Mineralogical and Chemical Characteristics of Raw and Modified Clays and Their Application in Arsenic and Fluoride Removal: Review

Clay and clay minerals have always been used since the ancient times for making ceramic materials and also as a building material. Over the past decades, there has been a growing trend in their applicability in different areas such as industries, environmental remediation and water treatment sectors. The growing trend is mainly associated with the fact that they are chemically and mechanically stable, have higher specific surface area and cation exchange capacity. Furthermore, clays can be modified to improve their functionalities in different sectors. In this chapter, we present a review of the structural, mineralogical and chemical properties of clay and the effect of surface modification in their structures. We further looked at their applicability in arsenic and fluoride removal in their raw and also in their modified form. Although the literature showed that modified clay minerals yields higher adsorption capacity as compared to raw clays little nothing has been reported yet in relation to the cost of modifying clays with chemical species. As such new studies should also elaborate on the cost effectiveness of modifying clay minerals with chemical species

Hydrothermal Conversion of South African Coal Fly Ash into Pure Phase Zeolite Na‐P1

South African coal combustion power utilities generate huge amounts of coal fly ash that can be beneficiated into zeolitic products. This chapter reports on the optimization of the presynthesis and synthesis conditions for a pure‐phase zeolite Na‐P1 from selected South African coal fly ashes. The hydrothermal treatment time, temperature, and molar quantities of water during the hydrothermal treatment step were successfully optimized. The optimum hydrothermal treatment time and temperature were 48 h and 140°C, respectively. Pure‐phase zeolite Na‐P1 was obtained with a molar regime of 1 SiO2:0.36 Al2O3:0.59 NaOH:0.49 H2O at an aging temperature of 47°C for 48 h. The optimized conditions were applied to two fly ashes from two coal‐fired power utilities, and high‐purity zeolite Na‐P1 was obtained. The third coal fly ash with a different chemical composition gave a low‐quality Na‐P1 under the optimized conditions. The cation exchange capacity for the high‐purity zeolite phase was 4.11 mEq/g, indicating that the adjustment of reactant composition and presynthesis or synthesis parameters leads to yields of high‐quality zeolite Na‐P1. The results also show that conversion of the coal fly ash into high‐purity zeolite also depends on the chemical and mineralogical composition of the coal fly ash

Chemical Partitioning and Mobility of Trace Elements in Dry Disposed Weathered Ash Conditioned with High-Saline Effluents

Weinvestigated the mobility of inorganic elements in the ash dump due to chemical interaction of weathered dry disposed ash conditioned with high-saline effluents and ingressed CO2 from atmosphere and percolating rainwater. Drilled ash core samples collected from dry disposed ash dump at a South African coal-burning power station were characterized using X-ray diffraction (XRD) and X-ray fluorescence (XRF) analyses. A modified sequential extraction procedure was selected to determine the mineralogical association of the investigated elements in the 1-year-old drilled ash cores. Major mineral phases are quartz and mullite and other minor phases included hematite, lime, calcite, anorthite, mica, and enstatite. Mica and calcite in the ash cores is attributed to carbonation process, which led to long-term reduction in pore water pH. The 2-week-old ash cores are sialic but the 1-year-old ash cores were both sialic and ferrocalsialic in chemical composition. The ferrocalsialic nature of 1-year-old ash cores could be attributed to drastic changes in feed coal in the power station. The chemical index of alteration (CIA) and chemical index of weathering (CIW) values suggest a relatively high degree of weathering. The changes in CIA and CIW values in the ash cores depend on the pore water pH, leaching rate, carbonation process, and possibly the conversion of the alkali and alkali earth metals into carbonates. Multivariate analysis results suggest that the major oxides and carbon percent show differences and have a greater contribution to the differentiation in the 1-year-old ash cores. Trace elements such as Mo, Cr, and Se show high mobility but As, B, and Pb exhibit fairly low mobility in the water-soluble fraction. Aconsiderable mobility of trace elements in the exchangeable and carbonate fractions is attributed to the alkaline nature and pore water pH. A decreasing response of As, Mo, Cr, and Pb in the reducible fraction with depth suggests immobility attributed to coprecipitation with the Fe- and Mn-oxide phases. On the contrary, the increasing response of Pb, Mo, and B in the carbonate fraction with depth implies mobility due to dissolution and flushing of soluble major chemical phases, as evident in the pore water pH. A considerable amount of B and Pb are concentrated in the residual fraction of 1-year-old ash cores. This suggests that, under natural settings, these elements will not be released in solution over a long time; therefore, they are not considered to be an environmental risk

A Geochemical Analytical Scheme for the Appraisal of Partitioning and Mobility of Major elements in Weathered Dry Disposed Coal Fly Ash

South Africa is endowed with significant deposits of coal which is utilized in electricity generation to meet the nation’s energy demand. A large volume of waste solid residue from the combustion of pulverized feed coal in power stations is dry disposed in stock piles or dumps. Chemical interactions of dry disposed fly ash with ingressed CO2 from the atmosphere and infiltrating rain water would cause dissolution of the soluble components in the fly ash matrix. Chemical partitioning and mobility of major elements in samples from cores drilled into serially stacked weathered dry disposed fly ash were investigated using a modified five steps sequential extraction scheme. A total acid digestion was carried out on the original ash core samples prior to extraction to validate the extraction procedure. The geochemical distribution of the investigated major elements in 59 drilled core samples was determined by x-ray fluorescence and inductively coupled plasma mass spectrometry. The relationship between SiO2 and chemical index of alteration (CIA) showed 8 year and 20-year-old core samples have a moderate to high degree of weathering. Conversely, 1-year-old cores samples showed characteristics between low and moderate-high degrees of weathering. A cluster and discriminant analysis of the major elements was also able to reveal the subtle chemical alteration differences of the core samples. Functional analysis revealed the disparities in the dissolution patterns of major soluble components in the matrix of the drilled core samples. Modified sequential extractions revealed high concentration of the major species in the leachates for every mineralogical fraction; although the bulk of the major elements are locked up in the insoluble phase of the core samples (i.e. residual fraction) which would not be released under normal environmental conditions. It is noteworthy that the concentration of major elements in the labile fractions (water soluble + exchangeable + carbonate) was high and this has implications for the long-term durability of residual mineral phases. Relative enrichment and depletion trends of major elements are promoted by heterogeneity in the ash dump (i.e. moisture content), gradual reduction of pore water pH and continuous brine and water irrigation.Key words: Coal fly ash; Weathering; Sequential extraction scheme; Cluster analysis; Factor Analysis

Mineralogy and Geochemical Appraisal of Paleo-Redox Indicators in Maastrichtian Outcrop Shales of Mamu Formation, Anambra Basin, Nigeria

The Mamu Formation exhibits two types of shales, viz. grey and dark shales. The geochemical and mineralogical compositions of these shales were investigated using X-ray fluorescence (XRF) and Laser Ablation- Inductively Coupled Plasma Spectrometry (LA-ICPMS) and X-ray diffraction techniques. The basal part of the section is characterized by presence of quartz and kaolinite as the major crystalline minerals with minor quantity of hematite. The presence of hematite in the basal part of the shale sequence suggests oxidizing diagenetic environment of deposition. The second geochemically specific interval (upper part) is characterised by quartz and kaolinite as major crystalline minerals with traces of halloysite and grossite. The ternary plot of these major elements indicates the majority of shale samples examined are variably enriched with SiO2 relative to Al2O3 and CaO. The positive correlations of K2O, TiO2, and Na2O, with Al2O3 indicate that these elements are associated entirely with detrital phases. Some trace elements such as Cr, Ni, and V are positively correlated with Al2O3 which suggest that these elements may be bound in clay minerals and concentrated during weathering. The K2O/Al2O3 ratio is close to the lower limit of clay mineral range, which suggests that kaolinite is the dominant clay minerals. The Al2O3/TiO2 and low Cr/Ni ratios suggest that felsic components were the main components among the basement complex source rocks. The geochemical indices such as Th/Cr, Cr/Th, Th/Co and Th/Cr ratios suggest that these shales were derived from felsic source rocks. The chemical index of alteration values indicates that these shales have experienced strong chemical weathering at the source area. In addition, the depletion of Na and Ca also illustrates an intense chemical weathering of the source rocks. The mineralogical index of alteration values of the studied shale samples indicates an intense to extreme weathering of mineralogical components. The shale units exhibits different degrees of trace-element enrichment, with the approximate order of enrichment relative to an average shale being Co > Pb > Ni > Zr > Cu > Rb > V > Cr > Ba > V > Sr > U. The inverse correlation between Eh, pH, EC and TDS in outcrop Maastrichtian shale samples suggests well oxygenated environment of deposition. In addition, based on previously established thresholds, V/Cr, Ni/Co, Cu/Zn and U/Th ratios support that these shales were deposited under oxidizing diagenetic environment. Keywords: mineralogy, geochemistry, paleo-redox conditions, trace element enrichments, shales, Mamu Formation, Anambra basin, Nigeria

Geochemistry and mineralogy of the Campanian Sandstone of Lokoja-Basange Formation, Middle Niger Basin (Lokoja sub-basin), Nigeria: Implications for provenance, weathering, tectonic setting and paleo-redox condition

Twenty six road-cut sandstone samples from two lithological sections of Lokoja-Basange Formation in Middle Niger Basin (Lokoja sub-basin) situated by the side of Auchi-Igarra road (07º 07.201'N, 006º 13.011'E) were investigated using integrated mineralogical, geochemical and pore water chemistry studies. The medium to coarse grained sandstone bodies are poorly sorted suggestive of deposition in a low energy setting, probably in a shelf or floodplain. The observed variations in the sandstone colourations are attributed to the nature of the cementing materials. Based on the mineralogical composition, two specific geochemical intervals were established; the first interval revealed quartz and kaolinite as major crystalline minerals with traces of hematite. The second geochemical interval showed quartz and kaolinite as the major crystalline minerals with minor quantities of grossite and halloysite. The geochemical datasets obtained revealed mature, lithic arenites including sub-greywacke and protoquartzites. The inverse correlation between redox potential (Eh) and electrical conductivity (EC), total dissolved solids (TDS) and Mg (at 0.05 significant levels) suggest well oxygenated environment of deposition. The high chemical index of alteration (CIA), plagioclase index of alteration (PIA), and chemical index of weathering (CIW) indices revealed high detrital input dominated by intense chemical weathering. This process eventually led to the formation of clay minerals by hydration and leaching of all major cations, such as Ca+2, K+, and Na+, present in feldspar minerals. The average mineralogical index of alteration (MIA) values are indicative of intense to extreme weathering of mineralogical component of the detrital materials from the source areas. The studied sandstones samples are plotted in the field of the active and passive continental margin settings. The mean ratio of Ti/Zr also corroborates active and passive continental margin settings. The higher ratios of La/Y and La/Th and corresponding lower ratios of La/Co and Th/Co indicates felsic source rock. Moreover, the lower ratios of Ba/Sr, Cr/Zr, Ti/Zr and higher ratio of Zr/Y probably suggest felsic source rock. Based on the previously established thresholds, the low Cu/Zn ratios in the studied sandstone samples suggest deposition under oxidizing conditions. Keywords: Lokoja-Basange Formation, Middle Niger Basin, Mineralogy, Geochemistry, Pore water chemistry, provenance, tectonic setting, weathering, Redox proxy

Geochemical Partitioning of Major Elements in Brine Impacted Coal Fly Ash Residues

Fly ash-brine co-disposal technique has been considered as a way of disposing fly ash and brine (hyper-saline water) by some power stations in South Africa. This practice was aimed at using the fly ash to capture most of the elements in brine. However, the geochemical partitioning of the major elements in the waste materials after the fly ash-brine interaction has not been fully understood. This study focuses on understanding the geochemical partitioning of the major elements captured in the fly ash solid residues after the fly ash-brine interaction experiment. XRF and sequential extraction procedure were respectively applied to determine the chemical composition and partitioning of the major elements in fresh fly ash and the solid residues recovered after fly ash-brine interaction. The comparison of the results of the XRF analysis carried out on the fresh fly ash and the solid residues showed that the major elements such as Si, Ca, Mg and Na increased in the solid residues after the fly ash-brine interaction. This indicates that Ca, Mg and Na in the brine solution were captured by the fly ash during the interaction. However, the sequential extraction results showed that significant concentrations of Ca, Na and Mg were released into the water soluble, exchangeable and carbonate fractions. The results show that significant amounts of the elements captured in the fly ash solid residues during fly ash-brine interaction exist in the form which can be easily leached out when in contact with aqueous solution

An Investigative Study on the Chemical, Morphological and Mineralogical Alterations of Dry Disposed Fly Ash During Sequential Chemical Extraction

The hazardous elements associated with various physicochemical forms in coal fly ash are of environmental concern due to their leaching potential and subsequent contamination of surface and groundwater in the vicinity of the ash dump. Selective sequential extraction was performed on dry disposed fly ash samples from a coal-fired power station in Mpumalanga province, South Africa. The alteration of the chemical, morphological and mineralogical species of weathered fly ash during the selective sequential extraction was investigated using X-ray fluorescence (XRF), Nano-scan electron microscopy (NANOSEM) and X-ray powder diffraction (XRD). Insoluble residue from the water-soluble fraction is composed of amorphous alumino-silicate. The residues from exchangeable carbonate and Fe and Mn fractions consisted mostly of amorphous alumino-silicate spheres with a lesser quantity of iron-rich spheres. The iron-rich spheres are surrounded by amorphous alumino-silicate spheres.  The leaching behavior of trace metals (such as Ce, Y, Nb, Rb, U, and Tl) in weathered dry disposed fly ash was considered to have a dependency relationship with the components of SiO2, CaO, MgO, P2O5, and amount of unburned carbon. The decrease in the quantities of calcite with successive extraction could be considered as a marker of progress of sequential extraction technique. At the same time, the increase in the quantities of quartz could be also considered as an indicator of progress of the sequential extraction scheme. Trace elements bound to exchangeable or carbonate fraction during sequential chemical extraction were found associated with calcite. The elemental concentrations, as determined by electron dispersive x-ray spectroscopy (EDS), were consistent with XRF and XRD data. Therefore, the chemical extractant used in this study proved efficient for extraction of inorganic metals associated with various physicochemical forms in weathered fly ash.Key words: Coal fly ash; Selective sequential extraction; Major components; Trace elements; Morphology; Mineralogical compositio

Mobility and Transport of Inorganic Species in Weathered Hydraulic Disposed Coal Fly Ash: An Insight from Geochemical Fractionation and Statistical Evaluation

A large volume of coal fly ash generated through combustion process has raised environmental concerns due to possible release of potentially toxic species to the surface and groundwater systems. The chemical partitioning and mobility of elements in the hydraulic disposed ash dump was investigated using modified sequential extraction scheme. The geochemical distribution of the investigated elements in 33 drilled core samples was determined by x-ray fluorescence and inductively coupled plasma mass spectrometry. The ternary plot of major elements as determined by XRF showed that hydraulic disposed ash cores are sialic, ferrosialic and ferrocalsialic in chemical composition. The relationship between SiO2 and chemical index of alteration (CIA) showed low, moderate to high degree of weathering. These chemical compositions and degree of chemical weathering depend on the ash sampling point and ash interaction chemistry. The Na+ and K+ soluble salts showed evidence of leaching and downward migration in the water soluble fraction indicating that the hydraulic disposed ash dump is not a sustainable salt sink. The geochemical partitioning reveals that mobility and transport of potentially toxic metal species are governed by the pore water pH, ash interaction chemistry and the sampling point of the ash cores.  The chemical interaction of drilled core ash with the ingress CO2 and percolating rain water led to dissolution and co-precipitation of soluble major components in fly ash. This had led to incoherent patterns of elements in carbonate fraction of the ash cores.Key words: Modified sequential extraction; Hydraulic disposed ash; Chemical index of alteration; Pore water pH; Ash interaction chemistry; Moisture content; Chemical weatherin