Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by differential X-ray diffraction (DXRD)

Abstract

A dissolution test with 9 natural and synthetic schwertmannite and ferrihydrite samples was performed by reaction with 0.2 M ammonium oxalate at pH 3.0 in the dark. The method was coupled with differential X-ray diffraction (DXRD) to successfully detect schwertmannite at low concentrations in oxidized mine tailings. Rapid dissolution was observed for all schwertmannites (> 94% in 60 min) and natural 2-line ferrihydrites (> 85% in 60 min); however, synthetic 2-line and 6-line ferrihydrite dissolved slower (42 and 16% after 60 min, respectively). The results showed that it was not possible to distinguish between natural schwertmannites and ferrihydrites on the basis of their dissolution kinetics. Modeling of the schwertmannite dissolution curves, examinations of mineral shape by scanning electron microscopy, and Fe/S mole ratios of the dissolved fractions indicated that two different schwertmannite particle morphologies (spherical and web-like) occurred. Collapse of spherical (sea-urchin) schwertmannite aggregates seemed to control the dissolution kinetics according to a shrinking core model. In the case of web-like schwertmannite, dissolution could be modeled with a simple first order equation, and structural SO 4 2− may have affected the dissolution kinetics. No relationship was found between ferrihydrite particle shape and dissolution behavior in acid NH 4-oxalate. A 1-h extraction with 0.2 M NH 4-oxalate at pH 3.0 in the dark should be adequate to dissolve schwertmannite and natural 2-line ferrihydrite in most samples. In some cases, a fraction of secondary jarosite or goethite may also be dissolved, although at a slower rate. If only schwertmannite is of interest (e.g., determination by DXRD), a 15 min attack should be used to increase selectivity. A truly selective leach of schwertmannite and ferrihydrite should be based on dissolution tests, as a broad variety of dissolution kinetics can be observed in this mineral group.