A unique approach using sol-gel technology is presented for separating and recovering particulates and colloids from caustic waste slurries. The approach involves the addition of an alkali silicate and an organic gelling agent directly to the waste stream to immobilize particulates that range from macro sizes to submicron colloids. The particulates and colloids become trapped within a silica network that remains porous during the early stages of the sol-gel process. The freshly gelled monolith undergoes a process of syneresis, whereby the water and soluble salts are ejected from the monolith as it contracts. The approach has been illustrated by removal of ultrafine particulates from a Hanford Tank Waste simulant. Initial laboratory tests have shown that it is possible to produce silica monoliths in the presence of 4 M hydroxide. Analysis of the mother liquor produced during syneresis indicated quantitative recovery of the particulates within the monolith. The partitioning of ions between the silica gel and the mother liquor during syneresis correlates directly with the lyotropic series. Salt recoveries from the mother liquor in excess of 90% can be achieved. With a capability of recovering >99.999% of all particulates, including colloids, the process is more efficient than membrane filtration. This approach produces a rock-hard silica monolith that can be used directly as a feedstock to a-glass melter or can be consolidated to near theoretical density by sintering.