Nanostructured aluminosilicate from fly ash: Potential approach in waste utilization for industrial and medical applications

Journal Pre-proof Nanostructured Aluminosilicate from Fly Ash: Potential Approach in Waste Utilization for Industrial and Medical Applications

Santheraleka Ramanathan, Subash C.B. Gopinath, M.K. Md Arshad, Prabakaran Poopalan PII:

S0959-6526(19)34793-6

DOI:

https://doi.org/10.1016/j.jclepro.2019.119923

Reference:

JCLP 119923

To appear in:

Journal of Cleaner Production

Received Date:

03 September 2019

Accepted Date:

28 December 2019

Please cite this article as: Santheraleka Ramanathan, Subash C.B. Gopinath, M.K. Md Arshad, Prabakaran Poopalan, Nanostructured Aluminosilicate from Fly Ash: Potential Approach in Waste Utilization for Industrial and Medical Applications, Journal of Cleaner Production (2019), https://doi. org/10.1016/j.jclepro.2019.119923

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Journal Pre-proof

Nanostructured Aluminosilicate from Fly Ash: Potential Approach in Waste Utilization for Industrial and Medical Applications

Santheraleka Ramanathan1, Subash C.B. Gopinath1,2*, M.K. Md Arshad3, Prabakaran Poopalan3

1Institute

of Nano Electronic Engineering, Universiti Malaysia Perlis, 01000 Kangar, Perlis, Malaysia. 2School of Bioprocess Engineering, Universiti Malaysia Perlis, 02600 Arau, Perlis, Malaysia. 3School of Microelectronic Engineering, Universiti Malaysia Perlis, Pauh Putra, 02600 Arau, Perlis, Malaysia.

Correspondence to: Asso. Prof. Dr. Subash C.B. Gopinath ([email protected]) 1

Journal Pre-proof Abstract Fly ash is found as a significant solid waste released from power plants to the atmosphere, but its qualitative and quantitative consumptions for the sustainability are ambiguous. The main issues aroused with the disposal of fly ash are the requirement of a large land area for landfills, cause toxicity and pollution to the soil and groundwater due to the accumulation of heavy metals. Although fly ash is highly recommended for soil amelioration and cement manufacturing, the ultimate usage of the solid waste causes unsatisfactory effect to the ground system and cementitious product, respectively. Apart from direct utilization and disposal of fly ash, it has been well reported in literature for the synthesis of nanosized particles due to its enrichment in silica, kaolin, iron, and alumina. With this regard, aluminosilicates have been acknowledged as one of the prospective nanocomposites synthesized from fly ash. It has proven that naturally occurring geopolymerization of fly ash under alkaline medium results is in the formation of aluminosilicates. As such, synthetic aluminosilicates were highly encouraged to extract from fly ash in large scale due to their excellent physiochemical properties and applications. This overview intends to fill-up the knowledge gap through critically reviewing about fly ash waste for the synthesis of aluminosilicate nanocomposite. The applications of fly ash derived aluminosilicates in industries such as wastewater treatment, agriculture system and as antioxidants are gleaned. Besides the heavy industrial potential, this review encompasses the prospective alternative consumption of fly ash for the production of nanostructured aluminosilicates and their comprehensive assessment in medical applications, especially in drug carrier and drug delivery systems, bone engineering, biosensors, hemodialysis, and intestinal therapeutics. Keywords: Nanocomposite; Waste management; Nanoparticle; Medical diagnosis; Industrial use; Burnt waste 1. Introduction Coal combustion being the primary source of fly ash releases in tons, is due to a huge consumption for energy resources. Additionally, agriculture activities, road embankments, and other combustion-based ventures release a tremendous amount of fly ash as the byproduct with the flue gasses. In India, thermal power plants attribute about 70 % of total energy capacity and every bitumen of coal combustion generates 40 % of fly ash (Yadav and Fulekar, 2018). The threats cause by fly ash and its particles are important to identify and to 1

Journal Pre-proof develop an efficient disposal system for fly ash. Besides, using in cement and brick manufacturing industries, large amounts of fly ash are being dumped into lagoons as a part of landfill activity. Fly ash has been used for the land management in improving soil mineral; however, the percentage of solid waste production is higher than the consumption, leads to inappropriate disposal. It may cause soil degradation that endangers human health and environment (Oncioiu et al., 2018). Its adverse effects may cause clogs in natural drainage system originate from the contamination of groundwater with heavy metals of fly ash. The small particles of fly ash can easily escape from its storage causes gas or air pollution. Moreover, fly ash contains radioactive elements where the concentration depends on the source of fly ash as might be lower or higher after combustion. U, Th, Ru, Ra and K are enriched with radionucleotides in fly ash particles and their elements (Ferrarini et al., 2016; Singh et al., 2016). Since the toxicity of fly ash is severe to human health and environment, the effort to discover more efficient technique for fly ash disposal has never stop. Although various methods have been investigated and applied in industry, the proper management and application of fly ash as by-product for the external purposes are yet to be established for the secured and environmental friendly disposal. Instead of direct application in industries, fly ash is studied as raw material to extract minerals and particles. Fly ash has made signature edge in the synthesis of nanoscale particles. Silica, iron, aluminium and silver nanoparticles are highly recognized for the synthesis at nanoscale using fly ashes. Apart from nanoparticle, nanocrystalline aluminosilicate is one of the promising nanocomposites synthesized from fly ash. Silica and aluminium nanocomposite, commonly known as zeolite, is naturally found aluminosiliceous minerals originated from the alkaline earth metals. It is well-established in recent science and industrial technologies for its high porosity and ion-exchange properties (Álvaro et al., 2006; Mourhly et al., 2015; Ruíz-Baltazar et al., 2015). A large surface area over volume has been attained by the rigid tetrahedral structure of silica-aluminium nanocomposite poses an excellent absorption in liquid suspension with conjugation of organic and inorganic elements. The detachment of large imperial metal complexes to the building of precise crystal structure of the nanocomposite allows the silica-aluminium nanocomposite perform as an excellent catalyst in various chemical and biological applications complement with infinite type of elements at nanoscale (Channabasavaraj, 2017a; Czarna et al., 2016; Liu et al., 2016). Since aluminosilicates have been recognized as demanding naturally found rich minerals, researches are keen in looking for the possibilities in extracting aluminosiliceous minerals 2

Journal Pre-proof from the fly ash waste due to its high content of aluminium and silica (Cui et al., 2015; Thaw and Aye, 2016; Zhang et al., 2016). Incinerated coal, rice husk, coconut shell and many other kinds of waste have experimented for aluminosilicate extraction (Ferrarini et al., 2016; Hong et al., 2017). Several extraction methods are identified and implemented in real time extraction of aluminosilicate from fly ash. Alkaline geopolymerisation is the basic principle in synthesizing aluminosilicate from fly ash. The principle is manipulated with different processes and conditions according to the scale of aluminosilicate production (Georgiev et al., 2013; Suddaby, 2014; Whetten, 1989). In spite of all these, the extraction of aluminosilicates from fly ash is still abortive since its innovative implementation for human and environment safe is yet to be developed. Based on the above context, the present review comprises the synthesis of nanostructured aluminosilicate from fly ash waste for the industrial and biomedical applications (Figure 1). Instead of being dumped into pools, lagoons and disposed via landfill and land management activities, fly ash waste is highly recommended to be used as a source for aluminosilicate nanocomposite extraction. Although aluminosilicate nanocomposite has justified for its excellent physiochemical properties, its furtherance in biomedical is still in its primitive state. The significance of fly ash derived aluminosilicates in industries, especially in sustainable practice in wastewater treatment plants and soil enrichment in agriculture field, are discussed. Besides, the present review highlights the potential and precedence applications of fly ash derived aluminosilicates in biomedical applications. Additionally, simplified and large scale aluminosilicate synthesis through the multiple methods using different sources of fly ash waste is overviewed. Also, look into the real-time synthesis and application of aluminosilicate nanocomposite at large scale in industries for disease diagnostics and therapeutics, behaving as expanding nanoscaled-biological tool in the biomedical practices. In the synthesis of nanosize aluminosilicates for industrial and medical applications, this article aims to highlight the alternative method of consuming tons of fly ash solid waste generated around the world, leading primarily to a nature-friendly method of disposing solid waste and saving the environment. 2. Fly Ash Waste Fly ash is the fine-grained loose material obtained as the by-product of combustion of coal based items. The properties and characterization of fly ash waste solely depends on the source of fly ash and its degree of combustion and cooling rate (Yao et al., 2015). As 3

Journal Pre-proof acclaimed, coal is the major source of fly ash waste as it is highly consumed in manufacturing and agricultural industries (Li et al., 2019; Tang et al., 2019). Besides, the combustion of agricultural waste such as rice husk ash, coconut husk ash, sugarcane ash, corncob ash, and wheat straw ash are also contribute to a large portion in total fly ash generation. The physical properties of fly ash vary in term of its size, shape, color and its fineness. The size of fly ash particle varies from 1 to 100 µm with spherical shapes (Azizi et al., 2013). The examples of fly ash morphology are shown in Figure 2; indicate the examination of electron microscopic view of fly ashes in the presence of dusts and lumps. The degree of heating and cooling is the key feature of fly ash appearance. The higher carbon content cause the darker color of fly ash appeared as black. With less than 15 % of carbon content and high iron oxide compounds, fly ash appears moderately dark to light grey color (Jalal et al., 2015). Another important physical property of fly ash is its fineness that determines the degree of fly ash reactivity. The fineness is investigated through the sieve analysis either by wet or dry method and the measurement depends on the weight percentage of particles with a similar or lower size than 40 µm (Choudhary and Luhar, 2017). Chemical properties are the mostly used benchmark in the characterization of fly ash. Silica is the basic framework of fly ash particles, responsible for the alkaline activation in the chemical reactions. The alkaline activation of silica initiates the synthesis of aluminosilicate gel in the alkaline solution. The level of alumina composition is equally important as the silica composition, as the role of silica and alumina in chemical reaction cannot be segregated and usually expressed as silicon to aluminium (Si/Al) ratio (Cui et al., 2015; Zhang et al., 2016). The higher the ratio, will higher the strength of materials synthesized with silica and alumina. Aluminosilicate is one of the significant materials where the higher Si/Al ratio can be found. Another countable element found in fly ash is iron oxide which determines the color of the fly ash and also specific gravity of fly ash. Besides that, magnesium and sulfide found in fairly small amount since these elements are the composition of alkaline earth metals found in different sources of fly ash. The amount of unburnt carbon is also important to be identified in fly ash as it affects the compressive strength of cement and concretes using fly ashes (Dwivedi and Jain, 2014). 2.1 Toxicity of Fly Ash It is important to review the toxicity of fly ash as it has significant impact on fly ash discharge into settling ponds and landfills. Toxic heavy metals such as Hg, Cr, Ni, Pb, V, As, and Se are enriched in fly ash. When the concentrations of such toxic heavy metals exceed its 4

Journal Pre-proof usual concentration, it may cause a severe health effect to human and animals. For instance, chromium (VI) could cause carcinogenic changes relative to the damage of circulatory system in an organism when exposed to the concentrated chromium content fly ash (Jambhulkar et al., 2018). Moreover, accumulation of Pb in plants when it grow in fly ash polluted aqua-system, destroys the metabolism and effect the growth of plants (Kurda et al., 2018). Coal based thermal power plants are the second largest source of mercury in India, stresses that a high content of mercury is in the coal fly ash. The presence of methylated mercury in hydrological system of ash settled ponds disrupt the food chain and its ecosystem (Silva et al., 2019). Although fly ash well known as multi-nutrient solid waste, the extremely high concentration of heavy metals may causes damages to the living organism. Thus, the suitable disposal of fly ash waste and the usage in other profiting application will lead an effective utilization of the waste and solve the environmental issues. 2.2 Disposal of Fly Ash and its Regulatory Perspectives Management of fly ash with effective and sustainable practice encounters environmental and economic challenges to the power generators. The annual production of fly ash about 500 million tons are expected to rise the consumption in emerging economic industries of China and India. However, at present, only a small percentage of fly ash is economically utilized and a large part is still disposed in landfills with unknown long-term consequences. Land management is associated with the agriculture earth, show large capacity in fly ash consumption for disposal. It creates indirect platform in improving soil condition for the commendatory crop yield. This reduces the increasing number of landfills and its attendant environmental risks (Ferrando et al., 2019; Namiki et al., 2014; Ng et al., 2019). A recent case study was conducted in China, India and Australia on the quality and quantity of crop yield from the strategically consumed fly ash land, distributed detailed information on the pragmatic effect of fly ash on crop, and stresses the disposal of fly ash in soil for the land management. The high cost involved in transporting fly ash causes the economic constraints. The efforts in exploring all other possible applications for proper disposal, management and consumption have been a major concern for environmentalists and scientists. Apart from agriculture, fly ash is recommended to be used in heavy industries such as brick, ceramics and concretes, and also in bio-amelioration exertions for salinization (Ando et al., 2018; Azizi et al., 2014).

5

Journal Pre-proof 3. Aluminosilicate Nanocomposites Aluminosilicates first discovered by Cronsted in 1765, known as ‘boiling stone’. Later, the term ‘zeolites’ derived from Greek words ‘zeo’ means ‘to boil’ and ‘lithos’ means ‘the stone’. In 1862, the effort to synthesize aluminosilicate in laboratory was initiated by St. Claire Deville. However, the recognition of aluminosilicate synthesis was insignificant until Milton and Breck made their first successful synthesis of aluminosilicate from the industry bearing at Union Carbide, US in 1950s. Since that the development of gelation and crystallization act as the preliminary procedure for the conventional synthesis of aluminosilicate (Zhang and Ostraat, 2016). The team then discovers zeolite A, X and Y in the 1960s, categorized based on the Si/Al ratio where they are also recognized as aluminosilicate nanocomposite. In 1969, high-silica zeolite, known as ZSM-5 was synthesized by Argauer and Landolt for the first time. From 1970s, aluminosilicate has been recognized as one of the notable particles to be used in various applications, originated as a by-product in catalytic cracking in 1974. Then, there were variety structures of aluminosilicates were discovered, yet the main quest was on the goal of conquering the material for industrial applications. Besides, being an acid-base catalyst, SAPO-34, a silicoaluminophosphate was utilized in olefin fuel manufacturing industry during 2010, the greatest benchmark for the significant application of aluminosilicates (Zimmermann and Haranczyk, 2016). The necessity for classification of aluminosilicates commenced when large number of novel aluminosiliceous minerals were generated with the similar structure but with different elemental compositions. At first, the grouping of aluminosilicates was done on the basis of Si/Al ratio, where the low Si/Al ratio, from 0.5 to 1.5, categorized as zeolite A and zeolite X. When the Si/Al ratio falls in the range of 2 to 5, it is categorized as zeolite Y and zeolite L (Koohsaryan and Anbia, 2016). As the Si/Al ratio increases, ZSM-11, ZSM-5, EU-1, EU-2, erionite, mordenite and dealuminated Y, generally known in three capital letter codes (Ziraba et al., 2016). Apart from Si/Al ratio, a structural framework concept, which differentiates the types of aluminosilicates was introduced. The primary building units is usually in tetrahedral structure, mainly Al(III)O4, P(V)O4 and Si(IV)O4 that connects the framework with multiple topology. The primary unit for aluminosilicate framework known as sodalite unit comes in hexatetrahedral structure, sharing for tetrahedral rings. Aluminosilicate were then classified and named based on the number of sodalite rings connected through ‘O’ bridges in the material structure (Chen et al., 2016; Jha and Singh, 2013; Koshy and Singh, 2016). Figure 3a shows some of the most common types of aluminosilicate structures and their nomenclatures. The variation in aluminosilicate structure also influences the porosity of the material, based on its framework 6

Journal Pre-proof and dimension. The pore size of aluminosilicate is ranging in 4-13 Å with circular, elliptical, and clover-leaf like shapes. The pore aperture depending on its size, charge, positions, distribution, ordering, and coordination number in aluminosilicate, directs its applications (Nabih, 2018; Sangita et al., 2016). 3.1. Structure and Properties of Aluminosilicates Aluminosilicates are crystalline hydrated mineral with microporous cavity on its structure. The chemical structure is primary the tetrahedral (TO4), where ‘T’ could be silicon or aluminium bonded by oxygen and other neighboring tetrahedral units. As the silicon being replaces by aluminium, a high density negative charge is generated within aluminosilicate framework that has to be neutralized by alkaline cations (Ghasemi et al., 2018). These mobile cations exhibit different sizes and charge density that results are in various aluminosilicate molecular sieves and determines the availability of cation exchange in surrounding aqueous system (Ramanathan et al., 2019c, 2019a, 2019b). The feasibility of cation interchange between tetrahedral structures of aluminosilicate reveals its ion-exchange property (Moshoeshoe et al., 2017). The two main structural properties of aluminosilicate are the pore and channel size that creates platform to differentiate one from another porous aluminosilicates and discriminates the molecular sieve characteristics. The porous venture of aluminosilicate makes it admirable ion-exchangers for absorption and diffusion of cation molecules, molecular sieves and heterogeneous and electrochemical catalysts (Cody et al., 2014; Kisley et al., 2015). The cations within the pores and channels could be replaced by ingoing cation with different size and charge density. This regulates the selectivity of cation exchange, results in the removal of different ions from an aqueous system. The arrangement of atoms on aluminosilicate surface makes highly hydrophilic which further improves its absorption property. Aluminosilicates are excellent absorbents as they able to absorb polar oxidized particles and remove nonpolar particles. The large surface area with high porosity enables the zeolite to perform as good absorption and separation, heterogeneous and electrochemical catalyst in various applications (Hovhannisyan et al., 2018). 3.2. Extraction of Aluminosilicates from Fly Ash Aluminosilicates from fly ash are categorized into two types, natural and synthetic zeolites. The naturally occurring aluminosilicates are formed from the residual of environmental and geological phenomenon. The naturally generated ashes from volcanoes settle in lakes and seas, transform into aluminosilicate crystals under the alkaline medium (Feng et al., 2018; 7

Journal Pre-proof Iqbal et al., 2019; Oliveira et al., 2019). Clinoptilolite is the most common type of naturally found aluminosilicates having Si/Al ratio of 5, in least (Wattimena et al., 2017). It is widely used as fertilizers due to its high affinity towards ammonia. Synthetic aluminosilicates are artificially synthesized using minerals with a high amount of silica and aluminium (Channabasavaraj, 2017b; Mourhly et al., 2015; Ruíz-Baltazar et al., 2015). Aluminosilicates from chalk, clay, agriculture and industrial waste such as coal fly ash, rice husk ash and wheat straw ash are highly recognized, however these aluminosilicates tend to have impurities from the fly ash waste. Thus, it is necessary to imply appropriate method in synthesizing high purity aluminosilicates from fly ashes. Figure 3b-d shows the electron microscopic vision of synthetic aluminosilicates, whereas Figure 3e and 3f shows the naturally occurring aluminosilicate crystals. The synthetic method of preparing aluminosilicates is mainly categorized into two, high- and low-temperature synthesis. The high-temperature method is commonly known as a hydrothermal synthesis of aluminosilicates where a temperature, approximately 300 to 700 °C is used to synthesize aluminosilicate nanocomposites under the alkaline medium (Cheng et al., 2017). Figure 4a shows the process flow of aluminosilicate synthesis through the hydrothermal method in industries. Undoubtedly, hydrothermal method is the most discussed method in synthesizing aluminosilicates from fly ash due to its relatively low energy consumption and simplicity in relation to the broad range of aluminosilicate extracting methods. It is also highly welcomed in extracting high yield of aluminosilicates from fly ash. Hydrothermal method synthesizes thermostable and uniform porosity aluminosilicate crystals. Researchers claimed that hydrothermal method of fly ash derived aluminosilicates is excellent with physiochemical properties, as good as the silica gels (Abdullahi et al., 2017; Bhavani et al., 2017; Bortolatto et al., 2017). On the other hand, low-temperature aluminosilicate synthesis explains the extraction of aluminosilicate nanocomposite at 75100 °C. In contrast to hydrothermal method, it is an efficient way to synthesis amorphous aluminosilicate with less consumption of energy. Under alkaline medium, the lowtemperature synthetic method results in large and uniform porous surfaced aluminosilicate nanocomposites, which are highly valued in heterogonous catalysis and industrial applications (Wang et al., 2016). Figure 4b shows the simplest method of synthesizing nanostructured aluminosilicates, especially in the laboratory scale. Condensation and gelation of the alkaline treated fly ash are at neutral pH results in the formation of aluminosilicate gels. The simplest experimental technique practiced in extracting aluminosilicate using fly ash 8

Journal Pre-proof source is presented in Figure 4c (Keshavarz and Ahmad, 2013; Limberg et al., 2018; RuízBaltazar et al., 2015; Zhang et al., 2018). Although low temperature synthesizing method was predominantly acknowledged, the process of crystalline aluminosilicates found to be economically unattractive, especially on a large scale of production. In many reported studies, the yield of aluminosilicates from fly ash is moderately low, about 20 % for every 500 g. Thus, low temperature method of synthesizing aluminosilicate is least preferred for large scale production as it requires a long processing time, which indirectly results in a high consumption of energy source. In the innovation of utilizing fly ash for aluminosilicates synthesis, hydrothermal fusion method is introduced, where alkaline fusion is performed, followed by hydrothermal crystallization. The alkaline fusion is able to reduce the crystallization period of aluminosilicates during the hydrothermal crystallization (Bukhari et al., 2014; Deng et al., 2016; Wulandari et al., 2019). Microwave fusion and ultrasonic treatment are predominantly well known for fusion-hydrothermal method (Askari et al., 2013; Belviso et al., 2013). Certainly, alkaline fusion using microwave and ultrasound energy controls the crystal growth of aluminosilicates in the aging process and instantly increases the crystal growth rate prior to the high concentration of silica and aluminium species (Belviso et al., 2011). Ultrasonic energy has been reported in several researches after the dissolution of fly ash, mainly in the aging process to generate crystalline aluminosilicates in a short period. Ojumu et al. (2016) reported that synthesis of aluminosilicate from the coal fly ash through ultrasonic chemical treatment is proficient in South Africa and acclaimed as the promising alternative method for the hydrothermal fusion. The finding of the research reported that hydrothermal fusion has been successfully replaced by 10 minutes of high energy sonification at reduced operating temperature in generating pure phase crystalline nanostructured aluminosilicate (Ojumu et al., 2016). In another study by Ozdemir et al. (2017) have stated that the aging time for aluminosilicate crystal growth from the coal fly ash was reduced from 24 to 2 hour with the aid of a high intensity ultrasonic energy (Dere Ozdemir and Piskin, 2019). Recent study performed on the development of nanoscale aluminosilicate from coal fly ash using the low frequency ultrasonic waves has synthesized ~40 nm aluminosilicate crystal, emphasized the significant role of ultrasonic waves in the reduction of aging period of aluminosilicates and able to extract nanocrystalline aluminosilicates from fly ash at a high crystal growth rate (Susanto et al., 2018). Synthesizing nanostructured aluminosilicates from fly ash from every possible method have its own advantages and limitations. However, the core mechanism of every method is to convert silica and aluminium into nanostructured aluminosilicate crystal, and the selection of methods depends on the purity level of 9

Journal Pre-proof aluminosilicate to be achieved and the consumption of energy (GP et al., 2015; Sarah C. Larsen, 2007). 4. Industrial Applications of Fly Ash derived Aluminosilicates In early decades, natural aluminosilicates have proven for its potential applications in removal various contaminants from an aqueous system. However, the restricted pore size and channel in naturally occurring aluminosilicates impede its sorbent characteristics in trapping heavy metals, anions and dyes. Fly ash derived aluminosilicates possess multiple diversions in pore size and structure, empowers implementation in heavy industries such as wastewater treatment, lubricant and agriculture (Bose et al., 2015). 4.1. Aluminosilicates in Wastewater Treatment An ideal wastewater treatment is regulated by several liquid chemistries such as absorption, precipitation, coagulation, reverse osmosis, and catalytic reactions. To facilitate these reactions, fly ash derived aluminosilicates have been proven as excellent ion-exchanger and efficient sorbent in removal of heavy metals and sludges, owning to its high microporous cavity (Athar et al., 2019; Ma et al., 2019; Shi et al., 2020). Jie Xie et al. (2015) evaluated the synthesis of aluminosilicates from coal fly ash and its conjugation with lanthanum hydroxide for high efficient sorbent in phosphate removal from water. Since lanthanum has a high affinity for phosphate, it was incorporated with aluminosilicate for the removal of phosphate in wastewater. The absorption cavity of lanthanum with aluminosilicates was evaluated with real wastewater and lake water for long-term contacts. The research has proven that aluminosilicate incorporated with lanthanum exhibits a great absorbent cavity by removing 97.86 % and 97.27 % of phosphate from wastewater and lake water, respectively (Xie et al., 2015). In another study, aluminosilicates were extracted from Brazilian coal fly ash and it was investigated in removing ammonical nitrogen from swine wastewater. The characterization was justified that the aluminosilicate synthesized from the fly ash attains 82 % purity with a high CEC value (4.5 meq Ca2+ g-1). The obtained research results have proved that the fly ash derived aluminosilicate is able to remove 31 mg g-1 of ammonical nitrogen from the swine wastewater, owning displays equal or greater parameter with commercial aluminosilicate (Cardoso et al., 2015). On the other hand, mercury is a significant toxic pollutant to be removed from the wastewater as it can be easily transformed to methylmercury through the biochemical reactions. Fly ash derived aluminosilicates are investigated for mercury removal from wastewater. Aluminosilicate synthesized from Class F 10

Journal Pre-proof fly ash was tested for mercury absorption with artificial and real wastewater samples. About 13.20-575 mg dm-3 of mercury has successfully removed from artificial solution where the results obtained were >90 % sorption efficiency. Similarly, with real wastewater samples, 99 % sorption efficiency was achieved. Fly ash derived aluminosilicates have shown corresponding performances to the commercial products in mercury removal from wastewater (Czarna et al., 2016). In a recent work, nanoporous aluminosilicates were synthesized by the ultrasound assisted hydrothermal method using fly ash waste. The nanocomposite was investigated for its absorption cavity to remove heavy metals and dyes with various divalent ions. The research justified that aluminosilicate from fly ash absorbs the metal with 196. 2 mg g-1 as well as dye with 193.45 mg g-1, which shown at most performance in comparison with the commercially available aluminosilicates. The research emphasized the intense potential of fly ash derived aluminosilicate for the real time industrial wastewater treatment (Sivalingam and Sen, 2018). 4.2. Fly Ash derived Aluminosilicates in Agriculture Field Aluminosilicate owns stable crystalline structure, also known as alkaline zeolites. The stable cavity system is capable of retaining water and the negative charge loaded on its structure is capable of altering heavy metals (Azizi et al., 2014). The excellent cation exchange ability of aluminosilicate enables effortless interchange of nutrients and water from the soil to the plants. The incorporation of aluminosilicates in fertilizers enhances its performance in gas losses and immobilization. It improves the water retaining capacity of soil during dry seasons and reversibly loses water in response to the soil network without causing any harm to the both plant and soil structures (Baptista-Filho et al., 2011; Hashemi and Rezania, 2019). Aluminosilicate is able to regulate the soil balance with nutrients and toxic contaminants through the excellent cationic exchange framework. Aluminosilicates synthesized from coal fly ash, which are generated from the power plants in Xinjiang, China, were studied to be applied as fertilizer in releasing nutrients for the plant growth. The aluminosilicate synthesized from coal fly ash has proven as an effective high-nutrient fertilizer for growing crops in nutrient-limited soils and poor soil amendment which resolves the increasing amount of waste from coal combustion in Xinjiang (Li et al., 2014). Brazilian coal ash content up to 50 % of the mass constituent were investigated for the synthesis of aluminosilicate and its application as fertilizer. The research has successfully synthesized aluminosilicate through the hydrothermal method and applied the potassium fertilizer for wheat plant. A set of test was conducted by the team justifies aluminosilicate from Brazilian coal fly ash as potassic 11

Journal Pre-proof fertilizer for plants in greenhouse environment (Flores et al., 2017). In a recent work, both fly ash and aluminosilicate from fly ash were examined for the bioavailability of metals and nutrients in metal contaminated soil, which has cultivated with paddy rice. The research emphasized that aluminosilicate in metal contaminated soil, easily immobilize the metals and reduce the uptake of copper and zinc by the rice, but reduces the availability of nitrogen and phosphorus nutrient. The study has suggested a stable synchronization between the rate of metal immobilization and nutrient availability is necessary prior to the required state of rice paddy soil (Lee et al., 2019). 4.3. Fly Ash derived Aluminosilicates as Antioxidants Aluminosilicates empower more hydrophilic behavior than hydrophobic, making it to absorb polar oxidation products from the lubricants. The application of nanosized aluminosilicates in lubricant oil reduces the amount of oxidized products in the purified oil. Although several methods are well established as antioxidant additivation, they are not accepted for implementation in industries, due to the complicated and non-economic factors. Application of aluminosilicates as antioxidant has introduced more cost effective and eco-friendly technique in reducing oxidants in lubricants.

Kok-Hou et al. (2015) evaluated

aluminosilicates with different structural frameworks as antioxidant to preserve palm oil lubricant. The research presented total acid analysis on aluminosilicate added palm oil lubricant, where about 35-50 % acidic compounds are reduced, justifies the three dimensional porous aluminosilicates as eco-friendly antioxidant in prolonging the lifetime of palm oil lubricant (Tan et al., 2016, 2015). Moreover, aluminosilicate rich with molecular sieves examined as traditional antioxidant for base oil. Spectrophotometry, chromatography, and total acid number analysis revealed that aluminosilocates has shown outstanding performance in reducing oxidants in base oil, and reducing the rate of solid polymeric residue production (Tan et al., 2016). The literature encourages the implementation of aluminosilicates from fly ash wastes as eco-friendly antioxidant additives and the best candidate for lubricants due to its high cationic polarizability in hindering oil oxidations. 5. Medical Applications of Fly Ash derived Aluminosilicates Aluminosilicates are classified as non-toxic porous crystals. Thus, they are not only used as a catalyst in agriculture industries, but widely applied in biomedical industries. The mineral is regarded as safe for in vivo usage for human and animal therapeutics (Pavelić et al., 2018). The strong ion exchange property with a high absorptive catalyst aluminosilicates is feasible 12

Journal Pre-proof in the application of medicinal and pharmaceutical industries. However, few researches acclaimed that the fly ash derived aluminosilicates are cytotoxic, which may cause toxicity to the living cells and lead undesirable diseases to the human health (Thaw and Aye, 2016). Some naturally occurring aluminosilicates were reported as highly carcinogenic and cytotoxic. One of well-known fibrous aluminosilicate minerals is erionite, which forms in hollow rock shapes and own similar physiochemical property as asbestos. Erionite fibers were investigated via in vitro experiment with human monocyte U937 cells, which resulted in cell necrosis in 24 hours. The study justified erionite in causing severe diseases such as malignant mesothelioma and lung cancer (Cangiotti et al., 2018). In another study, sodium aluminosilicate rich in silica and alumina disrupts the metabolism of animals. An in vitro experiment was conducted with calves and proved that sodium aluminosilicate increases the concentration of silica and alumina in aorta, lung, kidney, spleen and muscles of calves and decreases the concentration of plasma. The condition damages the physiological composition of organism’s metabolism and its elements may cause fatality at extreme intake of sodium aluminosilicate in calves dietary supplementation (Turner et al., 2008). In spite of that, aluminosilicates have been proclaimed as ‘two-faced’ mineral since it is also recognized as a promising non-toxic mineral in biomedical applications. Since not all aluminosilicates are toxic or non-toxic, it can be concluded that the toxicity of aluminosilicates is depending on the source and nature of the mineral. Literature has reported several recent researches on fly ash derived aluminosilicates nanocrystals in medical and pharmaceutical applications. The technique of extracting aluminosilicates from fly ash waste directs the purity and crystalline property of aluminosilicates as it plays the main key in the medicinal applications. 5.1. Aluminosilicates as Drug Carrier and Drug Delivery One of the most outstanding medical applications of aluminosilicates is as nanocarrier for small drug molecules, charged ions and ensures the ultimate drug delivery system. Due to its distinctive porous structure with excellent biocompatibility, aluminosilicates are widely applied in floating drug delivery, sustain drug delivery and microencapsulation with drugs (Tan et al., 2016). Independent of its pore sizes, aluminosilicates are proficient in integrating with hydrophobic compounds, to solubilize water insoluble compounds in the midst of hydrophobic domain. These properties with enormous pore on its framework enables aluminosilicate to entrap drug molecules with high efficiency and release them at controllable system (Ferreira et al., 2016). Clinoptilolite, the most ancient natural aluminosilicate found on earth was proposed and affirmed as microporous anti-inflammatory drug carrier of pH 13

Journal Pre-proof controlled oral delivery of aspirin to treat gastric irritation in gastric mucosa. The research was furthered with other anti-inflammatory drugs which had issues associated with the oral drugs, such as diclofenac and piroxicam (Bacakova et al., 2018). Since then, clinoptilolite or zeolite X and Y are the promising drug carriers mainly for the oral drug delivery system, being the most convenient and the preferred route for drug administration. As such, aluminosilicates are incorporated with the multiple anti-inflammatory drugs for instant medical treatments. Through the simple method of conjugation and solvent evaporation, diclofenac sodium and piroxicam drugs were loaded with aluminosilicate nanocomposites as a therapeutic technique for gastrointestinal tract disease. The percentage of drug loaded and released against simulated gastric intestinal fluid samples was analyzed. Weight measurement and FTIR affirmed that about 90 % of drug loaded and released at controlled manner within a short period (Khodaverdi et al., 2016). Aluminosilicates loaded with anti-inflammatory drug are most welcomed on therapeutic medicines due to its ability in adjusting pH at variable electrolytes. Moreover, aluminosilicate was investigated in loading 14-driamycin as antiinflammatory drug to reduce the inflammatory and apoptotic markers in primary liver cell culture. The analysis was performed using the western blot by evaluating the protein expression level of inflammation markers, such as nuclear factor kappa B and tumor necrosis factor. The findings of the research pointed out that 14-driamycin-conjugated with aluminosilicate was significantly minimized the hepatotoxicity in primary liver cell line (p < 0.05) in relation with control cells treated with only adrimycin (Yapislar et al., 2016). In the wake of this research, mechanically active nanoporous aluminosilicates have been successfully loaded with anticancer drugs for cancer treatments. Being the most serious threat to human life, cancer diagnosis and its immediate therapeutics requires high efficient drug delivery systems. Doxorubicin, 5-flourouracil, and mitoxantrone have been successfully evaluated as anticancer drugs loaded with aluminosilicates and its efficient release at targeted tumor cells. Aluminosilicates without any fibers and negatively charged particles on its framework ensure it is non-carcinogenic and non-toxic compound, thus could be extensively used in anti-cancer drug delivery with metallic ions due to their high ion-exchange competency (Mastinu et al., 2019). The mechanism of anticancer drug-loaded aluminosilicates in decreasing cancer cell viability is shown in Figure 5. The aluminosilicate mineral with anticancer drugs endorse the tumor blood vessel at first, and then targets the tumor cells. Drug-loaded aluminosilicate diffuses through the tumor cells via endocytosis and targets the nucleus for cell lysis (Spanakis et al., 2014). Recent research presented on the 14

Journal Pre-proof evaluation of 5-fluorouracil drug loaded aluminosilicate for targeting adenocarcinoma cell in human colon and human gastric carcinoma cells revealed the effective encapsulation of tumor cells by aluminosilicates without affecting the cell line domain. In another in vitro study, aluminosilicates were justified as promising drug carrier for doxorubicin which shown the excellent instant tumor cell lysis of beta polymorph in human colon. Aluminosilicate conjugated with anticancer drug was revealed an inhibition of cell viability up to 585 folds in contrast to non-conjugated drug, emphasizing the potential of the nanocomposite in inducing cancer cell death (Amorim et al., 2012). Aluminosilicates are apparently used in chemotherapy drug for instance and huge amount of drug delivery to cancer patients. A recent research conducted by Subhapriya et al. (2018) in evaluating the ability of aluminosilicate was synthesized from coal fly ash as anticancer drug by in vitro studies to inhibit the proliferation of human breast cancer cell lines. The concentration dependent inhibition was shown by zeolite X on MCF-7 cell proliferation were studied through flow cytometry, which emphasized the early apoptotic death caused and also affirms the zero cytotoxicity in non-cancerous MCF-7 cells. Flow cytometric study performed through fluorescence and confocal microscopy indicated the cell death associated with apoptosis as the DNA fragments were observed in ladder form with the activation of mitochondrial dependent pathway. The research outcomes evidence the therapeutic properties of aluminosilicates from fly ash waste in the prevention and medication of human breast cancer (Subhapriya and Gomathipriya, 2018a). Further, Subhapriya expanded her research to evaluate aluminosilicate from fly ash as anti-proliferation agent in HeLa cells cervical cancer. A 20 µg/mL of aluminosilicate at maximum dosage induced in HeLa cell lines, in vitro delivered significant apoptotic effect in cancer cell lines without influence of cytotoxicity to normal cells, affirms that aluminosilicate from coal fly ash as a curative agent for the cancerous therapies (Subhapriya and Gomathipriya, 2018b). Aluminosilicates from fly ashes were also tested for delivering antimicrobial drugs such as antipathogenics, antibiotics, chemotherapeutics and metallic ions. Numerous researches have been presented on the antimicrobial property availed by drugs loaded aluminosilicates in curative therapeutics. The high porosity and large cavity in its framework enable a high loading efficiency of antimicrobial drugs and promising momentous delivery against the pathogens. At most cases, antimicrobial drug with various functional groups that allow interacting with positively charged surfactants, enables it to be loaded on porous aluminosilicates, known as surfactant modified aluminosilicates. Figure 6a illustrates the 15

Journal Pre-proof antimicrobial drug delivery by aluminosilicate nanocomposite in inhibiting the growth of pathogens. In a study, amoxicillin and hexadecyltrimetyl ammonium were attached on clinoptilolite through the surfactant where its relevant attachment were presented by peaks at 2849 and 2916 cm−1 in FTIR analysis. The antibacterial property of the surfactant modified clinoptilolite against Escherichia coli were examined and resulted minimum inhibition concentration of surfactant modified clinoptilolite revealed a significant antimicrobial drug loading ability of aluminosilicate in contract to the parent antibiotics (Nasirmahaleh et al., 2016). Aluminosilicate synthesized from the rice husk ash was analyzed for antibacterial attributes against gram negative bacteria (E. coli ATCC 11229 and Pseudomonas aeruginosa ATCC 15442) and gram positive bacteria (Staphylococcus aureus ATCC 6538 and Enterococcus faecalis ATCC 29212). The aluminosilicates were loaded with antibacterial copper ions at different concentrations and the attachment was analyzed through XRD and FTIR. Research showed that when higher the concentration of copper ion loading, the higher antibacterial activity against dense colonies of bacteria was noticed (Nik Malek et al., 2018). The finding of the research revealed that aluminosilicates extracted from fly ash are highly capable as drug carrier and drug delivery systems. In a recent study, aluminosilicate with high silica to aluminium ratio were functionalized with silver ions to examine the antimicrobial property against E. coli, P. aeruginosa and Candida albicans. Although silver ion alone possesses antimicrobial property, it was functionalized with aluminosilicate to evaluate its drug delivery property. Figure 6b shows the FESEM image of silver ions conjugated with aluminosilicate and the culture plates analyzed for bacterial inhibition. The results justified that silver ions conjugated with aluminosilicate improves the bacterial inhibition than silver ion alone as the inhibition zone with aluminosilicate increases by 6 mm (Figure 6b (iii)). The research claimed that aluminosilicate nanocomposite not only increases the drug delivery capacity, but also contributes in inhibiting the growth of pathogens in the absence of any antimicrobial drugs (Sánchez et al., 2017). 5.2. Aluminosilicate in Bone Engineering Aluminosilicates are widely acknowledged in bone engineering as an active bio-ceramic where it is effectively involved in the building of hard bone tissues. Some aluminosilicates with moderately higher ratio of Si/Al tend to mimic the mineral element of natural bone tissue. In order to elevate the potentiality of aluminosilicates in nurturing bone tissues, aluminosilicates were incorporated with certain chemicals/polymers to evoke the construction of bone tissue. For example, aluminosilicates were integrated with chitosan hybrid 16

Journal Pre-proof composites through the gel-hydrothermal synthesis. When tested with simulated body fluid, the composite promoted the formation of hydroxyapatite, which acts as antimicrobial agent for preventing the growth of pathogens and enrich the building of tissue in bone narrow (Yu et al., 2013). Similarly, aluminosilicates are also widely implemented in soft tissue engineering, especially in skin tissue repairing and wound healing. In a study, aluminosilicates were conjugated with ferric iron-diethyldithiocarbamate complexes support the healing and the viability NIH3T3 fibroblasts in vitro, further improved skin regeneration in rats in vivo. These beneficial effects were also mediated by the increased oxygen supply to the cells, because aluminosilicates act as oxygen reservoirs. At the same time, the scaffolds acted as antimicrobial substances, due to the drug that was conjugated with aluminosilicates. The ability of aluminosilicates in construction of soft and hard tissue engineering is not possible without its excellent drug carrier and drug delivery potentials (Ninan et al., 2015). In another study, aluminosilicates were incorporated with collagen and it was implanted into New Zealand white rabbits to heal the segmental femur bone defect. As the specimens were monitored for 15, 30 and 60 days, aluminosilicate-collagen composite has shown significant point of index in statistics of spongiosa index, indicates that the healing of femur bone at the 15 day of implantation. The implantation of entities of collagen and aluminosilicate has shown similar differences in healing bone defect that took about 60 days to heal. The research concluded that the incorporation of aluminosilicate-collagen composite in bone fracture healing should be considered, mainly to be used as scaffolds in bone fractures (Faraji et al., 2017). In a recent study, chitosan-aluminosilicate based scaffolds were fabricated using freeze-drying method. The research team worked on synthesizing scaffolds with different amount of aluminosilicates and evaluated its effect on human mesenchymal stem cell viability. The results indicated that low amount of aluminosilicate with chitosan has shown a good cell attachment and cell viability, however more in vivo studies were required to evident the achievement of the research (Akmammedov et al., 2017). 5.3. Aluminosilicates on Biosensor Biosensors are simple, inexpensive readout tools, fused with biomolecules of living organisms applied in various medical diagnoses in response with the power of microelectronics. The development of thin layer nanomaterials on the biosensing surface has recently received significant attention to enhance the biosensor's specificity and sensitivity. With this regard, aluminosilicate nanocomposite is one of the most promising surface enhancing nanomaterials in the development of high performance biosensing tools for 17

Journal Pre-proof harvesting and therapeutics of various diseases (Farka et al., 2017; Pohanka, 2019; Shrivastava et al., 2016). Figure 7 represents the possible applications of aluminosilicate nanomaterials in developing biosensors. In many cases, aluminosilicates were incorporated with other nanomaterials in relation to the type of biomolecule detection to enhance the sensitivity of biosensors. As such, aluminosilicates were modified with gold nanoparticles in upgrading the ion selective detection of creatinine using FET. The research investigated the detection limit of creatinine with different sizes and structures of aluminosilicates to evaluate the extent of gold attachment on different frameworks of aluminosilicates using ICP, STEMEDX and XPS analyses. The finding of the study revealed that gold-modified aluminosilicate improves the micro-environment for creatinine detection regardless of the particle sizes (Ozansoy Kasap et al., 2017). In another study, aluminosilicate conjugated with two metallic nanoparticles, copper and gold, which were incorporated with the carbon paste electrodes on electrochemical sensor for the detection of hydrazine. Cyclic voltammetry, amperometry, and chronoamperometry techniques were applied in the determination of hydrazine, resulted in 0.04 µM detection limit in only 3 s of response time with 99.53 μAmM−1 sensitivity. The research declares the synergistic properties of metallic particles on aluminosilicates in the development of a high sensitive biosensor (Amiripour et al., 2018). Recent literature also reported the significant role of aluminosilicate in enhancing specificity of biosensor in detection of DNA based diseases, especially for tumor biomarkers. Fluorescence biosensor modified with aluminosilicates was studied for the detection of HIV-1 DNA strands. The results of the study attained 1.2 nmol L−1 as the low detection limit, creates a significant platform towards the rational design of biosensors with aluminosilicate nanocomposites for achieving a high sensitive DNA detection of life endangered diseases (Pan et al., 2018). Further, aluminosilicates were functionalized with tannic acid and primary antibodies to enhance the signal amplification in sandwich type electrochemical immunosensor for the detection of avian 18 eucosis virus subgroup J (ALV-J). The sensor was first modified with magnetic nanoparticles and reduced graphene oxide incorporated with glassy carbon electrodes. The finding of the study emphasized on the operational stability and practical reproducibility of aluminosilicates to be an excellent carrier for antibodies and improves the signal transduction as well, prompting the wider use of aluminosilicates framework with multiple materials (Liu et al., 2018). The literatures have proven the significant advantages of aluminosilicates in biosensor, yet there were no study reported on the application of aluminosilicates from fly ash in biosensor application. Anderson et al. (2017) reported aluminosilicates from kaolinite for the fabrication of electrochemical urea biosensors. The 18

Journal Pre-proof results analyzed through X-ray diffraction analysis and cyclic voltammetry measurements justifies the excellent physiochemical properties of aluminosilicates extracted from kaolinite in immobilization of urease on gold electrodes for developing potentiometric biosensors (Anderson et al., 2017). As such, aluminosilicates from fly ash waste is highly encouraged for its application in developing high sensitive and specific biosensors for harvesting biomarkers of lethal diseases. 5.4. Aluminosilicates in Hemodialysis Aluminosilicates, due to their cavities and pores on a molecular scale, have been applied in hemodialysis for the removal of ammonia from a recirculating dialysate. Aluminosilicates can entrap exothermically large volumes of water in the open porous internal space of aluminosilicates. At the same time, aluminosilicates concentrate coagulation factors and platelets in hemorrhaging blood. One of the major challenge is developing portable and regenerable hemodialysis system for future state-of-art. Since aluminosilicates possess an excellent ion-exchange property, it is widely accepted as good ammonia ion exchange material and successfully implemented in hemodialysis system (Pellegrino et al., 2011). In a study, hemodiafiltration was introduced where the hemodialysis performed able to reduce 6675 % of urea in kidney failure patients. The performance of hemodiafiltration was investigated by the effect of hybrid electrospinning made up of zeolite 940-HOA (beta), polyacrylonitrile, and Fe3O4 together with nettle plants leaf. Nessler’s Reagent adsorption technique was used to measure the amount of urea/ammonia reduction in tested blood of dialysis patient’s samples. The finding of the results pointed out that hybrid elctrospinning is capable of reducing urea in tested blood samples and tolerates against the pressure and temperature of the dialysing system. The research justified the performance of aluminosilicate in enormous removal of ammonia and encourages the interfusion of aluminosilicates in hemodialysis (Akbar Esmaeili and Bahramimehr, 2019). In a latest study conducted by Raharjo et al. (2019), aluminosilicate imprinted polythersulfon membrane with cellulose acetate were fabricated and created a mixed-matrix membrane to eliminate creatinine from human serum. The results have concluded that aluminosilicate embedded membrane is able to remove creatinine up to 75 % and justified the applications to be highly considered in hemodialysis (To et al., 2019).

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Journal Pre-proof 5.5. Aluminosilicates for Intestinal Therapeutics Aluminosilicates act as healing supplement for animals. It is being used as nutrition to direct positive effect in the digestive tract of animals through strengthening the immune system and decontamination of foods. Dietary clinoptilolite improves the morphology of villi on the wall of intestines by reducing intestinal mucosa damage and inflammatory response to bacterial lipopolysaccharide (Valpotić et al., 2017). Similarly, aluminosilicates in human guts, effects the inflammatory metabolism and antioxidant activity. Humans who are active in sports experience high prevalence of intestinal complaints due to the change of blood flowing pressure from viscera to heart or skeletal muscle. These improper metabolisms described by several symptoms such as vomiting, intestinal cramp, diarrhea and nausea. Aluminosilicates are able to reduce pro-inflammatory and pro-oxidative processes in the gut and modulate the integrity of intestinal wall through zonulin secretion from enterocytes. A study conducted by Lamprecht et al. (2015) proved the clinoptilolite natural aluminosilicate able to reduce zonulin concentration in gut and improves the intestinal wall permeability. The study was conducted with 52 endurance-trained people who have consumed 1.85 g of clinoptilolite per day. After 12 weeks, the results of the study justifies that zonulin concentration reduced significantly (p < 0.05) than the baseline of tested individuals. The research claimed that aluminosilicates have beneficial effects in improving intestinal wall integrity along with enhancing anti-oxidant effects in human digestive tract (Lamprecht et al., 2015). However, aluminosilicates from fly ash has never been implemented in gastrointestinal supplements. It is important to emphasize aluminosilicates in having significant contribution in human health. Thus, it is highly encouraged to execute similar approaches as above in generating intestinal tract therapeutics with the aid of nanostructured aluminoslicates from fly ash. 6. Conclusion and Future Outlook The disposal of about 30 million tons fly ash annually is extremely challenging to date in order to lead a pollution free and safe environment in the world. Although landfill, land management and soil improvement activities involve the consumption of fly ash, it is inadequate to occupy the whole sum of fly ash waste. To expand the applications, fly ash is being consumed in heavy industries such as cement and brick production, but the percentage of consumption is very less. With time, fly ash has received a remarkable recognition in the synthesis of nanosize particles and composites. This article presented a critical review on the extraction of aluminosilicate nanocomposite from fly ash waste. The synthesis of fly ash derived aluminosilicates not only consumes the waste as one of possible sources but also 20

Journal Pre-proof provides an alternative method of recycling massive amount of fly ash in an environmentally friendly manner. Aluminosilicates are widely recognized in heavy industries, especially in wastewater treatments, soil amelioration and as antioxidants for lubricants. However, the implementation of aluminosilicates in medical application is still inattentive. Few researches were conducted on utilizing fly ash derived aluminosilicates in medical and pharmaceutical applications proved the obsolescence of the potential idea in the new era of the environmentally benign. The review validated that fly ash derived aluminosilicates as the excellent element in drug carrier and drug delivery systems, hemodialysis, wound treatment, bone formation and intestinal therapeutics. However, only few studies were performed in literature to uphold its application in medical field. Further studies are highly encouraged and required to prove that fly ash derived aluminosilicates are highly capable in diagnosing various diseases and play a superior role in therapeutics. Being a nanocomposite with large surface and outstanding properties, aluminosilicates are inspired to foster its application in antibody stabilization, cell viability, heamostatics, blood purification and gases and drug storages, especially with in vivo analyses. Since aluminosilicates from fly ash have been well established in drug delivery systems, it is more embraced to be used in such listed medical applications for advanced diagnosis and treatments of fatal diseases. In situ remediation studies would be quite useful to understand the effectiveness of fly ash derived aluminosilicates in large-scale resource recovery technologies and in vivo biomedical applications. Abbreviations U

Uranium

mm

Millimeter

Th

Thorium

µm

Micrometer

Ru

Ruthenium

%

Percentage

Ra

Radium

Å

Angstrom

K

Potassium

mg

Milligram

Si

Silicon

µg

Microgram

Al

Aluminium

mL

Milliliter

Hg

Mercury

µL

Microliter

Cr

Chromium

M

Molar

stNi

Nickel

µM

Micromolar 21

Journal Pre-proof Pb

Lead

nM

Nanomolar

V

Vanadium

p

Probability

As

Arsenic

Se

Selenium

Al(III)O4

Aluminium oxide

P(V)O4

Phosphorus oxide

Si(IV)O4

Silicon oxide

CEC

Cation Exchange Capacity Field Effect Transistor

FET ICP STEM-EDX

Inductively Coupled Plasma Scanning Transmission Electron MicroscopeEnergy Disperse Spectroscopy

FESEM FTIR XRD XPS

Fourier Transform Infrared Spectroscopy X-ray Diffraction Analysis Photoelectron Spectroscopy

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Journal Pre-proof Figure Legends Figure 1:

Schematic representation of overall view. The figure illustrates the generation of tremendous fly ashes from multiple types of sources. The fly ash waste is then undergoes a series of chemical treatment, purification and crystallization processes which develop aluminosilicates. Aluminosilicate nanomaterial made up of silica and aluminium at respective ratios, depending on the type of fly ash were applied and highly encouraged in the green implementation of fly ash derived aluminosilicates in medical applications are indicated.

Figure 2:

Sources and their fly ashes were shown. The color of fly ash varies based on the source and also the degree of heating and cooling of fly ash. The higher carbon content, shows the darker the color of fly ash, appeared as black ashes. The light grey colored ashes depicts low carbon content and high content of iron oxide compounds. (a) The scanning electron microscope (SEM) image shows the outer surface of rice husk ash. Reproduced with permission from (Bie et al., 2015) Copyright 2015 Elsevier Ltd. (b) Morphology of coconut husk ash after treated with mild NaOH were examined under SEM, indicates the development of porous structures particles. Reproduced with permission from (Islam et al., 2017) Copyright 2017 Elsevier Ltd. (c) SEM image of sugarcane ash after aging of 7 days shows the irregular fine and hard particles present in the ash. Reproduced with permission from (Joshaghani and Amin, 2017) Copyright 2017 Elsevier Ltd (d) Pith layer of corncob ash were observed under SEM, reveals the perforated ash particles which are lesser abrasive than sand. Reproduced with permission from (Ali et al., 2019) Copyright 2019 Elsevier Ltd.

Figure 3:

(a) Primary building units of aluminosilicates in tetrahedral structure. Shown with centrally located Si, Al, or P atoms, regarded as the finite component units for the building of secondary, and tertiary structure of aluminosilicates connected in a ring structure which results in various framework of aluminosilicates (FAU, EMT, LTA, SOD). (b) Spherical shaped aluminosilicate nanocomposite synthesized from biomass fly ash observed under SEM at 600 nm magnification and (c) at 500 nm magnification. Reproduced with the permission from (Nor Sharliza Mohd Safaai, Zainura Zainon Noor, Haslenda Hashim, Zaini Ujang, 2010) Copyright 2010 Elsevier Ltd. (d) SEM image of aluminosilicate. Shows spherical shape synthesized at room temperature using template free gel system were shown. Reproduced with the permission from (Valtchev et al., 2005) Copyright 2005 ACS pubs. (e) Digital images of stilbite canvasite and (f) clinoptilolite which were the most pioneer type of natural zeolites discovered by Crønsted in 1950s. Reproduced with permission from (Bacakova et al., 2018) Copyright 2005 RSC pubs. 36

Journal Pre-proof Figure 4:

Extraction techniques of nanostructured aluminosilicates. (a) Process flow diagram of hydrothermal method of nanostructured aluminosilicate extraction, mostly implemented in industries for large scale aluminosilicate production using fly ash waste. Hydrothermal method requires moderately high energy system to extract uniform size and shaped aluminosilicates. (b) Schematic illustration of aluminosilicate nanocomposite synthesis at laboratory scale through the simplified alkaline treatment method, followed by gelation and condensation to obtain the crystalline aluminosilicates at low temperature. (c) Experimental flowchart of synthesizing aluminosilicate nanocomposite using fly ash through simplest technique, applicable for small scale laboratory extraction.

Figure 5:

Schematic diagram illustrates aluminosilicates in medical application. Predominantly as drug carrier and in drug delivery systems, particularly is in detecting tumor cells. Figure shows the aluminosilicate conjugated with drug/antibody/aptamers through the relevant biocompatibility. The aluminosilicates are then injected into the blood stream where it targets the tumor blood vessel and then the tumor cells. Due to its large surface area/volume and porous cavity, aluminosilicates could easily diffuse through the cell membrane of tumor cells and release the anticancer drug and disintegrates the tumor cells. The similar strategy is also applicable when antimicrobial drugs are loaded with aluminosilicates, which kills the pathogenic bacteria in living organisms.

Figure 6:

(a) Schematic representation of aluminosilicate nanocomposite in antipathogenic drug delivery system. Aluminosilicate functionalized with antimicrobial drug allows the nanocomposite to carry high amount of drug and delivery in the presence of any pathogens. Thus, aluminosilicate functionalized drugs creates large inhibition zone, indicates the ability of nanocomposite in drug delivery system. (b) i. FESEM image of aluminosilicate conjugated with silver ions. ii. Fungal inhibiting zone shown by aluminosilicate alone in C. albicans cultured plate. A slight inhibition zone is observed, justifies the amtimicrobial property own by the nanocomposite. iii. Inhibition zone against C. albicans in response with silver ion functionalized with aluminosilicate. The large zone of fungal inhibition supports the significant contribution of aluminosilicate in antifungal property. Reproduced with permission from (Sánchez et al., 2017) Copyright 2017 Elsevier B.V. B.

Figure 7:

Graphical illustration represents the application of nanostructured aluminosilicates in medical diagnosis. As the growing nanobiotechnology fosters the deposition of nanomaterials on the biosensing surface, aluminosilicates synthesized from the fly ash waste are highly encouraged for the high sensitive biosensor development. Zeolite modified biosensor could be used for the diagnosis of biomarkers such as DNA, protein and antigen which 37

Journal Pre-proof are highly in need for the detection of lethal diseases. Besides, it is also applicable in the detection of charged ion molecules and also pH dependent electrolytes which is significant in the study of biomolecules with different pH and charged ions.

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Journal Pre-proof Table 1: Biopharmaceutical Applications of Aluminosilicate Nanocomposites from Fly Ash Fly ash source Coal fly ash

Coal fly ash

Rice husk ash

Aluminosilicate Medical type strategy Zeolite X Anti-proliferative drug delivery system to inhibit proliferation of cancer cell Zeolite X Anti-proliferative drug delivery system to inhibit proliferation of cancer cell Zeolite Y Antimicrobial drug delivery system

Target cells human breast cancer MCF-7 cells

References (Subhapriya and Gomathipriya, 2018a)

human cervical (Jang et al., (HeLa) cancer cells 2017)

Staphylococcus aureus , Enterococcus , faecalis Escherichia coli and Pseudomonas aeruginosa

(Nik Malek et al., 2018)

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Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

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Highlights 

Fly ash consists of crystalline mullite, quartz, iron oxides and other earth metals



Aluminosilicates as the prospective nanocomposite synthesized from fly ash



Focused on fly ash derived aluminosilicates in medical & industrial applications



Aluminosilicates are excellent for drug carrier, bone engineering & therapeutics

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Aluminosilicates are for waste management, soil amelioration and other industries