a b s t r a c tWe investigated the sorption of Cu by δ-MnO 2 , an analog for natural birnessite (layer-type Mn oxide) that is characterized by randomly stacked and curled nanosheets, a low to moderate vacancy content, and variable amounts of layer and interlayer Mn 3+ . The synthetic δ-MnO 2 used in this study had a Na:Mn molar ratio of 0.13, an average manganese oxidation number (AMON) of 3.85 after reaction, a specific surface area of 254 m 2 g −1 and a particle size of 2-4 nm in the ab plane. The maximum surface excess (q max ) value at pH 6 estimated from sorption data of 0.72 (0.64-0.83, 95% confidence interval) mol Cu mol −1 Mn far exceeded the nominal vacancy content for δ-MnO 2 (ca. 6-11% mol vacancy mol −1 Mn), thus implicating multiple binding sites for Cu. The large values of q max and specific surface area of the mineral suggest a major role for surface sites at the particle edges relative to vacancy sites. The extended X-ray absorption fine structure (EXAFS) spectra from δ-MnO 2 samples differ with respect to the EXAFS spectra for Cu(OH) 2 , CuO, and Cu 3 (CO 3 ) 2 (OH) 2 and Cu-sorbed by biogenic MnO 2 . The Cu K-edge EXAFS spectra show two second-shell peaks that can be modeled with Mn and Cu nearneighbors. Copper appears to bind dominantly at particle edges of δ-MnO 2 as dimers or polynuclear surface species. This sorption mechanism is consistent with the moderate vacancy content of δ-MnO 2 and explains the similarity in the EXAFS spectra from samples having surface loadings of 0.01 to 0.26 mol Cu mol −1 Mn. The strong proclivity of Cu to bind on the edge surfaces of nanoparticulate birnessite leads to very large surface excesses of Cu without the formation of a discreet precipitate, making the surface sites at the particle edges the dominant sorption site for Cu.