Synthesis, Characterization and In Vitro Antibacterial Evaluation of Pyrenacantha grandiflora Conjugated Silver Nanoparticles.

In the present study, silver nanoparticles (AgNPs) were synthesized using both the chemical and biological methods and conjugated with Pyrenacantha grandiflora extracts. These were then characterized and evaluated for antimicrobial activities against multi-drug resistant pathogens, such as methicillin-resistant Staphylococcus aureus (MRSA), Klebsiella pneumonia, and Escherichia coli. Nanoparticles were analyzed with UV-visible spectrophotometer, transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX). Silver nanoparticles, P. grandiflora extracts, and the conjugates were also analyzed with Fourier transform infrared spectroscopy (FTIR). As a result, quasi-sphere-shaped AgNPs with sizes ranging from 5 to 33 nm and spherically shaped AgNPs with sizes ranging from 3 to 25 nm were formed from chemical and biological synthesis, respectively. A well diffusion assay showed that the activity of silver nanoparticles was most improved with acetone extract against all tested bacteria with diameters in the range of 19-24 mm. The lowest MIC value of 0.0063 mg/mL against MRSA was observed when biologically synthesized AgNPs were conjugated with acetone and water extracts. Chemically synthesized silver nanoparticles showed the lowest MIC value of 0.0063 mg/mL against E. coli when conjugated with acetone and methanol extracts. This study indicates that silver nanoparticles conjugated with P. gandiflora tubers extracts exhibit strong antibacterial activities against multi-drug resistant bacterial pathogens. Therefore, biosynthesized conjugates could be utilized as antimicrobial agents for effective disease management due to the synergistic antibacterial activity that was observed.

The impact of artisanal mining on rehabilitation efforts of abandoned mine shafts in Sutherland goldfield, South Africa.

Abandoned gold mine sites are generally characterised by severe environmental problems and physical hazards. Because of socio-economic problems confronting communities around abandoned mine sites, historic and abandoned gold mines have become hot-spots for artisanal and small-scale miners. These mining activities at times thwart the efforts of rehabilitation at these sites. This article details how artisanal mining operations have frustrated rehabilitation efforts of abandoned mine shafts in the Sutherland goldfield. The field investigation of abandoned shafts and analysis of the nature of artisanal mining operations in the Sutherland goldfield revealed that artisanal mining involving digging around collars of sealed shafts is a major threat to the stability of the shafts and their sealing structures. In addition, artisanal mining operations have increased the safety risks of the abandoned shafts in the area. This has also been worsened by the fact that a large number of people, especially women and children, are exposed to the hazards of the abandoned mine sites. This article emphasises an urgent need for the development of holistic and cohesive strategies for dealing with the problems of abandoned gold mine shafts wherever they exist in the country as opposed to simply closing them up.

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.

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

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.

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.

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.

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 (H(2)O:SiO(2) 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 SiO(2): 0.36 Al(2)O(3): 0.59 NaOH: 0.49 H(2)O 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.

Fly ash-brine interactions: removal of major and trace elements from brine.

Fly ash and brine contain major and trace elements such as Na, Cl, Ca, SO(4), K, Mg, P, Si, Al, Fe, Mn, Cr, V and Ti in significant quantities. This study focuses on the leachability of species from fly ash and the removal of major and trace species from brine as the two waste streams interact. Another objective is to evaluate the effect of the interactions on the brine quality. Batch reaction tests were carried out on two different fly ashes and brine at different L/S ratios and different reaction times, and the supernatant analysed for major and trace species. Chemical analysis revealed that the unreacted brine solution contained high concentration of species such as Na, K, Ca, Mg, Cl and SO(4), while species such as As, Ba, Cd, Co, Cr, Mn, Pb and Ti were present in trace quantities. Analysis of the supernatants after the batch reaction tests (fly ash-brine interaction experiments) revealed that major species such as Na, Mg, Cl and SO(4), and trace elements such as As, Co, Pb, Zn, Ni and Cu were significantly removed from the brine solution while Ca, Ba, Sr, Cr and Mo were leached into the brine solution from the fly ashes. The removal of species from the brine solution was most prominent at L/S ratio 1:1. This indicates that the L/S ratio of the ash-brine system has a significant effect on the release of species from fly ash or the removal of species from brine solution. The final pH of the fly ash-brine solutions and the contact times were also observed to have a significant effect on the leaching from fly ash as well as the removal of major and trace species from the brine. The study also showed that some contaminant species can be removed from brine solution using 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.

Interaction of acid mine drainage with Ordinary Portland Cement blended solid residues generated from active treatment of acid mine drainage with coal fly ash.

Fly ash (FA) has been investigated as a possible treatment agent for Acid mine drainage (AMD) and established to be an alternative, cheap and economically viable agent compared to the conventional alkaline agents. However, this treatment option also leads to generation of solid residues (SR) that require disposal and one of the proposed disposal method is a backfill in coal mine voids. In this study, the interaction of the SR with AMD that is likely to be present in such backfill scenario was simulated by draining columns packed with SR and SR + 6% Ordinary Portland Cement (OPC) unsaturated with simulated AMD over a 6 month period. The evolving geochemistry of the liquid/solid (L/S) system was evaluated in-terms of the mineral phases likely or controlling contaminants attenuation at the different pH regimes generated. Stepwise acidification of the percolates was observed as the drainage progressed. Two pH buffer zones were observed (7.5-9 and 3-4) for SR and (11.2-11.3 and 3.5-4) for SR + 6% OPC. The solid residue cores (SR) appeared to have a significant buffering capacity, maintaining a neutral to slightly alkaline pH in the leachates for an extended period of time (97 days: L/S 4.3) while SR + 6% OPC reduced this neutralization capacity to 22 days (L/S 1.9). Interaction of AMD with SR or SR + 6% OPC generated alkaline conditions that favored precipitation of Fe, Al, Mn-(oxy) hydroxides, Fe and Ca-Al hydroxysulphates that greatly contributed to the contaminants removal. However, precipitation of these phases was restricted to the pH of the leachates remaining at neutral to circum-neutral levels. Backfill of mine voids with SR promises to be a feasible technology for the disposal of the SR but its success will greatly depend on the disposal scenario, AMD generated and the alkalinity generating potential of the SR. A disadvantage would be the possible re-dissolution of the precipitated phases at pH < 4 that would release the contaminants back to the water column. However extrapolation of this concept to a field scenario can greatly enhance beneficial application of fly ash (FA) and solid residues (SR) generated from treatment of AMD.

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.