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Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering in a semi-arid climate at an EPA Superfund Site in central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg(-1), respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in samples with the lowest pH, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s. (C) 2014 Elsevier Ltd. All rights reserved.