Neutral pH Research Articles

A novel technique of dual modified acid-washed layered double hydroxides-biochar for adsorption and as potential catalysts for electrochemical applications

The enhanced concentration of nitrate ions in wastewater delivered from industries has led to consequential environmental issues and severe health problems for humanity. Considering the advantages to the environment and being cost-effective, adsorption techniques based on biochar materials have appeared as a remarkable strategy to adsorb nitrate. Although the porous nature of the biochar materials aids in adsorption, the stability is a significant hindrance, thus limiting nitrate adsorption. Thus, in an effort to tackle this difficulty, layered double hydroxide (LDH) modified with cationic surfactant rice husk biochar is utilized to enhance the stability and the performance of nitrate adsorption. In the current research, pristine biochar (Pure-BC), surfactant-modified biochar (BC-S), varying concentrations of iron and magnesium-modified LDH with surfactant biochar materials (FM-SL, MF-SL) were synthesized, and batch experiments were conducted in order to explore their performance of nitrate adsorption. The acid-washed biochar exhibited novel rapid adsorption within a period of 10 min and a maximum adsorption capacity of 72 mg/g at neutral pH, whose mechanism was based on both physical and chemical adsorption. Further, the pristine and modified biochar materials were analyzed for their electrochemical behavior in order to explore their chemical reactivity and electron transfer kinetics, with an overpotential value of 67 mV. Thus, the prepared biochar materials, being inexpensive, exhibit potential adsorbents for the adsorption of nitrate from industrial sewage waters and display better electrochemical characteristics.

Methanization Test of Water Hyacinth and Azolla in Co-digestion and Fertilizing Value of Digestates in Benin (West Africa)

Faced with the need for an alternative energy source following the extreme pressure exerted on woody resources accompanied by the increase of aquatic pests which invade water resources, the construction of mini reactors producing clean energy, biogas based on these invasive plants becomes a challenge. This investigation aims to assess the methane production potential of water hyacinth and Azolla in co-digestion and the fertilizing quality of the digestates obtained. A bio methanization test based on various combinations of organic substrates composed of water hyacinth and Azolla alone or in co-digestion under laboratory conditions at mesophilic temperature and neutral pH after 27 days was carried out. The source of enrichment in anaerobic microorganisms for fermentation processes in micro bioreactors consists of fresh pig manure. It appears that the combination of organic substrates including 75% of water hyacinth generated the maximum quantity of methane which is 1234 liters for one ton of organic substrates. This methane production is 1.93 times greater than that of the bioreactor containing water hyacinth alone, 1.90 times that containing azolla, 1.5 times that containing 25% water hyacinth +75% azolla then 3.04 times that containing the bioreactor composed of a high proportion of crushed Azolla filiculoides. The digestates are rich in N, P, K, Ca and Mg and had an amending power according to the NFU 44051 standard. For the construction of bioreactors with aquatic pests for the benefit of communities, co-digestion with a combination of substrates with a high proportion of water hyacinth is suggested.

Revealing the vital role of sulfur site on the surface of pyrite in 1O2 formation for promoting ciprofloxacin degradation via peracetic acid activation

Pyrite has been widely utilized to activate oxidants for water treatment, yet the regulation of reactive oxygen species (ROS) by sulfur sites on its surface has been overlooked. In this study, the surface sulfur sites were regulated by thermal modification of natural pyrite in the N2 atmosphere (denoted as P-X, where X represented pyrolysis temperatures ranging from 400 to 700 °C), and these modified pyrites were employed to activate peracetic acid (PAA) for ciprofloxacin (CIP) degradation. The results revealed that the degradation rate of CIP increased as the reduced sulfur content increased, with the P600/PAA system achieving the highest apparent degradation rate (kobs = 0.0999 min−1). Quenching experiments and electron paramagnetic resonance (EPR) analysis identified various ROS involved in the P-X/PAA system, with hydroxyl radical (·OH) and singlet oxygen (1O2) identified as dominant reactive species responsible for CIP degradation. The reduced sulfur sites served as the primary active sites facilitating the conversion of organic radicals (·CH3C(O)OO) into superoxide radicals (·O2−) and 1O2. Furthermore, the P600/PAA system demonstrated robust adaptability under both acidic and neutral pH conditions, efficiently degrading CIP even in the presence of complex matrices such as Cl−, NO3−, SO42−, NH4+, or humic acid (HA) in water bodies, although HCO3− was found to inhibit CIP degradation. This study significantly enhances our understanding of the interaction between reduced sulfur sites and ROS in PAA-based advanced oxidation processes (AOPs), offering a promising technology for efficient antibiotic treatment in water purification.

A photocatalysis-self-Fenton system based on NCDs@ZnIn2S4 composites at neutral pH and low amount of Fe2+ for the effective degradation of antibiotics

Photocatalysis-self-Fenton combining photocatalytic production of H2O2 with Fenton reaction has been a hotspot, but the pH limitation and iron sludge production problems remain unsolved. Herein, we proposed a self-fenton system based on N-doped carbon dots modified ZnIn2S4 (NCDs@ZnIn2S4) composites that exhibits effective degradation of antibiotics under neutral pH using low amounts of Fe2+. The decoration of ZnIn2S4 with NCDs significantly increased the surface area, visible light absorption, charge transfer ability and oxygen adsorption ability. NCDs@ZnIn2S4 composites exhibited a high H2O2 production rate (1528 μM g−1•h−1) under visible light, which was 1.9 and 5.3 times higher than ZnIn2S4 and NCDs, respectively. Meanwhile, the Fe2+/NCDs@ZnIn2S4 system with a low concentration of Fe2+(1 mg/L) could remove over 95% levofloxacin and oxytetracycline within 30 min. Interestingly, the highest degradation efficiency occurred under neutral pH. Quenching experiments and analytical measurements indicated that the high catalytic performance under pH = 7 with low amounts of Fe2+ stemmed from the higher amount of inner-generate H2O2 under neutral pH and easy regeneration of Fe2+ by photoinduced electrons for high •OH yields. Additionally, the Fe2+/NCDs@ZnIn2S4 system exhibited high degradation performance under different water matrix and ultrahigh degradation efficiency towards levofloxacin under real sunlight irradiation. The work shows the prospects of photocatalysis-self-Fenton systems for overcoming the pH limitation and the difficulty of iron sludge separation in the purification of effluents.

Green biosynthesis of Ag-doped hetero-metallic oxide nanocomposite for efficient sunlight-driven photo-adsorptive degradation of carcinogenic naphthalene and phenanthrene

One of the most significant issues facing the world today is environmental contamination due to the polycyclic aromatic hydrocarbons, or PAHs release of reactive chemicals into the environment. Here, a green technology was used to synthesis the Ag doped Bi2O3@Co3O4 nanocomposite utilizing an extract from Azadirachta indica leaves. The morphological and structural examination of Ag doped Co3O4@Bi2O3 revealed an image in the form of a hollow spherical or flake adsorbed on a Ag surface with an increase surface area. New peaks in the FT-IR spectra of Ag–O and Co–O–Bi at 678 cm−1 and 1130 cm−1, respectively, show the coupling of Ag. Following this, under various reaction conditions (pollutant: 10–30 mg/L; catalyst: 10–30 mg; pH: 3–11, dark sunlight) the doped nanocomposite was assessed for the efficient removal of NAP and PHE. Ag doped Co3O4@Bi2O3 displayed maximum degradation of NAP (96 %) and PHE (94 %) at 10 mg/L conc. of each PAH with a 25 mg catalytic dose at neutral pH in the presence of direct sunlight. First-order kinetics followed by initial Langmuir adsorption constituted the degradation process. Predominant reactive species and safer metabolite formation in the photocatalysis process of PAHs were studied by scavenger and GC–MS analysis. The green nano photocatalyst that was created demonstrated excellent stability, sensitivity, and reusability (up to 8th cycles) during the degrading process, which likely qualified it for use in industrial uses.

Stabilization of arsenic-cadmium co-contaminated soil with the iron-manganese sludge derived amendment: Effects and mechanisms

An iron-manganese sludge-derived amendment was proposed to remediate arsenic (As) and cadmium (Cd) co-contaminated soil, with a strong adsorptive capacity across pH 4 to 10. The Langmuir model defined maximum adsorption at 78.17 mg/g for As(III), 110.48 mg/kg for As(V), and 65.77 mg/g for Cd(II). The X-ray photoelectron spectroscopy (XPS) spectra provided insights into the chemical interactions: As was predominantly complexed or ligand exchanged with iron(hydr)oxides. In contrast, cadmium exhibited a tendency to bond with acylamino and carboxyl groups, in addition to the ferric hydroxyl groups. Notably, 42.15% of the adsorbed As(III) was oxidized into As(V) by Mn(IV) oxides present in the amendment. The soil-verification experiment demonstrated that an amendment dosage of 40 g/kg was efficacious in reducing the leaching concentration of As and Cd to maintained below the safety thresholds of 0.1 mg/L and 0.01 mg/L, respectively, for pH levels 4 to 11, meeting the Chinese Surface Water Quality Standard V (GB3838-2002). After the stabilization, the exchangeable fractions of As and the acid-soluble fractions of Cd were significantly reduced, with these elements being transformed into more stable forms. The amendment maintained the soil's neutral pH and adjusted the soil physicochemical properties. This article presents a holistic approach by examining the organic-inorganic composite of iron-manganese oxides with polyacrylamide, modified as a stabilizing amendment for As and Cd co-contaminated soil. This innovative amendment adeptly navigates the previously conflicting stabilization mechanisms for anionic and cationic metals. Offering dual advantages, the amendment not only remediates soil but also addresses the disposal of waste, presenting a win-win solution for environmental management.

Optimizing Titanium Carbide-Silver Oxide Nanostructures for Targeted Cancer Therapy: Synthesis, Functionalization, and In Vitro Evaluations.

Introduction Cancer remains a significant health challenge, and nanoparticles (NPs) are promising candidates for cancer treatment due to their unique physicochemical properties and ability to selectively target tumour cells. Two-dimensional (2D) nanomaterials, such as MXenes, have attracted interest due to their electronic structures, optical properties, catalytic abilities, and exceptional physicochemical attributes. MXenes are highly suitable for surface functionalization or modification, and their unique properties make them promising candidates for various applications in the biological field. Silver-based compounds have shown remarkable potential in biomedical fields, with silver oxide (Ag₂O) NPs finding applications in various domains. The fabrication of titanium carbide (Ti₃C₂)-Ag₂O heterostructures has been investigated for their anti-cancer properties by conducting cell viability assays on different cell lines. Aim To synthesize and characterize Ti₃C₂-Ag₂O, and to assess its in vitro anti-cancer activity. Materials and methods Ti₃C₂ synthesis begins by dissolving Ti₃AlC₂ powder in a 50% v/v hydrofluoric (HF) acid solution, allowing the aluminium to be etched away. This process should be conducted with continuous stirring for 24 to 48 hours at ambient temperature. Following this, filter the resulting suspension to eliminate aluminium particles and HF, and subsequently wash the Ti₃C₂ MXene with distilled water until a neutral pH is attained. The MXene should then be dispersed in ethanol, and sonication in deionized (DI) water or an alternative solvent should be employed to achieve exfoliation into monolayer or few-layer MXenes. To prepare Ag₂O NPs, dissolve silver nitrate (AgNO₃) in DI water to create a 0.1 M solution, and concurrently prepare a separate 0.1 M sodium hydroxide (NaOH) solution. Introduce the NaOH solution to the AgNO₃ while stirring until a precipitate is observed. The mixture should then be filtered, washed with distilled water, and the NPs dried at 60°C for 12 hours. To fabricate the MXene-Ag₂O composite, disperse the MXene nanoflakes in a solvent through sonication, incorporate the Ag₂O NPs, and stir the mixture for 24 hours. Finally, centrifuge the resultant mixture to isolate the composite, wash it with solvent, and dry it under vacuum conditions. Results The presence of Ag₂O particles on Ti₃C₂ nanosheets was observed, and the high crystallinity of the compound was confirmed through X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM) analyses. These tests verified that the compound was free of impurities and exhibited anti-cancer properties. Conclusion The synthesis of Ti₃C₂ MXenes and Ag₂O NPs was achieved and confirmed through structural characterization methods, including SEM, XRD, and EDS. SEM provided detailed insights into the morphology and distribution of the nanostructures, while XRD and EDS verified their phase purity and elemental composition. Functionalization strategies were employed to enhance the stability and bioactivity of the nanocomposites. In vitro evaluations demonstrated promising anti-cancer activity, indicating that the Ti₃C₂-Ag₂O composites effectively target and inhibit cancer cell growth.

Identification of land fertility and farmer income after an earthquake natural disaster

Liquefaction is a phenomenon where saturated sand and silt take on the characteristics of a liquid during the intense shaking of an earthquake. It takes place when a quake has increased water pressure in saturated soil and made particles in the soil lose contact with each other, making the soil, particularly sandy soil, act like a liquid. On September 28, 2018, an earthquake was occurred which caused liquefaction and a tsunami in Central Sulawesi, Indonesia. This incident triggered a new phenomenon, namely liquefaction in several residential areas in Palu City, especially in the Balaroa and Petobo areas. The liquefaction phenomenon in Petobo Village caused changes in the shape of the land surface. The changes that occurred had an impact on decreasing soil fertility levels in the area along with low crop production and decreased farmer incomes. Soil fertility is a quality value of the soil's ability to provide nutrients for growth. This research aims to determine the level of fertility of agricultural land and the amount of farmer income as well as the best efforts to overcome changes in agricultural land after natural disasters. This research used a descriptive method with a population of all farmers living in the Petobo area affected by the earthquake and liquefaction. There were 25 informants who were determined using a purposive sampling technique. Soil samples were analyzed at the Soil Science laboratory, Faculty of Agriculture, Tadulako University, Palu. The method used in this study is a direct survey method in the field, then continued soil sampling at several points according to the coordinate points carried out by purposive sampling techniques. The status of soil chemical properties at 4 sample points affected by liquefaction and 2 sample point not affected by liquefaction in Petobo Village, which classified as very low to very high. Areas affected by liquefaction had neutral to slightly alkaline soil pH content, very low to low C-organic content, very low N-total content, very high P-total content, low K-total content, and have medium to high CEC content. Meanwhile, areas that are not affected by liquefaction had neutral soil pH content, very low to low C-organic content, very low N-total content, very high P-total content, low K-total content, and have medium to high CEC. The low level of soil fertility in this area means that crop production is also low. Changes in the amount of income experienced by affected farmers who initially had around 77.26 USD- 186.71 USD/month declined to 61.16 USD-77.26/month. This is due to changes in the polarization of farmers' work. Actions that can be implemented to increase soil fertility are correct soil management, use of organic fertilizers such as compost, manure, harvest residues such as (legume plant stover, rice straw) and the addition of chemical fertilizers according to the dosage.

Geochemical-hydromechanical couplings during water-serpentinized harzburgite interactions at 20°C and 30 bars

Interaction of groundwater with the serpentinized harzburgites of the upper mantle plays an important role in the geologic carbon cycle and serpentinization processes. In this study, an intact serpentinized harzburgite with more than 60% lizardite from the Semail ophiolite in Oman was reacted with water at near neutral pH and low PCO2 to observe its dissolution behavior and reaction path within the CaO-MgO-SiO2-CO2-H2O system at 20 °C and 30 bars. In the experiment, mass (i.e. H2O, ions) transfer is by diffusion and the selected temperature and pressure conditions mimic water-rock interactions at the shallow portions of most ultramafic rock hosted aquifers. Equilibrium activity-activity diagrams and thermodynamic data were used to compare the experimentally determined reaction path with the theoretical stability boundaries for minerals involved to investigate the evolution of bulk chemical composition, mineralogy, and water composition. The experiments demonstrated that (i) the water-rock interactions increased the pH of the aqueous phase from 5.9 to 7.5 over a period of 18 weeks; (ii) the dissolution of lizardite, orthopyroxene (enstatite), and clinopyroxene (diopside and augite) increased the concentration of Mg, Ca, and Si in the aqueous phase; (iii) the dissolution was incongruent with respect to Mg and Si, favoring Si release at pH > 6 due to (a) breaking of more reactive cation‑oxygen bonds that is consistent with the stoichiometry of magnesium for proton exchange reaction which favors a surface that is enriched in Mg at basic conditions, and (b) preferential dissolution of clinopyroxene Mg1.30Ca0.52Fe0.06Si2O6; (iv) the aqueous phase was undersaturated with respect to carbonate (e.g. calcite, magnesite, and hydromagnesite) and hydrous (e.g. lizardite, chrysotile, brucite, and talc) minerals; (v) the bulk chemical composition and mineralogy of the intact serpentinized harzburgite matrix did not change; (vi) the thermodynamic data can successfully predict water-intact serpentinized harzburgite behavior if the water chemical composition can be constrained; and (vii) no detectable macroscopic form of damage (e.g. microcracks forming as a result of differential stress fields due to changes in volume during chemical reaction) was observed.

Antimicrobial Peptide Hydrogel with pH-Responsive and Controllable Drug Release Properties for the Efficient Treatment of Helicobacter pylori Infection.

Helicobacter pylori is the primary cause of gastric adenocarcinoma, which afflicts more than half of the world's population and seriously affects human health. However, achieving efficient treatment of H. pylori infection by effective drug delivery and bioavailability after oral administration remains a challenge due to the harsh microenvironment, short drug retention time, and physiological barriers in the stomach. Moreover, H. pylori has shown resistance to many clinical antibiotics. Antimicrobial peptides (AMPs) exhibit substantial therapeutic efficacy against H. pylori, while they are not likely to induce drug resistance, suggesting their potential utility for the treatment of diseases related to H. pylori. In this paper, we report the design and synthesis of an AMP (GE33) hydrogel with pH-responsive and controlled peptide release properties, in which the minimal inhibitory concentration of the AMP against H. pylori is as low as 1 μg/mL. GE33 self-assembles into a stable peptide hydrogel under neutral pH conditions but decomposes into monomers or oligomers under acidic conditions. Upon oral administration of the hydrogel, the acidic gastric environment would facilitate rapid release of active AMP molecules from the hydrogel and immediate targeting of H. pylori in the stomach wall. Additionally, the remaining peptide is protected in the hydrogel, extending its retention time in the stomach, so that persistent drug release is achieved. The controlled and sustained release manner of the active molecule GE33, which enhances drug bioavailability, along with its excellent bactericidal efficacy opens a great potential for treating H. pylori infection.

Experimental study of foam stability and interfacial behaviour of cellulose nanocrystals-enhanced C22-tailed zwitterionic betaine surfactant

The intrinsic thermodynamic instability of foam systems significantly constrains their effectiveness in enhancing oil and gas recovery from unconventional reservoirs. This study investigated the foam properties and interfacial rheological characteristics of the EDAB/CNC/APG system, analyzing the influence of various factors including temperature, pH, and inorganic salts. The results indicated that the optimal concentration ratio for CNC-surfactant system consists of 0.3 % EDAB, 1.5 % CNC and 0.5 % APG by mass fraction. In this system, the addition of CNC forms a three-dimensional network structure at the gas–liquid continuous interface, significantly extending the drainage half-life of the system. At elevated temperatures, the intense molecular thermal motion disrupts the interactions between CNC and EDAB. This disruption leads to a decrease in surface tension and the viscoelastic modulus of interfacial expansion, resulting in an increase of foam volume but a decline in foam drainage half-life. Foam performance and interfacial rheological characteristics are optimal under neutral pH conditions and manifest higher stability in alkaline conditions compared to acidic conditions. In highly mineralized reservoirs (≥5.0 % salt concentration), inorganic salt ions shield the attraction between CNC and oppositely charged surfactants. This shielding weakens the cross-linking within CNC-surfactant systems, altering the structure of the liquid film interface and causing a sharp decrease in foam half-life. The C22-tailed zwitterionic betaine surfactant EDAB, enhanced by CNC, provides a novel, environmentally friendly, efficient, and safe approach to the exploitation of complex, low-permeability oil and gas reservoirs.

Electrocatalytic Dinitrogen Reduction to Ammonia Using Easily Reducible N-Fused Cobalt Porphyrins.

Single-site molecular electrocatalysts, especially those that perform catalytic conversion of N2 to NH3 under mild conditions, are highly desirable to derive fundamental structure-activity relations and as potential alternatives to the current energy-consuming Haber-Bosch ammonia production process. Combining theoretical calculations with experimental evidence, it has been shown that easily reducible cobalt porphyrins catalyze the six-electron, six-proton reduction of dinitrogen to NH3 at neutral pH and under ambient conditions. Two easily reducible N-fused cobalt porphyrins - CoNHF and CoNHF(Br)2 - reveal NRR activity with Faradic efficiencies between 6-7.5 % with ammonia yield rates of 300-340 μmol g-1 h-1. Contrary to this, much harder-to-reduce N-fused porphyrins - CoNHF(Ph)2 and CoNHF(PE)2 - reveal no NRR activity. The present study highlights the significance of tuning the redox and structural properties of single-site NRR electrocatalysts for improved NRR activity under mild conditions.

Schottky Interface Enabled Electrospun Rhodium Oxide Doped Gold for Both pH Sensing and Glucose Measurements in Neutral Buffer and Human Serum.

This study has focused on adjusting sensing environment from basic to neutral pH and improve sensing performance by doping electrodeposited gold (Au) with metal oxide for nonenzymatic glucose measurements in forming a Schottky interface for superior glucose sensing with detailed analysis for the sensing mechanism. The prepared sensor also holds the ability to measure pH with the identical electrospun metal oxide-electrodeposited Au, which composed a dual sensor (glucose and pH sensor) through applying chronoamperometry and open circuit potential methods. The rhodium oxide nanocoral structure was fabricated with an electrospinning precursor solution, followed by a calcination process, and it was mixed with electrodeposited nanocoral gold to form the Schottky interface by constructing a p-n type heterogeneous junction for improved sensitivity in glucose detection. The prepared materials were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectrometry (XPS), etc. The prepared materials were used for both pH responsive testing and amperometric glucose measurements. The rhodium oxide nanocoral doped gold demonstrated a sensitivity of 3.52 μA mM-1 cm-2 and limit of detection of 20 μM with linear range up to 3 mM glucose concentration compared to solely electrodeposited gold for a sensitivity of 0.46 μA mM-1 cm-2 and a limit of detection of 450 μM. The Mott-Schottky method was used for the analysis of an electron transfer process from noble metal to metal oxide to electrolyte in demonstrating the improved sensitivity at neutral pH for glucose measurements due to the Schottky barrier adjustment mechanism at an applied flat band potential of 0.3 V. This work opens a new venue in illustrating the metal oxide/metal materials in the glucose neutral response mechanism. In the end, human serum samples were tested against current commercial glucose meter to certify the accuracy of the proposed sensor.

Sustainable urea treatment by environmental-friendly and highly hydrophilic vesicle-like iron phosphate-based carbon

Despite the versatile potential applications of urea, its unfavorable characteristics for conventional treatment methods hinder its utilization. Therefore, this study developed vesicle-like iron phosphate-based carbon (IP@C400) as a breakthrough urea removal and recovery material for a wide range of urea-containing sources. IP@C400 rapidly exhibited an exceptional capacity (2242 mg/g in 1 h) across a wide range of pH, even in synthetic hemodialysis wastewater with high urea concentrations and diverse co-existing components, compared with the 60 prominent adsorbents. The adsorption process followed dual Pseudo-kinetic, Langmuir-isotherm models with the involvement of primary robust physical (i.e., H-bonding and electrostatic interaction) and chemical mechanisms (i.e., hydrolysis). Remarkably, IP@C400 can maintain high urea removal (90 %) or recovery efficiency (95 %) even after 10 cycles with minimal leakages of Fe and P (far below WHO and EUWFD standards)—a significant improvement over disposable options. IP@C400 could also perform efficiently on batch and a new approach integrating with a naturally accessible material based on the fixed-bed column using low-range urea realistic samples, achieving 65.2 L water over 10 cycles with undetected urea, neutral pH, and well-aligned water safety standards with a minimal adsorbent dose (0.1 g.L−1) and economical cost ($0.05 L-1). Lastly, its environmentally friendly nature, which contains essential nutrients for plant growth, further enhances its recyclability after release. Thus, IP@C400 offers a solution to environmental sustainability and the urgent ultrapure water issue that industries are facing.

​Statistical-based optimization and mechanism assessments of Arsenic (III)​ adsorption by ZnO-Halloysite nanocomposite​

Arsenic contamination in aqueous media is a serious environmental problem, especially in developing countries. In this research, the Box-Behnken response surface methodology was used to optimize the most relevant variables affecting arsenic adsorption on the ZnO-halloysite surface, including temperature, adsorbent dosage, pH, contact time, and As (III) initial concentration. The regression analysis indicated that the experimental data were appropriately fitted to a quadratic model with the adjusted R-squared value (R2) of 0.982 for As(III) adsorption capacity and a linear model with R2 of 0.931 for As(III) removal. The p-values for both adsorption capacity and removal efficiency were below 0.05, with F-values of 116.91 and 115.58, respectively, supporting the model’s validity. The optimum conditions for maximum removal of As(III) were determined through numerical and graphical optimization using the desirability function. It was found that the optimum conditions for adsorption were pH = 7.99, contact time of 3.99 h, As(III) initial concentration of 49.96 mg/L, and adsorbent dosage of 0.135 g/40 ml. The accuracy of the optimization procedure was confirmed by a confirmatory experiment, which showed a maximum arsenic removal of 91.31% and an adsorption capacity of 12.63 mg/g under optimized conditions. Moreover, XPS analysis was performed at different pH levels to investigate the As (III) adsorption mechanism. The results demonstrated that As(III) adsorption occurs at acidic and neutral pH levels. On the other hand, when pH is increased to 8, As (III) oxidizes to As (V), and then adsorption occurs.

Coupling UVC254 nm-LED/H2O2 and Fenton processes for disinfection and contaminants of emerging concern removal in continuous mode for wastewater reclamation in accordance with EU 2020/741

A novel strategy based on the sequential combination of UVC254 nm-LED/H2O2 and the Fenton process at neutral pH in continuous flow mode for wastewater reclamation has been assessed. The concentration of Escherichia coli (E. coli) reached water class A according to the European Union (EU) Regulation 2020/741 (≤10 CFU/100 mL) and a 87 ± 2 % of the contaminants of emerging concern (CECs) load was removed, complying with the new proposal regarding Urban Wastewater Treatment (Directive COM (2022) 541). To reach these results, initially the municipal wastewater secondary effluent was kept under UVC254 nm-LED/H2O2 process with a hydraulic residence time (HRT) of 5 min, a liquid depth of 5-cm and 1.8 mmol L−1 of H2O2. In the sequence, addition of Fe2+ to the outside of the UVC254 nm-LED reactor was added to acquire the desired concentration of 1.8 mmol L−1 Fe2+ (Fenton process). To obtain the same disinfection and CECs degradation by only UVC254 nm-LED/H2O2 process, 45 min-HRT were necessary. These results show that the coupled processes are the best strategy, given the reduction in HRT (from 45 to 5 min) and total cost (from 1.79 to 0.54 € m−3). In addition, new research on the application at pilot scale will encourage to evaluate the long-term toxicity of the reclaimed wastewater and to identify the main transformation products of the most abundant CECs.

Efficient degradation of methylene blue at near neutral pH based on heterogeneous Fenton-like system catalyzed by Fe2O3/MnO2

The contamination of aquatic environments by organic dye contaminants in industrial wastewater has attracted widespread global attention. The heterogeneous Fenton-like process presents an attractive method for degrading dye pollutants, especially when such reactions are conducted under neutral pH. In this study, Fe2O3/MnO2 composite was employed as a novel heterogeneous catalyst for activating hydrogen peroxide (H2O2) to oxidize and subsequently degrade methylene blue (MB) under neutral pH. Multiple characterization results have confirmed the presence of MnO2 and Fe2O3 as the primary phases of the synthesized compound catalyst. Degradation experiments have demonstrated that the degradation efficiency of MB approaches 100% under the conditions of H2O2 concentration of 0.30% and Fe2O3/MnO2 amount of 0.888 g/L. Furthermore, the Fe2O3/MnO2 catalyst exhibits consistent and outstanding catalytic activity within a broad pH range from 5 to 9 benefiting from the strong interface interaction in Fe2O3/MnO2. The investigation into the kinetics of the Fenton-like reaction indicates that the catalytic degradation of MB by Fe2O3/MnO2 in conjunction with H2O2 follows pseudo-first-order kinetics. Moreover, supplementary scavenging experiments have demonstrated the crucial role played by hydroxyl radicals (·OH) in the catalytic oxidation mechanism of MB. This study offers a promising catalyst for the treatment of dye-containing wastewater under neutral pH condition.

Synthesis and properties of oligopropylamines with photosensitive o-nitrobenzyl ester core

The o-nitrobenzyl ester group is known for more than 50 years as a convenient protecting group and fragment for the design of photosensitive systems, including drug delivery agents. Polymeric amines with these groups are promising systems for medical applications, but the lack of basic knowledge about the possible degradation of these compounds under physiological conditions restrains the development of real preparations. We synthesized five new polyamines with the insertion of the o-nitrobenzyl ester group into the chain, including an oligomeric mixture with a weight average number of amine groups equal to 21. The ester group in the polyamine chain was found to be sensitive to hydrolysis at neutral and alkaline pH values. The presence of an amine group near the ester group facilitates hydrolysis through coordination with a hydroxyl ion or water molecule. The catalytic action of the amine moieties is prevented by protonation of the amine at low pH values or by interaction with polymeric acid. The study of photodegradation of new polyamines by HPLC-MS showed the formation of a number of products, most of which were not considered in previous works with o-nitrobenzyl ester derivatives. The o-nitrobenzyl ester group is used in the design of gene delivery systems and other biomedical preparations as a fragment that can be degraded by light. Our results indicate that photodegradation of o-nitrobenzyl esters can produce a number of compounds whose structure and safety for living organisms must be evaluated before use. On the other hand, the discovered hydrolyzability of o-nitrobenzyl esters catalyzed by a neighboring amine group may find application in the development of drug delivery systems. We have shown that the lifetime of o-nitrobenzyl ester containing polyamines is sufficient for gene delivery. Self-degradation of the delivery agent after penetration into a living cell is a desirable case for the release of the delivered agent.

Causes of negatively charged meso-colloids formed in the coagulation process: Implication of the origin of foulants in the coagulation–membrane filtration process

Tiny colloids with a size similar to that of membrane pores are responsible for irreversible fouling in the pre-coagulation microfiltration membrane filtration process for drinking water treatment. Such colloidal particles are defined here as meso‑colloids, and the charge neutralization of meso‑colloids is demonstrated to be a key to controlling irreversible fouling. However, meso‑colloids remain negatively charged at neutral pH, the reason for which is still unclear. To increase the efficiency of membrane operation, additional knowledge about the causes and behaviors of meso‑colloids during pre-coagulation is indispensable. Therefore, in this study, meso‑colloids are fractionated after a series of jar tests, and their exact composition and charge properties are characterized. Two natural water samples, the adjusted water consisting of meso‑colloid fraction separated from one of the natural water samples and additional inorganic chemicals, and the adjusted water by the addition of appropriate inorganic chemicals into pure water are used for jar tests, which are conducted with and without the addition of the coagulant polyaluminum chloride (PACl). After the jar tests using two natural water samples, all of the meso‑colloids exhibit a negative charge under the conditions applied for the jar tests, indicating that charge neutralization is difficult. The composition of the meso‑colloids is found to be completely different depending on the water source used. Organic-rich water tends to generate meso‑colloids with a low Al/C (mass ratio of aluminum and organic carbon) ratio. In contrast, organic-poor water tends to produce meso‑colloids with a high Al/C ratio. From the results of the jar tests using two kinds of adjusted water samples, it is found challenging to neutralize meso‑colloids by PACl at neutral pH, because the overdose and underdose of PACl result in negatively charged biopolymer or negatively charged aluminum species. Therefore, the development of a new coagulant for specific use in the coagulation membrane filtration process is proposed, which can minimize the formation of negatively charged species even at neutral pH.

Solar light driven enhanced in photocatalytic activity of novel Gd incorporated ZnO/SnO2 heterogeneous nanocomposites

The Gd-doped ZnO/SnO2 nanocomposites with various atomic percentages (0, 0.5, 0.8, and 1.2 at%) of gadolinium (coded as GdZS0, GdZS1, GdZS2, and GdZS3) was synthesis via the sol–gel method and explored for photodegradation against dye solutions exposing solar light irradiation. The synthesized nanocomposites were characterized employing the XRD, FTIR, FE-SEM, Raman spectroscopy, BET analysis and UV–Vis spectrophotometer. The FE-SEM results indicated that the formation of nanoparticles to nanoflowers covered with Gd ions was observed with an increased doping concentration of Gd. The optical bandgap was evaluated and found in the range of 3.21–3.27 eV for GdZS nanocomposites. The GdZS nano-photocatalysts were investigated against the degradation of different organic dyes and GdZS3 shows the highest degradation efficiencies of 99.3%, 98.3% and 99.4% towards MO, MB and RhB dyes, respectively at neutral pH in aqueous media. Before and after photodegradation. Biological oxygen demand and chemical oxygen demand tests to make estimations of mineralization. The investigations are very promising for the degradation process in rare earth doped metal oxide nanocomposites. A plausible photodegradation mechanism of synthesized nanocomposites under investigation has also been proposed.