Enhanced chalcopyrite-catalyzed heterogeneous Fenton oxidation of diclofenac by ABTS.

The widely used 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) has gained growing attention in advanced oxidation processes (AOPs), whereas there was limited knowledge regarding the feasibility of ABTS in enhancing heterogeneous Fenton oxidation so far. Hereof, ABTS was introduced into the chalcopyrite (CuFeS2)- catalyzed heterogeneous Fenton oxidation process to degrade diclofenac (DCF), and the degradation efficiency was enhanced by 25.5% compared with CuFeS2/H2O2 process. The available reactive oxygen species (ROS) and the enhanced mechanism were elaborated. Experimental results uncovered that •OH was the dominant reactive species responsible for the DCF degradation in the CuFeS2/H2O2/ABTS process, and ABTS•+ was derived from both •OH and Fe(IV). The presence of ABTS contributed significantly to the redox cycle of surface Fe of CuFeS2, and the roles of reductive sulfur species and surface Cu(I) in promoting surface Fe cycling also could not be neglected. In addition, the effects of several influencing factors were considered, and the potential practicability of this oxidation process was examined. The results demonstrate that the CuFeS2/H2O2/ABTS process would be a promising approach for water purification. This study will contribute to the development of enhancing strategies using ABTS as a redox mediator for heterogeneous Fenton oxidation of pharmaceuticals.

Low additive peracetic acid enhanced sulfamethazine degradation by permanganate: A mechanistic study.

In this study, a novel water treatment process combining permanganate (Mn(VII)) and peracetic acid (PAA, CH3C(O)OOH) was employed to degrade sulfamethazine (SMT), a typical model contaminant. Simultaneous application of Mn(VII) and a small amount of PAA resulted in much faster oxidation of organics than a single oxidant. Interestingly, coexistent acetic acid played a crucial role in SMT degradation, while background hydrogen peroxide (H2O2) had a negligible effect. However, compared with acetic acid, PAA could better improve the oxidation performance of Mn(VII) and accelerate the removal of SMT more significantly. The mechanism of SMT degradation by Mn(VII)-PAA process was systematically evaluated. Firstly, based on the quenching experiments, electron spin resonance (EPR) results and UV-visible spectrum, singlet oxygen (1O2), Mn(III)aq and MnO2 colloids were the predominant active substances, while organic radicals (R-O•) showed negligible contribution. Then, the decay of Mn(VII) in the presence of PAA and H2O2 was investigated. It was found that the coexisting H2O2 accounted for almost all the decay of Mn(VII), PAA and acetic acid both had low reactivity toward Mn(VII). During the degradation process, acetic acid was able to acidify Mn(VII) and simultaneously acted as a ligand to form reactive complexes, while PAA mainly played a role of spontaneously decomposing to produce 1O2, they jointly promoted the mineralization of SMT. Finally, the degradation intermediates of SMT and their toxicities were analyzed. This paper reported the Mn(VII)-PAA water treatment process for the first time, which provided a promising approach for rapid decontamination of refractory organics-polluted water.

Graphene shell-encapsulated copper-based nanoparticles (G@Cu-NPs) effectively activate peracetic acid for elimination of sulfamethazine in water under neutral condition.

In this study, a graphene shell-encapsulated copper-based nanoparticles (G@Cu-NPs) was prepared and employed for peracetic acid (PAA) activation. The characterization of G@Cu-NPs confirmed that the as-prepared material was composed of Cu0 and Cu2O inside and encapsulated by a graphene shell. Experimental results suggested that the synthesized G@Cu-NPs could activate PAA to generate free radicals for efficiently removing sulfamethazine (SMT) under neutral condition. The formation of graphene shells could strongly facilitated electron transfer from the core to the surface. Radical quenching experiments and electron spin resonance (ESR) analysis confirmed that organic radicals (R-O•) and hydroxyl radicals (•OH) were generated in the G@Cu-NPs/PAA system, and R-O• (including CH3CO3• and CH3CO2•) was the main contributor to the elimination of SMT. The possible SMT degradation pathways and mechanisms were proposed, and the toxicity of SMT and its intermediates was predicted with the quantitative structure-activity relationship (QSAR) analysis. Besides, the effects of some key parameters, common anions, and humic acid (HA) on the removal of SMT in the G@Cu-NPs/PAA system were also investigated. Finally, the applicability of G@Cu-NPs/PAA system was explored, showing that the G@Cu-NPs/PAA system possessed satisfactory adaptability to treat different water bodies with admirable reusability and stability.

Advanced oxidation processes for water purification using percarbonate: Insights into oxidation mechanisms, challenges, and enhancing strategies.

Percarbonate (SPC) has drawn considerable attention due to its merits in the safety of handling and transport, stability, and price as well as environmental friendliness, which has been extensively applied in advanced oxidation processes (AOPs) for water decontamination. Nevertheless, comprehensive information on the application of SPC-AOPs for the treatment of organic compounds in aquatic media is scarce. Hence, the focus of this review is to shed light on the mechanisms of reactive oxygen species (ROS) evolution in typical SPC-AOPs (i.e., Fenton-like oxidation, photo-assisted oxidation, and discharge plasma-involved oxidation processes). These SPC-AOPs enable the formation of multiple reactive species like hydroxyl radical (•OH), superoxide radical (O2•-), singlet oxygen (1O2), carbonate radicals (CO3•-), and peroxymonocarbonate (HCO4-), which together or solely contribute to the degradation of target pollutants. Simultaneously, the potential challenges in practical applications of SPC-AOPs are systematically discussed, which include the influence of water quality parameters, cost-effectiveness, available active sites, feasible activation approaches, and ecotoxicity. Subsequently, enhancing strategies to improve the feasibility of SPC-AOPs in the practical implementation are tentatively proposed, which can be achieved by introducing reducing and chelating agents, developing novel activation approaches, designing multiple integrated oxidation processes, as well as alleviating the toxicity after SPC-AOPs treatment. Accordingly, future perspectives and research gaps in SPC-AOPs are elucidated. This review will hopefully offer valuable viewpoints and promote the future development of SPC-AOPs for actual water purification.

Adsorption and catalytic degradation of organic contaminants by biochar: Overlooked role of biochar's particle size.

Biochar (BC) is considered as a promising adsorbent and/or catalyst for the removal of organic contaminants. However, the relationship between the particle size of BC and its adsorption/catalysis performance is largely unclear. We therefore investigated the influence of particle size on the performance of BC pyrolyzed at 300-900 °C in trichloroethylene (TCE) adsorption and persulfate (PS) activation for sulfamethazine (SMT) degradation. The results showed that high-temperature pyrolyzed BC (BC900) presented superior adsorption capacity for TCE and excellent catalytic activity for PS activation to degrade SMT. Compared to 150-250 µm, 75-150 µm and pristine BC900, 0-75 µm BC900 showed the highest TCE adsorption efficiency, which increased by 19.5-62.3%. Similarly, SMT removal by BC900/PS systems also increased from 24.2% to 98.3% with decreasing BC particle size. However, the catalytic activity of BC after grinding was not significantly improved as expected, indicating the properties of biochar was not only controlled by size effect. Characterization measurements proved that small-sized BC tended to have larger specific surface area, more micropores, higher conductivity, rich graphitic domains and surface redox-active functional groups, thus resulting in an enhanced adsorption and catalytic ability of BC.

Insights into a novel CuS/percarbonate/tetraacetylethylenediamine process for sulfamethazine degradation in alkaline medium.

This work presents a novel CuS/percarbonate/tetraacetylethylenediamine (CuS/SPC/TAED) process for the degradation of sulfamethazine (SMT). Results indicated that the CuS/SPC/TAED process enabled the efficient generation of peracetic acid (PAA), which can be efficiently activated by CuS in alkaline reaction media, and 93.6% of SMT was degraded in 30 min. Mechanism study revealed that the available reactive oxygen species (ROS) including hydroxyl radical (•OH), carbonate radical (CO3•-), superoxide radical (O2•-), singlet oxygen (1O2), and organic radicals (R-O•). Among them, R-O• (acetyloxyl radical (CH3CO2•) and acetylperoxyl radical (CH3CO3•)) were confirmed to be the primary species that contributed to SMT degradation. Simultaneously, the role of sulfur species and carbonate ions were explored. It was found that the reductive O2•- and sulfur species rendered the efficient redox of Cu species. Besides, the effects of key influencing factors including SPC/TAED mole ratio, CuS dosage, initial pH, temperature, and nontarget matrix constituents on SMT degradation were examined. Finally, the degradation intermediates of SMT was identified, and the toxicity of these products was estimated by quantitative structure-activity relationship (QSAR) analysis. Overall, this work offers a new and simple strategy for antibiotic-polluted water remediation.

Degradation of sulfamethazine in water by sulfite activated with zero-valent Fe-Cu bimetallic nanoparticles.

In this work, zero-valent Fe-Cu bimetallic nanoparticles were synthesized using a facile method, and applied to activate sulfite for the degradation of sulfamethazine (SMT) from the aqueous solution. The key factors influencing SMT degradation were investigated, namely the theoretical loading of Cu, Fe-Cu catalyst dosage, sulfite concentration and initial solution pH. The experimental results showed that the Fe-Cu/sulfite system exhibited a much better performance in SMT degradation than the bare Fe0/sulfite system. The mechanism and possible degradation pathway of SMT in Fe-Cu/sulfite system were revealed. The reactive radicals that played a dominant role in the SMT degradation process were •OH and SO4•-, while the loading of Cu induced the synergistic effect between Fe and Cu. The redox cycle between Cu(I)/Cu(II) remarkably contributed to the conversion of Fe(III) to Fe(II), greatly enhancing the catalytic performance of Fe-Cu bimetal. In real groundwater applications, the Fe-Cu/sulfite system also exhibited satisfactory SMT degradation. The 30-day aging tests of Fe-Cu particles demonstrated that the aging of catalyst was not obviously affecting the removal of SMT. Furthermore, the reusability of catalyst was evidenced by the recycling experiments. This study provides a promising application of bimetal activated sulfite for enhanced contaminant degradation in groundwater.

Insights into the correlation between different adsorption/oxidation/catalytic performance and physiochemical characteristics of Fe-Mn oxide-based composites.

Fe-Mn oxide-based composites have been widely used in the solidification of heavy metals or the removal of organic pollutants, which can not only show excellent adsorption/oxidation performance, but also show catalytic activity for common oxidants. At present, the correlation between adsorption/oxidation/catalytic performance and physicochemical characteristics of these composites, and the underlying mechanisms are still unclear. Therefore, the main purpose of this review is to disclose the internal relationship between the physicochemical properties of Fe-Mn oxide-based composites and the pollutant removal performance. From the perspective of crystal phase, the basic units of Fe-Mn oxide composites are divided into Fe-Mn binary oxide (FMBO) and spinel MnFe2O4, and the two species were discussed separately in most chapters. The selected physicochemical properties mainly include the type of Fe-Mn oxide composites, surface-to-volume ratio, pore volume, pHpzc, crystal type, surface functional groups. Because the physicochemical properties that determine how effective Fe-Mn oxide material is at removing contaminants may differ as it performs different functions, we discussed the above problems under different application scenarios (adsorption, oxidation, and advanced oxidation process). Additionally, internal factor (Fe/Mn mole ratio) and external factors (pHini, co-ions and ionic strength) were analyzed, and several common synthetic strategies of these composites were presented.

In-depth exploration of toxicity mechanism of nanoscale zero-valent iron and its aging products toward Escherichia coli under aerobic and anaerobic conditions.

The bacteria toxicity of nanoscale zero-valent iron (nZVI) can be changed during its application in water treatment but the toxicity mechanism is still not well understood, particularly under anaerobic conditions. Here, the toxicity of nZVI and its aging products towards Escherichia coli (E. coli) and the mechanisms of extracellular and intracellular reactive oxygen species (ROS) damage were deeply probed in the presence and absence of oxygen in ultrapure water. Under aerobic conditions, the ROS damage primarily caused by the generation of extracellular free •OH can be a major contributor to the toxicity of nZVI to E. coli. By contrast, in anaerobic nZVI treatment system, the intracellular •OH can be quenched by benzoic acid which is a cell permeable quencher and the electron spin resonance (ESR) signals of 5,5-dimethy-1-pyrroline (DMPO)- •OH were evidently observed in system with the addition of F- which could desorb the surface •OH into solution. It indicated that the intracellular •OH adsorbed on the particle surface can also play an indispensable role in inactivating cells under anaerobic conditions. Moreover, nZVI can steeply decline the membrane potential, causing severe membrane disruption and therefore resulting in the stronger toxicity in anaerobic conditions. Furthermore, the chemical composition transformation of nZVI and generation of benign iron corrosion products (e.g., Fe3O4, γ-Fe2O3, γ-FeOOH) are mainly responsible for the reduced toxicity with the increasing aging time. These results provide insights into the extracellular and intracellular ROS damage occurred in aerobic and anaerobic nZVI treatment systems, offering more perspective to the risk assessment of nZVI application.

Sulfur or nitrogen-doped rGO supported Fe-Mn bimetal - organic frameworks composite as an efficient heterogeneous catalyst for degradation of sulfamethazine via peroxydisulfate activation.

In this work, sulfur/nitrogen modified reduced graphene oxide (S/N-rGO) was employed as both electron shuttle and support to fabricate Fe-Mn bimetallic organic framework@S/N-rGO hybrids (BOF@S/N-rGO) via a facile two-step solvothermal route. Compared with the transition metal ions (Fe2+/Mn2+), the classical metal oxide catalyst (Fe2O3 and Fe3O4) and nano zero-valent iron (nZVI), BOF@S/N-rGO catalyst can more effectively activate peroxydisulfate (PDS) with ultra-low concentration (0.05 mM) to degrade sulfamethazine (SMT). Quenching experiments, electron paramagnetic resonance (EPR) measurement and linear sweep voltammetry (LSV) showed that the activation pathways of PDS between the two catalysts were different. In BOF@N-rGO+PDS system, the degradation of SMT was mainly attributed to the oxidation of radicals including SO4•- and •OH, especially SO4•- . However, in BOF@S-rGO+PDS system, in addition to the radical pathway, there are also non-radical pathways, namely 1O2 and direct electron transfer. Furthermore, the applicability of BOF@S/N-rGO used in the PDS-mediated advanced oxidation processes (AOPs) was systematically investigated in terms of the effects of operating parameters and coexisting substance (anions and humic acid (HA)), the degradation of other pollutants, as well as the stability and reusability of the catalyst. This study proved that BOF@S/N-rGO was a promising activator of PDS with ultra-low concentration for the degradation of SMT.

A comparative study on the physicochemical properties, reactivity and long-term performance of sulfidized nanoscale zerovalent iron synthesized with different kinds of sulfur precursors and procedures in simulated groundwater.

There are plentiful ways to synthesize sulfidized nanoscale zerovalent iron (S-nZVI), and this study investigated the influence of sulfur reagents (Na2S, Na2S2O3, Na2S2O4) and sulfidation sequence (co-sulfidation and post-sulfidation method) on the physicochemical properties, reactivity, and long-term performance of S-nZVI in simulated groundwater. The results suggested that the co-sulfidized nZVI (S-nZVIco) has higher reactivity (∼2-fold) than S-nZVIpost due to the stronger electron transfer capacity, deriving from the higher content of Fe0 and reductive sulfur species. However, during aging, the reactivity of S-nZVIco would be lost more rapidly than S-nZVIpost, due to the faster corrosion of Fe0 and more oxidation of reductive sulfur species. S-nZVIpost has the superior long-term performance with the degradation rate of trichloroethylene (TCE) remained at 30%∼60% even after 90 d of aging. Sulfur precursors can control the selectivity of S-nZVI by affecting the sulfur speciation on the particle surface. The proportion of reductive sulfur species on S-nZVIpost synthesized by Na2S was higher than S-nZVIpost synthesized by Na2S2O3 or Na2S2O4, resulting in a higher selectivity of the former S-nZVIpost than the latter S-nZVIpost. In addition, sulfidation procedures and sulfur precursors did not affect the degradation pathway of TCE. Nevertheless, the degradation product distribution can be affected by the different physicochemical transformation of various types of S-nZVI with the aging time. These results indicated that sulfur reagents and sulfidation procedures have crucial effects on the reactivity and long-term performance of S-nZVI, which can be designed for the specific application scenarios.

Efficient degradation of sulfamethazine via activation of percarbonate by chalcopyrite.

In this work, the novel application of chalcopyrite (CuFeS2) for sodium percarbonate (SPC) activation towards sulfamethazine (SMT) degradation was explored. Several key influencing factors like SPC concentration, CuFeS2 dosage, reaction temperature, pH value, anions, and humic acid (HA) were investigated. Experimental results indicated that SMT could be effectively degraded in the neutral reaction media by CuFeS2/SPC process (86.4%, 0.054 min-1 at pH = 7.1). The mechanism of SPC activation by CuFeS2 was elucidated, which was discovered to be a multiple reactive oxygen species (multi-ROS) process with the coexistence of hydroxyl radical (•OH), carbonate radical (CO3•-), superoxide radical (O2•-), and singlet oxygen (1O2), as evidenced by quenching experiments and electron spin resonance (ESR) tests. The generated •OH via the traditional heterogeneous Fenton-like process would not only react with carbonate ions to yield other ROS but also involve in SMT degradation. The abundant surface-bound Fe(II) was deemed to be the dominant catalytic active sites for SPC activation. Meanwhile, it was verified that the reductive sulfur species, the interaction between Cu(I) and Fe(III) as well as the available O2•- derived from the activation of molecular oxygen and the conversion of •OH favored the regeneration of Fe(II) on CuFeS2 surface. Furthermore, the degradation intermediates of SMT and their toxicities were evaluated. This study presents a novel strategy by integrating transition metal sulfides with percarbonate for antibiotic-contaminated water treatment.

Recent advances in waste water treatment through transition metal sulfides-based advanced oxidation processes.

With the ever-growing water pollution issues, advanced oxidation processes (AOPs) have received growing attention due to their high efficiency in the removal of refractory organic pollutants. Transition metal sulfides (TMSs), with excellent optical, electrical, and catalytical performance, are of great interest as heterogeneous catalysts. These TMSs-based heterogeneous catalysts have been demonstrated to becapable and adaptable in water purification through advanced oxidation processes. The aim of this review is to conduct an exhaustive analysis and summary of recent progress in the application of TMSs-based AOPs for water decontamination. Firstly, the commonly used tuning strategies for TMSs-based catalysts are concisely introduced, including artificial size and shape control, composition control, doping, and heterostructure manufacturing. Then, a comprehensive overview of the current state-of-the-art progress on TMSs-based AOPs (i.e., Fenton-like oxidation, photocatalytic oxidation, and electro chemical oxidation processes) for wastewater treatment is discussed in detail, with an emphasis on their catalytic performance and involved mechanism. In addition, influencing factors of water chemistry, namely, pH, temperature, dissolved oxygen, inorganic species, and natural organic matter on the catalytic performance of established AOPs are analyzed. Furthermore, the reusability and stability of TMSs-based catalysts in these AOPs are also outlined. Finally, current challenges and future perspectives related to TMSs-based catalysts and their applications for AOPs wastewater treatment are proposed. It is expected that this review would shed some light on the future development of TMSs-based AOPs towards water purification.