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 alumi-nosilicate 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 (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.Web of Scienc

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 o 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.Web of Scienc

Synthesis and characterization of zeolites produced by ultrasonication of coal fly ash/NaOH slurry filtrates

Studies were conducted to determine if crystalline zeolites could be obtained from the filtrates of coal fly ash (CFA)/NaOH slurries through sonication. The CFA/NaOH slurries were obtained by aging CFA in 3 M NaOH for 24 h at 50 °C using a solid/liquid (S/L) ratio of 15 g/120 mL. FT-IR studies indicated that the ‘Lo’ regime ultrasonicated zeolite had higher intensities than that of the ‘Hi’ frequency ultrasonicated zeolite. The bands associated with the ‘Lo’ regime ultrasonicated zeolite were observed at 1066cm–1, 1400cm–1 and 3600cm–1, which were identified as Si-Oasymmetric stretch, Al-Oasymmetric stretch, O-Hbend and O-H asymmetric stretch, respectively. Based on PXRD studies, the zeolitic phases were most intense for the 90 min ultrasonicated zeolite. Powder X-ray diffraction studies showed that the phases initially in CFA, such as quartz and aluminosilicate, were converted into gismodine zeolite Na-P1. Morphological changes were seen as ultrasonication period was increased. At short ultrasonication times, irregularly shaped fused-like grain structures were observed, while at longer times separate grain-like structures became more apparent. Energy dispersive X-ray spectroscopy studies on the 90 min ultrasonicated zeolite indicated the presence of Na, O, Si and Al, which were important building-blocks for the zeolites

Optimization of Silica Extraction from Diatomaceous Earth using the Central Composite Design of Response Surface Methodology

This work evaluated the extraction efficiency of silica from diatomaceous earth (DE) by conventional solvent extraction (CSE) and ultrasound-assisted  extraction (UAE) under basic and acidic (HCl) conditions utilizing response surface methodology (RSM). A common statistical model was used to get the  best percentage yield and percentage purity using RSM. Experimental parameters such as stirring time, NaOH concentration (for CSE), sonication time,  NaOH/HCl concentration, cycle and amplitude (for UAE methods) were optimized using central composite design (CCD). The analytical responses, that is,  percentage yield and percentage purity, were analyzed using ANOVA and regression analysis. The linear coefficient of determination, R2 , was high and  precise. The overall yield and purity were highest for the UAE method under acid condition (pH 1–2, approximately), making it the most effective silica  extraction method from DE. For this method, the optimal conditions for extracting Si from DE were 2 h of sonication, 220 mL of 2.82 M HCl as a  leaching/extracting medium, 0.524 cycles and 72.6 % of amplitude. Under these conditions, 82 % of silica was yielded with a purity of about 95 %. The  experimental results indicate that high-quality silica can be produced from DE in high yield so that DE can be an alternative silica source.&nbsp

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 CFANPs 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

Appraisal of Fluoride Removal Capability of Al-Fe Oxide-Infused Diatomaceous Earth in a Continuous-Flow Fixed-Bed Column

This study was carried out to appraise the groundwater fluoride removal effectiveness of Al-Fe oxide-infused diatomaceous earth (DE) in a continuous-flow fixed-bed column. The adsorbent was optimally synthesized and then characterized. A glass column designed for the experiment was packed with the test adsorbent at specific doses. The effects of flow rate, influent fluoride concentration and bed height (adsorbent dose) on fluoride removal were evaluated by fixing the value of a parameter while varying the others. The breakthrough volume was the volume of treated water obtained until the concentration of fluoride in the treated water reached 1.5 mg/L, which is the World Health Organization’s maximum limit of fluoride in drinking water. The maximum breakthrough volume obtained in this study was 118.2 mL under the optimum conditions of influent F− concentration = 5 mg/L, 1 g of adsorbent with an initial bed height = 7.5 cm and a flow rate = 1.97 mL/min. Channeling and the presence of PO43− as a co-existing anion were limiting factors for the attainment of the breakthrough volume for groundwater defluoridation. Further work is encouraged to investigate a suitable binder that can hold the adsorbent particles firmly together, is not water-soluble, but remains water-permeable when dry. The resulting solid mass could then be pulverized into granules whose weight and rigidity would make them less susceptible to the channeling effect in the column

Optimization of Silica Extraction from Diatomaceous Earth using the Central Composite Design of Response Surface Methodology

ABSTRACT This work evaluated the extraction efficiency of silica from diatomaceous earth (DE) by conventional solvent extraction (CSE) and ultrasound-assisted extraction (UAE) under basic and acidic (HCl) conditions utilizing response surface methodology (RSM). A common statistical model was used to get the best percentage yield and percentage purity using RSM. Experimental parameters such as stirring time, NaOH concentration (for CSE), sonication time, NaOH/HCl concentration, cycle and amplitude (for UAE methods) were optimized using central composite design (CCD). The analytical responses, that is, percentage yield and percentage purity, were analyzed using ANOVA and regression analysis. The linear coefficient of determination, R2, was high and precise. The overall yield and purity were highest for the UAE method under acid condition (pH 1-2, approximately), making it the most effective silica extraction method from DE. For this method, the optimal conditions for extracting Si from DE were 2 h of sonication, 220 mL of 2.82 M HCl as a leaching/extracting medium, 0.524 cycles and 72.6 % of amplitude. Under these conditions, 82 % of silica was yielded with a purity of about 95 %. The experimental results indicate that high-quality silica can be produced from DE in high yield so that DE can be an alternative silica source. Keywords: Diatomaceous earth, silica, response surface methodology, ultrasound-assisted extraction, conventional solvent extraction.</jats:p

Effects of calcination temperature and solution pH on the defluoridation potential of Al/Fe oxide-modified diatomaceous earth: metal leaching and sorbent reuse

An evaluation of the effects of calcination temperature and solution pH on the fluoride removal capacity of Al/Fe oxide-modified diatomaceous earth was carried out. The sorbent was observed to be most effective and stable within the pH range 6.70–8.12, where the lowest concentrations of Al and Fe (&amp;lt;1 mg/L) in treated water were recorded. Thus, sorbent loss was minimal at that pH range. It was observed that the sorbent lost its efficiency and stability at calcination temperatures above 600 °C. Inductively coupled plasma-mass spectrometer analysis of metals in supernatants and thermogravimetric analysis of the sorbent showed that there was substantive loss of Al and Fe from the sorbent at temperatures above 600 °C because of evaporation. K2SO4 solution proved to be the best regenerant for spent sorbent compared to NaOH and Na2CO3, which caused sorbent loss owing to high solution pH. The CO32– from Na2CO3 bound to regenerated sorbent so much that it could not be displaced by fluoride during subsequent defluoridation experiments. Sorbent regenerated with 0.1 M K2SO4 solution could reduce 10 mg/L fluoride in artificial water at a dosage of 0.8 g/100 mL by 81.8% and 67.2% at the second and third cycles, respectively.</jats:p

Enhancing the Fluoride Adsorption Efficiency of Diatomaceous Earth Through Modification with Ce/Al/Fe Metal Oxides

Sustainable Development Goal 6.1 calls for the development of technologies to improve water quality for human consumption to ensure that there is clean drinking water for everyone by 2030. This study aims to contribute to the goal by synthesizing Ce/Al/Fe metal oxide-modified diatomaceous earth for the adsorption of fluoride from drinking water. Adsorption experiments were performed to determine the effectiveness of the Ce/Al/Fe metal oxide-modified diatomaceous earth in regard to fluoride adsorption. About 98% fluoride removal efficiency was obtained from an initial fluoride concentration of 5 mg/L, using a 0.6 g/100 mL adsorbent dosage, at an initial pH range from 4 to 10, after 50 min agitation time. The adsorption kinetics models revealed that fluoride adsorption occurred via chemisorption, while the isotherm models confirmed both monolayer and multilayer adsorption. Thermodynamic studies showed that the adsorption process was spontaneous, endothermic, and random, as denoted by the negative &Delta;G&deg;, positive &Delta;H&deg;, and positive &Delta;S&deg;, respectively. Regeneration studies showed that Ce/Al/Fe metal oxide-modified diatomaceous earth can be reused for eight successive regeneration&ndash;reuse cycles. This study revealed that the modification of diatomaceous earth with Ce/Al/Fe metal oxides enhances its fluoride adsorption capacity and that it is suitable for use in the defluoridation of groundwater