Effects of crystallinity of goethite: II. Rates of sorption and desorption of phosphate

Summary Eight samples of goethite ranging in surface area from 18 to 132 m 2 g ‐1 were mixed with phosphate at a range of pH values for periods which ranged from 0·5 h to 6 weeks. The sample with a surface area of 18 m 2 g ‐1 had been hydrothermally treated to improve its crystallinity. Its rate of reaction with phosphate depended on pH but was complete within a day. Its maximum observed reaction was close to the theoretical maximum for surface adsorption of 2·5 μmol m −2 . For the other samples, phosphate continued to react for up to 3 weeks and exceeded the value of 2·5 μmole m −2 . The duration and extent of the reaction depended on the crystallinity of the goethite. The results were closely described by a model in which the phosphate ions were initially adsorbed on to charged external surfaces. The phosphate ions then diffused into the particles. This was closely described using equations for diffusion into a cylinder. Samples of goethite which had been loaded with phosphate dissolved more slowly in HCl, and had a longer lag phase, than phosphate‐free goethite. For the hydrothermally treated goethite, HCl removed much of the phosphate when only a small proportion of the iron had been dissolved. For a poorly crystallized goethite, it was necessary to dissolve much more of the iron to obtain a similar removal of phosphate. Brief treatment with NaOH removed most of the phosphate from the hydrothermally treated goethite but only half the phosphate from a poorly crystallized goethite. These results are consistent with the idea that phosphate ions were not only bound on external surface sites but had also penetrated into meso‐ and micro‐pores between the domains of the goethite crystals and were then adsorbed on internal surface sites. This penetration tied the domains together more firmly thus increasing the lag phase for dissolution. Differences between sites for phosphate adsorption are therefore caused mainly by their location on either external or internal sites. Models that ignore this are incomplete.