The ultra-fine milled tailings generated during the processing of PGM ores in South Africa have a theoretical potential to sequester significant amounts of CO2 (similar to 14 Mt per annum) through mineral carbonation. Mg-bearing orthopyroxene is the major sequestrable mineral in these tailings, which also contains significant quantities of Ca-bearing plagioclase, as well as minor quantities of clinopyroxene, olivine, serpentine and hornblende. In this study, the feasibility of using PGM tailings to sequester CO2 has been investigated empirically using the two-step, pH swing method. The rates and extents of cation (Ca, Mg and Fe) extraction and subsequent carbonation were determined and compared. Both organic (oxalic and EDTA) and MCI solutions were utilised in the cation extraction step, which was conducted at time periods up to 8 h and at a temperature of 70 degrees C. The extents of cation dissolution were relatively low under all experimental conditions investigated, particularly for the case of Mg (between 3.3% and 5.0% extraction). A comparison of the extents of leaching with the mineralogical composition of the tailings indicated that the extracted Mg originated primarily from clinopyroxene, with the orthopyroxene remaining relatively inert under the experimental conditions. Subsequent carbonation of the acid leach solution after pH adjustment with NaOH resulted in the rapid formation of a number of carbonate minerals, including gaylussite (Na2Ca(CO3)(2).5(H(2)0)), magnesite (MgCO3), hydromagnesite (Mg-5(CO3)(4)(OH)(2-) "4H(2)0), dolomite (CaMg(CO3)(2)), ankerite (Ca(Fe,Mg)(CO3)(2)), and siderite (FeCO3). On the basis of these findings, further studies will be focused on developing a better understanding of the factors affecting the dissolution of Mg-bearing orthopyroxene minerals, and on exploring alternative leach reagents and conditions, with a view to developing a more effective process for the accelerated carbonation of PGM tailings. (C) 2013 Elsevier Ltd. All rights reserved.