『Abstract
Jarosite [KFe3(SO4)2(OH)6] is a mineral that
is common in acidic, sulphate-rich environments, such as acid
sulphate soils derived from pyrite-bearing sediments, weathering
zones of sulphide ore deposits and acid mine or acid rock drainage
(ARD/AMD) sites. The structure of jarosite is based on linear
tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from
slightly distorted FeO6 octahedra and SO4 tetrahedra. Batch dissolution experiments carried
out on synthetic jarosite at pH 2, to mimic environments affected
by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently
remediated with slaked lime (Ca(OH)2), suggest
first order dissolution kinetics. Both dissolution reactions are
incongruent, as revealed by non-ideal dissolution of the parent
solids and, in the case of the pH 8 dissolution, because a secondary
goethite precipitate forms on the surface of the dissolving jarosite
grains. The pH 2 dissolution yields only aqueous K, Fe, and SO4. Aqueous, residual solid, and computational
modelling of the jarosite structure and surfaces using the GULP
and MARVIN codes, respectively, show for the first time that there
is selective dissolution of the A- and T-sites, which contain
K and SO4, respectively, relative to Fe,
which is located deep within the T-O-T jarosite structure. These
results have implications for the chemistry of ARD/AMD waters,
and for understanding reaction pathways of ARD/AMD mineral dissolution.』
1. Introduction
2. Methods and materials
2.1. Experimental studies
2.1.1. Synthesis of jarosite
2.1.2. Characterisation of synthetic jarosite
2.1.3. Dissolution experiments
2.2. Computational modelling
3. Results
3.1. Characterisation of synthetic jarosite
3.2. Dissolution experiments
3.2.1. Dissolution at pH 2
3.2.1.1. Solution chemistry
3.2.1.2. Residual solids
3.2.2. Dissolution at pH 8
3.2.2.1. Solution composition
3.2.2.2. Residual solids
3.3. Computational modelling of the jarosite structure
3.3.1. Bulk structure
3.3.2. Surface structure
4. Discussion
4.1. Dissolution at pH 2 and 8
4.2. Environmental implications
5. Conclusions
Acknowledgments
References