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The mechanism of sulfate adsorption on goethite was investigated in situ using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Sulfate adsorption was investigated at ionic strengths between 0.005 and 0.1 M, reactant concentrations between 5 and 500 μM, and pH values between 3.5 and 9.0. It was determined that sulfate forms both outer-sphere and inner-sphere surface complexes on goethite at pH less than 6. At pH values greater than 6, sulfate adsorbs on goethite only as an outer-sphere complex. The relative amount of outer-sphere sulfate surface complexation increased with decreasing ionic strength. The spectrum of sulfate adsorbed on goethite was also compared to the infrared spectrum of synthetic schwertmannite, an iron(III) oxy-hydroxy-sulfate. It was determined that in situ spectra of both schwertmannite and adsorbed sulfate are quite similar, suggesting that a …