Degradation Of Emerging Contaminants Research Articles

Cu-Doped V-Based MOF Derivative VO2@Cu-VMOF as a Cathodic Catalyst for Electro-Fenton Degradation of Antibiotics.

In this study, the VO2@5%Cu-VMOF/graphite felt (GF) is prepared as an electro-Fenton cathode via hydrothermal process and low-temperature carbonization for efficient antibiotics degradation. The VO2@5%Cu-VMOF/GF cathode exhibit great ciprofloxacin (CIP) degradation performance over the pH range of 2.1-7.2, and CIP removal reached 98.1% within 60min at a pH of 3.4, with corresponding total organic carbon (TOC) removal of 68.7%. The cathode also showed desired catalytic performance toward various antibiotics decomposition. The great catalytic activity of the VO2@5%Cu-VMOF/GF cathode is attributed to lattice strain induced by Cu doping, and the elimination of the overpotential difference between the optimal oxygen reduction potential (OP ORR) and optimal metal reduction potential (OP MRR). Density Function Theory (DFT) calculations showed that Cu doping facilitated electrons accumulation around V atoms, and thus increased the content of low-valence metals in the cathode material. Four possible degradation pathways for CIP are proposed and intermediate toxicity is evaluated. This work advances the design and application of MOF derivatives as electro-Fenton cathodic materials for emerging contaminants degradation.

Enhanced removal of chiral emerging contaminants by an electroactive biofilter

50% of pharmaceuticals and 25% of herbicides used worldwide are chiral. Each enantiomer has a unique toxicity and biodegradation profile, affecting differently to organisms. Chirality plays a key role in the behavior of these emerging contaminants (ECs) in terms of their pharmacological or herbicidal activity, but this peculiarity is often overlooked in environmental research. The complexity of chiral ECs is underestimated, as the varying sensitivity of biological systems to enantiomers is rarely considered. Biofilters can promote the activity of specific microbial communities, facilitating the degradation of ECs, due to the greater interaction between water and microorganisms and their compact design. Here, we show that an electroactive biofilter can alter the chirality of drugs and herbicides in wastewater treatment, impacting their removal and toxicity. The electrochemical biofilter (BioeF) removed 80% of pharmaceuticals and 50–75% of herbicides, outperforming the conventional filter (ConF). BioeF also showed greater chiral alterations and lower ecotoxicity. This work provides the first evidence of a relationship between changes in contaminant chirality and detoxification capacity, enhanced by electroactive systems. The increased microbial activity observed in the BioeF suggests that bioelectrochemical systems offer a valuable advance for ECs removal and ecotoxicity reduction, addressing the environmental challenge posed by ECs.

High metal-loaded sub-nanocluster catalyst enhanced Fenton-like reaction activity for emerging contaminants degradation by generating high-valent copper

High-valent copper (Cu(III)) species are crucial intermediates in CH bond functionalization within both the biological and biomimetic processes, facilitated by copper enzymes and stabilized by multicopper oxidases. Herein, a nitrogen-doped copper sub-nanocluster catalyst (SNC) featured a high metal content (29.1 wt%) and uniform Cu distribution was synthesized by carbonizing the nanosheet-like metal–organic framework (MOF), enhancing bisphenol A degradation by activating peroxymonosulfate (PMS) to generate Cu(III). The degradation performance of the SNC outperformed the catalyst carbonized with the bulk-like MOF and matched the reported single-atom catalysts counterparts. Nitrogen doping decreased the electrons of Cu3d orbital, enhancing its bonding with the oxygen atom within the PMS molecule, thus promoting Cu(III) generation. The Cu-SNC/PMS system also showed robust resistance against anions, pH changes, and diverse water matrices. Importantly, it can selectively degrade electron-rich pollutants through oxygen atom transfer by Cu(III). This study provided new perspectives into SNC preparation, the controlled formation of high-valent metal species, and their role in Fenton-like reactions for pollutants degradation.

Valorizing waste activated sludge incineration ash to S-doped Fe2+@Zeolite 4A catalyst for the treatment of emerging contaminants exemplified by sulfamethoxazole

The global attention towards waste management and valorization has led to significant interest in recovering valuable components from sludge incineration ash (SIA) for the synthesis of functional environmental materials. In this study, the SIA was converted to an S-doped Fe2+-zeolite type catalyst (FZA) for the treatment of emerging contaminants (ECs), exemplified by sulfamethoxazole (SMX). Results demonstrate that FZA effectively catalyzed the activation of peracetic acid (PAA), achieving a remarkable degradation of 99.8% under optimized conditions. Mechanistic investigations reveal that the FZA/PAA system can generate ·OH, 1O2, O2·－, and Fe(Ⅳ), with ·OH playing a dominant role in ECs degradation. Additionally, the doped S facilitated electrochemical performance, Fe2+ regeneration and fixation in FZA. Practical application elucidated that the FZA/PAA system can work in complex environments to degrade various ECs without generating high-toxicity ingredients. Overall, valorizing SIA to FZA provides dual achievement in waste management and ECs removal.

Novel visible-light activated photocatalytic ultrafiltration membrane for simultaneous separation and degradation of emerging contaminants

Emerging contaminants (ECs) in secondary effluent of wastewater treatment plants (WWTPs) have received increasing attention due to their adverse effects on aquatic ecosystems and human health. Herein, visible-light responsive photocatalyst TM (TiO2 @NH2-MIL-101(Fe)) and resultant photocatalytic ultrafiltration (PUF, PVDF/TM) membrane were prepared to remove 32 typical compounds of antibiotics, 296 compounds of antibiotic resistance genes (ARGs), and their corresponding bacterial hosts. The construction of heterojunction photocatalyst promoted the electron transfer from NH2-MIL-101(Fe) to TiO2 and the formation of N-TiO2, enhancing visible-light (λ ≥ 420 nm) photocatalytic activity. With highly-hydrophilic surface and delicately-regulated pore structure, the initial water permeance of optimal PUF membrane significantly increased to 3912.2 L/m2/h at 1.0 bar. Meanwhile, membrane retention (via adsorption, electrostatic interaction, and steric hindrance) was improved due to the narrowed pore size, highly-negative surface charge and abundant functional groups. Additionally, hydroxyl radical (•OH) was the dominant active reactive oxygen species (ROS) for ECs degradation, and the narrowed pore structure could serve as microreactors to increase ROS concentration and reduce migration distance. Consequently, the removal efficiencies of antibiotics, bacteria and ARGs were 86.5 %, 91.4 % and 91.8 %, respectively. Overall, this novel visible-light-activated PUF membrane expands membrane application, and has great potential in ECs treatment.

Discovery of an End-to-End Pattern for Contaminant-Oriented Advanced Oxidation Processes Catalyzed by Biochar with Explainable Machine Learning.

The utilization of biochar-catalyzed peroxymonosulfate in advanced oxidation processes (BC-PMS AOPs) is widely acknowledged as an effective and economical method for mitigating emerging contaminants (ECs). Especially, state-of-the-art machine learning (ML) technology has been employed to accurately predict the reaction rate constants of EC degradation in BC-PMS AOPs, primarily focusing on three aspects: performance prediction, operating condition optimization, and mechanism interpretation. However, its real application in specific degradation optimization targeting different ECs is seldom considered, hindering the realization of contaminant-oriented BC-PMS AOPs. Herein, we propose a hierarchical ML pipeline to achieve an end-to-end (E2E) pattern for addressing this issue. First, the overall XGB model, trained with the comprehensive data set, can perform well in predicting the reaction constants of EC degradation in BC-PMS AOPs, additionally providing the basis for further analysis of various ECs. Then, the submodels trained with different EC clusters can offer specific strategies for the selection of the optimum option for BC-PMS AOPs of specific ECs with different HOMO-LUMO gaps, thus forming an E2E operating pattern for BC-PMS AOPs. This study not only increases our understanding of contaminant-oriented optimization of AOPs but also successfully bridges the gap between ML model development and its environmental application.

Facilitating interface tuning of metal-support interaction on the sepiolite surface for the enhancement of metronidazole removal

To achieve efficient catalytic activity for emerging contaminants degradation in water environment, this work creatively prepared a silicon-based catalyst (Co/ASepx), which built a metal-silicon framework in-situ growing on sepiolite (Sep) through hydrothermal synthesis, and further obtained via high-temperature pyrolysis. Then the Co/ASepx was used to activate peroxymonosulfate (PMS) to remove metronidazole (MNZ) from water environment. The results showed that the Co/ASepx presented a substantial number of Co/MgSiO3-Co interfacial structures, the introducing of interface engineering triggered the strong metal-support interaction between Co and Sep, then altered the surface electron distribution and regulated the coordination environment of the metal Co. The Co/ASep1-PMS system not only exhibited the significant MNZ removal performance, and the MNZ degradation rate in the Co/ASep1-PMS system was 5.4 times than that of the Co2+-PMS homogeneous catalytic system with the same Co dosage, but also presented low Co leaching and high cycling stability. Moreover, the quadruple mechanism of MNZ degradation were comprehensively revealed, in which was dominated by the singlet oxygen of the non-radical pathway. Lastly, this work provides a novel feasible way to build high-performance catalysts with low Co leaching and low cost for the outstanding removal efficiency of MNZ.

Degradation of emerging contaminants in synthetic hydrolyzed urine by UV/peracetic acid: Free radical chemistry, and toxicity analysis

The ecological impact of emerging contaminants (ECs) in aquatic environments has raised concerns, particularly with regards to urine as a significant source of such contaminants in wastewater. The current investigation used the UV/Peracetic Acid (UV/PAA) processes, an innovative advanced oxidation technology, to effectively separate two emerging pollutants from urine at its source, namely, ciprofloxacin (CIP) and bisphenol A(BPA). The research findings demonstrate that the presence of the majority of characteristic ions has minimal impact on the degradation of ECs. However, in synthetic hydrolyzed urine, only NH4+ inhibits the degradation of two types of ECs, with a more pronounced effect observed on CIP degradation compared to BPA.The impact of halogen ions, specifically Cl− and I−, on the degradation of CIP in synthetic hydrolyzed urine was a complex phenomenon. When these two halogen ions are present individually, the generation of reactive halogen species (RHS) within the system enhances the degradation of CIP. However, when both types of ions coexist, the formation of diatomic radical species partially inhibits degradation. In terms of BPA degradation, while the production of reactive chlorine species (RCS) to some extent hinders the reaction rate, the generation of reactive iodine species (RIS) promotes the overall process. CIP undergoes fragmentation of the piperazine and quinoline rings, decarboxylation, defluorination reactions, as well as substitution reactions, leading to the formation of products with simplified structures. The degradation of BPA occurs gradually through hydroxyl and halogen substitution as well as isopropyl cleavage. The preliminary toxicity analysis confirmed that the presence of halogen ions in urine resulted in the formation of halogenated products in two types of ECs, albeit with an overall reduction in toxicity. The UV/PAA processes was considered to be an effective and relatively safe approach for the separation of ECs in urine.

Remediation of imidacloprid and carbamazepine in polluted soil using TiO2 with LED lamps

Imidacloprid and carbamazepine are recognised as emerging contaminants (ECs) due to their ubiquitous presence in environmental compartments and their potential to cause undesirable ecological effects. Wastewater treatment plants are relevant routes for these compounds to enter environment since they are continuously released through treated wastewater. The progressively more extended custom of reusing treated wastewater for agricultural irrigation has also enlarged the risks for ECs accumulation in soil and their translocation to crops, posing a constant threat to both humans and wildlife. This work is aimed to study the behaviour of imidacloprid and carbamazepine and its main transformation products generated in soil during photocatalytic treatments using commercial TiO2 (Degussa P25) and ultraviolet light emitting diode (UV-LED) lamps as light source. Prior to remediation trial, the influence of catalyst load and soil moisture content in ECs degradation was studied. Experiments were performed using a photochemical reactor equipped with LED lamps running at 365 nm, exposing polluted soils to different treatments in presence and absence of photocatalyst. A significant degradation (93.4 and 96.2% for imidacloprid and carbamazepine, respectively) was observed after 4 days of photocatalytic treatment. The main transformation products were identified during the different treatments. Our results suggest that TiO2-photocatalytic treatment combined with UV-LED could be considered a promising technology to remove ECs from soils.

Critical perspective on the elimination of emerging contaminants from industrial wastewater via microbial electrochemical technologies

AbstractIndustrial water pollution originating from various industries like textile, dairy, oil, and petrochemical industries, etc. is a huge concern globally and has led to devastating effects on the environment due to the release of refractory emerging contaminants (ECs). These ECs of concern have attracted wide devotion from the scientific community due to their recalcitrant nature and disastrous effects on plants, aquatic life forms, and humans. In this regard, conventional wastewater treatment technologies such as coagulation, flocculation, membrane technologies, electrocoagulation, and other biological technologies like sequencing batch reactor, anaerobic up‐flow sludge blanket reactor, etc., are inefficient in removing ECs from the industrial effluent, while conventional advanced oxidation processes incur high cost due to the extensive requirement of energy for the degradation of ECs. To overcome this issue, microbial electrochemical technologies (METs) can be employed. For instance, METs have shown promising results in the degradation of various ECs, such as microbial fuel cells, which have shown nearly 92% to 98% removal of sulfamethoxazole with simultaneous power recovery. Alizarin yellow R, nitrobenzene, and Congo red were degraded by microbial electrolysis cells with removal efficiency in the range of 88% to 98%, demonstrating their superiority in the elimination of trace contaminants. Similarly, almost 100% mineralization of pyraclostrobin was noticed for the bio‐electro‐Fenton process, showing the elevated potential of these neoteric technologies for the remediation of recalcitrant pollutants. Thus, the current review article aims to critically analyze the intervention of METs for the elimination of ECs from industrial wastewater.

Sulfite activation by ultrasound for the degradation of emerging contaminants: The dependence of pollutant property and mechanistic study

The easy recombination of •OH radicals in ultrasonic processes (US) always leads to the inadequacy in degrading relatively hydrophilic pollutants. Herein, sulfite was activated by ultrasound and the US/S(IV) process was for the first time applied to degrade emerging contaminants (ECs) with different physicochemical properties. Kinetic analysis and density functional theory (DFT) calculation showed that LogP of ECs was the dominant factor affecting the degradation efficiency in both US and US/S(IV) processes, and the addition of S(IV) more significantly improved the degradation of compounds with low LogP, high EHOMO and low ΔE (ΔE = ELUMO – EHOMO). The main mechanism of sulfite activation was attributed to •OH rather than the heat. The recombination of •OH could be well inhibited by sulfite and more •OH and SO4•− radicals could be derived from SO3•− in the bulk phase with the presence of O2. Based on DFT and LC/MS analysis, the reactive sites of sulfamethoxazole (SMX) upon the attack from •OH and SO4•− were identified and three degradation pathways were proposed. The primary intermediates of SMX could be efficiently degraded into smaller compounds in US/S(IV) process. Moreover, US/S(IV) process showed stronger adaptability to a broad pH range and complex water matrix than US process. This work may provide new insights into the sulfite activation technologies and a promising alternative for efficient degradation of ECs with different physicochemical properties.

Kraft lignin-derived multi-porous carbon toward sustainable electro-Fenton treatment of emerging contaminants

Reclaiming biomass waste to carbon cathode is promising to construct a sustainable electrochemical system. Here, we developed a novel thermal foaming process to reform kraft lignin to a free-standing and multi-porous carbon foam, which can be used as carbon cathode for electro-Fenton treatment of emerging contaminants (ECs). Benefiting from the excellent physicochemical and electrochemical properties with multi-porous and graphitic structure, the synthesized carbon foam cathode enhanced the electrocatalytic generation of H2O2 and •OH, and subsequently promoted the mass transfer and interactions among reactants (i.e., O2, H2O2, Fe2+, •OH, natural organic matters, and ECs). Eventually, an efficient degradation of ECs was achieved most likely via the multi-step •OH addition, cleavage, and ring opening reactions. Overall, the outcomes of this work provide a sustainable and applicable design and strategy to upgrade lignin-containing biomass to carbon cathode for efficient ECs remediation.

Recent Advances in Black Phosphorous-Based Photocatalysts for Degradation of Emerging Contaminants.

The recalcitrant nature of emerging contaminants (ECs) in aquatic environments necessitates the development of effective strategies for their remediation, given the considerable impacts they pose on both human health and the delicate balance of the ecosystem. Semiconductor-based photocatalytic technology is recognized for its dual benefits in effectively addressing both ECs and energy-related challenges simultaneously. Among the plethora of photocatalysts, black phosphorus (BP) stands as a promising nonmetallic candidate, offering a host of advantages including its tunable direct band gap, broad-spectrum light absorption capabilities, and exceptional charge mobility. Nevertheless, pristine BP frequently underperforms, primarily due to issues related to its limited ambient stability and the rapid recombination of photogenerated electron-hole pairs. To overcome these challenges, substantial research efforts have been devoted to the creation of BP-based photocatalysts in recent years. However, there is a noticeable absence of reviews regarding the advancement of BP-based materials for the degradation of ECs in aqueous solutions. Therefore, to fill this gap, a comprehensive review is undertaken. In this review, we first present an in-depth examination of the fabrication processes for bulk BP and BP nanosheets (BPNS). The review conducts a thorough analysis and comparison of the merits and limitations inherent in each method, thereby delineating the most auspicious avenues for future research. Then, in line with the pathways followed by photogenerated electron-hole pairs at the interface, BP-based photocatalysts are systematically categorized into heterojunctions (Type I, Type II, Z-scheme, and S-scheme) and hybrids, and their photocatalytic performances against various ECs and the corresponding degradation mechanisms are comprehensively summarized. Finally, this review presents personal insights into the prospective avenues for advancing the field of BP-based photocatalysts for ECs remediation.

Preparation of MgIn2S4/g-C3N4 for enhanced ranitidine photocatalytic degradation activity via Z-scheme electron transfer

The evidence so far indicates that ranitidine (RAN) contains N-nitrosodimethylamine (NDMA), a strong carcinogen, which is extremely harmful to human health under long-term exposure. Hence, a well-design Z-scheme heterostructure composed of 3D MgIn2S4 micro-flower and 2D g-C3N4 nanosheets was fabricated and used to remove RAN. The optimal photocatalyst (MG-30) exhibited the fastest RAN degradation rate of 0.24685 min−1 within 30 min under visible light, which was 78.1 and 19.8 times higher than those of bare MgIn2S4 and g-C3N4, respectively. Impressively, MG-30 was exceedingly resistant to environmental variations including organic matter, inorganic salts and aqueous substrates. In the meantime, MG-30 boasted the merit such as wide pH range for RAN removal. The excellent results originated from the construction of Z-scheme heterojunctions, which improved the carrier separation efficiency and retained the strong redox ability of MG-30, thereby contributing to the creation of rich active species. Meanwhile, the 3D/2D structure of MgIn2S4/g-C3N4 overrode the limited reflection of visible light. The active species analyses revealed that superoxide radical (·O2−) and hydroxyl radical (·OH) mainly participated in RAN degradation. Furthermore, the possible degradation pathways of RAN and toxicity analysis of intermediates produced were presented. This work emphasizes practical application potential of Z-scheme heterostructure photocatalysts for emerging contaminants degradation in wastewater.

Selective formation of high-valent iron in Fenton-like system for emerging contaminants degradation under near-neutral and high-salt conditions

In view of the near-neutral and high-salt conditions, the Fenton technology with hydroxyl radicals (HO•) as the main reactive species is difficult to satisfy the removal of trace emerging contaminants (ECs) in pharmaceutical sewage. Here, a layered double hydroxide FeZn-LDH was prepared, and the selective formation of ≡Fe(IV)=O in Fenton-like system was accomplished by the chemical environment regulation of the iron sites and the pH control of the microregion. The introduced zinc can increase the length of Fe-O bond in the FeZn-LDH shell layer by 0.22 Å compared to that in Fe2O3, which was conducive to the oxygen transfer process between ≡Fe(III) and H2O2, resulting in the ≡Fe(IV)=O formation. Besides, the amphoteric hydroxide Zn(OH)2 can regulate the pH of the FeZn-LDH surface microregion, maintaining reaction pH at around 6.5–7.5, which could avoid the quenching of ≡Fe(IV)=O by H+. On the other hand, owing to the anti-interference of ≡Fe(IV)=O and the near-zero Zeta potential on the FeZn-LDH surface, the trace ECs can also be effectively degraded under high-salt conditions. Consequently, the process of ≡Fe(IV)=O generation in FeZn-LDH system can satisfy the efficient removal of ECs under near-neutral and high-salt conditions.

Highlight the plasma-generated reactive oxygen species（ROSs）dominant to degradation of emerging contaminants based on experiment and density functional theory

This paper aims to deeply analyze the degradation mechanism of emerging contaminants by dielectric barrier discharge (DBD) plasma through experiments and simulations. It was confirmed that DBD plasma exhibits a high degradation effect on three emerging contaminants by the generated reactive oxygen species (ROSs). Increasing the output power leads to higher ROSs production and higher degradation rates of emerging contaminants. At an input power of 94.6 W, the degradation rates of sulfamethoxazole (SMX), bisphenol A (BPA) and ciprofloxacin (CIP) reach 94.5 %, 92.9 %, and 98.6 %, respectively. Trapping agent experiments were conducted to investigate the role of ROSs (·OH, ·O2–, and 1O2) in emerging contaminants degradation. Notably, capturing of 1O2 led to a decrease of up to 31 % in the degradation rate of BPA. Electron spin resonance (ESR) tests confirmed the involvement of various ROSs, especially 1O2, in the degradation process. Density functional theory (DFT) was employed to further explore the action mechanism of ROSs in the DBD plasma system. For SMX and BPA, the degradation is initiated by the dissociation of annular structures, while for CIP, annular structures are directly opened by ROSs. These findings highlight the importance of 1O2 and ·OH in the degradation process. Finally, the toxicity of intermediates produced by ROSs-dominate to degradation was declined. This work can provide new insights and unique guidance on the plasma degradation mechanism of emerging contaminants.

Composting post-anaerobic digestion for emerging contaminant biodegradation: Impacts of operating conditions.

Sustainable manure management technologies are needed, and combining anaerobic digestion (AD) for energy generation and aerobic composting (AC) to stabilize digestate and remove emerging contaminants (ECs), including veterinary pharmaceuticals and steroid hormones, is promising. This study identified post-AD, AC operating conditions that maximized degradation of study ECs, expected to be present in cattle manure digested using treated municipal wastewater as the water source. Study ECs included sulfamethoxazole (SMX), chlortetracycline (CTC), oxytetracycline (OTC), estrone (E1), and naproxen (NPX). Composting conditions were simulated in bench-scale reactors, with microorganisms from digestate produced in an AD system (25L scale), by varying temperatures, pH, and carbon source compositions (representing food waste/manure co-digestion with different residence times). Results indicate maximum SMX biodegradation occurred at 35°C, pH 7, and with high levels of easily degradable carbon (≥99%, 99%, and 98%), and maximum E1 biodegradation occurred at 35°C, and with low levels of easily degradable carbon (≥97% and 99%). Abiotic degradation was responsible for the nearly complete removal of tetracyclines under all conditions and for partial degradation of NPX (between 20% and 48%). Microorganisms originating from the AD system putatively capable of SMX and E1 biodegradation, or of contributing to biodegradation during the AC phase, were identified, including phylotypes previously shown to biodegrade SMX (Brevundimonas and Alcaligenes).

ZnAl/ZnSn(OH) composite photocatalyst for emerging contaminants degradation in water

Layered double hydroxides (LDH) are a versatile group of lamellar inorganic solids with a brucite-like structure similar to hydrotalcite that has undergone multiple improvements to be applied in various fields such as carbon dioxide sequestration, catalysis, drug delivery, energy conversion, and storage, as well as environmental remediation. It is then that this material becomes interesting for its application in water treatment since it has various practical features, e.g. tunable structure, excellent thermal stability, memory effect, high specific surface, high dispersion and regenerative viability. By taking advantage of this versatility, in this research work, the synthesis and characterization of ZnAl hydrotalcite modified with Sn through the coprecipitation method is reported. The presence of hydrotalcite ZnAl, and Zinc hydroxystannate phases were observed in the X-ray diffraction spectra. In the same way, it was possible to observe through the SEM micrographs the morphology associated with the union of both phases; i.e. lamellar and microcubic. In the bandgap energy measurement, the shift of the hydrotalcite value is observed as well as the appearance of another signal of zinc hydroxystannate species. The obtained materials were evaluated for the photocatalytic degradation of acetaminophen to 20 ppm under UV light. ZnAl/ZnSn(OH)6 composite showed better efficiency in the paracetamol degradation under UV light. Additionally, studies of the variation of ZnAl/ZnSn(OH)6 ratio and pH values of the solution were carried out, achieving photodegradation efficiency > 95 %, after 60 min of irradiation, using 0.15 g of ZnAl/ZnSn(OH)6 photocatalyst at pH= 6. The reusability was evaluated by testing the material in photodegradation cycles.

New insights into degradation of emerging contaminants by S(IV)/Fe(VI) system in neutral water: Performance enhancement, reaction mechanisms and toxicity assessment

This study proposes a novel approach to enhance the degradation of emerging contaminants (ECs) in neutral water using the S(IV)/Fe(VI) system and identifies the significant role of high-valent iron (Fe(V)/Fe(IV)) in selective oxidation. In the complex of bisulfite and sulfite (B1S3)/Fe(VI) system, the degradation rates and pseudo-first-order rate constants of sulfamethoxazole (SMX), carbamazepine (CBZ), 2,4-dihydroxybenzophenone (BP-1) and 4,4′-sulfonyldiphenol (BPS) were higher than those achieved with single S(IV) activation Fe(VI). The results were attributed to the dominance of Fe(V)/Fe(IV) in the selective oxidations which involved the participation of HO• and SO4•−. In addition, the degradation mechanisms of SMX, CBZ, BP-1, and BPS were proposed, and the acute toxicity, chronic toxicity, developmental toxicity, and bioaccumulation factors of the transformation products were assessed. The results showed that the removal of ECs by the B1S3/Fe(VI) system resulted in a reduction in toxicity. The effects of experimental conditions and water matrix on the removal of ECs were evaluated and achieved satisfactory results in three different real water samples. The B1S3/Fe(VI) system was capable of rapid degradation of ECs at relatively low S(IV) and Fe(VI) doses, and the ultimate products (SO42− and Fe(III)) promoted coagulation, indicating multiple application scenarios and tremendous engineering potential.

Ferrous ion enhanced Fenton-like degradation of emerging contaminants by sulfidated nanosized zero-valent iron with pH insensitivity

In this study, the performance and mechanism of the integrated sulfidated nanosized zero-valent iron and ferrous ions (S-nZVI/Fe2+) system for oxygen activation to remove emerging contaminants (ECs) were comprehensively explored. The S-nZVI/Fe2+ system exhibited a 2.4–8.2 times of increase in the pseudo-first order kinetic rate constant for the oxidative degradation of various ECs compared to the S-nZVI system under aerobic conditions, whereas negligible removal was observed in both nZVI and nZVI/Fe2+ systems. Moreover, remarkable EC mineralization efficiency and benign detoxification capacity were also demonstrated in the S-nZVI/Fe2+ system. We revealed that dosing Fe2+ promoted the corrosion of S-nZVI by maintaining an acidic solution pH, which was conducive to O2 activation by dissolved Fe2+ and surface-absorbed Fe(II) to produce •OH. Furthermore, the generation of H* was enhanced for the further reduction of Fe(III) and H2O2 to Fe(II) and •O2–, resulting in the improvement of consecutive single-electron O2 activation for •OH production. Additionally, bisphenol A (BPA) degradation by S-nZVI/Fe2+ was positively correlated with the S-nZVI dosage, with an optimum S/Fe molar ratio of 0.15. The Fenton-like degradation process by S-nZVI/Fe2+ was pH-insensitive, indicating its robust performance over a wide pH range. This study provides valuable insights for the practical implementation of nZVI-based technology in achieving high-efficiency removal of ECs from water.