Phenolic Contaminants Research Articles

Homogenous Oxidizing Oligomerization Coupled with Coagulation for Water Purification

Natural manganese oxides could induce the intermolecular coupling reactions among small-molecule organics in aqueous environments, which is one of the fundamental processes contributing to natural humification. These processes could be simulated to design novel advanced oxidation technology for water purification. In this study, periodate (PI) was selected as the supplementary electron-acceptor for colloidal manganese oxides (Mn(IV)aq) to remove phenolic contaminants from water. By introducing polyferric sulfate (PFS) into the Mn(IV)aq/PI system and exploiting the flocculation potential of Mn(IV)aq, a post-coagulation process was triggered to eliminate soluble manganese after oxidation. Under acidic conditions, periodate exists in the H4IO6− form as an octahedral oxyacid capable of coordinating with Mn(IV)aq to form bidentate complexes or oligomers (Mn(IV)-PI*) as reactive oxidants. The Mn(IV)-PI* complex could induce cross-coupling process between phenolic contaminants, resulting in the formation of oligomerized products ranging from dimers to hexamers. These oligomerized products participate in the coagulation process and become stored within the nascent floc due to their catenulate nature and strong hydrophobicity. Through coordination between Mn(IV)aq and H4IO6−, residual periodate is firmly connected with manganese oxides in the floc after coagulation and could be simultaneously separated from the aqueous phase. This study achieves oxidizing oligomerization through a homogeneous process under mild conditions without additional energy input or heterogeneous catalyst preparation. Compared to traditional mineralization-driven oxidation techniques, the proposed novel cascade processes realize transformation, convergence, and separation of phenolic contaminants with high oxidant utilization efficiency for low-carbon purification.

Unraveling the Role of Humic Acid in the Oxidation of Phenolic Contaminants by Soluble Manganese Oxo-Anions.

Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.

Bioinspired bimetallic metal–organic framework nanozyme with laccase-mimicking activity for detection and removal of phenolic contaminants

Laccase, despite its eco-friendly nature, faces constraints due to cost and inherent vulnerability, restricting its widespread application. Therefore, pursuing the development of a robust laccase mimetic displaying exceptional activity remains an ongoing endeavor. This research synthesized a bimetallic metal–organic framework nanozyme (Cu-Mn MOF) with enhanced laccase-mimicking activity via a one-step solvothermal method. The diverse Cu redox valence state of the nanozyme mimics the multi-copper active center of laccase, which endows Cu-Mn MOF with laccase-mimicking activity. Incorporating Mn introduces a novel metal center into the MOF, creating a catalytic microenvironment. Bimetallic Cu-Mn synergistic interplay accelerates the electron transfer rate, resulting in enhanced laccase-mimicking activity. The Michaelis constant of Cu-Mn MOF for 2,4-dichlorophenol (2,4-DP) registers at 0.080 mM, displaying remarkable stability and recyclability even under stringent conditions, thereby achieving a comprehensive surpass of laccase. Accordingly, Cu-Mn MOF was utilized to degrade phenolic compounds and design a smartphone sensing platform to facilitate portable and visual detection of phenol. Utilizing the occurrence of Cu-S coordination, which accelerates the electron transfer rate, a thiourea-enhanced Cu-Mn MOF was designed to improve the degradation rate. The limit of detection (LOD) for smartphone platform is 0.159 μM, with a linear detection range of 1–40 μM. The detection method was applied to determine the phenol in spiked samples with the spiked recoveries rate of 96.05–104.30 % and the relative standard deviations less than ± 4 %. The outcomes of these applications reveal the vast application potential of Cu-Mn MOF in environmental engineering.

Date Leaves-Derived Submicron/Nano Carbon-Modified Glassy Carbon Electrode for Highly Sensitive and Simultaneous Detection of 1-Naphthol and 2-Naphthol

This study introduces a novel approach for synthesizing biomass derived carbon from date leaves waste, employing a straightforward combination of pyrolysis and ball milling processes. This process yields active carbon in submicron and nanometer sizes, characterized by detailed surface, structural, and compositional analyses, confirming suitability of the materials for electrochemical applications. Utilizing this synthesized carbon, we have developed a modified glassy carbon electrode (DLSNC/GCE) for the highly-sensitive and simultaneous detection of phenolic contaminants, specifically 1-naphthol (1-NP) and 2-naphthol (2-NP), which are crucial for environmental monitoring. The study describes two innovative fabrication methods for electrochemical sensors. The first method controls the direct oxidation of 1-NP and 2-NP, while the second method exploits redox peaks associated with quinone formation from dihydroxy naphthalene, revealing superior analytical performance for the simultaneous detection of the analytes. The electrochemical sensor demonstrated exceptional sensitivity and selectivity towards 1-NP and 2-NP. This revolution emphasizes the potential of using date leaves-derived carbon materials in constructing low-cost, efficient electrochemical sensors for environmental monitoring and electrochemical applications.

Removal of Phenol Contaminants from Aqueous Solution Using Pickering Emulsion Liquid Membrane Stabilized by Magnetic Nano-Fe3O4

In the current study, the effect of the nonionic surfactant (span 80) on the emulsification of a mixture of kerosene as a petroleum-based organic solvent and span80 as a green diluent in the ratio 1:1 was investigated. NaOH was used as the internal phase, and the stability of the emulsion was tested. The potential for extracting phenol from aqueous solutions without the use of a carrier agent has been explored using Pickering emulsion liquid membrane. Additionally, the impacts of experimental parameters include homogenizer speed, mixing speed, emulsification time, Fe3O4-Span 80 ratios, NaOH concentration, and internal to membrane volume ratio (I/O) on extraction effectiveness and emulsion stability. The findings demonstrated that after 9 minutes of contact time and a minimum breaking percent of 0.745% under ideal circumstances, more than 96% of phenol could be recovered. In addition thermodynamic analysis reveals that the extraction process was an endothermic and spontaneous in nature and the overall mass transfer coefficient was 1.115 m/s. Membrane materials and nanoparticles were recycled four time in the extraction of phenol with approximately the same efficiency and no significant breakage percent..

Selective removal of phenolic contaminants for carbon recycling by activated persulfate based on oxidative polymerization mechanism

A novel approach for selective removal of phenolic contaminants and polyphenols recycling based on oxidative polymerization is explored, which is significantly different from conventional degradation processes. Plenty of bridging OH− and lattice oxygen are bound on CuO@CuCeyO1+2y+x/2-IE due to strong coordination between Ce and O, which induced formation of Cu(III) with high redox potential. Cu(III) could not only form outer-sphere complexation with peroxymonosulfate (PMS) for enhancement of O2•– production involving series of chain reactions, but also promote O2•– conversion to singlet oxygen (1O2). Owing to electrophilicity, 1O2 preferentially attacked the phenolic hydroxyl group with the production of phenoxeniums ions, and phenoxide ions could immediately couple with negatively charged hydroxyl groups of other bisphenol A (BPA) molecular so as to make polymer chains get a sustained growth over CuO@CuCeyO1+2y+x/2-IE. Thus, CuO@CuCeyO1+2y+x/2-IE can selectively remove phenolic contaminants from water with low oxidant consumption, and simultaneously recycle more than 80 % of polyphenols. In summary, the present work demonstrated the predominant role and mechanism of 1O2 in triggering the oxidative polymerization of BPA, which contributed to construction of cost-efficient catalytic system for phenolic contaminants conversion into polyphenols.

Feasibility of phenolic contaminant removal from high-saline wastewater by chloride-mediated activation of peroxymonosulfate (PMS) and peracetic acid (PAA)

Phenolic pollutants are highly toxic and can affect the growth and reproduction of aquatic organisms, as well as contaminate drinking water resources, posing a significant threat to both ecological and human health. However, conventional biological treatment processes are constrained in treating high salinity organic wastewaters due to the potentially lethal effects of high concentrations of dissolved salts on microorganisms. While advanced oxidation processes have shown promise in removing phenolic contaminants from high-saline wastewater, their widespread application is always limited by the high costs associated with energy and chemical usage. In this study, we explored the potential application of directly introducing peroxymonosulfate (PMS) and peracetic acid (PAA) to high-salinity water for the removal of nine phenolic contaminants. By establishing a correlation between the degradation rate constants in the PMS/Cl– (kPMS) and PAA/Cl– (kPAA) systems and various molecule descriptors, two multiple linear regression models were developed to predict the degradation rate constants under investigation. Additionally, we selected bisphenol A (BPA) as the target contaminant and investigated the impact of common ions found in natural water, such as HCO3–, NO3–, and humic acid, on the removal of BPA using two systems. Finally, we conducted experiments using tap water and sewage water to demonstrate the practical application and performance of the two systems. These experiments aimed to provide valuable insights into the influence of background chloride on PMS and PAA activation, as well as the potential of direct PMS/PAA introduction for eliminating phenolic micropollutants from high-saline wastewaters.

Highly efficient adsorption and capture of prevalent phenolic contaminants from the real samples by trifluoromethyl-functionalized covalent organic frameworks

The specific removal of phenolic pollutants from aqueous medium based on the functionalized materials are great significant for the adsorption processes. The purposes of this work were to fabricate fluorine-containing covalent organic frameworks (COFs) sorbent with hydrophobic function and hydrogen bond acceptor capacity to investigate the key role of fluorine functional group in the sorption behavior for phenolic pollutants in the aqueous solutions. Here, two fluorinated COFs, named TFPT-PI-CF3 and TFPT-PI-2CF3, were facilely synthetized through the imine condensation reaction between tri-aldehyde and diamine pre-modified by trifluoromethyl group. The adsorption isotherms, kinetics, thermodynamic, and reusability of tow COFs for the adsorption and capture of prevalent phenolic contaminants (hydroquinone, catechol, resorcinol, phenol, and acetaminophen) from aqueous solution were inspected in detail. The maximum adsorption capacity for TFPT-PI-CF3 and TFPT-PI-2CF3 was calculated to be 576 and 567 mg·g−1 for hydroquinone by using linear Langmuir isotherm as an appropriate model, respectively. Adsorption mechanisms highlighted the synergistic effects of F–H hydrogen bonding and hydrophobic interactions as important design criteria for efficient removal of phenolic pollutions from water medium. Furthermore, the prepared fluorinated COFs were successfully applied to evaluate five phenolic contaminants in real water samples, which demonstrated that the fluorine-containing materials held great promise for the development of an accurate platform for the rapid removal of the hydroxyl contaminants.

Wastewater Treatment Using Membrane Bioreactor Technologies: Removal of Phenolic Contaminants from Oil and Coal Refineries and Pharmaceutical Industries.

Huge amounts of noxious chemicals from coal and petrochemical refineries and pharmaceutical industries are released into water bodies. These chemicals are highly toxic and cause adverse effects on both aquatic and terrestrial life. The removal of hazardous contaminants from industrial effluents is expensive and environmentally driven. The majority of the technologies applied nowadays for the removal of phenols and other contaminants are based on physio-chemical processes such as solvent extraction, chemical precipitation, and adsorption. The removal efficiency of toxic chemicals, especially phenols, is low with these technologies when the concentrations are very low. Furthermore, the major drawbacks of these technologies are the high operation costs and inadequate selectivity. To overcome these limitations, researchers are applying biological and membrane technologies together, which are gaining more attention because of their ease of use, high selectivity, and effectiveness. In the present review, the microbial degradation of phenolics in combination with intensified membrane bioreactors (MBRs) has been discussed. Important factors, including the origin and mode of phenols' biodegradation as well as the characteristics of the membrane bioreactors for the optimal removal of phenolic contaminants from industrial effluents are considered. The modifications of MBRs for the removal of phenols from various wastewater sources have also been addressed in this review article. The economic analysis on the cost and benefits of MBR technology compared with conventional wastewater treatments is discussed extensively.

Influence of Divalent Cation Inhibition and Dissolved Organic Matter Enhancement on Phenol Oxidation Kinetics by Manganese Oxides.

Manganese oxides can oxidize organic compounds, such as phenols, and may potentially be used in passive water treatment applications. However, the impact of common water constituents, including cations and dissolved organic matter (DOM), on this reaction is poorly understood. For example, the presence of DOM can increase or decrease phenol oxidation rates with manganese oxides. Furthermore, the interactions of DOM and cations and their impact on the phenol oxidation rates have not been examined. Therefore, we investigated the oxidation kinetics of six phenolic contaminants with acid birnessite in ten whole water samples. The oxidation rate constants of 4-chlorophenol, 4-tert-octylphenol, 4-bromophenol, and phenol consistently decreased in all waters relative to buffered ultrapure water, whereas the oxidation rate of bisphenol A and triclosan increased by up to 260% in some waters. Linear regression analyses and targeted experiments demonstrated that the inhibition of phenol oxidation is largely determined by cations. Furthermore, quencher experiments indicated that radical-mediated interactions from oxidized DOM contributed to enhanced oxidation of bisphenol A. The variable changes between compounds and water samples demonstrate the challenge of accurately predicting contaminant transformation rates in environmentally relevant systems based on experiments conducted in the absence of natural water constituents.

Levels, distribution, sources and human exposure pathways of alkylphenol and alkylphenol ethoxylates in indoor dust in Turkiye

Environmental phenolic chemicals, due to their widespread occurrence and potent estrogenic properties, pose a risk to human exposure. The phenolic organic contaminants alkylphenols (APs) and alkylphenol polyethoxylates (APEs) are used in various household applications, and they may enter to the environment during production and use, potentially appearing in indoor dust. However, little is known about the levels of environmental phenolics in indoor environments. In this study, five of these compounds namely octylphenol (OP), 4-Octylphenol Monoethoxylate (4-OPME), 4-tert-octylphenol (4-t-OP), 4-n-nonylphenol (4-n-NP) and nonylphenol diethoxylate (di-NPE) were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in household dust samples (n = 148) collected from Ankara, the capital of Turkiye. OP and 4-OPME was not present in any of the analyzed samples. The median concentrations of the 148 settling dust samples were 35, 520, and 1910 ng g−1 dust for 4-t-OP, 4-n-NP, and di-NPE, respectively. An assessment of the human (children and adults) exposure pathway to APs and APEs, which are recognized as endocrine-disrupting chemicals found in residential dust, revealed that it was approximately 3 times higher for children than for adults at both moderate and heavy exposure levels. The association between chemical exposure, house characteristics, and family lifestyle was investigated using a multivariate logistic regression model. According to the results of this model, while the high concentrations measured for 4-t-OP were not found to be associated with any of the household parameters, high levels of 4-n-NP and di-NPE were associated with the frequency of house cleaning, repairs made during the previous year, residential type, the number of occupants, flooring materials, and the purchase of new household items within the past year. This study provides a basis for prioritizing toxicology and exposure studies for EDCs and mixtures and may offer new tools for exposure assessment in health studies.

Cobalt-nickel phosphide supported on reduced graphene oxide for sensitive electrochemical detection of bisphenol A

Bisphenol A (BPA) is a commonly utilized phenolic contaminant in several manufacturing processes, contributing to environmental pollution. Therefore, the detection of BPA holds significant importance for monitoring water quality. In this work, we report a robust electrochemical detection method for BPA utilizing cobalt−nickel bimetal phosphide nanoparticles (CoNiP) supported on reduced graphene oxide (rGO). The CoNiP@rGO-modified glassy carbon electrode exhibits remarkable electrochemical activity in BPA detection. The detection mechanism is controlled by adsorption-mediated electron transfer, showcasing a low limit of detection (LOD) at 0.38 nM and a high sensitivity of 96.4 A M−1 cm−2 within the linear range of 0.001–8 μM. Furthermore, our developed sensor demonstrates good reproducibility and successfully detected BPA in actual water samples. The electrochemical activity of CoNiP@rGO was also characterized for hydroquinone (HQ) detected through a diffusion-controlled mechanism, displaying an excellent sensitivity of 36.4 A M−1 cm−2 across a broad linear range. These findings underscore the promising potential of CoNiP@rGO as a candidate for electrochemical detection of phenolic contaminants, especially in the sensing of BPA in environmental water samples. This efficacy is attributed to the modulation of its electronic properties, combined with its large electroactive surface area and low electron-transfer resistance.

High performance B2O3/MWCNTs and TiB/MWCNTs nano-adsorbents for the co-sorption of cyanide and phenol from refinery wastewater.

The refinery industry has witnessed tremendous activity aimed at producing petrochemicals for the benefit of the teeming populace. These activities are accompanied by the discharge of wastewater containing chemical substances and elements that have negative impacts on the ecosystem. The presence of phenol and cyanide contaminants in refinery wastewater poses serious health hazards to humans, necessitating their removal. In this study, boron oxide-doped multi-walled carbon nanotubes (B2O3/MWCNTs) and titanium boride-doped MWCNT (TiB/MWCNTs) nanoadsorbents were prepared via a wet impregnation method and characterized using High-Resolution Transmission Electron Microscopy (HR-TEM), X-Ray Diffraction (XRD), and X-ray Photoelectron Spectroscopy (XPS). HR-TEM images depict the nanostructure of the nanoadsorbent, the presence of doped materials, and the internal, external, and wall thickness of B2O3/MWCNTs and TiB/MWCNTs nanoadsorbents. XRD results indicate that the nanomaterials were monocrystalline with average crystallite sizes of 22.75 nm and 16.79 nm for B2O3/MWCNTs and TiB/MWCNTs, respectively. The formation of B2O3 and TiB was observable in the results obtained from the XPS at the binding energy of 192 and 193.1 eV, respectively. The application of the produced B2O3/MWCNTs and TiB/MWCNTs nanoadsorbents for the removal of phenol and cyanide from refinery wastewater was explored in a batch adsorption system. The effects of contact time, adsorbent dosage, and adsorption temperature were investigated. To the best of our knowledge, the incorporation of B2O3 and TiB in MWCNTs resulted in the highest adsorption capacities for phenol and cyanide from aqueous solutions. The highest percentage removal of 100% for phenol and 99.06% for cyanide was observed for the TiB/MWCNTs nanoadsorbent at a residence time of 70 minutes, a temperature of 60 °C, and 0.3 g of adsorbent. The isotherm models show that cyanide and phenol removal obeyed the Langmuir isotherm, indicating monolayer adsorption over B2O3/MWCNTs nanoadsorbent. Furthermore, cyanide and phenol removal depict multilayer adsorption on the TiB/MWCNT nanoadsorbent. The research shows that B2O3/MWCNTs are proficient in cyanide sorption, while TiB/MWCNT favors phenol sorption due to their respective adsorption capacities.

Novel Fenton-like Catalyst HKUST-1(Cu)/MoS2-3-C with Non-Equilibrium-State Surface for Selective Degradation of Phenolic Contaminants: Synergistic Effects of σ-Cu-Ligand and ≡Mo–OOSO3− Complex

Novel Fenton-like catalyst HKUST-1(Cu)/MoS2-3-C with a non-equilibrium-state surface was constructed for selective degradation of phenolic contaminants. Electron-polarized distribution facilitated the formation of σ-Cu-ligand between electron-poor Cu centre and phenolic compounds, which not only enhanced radicals generation but also accelerated the Cu(I)/Cu(II) redox. Meanwhile, ≡Mo–OOSO3− complexes formed by the electron-rich Mo centre and peroxymonosulfate (PMS), could directly oxidize phenolic contaminants with the generation of SO4•−. The radical quenching experiments and EPR tests indicated that both SO4•− and •OH played a dominant role in the reaction. Additionally, O2 could be reduced to O2•− by OVs and subsequently converted into 1O2 over the Mo centre. DFT calculation, FT-IR, and in situ Raman spectra analysis results demonstrated that phenolic compounds and PMS were respectively adsorbed by electron-poor Cu centre and electron-rich Mo centre, favouring the electrons transfer from phenolic contaminants to Mo centre for PMS activation. With synergistic effects of σ-Cu-ligand and ≡Mo–OOSO3− complexes, HKUST-1(Cu)/MoS2-3-C achieved a high degradation rate of phenolic contaminants and utilization efficiency of PMS.

Extraction of Phenol as Pollutant from Aqueous Effluents Using Hydrophobic Deep Eutectic Solvents

Due to their toxicity and persistence in the environment, phenolic pollutants pose a serious threat to the ecosystem. In this work, the performance of hydrophobic deep eutectic solvents (HDESs) for phenol removal from aqueous effluents is thoroughly investigated using COSMO-RS screening followed by experimental validation. The screening results of 73 HDESs showed that the efficacy of phenol removal is significantly affected by chain length, functional groups, and aromaticity. Trioctylphosphine oxide (TOPO)-based HDESs were found to be the most effective HDESs for phenol elimination combined either with menthol (Men), 1-hexanol (Hex), Decanoic acid (DecA), or Thymol (Thy) all in 1:1 molar ratios. The better phenol elimination abilities of the selected HDESs were confirmed by experimental LLE data obtained at 298.15 K and 101 kPa. In fact, it has been found that there is a positive correlation between extraction efficiency and phenol content. For instance, at a phenol concentration of 7%, TOPO:Men had the highest extraction efficiency (96%). Moreover, the physicochemical properties of the selected HDESs, such as density, viscosity, FTIR, 1HNMR, and TGA, were also measured. The results showed their high thermal stability and low water solubility, which makes them suitable for phenol extraction applications. This study shows that HDESs are capable of removing phenolic contaminants from aqueous effluents in a sustainable and efficient manner and that the selected TOPO-based HDESs are of particular interest for further research and application in phenol removal.

Fabrication and performance analysis of keratin based-graphene oxide nanocomposite to remove dye from tannery wastewater

In recent years, nanomaterials and composites have become increasingly significant as adsorbents in the removal of dyes and phenolic contaminants from wastewater. This study presents the development and application of a keratin-based graphene oxide nanocomposite, distinguished by its enhanced biocompatibility, cost-effectiveness, and strong affinity for organic compounds, making it highly effective in reducing dyes within tannery effluent. The nanocomposite was prepared via solution casting method, with dispersibility, chemical bonding, and morphology analyzed by UV–Vis spectroscopy, FTIR, and SEM, respectively. Furthermore, investigations of the influence of several factors, such as contact time, pH, and adsorbent dosage on the optimization of the process were conducted. An observation indicated a reduction of approximately 98.8 % in dye content within 20 min, achieved through the use of an adsorbent dosage of 1.5 g/L, with the solution pH maintained at 5. Subsequently, adsorption kinetics and isotherm modelling were analyzed. The results revealed that the adsorption process follows the pseudo-second-order kinetics and Freundlich isotherm models. Hence, the adsorption could be explained as chemisorption with a multilayer adsorption mechanism. Notably, a substantial reduction in parameters such as Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) was also achieved up to 62 % and 79 %, respectively. Therefore, the developed adsorbent could be suggested as a viable candidate for eliminating dyes from the wastewater, especially from the tannery effluent.

Sustainable waste utilization: Geopolymeric fly ash waste as an effective phenol adsorbent for environmental remediation

Rapid industrialization and urbanization generate significant waste, including fly ash, posing environmental challenges. Utilizing these materials is essential to mitigate impacts and promote sustainable development. This research paper focuses on the innovative application of geopolymeric fly ash (GEOFA) waste modified with titanium oxide (TiO2) (GEOFA-TiO2) as a promising adsorbent for the removal of phenol compounds from contaminated water. Analysis showed that the modification process resulted in the formation of functional groups such as -OH, which aided in the adsorption process. Adsorption studies were conducted to evaluate the influence of pH, temperature, and concentration on phenol removal. The maximum percentage removal of phenol was achieved at optimum conditions of pH 6 and a temperature of 25 °C, with an adsorption capacity of 166.7 mg/g. The adsorption process followed the Langmuir model, suggesting a monolayer adsorption mechanism and the thermodynamic studies revealed that the phenol adsorption onto GEOFA-TiO2 was an endothermic process with a promising affinity between phenol and the adsorbent. This study demonstrates the effective use of modified fly ash-based adsorbents to remove phenolic contaminants. By repurposing waste materials, this research addresses waste management challenges and promotes sustainable practices, reveling their potential for environmental remediation.

On the mechanism and selectivity of a novel iodine/peracetic acid process for the efficient and rapid elimination of micropollutants

In recent years, halogen radical-based advanced oxidation processes (AOPs) have shown promise for metal-free, highly selective elimination of phenolic pollutants with high mineralization. This study explored a novel approach combing peracetic acid (PAA) and naturally available I− to efficiently remove bisphenol A (BPA) over a broad pH range (2–8). A dose of 500 μM PAA and 100 μM I− at a pH of 3 completely eliminated 43.8 µM of BPA within 10 min. Aside from I−, two more halogen ions, Cl− and Br−, could also enhance BPA elimination in the presence of PAA. Based on quenching experiments and density functional theory (DFT) thermodynamic calculations, only I− among the three halogen ions can react with PAA (primarily through the single electron transfer pathway) to generate •I, which efficiently removes BPA. The Cl− and Br− only contribute partially to the BPA removal, mainly through HOCl and HOBr following the oxygen atom transfer pathway. The water matrices had no noticeable influence on the I−/PAA process, and eliminating micropollutants with electron-rich groups from actual water samples remained effective. This work proposes an innovative and feasible technique for PAA-based AOPs and showcases its promising applicability for the treatment of phenolic contaminants in wastewater.

Recyclable pickering emulsions for enzymatic phenol degradation of oily wastewater

Enzymatic degradation offers a sustainable solution for waterborne phenolic pollutants. However, its application within industrial, non-aqueous contexts — particularly in mitigating phenolic contaminants in oily wastewater — remains significantly challenging. To address this challenge, the present study exploits the potential of Fe3O4 @PDA nanoparticles to form oil-in-water Pickering emulsions for the enzymatic degradation process. The uniform stability of the prepared emulsion, with droplet sizes under 5 µm, protects enzyme activity and expands the water-oil interfacial area, leading to an enhancement in the efficiency of horseradish peroxidase (HRP) catalytic degradation. The application of this emulsion resulted in a substantial increase in the degradation rate of phenol, achieving 100% within 30 min as opposed to an only 13.6% without it. The study also highlights the excellent stability, reusability, and versatility of the Fe3O4 @PDA nanoparticles, enabled by magnetic separation and their ability to form emulsions with diverse oil phases. Consequently, our research offers valuable insights into the development of environmentally sustainable strategies for the degradation of phenolic contaminants in various industrial oily wastewater.

Neutral Phenolic Contaminants Are Not Necessarily More Resistant to Permanganate Oxidation Than Their Dissociated Counterparts: Importance of Proton-Coupled Electron Transfer.

Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH- as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and pKa values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.