Wilson M. Gitari

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 SiO2, Al2O3, Fe2O3 and CaO as the main components with Cr, Co, Ni, Cu, Zn, V and Pb as minor components. Ca, Mg, Na, K and SO4 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.

Optimization of hydrothermal synthesis of pure phase zeolite Na-P1 from South African coal fly ashes

This study was aimed at optimizing the synthesis conditions for pure phase zeolite Na-P1 from three coal fly ashes obtained from power stations in the Mpumalanga province of South Africa. Synthesis variables evaluated were: hydrothermal treatment time (12–48 hours), temperature (100–160°C) and varying molar quantities of water during the hydrothermal treatment step (H2O:SiO2 molar ratio ranged between 0–0.49). The optimum synthesis conditions for preparing pure phase zeolite Na-P1 were achieved when the molar regime was 1 SiO2: 0.36 Al2O3: 0.59 NaOH: 0.49 H2O and ageing was done at 47°C for 48 hours. The optimum hydrothermal treatment time and temperature was 48 hours and 140°C, respectively. Fly ashes sourced from two coal-fired power plants (A, B) were found to produce nearly same high purity zeolite Na-P1 under identical conditions whereas the third fly ash (C) lead to a low quality zeolite Na-P1 under these conditions. The cation exchange capacity for the high pure phase was found to be 4.11 meq/g. These results highlight the fact that adjustment of reactant composition and presynthesis or synthesis parameters, improved quality of zeolite Na-P1 can be achieved and hence an improved potential for application of zeolites prepared from coal fly ash.

Synthesis of hydroxy sodalite from coal fly ash using waste industrial brine solution

The effect of using industrial waste brine solution instead of ultra pure water was investigated during the synthesis of zeolites using three South African coal fly ashes as Si feedstock. The high halide brine was obtained from the retentate effluent of a reverse osmosis mine water treatment plant. Synthesis conditions applied were; ageing of fly ash was at 47°C for 48 hours, and while the hydrothermal treatment temperature was set at 140°C for 48 hours. The use of brine as a solvent resulted in the formation of hydroxy sodalite zeolite although unconverted mullite and hematite from the fly ash feedstock was also found in the synthesis product.

Attenuation of metal species in acidic solutions using bentonite clay: implications for acid mine drainage remediation

A laboratory batch experimental study has been carried out to evaluate the adsorption capacity of selected metal species in acid mine drainage (AMD) by bentonite clay. Bentonite clay was mixed with simulated AMD at specific solid–liquid (S/L) ratios and agitated in a reciprocating shaker and adsorption of selected toxic metals assessed over time. Cation exchange capacity varied from 1140 to 1290 meq kg−1. Contact of AMD with bentonite leads to increase in pH and a possible reduction in electrical conductivity and total dissolved solids. At constant agitation time of 60 min, the pH increased with dosage of bentonite. Removal of Mn2+, Al 3+, and Fe3+ was observed to be greatest at 60 min of agitation. Bentonite clay exhibits high adsorption for Al3+ and Fe3+ at concentration less than 300 mg L−1, while the capacity for Mn2+ was observed to be lower. Adsorption capacity for SO42− was low with a great percentage of the SO42− remaining in solution. Adsorption capacity of bentonite with more complex formulated AMD and gold tailing leachates was low for Fe3+, Al3+, and Mn2+. This indicates that optimum adsorption of bentonite clay is dependent on the chemistry of the AMD and its application might be site specific.

Partitioning of major and trace inorganic contaminants in fly ash acid mine drainage derived solid residues

Acid mine drainage was reacted with coal fly ash over a 24 h reaction time and species removal trends evaluated. The evolving process water chemistry was modeled by the geochemical code PHREEQC using WATEQ4 database. Mineralogical analysis of the resulting solid residues was done by X-ray diffraction analysis. Selective sequential extraction was used to evaluate the transfer of species from both acid mine drainage and fly ash to less labile mineral phases that precipitated out. The quantity of fly ash, volume of acid mine drainage in the reaction mixture and reaction time dictated whether the final solution at a given contact time will have a dominant acidic or basic character. Inorganic species removal was dependent on the pH regime generated at a specific reaction time. Sulphate concentration was controlled by precipitation of gypsum, barite, celestite and adsorption on iron-oxy-hydroxides at pH > 5.5. Increase of pH in solution with contact time caused the removal of the metal ions mainly by precipitation, co-precipitation and adsorption. PHREEQC predicted precipitation of iron, aluminium, manganese-bearing phases at pH 5.53–9.12. An amorphous fraction was observed to be the most important in retention of the major and minor species at pH > 6.32. The carbonate fraction was observed to be an important retention pathway at pH 4–5 mainly due to initial local pockets of high alkalinity on surfaces of fly ash particles. Boron was observed to have a strong retention in the carbonate fraction.

The leaching behaviour and geochemical fractionation of trace elements in hydraulically disposed weathered coal fly ash

A five-step sequential extraction (SE) procedure was used to investigate the leaching behaviour and geochemical partitioning of the trace elements As, Zn, Pb, Ni, Mo, Cr and Cu in a 20-year-old fly ash (FA) dump. The weathered FA, which was hydraulically co-disposed with salt laden brine in slurry form (FA: brine ratio of 1:5), was analyzed and compared with fresh FA. The weathered FA samples were collected from three cores, drilled at a coal-fired power station in the Republic of South Africa while the fresh FA sample was collected from the hoppers in the ash collection system at the power station. The FA samples were sequentially leached using: ultrapure water; ammonium acetate buffer solution (pH 7); ammonium acetate buffer solution (pH 5); hydroxylamine hydrochloride in nitric acid (pH 2) and finally the residues were digested using a combination of HClO4: HF: HNO3 acids. Digestion of as received (unleached) FA samples was also done using a combination of HClO4: HF: HNO3 acids in order to determine the total metal content. The trace element analysis was done using ICP-OES (Varian 710-ES). The SE procedure revealed that the trace elements present in the fresh FA and the weathered FA samples obtained from the three cores could leach upon exposure to different environmental conditions. The trace elements showed continuous partitioning between five geochemical phases i.e., water soluble fraction, exchangeable fraction, carbonate fraction, Fe and Mn fraction and residual fraction. Although the highest concentration of the trace elements (ranging 65.51%–86.34%) was contained in the residual fraction, a considerable amount of each trace element (ranging 4.42%–27.43%) was released from the labile phases (water soluble, exchangeable and carbonate fractions), indicating that the trace species readily leach from the dumped FA under environmental conditions thus pose a danger to the receiving environment and to groundwater.

Mineralogy and Mobility Patterns of Chemical Species in Weathered Coal Fly Ash

Abstract Chemical interactions of disposed coal fly ash with O2, CO2, and infiltrating rain-water lead to chemical alteration, flushing/leaching of soluble chemical species locked in different physico-chemical forms as the coal fly ash is aging. This study was carried out to gain insight into the chemical alterations and its effects on the mobility patterns of chemical species in weathered coal fly ash. Weathered coal fly ash samples of ages 1 year and 20 years were sampled at a coal burning power station in the Mpumalanga Province, South Africa. The chemical and mineralogical compositions of the weathered coal fly ash were investigated using X-ray fluorescence spectrometry, inductive coupled plasma-optical emission spectrometry, ion chromatography, X-ray diffraction, and Fourier transform infrared spectroscopy. X-ray fluorescence results showed the presence of major oxides, such as SiO2, Al2 O 3, Fe2 O 3, while CaO, K2O, TiO2, MnO, MgO, P2 O 5, and SO3 occur in minor concentrations. The major elements, such as Fe, Si, Mg, K, and Mn, showed increasing trends down the depth of the core, while Ti and Al show decreasing trends down the depth of the core (20-year-old coal fly ash). Trace metals, such as P and Zn, show increasing trends down the depth, while Ba, Ni, Pb, Sr, V, and Cr increase up the depth of the core (20-year-old ash). The trace metals distribution patterns in 1-year-old ash showed increasing trends down the depth of the core for Cr, Ni, Pb, Y, S, and P, while Ba and Sr decrease down the depth of the core. Major mineral phases as revealed by X-ray diffraction include quartz and mullite. Other minerals identified are hematite, calcite, lime, anorthite, mica, and enstatite. The pH of interstitial pore water for 1-year-old and 20-year-old coal fly ash ranged from 9.0–10.6 and 7.2–9.9, respectively, while in the 2-week-old coal fly ash ranged from 9.9–10.9. Analysis of extracted pore water shows that several toxic metals, such as B, Cr, As, Mo, and Se, are leaching from the weathered ash. The core ash samples in contact with the atmosphere and those at the saturation point record the highest availability of chemical species, such as Mg, Ca, Fe, K, Na, B, Cr, As, Mo, and Se in pore water. The 1-year-old and 20-year-old coal fly ash cores showed a lower pH and greater leaching/flushing of the soluble buffering constituents than the 2-week-old placed ash.

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.

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result its imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not encapsulate the salt or act as a sustainable salt sink due to over time reduction in pore water pH. The leaching behaviours of Ca, Mg, Na+, K+, Se, Cr and Sr are controlled by the pH of the leachant in both fresh and unsaturated weathered ash. Other trace metals like As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. The precipitation of minor quantities of secondary mineral phases in the unsaturated weathered ash has significant effects on the acid susceptibility and leaching patterns of chemical species in comparison with fresh ash. The unsaturated weathered ash had lower buffering capacity at neutral pH (7.94-8.00) compared to fresh (unweathered) ash. This may be due to the initial high leaching/flushing of soluble basic buffering constituents from fly ash after disposal. The overall results of the acid susceptibility tests suggest that both fresh ash and unsaturated weathered ash would release a large percentage of their chemical species when in contact with slightly acidified rain. Proper management of ash dumps is therefore essential to safeguard the environmental risks of water percolation in different fly ashes behaviour.

Synthesis and performance evaluation of Al/Fe oxide coated diatomaceous earth in groundwater defluoridation: Towards fluorosis mitigation

ABSTRACT The quest to reduce fluoride in groundwater to WHO acceptable limit of 1.5 mg/L to prevent diseases such as teeth mottling and skeletal fluorosis was the motivation for this study. Al/Fe oxide-modified diatomaceous earth was prepared and its defluoridation potential evaluated by batch method. The sorbent with pHpzc 6.0 ± 0.2 is very reactive. The maximum 82.3% fluoride removal attained in 50 min using a dosage of 0.3 g/100 mL in 10 mg/L fluoride was almost attained within 5 min contact time; 81.3% being the percent fluoride removal at 5 min contact time. The sorbent has a usage advantage of not requiring solution pH adjustment before it can exhibit its fluoride removal potential. A substantial amount of fluoride (93.1%) was removed from solution when a sorbent dosage of 0.6 g/100 mL was contacted with 10 mg/L fluoride solution for 50 min at a mixing rate of 200 rpm. The optimum adsorption capacity of the adsorbent was 7.633 mg/g using a solution containing initially 100 mg/L fluoride. The equilibrium pH of the suspensions ranged between 6.77 and 8.26 for 10 and 100 mg/L fluoride solutions respectively. Contacting the sorbent at a dosage of 0.6 g/100 mL with field water containing 5.53 mg/L at 200 rpm for 50 min reduced the fluoride content to 0.928 mg/L—a value below the upper limit of WHO guideline of 1.5 mg/L fluoride in drinking water. The sorption data fitted to both Langmuir and Freundlich isotherms but better with the former. The sorption data obeyed only the pseudo-second-order kinetic, which implies that fluoride was chemisorbed.