The effect of carbonized zeolitic imidazolate framework-67 (ZIF-67) support on the reactivity and selectivity of bimetal-catalytic aqueous NO3- reduction.

A metallic catalyst, Cobalt N-doped Carbon (Co@NC), was obtained from Zeolitic-Imidazolate Framework-67 (ZIF-67) for efficient aqueous nitrate (NO3-) removal. This advanced catalyst indicated remarkable efficiency by generating valuable ammonium (NH3/NH4+) via an environmentally friendly production technique during the nitrate treatment. Among various metals (Cu, Pt, Pd, Sn, Ru, and Ni), 3.6%Pt-Co@NC exhibited an exceptional nitrate removal, demonstrating a complete removal of 60 mg/L NO3--N (265 mg/L NO3-) in 30 min with the fastest removal kinetics (11.4 × 10-2 min-1) and 99.5% NH4+ selectivity. The synergistic effect of bimetallic Pt-Co@NC led to 100% aqueous NO3- removal, outperforming the reactivity by bare ZIF-67 (3.67%). The XPS analysis illustrated Co's promotor role for NO3- reduction to less oxidized nitrogen species and Pt's hydrogenation role for further reduction to NH4+. The durability test revealed a slight decrease in NO3- removal, which started from the third cycle (95%) and slowly proceeded to the sixth cycle (80.2%), while NH4+ selectivity exceeded 82% with no notable Co or Pt leaching throughout seven consecutive cycles. This research shed light on the significance of the impregnated Pt metal and Co exposed on the Co@NC surface for the catalytic nitrate treatment, leading to a sustainable approach for the effective removal of nitrate and economical NH4+ production.

Recent advances in the application of magnetic materials for the management of perfluoroalkyl substances in aqueous phases.

Perfluoroalkyl substances (PFASs) are a class of artificially synthesised organic compounds extensively used in both industrial and consumer products owing to their unique characteristics. However, their persistence in the environment and potential risk to health have raised serious global concerns. Therefore, developing effective techniques to identify, eliminate, and degrade these pollutants in water are crucial. Owing to their high surface area, magnetic responsiveness, redox sensitivity, and ease of separation, magnetic materials have been considered for the treatment of PFASs from water in recent years. This review provides a comprehensive overview of the recent use of magnetic materials for the detection, removal, and degradation of PFASs in aqueous solutions. First, the use of magnetic materials for sensitive and precise detection of PFASs is addressed. Second, the adsorption of PFASs using magnetic materials is discussed. Several magnetic materials, including iron oxides, ferrites, and magnetic carbon composites, have been explored as efficient adsorbents for PFASs removal from water. Surface modification, functionalization, and composite fabrication have been employed to improve the adsorption effectiveness and selectivity of magnetic materials for PFASs. The final section of this review focuses on the advanced oxidation for PFASs using magnetic materials. This review suggests that magnetic materials have demonstrated considerable potential for use in various environmental remediation applications, as well as in the treatment of PFASs-contaminated water.

Unveiling the oxidation mechanism of persistent organic contaminants via visible light-induced dye-sensitized reaction by red mud suspension with peroxymonosulfate.

A dye-sensitized photocatalysis system was developed for degrading persistent organic contaminants using solid waste (i.e., red mud, RM) and peroxymonosulfate (PMS) under visible light. Complete degradation of acid orange 7 (AO7) was achieved in RM suspension with PMS, where the co-existence of amorphous FeO(OH)/α-Fe2O3 was the key factor for PMS activation. The experimental results obtained from photochemical and electrochemical observations confirmed the enhanced PMS activation due to the Fe-OH phase in RM. DFT calculations verified the acceleration of PMS activation due to the high adsorption energy of PMS on FeO(OH) and low energy barrier for generating reactive radicals. Compared to the control experiment without AO7 showing almost no degradation of other organic contaminants (phenol, bisphenol A, 4-chlorophenol, 4-nitrophenol, and benzoic acid), photo-sensitized AO7* enhanced electron transfer in the FeIII/FeII cycle, dramatically enhancing the degradation of organic contaminants via radical (•OH, SO4•-, and O2•-) and non-radical (dye*+ and 1O2) pathways. Therefore, the novel finding of this study can provide new insights for unique PMS activation by heterogeneous Fe(III) containing solid wastes and highlight the importance of sensitized dye on the interaction of PMS with Fe charge carrier for the photo-oxidation of organic contaminants under visible light.

Advances in Fe-modified lignocellulosic biochar: Impact of iron species and characteristics on wastewater treatment.

Lignocellulosic biomass is an attractive feedstock for biochar production owing to its high abundance and renewability. Various modified biochars have been extensively studied for wastewater treatment to improve the physical and chemical properties of lignocellulosic biochar (L-BC). Particularly, Fe-modified L-BCs have garnered attention owing to the abundance and eco-friendliness of Fe and the outstanding ability to remove various organic and inorganic contaminants via adsorption, oxidation, reduction, and catalytic reactions. Different iron species (e.g., Fe(0), Fe (hydr)oxide, Fe sulfide, and Fe-Metal) are formed during the preparation of Fe-L-BCs, which can completely differentiate the physical and chemical properties of BCs. This review discusses the advances in the synthesis of different Fe-L-BCs, specific changes in the physical and chemical properties of Fe-L-BCs upon Fe addition, and their impacts on wastewater treatment. The results of this review can demonstrate the unique advantages and drawbacks of Fe-L-BCs for the removal of different types of pollutants.

Advancements in TiO2-based photocatalysis for environmental remediation: Strategies for enhancing visible-light-driven activity.

Researchers have focused on efficient techniques for degrading hazardous organic pollutants due to their negative impacts on ecological systems, necessitating immediate remediation. Specifically, TiO2-based photocatalysts, a wide-bandgap semiconductor material, have been extensively studied for their application in environmental remediation. However, the extensive band gap energy and speedy reattachment of electron (e-) and hole (h+) pairs in bare TiO2 are considered major disadvantages for photocatalysis. This review extensively focuses on the combination of semiconducting photocatalysts for commercial outcomes to develop efficient heterojunctions with high photocatalytic activity by minimizing the e-/h+ recombination rate. The improved activity of these heterojunctions is due to their greater surface area, rich active sites, narrow band gap, and high light-harvesting tendency. In this context, strategies for increasing visible light activity, including doping with metals and non-metals, surface modifications, morphology control, composite formation, heterojunction formation, bandgap engineering, surface plasmon resonance, and optimizing reaction conditions are discussed. Furthermore, this review critically assesses the latest developments in TiO2 photocatalysts for the efficient decomposition of various organic contaminants from wastewater, such as pharmaceutical waste, dyes, pesticides, aromatic hydrocarbons, and halo compounds. This review implies that doping is an effective, economical, and simple process for TiO2 nanostructures and that a heterogeneous photocatalytic mechanism is an eco-friendly substitute for the removal of various pollutants. This review provides valuable insights for researchers involved in the development of efficient photocatalysts for environmental remediation.

Use of thermally activated Fenton sludge for Cd removal in zinc smelter wastewater: Mechanism and feasibility of Cd removal.

Fenton sludge is a byproduct of the Fenton process that contains large amounts of Fe and Ca. Because of the secondary contamination generated during the disposal of this byproduct, ecofriendly treatment methods are needed. In this study, we used Fenton sludge to remove the Cd discharged from a zinc smelter factory, using thermal activation to enhance the Cd adsorption capacity. Among the various temperatures considered (300-900 °C), the Fenton sludge that was thermally activated at 900 °C (TA-FS-900) adsorbed the highest amount of Cd because of its high specific surface area and high Fe content. Cd was adsorbed onto TA-FS-900 via complexation with C-OH, C-COOH, FeO-, and FeOH and cation exchange with Ca2+. The maximum adsorption of TA-FS-900 was 260.2 mg/g, indicating that TA-FS-900 is an efficient adsorbent, comparable to those reported in the literature. The initial Cd concentration in the zinc smelter wastewater discharged was 105.7 mg/L, 98.4% of which was removed by applying TA-FS-900, suggesting the applicability of TA-FS-900 for real wastewater containing high concentrations of various cations and anions. The leaching of heavy metals from TA-FS-900 was within the EPA standard limits. We concluded that the environmental impact of Fenton sludge disposal can be reduced, and the use of Fenton sludge can add value to the treatment of industrial wastewater in terms of the circular economy and environment.

Seizure-induced neutrophil adhesion in brain capillaries leads to a decrease in postictal cerebral blood flow.

Cerebral hypoperfusion has been proposed as a potential cause of postictal neurological dysfunction in epilepsy, but its underlying mechanism is still unclear. We show that a 30% reduction in postictal cerebral blood flow (CBF) has two contributing factors: the early hypoperfusion up to ∼30 min post-seizure was mainly induced by arteriolar constriction, while the hypoperfusion that persisted for over an hour was due to increased capillary stalling induced by neutrophil adhesion to brain capillaries, decreased red blood cell (RBC) flow accompanied by constriction of capillaries and venules, and elevated intercellular adhesion molecule-1 (ICAM-1) expression. Administration of antibodies against the neutrophil marker Ly6G and against LFA-1, which mediates adhesive interactions with ICAM-1, prevented neutrophil adhesion and recovered the prolonged CBF reductions to control levels. Our findings provide evidence that seizure-induced neutrophil adhesion to cerebral microvessels via ICAM-1 leads to prolonged postictal hypoperfusion, which may underlie neurological dysfunction in epilepsy.

Aging and reactivity assessment of nanoscale zerovalent iron in groundwater systems.

In this study, changes in the reactivity of nanoscale zerovalent iron (NZVI) in five different groundwater (GW) systems under anoxic and oxic conditions were examined over a wide range of aging time (0 - 60 d). p-nitrophenol (p-NP) was used as a redox-sensitive probe, whereas nalidixic acid (NA), a typical antibiotic found in the natural environment, was used as a sorbing compound. Investigation of the p-NP reduction in pure water systems showed that NZVI lost 41% and 98% of its reductive activity under anoxic and oxic conditions after 60 d, while enhancement of its reactivity was observed after short-term aging in GW (1 - 5 d), followed by a further decline. This behavior has been ascribed to the formation of secondary Fe(II)-bearing phases, including magnetite and green rust, resulting from NZVI aging in GW. Adsorption experiments revealed that GW-anoxic-aged NZVI samples exhibited a good affinity toward NA, and a greater NA adsorption (∼27 µmol g - 1) than that of pristine NZVI (∼2 µmol g - 1) at alkaline pH values. Surface complexation modeling showed that the enhanced adsorption of NA onto secondary minerals can be attributed to the Fe(II)-NA surface complexation. This considerable change in the reductive ability and the adsorption capacity of NZVI arising from groundwater corrosion calls for greater attention to be paid in assessment studies, where NZVI is injected for long-term remediation in groundwater.

Unveiling the positive effect of mineral induced natural organic matter (NOM) on catalyst properties and catalytic dechlorination performance: An experiment and DFT study.

Herein, we report the significant effects of natural organic matter contained in natural zeolite (Z-NOM) on the physicochemical characteristics of a Ni/Fe@natural zeolite (NF@NZ) catalyst and its decontamination performance toward the dechlorination of trichloroethylene (TCE). Z-NOM predominantly consists of humic-like substances and has demonstrable utility in the synthesis of bimetallic catalysts. Compared to NF@NZ600C (devoid of Z-NOM), NF@NZ had increased dispersibility and mobility and showed significant enhancement in the catalytic dechlorination of TCE owing to the encapsulation of Ni0/Fe0 nanoparticles by Z-NOM. The results of corrosion experiments, spectroscopic analyses, and H2 production experiments confirmed that Ni0 acted as an efficient cocatalyst with Fe0 to enhance the dechlorination of TCE to ethane, and Z-NOM-capped Ni0 showed improved adsorption of TCE and atomic hydrogen on their reactive sites and oxidation resistance. The density functional theory (DFT) studies have substantiated the improved adsorption of TCE due to the presence of NOM (especially by COOH structure) and the enhanced charge density at the Ni site in the Ni/Fe bimetal alloy for the stronger adsorption of hydrogen atoms that ultimately enhanced the TCE reduction reaction. These findings illustrate the efficiency of NOM containing natural minerals toward the synthesis of bimetallic catalysts for practical applications.

The role of Fe dissolution in olivine-hydroxylamine-induced Fenton reaction for enhanced oxidative degradation of organic pollutant.

In this study, a dye pollutant (methyl orange, MO) was effectively oxidized in a hydroxylamine (HA)-assisted Fenton system using various Al/Si/Fe- and Fe-containing minerals. The fastest degradation kinetics of MO were observed in the olivine-HA Fenton system, whereas other Al/Si/Fe and Fe-rich minerals (magnetite and lepidocrocite) demonstrated much slower degradation kinetics. The degradation rate constants were proportional to dissolved Fe(II) quantities in mineral suspensions (R2 = 0.98), indicating the crucial role of dissolved Fe(II) quantity in HA-assisted Fenton reactions. Radical scavenging and electron spin resonance results revealed that MO was dominantly oxidized by ·HO produced in the olivine-HA Fenton system. The continuous production of aqueous Fe(II) via direct Fe(II) dissolution at a pH of 3 and further Fe dissolution from the reductive dissolution of surface Fe(III) by HA was the main driving force for efficient MO degradation. Furthermore, lowering the pH by the addition of hydroxylamine hydrochloride resulted in the effective removal of MO under various pH conditions (3-9), indicating the additional advantage of HA use in Fenton reactions. Liquid chromatography-mass spectroscopy analysis revealed that the cleavage of C-N and C-C bonds, demethylation, hydroxylation, and dehydroxylation were the main processes for MO oxidation in the olivine-HA Fenton system.

NaOH-assisted H2O2 post-modification as a novel approach to enhance adsorption capacity of residual coffee waste biochars toward radioactive strontium: Experimental and theoretical studies.

In this study, NaOH-assisted H2O2 post-modification was proposed as a novel strategy to enhance the adsorption of radioactive strontium (Sr) onto residual coffee waste biochars (RCWBs). To validate its viability, the adsorption capacities and mechanisms of Sr(II) using pristine (RCWBP), H2O2 post-modified (RCWBHP), and NaOH-assisted H2O2 post-modified residual coffee waste biochars (RCWBNHP) were experimentally and theoretically investigated. The highest adsorption capacity of Sr(II) for RCWBNHP (10.91 mg/g) compared to RCWBHP (5.57 mg/g) and RCWBP (5.07 mg/g) was primarily attributed to higher negative surface zeta potential (RCWBNHP = -5.66 → -30.97 mV; RCWBHP = -0.31 → -11.29 mV; RCWBP = 1.90 → -10.40 mV) and decoration of Na on the surfaces of RCWBP via NaOH-assisted H2O2 post-modification. These findings agree entirely with the theoretical observations that the adsorption of Sr(II) onto RCWBP and RCWBHP was controlled by electrostatic interactions involving carbonyls whereas enriched carboxylic acids and decorated Na on the surfaces of RCWBNHP through the replacement of Mg and K by NaOH-assisted H2O2 modification stimulated electrostatic interactions and cation exchanges governing the adsorption of Sr(II). Hence, NaOH-assisted H2O2 post-modification seemed to be practically applicable for improving the adsorption capacity of Sr(II) using RCWB-based carbonaceous adsorbents in real water matrices.

Quasi-Solid-State SiO2 Electrolyte Prepared from Raw Fly Ash for Enhanced Solar Energy Conversion.

Quasi-solid-state electrolytes in dye-sensitized solar cells (DSSCs) prevent solvent leakage or evaporation and stability issues that conventional electrolytes cannot; however, there are no known reports that use such an electrolyte based on fly ash SiO2 (FA_SiO2) from raw fly ash (RFA) for solar energy conversion applications. Hence, in this study, quasi-solid-state electrolytes based on FA_SiO2 are prepared from RFA and poly(ethylene glycol) (PEG) for solar energy conversion. The structural, morphological, chemical, and electrochemical properties of the DSSCs using this electrolyte are characterized by X-ray diffraction (XRD), high-resolution field-emission scanning electron microscopy (HR-FESEM), X-ray fluorescence (XRF), diffuse reflectance spectroscopy, electrochemical impedance spectroscopy (EIS), and incident photon-to-electron conversion efficiency (IPCE) measurements. The DSSCs based on the quasi-solid-state electrolyte (SiO2) show a cell efficiency of 5.5%, which is higher than those of nanogel electrolytes (5.0%). The enhancement of the cell efficiency is primarily due to the increase in the open circuit voltage and fill factor caused by the reduced electron recombination and improved electron transfer properties. The findings confirm that the RFA-based quasi-solid-state (SiO2) electrolyte is an alternative to conventional liquid-state electrolytes, making this approach among the most promising strategies for use in low-cost solar energy conversion devices.

Adsorption of Chromate Ions by Layered Double Hydroxide-Bentonite Nanocomposite for Groundwater Remediation.

Herein, magnesium/aluminum-layered double hydroxide (MgAl-LDH) and bentonite (BT) nanocomposites (LDH-BT) were prepared by co-precipitation (CP), exfoliation-reassembly (ER), and simple solid-phase hybridization (SP). The prepared LDH-BT nanocomposites were preliminarily characterized by using powder X-ray diffractometry, scanning electron microscopy, and zeta-potentiometry. The chromate adsorption efficacies of the pristine materials (LDH and bentonite) and the as-prepared nanocomposites were investigated. Among the composites, the LDH-BT_SP was found to exhibit the highest chromate removal efficiency of 65.7%. The effect of varying the LDH amount in the LDH-BT composite was further investigated, and a positive relationship between the LDH ratio and chromate removal efficiency was identified. The chromate adsorption by the LDH-BT_SP was performed under various concentrations (isotherm) and contact times (kinetic). The results of the isotherm experiments were well fitted with the Langmuir and Freundlich isotherm model and demonstrate multilayer chromate adsorption by the heterogeneous LDH-BT_SP, with a homogenous distribution of LDH nanoparticles. The mobility of the as-prepared LDH-BT_SP was investigated on a silica sand-filled column to demonstrate that the mobility of the bentonite is dramatically decreased after hybridization with LDH. Furthermore, when the LDH-BT_SP was injected into a box container filled with silica sand to simulate subsurface soil conditions, the chromate removal efficacy was around 43% in 170 min. Thus, it was confirmed that the LDH-BT prepared by solid-phase hybridization is a practical clay-based nanocomposite for in situ soil and groundwater remediation.

Deep brain stimulation of the anterior nuclei of the thalamus can alleviate seizure severity and induce hippocampal GABAergic neuronal changes in a pilocarpine-induced epileptic mouse brain.

Deep brain stimulation (DBS) of the anterior nucleus of the thalamus (ANT) has been widely used as an effective treatment for refractory temporal lobe epilepsy. Despite its promising clinical outcome, the exact mechanism of how ANT-DBS alleviates seizure severity has not been fully understood, especially at the cellular level. To assess effects of DBS, the present study examined electroencephalography (EEG) signals and locomotor behavior changes and conducted immunohistochemical analyses to examine changes in neuronal activity, number of neurons, and neurogenesis of inhibitory neurons in different hippocampal subregions. ANT-DBS alleviated seizure activity, abnormal locomotor behaviors, reduced theta-band, increased gamma-band EEG power in the interictal state, and increased the number of neurons in the dentate gyrus (DG). The number of parvalbumin- and somatostatin-expressing inhibitory neurons was recovered to the level in DG and CA1 of naïve mice. Notably, BrdU-positive inhibitory neurons were increased. In conclusion, ANT-DBS not only could reduce the number of seizures, but also could induce neuronal changes in the hippocampus, which is a key region involved in chronic epileptogenesis. Importantly, our results suggest that ANT-DBS may lead to hippocampal subregion-specific cellular recovery of GABAergic inhibitory neurons.

Advances in application of g-C3N4-based materials for treatment of polluted water and wastewater via activation of oxidants and photoelectrocatalysis: A comprehensive review.

Recently, graphitic carbon nitride (g-C3N4) has received significant attention as a non-metallic, visible-light-activated photocatalyst for treating water and wastewater by degrading contaminants. Accordingly, previous review articles have focused on the photocatalytic properties of g-C3N4-based materials. However, g-C3N4 has several other notable features, such as high adsorption affinity towards aromatic substances and heavy metals, high thermal and chemical resistances, good compatibility with various materials, and easily scalable synthesis; therefore, in addition to simple photocatalysis, it can be widely used in other decontamination systems based on activation of oxidants and electrocatalysis. This critical review provides a comprehensive summary of recent advancements in g-C3N4-based materials and their use in treating polluted water and wastewater via the following routes (1) activation of oxidizing agents (e.g., hydrogen peroxide, ozone, peroxymonosulfate, and persulfate): and (2) photoelectrocatalysis using fabricated g-C3N4-based photocathodes and photoanodes. For each route, we briefly summarize the primary mechanisms, distinctive features, and performances of various water treatment systems using g-C3N4-based catalysts. We also highlight the specific roles of g-C3N4 in improving the efficiencies of these treatment processes. The advantages and limitations of previously reported water treatment systems using g-C3N4-based materials are also described and compared in this review. Finally, we discuss the challenges and prospects of improving g-C3N4-based water purification applications.

The enhanced reduction of bromate by highly reactive and dispersive green nano-zerovalent iron (G-NZVI) synthesized with onion peel extract.

In this study, novel green nano-zerovalent iron (G-NZVI) is synthesized for the first time using onion peel extract for the prevention of rapid surface oxidation and the enhancement of particle dispersibility with a high reductive capacity. The results from various surface analyses revealed that the spherical shape of G-NZVI was fully covered by the onion peel extract composed of polyphenolic compounds with C[double bond, length as m-dash]C-C[double bond, length as m-dash]C unsaturated carbon, C[double bond, length as m-dash]C, C-O, and O-H bonds, resulting in high mobility during column chromatography. Furthermore, the obtained G-NZVI showed the complete removal of 50 mg L-1 of bromate (BrO3 -) in 2 min under both aerobic (k = 4.42 min-1) and anaerobic conditions (k = 4.50 min-1), showing that G-NZVI had outstanding oxidation resistance compared to that of bare NZVI. Moreover, the observed performance of G-NZVI showed that it was much more reactive than other well-known reductants (e.g., Fe and Co metal organic frameworks), regardless of whether aerobic or anaerobic conditions were used. The effects of G-NZVI loading, the BrO3 - concentration, and pH on the BrO3 - removal kinetics using G-NZVI were also investigated in this study. The results provide the novel insight that organic onion peel waste can be reused to synthesize highly reactive anti-oxidative nanoparticles for the treatment of inorganic chemical species and heavy metals in water and wastewater.

Differential contribution of excitatory and inhibitory neurons in shaping neurovascular coupling in different epileptic neural states.

Understanding the neurovascular coupling (NVC) underlying hemodynamic changes in epilepsy is crucial to properly interpreting functional brain imaging signals associated with epileptic events. However, how excitatory and inhibitory neurons affect vascular responses in different epileptic states remains unknown. We conducted real-time in vivo measurements of cerebral blood flow (CBF), vessel diameter, and excitatory and inhibitory neuronal calcium signals during recurrent focal seizures. During preictal states, decreases in CBF and arteriole diameter were closely related to decreased γ-band local field potential (LFP) power, which was linked to relatively elevated excitatory and reduced inhibitory neuronal activity levels. Notably, this preictal condition was followed by a strengthened ictal event. In particular, the preictal inhibitory activity level was positively correlated with coherent oscillating activity specific to inhibitory neurons. In contrast, ictal states were characterized by elevated synchrony in excitatory neurons. Given these findings, we suggest that excitatory and inhibitory neurons differentially contribute to shaping the ictal and preictal neural states, respectively. Moreover, the preictal vascular activity, alongside with the γ-band, may reflect the relative levels of excitatory and inhibitory neuronal activity, and upcoming ictal activity. Our findings provide useful insights into how perfusion signals of different epileptic states are related in terms of NVC.

Characterization of rare earth elements present in coal ash by sequential extraction.

Although it has recently been reported that notable amounts of rare earth elements (REEs) are present in the residual coal ash, little is currently known regarding the association of these elements with the coal ash matrix, thereby limiting the potential for extraction of REEs from coal ash. In this study, we analyzed the binding characteristics of REEs within coal ash via sequential extraction and examined REE recovery during a coal ash recycling process. Major components of coal ash were found to be mineral oxides, mainly composed of Si, Fe, Al, and Ca, and residual carbons. Bottom and fly ashes were found to contain 185.8 mg/kg and 179.2 mg/kg of REEs, respectively. Tessier sequential extraction confirmed that 85 % of REEs are included in the residual fraction of both bottom and fly ashes. Furthermore, BCR sequential extraction revealed that 60-70 % of REEs are contained within the residual fraction, thereby indicating that REEs are strongly bound in both bottom and fly ashes and the use of very strong acids is required for the thorough extraction of REEs from coal ash. Additionally, it was found that 46.3 % of REEs can be recovered from the wastewaters produced during the process of coal ash-derived zeolite synthesis.

Competitive adsorption of pharmaceuticals in lake water and wastewater effluent by pristine and NaOH-activated biochars from spent coffee wastes: Contribution of hydrophobic and π-π interactions.

This study investigated the competitive adsorption mechanisms of pharmaceuticals (i.e., naproxen, diclofenac, and ibuprofen) toward the pristine and NaOH-activated biochars from spent coffee wastes (SCW) in lake water and wastewater effluent. The kinetic and isotherm studies revealed that the improved physicochemical characteristics and physically homogenized surfaces of the pristine SCW biochar through the chemical activation with NaOH were beneficial to the adsorption of pharmaceuticals (competitive equilibrium adsorption capacity (Qe, exp): NaOH-activated SCW biochar (61.25-192.07 µmol/g) > pristine SCW biochar (14.81-20.65 µmol/g)). The adsorptive removal of naproxen (Qe, exp = 14.81-18.81 µmol/g), diclofenac (Qe, exp = 15.73-20.00 µmol/g), and ibuprofen (Qe, exp = 16.20-20.65 µmol/g) for the pristine SCW biochar showed linear correlations with their hydrophobicity (log D at pH 7.0: ibuprofen (1.71) > diclofenac (1.37) > naproxen (0.25)). However, their Qe, exp values for the NaOH-activated SCW biochar (naproxen (176.39-192.07 µmol/g) > diclofenac (78.44-98.74 µmol/g) > ibuprofen (61.25-80.02 µmol/g)) were inversely correlated to the order of their log D values. These results suggest that the reinforced aromatic structure of the NaOH-activated SCW biochar facilitated the π-π interaction. The calculated thermodynamic parameters demonstrated that the competitive adsorption of pharmaceuticals on the NaOH-activated SCW biochar compared to pristine SCW biochar occurred more spontaneously over the entire pH (5.0-11.0) and ionic strength (NaCl: 0-0.125 M) ranges. These observations imply that the NaOH-activated SCW biochar might be potentially applicable for the removal of pharmaceuticals in lake water and wastewater effluent.