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In this work, a surface cationized inorganic–organic hybrid foam was produced from porous geopolymer (GP) and cellulose nanocrystals (CNCs). GPs were synthesized from alkali-activated metakaolin using H₂O₂ as a blowing agent and hexadecyltrimethylammonium bromide (CTAB) as a surfactant. These highly porous GPs were combined at pH 7.5 with cationic CNCs that had been synthesized from dissolving pulp through periodate oxidation followed by cationization in a deep eutectic solvent. The GP-CNC hybrid foams were employed as reactive filters in the removal of the anionic dye, methyl orange (MO; 5–10 mg/L, pH 7). The effects of a mild acid wash and thermal treatments on the structure, properties, and adsorption capacity of the GPs with CNCs and MO were investigated. The CNCs aligned as films and filaments on the surfaces of the neutralized GPs and the addition of CNCs improved MO removal by up to 84% compared with the reference sample. In addition, CTAB was found to disrupt the attachment of CNCs on the pores and improve adsorption of MO in the GPs with and without CNCs.

In this work, we compared the main characteristics of highly porous geopolymer components for water treatment applications manufactured by 3D printing, direct foaming, or granulation. Furthermore, different approaches to impregnate the materials with Ag or Cu were evaluated to obtain filters with disinfecting or catalytic properties. The results revealed that all of the investigated manufacturing methods enabled the fabrication of components that possessed mesoporosity, suitable mechanical strength, and water permeability, even though their morphologies were completely different. Total porosity and compressive strength values were 28 vol% and 16 MPa for 3D-printed, 70–79 vol% and 1 MPa for direct-foamed, and 27 vol% and 10 MPa for granule samples. Both the filter preparation and the metal impregnation method affected the amount, oxidation state, and stability of Ag and Cu in the filters. However, it was possible to prepare filters with low metal leaching between a pH of 3–7, so that the released Ag and Cu concentrations were within drinking water standards.

Abstract This paper investigates the effects of reinforcing one-part alkali-activated slag binders (OAASs) with different types of fiber (steel, polyvinyl alcohol [PVA], basalt, and cellulose) and fiber combinations (single and hybrid) on the mechanical and durability properties of OAASs. All OAASs were reinforced by a 1% fiber volume fraction. Compressive and flexural strengths were the mechanical properties, which were addressed. The durability of the reinforced OAASs was examined based on water absorption by immersion and capillary, acid resistance, high temperature resistance, carbonation resistance, and freeze/thaw resistance. The experimental results showed that the fiber type and combination greatly affects the mechanical and durability properties of OAASs. Moreover, the influence of fiber type and combination on high temperature resistance and freeze/thaw resistance is greater than the influence on acid resistance and carbonation resistance. Graphic Abstract

The synergistic combination of different nanomaterials for improved performance in environmental applications such as the removal of aqueous micropollutants has attracted increasing interest in recent years. This study demonstrates a novel sequential adsorption–aggregation concept that harnesses tubular halloysite nanotubes (HNTs) and flexible cellulose nanofibrils (CNFs) for the removal of a small, anionic dye molecule, chrome azurol S, from water. Hollow HNTs were first allowed to interact with the aqueous dye solution, after which the dye-loaded colloidal nanotubes were aggregated and separated from the water phase with cationized CNFs. The combination of 25 mg CNFs with 1 g HNTs at pH 7 resulted in efficient removal of dye (80%) and turbidity (~100%) and the removal of dye was further promoted in more acidic conditions (within the pH range of 6–8.5) because of the attractive electrostatic interactions. Cationic CNFs not only enabled the separation of dye-loaded clay particles from the water phase through a rapid aggregation but also participated in dye removal through adsorption (~20%). In comparison with nano-sized HNTs, the dye removal performance of micro-sized and chemically similar kaolin was poor (43%). Given the good availability of both HNTs and CNFs and the low consumption of the more expensive component (i.e., CNFs) in the process, the concept is straightforward, readily applicable, environmentally benign, and potentially cost-effective.

Concrete production is globally a major water consumer, and in general, drinking-quality water is mixed in the binder. In the present study, simulated sea water and reverse osmosis reject water were used as batching water for one-part (dry-mix) alkali-activated blast furnace slag mortar. Alkali-activated materials are low-CO2 alternative binders gaining world-wide acceptance in construction. However, their production requires approximately similar amount of water as regular Portland cement concrete. The results of the present study revealed that the use of saline water did not hinder strength development, increased setting time, and did not affect workability. The salts incorporated in the binder decreased the total porosity of mortar, but they did not form separate phases detectable with X-ray diffraction or scanning electron microscopy. Leaching tests for monolithic materials revealed only minimal leaching. Furthermore, results for crushed mortars (by a standard two-stage leaching test) were within the limits of non-hazardous waste. Thus, the results indicated that high-salinity waters can be used safely in one-part alkali-activated slag to prepare high-strength mortars. Moreover, alkali-activation technology could be used as a novel stabilization/solidification method for reverse osmosis reject waters, which frequently pose disposal problems.

Geopolymers have been recently explored as sorbents for wastewater treatment, thanks to their mechanical and chemical stability and to their low-energy manufacturing process. One specific application could be the removal of ammonium (NH4+) through exchange with Na+ ions. Additive manufacturing (AM) represents an especially interesting option for fabrication, as it allows to tailor the size, distribution, shape, and interconnectivity of pores, and therefore the access to charge-bearing sites. The present study provides a proof of concept for NH4+ removal from wastewater using porous geopolymer components fabricated via direct ink writing (DIW) AM approach. A metakaolin-based ink was employed for the fabrication of a log-pile structure with 45° rotation between layers, producing continuous yet tortuous macropores which are responsible for the high permeability of the sorbents. The ink consolidates in an amorphous, mesoporous network, with the mesopores acting as preferential sites for ion exchange. The printed sorbents were characterized for their physicochemical and mechanical properties and the NH4+ removal capacity in continuous-flow column experiments by using a model effluent. The lattices present high permeability and high cation exchange capacity and maintained a high amount of active ions after four cycles, allowing to reuse them multiple times.

Micropollutants escaping conventional wastewater treatment processes pose a threat to biota and the environment. Amongst micropollutants, small and ionizable organic compounds are particularly challenging, since their removal depends significantly on prevailing conditions. In this study, anionic cellulose nanofibrils (CNFs) were shown to perform as promising adsorbents for an ionizable pharmaceutical, salbutamol. The adsorbents were produced from wood cellulose through succinylation pretreatment in urea-LiCl deep eutectic solvent (DES), followed by a nanofibrillation procedure. The impact of pH, contact time, salbutamol concentration, and adsorbent dose on salbutamol uptake were investigated in batch adsorption studies. Based on the results, the chemical modification of cellulose significantly enhanced the adsorption of salbutamol. The adsorption efficiency was mainly dependent on the charge and colloidal stability of the anionic nanofibril suspension rather than the charge of salbutamol, because the adsorption was considerably improved at pH > 7 due to the deprotonation of the cellulose carboxyl groups. The experimental maximum adsorption capacity was 196 mg/g. This study highlights the potential of cellulose nanomaterial adsorbents and the importance of controlling the charge of the adsorbent material when developing solutions for ionizable micropollutant removal.

The aim of this study was the valorization of paper sludge waste from paper industry in designing one-part geopolymer cement using ground granulated blast furnace slag as main precursor. The effects of increasing the amount of paper sludge pretreated with a constant amount of sodium hydroxide (2% of slag) on mechanical strength, heat evolution, setting time and durability were analyzed. The reaction products were characterized using X-ray diffraction and thermogravimetric analysis. The findings showed that paper sludge can successfully be used as a secondary source of calcium carbonate in the one-part (“just add water”) geopolymer. The compressive strength of the cured geopolymer increased with increasing the amount of paper sludge, and the non-reacted sludge acted as a filler. The maximum strength (42 MPa, 28 d) was reached at 18 wt-% paper sludge addition. The main reaction products were calcium aluminate silicate hydrate and hydrotalcite-like cementitious gels. From the perspective of its blast-furnace slag content, strength properties, water absorption and setting time, the one-part geopolymer cement could be classified as a CEM IIIC and Type 32.5N class cement under the European standard EN-197.

In the present experimental/numerical study, a combination of ceramic waste and ground-granulated blast furnace slag were used in the preparation of one-part alkali-activated binders. Moreover, the effect of fiber type and content on hardened-state properties and shrinkage was studied under two different curing conditions. In the first stage of this study water absorption, compressive strength, and flexural strength were assessed. Subsequently, the flexural performance of fiber-reinforced binders was simulated and predicted using finite element models under concentrated and distributed flexural loading, respectively. The experimental results showed that fibers improved mechanical properties, and enhancement was governed by fiber type and curing conditions. Moreover, the numerical results indicated that the developed fiber-reinforced binders offer a flexural load-carrying capacity in the range of 10–40 kN/m2 and permissible service loads were well below the ultimate capacity.

Alkali-activated materials (AAM) are recognized as potential alternatives to ordinary Portland cement (OPC) in order to limit CO2 emissions as well as beneficiate several wastes into useful products. However, the alkali activation process involves concentrated aqueous alkali solutions, which are corrosive, viscous, and, as such, difficult to handle and not user friendly. Consequently, the development of so-called one-part or “just add water” AAM may have greater potential than the conventional two-part AAM, especially in cast-in-situ applications. One-part AAM involves a dry mix that consists of a solid aluminosilicate precursor, a solid alkali source, and possible admixtures to which water is added, similar to the preparation of OPC. The dry mix can be prepared at elevated temperatures to facilitate the reactivity of certain raw materials. This review discusses current studies of one-part AAMs in terms of raw materials, activators, additives, mechanical and physical properties, curing mechanisms, hydration products, and environmental impacts.

Geopolymers are functional materials that can be used in various environmental applications such as adsorbents in pollutant removal from wastewaters. Metakaolin geopolymer (MK-GP) has been proven to be especially suitable for ammonium (NH4 +) removal. In this research, the optimal reagent and raw material ratios in the preparation of MK-GP in terms of NH4 + adsorption capacity were investigated. The response surface methodology based on the face-centered central composite design was used to optimize the levels of three factors: the amounts of hydroxide, silicate, and metakaolin. In addition, the effect of Na or K as the charge-balancing cation was studied. Empirical models were fitted to the experimental data using multiple linear regression. The significance of the models was confirmed by means of analysis of variance. Optimal NH4 + removal efficiency was achieved when the amounts of hydroxide and silicate were maximized, the amount of metakaolin was minimized, and Na-based reagents were used. These trends are most likely a result of optimized conversion of metakaolin into MK-GP.

Peracids have gained interest in the water treatment over the last few decades. Peracetic acid (CH3CO3H) has already become an accepted alternative disinfectant in wastewater disinfection whereas p...

Blast-furnace slag and metakaolin were geopolymerised, modified with barium or treated with a combination of these methods in order to obtain an efficient SO4(2-) sorbent for mine water treatment. Of prepared materials, barium-modified blast-furnace slag geopolymer (Ba-BFS-GP) exhibited the highest SO4(2-) maximum sorption capacity (up to 119mgg(-1)) and it compared also favourably to materials reported in the literature. Therefore, Ba-BFS-GP was selected for further studies and the factors affecting to the sorption efficiency were assessed. Several isotherms were applied to describe the experimental results of Ba-BFS-GP and the Sips model showed the best fit. Kinetic studies showed that the sorption process follows the pseudo-second-order kinetics. In the dynamic removal experiments with columns, total SO4(2-) removal was observed initially when treating mine effluent. The novel modification method of geopolymer material proved to be technically suitable in achieving extremely low concentrations of SO4(2-) (

Soapstone is a soft, magnesium-rich mineral widely used in the production of carved objects and architectural elements, for instance. The processing of soapstone causes the formation of significant amounts of waste powder, which is largely landfilled at the moment. The aim of the present study is to evaluate the suitability of soapstone waste as the main binder for the alkali-activation process using sodium silicate and hydroxide solutions as activators. The results demonstrate that soapstone alone reacts to some extent (compressive strength of 13 MPa at 28 day age), but mechanical properties are improved significantly after replacing 20% of soapstone by metakaolin (compressive strength of 31 MPa at 28 d age). The obtained mechanical properties are closely similar to those of virgin soapstone. Durability properties of the developed alkali-activated binders were similar or better than typical Portland cement-based binders in terms of high temperature, acid, and freeze-thaw resistance, and sorptivity. The material costs alkali-activated soapstone mortar were estimated as approximately 70 €/t. Thus, the results enable utilizing currently underexploited soapstone waste in a sustainable and economically interesting way.

Sulfate (SO₄²⁻) is a ubiquitous anion in natural waters. It is not considered toxic, but it may be detrimental to freshwater species at elevated concentrations. Mining activities are one significant source of anthropogenic sulfate into natural waters, mainly due to the exposure of sulfide mineral ores to weathering. There are several strategies for mitigating sulfate release, starting from preventing sulfate formation in the first place and ending at several end-of-pipe treatment options. Currently, the most widely used sulfate-removal process is precipitation as gypsum (CaSO₄·2H₂O). However, the lowest reachable concentration is theoretically 1500 mg L⁻¹ SO₄²⁻ due to gypsum’s solubility. At the same time, several mines worldwide have significantly more stringent sulfate discharge limits. The purpose of this review is to examine the process options to reach low sulfate levels (< 1500 mg L⁻¹) in mine effluents. Examples of such processes include alternative chemical precipitation methods, membrane technology, biological treatment, ion exchange, and adsorption. In addition, aqueous chemistry and current effluent standards concerning sulfate together with concentrate treatment and sulfur recovery are discussed.

Ammonium (NH₄⁺) removal from municipal wastewater poses challenges with the commonly used biological processes. Especially at low wastewater temperatures, the process is frequently ineffective and difficult to control. One alternative is to use ion-exchange. In the present study, a novel NH4+ ion-exchanger, metakaolin geopolymer (MK-GP), was prepared, characterised, and tested. Batch experiments with powdered MK-GP indicated that the maximum exchange capacities were 31.79, 28.77, and 17.75 mg/g in synthetic, screened, and pre-sedimented municipal wastewater, respectively, according to the Sips isotherm (R² ≥ 0.91). Kinetics followed the pseudo-second-order rate equation in all cases (kp₂ = 0.04–0.24 g mg⁻¹ min⁻¹, R² ≥ 0.97) and the equilibrium was reached within 30–90 min. Granulated MK-GP proved to be suitable for a continuous column mode use. Granules were high-strength, porous at the surface and could be regenerated multiple times with NaCl/NaOH. A bench-scale pilot test further confirmed the feasibility of granulated MK-GP in practical conditions at a municipal wastewater treatment plant: consistently

The mining industry is a major contributor of various toxic metals and metalloids to the aquatic environment. Efficient and economical water treatment methods are therefore of paramount importance. The application of natural or low-cost sorbents has attracted a great deal of interest due to the simplicity of its process and its potential effectiveness. Geopolymers represent an emerging group of sorbents. In this study, blast-furnace-slag and metakaolin geopolymers and their raw materials were tested for simultaneous removal of Ni(II), As(III) and Sb(III) from spiked mine effluent. Blast-furnace-slag geopolymer proved to be the most efficient of the studied materials: the experimental maximum sorption capacities for Ni, As and, Sb were 3.74 mg/g, 0.52 mg/g, and 0.34 mg/g, respectively. Although the capacities were relatively low due to the difficult water matrix, 90–100% removal of Ni, As, and Sb was achieved when the dose of sorbent was increased appropriately. Removal kinetics fitted well with the pseudo-second-order model. Our results indicate that geopolymer technology could offer a simple and effective way to turn blast-furnace slag to an effective sorbent with a specific utilization prospect in the mining industry.

The growth of global construction has contributed to an inevitable increase in the amount of construction and demolition (C&D) waste, and the recycling of C&D waste as aggregates in concrete is receiving increased interest, resulting in less demand for normal aggregates and bringing a potential solution for the landfilling of wastes. Recently, several studies have focused on the use of C&D waste in alkali-activated concrete to move one step closer to sustainable concretes. This paper focuses on the main mechanisms of using C&D waste in the resulting physical, mechanical, and durability properties of alkali-activated concrete in fresh and hardened state properties. The main difficulties observed with recycled aggregates (RA) in concrete, such as high levels of water demand, porous structure, and low mechanical strength, occur in RA alkali-activated concretes. These are associated with the highly porous nature and defects of RA. However, the high calcium concentration of RA affects the binder gel products, accelerates the hardening rate of the concrete, and reduces the flowability of alkali-activated concretes. For this reason, several techniques have been investigated for modifying the water content and workability of the fresh matrix and for treating RA and RA/alkali-activated binder interactions to produce more sustainable alkali-activated concretes.