The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite (alpha-FeOOH) and natro-jarosite (Na(3)Fe(3)(SO(4))(2)(OH)(6)) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 microM Cu(SO(4)) with 10, 25, or 50 microM Na(2)HAsO(4) at pH 5.65 and allowing the mixture to react in 10 m(2) L(-1) goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO(4)) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu(4)(OH)(6)SO(4)), and hydrated clinoclase (Cu(3)(AsO(4))(2)2H(2)O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of structural oxyanions in the case of jarosite. On goethite, the copper-arsenate precipitate was similar to hydrated clinoclase, while on jarosite, a euchroite-like precipitate (Cu(2)[AsO(4)](OH)3H(2)O, P 2(1)2(1)2(1)) had formed. Despite under-saturated solution conditions, the formation of these precipitates may have occurred due to a seed-formation effect from densely surface adsorbed Cu(II) and As(V) for which the "new" saturation index was significantly lower than homogeneous values would otherwise suggest. Synergistic reactions between two co-sorbates of fundamentally different surface adsorption behaviour can thus be achieved if the number of available sites for surface adsorption is limited.