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This study follows the paths of 32 chemical elements in the arid to semi-arid realm of the western Andes, between 27 degrees and 33 degrees S, a region hosting important ore deposits and mining operations. The study encompasses igneous rocks, soils, river and stream sediments, and tailings deposits. The chemical elements have been grouped according to the Goldschmidt classification, and their concentrations in each compartment are confronted with their expected contents for different rock types based on geochemical affinities and the geologic and metallogenic setting. Also, the element behavior during rock weathering and fluvial transport is here interpreted in terms of the ionic potentials and solubility products. The results highlight the similarity between the chemical composition of the andesites and that of the average Continental Crust, except for the higher V and Mn contents of the former, and their depletion in Mg, Ni, and Cr. The geochemical behavior of the elements in the different compartments (rocks, soils, sediments and tailings) is highly consistent with the mobility expected from their ionic potentials, their sulfates and carbonates solubility products, and their affinities for Fe and Mn hydroxides. From an environmental perspective, the low solubility of Cu, Zn, and Pb due to climatic, chemical, and mineralogical factors reduces the pollution risks related to their high to extremely high contents in source materials (e.g., rocks, altered zones, tailings). Besides, the complex oxyanions of arsenic get bound by colloidal particles of Fe-hydroxides and oxyhydroxides (e.g., goethite), thus becoming incorporated to the fine sediment fraction in the stream sediments. (C) 2016 Elsevier Ltd. All rights reserved.