Removal Of Fluoride Ions Research Articles

Recent Advances in Adsorption Techniques for the Removal of Fluoride Ions from Wastewater: A Review

Recent Advances in Adsorption Techniques for the Removal of Fluoride Ions from Wastewater: A Review

Defluoridation of Groundwater Using Low-cost Adsorbents

Excessive fluoride in groundwater poses significant health risks to millions of people worldwide, necessitating effective and accessible defluoridation methods. This study investigates the use of column filtration for removing fluoride from groundwater. The study employs a systematic approach to evaluate the performance of different adsorbent materials in a fixed-bed column setup. Various materials were tested as adsorbents in column, including Brick powder, Neem leaf powder, Lime, Sawdust, and Vetiver. The research examines the effects of key operational parameters such as bed depth, flow rate, and initial fluoride concentration on the overall removal efficiency. Experiments were conducted using groundwater to assess the method's effectiveness. Results indicated that column filtration can effectively reduce fluoride concentrations to below the World Health Organization's recommended limit of 1.5 mg/L. This report contributes to the development of efficient, cost-effective, and sustainable solutions for groundwater defluoridation. All adsorbents used were inexpensive materials, available easily in nature and locally at village or rural level. Some of the adsorbents were very effective in removal of fluoride ion and can be used as defluoridating agents but they impart color and turbidity to the groundwater. Among all the adsorbents used, Vetiver demonstrated higher removal efficiency of 78% followed up by limestone 77% removal but hindered by its precipitation. Sawdust and brick powder were also efficient up to a certain extent of 72% and 69% respectively in adsorbing fluoride ions. Neem leaves powder was found to be least effective in adsorbing showing about 50% removal efficiency.

Enhanced removal of fluoride ions using lanthanum-doped coconut shell biochar in PVDF ultrafiltration membranes

Fluoride contamination in surface and ground water poses significant health risks, necessitating a low-energy, cost-effective removal method. Herein, an ultrafiltration (UF) adsorptive membrane doped with lanthanum (La)-based coconut shell biochar was synthesized to effectively remove fluoride ions. Based on the results of adsorption and membrane separation performance, it was found that La-based biochar showed a significantly higher adsorption capacity (126.7 mg F/g) compared to bare biochar (27.41 mg F/g), due to the oxygen-containing functional groups from La2O2CO3 that enhance binding sites and electrostatic attraction for fluoride ions. Furthermore, the addition of La-modified adsorbent to the polyvinylidene fluoride (PVDF) UF membrane markedly altered its structure and surface properties, changing the pore structure to porous, narrowing pore size, increasing active adsorption sites, and improving hydrophilicity. These changes boosted fluoride ion rejection from 9.53 % to 62.07 % with tiny effect on membrane permeability. More important, this UF adsorptive membrane exhibited excellent antifouling ability with the lowest flux decline (J/J0 =0.450) compared to pristine PVDF membrane (J/J0 =0.142), which was owing to the better improved surface properties. In all, this study provides a novel strategy for efficient, economic and selective separation of fluoride ions and further extends the application of UF to the field of ion removal.

Adsorption Isotherm, Kinetic and Thermodynamic Studies for Removal of Fluoride Ions from Drinking Water Using Modified Natural Pumice

This study aimed to modify pumice using aluminum chloride as an adsorbent for defluoridation. Batch and column experiments were carried out to evaluate the effects of pH, initial fluoride concentration, contact time, dose, and temperatur. The modified pumice adsorbent showed good fluoride removal in both batch and column studies. Fluoride up-take was observed to be effective >7%, at pH 6.5-7.5, and adsorption equilibrium time was observed at 60 min. the adsorption results were modelled using kinetic and isotherm models. Experimental data indicated that fluoride adsorption follows the second pseudo-order kinetics model (R2 > 0.99) and fits well with both the Freundlich and Langmuir isotherm models, which showed favorability for the adsorption of fluoride with a maximum capacity of 0.083 mg/g. The negative values of ∆Ho and ∆Go indicate that the adsorption process was feasible, exothermic, and spontaneous. The column performance showed the best fluoride uptake efficiency, with a breakthrough capacity of 0.48 mg/g. The %R was approximately %100 using0.1M NaOH. Fluoride levels in real wells water decreased dramatically (e.g. 4.1-0.88, 7.1-1.54, and 6.2-1.46 mg/L). The results revealed that modified pumice has the potential for fluoride removal from drinking water.

High-performance fluoride removal by Fe/N co-doped microporous carbon: Mechanism of capacitive deionization with FeNx sites

Fluoride pollution is becoming increasingly serious with industrial growth. Controlling fluoride pollution have become important environmental issues of global concern. Transition metal nitrides are excellent CDI electrode materials due to their excellent conductivity and electrochemical stability. In this study, FeNx/C was synthesized as an electrode material for using the capacitive deionization (CDI) technique to achieve the effective removal of fluoride ions from wastewater. Its high specific surface area (463.278 mg/g) and high capacitance (44.29 F/g) were demonstrated and it had a high adsorption capacity of 158.33 mg/g. FeN3 and FeN4 were used as the main sites as capacitive deionization for removing fluoride from the water by chemisorption and hydrogen bonding. The higher adsorption energy by density functional calculation also indicated that the existence of Fe-N coordination bond effectively improved its electrosorption capacity. This study is beneficial to provide references and research ideas for removing fluoride in the CDI field.

Mechanism of Enhanced Fluoride Adsorption Using Amino-Functionalized Aluminum-Based Metal–Organic Frameworks

Due to the increasing fluoride concentrations in water bodies, significant environmental concerns have arisen. This study focuses on aluminum-based materials with a high affinity for fluorine, specifically enhancing metal–organic frameworks (MOFs) with amino groups to improve their adsorption and defluorination performance. We systematically investigate the factors influencing and mechanisms governing the adsorption and defluorination behavior of amino-functionalized aluminum-based MOF materials in aqueous environments. An SEM, XRD, and FT-IR characterization confirms the successful preparation of NH2-MIL-101 (Al). In a 10 mg/L fluoride ion solution at pH 7.0, fluoride ion removal efficiency increases with the dosage of NH2-MIL-101 (Al), although the marginal improvement decreases beyond 0.015 g/L. Under identical conditions, the fluoride adsorption capacity of NH2-MIL-101 (Al) is seven times greater than that of NH2-MIL-101 (Fe). NH2-MIL-101 (Al) demonstrates effective fluoride ion adsorption across a broad pH range, with superior fluoride uptake in acidic conditions. At a fluoride ion concentration of 7 mg/L, with 0.015 g of NH2-MIL-101 (Al) at pH 3.0, adsorption equilibrium is achieved within 60 min, with a capacity of 31.2 mg/g. An analysis using adsorption isotherm models reveals that the fluoride ion adsorption on NH2-MIL-101 (Al) follows a monolayer adsorption model, while kinetic studies indicate that the predominant adsorption mechanism is chemical adsorption. This research provides a scientific basis for the advanced treatment of fluoride-containing wastewater, offering significant theoretical and practical contributions.

Effective removal of fluoride ions from contaminated water using electrochemical techniques: A critical review on recent developments and environmental perspective

Worldwide, water pollution poses significant threats to human health, with fluoride contamination emerging as a critical hazard. High fluoride concentrations in water cause severe health impacts, including dental and skeletal fluorosis, neurological damage, and harm to the parathyroid gland, cardiovascular, and reproductive systems. Electrochemical technique is one of the most widely used treatment technologies that has been extensively studied and provides a very effective, low-cost method of removing fluoride from contaminated water. The review reports the comprehensive electrochemical strategies for fluoride ions removal. The sources, toxicity, and impacts of fluoride pollution on health are discussed in this review. A comprehensive analysis of current electrochemical methods, including electrolysis, electrocoagulation, and the electro-fenton process, was provided in the context to facilitate the efficient removal of fluoride ions from wastewater. These methods exhibit high removal efficiencies, reaching up to 95 %, and offer scalability and operational flexibility, making them suitable for both centralized and decentralized water treatment systems. Furthermore, the recent advancements in the development of electrochemical technique for fluoride removal are critically reviewed. This study has prospected the recent developments, recommendations and future outlooks on electrochemical technique for fluoride removal.

Simultaneous precipitation removal of fluoride ion and chloride ion from smelting waste acid using renewable remover

Purification and reuse is a potential method of smelting waste acid disposal. High concentrations of fluoride and chloride in waste acid are harmful impurity and must be removed. Previous studies have shown that fluoride removal with rare earth and chloride removal with bismuth have similar cyclic process of "precipitation removal-agent regeneration" and similar reaction conditions. In this paper, a method of simultaneous precipitation removal of F− and Cl− from waste acid using La(OH)3 and Bi2O3 as a mixed remover was proposed, and the mixed remover is regenerated by sodium hydroxide solution for the recycling of the remover. Thermodynamic analysis of La3+-Bi3+-F−-Cl−-H2O system verified the feasibility of simultaneous removal. The experimental results showed that under the optimum reaction conditions, the removal efficiencies of F− and Cl− were 93.67 % and 96.47 %, respectively, and the concentrations of F− and Cl− in the solution after removal were 66.70 mg/L and 71.10 mg/L, respectively. Under the optimum conditions, the regeneration efficiencies of La(OH)3 and Bi2O3 were 96.80 % and 96.95 %, respectively. The proposed process has the advantages of no waste output, short process, and low energy consumption and provides an environmentally friendly method of removing fluoride and chloride from waste acid.

Adsorption of Fluoride Ions Using Si–Al–Mg Layered Double Hydroxides

ABSTRACT Removal of fluoride ions from water environments has become a research topic because high concentrations of fluoride ions in drinking water are harmful to the human body. The adsorption of fluoride ions by a Si – Al – Mg layered double hydroxide (LDH) was investigated in this study. The prepared adsorbent had a hydrotalcite-like LDH structure, which was decomposed by calcination and reconstructed upon contacting water. The adsorption process followed pseudo-second-order kinetics. Granulation of the adsorbent for application to chromatographic operation decreased the adsorption rate constant. Adsorption of fluoride ions was high at 7 < pHeq <10 and decreased at higher pHs. The adsorption mechanism involved ion exchange between the fluoride ions in aqueous solution and chloride ions in the adsorbent as well as physisorption via van der Waals forces. The adsorbent was selective towards fluoride ions over nitrate and sulfate ions, although the adsorption of fluoride ions was suppressed in the presence of chloride, carbonate, and phosphate ions. Chromatographic operation using the granulated adsorbent with an alumina-based binder was characterized by slow kinetics, necessitating a low flow rate for the feed solution. The prepared adsorbent was also used to selectively adsorb fluoride ions from simulated wastewater produced by the semiconductor manufacturing process.

Double cross-linked chitosan sponge encapsulated with ZrO2/soy protein isolate amyloid fibrils nanoparticles for the fluoride ion removal from water

Fluoride ion pollution in water has become a serious threat to the water environment and human health. Adsorption is a promising means of fluoride removal, but it also faces challenges such as the difficult separation and recovery of powdered particles, the leaching of modified coatings from adsorbents, and the structural disintegration of macroscopic adsorbents. For addressing the above challenges, glutaraldehyde/polyvinyl alcohol co-crosslinked ZrSAF/chitosan spongy composites (ZrS/GPCS) were prepared by utilizing encapsulation strategies and cross-linking. ZrS/GPCS-1, ZrS/GPCS-3 and ZrS/GPCS-4 were prepared due to the different amounts of cross-linking agents. The results showed that their fluoride ion adsorption capacities were 42.02, 44.44 and 39.84 mg/g, respectively. The removal of fluoride ions by ZrS/GPCS was maintained at >80 % in the pH range of 4–10. The addition of glutaraldehyde and polyvinyl alcohol affected the contact efficiency of fluoride ions with chitosan and ZrSAF, influencing the adsorption rate and adsorption effect. Glutaraldehyde, polyvinyl alcohol and ZrSAF improved the thermal stability, mechanical properties and structural integrity of chitosan matrix. Both the chitosan matrix and the internal ZrSAF played an important role in fluoride removal, and the removal mechanisms included electrostatic interaction, hydrogen bonding, and complexation.

Highly efficient removal and real-time visual detection of fluoride ions using ratiometric CAU-10-NH2@RhB: Probe design, sensing performance, and practical applications

The extensive use of fluoride in agriculture, industry, medicine, and daily necessities has raised growing concerns about fluoride residue. To date, real-time visual detection and efficient removal of fluoride ions from water remain greatly desirable. Herein, nano-CAU-10-NH2@RhB is introduced as a ratiometric fluorescent probe and efficient scavenger for the intelligent detection and removal of fluoride ions. CAU-10-NH2@RhB is readily obtained through one-pot synthesis and exhibits high sensitivity and selectivity for real-time fluoride ion detection, with a naked-eye distinguishable color change from pink to blue. A portable device for point-of-care testing was developed based on color hue analysis readout using a smartphone. A quantitative response was achieved across a wide concentration range, with a detection limit of 54.2 nM. Adsorption experiments suggest that nano-CAU-10-NH2@RhB serves as an efficient fluoride ion scavenger, with a fluoride adsorption capacity of 49.3 mg/g. Moreover, the mechanistic study revealed that hydrogen bonds formed between fluoride ions and amino groups of CAU-10-NH2@RhB are crucial for the detection and adsorption of fluoride ions. This analysis platform was also used for point-of-care quantitative visual detection of fluoride ions in food, water, and toothpaste.

Removal of arsenic and fluoride ions from aqueous solutions using electronic waste-derived adsorbent

Printed Circuit Boards are the fundamental component of almost every electronic device with usage intensifying at an average rate of 8.7 %. However, this leads to a generation of 45 million tons of electronic waste (E-waste) annually posing significant and concerning environmental risks. Recycling these waste printed circuit boards (PCBs) is vital, in terms of environmental pollution, prevention and resource recycling. Activating these non-metallic fractions of the printed circuit boards results in the development of unique textural properties and functionalities which resemble aluminosilicates; confirmed by FTIR, XRD, XPS, XRF, and TGA and could potentially be applied for the uptake of Fluoride and Arsenate. In this study, Activated Non-metallic fraction of the Printed Circuit Boards (A-NMP) was used to investigate various physio-chemical parameters, including contact time, pH, adsorbent dose, and initial concentration to optimize the reaction conditions for the uptake of F− and As(V) from aqueous solutions and, compared its adsorption capacity with other natural and synthetic aluminosilicate. The maximum adsorption capacity comes out to be 4.33 mg g−1 and 4.65 μg g−1 for F− and As(V) and best fit to Langmuir and Freundlich adsorption isotherms, respectively. Kinetic modelling reveals that the adsorption of F− follows pseudo-first-order kinetics whereas, As(V) follows pseudo-second-order kinetics. Moreover, Intra-particle diffusion revealed a chemisorption-controlled process for both the adsorbates. Furthermore, in a binary component system the F− and As(V) showed the maximum percentage removal of 92 % and 76 %, respectively at pH 5, and best fit to Langmuir adsorption isotherm.

Development of a limestone-based ballasted material for enhanced co-removal of turbidity and fluoride from coal mine water: An efficacy study

The rapid progression of coal mining technology in recent years has resulted to the discharge of mine water with excessively high levels of turbidity and fluoride, presenting a complex contamination issue. This study develop an innovative limestone-based ballasted material, integrating it with ballasted flocculation technology. The synergistic effects of surface flocculation and adsorption have enabled the simultaneous and efficient removal of high concentrations of turbidity and fluoride. The influence of various parameters, including the dosage of the coagulant, flocculant, ballasted material, and the stability under long-term continuous operation, on the performance of this new technology was investigated. Findings indicate that an increase in the dosage of the coagulant, polyaluminum chloride (PAC), positively affects the removal of turbidity and fluoride ions, with an optimal dosage of 60 mg/L. The addition of polyacrylamide (PAM) showed that both conventional and ballasted coagulation techniques exhibit an initial increase followed by a decrease in turbidity removal efficiency, and an ascending trend in fluoride removal efficiency, with an optimal PAM dosage of 1.0 mg/L. The dosage of the new ballasted material was determined based on the initial water turbidity and fluoride concentrations, an increase in its dosage led to a progressive reduction in effluent turbidity and a corresponding increase in fluoride removal. A 30-day continuous operation confirmed the stability of the new process, with a treatment cost of approximately 2.67 $/t. The pseudo-first-order kinetic model and the Langmuir adsorption isotherm equation provided satisfactory fits to the treatment data, suggesting that both conventional and ballasted coagulation involve a combination of surface adsorption and intraparticle diffusion mechanisms for the removal of turbidity and fluoride.

Enhancing fluoride ion removal from aqueous solutions and glass manufacturing wastewater using modified orange peel biochar magnetic composite with MIL-53

In this study, we developed new adsorbents derived from orange peel biochar (BCOP) and enhanced them with CoFe2O4 magnetic nanoparticles (BCOP/CoFe2O4) and MIL-53(Al) (BCOP/CoFe2O4/MIL-53(Al)). These adsorbents were utilized to remove fluoride (FL) ions from aqueous solutions. We analyzed the properties of these adsorbents using a range of techniques, including FTIR, XRD, SEM, EDX-Map, VSM, Raman spectroscopy, and BET. Our findings indicate that the components interact effectively with one another. Specifically, the BCOP/CoFe2O4/MIL-53(Al) sample exhibited a specific surface area of 196.430 m2/g and a magnetic saturation value of 9.704 emu/g. The maximum FL ion adsorption capacities for BCOP, BCOP/CoFe2O4, and BCOP/CoFe2O4/MIL-53(Al) were 7.618, 16.330, and 37.320 mg/g, respectively, indicating that the modifications significantly enhanced the adsorption capacity. The optimum fluoride ion removal rates using BCOP, BCOP/CoFe2O4, and BCOP/CoFe2O4/MIL-53(Al) were 97.88%, 98.23%, and 99.06%, respectively, at adsorbent doses of 2.5, 1.5, and 0.8 g/L, contact times of 90, 70, and 50 min, pH 4, temperature 50 °C, and a FL concentration of 10 mg/L. Thermodynamic studies revealed that the adsorption process was spontaneous and endothermic, with increased randomness between the adsorbent and fluoride ions. Kinetic analyses showed that fluoride ion adsorption by BCOP/CoFe2O4/MIL-53(Al) followed a pseudo-second-order (PSO) model, while BCOP and BCOP/CoFe2O4 followed a pseudo-first-order (PFO) model. Additionally, the equilibrium data for fluoride ion adsorption on BCOP/CoFe2O4/MIL-53(Al) adhered to the Freundlich model, whereas the other samples conformed to the Langmuir model. The study evaluates the effectiveness of BCOP, BCOP/CoFe2O4, and BCOP/CoFe2O4/MIL-53(Al) in removing FL ions from glass manufacturing wastewater, highlighting the superior performance of the magnetic composite due to its enhanced surface area and functional groups. Notably, the adsorbents demonstrated good regenerative capabilities, maintaining high performance over multiple adsorption cycles.

Cerium-based metal-organic-frameworks with ligand tuning of the microstructures for fluoride adsorption: linear and nonlinear kinetic and isotherm adsorption models.

We present the synthesis and characterisation of three Ce-based metal-organic frameworks (Ce-MOFs) using fumaric acid (Fu), terephthalic acid (BDC), and trimesic acid (H3BTC) as linkers. The use of different linkers influenced the size of the MOF particles, surface area, crystallinity, and microporous structure. The successful implementation of Ce-Fu, Ce-BDC, and Ce-H3BTC MOFs for fluoride ion removal from wastewater was carried out, in which Ce-Fu MOFs exhibited a maximum adsorption capacity (AC) of 64.2 mg g-1. The study also reveals that the use of ultrasound as a mediator for adsorption study over conventional method gives rapid adsorption rate, in which 85% of the fluoride uptake took place just in 10 min and achieved maximum AC in 30 min. The kinetics data were most accurately explained by the pseudo-second-order model (PSO). The existence of co-ions such as NO3-, Cl-, HCO3-, SO42-, Br-, CO32-, and PO43- has a substantial effect on fluoride removal. The mechanism between the fluoride ions and the MOF surface took place via the electrostatic force and the ion exchange process, confirmed using X-ray photoelectron spectroscopy (XPS) and delsa nano. The material is sustained its relatively higher F- ions removal efficiency up to the five cycles. This research might help in the development of novel microporous Ce-based MOFs since it possesses a highly stable crystalline structure in water, suggesting a promising role in aqueous applications.

Highly porous P(DVB-AMPS) copolymer with tailored surface engineering for efficient fluoride capture from water

Surface engineering, especially surface hydrophilicity and active binding sites are crucial for porous polymers in the removal of fluoride ions from water. Herein, a novel P(DVB-AMPS) copolymer with tailored surface engineering was designed through a one-step polymerization method by incorporating diethylene-benzene (DVB) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). AMPS endows abundant active binding sites and provides P(DVB-AMPS) with both hydrophilicity and affinity for fluoride ions, while the monomer DVB acting as a crosslinker, facilitating pore generating. The surface hydrophilicity of P(DVB-AMPS) could be easily tuned by increasing the amounts of AMPS with the contact angle decreased from 126° (PDVB) to 52°. Furthermore, P(DVB-AMPS) material maintains a large specific surface area of 428 m2 · g[Formula: see text] and preserves its highly porous structure. P(DVB-AMPS) exhibits an efficient adsorption capacity (51.9 mg · g[Formula: see text]) and a rapid adsorption rate (6.83 mg · g[Formula: see text] · min[Formula: see text]), which demonstrates competitive performance compared with previous reports. Importantly, the material possesses highly selective adsorption toward fluoride. The excellent adsorption performance of P(DVB-AMPS) is attributed to the high porosity, improved surface hydrophilicity and active binding sites. This work not only provides a new strategy for designing high-performance adsorbents but also offers a novel polymer material for the efficient capture of fluoride ions from water.

Adsorption of fluoride ion on Al/La modified acidified attapulgite composite materials

This study developed a novel fluoride ion adsorbent material (Al/La-A) for efficient removal of fluoride ions in water. The crystal structure, elemental composition, surface morphology, specific surface area, thermal stability and surface electronegativity before and after modification were explored using FTIR, XRD, XPS, SEM-EDS, BET, TG-DSC, and zeta potential measurements. Results showed that the fluoride ion adsorption capacity of Al/La-A reached 130.42 mg/g, with the surface area increasing from 65.66 m2/g to 111.68 m2/g, respectively, compared to unmodified attapulgite. Al/La-A maintained excellent fluoride ion removal performance over a wide pH range, with the best adsorption at pH 2. Coexisting ion experiments indicated weak competitive adsorption effects of Cl-, SO42-, and HCO3–, with fluoride ion adsorption remaining above 100 mg/g in the presence of different concentrations of coexisting anions. After 5 adsorption–desorption cycles, Al/La-A exhibited strong adsorption capacity and reusability. The fitting of Langmuir adsorption model and pseudo-second-order kinetic model to the adsorption of fluoride ions on Al/La-A indicated that the adsorption of fluoride ions on Al/La-A was primarily monolayer chemical adsorption. The adsorption mechanism of fluoride ions involved electrostatic interactions, ion exchange, and coordination complexation. This study provides a new research approach for the optimal utilization of attapulgite-based adsorbent materials and the efficient removal of fluoride-containing wastewater.

Aluminum-Crosslinked Nanocellulose Scaffolds for Fluoride Removal.

Anionic carboxylated cellulose nanofibers (CNF) are effective media to remove cationic contaminants from water. In this study, sustainable cationic CNF-based adsorbents capable of removing anionic contaminants were demonstrated using a simple approach. Specifically, the zero-waste nitro-oxidization process was used to produce carboxylated CNF (NOCNF), which was subsequently converted into a cationic scaffold by crosslinking with aluminum ions. The system, termed Al-CNF, is found to be effective for the removal of fluoride ions from water. Using the Langmuir isotherm model, the fluoride adsorption study indicates that Al-CNF has a maximum adsorption capacity of 43.3 mg/g, which is significantly higher than that of alumina-based adsorbents such as activated alumina (16.3 mg/g). The selectivity of fluoride adsorption in the presence of other anionic species (nitrate or sulfate) by Al-CNF at different pH values was also evaluated. The results indicate that Al-CNF can maintain a relatively high selectivity towards the adsorption of fluoride. Finally, the sequential applicability of using spent Al-CNF after the fluoride adsorption to further remove cationic contaminant such as Basic Red 2 dye was demonstrated. The low cost and relatively high adsorption capacity of Al-CNF make it suitable for practical applications in fluoride removal from water.

Simultaneous removal of fluorine and dissolved silica from semiconductor wastewater by an in-situ crystal nucleation method towards near-zero liquid discharge

Near-zero liquid discharge (Near-ZLD) treatment process for semiconductor (SC) wastewater often encounters membrane fouling caused by calcium fluoride (CaF2) and silicates, which affect the process stability and efficiency. However, achieving low chemical dosing while simultaneously removing fluoride ions (F−) and dissolved silica (D-SiO2) remains a significant challenge in SC wastewater treatment. This study developed an in-situ crystal nucleation (ICN) method for Near-ZLD pretreatment, ensuring the simultaneous removal of F− (<8.0 mg/L) and D-SiO2 (<6.0 mg/L) to meet Near-ZLD requirements while mitigating membrane fouling. The method induced the in-situ generation of CaF2 seeds through a simple process adjustment without external additions, promoting the growth of CaF2 particles size and enhancing the subsequent coagulation effect. Consequently, membrane fouling was significantly reduced, and its reversibility was increased by more than ten-fold. In addition, the coagulant dosing was further optimized (Fe/Al mixed coagulants), which enhanced the acid-base interaction between the membrane surface and flocs, reducing irreversible membrane fouling by 70 %. In practical applications, the ICN method consistently achieved a 104.87 % increase in membrane flux compared to the conventional method, significantly extending the membrane's service life. This method provides a new perspective with practical guidance for the stable and efficient Near-ZLD operation in SC wastewater.

Efficient adsorptive removal of low concentration fluoride ions from water by cellulose beads with trapped CeO2 nanoparticles

The high electronegativity and solubility of fluoride ions (F-) in water at low concentrations pose challenges for their treatment and recovery. To effectively adsorb F-, cellulose beads with trapped CeO2 nanoparticles (CeO2@CBs) were fabricated from a NaOH/urea aqueous solution by the optimal extrusion dropping technology. The CeO2@CBs exhibited a maximum removal efficiency of 99.15 % for 10.0 mg L−1 F- at 45°C, pH=3.0 and an adsorbent dose of 1.0 g. The CeO2@CBs were characterized using SEM-EDS, FT-IR, XRD, and XPS. These findings demonstrate that CeO2 nanoparticles were uniformly entrapped in cellulose beads and reveal that the removal mechanism involves anionic exchange and electrostatic attractions between protonated hydroxyl on CeO2@CBs surface and F-. The results show that the anion competition sequence that affects the F- adsorption efficiency was Cl−<NO3−<SO42−<PO43−. CeO2@CBs were directly packed into columns, exhibiting exceptional adsorption efficacy and remarkable stability in column experiments. Even after three desorption cycles, the adsorption performance remained above 95 %. Because the designed CeO2@CBs have a simple preparation process, high adsorption efficiency and environmental friendliness, they can provide valuable insights for designing new adsorbents and removing F- from aqueous solutions.