Neuroprotective effects of punicalagin and/or micronized zeolite clinoptilolite on manganese-induced Parkinson's disease in a rat model: Involvement of multiple pathways.

BACKGROUND: Manganism, a central nervous system dysfunction correlated with neurological deficits such as Parkinsonism, is caused by the substantial collection of manganese chloride (MnCl2) in the brain. OBJECTIVES: To explore the neuroprotective effects of natural compounds, namely, micronized zeolite clinoptilolite (ZC) and punicalagin (PUN), either individually or in combination, against MnCl2-induced Parkinson's disease (PD). METHODS: Fifty male albino rats were divided into 5 groups (Gps). Gp I was used as the control group, and the remaining animals received MnCl2 (Gp II-Gp V). Rats in Gps III and IV were treated with ZC and PUN, respectively. Gp V received both ZC and PUN as previously reported for the solo-treated plants. RESULTS: ZC and/or PUN reversed the depletion of monoamines in the brain and decreased acetyl choline esterase activity, which primarily adjusted the animals' behavior and motor coordination. ZC and PUN restored the balance between glutamate/γ-amino butyric acid content and markedly improved the brain levels of brain-derived neurotrophic factor and nuclear factor erythroid 2-related factor 2/heme oxygenase-1 and decreased glycogen synthase kinase-3 beta activity. ZC and PUN also inhibited inflammatory and oxidative markers, including nuclear factor kappa-light-chain-enhancer of activated B cells, Toll-like receptor 4, nucleotide-binding domain, leucine-rich-containing family, pyrin domain-containing-3 and caspase-1. Bcl-2-associated X-protein and B-cell leukemia/lymphoma 2 protein (Bcl-2) can significantly modify caspase-3 expression. ZC and/or PUN ameliorated PD in rats by decreasing the levels of endoplasmic reticulum (ER) stress markers (p-protein kinase-like ER kinase (PERK), glucose-regulated protein 78, and C/EBP homologous protein (CHOP)) and enhancing the levels of an autophagy marker (Beclin-1). DISCUSSION AND CONCLUSION: ZC and/or PUN mitigated the progression of PD through their potential neurotrophic, neurogenic, anti-inflammatory, antioxidant, and anti-apoptotic activities and by controlling ER stress through modulation of the PERK/CHOP/Bcl-2 pathway.

Green Synthesis of New Derivatives of Iminothiazole Using Cefixime and Removing Organic Pollutants from Aqueous Environment by Employing Cu@KF/Clinoptilolite NPs.

AIMS AND OBJECTIVE: In this research, multicomponent reactions of cefixime, isothiocyanates, and alkyl bromides were carried out for the synthesis of new iminothiazole derivatives with high yields in water as the solvent at room temperature in the presence of catalytic amounts of Cu@KF/CP NPs as catalysts. Also, the ability of Cu@KF/Clinoptilolite nanoparticles (NPs) to adsorb and remove 4-NP and cefixime from water was investigated. The Cu@KF/Clinoptilolite nanoparticles were synthesized by employing a water extract of Petasites hybridus rhizomes. MATERIALS AND METHODS: For this experiment, all of the components obtained from Fluka and Merck were subjected to further purification. The antibiotic used in this investigation, cefixime, was obtained from a pharmaceutical facility situated in Sari, Mazandaran, Iran. The antibiotic factory is located in Sari City, Iran. All solutions were prepared using distilled water. The shape of Cu@KF/CP nanoparticles was analyzed using images obtained from a Holland Philips XL30 scanning electron microscope. An analysis was performed on the crystalline structure of Cu@KF/CP nanoparticles (NPs), and a room temperature X-ray diffraction (XRD) examination was carried out utilizing a Holland Philips Xpert X-ray powder diffractometer. The X-ray diffraction (XRD) examination was conducted using CuK radiation, which has a wavelength of 0.15406 nm. The analysis covered a 2ε angle range from 20 to 80°. The nanostructures that were produced were chemically analyzed using X-ray energy dispersive spectroscopy (EDS) with an S3700N equipment. The morphology and dimensions of Cu@KF/CP nanoparticles were characterized using a Philips EM208 transmission electron microscope operated at an acceleration voltage of 90 kV. RESULTS: The primary objective of this study was to develop a sustainable approach for producing new iminothiazole derivatives 4. This was achieved using a highly efficient three-component reaction combining cefixime 1, isothiocyanates 2, and alkyl bromides 3. The reaction was carried out in water at ambient temperature, using Cu@KF/CP NPs as a highly effective catalyst, leading to excellent yields. Moreover, the study findings showed that the synthesized compounds demonstrated a significant antioxidant activity compared to conventional antioxidants. The antibacterial efficacy of the synthesized compounds was evaluated against both Gram-positive and Gram-negative bacteria. Furthermore, Cu@KF/CP nanoparticles were utilized to adsorb CFX and 4-NP from water-based solutions. CONCLUSION: This study showcases the effective synthesis of innovative iminothiazole derivatives through the use of multicomponent reactions, involving the combination of cefixime, isothiocyanates, and alkyl bromides. The reactions were conducted in a water-based solvent. The reactions were carried out at room temperature, utilizing Cu@KF/CP NPs as catalysts. The Cu@KF/CP nanoparticles, a newly developed heterogeneous nanocatalyst, were synthesized and evaluated utilizing X-ray diffraction (XRD), fieldemission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) research techniques. Cu@KF/CP nanoparticles are utilized to adsorb CFX and 4-NP from water-based solutions. The objects were manufactured using a straightforward and uncomplicated approach. The BET surface area of Cu@KF/CP NPs was measured to be 201.8 m2/g. The experimental equilibrium data was evaluated by applying the isotherms of the Langmuir, Freundlich, Dubinin-Radushkevich, and Redlich-Peterson models. Additionally, we examined the catalytic efficiency of Cu@KF/CP nanoparticles (NPs) in reducing various colors in water.

Alginate/clinoptilolite beads as a novel adsorbent for reducing the salinity of industrial wastewater: adsorption kinetics and isotherm study.

Treatment and desalination of unconventional water are considered important alternatives to combat water scarcity in Tunisia. This study demonstrates a viable approach to the increasing possibility of the salinity reduction of industrial effluent through adsorption. In this work, a novel alginate complex was developed for reducing the salinity of the industrial wastewater to be reinjected and reused again within the industrial process and even in agriculture. The Calcium alginate/clinoptilolite beads (Ca-Alg/Clino beads) were prepared using sodium alginate (2%) solution and calcium chloride (4%) solution as the crosslinking agent with clinoptilolite. Batch experiments were carried out to test the adsorption capacity of the synthetised Ca-Alg/Clino beads. It was found that the salinity reduction process depends strongly on the pH, the adsorbent mass, the interaction time, and the initial salt concentration. The highest reduction efficiency and salinity reduction were achieved at pH (6-7). Batch adsorption experiments indicated that Ca-Alg/Clino beads allow an excellent salinity reduction of up to 96.83% for a dosage adsorbent/water of 2 g/L and a salinity of 6 g/L at a contact time of 20 min. The maximum adsorption capacity (qmax) was 30.1 mg/g. The optimal adsorption pH was 7. The adsorption isotherms data follow well the Langmuir model. The separation factor, RL = 0.74, indicates that the adsorption process is favourable. The kinetics data favour the pseudo-second-order model. The fabricated beads can be reused 5 times without any weight loss. This material has excellent efficiency when applied to real environmental water.

Unveiling the Broad-Spectrum Virucidal Potential of Purified Clinoptilolite-Tuff.

Due to its remarkable surface properties, natural clinoptilolite-tuff interacts with a variety of biochemical, pharmaceutical, chemical, and microbiological entities, including human viruses. In the present work, the virucidal activity of purified clinoptilolite-tuff (PCT) was investigated using a variety of viruses, differing in their structure and composition. Influenza A virus, Herpes Simplex virus, Rhinovirus, and Parvovirus were chosen to represent enveloped and non-enveloped viruses with RNA and DNA genomes. Beside human viruses, Canine Parvovirus and bacteriophages T4 and MS2 were used to represent animal and bacterial viruses, respectively. The virucidal activity of PCT was quantified by examining the residual viral activity on susceptible cell lines upon incubation with PCT. A wide range of antiviral efficiencies was observed, ranging from up to 99% for Herpes Simplex virus to no activity for Rhinovirus and both bacteriophages. This study reveals that the virucidal potential of PCT is not universal and depends on a complex set of factors including virus structure and medium composition. The environmental and medical implications of this research are discussed for uses such as wastewater treatment or wound healing.

Feeding or pen surface application of clinoptilolite with different particle sizes: impact on nitrogen utilization and manure ammonia emissions in feedlot cattle.

This study investigated the effects of feeding clinoptilolite (CLN; 2.5% of diet dry matter) with a particle size of either 30- or 400-µm on ruminal fermentation characteristics, measures of nitrogen (N) utilization, and manure ammonia-N (NH3) emissions in feedlot cattle. The impact of directly applying 30- or 400-µm CLN to the pen surface (2,250 kg/ha) on manure NH3-N emissions was also evaluated. Six beef heifers were used in a replicated 3 × 3 Latin square design with 21-d periods. Dietary treatments were 1) finishing ration with no supplement (CON), 2) CON + 30-µm CLN (CLN-30), and 3) CON + 400-µm CL (CLN-400). Intake was measured daily. To evaluate fermentation characteristics, ruminal fluid was collected on day 19. Indwelling pH loggers were used to measure ruminal pH from days 15 to 21. Blood was collected 3-h post-feeding on day 21 for metabolite analysis. Fecal grab and urine spot samples were also collected from days 19 to 21 to measure nutrient digestibility, route of N excretion, and in vitro NH3 emissions. There was no diet effect (P ≥ 0.12) on nutrient intake and apparent total tract digestibility, and ruminal short-chain fatty acid profile and pH. Ruminal NH3 concentration, which was lower (P = 0.04) for CLN-30 than CON heifers, did not differ between CON and CLN-400 heifers. Although there was no diet effect (P = 0.50) on plasma urea-N (PUN) concentration, proportion of urea-N excreted in urine was lower (P = 0.01) for CLN-30 than CON and CLN-400 heifers. Urinary NH3-N excretion, which was greater (P ≤ 0.04) for CLN-400 than CON heifers, did not differ between CLN-30 and CLN-400 heifers. Feeding CLN also increased (P ≤ 0.02) fecal excretion of potassium (K) and iron (Fe) and reduced (P = 0.01) urinary excretion of calcium (Ca). There was a treatment × time interaction (P = 0.01) for NH3 emission rate, which was greatest within the first 36 h of incubation and was lower for manure from CLN-400 compared to CON and CLN-30 heifers and pen surface application treatments. Cumulative NH3 emissions were lower (P < 0.01) for manure from CLN-400 compared to CON and CLN-30 heifers and the pen surface application treatments. Although surface application was ineffective, feeding 400-µm CLN to finishing cattle could result in a beneficial decrease in manure NH3 emissions. However, changes in fecal and urine excretion of minerals like K and Ca, which suggest a decrease in bioavailability, need to be considered when feeding CLN in finishing cattle diets.

There is interest in developing strategies that limit ammonia emissions from confined feeding operations, as it leads to both air and water pollution. Feeding zeolites like clinoptilolite (CLN) or directly applying them to pen surfaces to bind ammonia represents possible mitigation strategies. Although this could impact its effectiveness, there still is limited information on whether the particle size of CLN influences the binding of ammonia when fed or surface applied. Therefore, this study evaluated the effects of feeding supplemental CLN with a small (30-µm) or large particle size (400-µm) to finishing cattle on ruminal fermentation parameters, route of nitrogen excretion, and manure ammonia emissions. We also evaluated the effects of applying 30- and 400-µm CLN directly to the pen surface on manure ammonia emissions. Only CLN with the small particle size (30 µm) was effective in binding ruminal ammonia, which reduced the amount of urea excreted in urine. However, ammonia emissions were only lower for manure from finishing cattle fed CLN with the large particle size. Applying CLN to the pen surface was not effective in reducing ammonia emissions. There were also indications that fed CLN reduced bioavailability of potassium and iron.

Odors Adsorption in Zeolites Including Natural Clinoptilolite: Theoretical and Experimental Studies.

This publication presents the results of combined theoretical and experimental research for the potential use of natural clinoptilolite zeolite (CLI) as an odor-adsorbing material. In this study of adsorption capacity, CLI of various granulation was used and its modifications were made by ion exchange using Sn and Fe metals to check whether the presence of metals as potential active centers does not lead to catalytic processes and may lead to enhanced absorption of odorous substances through their adsorption on the created metallic forms. Additionally, in order to increase the specific surface area, modifications were made in the form of hierarchization in an acidic environment using hydrochloric acid to also create the hydrogen form of zeolite and thus also check how the material behaves as an adsorbent. To compare the effect of CLI as a sorption material, synthetic zeolite MFI was also used-as a sodium form and after the introduction of metals (Sn, Fe). The above materials were subjected to adsorption measurements using odorous substances (including acetaldehyde, dimethylamine, pentanoic acid and octanoic acid). Based on the measurements performed, the most advantageous material that traps odorants is a natural material-clinoptilolite. Depending on the faction, its ability varies for different compounds. In the case of acetaldehyde, an effective material is clinoptilolite with a grain size of up to 2 mm. In the case of carboxylic acids, it is material after hierarchization with a fraction of 3-4 mm. In the case of theoretical calculations, information was obtained to show that metallic centers are more stable above oxygen, which is associated with the skeletal aluminum in clinoptilolite.

Effect of Zeolite Incorporation on the Ion Release Properties of Silver-Reinforced Glass Ionomer Cement.

BACKGROUND: Zeolite can release antimicrobial silver ions in a targeted and controlled manner for an extended time, selectively inhibiting the growth of pathogenic oral bacteria when added to dental materials. The objective of this study was to investigate the effect of the addition of zeolite to silver-reinforced glass ionomer cement on the release of silver ions over time. METHODS: Five concentrations of silver-zeolite (0%, 0.5%, 1%, 2%, 4% wt) were incorporated into silver-reinforced GIC in the form of 10 mm × 2 mm circular disks (n = 5). The disks were incubated in deionized water at 37 °C and ion release from the samples was measured at 1, 2, 7, and 30 days after immersion by inductively coupled atomic emission spectroscopy. RESULTS: Incorporating silver-zeolite increased silver ion release from silver-reinforced GIC disks compared to the control disks (p < 0.05), while incorporating zeolite alone had no effect. Higher concentrations of added silver-zeolite resulted in increased silver ion release. Sustained silver ion release was observed for up to 30 days. CONCLUSION: Adding silver-zeolite to silver-reinforced GIC may enhance its extended antibacterial effect in the oral cavity.

Purified Clinoptilolite-Tuff as an Efficient Sorbent for Food-Derived Peanut Allergens.

The avoidance of allergen intake is crucial for persons affected by peanut allergy; however, the cross-contamination of food is common and leads to unpredictable consequences after the consumption of supposedly "safe" food. The aim of the present study was to eliminate harmful traces of peanut allergens from food using purified clinoptilolite-tuff (PCT)-a specially processed zeolite material. Analyses were performed using a peanut ELISA and a Coomassie blue (Bradford) assay. Mimicking conditions of the human gastrointestinal tract demonstrated a higher efficacy of PCT in the intestine (pH 6.8) than in the stomach (pH 1.5). Adsorption rates were fast (<2 min) and indicated high capacities (23 µg and 40 µg per 1 mg of PCT at pH 1.5 and pH 6.8, respectively). Allergenically relevant peanut protein concentrations were sorbed in artificial fluids (32 µg/mL by 4 mg/mL of PCT at pH 1.5 and 80.8 µg/mL by 0.25 mg/mL of PCT at pH 6.8) when imitating a daily dose of 2 g of PCT in an average stomach volume of 500 mL. Experiments focusing on the bioavailability of peanut protein attached to PCT revealed sustained sorption at pH 1.5 and only minor desorption at pH 6.8. Accompanied by gluten, peanut proteins showed competing binding characteristics with PCT. This study therefore demonstrates the potential of PCT in binding relevant quantities of peanut allergens during the digestion of peanut-contaminated food.

Adsorption efficiency of chitosan/clinoptilolite (CS/CZ) composite for effective removal of Cd+2 and Cr+6 ions from wastewater effluents of dairy cattle farms.

The wastewater effluent is responsible for the major ecological impact of the dairy sectors. To avoid the negative consequences of heavy metal pollution on the ecosystem, creative, affordable, and efficient treatment methods are now required before the effluent flows into the surrounding area. This study was aimed at assessing the effectiveness of three different adsorbents for Cd+2 and Cr+6 ions from wastewater effluents of dairy farms, including chitosan (CS), clinoptilolite zeolite (CZ), and chitosan/clinoptilolite zeolite (CS/CZ) composite. The adsorption kinetics of the CS/CZ composite were established using the effects of the key variables (pH, agitation speed, adsorbent concentrations, and contact durations). The removal (%) and adsorption capacities, qe (mg/g), were calculated using the data from the adsorption kinetics. Wastewater samples (n = 60) were collected from the wastewater effluents of five farms. Cd+2 and Cr+6 ion concentrations in all collected samples were determined. Following the CS/CZ composite creation, it was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (X-RD), and Fourier-transform infrared spectrum (FT-IR). The CS/CZ composite had an adsorption capacity of 92.4 and 96.5 mg/g for both Cd+2 and Cr+6 ions at a concentration of 2.0 g/100 ml, respectively, while the CZ adsorption capacities for the two ions were 87.5 mg/g and 61.0 mg/g, respectively, at 4.0 g/100 ml concentration. The CS was achieved at 55.56 mg/g and 33.3 mg/g, respectively, at the same concentration. The efficiency of heavy metal removal was enhanced by increasing adsorbent concentration, agitation speed, and contact duration. Using CS/CZ composite at 2.0 g/100 ml concentration, 180 min of contact time, and 300 rpm agitation speed, the greatest removal efficiencies for Cd+2 and Cr+6 ions (96.43 and 98.75%, respectively) were demonstrated.

Zeolite and Neurodegenerative Diseases.

Neurodegenerative diseases (NDs), characterized by progressive degeneration and death of neurons, are strongly related to aging, and the number of people with NDs will continue to rise. Alzheimer's disease (AD) and Parkinson's disease (PD) are the most common NDs, and the current treatments offer no cure. A growing body of research shows that AD and especially PD are intricately related to intestinal health and the gut microbiome and that both diseases can spread retrogradely from the gut to the brain. Zeolites are a large family of minerals built by [SiO4]4- and [AlO4]5- tetrahedrons joined by shared oxygen atoms and forming a three-dimensional microporous structure holding water molecules and ions. The most widespread and used zeolite is clinoptilolite, and additionally, mechanically activated clinoptilolites offer further improved beneficial effects. The current review describes and discusses the numerous positive effects of clinoptilolite and its forms on gut health and the gut microbiome, as well as their detoxifying, antioxidative, immunostimulatory, and anti-inflammatory effects, relevant to the treatment of NDs and especially AD and PD. The direct effects of clinoptilolite and its activated forms on AD pathology in vitro and in vivo are also reviewed, as well as the use of zeolites as biosensors and delivery systems related to PD.

Fundamental properties and sustainable applications of the natural zeolite clinoptilolite.

This review explores a set of sustainable applications of clinoptilolite, a natural zeolite abundant around the world in different localities. Thanks to its physico-chemical properties this material is extremely versatile for several applications, ranging from environmental catalysis and CO2 removal to industrial and agricultural wastewater purification, aquaculture, animal feeding, and food industry but also medical applications and energy storage systems. Due to the presence of cations in its framework, it is possible to tune the material's features making it suitable for adsorbing specific compounds. Thus, this review aims to provide insight into developing new technologies based on the use of this material that is sustainable, not harmful for humans and animals, naturally abundant, and above all cost-effective. Furthermore, it is intended to promote the use of natural materials in various areas with a view to sustainability and to reduce as far as possible the use of chemicals or other materials whose synthesis process can have a polluting effect on the environment.

Green Flame-Retardant Blend Used to Improve the Antiflame Properties of Polypropylene.

The flammability properties of polymers and polymeric composites play an important role in ensuring the safety of humans and the environment; moreover, flame-retardant materials ensure a greater number of applications. In the present study, we report the obtaining of polypropylene (PP) composites contain a mixture of two green flame retardants, lignin and clinoptilolite, by melt extrusion. These additives are abundantly found in nature. Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), mechanical properties, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), cone calorimetry, UL-94, and carbonized residues analysis were carried out. TGA analysis shows that PPGFR-10 and PPGFR-20 compounds presented better thermal stability with respect to PP without flame retardants. The conical calorimetric evaluation of the composites showed that PPGFR-10 and PPGFR-20 presented decreases in peak heat release rates (HRRs) of 9.75% and 11.88%, respectively. The flammability of the composites was evaluated with the UL-94 standard, and only the PPGFR-20 composite presented the V-0 and 5VB classification, which indicates good flame-retardant properties. Additives in the polymer matrix showed good dispersion with few agglomerates. The PPGFR-20 composite showed an FRI value of 1.15, higher percentage of carbonized residues, and UL-94 V-0 and 5VB rating, suggesting some kind of synergy between lignin and clinoptilolite, but only at high flame-retardant concentrations.

Physicochemical properties and fractal characterizations of the functionalized porous clinoptilolites for controlling alginate delivery in growing cauliflower and leaf mustard.

Using natural clinoptilolite (NCP) as a carrier and alginate (Alg)-calcium as an active species, the porous silicon calcium alginate nanocomposite (Alg-Ca-NCP) was successfully fabricated via adsorption-covalence-hydrogen bond. Its structural features and physicochemical properties were detailed investigated by various characterizations. The results indicated that Alg-Ca-NCP presented the disordered lamellar structures with approximately uniform particles in size of 300-500 nm. Specially, their surface fractal evolutions between the irregular roughness and dense structures were demonstrated via the SAXS patterns. The results elucidated that the abundant micropores of NCP were beneficial for unrestricted diffusing of Alg-Ca, which was conducive to facilitate a higher loading and sustainable releasing. The Ca content of leaf mustard treated with Alg-Ca-NCP-0.5 was 484.5 mg/100g on the 21st day, higher than that by water (CK) and CaCl2 solution treatments, respectively. Meanwhile, the prepared Alg-Ca-NCPs presented the obvious anti-aging effects on peroxidase drought stress of mustard leaves. These demonstrations provided a simple and effective method to synthesize Alg-Ca-NCPs as delivery nanocomposites, which is useful to improve the weak absorption and low utilization of calcium alginate by plants.

Oviposition-Deterrent Effect of a High-Quality Natural Zeolite on the Olive Fruit Fly Bactrocera oleae, under Different Conditions of Temperature and Relative Humidity.

In recent years, the number of available chemical pesticides has been dramatically reduced, urging the need for the discovery of alternatives to chemical pesticide products such as, among others, natural zeolites (zeolitic rocks). We determined the mineralogical and chemical composition of a specific and continuous layer of zeolitic rock sample (ZeotP) from Petrota, Evros, Greece, and evaluated its oviposition-deterrent effect on the olive fruit fly Bactrocera oleae Gmelin (Diptera: Terphritidae). The tested natural zeolite contained 70 wt. % clinoptilolite, 18 wt. % amorphous material, 7 wt. % feldspars, 4 wt. % cristobalite, and 1 wt. % quartz. We tested the oviposition-deterrent effect of ZeotP mixed or not with an emulsifier adjuvant, NU-FILM-P®, in water and applied it to the surface of olive fruits. The ZeotP oviposition-deterrent effect on the olive fly was very high under a series of tested temperatures (17 °C, 20 °C, 25 °C, and 30 °C) and RHs (23%, 33%, 55%, 75%, and 94%). In addition, the ZeotP residual deterrent effect after equable water spraying was high, like the respective effect of the pyrethroid insecticide Decis® (deltamethrin). Our results may contribute to the effective control of the olive fruit fly using an alternative to chemical pesticides: natural zeolite (zeolitic rocks) products.

Modification of natural zeolites and their applications for heavy metal removal from polluted environments: Challenges, recent advances, and perspectives.

In recent decades, environmental pollution has become a significant problem for human health and environmental impact. The high accumulation of heavy metals in waters and soils from different sources was conducted by finding efficient and environmentally friendly treatment methods and materials for their removal. Natural zeolites have found wide-ranging applications in environmental remediation and protection, considering various treatment and modification methods designed to enhance the natural zeolites' adsorptive or ion-exchange capabilities for increased efficiency. This paper briefly consolidates the recent scientific literature related to the main characteristics of natural and modified zeolites, the advantages and limitations of their environmental remediation application, and summarizes the methodologies applied to natural zeolites in order to improve their properties. Their application for removing heavy metals from water systems and soils is also comprehensively discussed. This review highlights the excellent potential of natural zeolites to be used after specific treatment or modification as a sustainable and green material to solve numerous environmental pollution issues.

Removal of perfluoroalkyl acids from aqueous media by surfactant-modified clinoptilolites.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are environmentally persistent, bioaccumulating, and toxic compounds that have attracted global attention. It is challenging to reduce the residual concentrations of these compounds to safe discharge limits. In this study, batch experiments were performed to evaluate natural clinoptilolite and clinoptilolites modified (MC) with cetylpyridinium chloride (CPC-MC), didodecyldimethylammonium bromide (DDAB-MC), hexadecyltrimethylammonium bromide (HDTMA-MC), and tetramethylammonium chloride (TMA-MC) as cost-effective aqueous PFAS adsorbents. The removal capacities of the adsorbents for the majority of the PFASs decreased in the following order: DDAB-MC > CPC-MC ≫ modified natural clinoptilolite with hexadecyltrimethyl ammonium bromide (HDTMA-MC) ≫ modified natural clinoptilolite with tetramethylammonium chloride (TMA-MC) ≈ natural clinoptilolite modified with NaCl (NC). In particular, CPC-MC and DDAB-MC reduced PFASs concentration in 50 µg/L by up to 98% for perfluorooctane sulphonate. Within 30 min, CPC-MC (30.5 µg/L) and DDAB-MC (32.1 µg/L) met the PFOS water quality criterion of 36 µg/L in inland surface waters. Both adsorbents met this criterion at the highest solution volume (40 mL) and 0.125 g/L (solid-to-liquid ratio of 1:8). PFASs with short hydrocarbon chains competed more for adsorption. PFASs with sulphonate functional groups were also adsorbed more than carboxyl groups in single- and multi-PFAS solutions. The modified surfaces of clinoptilolites controlled PFAS adsorption through hydrophobic and electrostatic interactions. PFAS removal with surfactant-modified clinoptilolites is cost-effective and protects aquatic environments by using surplus natural materials.

Bolivian natural zeolite as a low-cost adsorbent for the adsorption of cadmium: Isotherms and kinetics.

Population growth in recent years has led to increased wastewater production and pollution of water resources. This situation also heavily affects Bolivia, so wastewater treatment methods and materials suitable for Bolivian society should be explored. This study investigated the natural Bolivian Zeolite (BZ) and its NaCl-modified structure (NaBZ) as adsorbents for cadmium removal from water. The natural BZ and the modified form NaBZ were investigated by different physicochemical characterization techniques. Furthermore, XPS and FT-IR techniques were used to investigate the adsorption mechanisms. The cadmium adsorption on BZ and NaBZ was analyzed using various mathematical models, and the Langmuir model provided a better description of the experimental adsorption data with cadmium adsorption capacities of 20.2 and 25.6 mg/g for BZ and NaBZ, respectively. The adsorption followed the pseudo-second order kinetics. The effect of different parameters, such as initial cadmium concentration and pH on the adsorption was studied. In addition, the results of the regeneration test indicated that both BZ and NaBZ can be regenerated by using hydrochloric acid (HCl). Finally, the adsorption experiment of BZ and NaBZ on a real water sample (brine from Salar de Uyuni salt flat) containing a mixture of different heavy metals was carried out. The results obtained in this study demonstrate the effectiveness of natural BZ and modified NaBZ in the removal of heavy metals from wastewater.

Optimization and evaluation of the distribution of Fischer-Tropsch products over a cobalt-based catalyst utilising design expert software.

Modelling biomass to liquid via the Fischer-Tropsch synthesis (FTS) system allows researchers to investigate the most efficient parameters while running the system under optimal conditions. As part of the design of experiments (DOE) procedure, a special data simulation method based on response surface methodology (RSM) is utilized to thoroughly analyse the impact of operating circumstances. The objective of this study was to examine the factors that affect the production of C1, C2-C4, and C5+ in FTS process, and then optimize the critical factors utilising factorial design and response surface techniques. The parameters evaluated were reaction temperature, reaction pressure and the crystallite size of cobalt. The effects of these factors and their potential for synergy were explored simultaneously using multivariate DOE, with the yield of different hydrocarbon composition selectivity's as the measured responses. In the concept generation phase, optimization was based on the literature consulted, which proved to be an effective method for determining the optimization parameters. The detailed conceptual design included the generation of models using statistical methods and response surface models. Finally, the optimized design was validated using catalysts and parameters obtained during the optimization process, and this were compared to the output recorded in the theoretical modelling. The optimized parameters resulted in performance consistency, with the theoretical model for each group of hydrocarbons being validated by actual experiments. The established models were seen to characterize hydrocarbon distributions accurately and repeatedly over a wide range of reaction conditions (200-270 °C, 5-20 Bar, and 3-26 nm) using a cobalt-based catalyst. According to the detailed quantitative models developed, for higher C5+ production, 220 °C, 10 barg and 11 nm (cobalt crystallite) benchmark parameters were set to produce 19.3 % C1, 11.4 % C2-C4 and 69 % C5+ selectivity's. Comparative analysis showed a 1.9 %, 3.9 % and 0.3 % percentage difference between the theoretical output and the actual output of C1, C2-C4 and C5+, respectively.

Synthesis of amorphous-MnO2/Clinoptilolite and its utilization for NH4+-N oxidation in an anoxic environment.

Mediating the anoxic ammonia oxidation with manganese oxide (MnOx) can reduce the requirements of dissolved oxygen (DO) concentrations in constructed wetlands (CWs) and improve the removal of ammonium nitrogen (NH4+-N). Recent studies that employed natural manganese ore and/or mine waste as substrates in CWs may develop potentially negative environmental effects due to leachates. However, removing NH4+-N by anoxic ammonia oxidation is influenced by the crystal form of MnOx. In this study, a novel clinoptilolite-based amorphous-MnO2 (amorphous-MnO2/clinoptilolite) was synthesized by the sol-gel method as an alternative substrate to improve the efficiency of anoxic ammonia oxidation and reduce the impact of Mn ion leaching. According to the anoxic ammonia oxidation experiment of clinoptilolite, amorphous-MnO2/clinoptilolite, and manganese ore on NH4+-N, the amounts of NH4+-N removed were 24.55 mg/L/d, 44.55 mg/L/d, and 11.04 mg/L/d, respectively, and the initial NH4+-N concentration was 49.53 mg/L. These results indicated that the amorphous-MnO2/clinoptilolite had both the adsorption and the anoxic ammonia oxidation performance. The recycling experiment demonstrated that the effect of anoxic ammonia oxygen mediated by amorphous-MnO2 would not diminish with the gradual saturation of clinoptilolite for NH4+-N. Furthermore, the anoxic ammonia oxidation consumed NH4+-N in the clinoptilolite, which restored the adsorption capacity of the clinoptilolite and simultaneously decreased the leakage of manganese ions in the process, making it environmentally friendly. Therefore, the amorphous-MnO2/clinoptilolite provided an excellent substrate material for the constructed wetland under an anoxic environment, which greatly improved the nitrogen removal capacity compared to existing substrate materials.

Neodymium sorption on the Na-form of Transcarpathian clinoptilolite.

The sorption properties of Na-modified Ukrainian Transcarpathian clinoptilolite towards neodymium aqueous solutions under dynamic conditions have been investigated. The sorption capacity of the Na-from of Transcarpathian clinoptilolite towards Nd(III) significantly depends on the concentration of neodymium salt, the pH of the solution, and the heat treatment temperature of the sorbent. Nd(III) is most efficiently sorbed from slightly alkaline solutions (pH 8.5), mainly by adsorption of neutral hydrolyzed forms of Nd(OH)3 on the surface of Na-clinoptilolite samples preheated at 75 °C. During the passage of an Nd(III) solution with a concentration of 1 µg mL-1 through the sorbent at a rate of 3 mL min-1 under optimal conditions, the sorption capacity of Na-clinoptilolite is 7.2 mg g-1, which is in 4 and 2.3 times higher than that of natural and acid-modified forms of this zeolite. It is shown that under the experimental conditions with an increase in the flow rate, the thickness of the stationary surface layer decreases, which leads to a decrease in the sorption capacity of Na-clinoptilolite. The best Nd(III) desorbents are solutions of mineral acids and acidified solutions of alkali metal salts (except NaCl), which provide 93-98 % extraction of lanthanide from the zeolite matrix. The method for neodymium trace amounts preconcentration from aqueous solutions in a solid-phase extraction mode with a further determination of this rare earth element by a spectrophotometric method was developed. The detection limit of this method is 0.75 ng mL-1 and the linearity was evaluated in the range of 2.5-500 ng mL-1.