The adsorption of sulphate on magnetite was studied in-situ using ATR-FTIR spectroscopy, Synthetic magnetite particles were deposited on a ZnSe internal reflection element and the spectra of sulphate adsorbed at pH 4-8.5 were recorded. Two different ionic strengths were used viz. 0.01 M and 0.1 M NaCl. The spectra of adsorbed sulphate on magnetite coated ZnSe were compared with the spectra Of sulphate solutions at the same pH values and in contact with uncoated ZnSe. The spectrum of adsorbed sulphate at pH 4 showed three maxima at 979, 1044, and 1115 cm(-1) indicating a monodentate adsorption in which the T-d symmetry of SO42- is lowered to C-3v. At pH 6.5, sulphate adsorbed as an outer-sphere complex with two weak bands appearing at 1102 and 980 cm(-1). Moreover, spectra of the adsorbed sulphate at pH 4 were recorded as a function of time and sulphate concentration. The equilibrium absorbance at different concentrations fitted a Langmuir type adsorption isotherm. The Langmuir affinity constant K at pH 4 was determined from the slope and intercept of the Langmuir plot to be K = 1.2344 x 10(4) M-1 and the Gibbs free energy of adsorption Delta G(ads)(0) was estimated from this Value to be -33.3 kJ/mol. Kinetic analysis indicated that adsorption at pH 4 is fast, whilst the desorption kinetic at the same pH is very slow. In addition, the effect of Ca ions on sulphate adsorption was also Studied. It was shown that Ca ions increased the sulphate adsorption on magnetite at pH 8.5. (C) 2009 Elsevier Inc. All rights reserved.