Application of mine water leaching protocol on coal fly ash to assess leaching characteristics for suitability as a mine backfill material.

Over the years, coal mining in the Mpumalanga Province of South Africa has negatively affected the environment by causing pollution of water resources, land subsidence and spontaneous coal combustion. Previous studies show that in-situ treatment of acid mine drainage (AMD) using coal fly ash (CFA) from local power stations was possible and sludge recovered out of such treatment can be used to backfill mines. In this article, the authors have attempted to understand the leaching characteristics of CFA when placed underground as a backfill material using the mine water leaching protocol (MWLP). The results show that the migration of contaminants between the coal fly ash and the AMD in the mine voids depends on the pH and quality of the mine water. While backfilling mine voids with CFA can neutralize and scavenge between 50% and 95% of certain environmentally sensitive elements from AMD such as Fe, Al, Zn, Cu, Ni, Co and Mn. At this moment, it is also important to point out that certain scavenged/removed contaminants from the AMD during initial phases of backfilling can be remobilized by the influx of acidic water into the mine voids. It has therefore been concluded that, while CFA can be used to backfill mine voids, the influx of fresh acidic mine water should be avoided to minimize the remobilization of trapped contaminants such as Fe, Al, Mn and As. However, the pozzolanic material resulting from the CFA-AMD interaction could prevent such influx.

Fate of the naturally occurring radioactive materials during treatment of acid mine drainage with coal fly ash and aluminium hydroxide.

Mining of coal is very extensive and coal is mainly used to produce electricity. Coal power stations generate huge amounts of coal fly ash of which a small amount is used in the construction industry. Mining exposes pyrite containing rocks to H2O and O2. This results in the oxidation of FeS2 to form H2SO4. The acidic water, often termed acid mine drainage (AMD), causes dissolution of potentially toxic elements such as, Fe, Al, Mn and naturally occurring radioactive materials such as U and Th from the associated bedrock. This results in an outflow of AMD with high concentrations of sulphate ions, Fe, Al, Mn and naturally occurring radioactive materials. Treatment of AMD with coal fly ash has shown that good quality water can be produced which is suitable for irrigation purposes. Most of the potentially toxic elements (Fe, Al, Mn, etc) and substantial amounts of sulphate ions are removed during treatment with coal fly ash. This research endeavours to establish the fate of the radioactive materials in mine water with coal fly ash containing radioactive materials. It was established that coal fly ash treatment method was capable of removing radioactive materials from mine water to within the target water quality range for drinking water standards. The alpha and beta radioactivity of the mine water was reduced by 88% and 75% respectively. The reduced radioactivity in the mine water was due to greater than 90% removal of U and Th radioactive materials from the mine water after treatment with coal fly ash as ThO2 and UO2. No radioisotopes were found to leach from the coal fly ash into the mine water.

Sulphate removal from sodium sulphate-rich brine and recovery of barium as a barium salt mixture.

Sulphate removal from sodium sulphate-rich brine using barium hydroxide and recovery of the barium salts has been investigated. The sodium sulphate-rich brine treated with different dosages of barium hydroxide to precipitate barium sulphate showed sulphate removal from 13.5 g/L to less than 400 mg/L over 60 min using a barium to sulphate molar ratio of 1.1. The thermal conversion of precipitated barium sulphate to barium sulphide achieved a conversion yield of 85% using coal as both a reducing agent and an energy source. The recovery of a pure mixture of barium salts from barium sulphide, which involved dissolution of barium sulphide and reaction with ammonium hydroxide resulted in recovery of a mixture of barium carbonate (62%) and barium hydroxide (38%), which is a critical input raw material for barium salts based acid mine drainage (AMD) desalination technologies. Under alkaline conditions of this barium salt mixture recovery process, ammonia gas is given off, while hydrogen sulfide is retained in solution as bisulfide species, and this provides basis for ammonium hydroxide separation and recovery for reuse, with hydrogen sulfide also recoverable for further industrial applications such as sulfur production by subsequent stripping.

Integrated acid mine drainage management using fly ash.

Fly Ash (FA) from a power station in South Africa was investigated to neutralise and remove contaminants from Acid Mine Drainage (AMD). After this primary treatment the insoluble FA residue namely solid residue (SR) was investigated as a suitable mine backfill material by means of strength testing. Moreover, SR was used to synthesise zeolite-P using a two-step synthesis procedure. Furthermore, the zeolite-P was investigated to polish process water from the primary FA-AMD reaction. The main objective of this series of investigations is to achieve zero waste and to propose an integrated AMD management using FA. Fly Ash was mixed with AMD at various predetermined FA-AMD ratios until the mixtures achieved circumneutral pH or higher. The supernatants were then analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Ion Chromatography (IC) for cations and anions respectively. The physical strength testing of SR was carried out by mixing it with 3% Ordinary Portland Cement (OPC) and curing for 410 days. Synthesis of zeolite-P using SR was carried out by two step synthesis procedure: ageing for 24 hours followed by a mild hydrothermal synthesis at 100°C for 4 days. The polishing of process water from primary AMD treatment using FA was ascertained by mixing the process water with zeolite at a liquid to solid ratio of 100:1 for 1 hour. The results indicated that FA can be successfully used to ameliorate AMD. High removal of major AMD contaminants Fe, Al, Mg, Mn and sulphate was achieved with the ash treatment and trace elements such as Zn, Ni, Cu and Pb were also removed by the FA. Strength testing over 410 days indicated that the material gained strength over the testing period. The maximum unconfined compressive strength and elastic modulus was observed to be approximately 0.3 MPa and 150 Mpa respectively. The X-ray diffraction (XRD) analysis of the synthesized product indicated that SR was successfully converted into zeolite-P with some mullite phase remaining as a result of incomplete conversion of the feedstock SR. The zeolite-P was used as an ion exchange material to remove selective elements from the process water. Elements such as Ca, Sr, Ba and V were successfully removed from the process water with the zeolite-P. Only marginal removal of Mo was observed during the experiments. It was also observed that Na was exchanged into the solution. This study successfully demonstrated zero waste concepts and an integrated AMD management scheme using FA was developed in this study. The implementation of this technology will address FA storage problem as well as costs associated with AMD treatment.

Leaching characteristics of selected South African fly ashes: effect of pH on the release of major and trace species.

Fly ash samples from two South African coal-fired power stations were subjected to different leaching tests under alkaline and acidic conditions in an attempt to assess the effect of pH on the leachability of species from the fly ashes and also assess the potential impact of the fly ashes disposal on groundwater and the receiving environment. To achieve this, German Standard leaching (DIN-S4) and Acid Neutralization Capacity (ANC) tests were employed. Mineralogical characterization of the fresh fly ashes revealed mullite and quartz as the major mineral phases with minor peaks of CaO and calcite. Chemical characterization by X-ray fluorescence (XRF) spectrometry revealed that the two fly ashes are similar, and consist of SiO(2), Al(2)O(3), Fe(2)O(3) and CaO as the main components with Cr, Co, Ni, Cu, Zn, V and Pb as minor components. Ca, Mg, Na, K and SO(4) were significantly leached into solution under the two leaching conditions with the total amounts in ANC leachates higher than that of DIN-S4. This indicates that a large fraction of the soluble salts in unweathered fly ash are easily leached. These species represents the fraction that can be flushed off initially from the surface of ash particles on contacting the ash with water. Al and Si were only observed in the leachates of the ANC test. Results obtained from the total acid-digestion and DIN-S4 leaching test indicated some toxic elements in the fly ashes are not easily solubilized. The amounts of toxic trace elements such as As, Se, Cd, Cr and Pb leached out of the fly ashes when in contact with de-mineralized water (DIN-S4 test) were low and below the Target Water Quality Range (TWQR) of South Africa. This is explained by their low concentrations in the fly ashes and their solubility dependence on the pH of the leaching solution. However the amounts of some minor elements such as B, Mn, Fe, As and Se leached out at lower pH ranging between 10 to 4 (ANC test) were slightly higher than the TWQR, an indication that the pH of the leaching solution plays a significant role on the leaching of species in fly ash. The high concentrations of the toxic elements released from the fly ashes at lower pH gives an indication that the disposal of the fly ash could have adverse effects on the receiving environment if the pH of the solution contacting the ashes is not properly monitored. The study indicated that on contact with water in a disposal scenario fly ash will release high amounts of soluble species.