The chemical behavior of transuranium elements in natural aquifer systems is governed by a variety of geochemical reactions, such as dissolution reaction (solubility), hydrolysis, complexation with inorganics or organics, redox reaction, colloid formation, geochemical interaction with surfaces of various minerals, coprecipitation, mineralization, etc. This paper reviews the present state of knowledge on some of these particular reactions. The emphasis here is on how the individual reactions can be appraised for long-term prediction of the geochemical behavior of transuranium elements in the natural environment. of the various possible reactions, the primary thermodynamic processes are discussed with notable examples: dissolution of transuranium compounds in aquatic solution; complexation with important anions present in groundwater; and colloid generation. Various laser spectroscopic methods in use for chemical speciation are mentioned briefly for their spectroscopic capability, as well as for their applicability. The present paper attempts to better understand the migration behavior of transuranium elements in natural aquifer systems.