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Although great strides have been made towards understanding REE geochemical behavior in marine environment, considerably less effort has been directed towards the studies of geochemical behavior of REEs in natural terrestrial waters. This monograph, therefore, first develops an easily employed predictive tool for REE complexation with both inorganic and organic ligands in natural water using a well known metal-organic matter speciation code (Humic Ion-Binding Model V). Then, this monograph studies the concentrations, fractionation patterns, and speciation of REEs along groundwater flow path in the Carrizo Sand aquifer (Texas) and discusses the controlling factors on REE geochemistry. Finally, this monograph investigates the adsorption behavior of REEs onto Carrizo sand by batch experiments and develops a surface complexation model for REE adsorption onto natural aquifer sand. This monograph will be of interest to graduate students as well as professionals of the earth and environmental sciences in both academic and industry.