Electrical breakdown in liquid-phase processing on an enhancement of 7-hydroxymitragynine conversion from mitragynine in Mitragyna speciose (Kratom).

This study investigates the impact of the Electrical Breakdown in Liquid-phase (EBL) process on alkaloid transformation in Mitragyna speciose (Kratom) leaves, focusing on the conversion of mitragynine (MG) to 7-hydroxy mitragynine (7-OH-MG) by using advanced oxidation processes (AOPs). A novel reactor has been developed to enhance plasma exposure to Kratom leaf powdered solutions during the EBL process. Two distinct electrical voltage characteristics, half-positive and negative half-waves, have been utilized for the EBL, with an output voltage of 4.57 kVpeak at a no-load condition and a frequency of 50 Hz. The experimental findings demonstrate a time-dependent enhancement in the transformation process. The highest yield of 7-OH-MG, reaching 2,485 ± 134 µg/g of dried Kratom leaves weight, has been attained with the EBL processing generated by positive half-wave voltage after 20 min of EBL exposure. Notably, the EBL processing generated by positive half-wave voltage has outperformed the one generated by negative half-wave voltage by a significant factor of 2.01.

Rapid and Highly Selective Fe(IV) Generation by Fe(II)-Peroxyacid Advanced Oxidation Processes: Mechanistic Investigation via Kinetics and Density Functional Theory.

High-valent iron (Fe(IV/V/VI)) has been widely applied in water decontamination. However, common Fe(II)-activating oxidants including hydrogen peroxide (H2O2) and persulfate react slowly with Fe(II) and exhibit low selectivity for Fe(IV) production due to the cogeneration of radicals. Herein, we report peroxyacids (POAs; R-C(O)OOH) that can react with Fe(II) more than 3 orders of magnitude faster than H2O2, with high selectivity for Fe(IV) generation. Rapid degradation of bisphenol A (BPA, an endocrine disruptor) was achieved by the combination of Fe(II) with performic acid (PFA), peracetic acid (PAA), or perpropionic acid (PPA) within one second. Experiments with phenyl methyl sulfoxide (PMSO) and tert-butyl alcohol (TBA) revealed Fe(IV) as the major reactive species in all three Fe(II)-POA systems, with a minor contribution of radicals (i.e., •OH and R-C(O)O•). To understand the exceptionally high reactivity of POAs, a detailed computational comparison among the Fenton-like reactions with step-by-step thermodynamic evaluation was conducted. The high reactivity is attributed to the lower energy barriers for O-O bond cleavage, which is determined as the rate-limiting step for the Fenton-like reactions, and the thermodynamically favorable bidentate binding pathway of POA with iron. Overall, this study advances knowledge on POAs as novel Fenton-like reagents and sheds light on computational chemistry for these systems.

Highly selective regulation of non-radical and radical mechanisms by Co cubic assembly catalysts for peroxymonosulfate activation.

Peroxymonosulfate (PMS) activation on efficient catalysts is a promising strategy to produce sulfate radical (SO4-) and singlet oxygen (1O2) for the degradation of refractory organic pollutants. It is a great challenge to selectively generate these two reactive oxygen species, and the regulation mechanism from non-radical to radical pathway and vice versa is not well established. Here, we report a strategy to regulate the activation mechanism of PMS for the selective generation of SO4- and 1O2 with 100 % efficiency by sulfur-doped cobalt cubic assembly catalysts that was derived from the Co-Co Prussian blue analog precursor. This catalyst showed superior catalytic performance in activating PMS with normalized reaction rate increased by 87 times that of the commercial Co3O4 nanoparticles and had much lower activation energy barrier for the degradation of organic pollutant (e.g., p-chlorophenol) (18.32 kJ⋅mol-1). Experimental and theoretical calculation results revealed that S doping can regulate the electronic structure of Co active centers, which alters the direction of electron transfer between catalyst and PMS. This catalyst showed a strong tolerance to common organic compounds and anions in water, wide environmental applicability, and performed well in different real-water systems. This study provides new opportunities for the development of metal catalyst with metal-organic frameworks structure and good self-regeneration ability geared specifically towards PMS-based advanced oxidation processes applied for water remediation.

Reactive Oxygen Species (ROS)-Mediated Antibacterial Oxidative Therapies: Available Methods to Generate ROS and a Novel Option Proposal.

The increasing emergence of multidrug-resistant (MDR) pathogens causes difficult-to-treat infections with long-term hospitalizations and a high incidence of death, thus representing a global public health problem. To manage MDR bacteria bugs, new antimicrobial strategies are necessary, and their introduction in practice is a daily challenge for scientists in the field. An extensively studied approach to treating MDR infections consists of inducing high levels of reactive oxygen species (ROS) by several methods. Although further clinical investigations are mandatory on the possible toxic effects of ROS on mammalian cells, clinical evaluations are extremely promising, and their topical use to treat infected wounds and ulcers, also in presence of biofilm, is already clinically approved. Biochar (BC) is a carbonaceous material obtained by pyrolysis of different vegetable and animal biomass feedstocks at 200-1000 °C in the limited presence of O2. Recently, it has been demonstrated that BC's capability of removing organic and inorganic xenobiotics is mainly due to the presence of persistent free radicals (PFRs), which can activate oxygen, H2O2, or persulfate in the presence or absence of transition metals by electron transfer, thus generating ROS, which in turn degrade pollutants by advanced oxidation processes (AOPs). In this context, the antibacterial effects of BC-containing PFRs have been demonstrated by some authors against Escherichia coli and Staphylococcus aureus, thus giving birth to our idea of the possible use of BC-derived PFRs as a novel method capable of inducing ROS generation for antimicrobial oxidative therapy. Here, the general aspects concerning ROS physiological and pathological production and regulation and the mechanism by which they could exert antimicrobial effects have been reviewed. The methods currently adopted to induce ROS production for antimicrobial oxidative therapy have been discussed. Finally, for the first time, BC-related PFRs have been proposed as a new source of ROS for antimicrobial therapy via AOPs.

Revisiting the Electron Transfer Mechanisms in Ru(III)-Mediated Advanced Oxidation Processes with Peroxyacids and Ferrate(VI).

The potential of Ru(III)-mediated advanced oxidation processes has attracted attention due to the recyclable catalysis, high efficiency at circumneutral pHs, and robust resistance against background anions (e.g., phosphate). However, the reactive species in Ru(III)-peracetic acid (PAA) and Ru(III)-ferrate(VI) (FeO42-) systems have not been rigorously examined and were tentatively attributed to organic radicals (CH3C(O)O•/CH3C(O)OO•) and Fe(IV)/Ru(V), representing single electron transfer (SET) and double electron transfer (DET) mechanisms, respectively. Herein, the reaction mechanisms of both systems were investigated by chemical probes, stoichiometry, and electrochemical analysis, revealing different reaction pathways. The negligible contribution of hydroxyl (HO•) and organic (CH3C(O)O•/CH3C(O)OO•) radicals in the Ru(III)-PAA system clearly indicated a DET reaction via oxygen atom transfer (OAT) that produces Ru(V) as the only reactive species. Further, the Ru(III)-performic acid (PFA) system exhibited a similar OAT oxidation mechanism and efficiency. In contrast, the 1:2 stoichiometry and negligible Fe(IV) formation suggested the SET reaction between Ru(III) and ferrate(VI), generating Ru(IV), Ru(V), and Fe(V) as reactive species for micropollutant abatement. Despite the slower oxidation rate constant (kinetically modeled), Ru(V) could contribute comparably as Fe(V) to oxidation due to its higher steady-state concentration. These reaction mechanisms are distinctly different from the previous studies and provide new mechanistic insights into Ru chemistry and Ru(III)-based AOPs.

Preparation of MWCNT/CoMn2O4 nanocomposite for effectual degradation of picric acid via peroxymonosulfate activation.

In recent years, using nanomaterials based on multi-wall carbon nanotubes (MWCNT) through the activation of peroxymonosulfate (PMS) has attracted more attention to the degradation of organic pollutants. This research presented a new route for the synthesis of MWCNT/CoMn2O4 nanocomposite for the degradation of picric acid using advanced oxidation processes (AOPs). Firstly, CoMn2O4 nanoparticles were prepared and then loaded on MWCNT using ultrasonic waves. The results of various analyzes confirmed the successful loading of nanoparticles on carbon nanotubes. As the degradation process proceeds through oxidation processes, the high electronic conductivity of MWCNT and the active sites of Mn and Co in the nanocomposite play an essential role in activating PMS to generate reactive oxygen species (ROS). An investigation of the reaction mechanism in different conditions showed that the highest speed of picric acid decomposition in the presence of nanocomposite (98%) was in 47 min. However, the scavenger test showed that HO· and SO4·- radicals are more important in the degradation process. Meanwhile, the results showed that removing picric acid using MWCNT/CoMn2O4 was more effective than CoMn2O4 alone and confirmed the interaction effect of MWCNT nanotubes with AB2O4 nanocatalyst.

Advances and challenges in the removal of organic pollutants via sulfate radical-based advanced oxidation processes by Fe-based metal-organic frameworks: A review.

Organic contaminants, notorious for their complexity and resistance to degradation, are prevalent in aquatic environments, posing severe threats to ecosystems. Sulfate radical-based advanced oxidation processes (SR-AOPs), known for their stability and high effectiveness, have become a common choice for treating organic wastewater. Metal-organic framework materials (MOFs) have garnered substantial attention due to their facile chemical manipulation, unique structural configurations, and other favorable properties. Therefore, this article critically reviews recent advances in research involving the utilization of Fe-based MOFs (Fe-MOFs) and their derivatives in SR-AOPs. Specifically, it highlights the manipulation of influencing factors within the system to enhance the degradation of organic pollutants. The mechanisms and applications underlying the degradation of organic pollutants in the SR-AOPs system are also elucidated.

Degrading surface-water-based natural organic matter and mitigating haloacetonitrile formation during chlorination: Comparison of UV/persulfate and UV/hydrogen peroxide pre-treatments.

Haloacetonitriles (HANs) are unregulated disinfection by-products that are more toxic than regulated species. Therefore, efficient decomposition of HAN precursors prior to disinfection is crucial for allaying the potential HAN-induced health risks. This study investigated the key roles of ultraviolet-activated persulfate (UV/PS) treatment in alleviating HAN formation. The effects of UV/PS treatment were evaluated by correlating with the characteristics of organic matter in surface water and comparing with conventional UV/H2O2 treatment. Upon irradiating raw water samples and a Suwannee River humic acid solution spiked with 10 mM PS or H2O2 with 254 nm UV light, UV/PS treatment was found to be more potent than UV/H2O2 in mitigating the HAN production and degrading organic substances; moreover, UV/PS treatment effectively decreased the dissolved organic nitrogen (DON) content. In contrast, UV/H2O2 treatment did not induce any noticeable reduction in DON level. Furthermore, both UV/PS and UV/H2O2 treatments reduced the dichloroacetonitrile (DCAN) formation potential (FP), leading to strong correlations with the degradation of aromatic and humic-acid-like compounds. Notably, UV/PS treatment efficiently decreased the FP of bromochloroacetonitrile (BCAN) and dramatically reduced that of dibromoacetonitrile (DBAN) after a sharp increase; however, UV/H2O2 treatment gradually increased the DBAN-FP. Bromide was activated by sulfate radicals during UV/PS treatment, negatively correlating with the BCAN-FP and DBAN-FP, indicating that the formation of reactive bromine species increased the DBAN-FP; however, excessive oxidation possibly led to the recovery of inorganic bromine for decreasing the BCAN-FP and DBAN-FP. Additionally, UV/PS treatment effectively suppressed toxicity owing to its high reduction rate for brominated HANs; in contrast, UV/H2O2 treatment resulted in less significant BCAN and DBAN reductions, leading to minimal net reduction in toxicity. Overall, UV/PS treatment was remarkably effective at diminishing the toxicity of brominated HANs, underscoring its potential to mitigate drinking-water-related health risks.

Comparative study of different ultrasound based hybrid oxidation approaches for treatment of real effluent from coke oven plant.

The present study investigates the treatment of real coke plant effluent utilising several ultrasound-based hybrid oxidation approaches including Ultrasound (US) alone, US + catalyst, US + H2O2, US + Fenton, US + Ozone, and US + Peroxone, with main objective as maximizing the reduction of chemical oxygen demand (COD). Ultrasonic horn at power of 130 W, frequency as 20 kHz and duty cycle as 70% was applied. Study with varying catalyst (TiO2) dose from 0.5 g/L - 2 g/L revealed 1 g/L as the optimum dose resulting in 65.15% reduction in COD. A 40 ml/L dose of H2O2 was shown to be optimal, giving an 81.96% reduction in COD, based on the study of varied doses of H2O2 from 20 ml/L to 60 ml/L. US + Fenton reagent combination at optimum Fe2+/H2O2 (w/v) ratio of 1:1 resulted in a COD reduction of 85.29% whereas reduction of COD as 81.75% was obtained at the optimum flow rate of ozone as 1 LPM for US + Ozone approach. US + Peroxone demonstrated the best efficiency (90.48%) for COD reduction. To find the toxicity effects, the treated (US + peroxone) and non-treated samples were tested for the growth of bacterial cultures. It was observed that the toxicity of the treated sample increased only marginally after treatment. High-resolution liquid chromatography mass spectrometry (HR-LCMS) analysis was also performed to establish intermediate compounds. Overall, the coupling of ultrasound with oxidation processes produced better results with US + Peroxone established as best treatment approach for coke plant effluent.

Comprehensive two-dimensional liquid chromatography with high resolution mass spectrometry to investigate the photoelectrochemical degradation of environmentally relevant pharmaceuticals and their degradation products in water.

The widespread presence of organic micropollutants in the environment reflects the inability of traditional wastewater treatment plants to remove them. In this context, advanced oxidation processes (AOPs) have emerged as promising quaternary wastewater treatment technologies since they efficiently degrade recalcitrant components by generating highly reactive free radicals. Nonetheless, the chemical characterization of potentially harmful byproducts is essential to avoid the contamination of natural water bodies with hazardous substances. Given the complexity of wastewater matrices, the implementation of comprehensive analytical methodologies is required. In this work, the simultaneous photoelectrochemical degradation of seven environmentally relevant pharmaceuticals and one metabolite from the EU Watch List 2020/1161 was examined in ultrapure water and simulated wastewater, achieving excellent removal efficiencies (overall >95%) after 180 min treatment. The reactor unit was linked to an online LC sample manager, allowing for automated sampling every 15 min and near real-time process monitoring. Online comprehensive two-dimensional liquid chromatography (LC × LC) coupled with high resolution mass spectrometry (HRMS) was subsequently used to tentatively identify degradation products after photoelectrochemical degradation. Two reversed-phase liquid chromatography (RPLC) columns were used: an SB-C18 column operated with 5 mM ammonium formate at pH 5.8 (1A) and methanol (1B) as the mobile phases in the first dimension and an SB-Aq column using acidified water at pH 3.1 (2A) and acetonitrile (2B) as the mobile phases in the second dimension. This resulted in a five-fold increase in peak capacity compared to one-dimensional LC while maintaining the same total analysis time of 50 min. The LC x LC method allowed the tentative identification of 12 venlafaxine, 7 trimethoprim and 10 ciprofloxacin intermediates. Subsequent toxicity predictions suggested that some of these byproducts were potentially harmful. This study presents an effective hybrid technology for the simultaneous removal of pharmaceuticals from contaminated wastewater matrices and demonstrates how multidimensional liquid chromatography techniques can be applied to better understand the degradation mechanisms after the treatment of micropollutants with AOPs.

Ultrasound for the degradation of endocrine disrupting compounds in aqueous solution: A review on mechanisms, influence of operating parameters and cost estimation.

Availability of drinking water is one of the basic humanitarian goals but remains as a grand challenge that the world is facing today. Currently, water bodies are contaminated not only with conventional pollutants but also with numerous recalcitrant pollutants, such as PPCPs, endocrine disrupting compounds, etc. These emerging pollutants require special attention because of their toxicity to living organisms, bio-resistant and can sustain even after primary and secondary treatments of wastewater. Among different treatment technologies, sonolysis is found to be an innovative and promising technique for the treatment of emerging pollutants present in aqueous solution. Sonolysis is the use of ultrasound to enhance or alter chemical reactions by the formation of free radicals and shock waves which ultimately helps in degradation of pollutants. This review summarizes several studies in the sonochemical literature, including mechanisms of sonochemical process, physical and chemical effects of ultrasound, and the influence of several process variables such as ultrasound frequency, power density, temperature and pH of the medium on degradation performance for endocrine disrupting compounds. In addition, this review highlighted techno-economic perspectives focusing on the total cost required for translating the ultrasound-based processes on a large scale. Overall, the objective of this study is to exhibit a critical review of information available in the literature to encourage and promote future research on sonolysis for the degradation of Endocrine Disrupting Compounds (EDCs).

Highly efficient activation of periodate by a manganese-modified biochar to rapidly degrade methylene blue.

In this study, the manganese oxide/biochar composites (Mn@BC) were synthesized from Phytolacca acinosa Roxb. The Mn@BC was analyzed via techniques of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). The results show that MnOx is successfully loaded on the surface of BC, and the load of MnOx can increase the number of surface functional groups of BC. X-ray photoelectron spectroscopy (XPS) shows that MnOx loaded on BC mainly exists in three valence forms: Mn(Ⅱ), Mn(Ⅲ), and Mn(Ⅳ). The ability of Mn@BC to activate periodate (PI) was studied by simulating the degradation of methylene blue (MB) dye. The degradation experiment results showed that the MB removal rate by the Mn@BC/PI system reached 97.4% within 30 min. The quenching experiment and electron paramagnetic resonance (EPR) analysis confirmed that Mn@BC can activate PI to produce iodate (IO3•), singlet oxygen (1O2), and hydroxyl radical (•OH), which can degrade MB during the reaction. Response surface methodology (RSM) based on Box-Behnken Design (BBD) was used to determine the interaction between pH, Mn@BC and PI concentration in the Mn@BC/PI system, and the optimum technological parameters were determined. When pH = 5.4, Mn@BC concentration 0.56 mg/L, PI concentration 1.1 mmol/L, MB removal rate can reach 98.05%. The cyclic experiments show that Mn@BC can be reused. After four consecutive runs, the removal rate of MB by the Mn@BC/PI system is still 82%, and the Mn@BC/PI system also shows high performance in treating MB in actual water bodies and degrading other pollutants. This study provides a practical method for degrading dyes in natural sewage.

One-electron oxidant-induced transformation of dissolved organic matter: Optical and antioxidation properties and molecules.

Dissolved organic matter (DOM) is a major sink of radicals in advanced oxidation processes (AOPs) and the radical-induced DOM transformation influences the subsequent water treatment processes or receiving waters. In this study, we quantified and compared DOM transformation by tracking the changes of dissolved organic carbon (DOC), UVA254, and electron donating capacity (EDC) as functions of four one-electron oxidants (SO4•-, Cl2•-, Br2•-, and CO3•-) exposures as well as the changes of functional groups and molecule distribution. SO4•- had the highest DOC reduction while Cl2•- had the highest EDC reduction, which could be due to their preferential reaction pathways of decarboxylation and converting phenols to quinones, respectively. Br2•- and CO3•- induced less changes in DOC, UVA254, and EDC than SO4•- and Cl2•-. Additionally, DOM enriched with high aromatic contents tended to have higher DOC, UVA254, and EDC reductions. Decreases in hydroxyl and carboxyl groups and increases in carbonyl groups were observed in these four types of radicals treated DOM using Fourier transform infrared spectroscopy. High resolution mass spectrometry using FTICR-MS showed that one-electron oxidants preferred to attack unsaturated carbon skeletons and transformed into molecules featuring high saturation and low aromaticity. Moreover, SO4•- was inclined to decrease oxidation state of carbon and O/C of DOM due to its strong decarboxylation capacity. This study highlights the distinct DOM transformation by four one-electron oxidants and provides comprehensive insights into the reactions of one-electron oxidants with DOM.

Recent Advances in Nanoscale Zero-Valent Iron (nZVI)-Based Advanced Oxidation Processes (AOPs): Applications, Mechanisms, and Future Prospects.

The fast rise of organic pollution has posed severe health risks to human beings and toxic issues to ecosystems. Proper disposal toward these organic contaminants is significant to maintain a green and sustainable development. Among various techniques for environmental remediation, advanced oxidation processes (AOPs) can non-selectively oxidize and mineralize organic contaminants into CO2, H2O, and inorganic salts using free radicals that are generated from the activation of oxidants, such as persulfate, H2O2, O2, peracetic acid, periodate, percarbonate, etc., while the activation of oxidants using catalysts via Fenton-type reactions is crucial for the production of reactive oxygen species (ROS), i.e., •OH, •SO4-, •O2-, •O3CCH3, •O2CCH3, •IO3, •CO3-, and 1O2. Nanoscale zero-valent iron (nZVI), with a core of Fe0 that performs a sustained activation effect in AOPs by gradually releasing ferrous ions, has been demonstrated as a cost-effective, high reactivity, easy recovery, easy recycling, and environmentally friendly heterogeneous catalyst of AOPs. The combination of nZVI and AOPs, providing an appropriate way for the complete degradation of organic pollutants via indiscriminate oxidation of ROS, is emerging as an important technique for environmental remediation and has received considerable attention in the last decade. The following review comprises a short survey of the most recent reports in the applications of nZVI participating AOPs, their mechanisms, and future prospects. It contains six sections, an introduction into the theme, applications of persulfate, hydrogen peroxide, oxygen, and other oxidants-based AOPs catalyzed with nZVI, and conclusions about the reported research with perspectives for future developments. Elucidation of the applications and mechanisms of nZVI-based AOPs with various oxidants may not only pave the way to more affordable AOP protocols, but may also promote exploration and fabrication of more effective and sustainable nZVI materials applicable in practical applications.

Novel photoelectrochemical 3D-system for water disinfection by deposition of modified carbon nitride on vitreous carbon foam.

Graphitic carbon nitride (GCN) is an optical semiconductor with excellent photoactivity under visible light irradiation. It has been widely applied for organic micropollutant removal from contaminated water, and less investigated for microorganisms' inactivation. The photocatalytic degradation mechanism using GCN is attributed to a series of reactions with reactive oxygen species and photogenerated holes that can be boosted by modifying its physical-chemical structure. This work reports a successful improvement of the overall photocatalytic and electrocatalytic activities of the pristine material by thermal and chemical modification by a copolymerisation synthesis method. The copolymerisation of dicyandiamide as a precursor with barbituric acid strongly reduced photoluminescence due to the enhanced charge separation thus improving the catalyst efficiency under visible light irradiation. The material with 1.6 wt% of barbituric acid showed the best photocatalytic performance and electrochemical properties. This photocatalyst was selected for immobilisation on a conductive carbon foam, which promotes a higher electrochemical active surface area and enhanced mass transfer. This three-dimensional metal-free electrode was employed for the photoelectrochemical inactivation of two different microorganisms, Escherichia coli, and Enterococcus faecalis, obtaining removals below the detection limit after 30 min in simulated faecal-contaminated waters. This photoelectrochemical reactor was also applied to treat polluted river and urban waste waters, and the faecal contamination indicators were vastly reduced to values below the detection limit in 60 min in both cases, showing the wide applicability of this innovative photoelectrode for different types of polluted aqueous matrices.

Multi-pathway on peroxymonosulfate activation by single cobalt atoms incorporated on CuO with enriched oxygen vacancies for high-efficient oxidation of tetracycline.

The development of single atom catalysts (SACs) with superior catalytic performance is a long-term goal for peroxymonosulfate (PMS) activation in advanced oxidation processes (AOPs). A novel SACs that single Co atoms anchored on CuO with enriched oxygen vacancies (Ov) is synthesized successfully by choosing a metal oxide as the carrier creatively. 100% of tetracycline (TC) can be removed by Co-CuO (Ov)/PMS system within 3 min. The corresponding reaction rate constant is 3.1068 min-1, which is much higher than that of CuO (Ov), ZIF-CoN4-C, Co-CuO (without Ov) and CoNP-CuO (Ov), respectively. Co(II) is the primary source of radical pathway (·OH and SO4·-), and its regeneration is promoted by Cu(Ⅰ). The enriched Ov is the major contribution to the nonradical pathway, which promotes the singlet oxygen (1O2) generation together with accelerates the electron transfer from TC to catalyst-PMS*. Besides, the Co-CuO (Ov) exhibits an excellent stability and anti-interference capability. This study highlights a novel strategy to promote PMS activation by incorporating the single metal atoms on a metal oxide carrier with defects to accelerate the redox of dominate metal and stabilize the metal atoms simultaneously, which may inform the design for the next generation of SACs in AOPs.

Effects of wavelength on the treatment of contaminants of emerging concern by UV-assisted homogeneous advanced oxidation/reduction processes.

Pollutants of emerging concern in aqueous environments present a significant threat to both the aquatic ecosystem and human health due to their rapid transfer. Among the various treatment approaches to remove those pollutants, UV-assisted advanced oxidation/reduction processes are considered competent and cost-effective. The treatment effectiveness is highly dependent on the wavelength of the UV irradiation used. This article systematically discusses the wavelength dependency of direct photolysis, UV/peroxides, UV/chlor(am)ine, UV/ClO2, UV/natural organic matter, UV/nitrate, and UV/sulfite on the transformation of contaminants. Altering wavelengths affects the photolysis of target pollutants, photo-decay of the oxidant/reductant, and quantum yields of reactive species generated in the processes, which significantly impact the degradation rates and formation of disinfection byproducts. In general, the degradation of contaminants is most efficient when using wavelengths that closely match the highest molar absorption coefficients of the target pollutants or the oxidizing/reducing agents, and the contribution of pollutant absorption is generally more significant. By matching the wavelength with the peak absorbance of target compounds and oxidants/reductants, researchers and engineers have the potential to optimize the UV wavelengths used in UV-AO/RPs to effectively remove pollutants and control the formation of disinfection byproducts.

Titania/reduced graphene oxide nanocomposites (TiO2/rGO) as an efficient photocatalyst for the effective degradation of brilliant green in aqueous media: effect of peroxymonosulfate and operational parameters.

This study is focused on synthesis of highly efficient Titania/reduced Graphene Oxide (TiO2/rGO) nanocomposites by means of simple hydrothermal technique. The TiO2/rGO were synthesized in different ratios of 0.5, 1.0, 2.0, and 3% by varying the concentration of rGO while the concentration of TiO2 was kept constant and the obtained samples were designated as TrG0.5, TrG1, TrG2, and TrG3 respectively. Different characterization techniques (SEM, TEM, HRTEM, XRD, EDX, TGA, UV-DRS, PL, EIS, and BET) showed high crystallinity, small crystallite size (18.4 nm), high thermal stability, high purity, low band gap energy (Eg = 3.12 eV), and high surface area (65.989 m2/g) for the as-synthesized TiO2/rGO nanocomposite. The efficiencies of TiO2/rGO were determined in terms of brilliant green (BG) dye degradation in aqueous media under UV light. The results revealed that 2% TiO2/rGO (TrG2) showed high efficiency for BG degradation with the kapp of 0.023 min-1 compared to TiO2 alone (kapp of 0.006 min-1). The rate of BG degradation was further synergised by the addition of peroxymonosulfate (PMS) to the system. The degradation of BG was improved to 99.4% by the incorporation of PMS in aqueous media compared to TrG2 alone. Furthermore, the degradation of BG was also examined in various media (neutral, acidic, and basic). The results revealed that by increasing pH of the medium from 3.85 to 8.2 the degradation of BG was enhanced from 99.4 to 99.9% with the corresponding kapp of 0.0602 min-1. Moreover, the photocatalytic degradation of BG followed the pseudo-first-order kinetics. Radical scavenging experiments showed that ●OH and SO4●- were the main species responsible for the degradation of BG under UV light. Besides, for determining the efficiency of as-synthesized TrG2/PMS system, the degradation of BG was also performed in various water types (distilled water, tape water, synthetic wastewater, and industrial wastewater). The degradation products (DPs) of BG and their corresponding pathways were proposed, accordingly.

Recent advances in advanced oxidation processes (AOPs) for the treatment of nitro- and alkyl-phenolic compounds.

The presence of phenolic compounds in the aquatic environment has posed severe risks due to their toxicity. Among the phenolic families, nitro- and alkyl-phenolic compounds have been categorized as precedence contaminants by the United States Environmental Protection Agency (US EPA). Therefore, efficient treatment methods for wastewater containing nitro- and alkyl-phenolic compounds are urgently needed. Due to the advantages of creating reactive species and generating efficient degradation of hazardous contaminants in wastewater, advanced oxidation processes (AOPs) are well-known in the field of treating toxic contaminants. In this review paper, the recent directions in AOPs, catalysts, mechanisms, and kinetics of AOPs are comprehensively reviewed. Furthermore, the conclusion summarizes the research findings, future prospects, and opportunities for this study. The main direction of AOPs lies on the optimization of catalyst and operating parameters, with industrial applications remain as the main challenge. This review article is expected to present a summary and in-depth understanding of AOPs development; and thus, inspiring scientists to accelerate the evolution of AOPs in industrial applications.

MgxCu-biochar activated peroxydisulfate triggers reductive species for the reduction and enhanced electron-transfer degradation of electron-deficient aromatic pollutants.

In wastewater treatment by persulfate-based advanced oxidation processes (PS-AOPs), electron-deficient aromatic pollutants (EDAPs) are refractory to nonradical pathway. To explore an efficient degradation pathway for EDAPs, MgxCu-biochar (BC) (x = 0.5, 1, 1.5) activated peroxydisulfate (PDS) was developed, which could trigger reductive species (•H) to reduce EDAPs first, and subsequently facilitate electron-transfer degradation of reduced intermediates. The roles of Mg-doping in MgxCu-BC to promote PDS activation and 2,4-dibromophenol (DBP) degradation were investigated. The mechanisms were then explored via electron paramagnetic resonance (EPR), chemical probes and Density Functional Theory (DFT) calculations. The results showed that Mg-doping improved metal-support interactions (MSIs) of MgxCu-BC, inducing •H formation via electron transfer from Cu atoms during PDS activation, which was thermodynamically favorable. The degradation rate of DBP (kobs, 0.0494 min-1) and Br- release (5.35 mg L-1) in Mg1Cu-BC systems were more 31 and 33 times than that in Cu-BC/PDS system, respectively. The degradation mechanism of •H-enhanced electron transfer processes was that •H attacked one Br group of DBP, and then debrominated intermediates were mineralized by electron transfer processes in the Mg1Cu-BC/PDS system. Overall, this study reports a novel pathway in PS-AOPs for selective degradation of EDAPs in wastewaters.