers 3500 km2 in the upstream part of the closed catchment basin of the salt crust of Uyuni. This crust is a remnant of the saline Lake Tauca, which covered the area about 15,000 years ago. In the downstream part of the aquifer, the Cl concentration of ground water and Cl content in the unsaturated zone exceed 20 meq/L and 18 kg/m2, respectively. With the present hydrological conditions under semiarid conditions, the ground water residence time in the study area exceeds 3000 years. Transient simulations over 11,000 years were made using initial conditions as the retreat of Lake Tauca and taking into account a low recharge during the arid mid-Holocene period. The modeling simulates ground water flow, Cl transport, and ground water residence time. It includes the evaporation from the aquifer that leads to the accumulation of chloride in the unsaturated zone. Results of the modeling are consistent with the observations if it is assumed that the Cl previously accumulated in the unsaturated zone was flushed back into the aquifer around 2000 years B.P., contemporaneously with the end of the arid period.