Iron nanoparticles prepared from South African acid mine drainage for the treatment of methylene blue in wastewater.

In this study, three acid mine drainage (AMD) sources were investigated as potential sources of iron for the synthesis of iron nanoparticles using green tea extract (an environmentally friendly reductant) or sodium borohydride (a chemical reductant). Electrical conductivity (EC), total dissolved solids (TDS), dissolved oxygen (DO), oxidation-reduction potential (ORP), ion chromatography (IC), and inductively coupled plasma-mass spectroscopy (ICP-MS) techniques were used to characterize the AMD, and the most suitable AMD sample was selected based on availability. Additionally, three tea extracts were characterized using ferric-reducing antioxidant power (FRAP) and 2,2-diphenyl-1-picryl-hydrazine-hydrate (DPPH), and the most suitable environmentally friendly reductant was selected based on the highest FRAP (1152 µmol FeII/g) and DPPH (71%) values. The synthesized iron nanoparticles were characterized and compared using XRD, STEM, Image J, EDS, and FTIR analytical techniques. The study shows that the novel iron nanoparticles produced using the selected green tea (57 nm) and AMD were stable under air due to the surface modification by polyphenols contained in green tea extract, whereas the nanoparticles produced using sodium borohydride (67 nm) were unstable under air and produced a toxic supernatant. Both the AMD-based iron nanoparticles can be used as Fenton-like catalysts for the decoloration of methylene blue solution. While 99% decoloration was achieved by the borohydride-synthesized nanoparticles, 81% decoloration was achieved using green tea-synthesized nanoparticles.

Acylation of Anisole With Benzoyl Chloride Over Rapidly Synthesized Fly Ash-Based HBEA Zeolite.

Stable HBEA zeolite with high surface area and strong acid sites was synthesized from coal fly ash-based silica extract via indirect hydrothermal synthesis. The rapid HBEA hydrothermal crystallization times of 8, 10, and 12 h were achieved through a reduced molar water fraction in the synthesis composition. The HBEA zeolites prepared from fly ash silica extract exhibited well-defined spheroidal-shaped crystal morphology with uniform particle sizes of 192, 190, or 239 nm obtained after 8, 10, or 12 h of synthesis time, respectively. The high surface area and the microporous area of 702 and 722 m2/g were achieved as a function of shorter hydrothermal synthesis durations (10 and 24 h, respectively) compared to 48 or 72 h, which resulted in HBEA zeolites with lower surface areas of 538 and 670 m2/g. Likewise, temperature-programmed desorption measurements of fly ash-based HBEA zeolites revealed the presence of weak and strong acid sites in the zeolite. The submicron crystal sizes with a well-defined porosity of HBEA zeolites enhanced the diffusion of anisole and benzoyl chloride molecules toward the active acid sites and hence showed better conversion and selectivity in acylation products. High conversion of benzoyl chloride with anisole was achieved, reaching up to 83% with a 93-96% selectivity toward 4-methoxyacetophenone.

Removal of Pharmaceutical Residues from Water and Wastewater Using Dielectric Barrier Discharge Methods-A Review.

Persistent pharmaceutical pollutants (PPPs) have been identified as potential endocrine disruptors that mimic growth hormones when consumed at nanogram per litre to microgram per litre concentrations. Their occurrence in potable water remains a great threat to human health. Different conventional technologies developed for their removal from wastewater have failed to achieve complete mineralisation. Advanced oxidation technologies such as dielectric barrier discharges (DBDs) based on free radical mechanisms have been identified to completely decompose PPPs. Due to the existence of pharmaceuticals as mixtures in wastewater and the recalcitrance of their degradation intermediate by-products, no single advanced oxidation technology has been able to eliminate pharmaceutical xenobiotics. This review paper provides an update on the sources, occurrence, and types of pharmaceuticals in wastewater by emphasising different DBD configurations previously and currently utilised for pharmaceuticals degradation under different experimental conditions. The performance of the DBD geometries was evaluated considering various factors including treatment time, initial concentration, half-life time, degradation efficiency and the energy yield (G50) required to degrade half of the pollutant concentration. The review showed that the efficacy of the DBD systems on the removal of pharmaceutical compounds depends not only on these parameters but also on the nature/type of the pollutant.

Characterization of electron beam deposited Nb2O5 coatings for biomedical applications.

Niobium oxide coatings deposited on Ti6Al4V substrates by electron beam deposition and annealed in air at 600 °C and 800 °C were evaluated for their suitability towards dental, maxillofacial or orthopaedic implant applications. A detailed physico-chemical properties investigation was carried out in order to determine their elemental and phase composition, surface morphology and roughness, mechanical properties, wettability, and corrosion resistance in simulated body fluid solution (pH = 7.4) at room temperature. The biocompatibility of the bare Ti6Al4V substrate and coated surfaces was evaluated by testing the cellular adhesion and viability/proliferation of human osteosarcoma cells (MG-63) after 72 h of incubation. The coatings annealed at 800 °C exhibit more phase pure nanocrystalline Nb2O5 surfaces with enhanced wettability, reduced porosity and enhanced corrosion resistance properties making them good candidate for dental, maxillofacial or orthopaedic implant applications.

Environmental evaluation and nano-mineralogical study of fresh and unsaturated weathered coal fly ashes.

Coal combustion and the disposal of combustion wastes emit enormous quantities of nano-sized particles that pose significant health concerns on exposure, particularly in unindustrialized countries. Samples of fresh and weathered class F fly ash were analysed through various techniques including X-ray fluorescence (XRF), X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), field-emission gun scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM) coupled with energy dispersive x-ray spectroscopy (EDS), and Raman Spectroscopy. The imaging techniques showed that the fresh and weathered coal fly ash nanoparticles (CFA-NPs) are mostly spherical shaped. The crystalline phases detected were quartz, mullite, ettringite, calcite, maghemite, hematite, gypsum, magnetite, clay residues, and sulphides. The most abundant crystalline phases were quartz mixed with Al-Fe-Si-K-Ti-O-amorphous phases whereas mullite was detected in several amorphous phases of Al, Fe, Ca, Si, O, K, Mg, Mn, and P. The analyses revealed that CFA-NPs are 5-500 nm in diameter and encapsulate several potentially hazardous elements (PHEs). The carbon species were detected as 5-50 nm carbon nanoballs of graphitic layers and massive fullerenes. Lastly, the aspects of health risks related to exposure to some detected ambient nanoparticles are also discussed.

Factors influencing pigment production by halophilic bacteria and its effect on brine evaporation rates.

The disposal of reject brine, a highly concentrated waste by-product generated by various industrial processes, represents a major economic and environmental challenge. The common practice in dealing with the large amounts of brine generated is to dispose of it in a pond and allow it to evaporate. The rate of evaporation is therefore a key factor in the effectiveness of the management of these ponds. The addition of various dyes has previously been used as a method to increase the evaporation rate. In this study, a biological approach, using pigmented halophilic bacteria (as opposed to chemical dyes), was assessed. Two bacteria, an Arthrobacter sp. and a Planococcus sp. were selected due to their ability to increase the evaporation of synthetic brine. When using industrial brine, supplementation of the brine with an iron source was required to maintain the pigment production. Under these conditions, the Planococcus sp. CP5-4 produced a carotenoid-like pigment, which resulted in a 20% increase in the evaporation rate of the brine. Thus, the pigment production capability of halophilic bacteria could potentially be exploited as an effective step in the management of industrial reject brines, analogous to the crystallizer ponds used to mine salt from sea water.

Review of the methods for determination of reactive oxygen species and suggestion for their application in advanced oxidation induced by dielectric barrier discharges.

Advanced oxidation processes (AOPs) particularly non-thermal plasmas based on electrical discharges have been widely investigated for water and wastewater treatment. Dielectric barrier discharges (DBDs) generate large amounts of selective and non-selective reactive oxygen species (ROS) such as ozone, hydrogen peroxide, atomic oxygen, superoxide molecular anions and hydroxyl radicals, having been proved to be efficient for water decontamination among various forms of electrical discharge systems. The detection and quantification methods of these oxygen species in non-thermal plasmas have been reviewed. However, their application in dielectric barrier discharge has not been well studied. It is therefore imperative to summarise the various detection and quantification methods for oxygen-based species determination in AOPs, aqueous systems and non-thermal plasma processes. Thereafter, reviewed methods are suggested for the determination of ROS in DBD configurations to understand the consumption trend of these oxidants during treatment of water effluents and to evaluate the performance of the treatment reactor configuration towards the degradation of targeted pollutants.

Nano-TiO2, ultrasound and sequential nano-TiO2/ultrasonic degradation of N-acetyl-para-aminophenol from aqueous solution.

The application of nano-TiO2 as adsorbent combined with ultrasound for the degradation of N-acetyl-para-aminophenol (AAP) from aqueous solution was investigated. The nano-TiO2 was characterized by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). Experimental results revealed that the adsorption of AAP by nano-TiO2 fitted the pseudo-second-order kinetic model, the equilibrium could be explained by the Freundlich isotherm and the treatment process is exothermic. The optimum removal efficiency of AAP (128.89 mg/g (77.33%)) was achieved at pH 4 when 0.03 g of nano-TiO2 was mixed with 50 mL of 100 mg/L AAP aqueous solution at ambient temperature, 60 min contact time, and a stirring speed of 120 rpm. Ultrasound at 20 kHz and pH 3 was favorable and it resulted in 52.61% and 57.43% removal efficiency with and without the addition of nano-TiO2, respectively. The degradation of AAP by ultrasound followed by nano-TiO2 treatment resulted in approximately 99.50% removal efficiency. This study showed that a sequential ultrasound and nano-TiO2 treatment process could be employed for the removal of AAP or other emerging water and wastewater contaminants.

Evaluation of cytotoxicity and inflammatory activity of wastewater collected from a textile factory before and after treatment by coagulation-flocculation methods.

Effective treatment of textile effluent prior to discharge is necessary in order to avert the associated adverse health impacts on human and aquatic life. In the present investigation, coagulation/flocculation processes were evaluated for the effectiveness of the individual treatment. Effectiveness of the treatment was evaluated based on the physicochemical characteristics. The quality of the pre-treated and post-flocculation treated effluent was further evaluated by determination of cytotoxicity and inflammatory activity using RAW264.7 cell cultures. Cytotoxicity was determined using WST-1 assay. Nitric oxide (NO) and interleukin 6 (IL-6) were used as biomarkers of inflammation. NO was determined in cell culture supernatant using the Griess reaction assay. The IL-6 secretion was determined using double antibody sandwich enzyme linked immunoassay (DAS ELISA). Cytotoxicity results show that raw effluent reduced the cell viability significantly (P < 0.001) compared to the negative control. All effluent samples treated by coagulation/flocculation processes at 1 in 100 dilutions had no cytotoxic effects on RAW264.7 cells. The results on inflammatory activities show that the raw effluent and effluent treated with 1.6 g/L of Fe-Mn oxide induced significantly (P < 0.001) higher NO production than the negative control. The inflammatory results further show that the raw effluent induced significantly (P < 0.001) higher production of IL-6 than the negative control. Among the coagulants/flocculants evaluated Al2(SO4)3.14H2O at a dosage of 1.6 g/L was the most effective to remove both toxic and inflammatory pollutants. In conclusion, the inflammatory responses in RAW264.7 cells can be used as sensitive biomarkers for monitoring the effectiveness of coagulation/flocculation processes used for textile effluent treatment.

Synthesis of zeolite A from coal fly ash using ultrasonic treatment--A replacement for fusion step.

The synthesis of zeolites from fly ash has become an increasingly promising remedy to the crisis of coal fly ash production and disposal in South Africa. In recent studies, South African fly ash was proven to be a suitable feedstock for the synthesis of essential industrially used zeolite A. However, the process involves a costly energy intensive step whereby fly ash is fused at high temperatures, which may make the process economically unattractive on a large scale. The aim of this study is to investigate the possibility of replacing high temperature fusion with less energy intensive sonochemical treatment for the synthesis of zeolite A. Sonochemical treatment was first thought possible due to the violent cavitation caused by high intensity sonication. The results of the study showed that fusion can be replaced by 10 min of high intensity sonication. The incorporation of sonication also consequently reduced the crystallization temperature of the process making it possible to synthesize a pure phase zeolite A at lower temperatures and reduced times. This study effectively developed a novel process to replace the energy intensive fusion step with a short, easy and inexpensive treatment. Scale up of this synthesis approach may proffer a promising alternative option to the anticipated energy demand of the synthesis of fly ash-based zeolite with fusion method.

Synthesis of zeolite NaA membrane from fused fly ash extract.

Zeolite-NaA membranes were synthesized from an extract of fused South African fly ash on a porous titanium support by a secondary growth method. The influence of the synthesis molar regime on the formation of zeolite NaA membrane layer was investigated. Two synthesis mixtures were generated by adding either aluminium hydroxide or sodium aluminate to the fused fly ash extract. The feedstock material and the synthesized membranes were characterized by X-diffraction (XRD), scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (XRF). It was found by XRD and SEM that the cubic crystals of a typical zeolite NaA with a dense intergrown layer was formed on the porous Ti support. The study shows that the source of Al used had an effect on the membrane integrity as sodium aluminate provided the appropriate amount of Na(+) to form a coherent membrane of zeolite NaA, whereas aluminium hydroxide did not. Morphological, the single hydrothermal stage seeded support formed an interlocked array of zeolite NaA particles with neighbouring crystals. Also, a robust, continuous and well-intergrown zeolite NaA membrane was formed with neighbouring crystals of zeolite fused to each other after the multiple stage synthesis. The synthesized membrane was permeable to He (6.0 × 10(6) L m(-2)h(-1) atm(-1)) and CO2 (5.6 × 10(6) L m(-2)h(-1) atm(-1)), which indicate that the layer of the membrane was firmly attached to the porous Ti support. Membrane selectivity was maintained showing membrane integrity with permselectivity of 1.1, showing that a waste feedstock, fly ash, could be utilized for preparing robust zeolite NaA membranes on Ti support.

Leaching and antimicrobial properties of silver nanoparticles loaded onto natural zeolite clinoptilolite by ion exchange and wet impregnation.

This study aimed to compare the leaching and antimicrobial properties of silver that was loaded onto the natural zeolite clinoptilolite by ion exchange and wet impregnation. Silver ions were reduced using sodium borohydride (NaBH4). The leaching of silver from the prepared silver-clinoptilolite (Ag-EHC) nanocomposite samples and their antimicrobial activity on Escherichia coli Epi 300 were investigated. It was observed that the percentage of silver loaded onto EHC depended on the loading procedure and the concentration of silver precursor used. Up to 87% of silver was loaded onto EHC by wet impregnation. The size of synthesized silver nanoparticles varied between 8.71-72.67 nm and 7.93-73.91 nm when silver was loaded by ion exchange and wet impregnation, respectively. The antimicrobial activity of the prepared nanocomposite samples was related to the concentration of silver precursor used, the leaching rate and the size of silver nanoparticles obtained after reduction. However, only in the case of the nanocomposite sample (Ag-WEHC) obtained after loading 43.80 ± 1.90 µg of Ag per gram zeolite through wet impregnation was the leaching rate lower than 0.1 mg L-1 limit recommended by WHO, with an acceptable microbial killing effect.

Degradation of organic pollutants and microorganisms from wastewater using different dielectric barrier discharge configurations--a critical review.

The growing global drinking water crisis requires the development of novel advanced, sustainable, and cost-effective water treatment technologies to supplement the existing conventional methods. One such technology is advanced oxidation based on dielectric barrier discharge (DBD). DBD such as single and double planar and single and double cylindrical dielectric barrier configurations have been utilized for efficient degradation of recalcitrant organic pollutants. The overall performance of the different DBD system varies and depends on several factors. Therefore, this review was compiled to give an overview of different DBD configurations vis-a-viz their applications and the in situ mechanism of generation of free reactive species for water and wastewater treatment. Our survey of the literature indicated that application of double cylindrical dielectric barrier configuration represents an ideal and viable route for achieving greater water and wastewater purification efficiency.

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.

In situ ultrasonic diagnostic of zeolite X crystallization with novel (hierarchical) morphology from coal fly ash.

In this paper the applicability of an in situ ultrasonic diagnostic technique in understanding the formation process of zeolite X with a novel morphology was demonstrated. The complexity of the starting fly ash feedstock demands independent studies of the formation process for each type of zeolite since it is not known whether the crystallization mechanism will always follow the expected reaction pathway. The hierarchical zeolite X was noted to follow a solution phase-mediated crystallization mechanism which differs from earlier studies of the zeolite A formation process from unaged, clear solution extracted from fused fly ash. The use of the in situ ultrasonic monitoring system provided sufficient data points which enabled closer estimation of the time of transition from the nucleation to the crystal growth step. In order to evaluate the effect of temperature on the resulting in situ attenuation signal, synthesis at three higher temperatures (80, 90 and 94 °C) was investigated. It was shown, by the shift of the US-attenuation signal, that faster crystallization occurred when higher temperatures were applied. The novel hierarchical zeolite X was comprised of intergrown disc-like platelets. It was further observed that there was preferential growth of the disc-shaped platelets of zeolite X crystals in one dimension as the synthesis temperature was increased, allowing tailoring of the hierarchical morphology.

Distributional Fate of Elements during the Synthesis of Zeolites from South African Coal Fly Ash.

The synthesis of zeolites from South African coal fly ash has been deemed a viable solution to the growing economical strain caused by the disposal of ash in the country. Two synthesis routes have been studied thus far namely the 2-step method and the fusion assisted process. Fly ash contains several elements originating from coal which is incorporated in the ash during combustion. It is vital to determine the final destination of these elements in order to unveil optimization opportunities for scale-up purposes. The aim of this study was to perform a material balance study on both synthesis routes to determine the distributional fate of these elements during the synthesis of zeolites. Zeolites were first synthesized by means of the two synthesis routes. The composition of all raw materials and products were determined after which an overall and elemental balance were performed. Results indicated that in the 2-step method almost all elements were concentrated in the solid zeolite product while during the fusion assisted route the elements mostly report to the solid waste. Toxic elements such as Pb, Hg, Al, As and Nb were found in both the supernatant waste and washing water resulting from each synthesis route. It has also been seen that large quantities of Si and Al are wasted in the supernatant waste. It is highly recommended that the opportunity to recycle this liquid waste be investigated for scale-up purposes. Results also indicate that efficiency whereby Si and Al are extracted from fused ash is exceptionally poor and should be optimized.

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.

Chemical, mineralogical and morphological changes in weathered coal fly ash: a case study of a brine impacted wet ash dump.

The mobility of species in coal fly ash (FA), co-disposed with brine using a wet ash handling system, from a coal fired power generating utility has been investigated. The study was conducted in order to establish if the wet ash dump could act as a salt sink. The ash was dumped as a slurry with 5:1 brine/ash ratio and the dam was in operation for 20 years. Weathered FA samples were collected along three cores at a South African power station's wet ash dump by drilling and sampling the ash at 1.5 m depth intervals. A fresh FA sample was collected from the hoppers in the ash collection system at the power station. Characterization of both fresh FA and weathered FA obtained from the drilled cores S1, S2 and S3 was done using X-ray diffraction (XRD) for mineralogy, X-ray fluorescence (XRF) for chemical composition and scanning electron microscopy (SEM) for morphology. Analysis of extracted pore water and moisture content determination of the fresh FA and the weathered FA obtained from the drilled cores S1, S2 and S3 was done in order to evaluate the physico-chemical properties of the FA. The XRD analysis revealed changes in mineralogy along cores S1, S2 and S3 in comparison with the fresh FA. The SEM analysis revealed spherical particles with smooth outer surfaces for the fresh FA while the weathered ash samples obtained from cores S1, S2 and S3 consisted of agglomerated, irregular particles appearing to be encrusted, etched and corroded showing that weathering and leaching had occurred in the ash dump. The moisture content (MC) analysis carried out on the fresh FA (1.8%) and the weathered FA obtained from the drilled cores S1 (41.4-73.2%), S2 (30.3-94%) and S3 (21.7-76.2%)indicated that the ash dump was water logged hence creating favourable conditions for leaching of species. The fresh fly ash (n = 3) had a pH of 12.38 ± 0.15, EC value of 4.98 ± 0.03 mS/cm and TDS value of 2.68 ± 0.03 g/L, the pH of the drilled core S1 (n = 45) was 10.04 ± 0.50, the EC value was 1.08 ± 0.14 mS/cm and the TDS value was 0.64 ± 0.08 g/L. Core S2 (n = 105) had pH of 10.04 ± 0.23; EC was 1.08 ± 0.06 mS/cm and TDS was 0.64 ± 0.04 g/L, while core S3 (n = 66) had pH of 11.04 ± 0.09; EC was 0.99 ± 0.03 mS/cm and TDS was 0.57 ± 0.01 g/L. The changes in pH values can be attributed to the dissolution and flushing out of alkaline oxides like CaO and MgO from the dumped ash. The variations in pH values shows that the fly ash is acidifying over time and metal mobility can be expected under these conditions. The large decrease of EC in the drilled ash cores S1, S2 and S3 compared to the fresh ash indicated a major loss of ionic species over time in the ash dump. The XRF analysis showed the progressive dissolution of the major aluminosilicate ash matrix which influenced the release of minor and trace elements into the pore water enhancing their mobility as the ash dam acidified over time. Brine co-disposal on the ash may have been responsible for the slight enrichment of some species such as Na (0.27-0.56%), SO4(2-) (0.06-0.08%), Mg (0.57-0.96 %) and K (0.02-0.34%) in the disposed weathered FA. However, there was no significant accumulation of these species in the disposed FA despite continuous addition of large volumes of highly saline brine over the 20 year period that the dump existed, indicating that the ash dam was incapable of holding salts and continually released elements to the environment over the lifetime of the dam.

Comparison of CO2 capture by ex-situ accelerated carbonation and in in-situ naturally weathered coal fly ash.

Natural weathering at coal power plants ash dams occurs via processes such as carbonation, dissolution, co-precipitation and fluid transport mechanisms which are responsible for the long-term chemical, physical and geochemical changes in the ash. Very little information is available on the natural carbon capture potential of wet or dry ash dams. This study investigated the extent of carbon capture in a wet-dumped ash dam and the mineralogical changes promoting CO2 capture, comparing this natural phenomenon with accelerated ex-situ mineral carbonation of fresh fly ash (FA). Significant levels of trace elements of Sr, Ba and Zr were present in both fresh and weathered ash. However Nb, Y, Sr, Th and Ba were found to be enriched in weathered ash compared to fresh ash. Mineralogically, fresh ash is made up of quartz, mullite, hematite, magnetite and lime while weathered and carbonated ashes contained additional phases such as calcite and aragonite. Up to 6.5 wt % CO2 was captured by the fresh FA with a 60% conversion of calcium to CaCO3 via accelerated carbonation (carried out at 2 h, 4Mpa, 90 °C, bulk ash and a S/L ratio of 1). On the other hand 6.8 wt % CO2 was found to have been captured by natural carbonation over a period of 20 years of wet disposed ash. Thus natural carbonation in the ash dumps is significant and may be effective in capturing CO2.

Waste Minimization Protocols for the Process of Synthesizing Zeolites from South African Coal Fly Ash.

Production of a high value zeolite from fly ash has been shown to be an avenue for the utilization of South African fly ash which presently constitutes a huge disposal problem. The synthesis of zeolites Na-P1 and analcime on a micro-scale has been successful and preliminary investigation shows that scale-up synthesis is promising. However, the post-synthesis supernatant waste generated contains high levels of NaOH that may constitute a secondary disposal problem. A waste minimization protocol was developed to reduce the volume of waste generated with a view to enhancing the feasibility of the scale synthesis. Series of experiments were conducted in 100 mL jacketed batch reactors. Fly ash was reacted with 5 Mol NaOH on a 1:1 mass basis during the aging step, followed by hydrothermal treatment in which ultrapure water was added to the slurry. This study shows that by re-introducing the supernatant waste into the experiments in such a way that it supplies the required reagent (NaOH) for the zeolite synthesis, zeolite Na-P1 and analcime can be synthesized. It also shows that the synthesis process can be altered to allow up to 100% re-use of the supernatant waste to yield high value zeolitic products. This study effectively constructed two protocols for the minimization of waste generated during the synthesis of zeolites from South African coal fly ash. This result could be used to establish a basis for legal and environmental aspects involved in the commission of a full-scale plant synthesizing zeolites NaP1 and analcime.