The kinetics of Cu2+ adsorption/desorption on goethite (alpha-FeOOH) was evaluated using the pressure-jump (p-jump) relaxation technique. This technique provides kinetic and mechanistic information for reactions occurring on millisecond time scales. A double relaxation event was observed for Cu2+ adsorption/desorption on goethite. The rate of these relaxations (r) decreased with an increase in pH, along the adsorption edge. The mechanism ascribed to the relaxations is the formation of a monodentate inner-sphere Cu2+/goethite surface complex. The calculated intrinsic rate constant for adsorption (k1'int) was 10(6.81) L mol-1 s-1 and was about 2 orders of magnitude larger than the intrinsic rate constant for desorption (k-1'int = 10(4.88) L mol-1 s-1). Using results from this study and others, it was established that the rate of adsorption of divalent metal cations on goethite was directly related to the rate of removal of a water molecule from the primary hydration sphere of a particular divalent metal cation.