Effective removal and adsorption mechanism of fluoride from water by biochar-based Ce(III)-La(III)-crosslinked sodium alginate hybrid hydrogel.

An eco-friendly macroparticle biochar (BC)-based Ce(III)-La(III) crosslinked sodium alginate (SA) hybrid hydrogel (BC/Ce-SA-La) was synthesized by droplet polymerization and characterized by SEM-EDS, XRD, FTIR, UV-Vis and XPS. The effects of dosage, pH, contact time, temperature and coexisting ions on the F- ions removal by hybrid hydrogel, and the adsorption performance, interaction mechanism and reusability were investigated. The results demonstrate that the composite has a fancy wrinkle structure with a particle size of about 1.8 mm and abundant porosity on the surface. The removal rate of F- ions by BC/Ce-SA-La reached 90.2 % under the conditions of pH 2.0, 200 min of contact time and 298 K. The adsorption behavior was perfectly explained by Langmuir model, and the maximum adsorption capacity reached 129 mg/g. The adsorption process was an endothermic spontaneous reaction and followed Pseudo-second-order rate model. The strong adsorption was attributed to multi-interactions including complexation, hydrogen bonding and electrostatic adsorption between the composite and F- ions. Coexisting ions hardly interfered with the adsorption of F- ions by BC/Ce-SA-La except for a slight effect of phosphate. The composite after F- ion adsorption was easily separated and could be reused at least three times. BC/Ce-SA-La is a cost-effective and promising granular biosorbent.

Process Intensification for Enhanced Fluoride Removal and Recovery as Calcium Fluoride Using a Fluidized Bed Reactor.

This study explored the feasibility of fluoride removal from simulated semiconductor industry wastewater and its recovery as calcium fluoride using fluidized bed crystallization. The continuous reactor showed the best performance (>90% fluoride removal and >95% crystallization efficiency) at a calcium-to-fluoride ratio of 0.6 within the first 40 days of continuous operation. The resulting particle size increased by more than double during this time, along with a 36% increase in the seed bed height, indicating the deposition of CaF2 onto the silica seed. The SEM-EDX analysis showed the size and shape of the crystals formed, along with the presence of a high amount of Ca-F ions. The purity of the CaF2 crystals was determined to be 91.1% though ICP-OES analysis. Following the continuous experiment, different process improvement strategies were explored. The addition of an excess amount of calcium resulted in the removal of an additional 6% of the fluoride; however, compared to this single-stage process, a two-stage approach was found to be a better strategy to achieve a low effluent concentration of fluoride. The fluoride removal reached 94% with this two-stage approach under the optimum conditions of 4 + 1 h HRT combinations and a [Ca2+]/[F-] ratio of 0.55 and 0.7 for the two reactors, respectively. CFD simulation showed the impact of the inlet diameter, bottom-angle shape, and width-to-height ratio of the reactor on the mixing inside the reactor and the possibility of further improvement in the reactor performance by optimizing the FBR configuration.

Amendment of Sargassum oligocystum bio-char with MnFe2O4 and lanthanum MOF obtained from PET waste for fluoride removal: A comparative study.

The use of biomass and waste to produce adsorbent reduces the cost of water treatment. The bio-char of Sargassum oligocystum (BCSO) was modified with MnFe2O4 magnetic particles and La-metal organic framework (MOF) to generate an efficient adsorbent (BCSO/MnFe2O4@La-MOF) for fluoride ions (F-) removal from aqueous solutions. The performance of BCSO/MnFe2O4@La-MOF was compared with BCSO/MnFe2O4 and BCSO. The characteristics of the adsorbents were investigated using various techniques, which revealed that the magnetic composites were well-synthesized and exhibited superparamagnetic properties. The maximum adsorption efficiencies (BCSO: 97.84%, BCSO/MnFe2O4: 97.85%, and BCSO/MnFe2O4@La-MOF: 99.36%) were achieved under specific conditions of pH 4, F- concentration of 10 mg/L, and adsorbent dosage of 3, 1.5, and 1 g/L for BCSO, BCSO/MnFe2O4, and BCSO/MnFe2O4@La-MOF, respectively. The results demonstrated that the experimental data adheres to a pseudo-second-order kinetic model. The enthalpy, entropy, and Gibbs free energy were determined to be negative; thus, the F- adsorption was exothermic and spontaneous in the range of 25-50 °C. The equilibrium data of the process exhibited conformity with the Langmuir model. The maximum adsorption capacities of F- ions were determined as 10.267 mg/g for BCSO, 14.903 mg/g for the BCSO/MnFe2O4, and 31.948 mg/g for BCSO/MnFe2O4@La-MOF. The KF and AT values for the F- adsorption were obtained at 21.03 mg/g (L/mg)1/n and 100 × 10+9 L/g, indicating the pronounced affinity of the BCSO/MnFe2O4@La-MOF towards F- than other samples. The significant potential of the BCSO/MnFe2O4@La-MOF magnetic composite for F- removal from industrial wastewater, makes it suitable for repeated utilization in the adsorption process.

Removal of Fluoride from Aqueous Solution Using Shrimp Shell Residue as a Biosorbent after Astaxanthin Recovery.

Natural astaxanthin has been widely used in the food, cosmetic, and medicine industries due to its exceptional biological activity. Shrimp shell is one of the primary natural biological sources of astaxanthin. However, after astaxanthin recovery, there is still a lot of chitin contained in the residues. In this study, the residue from shrimp (Penaeus vannamei) shells after astaxanthin extraction using ionic liquid (IL) 1-ethyl-3-methyl-imidazolium acetate ([Emim]Ac) was used as a bioadsorbent to remove fluoride from the aqueous solution. The results show the IL extraction conditions, including the solid/liquid ratio, temperature, time, and particle size, all played important roles in the removal of fluoride by the shrimp shell residue. The shrimp shells treated using [Emim]Ac at 100 °C for 2 h exhibited an obvious porous structure, and the porosity showed a positive linear correlation with defluorination (DF, %). Moreover, the adsorption process of fluoride was nonspontaneous and endothermic, which fits well with both the pseudo-second-order and Langmuir models. The maximum adsorption capacity calculated according to the Langmuir model is 3.29 mg/g, which is better than most bioadsorbents. This study provides a low-cost and efficient method for the preparation of adsorbents from shrimp processing waste to remove fluoride from wastewater.

Enhanced fluoride adsorption from aqueous solution by zirconium (IV)-impregnated magnetic chitosan graphene oxide.

In this study, zirconium (IV)-impregnated magnetic chitosan graphene oxide (Zr-MCGO) was synthesized for removing fluoride from aqueous solution in batch mode. Characterization approaches (pHpzc, FTIR, SEM, XRD, VSM, Raman, BET, and XPS) proved the successful incorporation of Zr into the adsorbent. Zr-MCGO exhibited a relatively favorable and stable capacity of defluoridation at lower pH with a wide range of pH from 4.0 to 8.0, while there was slightly negative effect of ionic strength on adsorption. In addition, Elovich kinetic model and Koble-Corrigan isotherm model could describe the uptake of fluoride well. The adsorption capacity was 8.84 mg/g at 313 K and Zr-MCGO was easily separated from mixtures using external magnet. Based on the experiments and XPS, electrostatic force, ligand exchange, and Lewis acid-base interaction might be potential adsorption mechanisms. Pseudo-second-order model was more compatible with the desorption process by 0.01 mol/L NaHCO3 solution. Therefore, Zr-MCGO was a promising candidate for defluoridation on wastewater pollution remediation.

Design and synthesis of amine grafted graphene oxide encapsulated chitosan hybrid beads for defluoridation of water.

The promising adsorbent like graphene oxide (GO), chitosan (CS) and amine functionalized graphene oxide (AGO) decorated chitosan (CS) namely AGO@CS composite beads was efficiently prepared for defluoridation studies. The prepared AGO@CS composite beads possess enriched defluoridation capacity (DC) of 4650 mgF- kg-1. Batch method was used to optimize the maximum DC of AGO@CS composite beads. The physicochemical properties of AGO@CS composite beads were explored by numerous instrumental techniques viz., FTIR, Raman, XPS, SEM and TGA investigation. The experimental values of AGO@CS composite beads for fluoride removal at various temperature conditions were assessed with adsorption isotherms, kinetic and thermodynamic studies. The possible defluoridation mechanism of AGO@CS beads was mostly proposed that electrostatic attraction. The reusability and field investigation results of AGO@CS beads shows they are regenerable and applicable at field circumstances.

Development of a novel Artemia eggshell-zirconium nanocomposite for efficient fluoride removal.

Fluoride pollution in water has attracted widespread concern worldwide. In this study, an Artemia eggshell-zirconium (Aes-Z) nanocomposite has been used for fluoride removal. Material characterization results showed that nano-ZrO2 was immobilized on the inner surface of the Artemia eggshell, and there was no pore blockage on the composite material. Various parameters influencing on the fluoride removal, including treatment time, composite dosage, pH, initial fluoride concentration, and other anions, were analyzed. The removal efficiency of the composite material was better than that of the single zirconia material. The removal percentage of fluoride reached 93% in 30 min with an initial fluoride concentration of 10 mg/L and a nanocomposite dosage of 8.0 g/L. The composite material had a high removal efficiency for fluoride in the pH region 4.0-10.0. The adsorption of fluoride was not influenced by the common anions (e.g., Cl-, SO42-, and NO3-) in water. The regeneration revealed that the Aes-Z composite material could be reused and remove fluoride effectively in four cycles. The pseudo-second-order rate model adequately represented the adsorption kinetics of the Aes-Z composite material. A possible, defluoridation mechanism of the Aes-Z composite material was also proposed. This study demonstrates that Aes-Z is a promising adsorbent material for fluoride removal.

Fluoro-functionalized stationary phases for electrochromatographic separation of organic fluorides.

Fluorous affinity means remarkably specific interaction between highly organic fluorides. This work aims to explore the potential of fluoro-functionalized stationary phase for the separation of organic fluorides by means of fluorous-fluorous interaction. Here, by using the Michael addition strategy between 1H,1H,2H,2H-perfluorodecanethiol (PFDT) and polydopamine (PD), a novel fluoro-functionalized stationary phase was synthesized for open-tubular capillary electrochromatography (OT-CEC). The PFDT@PD was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray Photoelectron Spectrometer (XPS). The PFDT@PD@capillary exhibited outstanding separation performance towards neutral compounds (such as alkylbenzenes and chlorobenzenes) and organic fluorides (such as fluorobenzenes and perfluoroalkyl methacrylates etc.) with high resolution and high separation efficiency by hydrophobic interaction and fluorous-fluorous interaction. In addition, the column shows good stability and reproducibility. The relative standard deviations (RSDs) of the retention time for intra-day (n = 5) and inter-day (n = 3) runs and between columns (n = 3) are less than 0.39%, 1.22% and 3.87%, respectively. This novel type of fluoro-functionalized stationary phase represents a great application potential in organic fluorides separation field.

Mechanism of simultaneous removal of aluminum and fluoride from aqueous solution by La/Mg/Si-activated carbon.

La/Mg/Si-activated carbon derived from palm shell has been a suitable material for removal of aluminum and fluoride from aqueous solution. In the study, the mechanism of simultaneous removal of aluminum and fluoride by La/Mg/Si-activated carbon (La/Mg/Si-AC) was investigated to understand its high efficiency. It was found that the removal of aluminum and fluoride by La/Mg/Si-AC was favored at lower pH compared to the point of zero charge of La/Mg/Si-AC and high temperature. Adsorption capacity of Al(OH)4- was about 10 times higher than that of F- due to the strong binding affinity of Al(OH)4- on protonated surface and competition between F- and OH- toward charged adsorption site. Kinetics results showed that the aluminum and fluoride adsorption were explained using the pseudo-second-order kinetic model and intra-particle diffusion model. Adsorption process of Al(OH)4- and F- was driven by the potential rate-limiting step involved in mass transport process occurred on the boundary diffusion layer of porous adsorbent surface. Electrostatic interaction between protonated surface of La/Mg/Si-AC and negatively charged ions (i.e., Al(OH)4- and F-) as well as ion-exchange between hydroxide and ionic metal species were important mechanisms in the process of aluminum and fluoride adsorption. Driving forces for adsorption of individual Al(OH)4- and F- were not entirely different. Identifying the dominant mechanism will be helpful in understanding the adsorption process and developing new adsorbent.

Deboronation-Induced Ratiometric Emission Variations of Terphenyl-Based Closo-o-Carboranyl Compounds: Applications to Fluoride-Sensing.

Closo-o-carboranyl compounds bearing the ortho-type perfectly distorted or planar terphenyl rings (closo-DT and closo-PT, respectively) and their nido-derivatives (nido-DT and nido-PT, respectively) were synthesized and fully characterized using multinuclear NMR spectroscopy and elemental analysis. Although the emission spectra of both closo-compounds exhibited intriguing emission patterns in solution at 298 and 77 K, in the film state, closo-DT mainly exhibited a π-π* local excitation (LE)-based emission in the high-energy region, whereas closo-PT produced an intense emission in the low-energy region corresponding to an intramolecular charge transfer (ICT) transition. In particular, the positive solvatochromic effect of closo-PT and theoretical calculation results at the first excited (S1) optimized structure of both closo-compounds strongly suggest that these dual-emissive bands at the high- and low-energy can be assigned to each π-π* LE and ICT transition. Interestingly, both the nido-compounds, nido-DT and nido-PT, exhibited the only LE-based emission in solution at 298 K due to the anionic character of the nido-o-carborane cages, which cannot cause the ICT transitions. The specific emissive features of nido-compounds indicate that the emissive color of closo-PT in solution at 298 K is completely different from that of nido-PT. As a result, the deboronation of closo-PT upon exposure to increasing concentrations of fluoride anion exhibits a dramatic ratiometric color change from orange to deep blue via turn-off of the ICT-based emission. Consequently, the color change response of the luminescence by the alternation of the intrinsic electronic transitions via deboronation as well as the structural feature of terphenyl rings indicates the potential of the developed closo-o-carboranyl compounds that exhibit the intense ICT-based emission, as naked-eye-detectable chemodosimeters for fluoride ion sensing.

Niveles de fluoruro en dentífricos y colutorios / Fluoride levels in toothpaste and mouthwashes

INTRODUCCIÓN: El uso de dentífricos y enjuagues bucales o colutorios que tienen fluoruro en su composición se ha ampliado ya que se ha demostrado que este elemento tiene una alta actividad contra las bacterias cariogénicas. Sin embargo, una ingesta excesiva de cualquiera de estos productos, puede producir intoxicaciones que conducen a diversas patologías a largo plazo. OBJETIVOS: El objetivo de este estudio es determinar el contenido de fluoruro de productos dentales (dentífricos y colutorios) para evaluar si existe algún tipo de riesgo al ingerir accidentalmente grandes cantidades de estos en ciertos grupos de población y comparar los niveles experimentales con los declarados en el etiquetado. MATERIAL Y MÉTODOS: Se han analizado un total de 117 muestras de productos dentales mediante potenciometría con electrodo de ion selectivo de fluoruro. RESULTADOS Y DISCUSIÓN: Se ha registrado la mayor concentración de fluoruro (18412±0.009 mg/kg) en el dentífrico Vitis® junior sabor tutti frutti. El mayor nivel de fluoruro encontrado en los colutorios (2703±38.4 mg/L) ha sido registrado en la marca Lacer® Oros. CONCLUSIONES: No existe ningún tipo de riesgo si el cepillado se realiza correctamente y, en el caso de los niños, de forma supervisada para evitar ingestiones accidentales. No obstante, de producirse, se necesitarían cantidades muy altas de estos productos para desencadenar un efecto tóxico a corto y largo plazo

INTRODUCTION: The use of dentifrices and mouthwashes or mouthwashes that have fluoride in their composition has been extended since it has been shown that this element has a high activity against cariogenic bacteria. However, excessive intake of any of these products can cause poisoning that leads to various long-term pathologies. OBJECTIVES: The objective of this study is to determine the fluoride content of dental products (dentifrices and mouthwashes) to assess whether there is any type of risk by accidentally ingesting large amounts of these in certain population groups and comparing the experimental levels with those declared in the labelling. MATERIAL AND METHODS: A total of 117 samples of dental products have been analyzed by potentiometry with fluoride selective ion electrode. RESULTS AND DISCUSSION: The highest concentration of fluoride (18412±0.009 mg/kg) has been recorded in the Vitis® junior tutti frutti flavor toothpaste. The highest level of fluoride found in mouthwashes (2703±38.4 mg/L) has been registered under the Lacer® Oros brand. CONCLUSIONS: There is no risk if brushing is done correctly and, in the case of children, in a supervised way to avoid accidental ingestion. However, if produced, very high amounts of these products would be needed to trigger a toxic effect in the short and long term

Modified Crushed Oyster Shells for Fluoride Removal from Water.

Elevated concentrations of fluoride ions (F-) in natural groundwater are a worldwide problem. Discarded oyster shells were ground to ≤100 µm particle size to produce oyster shell powder (OS). A subset of the OS was heated to produce calcined oyster shell (COS). A subset of the COS was further treated with 1 M phosphoric acid to produce phosphoric-acid-treated oyster shell (POS). OS and COS were combined with phosphoric acid (1.6 mM and 3.2 mM) to produce OS + P (oyster shell with phosphoric acid) and COS + P (calcined oyster shell with phosphoric acid). OS and COS removed 46% and 50% (10 g/L of sorbent dose) but POS, OS + P and COS + P removed 96%, 100% and 76% (1 g/L of sorbent dose) when the initial concentration of fluoride was 10 mg/L. The sorption kinetics of POS, OS + P and COS + P followed second-order reaction rates, and sorption isotherms of all sorbents were well-described by the Freundlich sorption isotherm. These results indicate that oyster shells can be an effective sorbent for fluoride removal, with the added benefit of re-use of a waste product.

Removal of fluoride from multicomponent water solutions with the use of monovalent selective ion-exchange membranes.

Fluorine is a chemical element which is often present in natural environment. According to the World Health Organization (WHO) standards fluoride content in drinking water cannot be higher than 1.5 mg F-/L. Nitrate was also found in many regions in the world. According to guidelines its content in drinking water cannot exceed 50 mg NO3-/L. Ingestion of fluoride and nitrate in excess leads to various health issues. There are many methods of fluoride removal, e.g. reverse osmosis, ion exchange or electrodialysis (ED). The aim of the research was to evaluate the influence of nitrate on fluoride separation by electrodialysis with monovalent selective ion-exchange membranes (PC-MVA and PC-MVK). During experiments the laboratory installation PCCell BED-1-System was applied. The ED tests were conducted at constant current density (0.78, 1.72, and 2.34 mA/cm2). Model solutions containing fluoride (5, 10, 15 mg F-/L), nitrate (15, 30, 45 mg NO3-/L) and sodium chloride (0.5 g NaCl/L) were applied. The obtained results showed that the ED process with monovalent selective ion-exchange membranes allowed to decrease fluoride content in product water below the WHO guidelines. It was observed that competition between nitrate and fluoride ions occurred during their transport through the anion-exchange membranes. The energy demand was dependent on the current density as well as on the salt concentration in treated solutions.

Synthesis of Chitosan-Polyvinyl Alcohol Biopolymers to Eliminate Fluorides from Water.

The fluoride content in groundwater varies depending on geological configuration. Fluoride problems tend to occur in places where these minerals are most abundant in rocks. The objective of the present work was to synthesize four biopolymers based on chitosan-polyvinyl alcohol (Ch-PVA) cross-linked with sodium tripolyphosphate pentabasic (TPP) and ethylene glycol diglycidyl ether (EGDE) and determine their ability to remove fluoride from water. The characterization of the Ch-PVA beads was performed by way of Scanning Electron Microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The percentage of humidity and the point of zero charge were determined. The Ch-PVA beads showed a surface area of 63.87 m2 g-1, a pore size of 7.6 nm, a point of zero charge of 7.4, and 98.6% humidity. The kinetic adsorption study was adjusted to the pseudo-second-order model and the adsorption equilibrium data were adjusted to the Freundlich adsorption isotherm, showing a maximum fluoride adsorption capacity of 12.64 mg.g-1 at pH 7 and 30 °C, for the beads of Ch-PVA-NaOH-TPP. According to the thermodynamic parameters: -∆Go, +∆Ho and -∆So, fluoride adsorption is spontaneous, endothermic in nature and there is no random energy change in the solid/liquid interface during the adsorption process.

Evaluation of the feasibility of short-term electrodialysis for separating naturally occurring fluoride from instant brick tea infusion.

BACKGROUND: Removing excessive naturally occurring fluoride from tea and/or infusions is difficult because the process has low efficiency and causes secondary pollution. In this study, a novel electrodialysis (ED) technology was developed. We examined the effect of crucial parameters (electrolyte concentration, operation voltage, ED duration and initial concentration of the tea infusion) on defluoridation performance using a highly efficient ion-exchange membrane with five-compartment cells. RESULTS: The most effective ED system results were obtained at an electrolyte concentration of 10 g kg-1 and operating voltage of 20 V. Moreover, the fluoride removal capacity (10.70-66.93%) was highly dependent on the ED duration (1-15 min) and initial concentration of the tea infusion (0.5-10 g kg-1 ). The longer the ED duration and the lower the initial concentration, the higher was the defluoridation performance. During ED, limited loss of the main inclusions (total polyphenols, catechins, caffeine and selected ions) was observed. Furthermore, the D201 anion resin-filled ED stack (0.5-5 g) and improvement of concentrate compartment electrolyte (≥5 times the dilute compartment electrolyte) in the ED system enhanced the defluoridation rate significantly. CONCLUSION: ED is a potentially effective method that can be used for defluoridation in the deep processing of tea products. © 2019 Society of Chemical Industry.

Fluoride removal by palm shell waste based powdered activated carbon vs. functionalized carbon with magnesium silicate: Implications for their application in water treatment.

In this study, palm shell activated carbon powder (PSAC) and magnesium silicate (MgSiO3) modified PSAC (MPSAC) were thoroughly investigated for fluoride (F-) adsorption. F- adsorption isotherms showed that PSAC and MPSAC over-performed some other reported F- adsorbents with adsorption capacities of 116 mg g-1 and 150 mg g-1, respectively. Interestingly, the MgSiO3 impregnated layer changed the adsorption behavior of F- from monolayer to heterogeneous multilayer based on the Langmuir and Freundlich isotherm models verified by chi-square test (X2). Thermodynamic parameters indicated that the F- adsorption on PSAC and MPSAC was spontaneous and exothermic. PSAC and MPSAC were characterized using FESEM-EDX, XRD, FTIR and XPS to investigate the F- adsorption mechanism. Based on the regeneration tests using NaOH (0.01 M), PSAC exhibited poor regeneration (<20%) while MPSAC had steady adsorption efficiencies (∼70%) even after 5 regeneration cycles. This is due to highly polarized C-F bond was found on PSAC while Mg-F bond was distinguished on MPSAC, evidently denoting that the F- adsorption is mainly resulted from the exchange of hydroxyl (-OH) group. It was concluded that PSAC would be a potential adsorbent for in-situ F- groundwater remediation due to its capability to retain F- without leaching out in a wide range pH. MPSAC would be an alternative adsorbent for ex-situ F- water remediation because it can easily regenerate with NaOH solution. With the excellent F- adsorption properties, both PSAC and MPSAC offer as promising adsorbents for F- remediation in the aqueous phase.

Experimental and model study for fluoride removal by thermally activated sepiolite.

The present investigation demonstrates the preparation of thermally activated sepiolite for effective removal of fluoride via adsorption from an aqueous solution. The thermal treatments on sepiolite were conducted at different temperatures (300-950 °C) for 4 h in an N2 atmosphere, and the thermally activated sepiolite was characterized using a field emission scanning electron microscope (FESEM), X-ray diffractometry (XRD), X-ray fluorescence (XRF), a differential scanning calorimetry-thermogravimetric analyzer (DSC-TGA), and a surface area analyzer. Sepiolite that was treated at 950 °C was shown to have a higher fluoride removal efficiency than other temperatures. The fluoride removal was evaluated under different experimental conditions such as solution pH, adsorbent dose, reaction time, initial concentration, temperature, presence of co-existing ions, and reuses. The kinetic and equilibrium adsorption results were well described by the pseudo-second-order kinetic model and Langmuir isotherm, respectively, and adsorption of fluoride onto thermally activated sepiolite was endothermic and spontaneous in nature. The Langmuir maximum adsorption capacity (169.95 mg/g) was superior to the literature value. The thermally activated sepiolite was also effective in a continuous flow system for treating fluoride. Thus, this thermally activated sepiolite is expected to be used as an effective adsorbent for the removal of fluoride in water.

Biomaterial functionalized cerium nanocomposite for removal of fluoride using central composite design optimization study.

Excess fluoride concentration in drinking water is a global issue, as this has an adverse effect on human health. Several adsorbents have been synthesized from natural raw material to remove fluoride from water. Reported adsorbents have some problems with the leaching of metal ions, fewer adsorption sites, and low adsorption capacity. Therefore, to address this, an effective biomaterial derived from the Luffa cylindrica (LC), containing many active sites, was integrated with a nano form of cerium oxide to form a robust, biocompatible, highly porous, and reusable LC-Ce adsorbent. This synthesized biosorbent offers better interaction between the active sites of LC-Ce and fluoride, resulting in higher adsorption capacity. Several factors, influence the adsorption process, were studied by a central composite design (CCD) model of statistical analysis. Langmuir's and Freundlich's models well describe the adsorption and kinetics governed by the pseudo-second-order model. The maximum monolayer adsorption capacity was found to be 212 and 52.63 mg/g for LC-Ce and LC, respectively determined by the Langmuir model. Detailed XPS and FTIR analyses revealed the underlying mechanism of fluoride adsorption via ion-exchange, electrostatic interaction, H-bonding, and ion-pair formation. All the results indicate that LC-Ce could serve as a suitable adsorbent for efficient fluoride removal (80-85%).

Fluoride removal by Ca-Al-CO3 layered double hydroxides at environmentally-relevant concentrations.

In this study, F- removal by Ca-Al-CO3 layered double hydroxides (LDHs) was investigated at environmentally-relevant concentration ranges (2-12 mg/L) to below the WHO guideline, with an emphasis on the effect of LDHs' modification, as well as the effects of initial F- concentration, adsorbent dose, pH, temperature and co-existing ions. Ca-Al-CO3 LDHs, either untreated, calcined or microwave treated, showed affinity for the removal of F- from synthetic groundwater with capacities of 6.7-8.4 mg F-/g LDHs at groundwater-relevant pH, with a higher F- removal capacity at lower pH (<8) and lower temperature (12 °C, as compared to 25 °C & 35 °C). Since calcination and microwave treatment resulted in only marginal defluorination improvements, using untreated LDHs appears the practically most feasible option. For the untreated LDHs, competition with Cl- and NO3- was not observed, whereas at higher HCO3- and SO42- concentrations (>250 mg/L) a slight reduction in F- removal was observed. This study indicates the potential of Ca-Al-CO3 LDHs as a cost-effective F- removal technology, particularly when locally sourced and in combination with low-cost pH correction.

Fluoride removal using a chelating resin containing phosphonic-sulfonic acid bifunctional group.

S9570-Fe(III), a modified chelating resin containing sulphonated monophosphonic acid bifunctional groups, was used for the fluoride removal from aqueous phase for the first time. The results specified that S9570-Fe(III) exhibited better adsorption towards the fluoride ions as compared to the other commonly used chelating resins having monofunctional group such as iminodiacetic acid, sulfonic acid or carboxylic acid. Adsorption thermodynamic and kinetic studies of S9570-Fe(III) chelating resin for the fluoride also have been carried out. The thermodynamic results demonstrated that the adsorption was a spontaneous process accompanied with a gradual decrease in entropy and the low temperature was favorable for the fluoride ion adsorption. The kinetic experiments showed that the resin exhibited a rapid initial adsorption behavior and the adsorption process more complied with the pseudo-second order reaction model which indicating that the whole adsorption process was controlled by a combined mechanism of intraparticle diffusion and chemical sorption. Adsorption mechanism of S9570-Fe(III) resin for fluoride ions was predicted. The study demonstrated the effectiveness of the phosphoric-sulfonic acid bifunctional group chelating resin to remove fluoride, and provided a novel type removal method for the fluoride.