Reducing the environmental footprint of cement is an absolute necessity to meet the commitments of COP26 and to limit global warming to + 1.5°C compared to the pre-industrial level. In this context, particular interest has developed in recent years in the use of calcined clays as supplementary cementitious materials (SCMs). Due to their high reactivity, large reserves and homogeneous distribution on the earth's surface, calcined clays represent a viable alternative to conventional SCMs. Clay minerals are highly variable and numerous, each with their own characteristics. As a result, not all of them have potential for use as SCMs. The present paper investigated the use of palygorskite (a clay that has been relatively poorly studied) as an SCM. Two commercial palygorskites of different grades were selected and their calcination was studied by X-ray diffraction and pozzolanic activity tests. Blended cements incorporating 20% of each calcined palygorskite were prepared and the mechanical performance and resistivity of the mortars measured. The results show that the optimum calcination temperature is 800°C (allowing complete amorphization of the clay fraction and the highest pozzolanic reactivity) for both clays. Mortars made with 80% ordinary Portland cement (OPC) blended with 20% of 800°C calcined palygorskite allowed a significant increase in compressive strength and electrical resistivity compared to the reference (100% OPC). The clay sample with palygorskite as the dominant mineral exhibited the greatest pozzolanic reactivity and mechanical performance in cementitious systems, confirming that palygorskite is a clay mineral with a significant potential for a use as a SCM. The second sample with smaller palygorskite content also allowed a significant increase in mechanical performance. This demonstrated that it is not necessary to use high-purity samples and enhances the value of this type of material.

High temperature and a large salt content weaken the surface hydration ability of clay particles in drilling fluid, reduce zeta potential, agglomerate clay particles, increase particle size, and destroy the stability of drilling mud. A filtrate reducer is required, therefore, to maintain the zeta potential of the clay, prevent the agglomeration of clay particles, and maintain good performance of the drilling mud at high temperature and high salt content. To prepare temperature- and salt-resistant polymer filtrate reducer, a betaine monomer was synthesized and copolymerized with a conventional monomer. A betaine monomer 3-(dimethyl (4-vinyl benzyl) ammonia) propyl sulfonate (DVBAPS) was synthesized and then used to create a copolymer filtrate reducer. The copolymer filtrate reducer, referred to as PAAAND, was prepared by free radical copolymerization with 2-acrylamide-2-methylpropane sulfonic acid, acrylic acid, N-vinyl pyrrolidone, acrylamide, and DVBAPS. The optimum synthesis conditions were determined by single factor evaluation, and the chemical structure of the PAAAND was confirmed by Fourier-transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy. Results from particle-size distribution and zeta-potential measurements showed that PAAAND increased the zeta potential of clay particles and the distribution width of particles size, which served to maintain the stability of the drilling mud under high-temperature and high-salt conditions. The results of scanning electron microscopy showed that PAAAND made the filter cake formed by clay particles smoother and denser, which reduced filtration loss. The reduction in filtrate loss continued even after aging at high temperature, and, thus, PAAAND performed better than commercial products.

The formation of 2:1 and 1:1 phyllosilicates in Fe–Si–O–H systems occurs in various geological and engineering settings; however, the identification and characterization of these minerals is very challenging due to the limited amount that is accessible, the very small particle size, and often the large degree of heterogeneity of these samples. To overcome these drawbacks, the synthesis of iron-rich phyllosilicates was attempted in this study with an initial Fe/Si molar ratio ranging from 0.50 to 2.33. The synthesis was performed at 150°C under hydrothermal conditions over a period of 7 days. Synthesis products were characterized by X-ray diffraction and fluorescence, by infrared, Raman, and Mössbauer spectroscopies, and by transmission electron microscopy. Results revealed that the stability field of the 2:1 clay mineral was wider than that of the 1:1 clay mineral. The 2:1 clay mineral was less sensitive to redox conditions compared to the 1:1 clay mineral. In addition, a heterogeneity of phases formed (iron oxides, nontronite, cronstedtite, or greenalite) was identified.

South Africa is a net importer of fertilizer products, importing all of its potassium, as well as 60–70% of its nitrogen requirements. Thus, domestic prices are impacted significantly by international prices, shipping costs, and exchange rates. Producing these fertilizers locally would be far more economical. Phlogopite, a rich source of potassium, is discarded in large quantities during mining operations; the objective of the present study, therefore, was to determine the acid-leaching characteristics and behavior of phlogopite as a means of releasing potassium. Phlogopite samples were leached with nitric acid (source of nitrogen for fertilizers) at various concentrations, temperatures, and reaction times. The feed phlogopite and leached residue samples corresponding to conversions of 14% (LP1), 44% (LP2), and 100% (LP3) were collected and analyzed using X-ray fluorescence spectroscopy (XRF), X-ray diffractometry (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), Brunauer–Emmett–Teller surface area and porosity analysis (BET), thermogravimetric analysis (TGA), and field emission gun-scanning electron microscopy (FEG-SEM). The feed phlogopite was highly crystalline. The absence of defects in the lattice meant that the motion of H+ atoms penetrating into the lattice was restricted, suggesting internal diffusion-controlled leaching. Furthermore, results obtained from the various analytical techniques corroborated each other in terms of the release of cations during leaching. All leaching experiments were conducted batchwise, in a closed system. The gravimetric data from the experiments were used to identify a suitable model which predicts accurately the leaching behavior. The reaction was found to be internal diffusion-controlled, and the D1 model, which represents one-dimensional diffusion through a flat plate, predicts the leaching behavior most accurately. The observed activation energies (Ea) and pre-exponential constants (k0) varied with initial nitric acid concentration ([H+]0).

The compressibility behavior of clays is governed by the electrical double layer formed around the clay particles. The Gouy-Chapman diffuse double layer theory is often utilized to predict the compressibility behavior of clay minerals. The theory does not consider the effect of the size of the cations, however, and thus predicts unrealistically small void ratios for compacted bentonites under large mechanical pressures expected in high-level nuclear waste-repository applications. In this study, the Stern layer was introduced to incorporate the cation size effect in the prediction of the compressibility behavior of bentonites. The overall diffuse double-layer thickness at large pressures was much smaller than the initially assumed Stern layer thickness based on the exchangeable cation size for all the bentonites studied. A compressible Stern layer was, therefore, considered for the first time in the prediction of the compressibility behavior of bentonites. The compression behavior of the Stern layer under the applied loading is influenced by the ratio of the mid-plane to the Stern potential, which is dependent on the type and composition of the exchangeable cations on the clay surface. Stern layer compression was initiated when the potential ratio was in the range 0.65–0.75 for bentonites with various surface cation characteristics. The incorporation of cation size and a compressible Stern layer provided significant improvements over the existing models in predicting the compressibility behavior of bentonites over a wide pressure range. The compressibility data predicted by the proposed model showed very good agreement with the data measured for five bentonites from the literature in the pressure range 0.1–42 MPa.

Hydrothermal solutions related to magmatic intrusions that occurred during the Oligo-Miocene resulted in advanced multi-stage alterations and, to varying degrees, kaolinization over a wide area of the Biga Peninsula. The most important formations in these kaolin deposits occurred along the NE–SW-trending Çan-Etili-Bayramiç fault zone. The Bahadırlı, Duman, and Çaltıkara quarries are well preserved kaolin deposits throughout these fault zones located within the Çan Volcanics. Mineralogical, geochemical, and isotopic analyses were performed to identify the environments of formation of kaolins and the origin of the hydrothermal solution that led to the formation of these deposits.

The mineralogical assemblages of each of the quarries differ from each other. The Bahadırlı kaolin quarry comprises kaolinite + alunite ± quartz ± smectite ± plagioclase ± K-feldspar. The Çaltıkara kaolin deposits consist of kaolinite + quartz + alunite ± iron-oxide and ore minerals. The Duman kaolin quarry was considered in two different slopes as a hanging wall block and a footwall block, and the blocks contain kaolinite + quartz + plagioclase ± smectite and kaolinite ± alunite ± smectite ± quartz ± plagioclase ± K-Feldspar ± gypsum, respectively. During petrographic investigations, it was observed that kaolinization occurred generally in K-feldspar and plagioclase phenocrysts and partially in the matrix. Mineralogical and micromorphological investigations revealed that the kaolin group includes the dioctahedral minerals kaolinite and halloysite. According to the trace element contents of the kaolinites, the Çaltıkara and Bahadırlı deposits had a hypogene origin, while the Duman deposit had a supergene origin. δ18O isotopic values of kaolinites ranged from +10.3 to +18.3‰. δ34S isotopic values ranged from –17.2 to +20.2‰ of alunite, galena, and pyrite minerals, which indicate different formation environments for the kaolin quarries. 40Ar/39Ar dating of alunite revealed that the timing of acid-sulfate alteration was compatible with the magmatic intrusions. All these data revealed the mineralogical, chemical, and isotopic differences caused by the effect of different hydrothermal processes in three kaolin deposits located on the same fault zone, close to each other and similar in age.

Clays and clay minerals dissolve over a broad pH range, such as during sediment diagenesis and in a variety of applications, including nuclear waste storage, landfills, and geopolymer binders in the construction industry. The solubility depends on process parameters (pH, temperature, pressure, etc.) and material properties (phase content, clay mineral composition, particle size, etc.). Pretreatments such as calcination or severe grinding change the material properties and could enhance solubility, which is called activation. The aim of the current study was to determine the solubility of three different clay minerals after calcination (metakaolinite, metamontmorillonite, and metaillite) in high molar alkaline solutions (NaOH) up to 10.79 mol/L and pH = 14.73. Furthermore, the solubility of an Al(OH)3 powder in alkaline solution (NaOH) was analyzed, as it can be used to adjust the Si:Al ratio of geopolymer precursors. The residues of the clay minerals after the alkaline treatment were investigated to disclose potential alterations in their phase contents. Based on the results of the thermal and alkaline activation, conclusions about the suitability as geopolymer precursors were made. All clay minerals showed an increase in solubility proportional to the concentration of the alkaline solution. The solubility decreased in the order metakaolinite > metamontmorillonite > metaillite. Thereby, dissolution was incomplete for all three clay minerals (<90%) after 7 days and congruent for metakaolinite and metaillite but incongruent for metamontmorillonite.

Clay minerals in Gamalama volcanic soil have not yet been identified thoroughly. The soil is estimated to contain nanoscale natural clays, such as halloysite or imogolite. The occurrence of nanoclays in the soil will support the development of many applications in nanotechnologies from nature. The objective of the present study was to characterize soil samples from five different locations around the volcano at three different depths from the soil surface. A total of 50 g of dry soil sample was stirred slowly in 300 mL of distilled water. Stirring was stopped after the addition of 10 mL of 30% H2O2 and then allowed to stand for 24 h. The small floating particles with dimensions of <2 μm were separated from the mixture and collected using a centrifuge at 4000 rpm (1790×g) for 30 min. About 5 g of solid sample was obtained for further characterization. X-ray diffraction results showed the presence of halloysite, allophane, and kaolinite. Morphology analysis by scanning and transmission electron microscopy of some representative samples showed short tubes 10–20 nm in diameter and 50–100 nm long with the halloysite structure. Halloysite was found at 70 cm depth from the soil surface at almost all locations. The surface area determined by the surface area analyzer using the BET equation was as much as 112.51 m2/g. This surface area is thought to be the largest ever determined for a natural nanoclay, paving the way for future application as catalytic or photocatalytic-supporting materials.

Compacted bentonite–sand mixture is proposed widely as backfill in geological repositories for disposal of radioactive waste in many countries because this material has significant swelling capacity and low water permeability. Development of the swelling pressure of backfills upon hydration is related closely to the stability of the host rock in the geological repository. No systematic experimental studies have been carried out to explore the effect of a water phase on the swelling pressure and water retention of bentonite–sand mixtures with insignificant osmotic suction. The objective of the current study was to examine experimentally the influence of a water phase involving liquid water and water vapor on swelling pressure and water retention of a bentonite–sand mixture with insignificant osmotic suction. Swelling-pressure tests with suction control and water-retention measurements under constant-volume conditions were performed on the compacted bentonite–sand mixture with a dry density of 1.80 g/cm3. Osmotic and vapor equilibrium techniques were used to make identical specimens adsorb liquid water and water vapor, respectively. The experimental results showed that the water phase had almost no effect on the swelling-pressure patterns of the unsaturated bentonite–sand mixture upon hydration over a suction range from 27 to 3 MPa. The swelling pressure increased significantly with decreasing suction from 27 to 3 MPa, regardless of the mixture adsorbing either the liquid water or water vapor. Nevertheless, the water phase had a considerable impact on both the swelling pressure and water retention of the unsaturated bentonite–sand mixture upon hydration over the same suction range. For a given value of suction in the range above, the swelling pressure and the water content of the bentonite–sand upon adsorption of liquid water were greater than those upon adsorption of water vapor. The influence of the water phase on the swelling pressure and the water retention of the bentonite–sand mixture with insignificant osmotic suction is related mainly to the hydration or swelling mechanism of Ca-rich bentonite.

Clays are abundant materials in the Amazon region and have been used historically by ancient Amazonian people to produce ceramic and cosmetics products. The current study aimed to evaluate the potential of four clays from the metropolitan area of Manaus, each with a different color, for cosmetics applications. Two clays were collected in the Ponta Negra region (red and gray in color) in Manaus, one in Careiro (white), and one in Itacoatiara (black). After drying in an oven for 24 h at 105°C, the four clays were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), infrared (IR) spectroscopy, thermogravimetry (TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), particle-size analysis, and detection of microorganisms. The amounts of Al, Si, Cl, K, Ca, Ti, Cr, Fe, Zn, P, and S in all samples were below the limits for use in cosmetics. The main phases identified were kaolinite 1A, quartz, gibbsite, and the rare kaolinite 2M. Approximately 40 wt.% of each sample was in the < 20 μm particle-size range. Analyses by SEM revealed pseudo-hexagonal kaolinite structures with nano-islands and nanocrystallites. The low toxicity, mineralogic compositions, and particle-size findings suggest that Amazonian clays are promising for cosmetics applications.

Removing trace water from oil is an important industrial process and is commonly accomplished using vacuum filtration. The drawbacks of this method, however, are: poor efficiency, large oil loss, and significant energy consumption. The objective of the current study was to develop a better system to solve these problems using a sodium polyacrylate (PAA-Na)-modified bentonite as the dehydrating agent and, for the first time, to apply it to transformer oil. PAA-Na was prepared by aqueous solution polymerization. A dehydration test was carried out to determine the optimum addition of PAA-Na, and the highest dehydration rate of 76.5% was obtained with the addition of 20 wt.% PAA-Na. The steady dehydration rate of the PAA-Na-modified bentonite was better than that of other adsorbents (calcium chloride, zeolite 5A, unmodified bentonite). The process of adsorbing saturated water vapor on PAA-Na modified bentonite was studied and interpreted from the aspects of adsorption isotherms and thermodynamic properties. The results showed that the adsorption isotherm data followed the Freundlich isotherm model and the thermodynamic parameters indicated that the process was endothermic. Fourier-transform infrared spectroscopy results revealed that PAA-Na was synthesized successfully and it had a huge proportion of hydrophilic groups. According to thermogravimetric analysis, the PAA-Na-modified bentonite was stable up to 200°C, giving a flexible region for pretreatment and regeneration. X-ray diffraction showed no change in the diffraction pattern before and after modification. Moreover, considering the results of scanning electron microscopy and surface-area analyses, one may safely say that PAA-Na was distributed homogeneously on the surface of the bentonite. In addition, PAA-Na-modified bentonite exhibited a high dehydration rate in xylene, naphtha, and diesel, indicating a broad range of applications.

Differences in the properties of clay minerals cause formation damage under the condition of thermal production in heavy-oil reservoirs; asphaltenes adsorbed on clay minerals exacerbate the formation damage. The purpose of the present study was to reveal the variation in clay minerals and the adsorption behavior of asphaltenes on clay mineral surfaces under thermal recovery conditions. Volume changes and transformations of typical clay minerals were studied under various conditions (80 and 180°C, pH 9 and 11, aqueous and oven-dry conditions). On this basis, the adsorption behavior and mechanism of asphaltenes on the surfaces of clay minerals in various simulated conditions were investigated. The adsorption mechanism was revealed using kinetics and isothermal adsorption models. The results showed that the volume of montmorillonite expanded by up to 159.13% after water–rock interaction at 180°C with pH 11; meanwhile, the conversion rates of kaolinite and illite to montmorillonite were 6.6 and 7.8%, respectively. The water–rock interaction intensified the volume changes and transformations of clay minerals under thermal conditions. The amounts of asphaltene adsorbed on clay minerals at 180°C were greater than those at 80°C. The adsorption process of asphaltenes was inhibited under aqueous conditions. The abilities of the constituent minerals to bind asphaltenes was in order: montmorillonite > chlorite > kaolinite > illite > quartz sand. The adsorption process of asphaltenes yielded high coefficients of regression with both the Freundlich and Langmuir models under oven-dry (>0.99) and aqueous (>0.98) conditions. At 180°C under aqueous conditions, the water film significantly inhibited the adsorption of asphaltene on the clay minerals. The adsorption process of asphaltenes, therefore, could be regarded as the adsorption occurring at lower concentrations under oven-dry conditions.

In order to develop high-performance adsorbents to remove toxic methylene blue (MB) from wastewater, palygorskite (Plg) was utilized as a template to prepare palygorskite/carbon (Plg/C) composites by using a hydrothermal reaction in the presence of glucose. The porous Plg/C composites were then activated with ZnCl2. The effects of the dose of the activator and the activation temperature on the crystal structure, micro-morphology, specific surface area, and adsorption performance of the porous Plg/C composites were studied systematically here. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicated that the crystal structure of Plg was destroyed during the activation process and irregular porous carbon was closely attached to the residual aluminosilicate skeleton. The activation was optimized at 400°C with a ZnCl2:Plg/C impregnation ratio of 2:1. The sample had a specific surface area of 1497.88 m2/g, together with a total pore volume and micropore volume of 1.0355 and 0.5464 cm3/g, respectively. The MB adsorption capacity was 381.04 mg/g. Such inexpensive, high-performance, porous Plg/C composites could find potential applications in wastewater treatment.

Montmorillonite (Mnt)-based solid acids have a wide range of applications in catalysis and adsorption of pollutants. For such solid acids, the acidic characteristic often plays a significant role in these applications. The objective of the current study was to examine the effects of H3PO4-activation and supporting WO3 on the textural structure and surface acidic properties of Mnt. The Mnt-based solid acid materials were prepared by H3PO4 treatment and an impregnation method with a solution of ammonium metatungstate (AMT) and were examined as catalysts in the dehydration of glycerol to acrolein. The catalysts were characterized by nitrogen adsorption-desorption, powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultraviolet-visible (DR UV-Vis) spectroscopy, temperature programmed desorption of NH3 (NH3-TPD), diffuse reflectance Fourier-transform infrared (DR FTIR) spectroscopy of adsorbed pyridine, and thermogravimetric (TG) analyses. The phosphoric acid treatment of Mnt created Brönsted and Lewis acid sites and led to increases in specific surface areas, porosity, and acidity. WO3 species influenced total acidity, acid strength, the numbers of Brönsted and Lewis acid sites, and catalytic performances. A high turnover frequency (TOF) value (31.2 h−1) based on a maximal 60.7% yield of acrolein was reached. The correlation of acrolein yield with acidic properties indicated that the cooperative role of Brönsted and Lewis acid sites was beneficial to the formation of acrolein and a little coke deposition (<3.3 wt.%). This work provides a new idea for the design of solid acid catalysts with cooperative Brönsted and Lewis acidity for the dehydration of glycerol.

Smectites are a group of minerals traditionally analyzed by thermal methods due to their exceptionally large adsorbed-water contents and the presence of OH groups, which makes them unique among all common soil- and rock-forming minerals. The dehydration reaction of smectite is a low-temperature endothermic effect that ends typically below 200°C. Although the removal of bulk interlayer water requires activation energy (Ea) of just above 30 kJ/mol, the removal of the last few H2O molecules attached strongly to interlayer cations requires Ea > 100 kJ/mol. Dehydroxylation is the loss of structural OH groups that proceeds as evolution of H2O molecules out of the smectite structure and occurs in the 300–900°C range. In trioctahedral species, dehydroxylation is combined with recrystallization and proceeds usually at > 700°C. In dioctahedral species, the temperature of dehydroxylation is controlled by the type of octahedral vacancy, having trans-vacant and cis-vacant distinguished by the boundary at ~ 600°C, and by the octahedral cation–OH bond strength, following the order Mg > Al > Fe. The Ea of dehydroxylation correlates linearly with the temperature of maximum dehydroxylation; from > 170 kJ/mol for Cs+-exchanged beidellite and nontronite, through ~ 300 kJ/mol in Mg-rich montmorillonite, to > 500 kJ/mol in trioctahedral saponite. Dehydration and dehydroxylation of smectites can be accompanied by a number of other phenomena, such as dehydrogenation or defluorination. At high temperatures, smectite amorphization and recrystallization occurs. Unless amorphized and/or recrystallized, smectites can undergo rehydration and rehydroxylation, which are opposite reactions to dehydration and dehydroxylation, respectively. This review discusses the details of the above-mentioned thermal reactions of smectites, focusing on thermogravimetric methods, evolved gas analysis, and structural alterations. Factors affecting the accuracy and precision of thermal analysis of smectite are discussed along with examples of best laboratory practices. The paper also provides the most recent description and critical evaluation of smectite reaction kinetics.

Many kaolinites are known to exhibit limited intercalation capacity which affects their usage. Some reports have linked this lack of reactivity to particular structural features or to slow kinetics; others recommended increasing intercalation temperature as a remedy. The purpose of the current study was to investigate systematically the N-methylformamide (NMF) intercalation capacity of three kaolinites differing in layer stacking order (KGa-1b, KGa-2, and Imerys Hywite Alum) in the 5–150°C temperature range. Near-infrared spectroscopy (NIR) was employed to record the full kinetics of intercalation in closed systems with excess NMF. Increasing intercalation temperature accelerated the reaction, but the NMF uptake decreased and eventually vanished. Complementary thermogravimetric analysis (TGA) confirmed this unexpected trend. All kaolinites exhibited the same behavior, but the amount of inert material was in the order of their stacking-fault concentration at all temperatures: KGa-2 > Hywite > KGa-1b. Subjecting the samples to stepwise temperature changes showed that, once intercalated, the NMF could not deintercalate and was removed from equilibrium with the surrounding fluid. Thus, intercalation capacity was not a unique feature of the material because it depended on thermal history. As stacking order and thermal history had no detectable effect on the NMF-hosting environment, the unusual temperature dependence was attributed tentatively to the adverse effect of temperature on the adsorption of NMF on the edges of the crystallites, which is a prerequisite for intercalation.

Glauconites occurring within the Ukra Member of Kutch Basin have remained unexplored in terms of their economic significance. The present study aimed to present a detailed physicochemical characterization of glauconite occurring in the siliciclastic rocks of Guneri and Umarsar area of the Kutch district, Gujarat, India to explore their economic potential. The study involved an integrated petrographical, mineralogical, and geochemical investigation of glauconitic rocks to highlight the occurrence, nature, and maturity of glauconite. The characterization was carried out using X-ray diffraction (XRD), X-ray fluorescence (XRF), and electron probe microanalysis (EPMA) combined with energy dispersive X-ray (EDX), Field emission gun scanning electron microscopy (FEG-SEM), Fourier-transform infrared spectroscopy (FTIR), and inductively coupled plasma mass spectroscopy (ICP-MS). Petrographic and bulk XRD analysis revealed that the glauconite occurs as green pellets constituting ~30 and 40% of the glauconitic sandstone and shale, respectively. Whole-rock analysis showed that the value of K2O varies considerably from 3.93 wt.% (sandstone) to 5.63 wt.% (shale). Mineral chemistry indicated the distinctive chemical composition of glauconite pellets containing 7.4–8.4 wt.% of K2O. The parameters, such as the distance between the (001) and (020) peaks and the large K2O content (~8 wt.%) of the glauconite fraction reflect an evolved to highly evolved stage of maturation. The morphological and spectral signatures further support the high degree of maturation in glauconites. Trace-element analysis implied that the glauconitic sandstone and shale contain elements such as Zn, Mn, Cu, Co, Mo, and Ni, which serve as essential micronutrients for plants. These data sets collectively constitute part of a preliminary study which is prerequisite to beneficiation, but further evaluation of its potential as a potash fertilizer also is needed.