Chemical compositions and leaching behaviour of some South African fly ashe
Fly ash is the most abundant of the waste materials generated from coal combustion in coal-fired power stations. South Africa uses more than 100 million tonnes of low grade bituminous coal annually to produce cheap electricity thereby generating huge amounts of fly ash each year. The disposal of fly ash has been a major concern to the world because of its potential environmental impact due to the possible leaching of the toxic elements contained in fly ash. This study centres on the chemical characterization and leaching behaviour of the fly ashes generated from SASOL Synfuels and ESKOM power station at Secunda and Tutuka in South Africa respectively. The aim is to understand the composition of the fly ashes and to determine the leachability of species from the ashes in order to predict the environmental effect of the different ash handling system of the coalfired stations (wet disposal system in Secunda and dry disposal system in Tutuka). Several leaching methods were employed in this study in order to develop a methodology for evaluating and modelling ash system and were able to discriminate between ash types and model ash handling system. Fly ashes from the two South African coal-fired stations were subjected to total acid-digestion and XRF analyses in order to determine the total amounts of major and minor species contained in the fly ashes. The total acid-digestion test and the XRF analysis revealed that the major species such as Al, Si, Ca, Na, Mg, K, Sr, Ba and S04, and minor species such as Fe, Ti, V, Mn, Cr, Ni and Cu were present in both fly ashes in fairly similar concentrations. The mineralogical characterization by XRD of Secunda and Tutuka fly ashes revealed mullite and quartz as the major mineral phases with minor peaks of CaO and calcite. Several leaching tests and different leaching conditions were employed in this study in order to develop a standardized replicable methodology for environmental impact assessment and for modelling the impact of different ash handling scenarios. The fly ashes were exposed to these different leaf leachant of different pHs on the leachability of species from the fly ashes. To achieve this, DIN-S4, TCLP and ANC tests were employed. The natural pH of the fly ash leachates were very high ranging between 12.56 and 13.08. The DIN-S4 leaching test revealed that the easily soluble species of the fly ashes include Ca, Mg, Na, K and S04 and various toxic elements. The leachates from the TCLP test recorded higher concentrations of Ca, Mg, Na, K and S04 which was attributed to the slight decrease in the pH due to the addition of a acidic leachant with a pH of 2.88. Comparison of the amount leached (DIN-S4) from the fly ashes with the total concentrations of each of the components of the fly ashes (determined by the total acid-digestion), the percentage of each of the readily soluble species ranged from 15-24.23% for Ca, 0.23-0.45% for K, 0.58-0.82% for Na, 0.0047-0.007% for Mg, 0.96-3.33% for Ba and 0.012-1.51 % for S04 per dry mass of each component in the fly ash. The ANC test revealed the effect of a leachant of specified pH on the release of species from the fly ashes with concentrations of the major and minor species leached out of the fly ashes found to be higher than the concentrations released into the leachates when DIN-S4 and TCLP test were considered at specific pH and showed the pH dependence of the solubility and release of species. These tests also showed the effect of the liquid to solid ratio upon leachability of species. In addition to the batch leaching tests mentioned above, dissolution kinetics and up-flow percolation tests were carried out on the fly ashes to determine the leaching behaviours of the fly ashes over time and the factors controlling the release of species from the fly ashes in the long term. The dissolution kinetics test was done for an extended period of 60 days with recycle of the leachant and the up-flow percolation test was carried out with constant leachant renewal until a liquid/solid ratio of 20 was attained (:::::;9d0ays). The geochemical computer code PHREEQC and MINTEQ database was used for geochemical modelling of the leachates at various reaction times and LIS ratios. The geochemical modelling results revealed that the release of the species from the fly ashes is controlled by the solubility of mineral phases in many case except for Na. The release of Ca, S04, Mg, Ba and Sr in the leachates of the fly ashes were predicted to be controlled by portlandite, gypsum, brucite, barite and celestite respectively while birnessite, magnetite, BaCr04, CaMo04 and Ba(As04h were predicted to be the mineral phases controlling the release of Mn, Fe, Cr, Mo and As respectively. The pH of the leachates plays a significant role in the leaching of both major and minor species from the fly ashes. The concentrations of species leached into solution at low pH (ANC and TCLP) were higher than the concentrations released at high pH (DIN-S4, dissolution kinetics and up-flow percolation tests). The amounts of the toxic elements such as As, Se, Cd, Cr and Pb that leached out of the fly ashes when in contact with demineralized water (DIN-S4) were very low and below the target water quality range (TWQR) of South African Department of Water Affairs and Forestry (DWAF), but the amounts of As and Se leached out by acidic leachant applied in the TCLP test and at lower pH ranging between 8 and 10 the case of the ANC test were slightly higher than the TWQR, which is an indication that the pH of the leaching solution and the contact time playa significant role on the leaching of species out of the fly ashes. This study revealed that the leaching of species from the fly ashes depends on various factors which include: physical and chemical characteristics and mineralogical composition of the fly ashes, the total concentrations of species in the ash, the rate of flow through the ash system and more importantly the pH of the leachant to which the ash system is exposed to. The results of different experiments and analysis carried out on the two South African fly ashes (Secunda and Tutuka fly ashes) showed that, despite the high concentrations of soluble species or leachable elements in the fly ashes, the leaching of major, minor and trace elements into the soils and the groundwater could be minimized if certain conditions such as avoiding acidic precipitation that could reduce the pH of the ash system are adhered to. The leaching trends of the species and the geochemical modelling data also showed that the formation of secondary mineral phases could reduce the release of toxic elements, the release of which would require aggressive low pH leachants, high flow rate, high recharge and long-term leaching for the dissolution of the formed mineral phases. In conclusion, the combination of the leaching tests employed in this study gives information on the leaching behaviour of the Secunda and Tutuka fly ashes and the factors controlling the leaching of the elements from the fly ashes. This study has been able to show that elements are leached out of the fly ashes at both alkaline and acidic pH. It is also revealed in the study that the disposal techniques employed by the coal-fired stations which were simulated by using the dissolution kinetics and up-flow percolation tests are adequate methods for modelling of the ash disposal scenario. These two methods show that the dry disposal system at Tutuka will encourage equilibration of the ash/water system thereby facilitating the precipitation of mineral phases that could control the release of both major and minor species from the fly ash, whereas the wet ashing system at Secunda may expose the ash to sufficient flow to rapidly leach species out into the environment.