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Iron is one of the most abundant elements in the Universe and Earth's surfaces, and undergoes a redox change of approximately 0.77 mV in changing between its +2 and +3 states. Many contemporary terrestrial organisms are deeply connected to inorganic geochemistry via exploitation of this redox change, and iron redox reactions and catalysis are known to cause significant changes in the course of complex abiotic reactions. These observations point to the question of whether iron may have steered prebiotic chemistry during the emergence of life. Using kinetically naive in silico reaction modeling we explored the potential effects of iron ions on complex reaction networks of prebiotic interest, namely the formose reaction, the complexifying degradation reaction of pyruvic acid in water, glucose degradation, and the Maillard reaction. We find that iron ions produce significant changes in the connectivity of various known diversity-generating reaction networks of proposed prebiotic significance, generally significantly diversifying novel molecular products by ~20%, but also adding the potential for kinetic effects that could allow iron to steer prebiotic chemistry in marked ways. [ABSTRACT FROM AUTHOR]

The objective of this study was to evaluate the potential of novel poloxamer thermosensitive hydrogels (PTHs) formulations for prolonged release of iron dextran particles (IDP) for intramuscular (IM) injection. The thermosensitive behaviour helps to avoid hepcidin overexpression and toxicity by releasing IDPs without iron accumulation in injection or deposit sites. We hypothesized that novel PTH formulation would prolong iron liberation compared to the commercial iron dextran formulation (FEDEX). PTHs loaded with IDPs were developed with increasing iron content (0.1, 0.2 and 0.4 g of iron/g of poloxamer) and characterized as a prolonged release IM iron supplement. The PTHs had a biocompatible pH for IM injection (6.4) and thermosensitive viscosity, increasing from ∼50 (4 °C) to ∼3000 mPa.s (37 °C). PTHs were successfully injected in the sol state (at 4 °C) into pork meat at 37 °C, transitioning to the gel state in situ (in ∼60-190 s). Structural characterization indicated that there were no PTH-IDP chemical interactions, suggesting that IDP entrapment in PTHs was physical upon gelation. In vitro release studies revealed that iron release from PTH (0.4 g of iron/g of poloxamer) reached 100 % by day 10, whereas 100 % release from FEDEX was complete in 4 h. This novel iron PTH formulation achieved a 60 times long iron release compared to the commercial product. In conclusion, the reported strategy shows adequate IDP entrapment/release properties for prolonged iron release following ex vivo IM injection using biocompatible materials. These results provide a strong basis for future preclinical evaluation to elucidate aspects such as drug release, local irritation, biocompatibility, and efficacy., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

A facile hydrothermal route was employed for the synthesis of iron-nickel bimetal organic frameworks (Fe-Ni bi-MOFs) and composite with an acid functionalized multi-walled carbon nanotubes (Fe-Ni MOF/f-MWCNTs) for electrochemical detection of tartrazine. The as-prepared Fe-Ni MOF/f-MWCNTs was confirmed by the several physicochemical studies. A micro spindle shaped, highly porous, and crystalline Fe-Ni MOF/f-MWCNTs was noticed. The high sensitivity and stability of Fe-Ni MOF/f-MWCNTs/GCE modified electrode was analyzed. Due to its high porosity nature, the analyte molecule effectively gets adsorbed on the modified electrode and undergo electrochemical oxidation effectively. The modified electrode exhibits low limit of detection (LOD) and limit of quantification (LOQ) as 0.04 × 10 -6 mol/L and 0.13 × 10 -6 mol/L towards tartrazine. These results reveal the potential applications of Fe-Ni MOF/f-MWCNTs/GCE as modified electrode material for sensitive detection of tartrazine along with its robust reproducibility, stability, and effective sensing properties., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Milk-type beverages are popular vegan products requiring iron and calcium fortification to improve their nutritional value, as iron deficiency is the world's most prevalent nutritional problem. This research aimed to develop and characterize an extruded common bean (Phaseolus vulgaris L.)-based milk-type beverage added with bean protein isolate and iron. The formulations included flavors (non-flavored, vanilla, and nut) and two iron concentrations (2 and 3 mg FeSO 4 /100 mL). Extrusion increased the beverages' protein (+17.38 %) and starch digestibility, and reduced their antinutritional compounds (trypsin inhibitors, condensed tannins, and carbonates). Developed beverages' formulations differed from a commercial soybean beverage in their physicochemical properties but were more nutritious (protein: 3.33-3.44 %; fiber: 3.43-4.08 %). Iron-added beverages displayed a medium sensory acceptance (best overall likeness: 5.3-6.2). The developed beverage is a suitable, sensory-accepted, and nutritious bean-based beverage, suggesting novel research lines improving vegan beverage formulations to increase average daily iron intake., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Single-atom nanozymes have garnered significant attention due to their exceptional atom utilization and ability to establish well-defined structure-activity relationships. However, conventional pyrolytic synthesis methods pose challenges such as high energy consumption and random local environments at the active sites, while achieving non-pyrolytic synthesis of single-atom nanozymes remains a formidable technical hurdle. The present study focuses on the synthesis of laccase-like iron-based single-atom nanozymes (Fe-SAzymes) using a non-pyrolysis method facilitated by microwave irradiation. Under low iron loading conditions, Fe-SAzymes exhibited significantly enhanced laccase activity (12.1 U/mg), surpassing that of laccase by 24-fold. Moreover, Fe-SAzymes demonstrated efficient catalytic oxidation of epinephrine (EP), enabling its colorimetric detection. Owing to the remarkable laccase activity of Fe-SAzymes, the conventional nanozymes EP detection time was reduced from 60 min to 20 min, with an impressive low detection limit as low as 2.95 μM. In addition, an ultra-sensitive fluorescence method for EP detection was developed using the internal filter effect of EP oxidation products and CDs combined with carbon dots probe. The detection limit of fluorescence method was only 0.39 μM. Therefore, an visual, fast, and highly sensitive dual-mode EP detection strategy has great potential in the clinical diagnostic industry., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The formation of flocs is crucial in the coagulation process of water treatment. However, the nature of ligand exchange on the surface of primary nanoparticles (PNPs) during floc formation requires further investigation to enhance our understanding of the coagulation mechanism. Phosphate (P) is a ubiquitous nutrient ion in aquatic surface water, in this study, the impact of P on floc growth under different pH conditions were investigated. The results revealed that floc growth patterns depended on both P dosage and pH. The mode of ligand exchange between P and in-situ formed ferric hydroxide within a pH range of 5 to 10 was further explored, and remarkable disparities in pH changes induced by P addition were observed. At lower pH levels, OH - release occurred relatively slowly, stabilizing with continued P addition. At neutral pH, OH - release was comparatively higher with P addition, while under alkaline conditions, both the quantity of OH - and its release rate decreased. It was deduced that Fe-OH 2 1/2+ sites function as "active sites," while Fe-OH 1/2- sites act as "inert sites" on the surface of PNPs formed during flocculation. These sites are crucial in the interconnections between flocs formed during coagulation and in floc growth. Analyses of Fe PNPs by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), with and without P addition, revealed that the introduction of P inhibits or interferes with the self-crystallization of Fe PNPs through chemical coordination reactions. The results offer deeper insights into the coagulation mechanism and the transformation of Fe flocs in raw waters containing P during water treatment practices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Rapid sand filters are established and widely applied technologies for groundwater treatment. In these filters, main groundwater contaminants such as iron, manganese, and ammonium are oxidized and removed. Conventionally, intensive aeration is employed to provide oxygen for these redox reactions. While effective, intensive aeration promotes flocculent iron removal, which results in iron oxide flocs that rapidly clog the filter. In this study, we operated two parallel full-scale sand filters at different aeration intensities to resolve the relative contribution of homogeneous, heterogeneous and biological iron removal pathways, and identify their operational controls. Our results show that mild aeration in the LOW filter (5 mg/L O 2, pH 6.9) promoted biological iron removal and enabled iron oxidation at twice the rate compared to the intensively aerated HIGH filter (>10 mg/L O 2, pH 7.4). Microscopy images showed distinctive twisted stalk-like iron solids, the biosignatures of Gallionella ferruginea, both in the LOW filter sand coatings as well as in its backwash solids. In accordance, 10 times higher DNA copy numbers of G. ferruginea were found in the LOW filter effluent. Clogging by biogenic iron solids was slower than by chemical iron flocs, resulting in lower backwash frequencies and yielding four times more water per run. Ultimately, our results reveal that biological iron oxidation can be actively controlled and favoured over competing physico-chemical routes. The production of more compact and practically valuable iron oxide solids is of outmost interest. We conclude that, although counterintuitive, slowing down iron oxidation in the water before filtration enables rapid iron removal in the biofilter., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Phosphonates are widely used scale inhibitors, but the residual phosphonates in drainage are challenging to remove because of their chelating capacity and resistance to biodegradation. Here, we reported a highly efficient and robust Fe-electrocoagulation (Fe-EC) system for phosphonate removal. Surprisingly, we found for the first time that phosphonates like NTMP were more efficiently removed under anoxic conditions (80% of total soluble phosphorus (TSP) in 4 min) than oxic conditions (0% of TSP within 6 min) in NaCl solution. A similar phenomenon was observed when other phosphonates, such as EDTMP and DTPMP, were removed, highlighting the importance of iron complexation and floc formation toward phosphonate removal with Fe-EC. We also showed that the removal efficiency of NTMP by electrochemically in-situ formed flocs (97%) was much higher than post-adsorption systems (ex-situ, 40%), revealing that the growth of flocs consumed the active site for NTMP adsorption. Beyond the removal of TSP, 10 % of NTMP-P was also degraded after the electrolysis phase, evidenced by the evolution of phosphate-P. However, this did not happen in anoxic or chemical coagulation processes, which confirms the formation of reactive oxygen species via Fe(II) oxidation in the oxic Fe-EC system. The primary removal mechanism of phosphonates is due to their complexation with iron (hydr)oxide generated in the Fe-EC system by forming a Fe-O-P bond. Encouragingly, the Fe-EC system exhibits comparable or even better performance in treating phosphonate-laden wastewater (i.e., cooling water). Our preliminary cost calculation suggests the proposed system (€ 0.009/m 3 ) has a much lower OPEX under oxic conditions than existing approaches. This study sheds light on the removal mechanism of phosphonate and the treatment of phosphonate-laden wastewater by playing with the iron complexion and flocs formation in classical Fe-EC systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Iron-based biochar exhibits great potential in degrading emerging pollutants and remediation of water environments. In this study, a highly efficient catalytic Fe 0 /biochar (MZB-800) was synthesized by the co-pyrolysis of poplar sawdust and K 2 FeO 4 at 800 °C. A novel water purification technology of pre-reduction followed by PMS activation for MZB-800 was proposed to degrade the refractory 2,4-dichlorophenoxyacetic acid (2,4-D) pesticide. The corrosive effect of the strong oxidizing potassium salt endowed the MZB-800 surface with more Fe 0 and porous structure, achieving greater 2,4-D adsorption binding energy. The removal efficiency of MZB-800 on 2,4-D was greater than that of biochar (BC) and conventional Fe 0 /biochar (Fe-BC) prepared by FeCl 3 ·6 H 2 O as the precursor. The proposed novel water purification technology showed the synergistic effect between the interfacial pre-reduction and the PMS activation derived by MZB-800. Regarding 2,4-D degradation and dechlorination performance, the synergistic coefficient between pre-reduction and subsequent PMS activation for MZB-800 were 2 and 1.4 respectively. Based on the normalized kinetic analysis and the Langmuir-Hinshelwood model, we proposed the underlying mechanism of MZB-800 interfacial pre-reduction and subsequent PMS activation for synergistic removal of 2,4-D. The large amount of Fe 2+ and hydroxyl density accumulated by the Fe 0 and hydroquinone structures on the MZB-800 surface during the pre-reduction stage provided abundant active sites for the subsequent activation of PMS. The improved activation reaction rate generated more reactive oxygen species, further strengthening the removal efficiency of 2,4-D. This work manifested that the novel water purification technology of pre-reduction/PMS activation of iron-based biochar is feasible for removing emerging pollutants in the water environment. ENVIRONMENTAL IMPLICATION: Extensive abuse of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide with high solubility and refractory degradation has caused environmental pollution and ecological deterioration. This manuscript described a novel water purification technology, centered on high-efficiency Fe 0 /biochar and utilizing pre-reduction and PMS reactivation strategies to synergistically degrade 2,4-D, which had strong environmental relevance. By elucidating the synergistic removal mechanism, the research provided valuable insights into removing emerging pollutants, thus promoting environmental sustainability and safeguarding ecosystem health. Overall, it is of high importance to provide a feasible and efficient method for removing hazardous 2,4-D from water environments, which contributes to addressing pressing environmental problems., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Biodegradation, while cost-effective, is hindered by the requirement for specialized microorganisms and co-contaminants. Innovative biological technologies like the microbially driven Fenton reaction, hold promise for enhancing degradation efficiency. However, the intricate biochemical processes and essential steps for effective degradation in such systems have remained unclear. In this study, we harnessed the potential of the microbially driven Fenton reaction by employing Shewanella oneidensis MR-1 (MR-1). Our approach showcased remarkable efficacy in degrading a range of contaminants, including sulfadimethoxine (SDM), 4,4'-dibromodiphenyl ether (BDE-15) and atrazine (ATZ). Using SDM as a model contaminant of emergent contaminants (ECs), we unveiled that biodegradation relied on the generation of hydroxyl radicals (•OH) and involvement of oxidoreductases. Transcriptomic analysis shed light on the pivotal components of extracellular electron transfer (EET) during both anaerobic and aerobic periods. The presence of reactive oxidizing species induced cellular damage and impeded DNA repair, thereby affecting the Mtr pathway of EET. Moreover, the formation of vivianite hindered SDM degradation, underscoring the necessity of maintaining iron ions in the solution to ensure sustainable and efficient degradation. Overall, this study offers valuable insights into microbial technique for ECs degradation, providing a comprehensive understanding of degradation mechanisms during aerobic/anaerobic cycling., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Iron-based adsorbents are commonly used to remove arsenic (As) from water for drinking water purposes. Here, we study the role of biological As(III) oxidation on iron-based adsorbents in filters and its effect on overall As uptake. A lab-scale filter with iron oxide coated sand (IOCS), a commonly used adsorbent, was operated with water containing As(III) and As(V), while water samples were taken periodically over its height. As(III) oxidation initiated after approximately 10 days and increased to a first order rate constant of 0.09 s -1 after 57 days resulting in full oxidation of As(III) in <50 s. Consequently, the filter shifted from an As(III) to an As(V) adsorbing filter. Oxidation was not observed after inhibiting the microbial activity using sodium azide confirming its biogenic nature. This implies that As(III) oxidizing biomass can grow on iron-based adsorbents in water filters without requiring inoculation. As the experimental conditions were similar to full-scale As treatment plants, we believe that biological As(III) oxidation is widely overlooked in these systems. Occurrence of biological oxidation is, however, beneficial for removal, as at pH <8 the adsorption capacity for As(V) can be up to 10-fold higher than for As(III). With these new insights, arsenic treatment using iron-based adsorbents can be further optimized. We suggest a more robust new design with a biological active As(III) oxidizing top layer and an As(V) adsorbing bottom layer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The biogeochemical cycle of biogenic manganese oxides (BioMnOx) is closely associated with the environmental behavior and fate of various pollutants. It is significantly interfered by many metals, such as Cu and Fe. However, the bacterial molecular responses are not clear. Here, the effects of Cu(II) and Fe(III) on oxidation of manganese by Pseudomonas putida MnB1 and the bacterial molecular response mechanisms have been studied. The bacterial oxidation of manganese were promoted by both Fe(III) and Cu(II) and the final manganese oxidation rate of the Cu(II) group exceeded 16 % that of the Fe(III) group. The results of transcriptome indicated that Cu(II) promoted manganese oxidation by up-regulating the expression levels of multicopper oxidase (MCO) and peroxidase(POD), and by stimulating electron transfer, while Fe(III) promoted this process by accelerating the electron transfer and nitrogen cycling, and activating POD. The protein-protein interaction (PPI) network indicated that the MCO genes (mnxG and mcoA) were directly linked to the copper homeostasis proteins (cusA, cusB, czcC and cusF). Cytochrome c was closely related to the genes related to nitrogen cycling (glnA, glnL, and putA) and electrons transfer (cycO, cycD, nuoA, nuoK, and nuoL), which also promoted manganese oxidation. This study provides a molecular level insight into the oxidation of Mn(II) by Pseudomonas putida MnB1 with Cu(II) and/or Fe(III) ions., Competing Interests: Declaration of Competing Interest We declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Membrane distillation (MD) offers promise for recycling shale gas produced water (SGPW), while membrane fouling is still a major obstacle in standalone MD. Herein, sodium percarbonate (SPC) oxidation was proposed as MD pretreatment, and the performance of the single MD, SPC-MD hybrid process and Fe(II)/SPC-MD hybrid process for SGPW treatment were systematically evaluated. Results showed that compared to raw SGPW, the application of SPC and Fe(II)/SPC led to the decrease of the fluorescent organics by 28.54 % and 54.52 %, respectively. The hydrophobic fraction decreased from 52.75 % in raw SGPW to 37.70 % and 27.20 % for SPC and Fe(II)/SPC, respectively, and the MD normalized flux increased from 0.19 in treating raw SGPW to 0.65 and 0.81, respectively. The superiority of SPC oxidation in reducing the deposited membrane foulants and restoring membrane properties was further confirmed through scanning electron microscopy observation, attenuated total reflection fourier transform infrared, water contact angle and surface tension analyses of fouled membranes. Correlation analysis revealed that hydrophobic/hydrophilic matters and fluorescent organics in SGPW took a crucial role in MD fouling. The mechanism of MD fouling mitigation by Fe(II)/SPC oxidation was attributed to the decrease in concentrations and hydrophobicity of organic by synergistic oxidation, coagulation and adsorption., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The transmission of antibiotic resistance genes (ARGs) and the propagation of antibiotic resistant bacteria (ARB) threaten public health security and human health, and greener and more efficient disinfection technologies are expected to be discovered for wastewater treatment. In this study, natural pyrite and ascorbic acid (AA) were proposed as environmental-friendly activator and reductant for periodate (PI) activation to inactivate ARB. The disinfection treatment of PI/pyrite/AA system could inactivate 5.62 log ARB within 30 min, and the lower pH and higher PI and natural pyrite dosage could further boost the disinfection efficiency. The 1 O 2 and SO 4 •- were demonstrated to be crucial for the inactivation of ARB in PI/pyrite/AA system. The disinfection process destroyed the morphological structure of ARB, inducing oxidative stress and stimulating the antioxidant system. The PI/pyrite/AA system effectively reduced the intracellular and extracellular DNA concentration and ARGs abundance, inhibiting the propagation of ARGs. The presence of AA facilitated the activation of PI with natural pyrite and significantly increased the concentration of Fe 2+ in solution. The reusability of natural pyrite, the safety of the disinfection by-products and the inhibition of ARB regeneration indicated the application potential of PI/pyrite/AA system in wastewater disinfection., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Nano zero-valent iron (NZVI) has been shown to effectively enhance the chain elongation (CE) process, addressing the issue of limited yield of medium-chain carboxylic acids (MCCA) from organic wastewater. However, the specific impact of NZVI on the metabolism of CE bacteria (CEB) is not well understood. In this study, it was aimed to investigate the mechanism by which an optimal concentration of NZVI influences CE metabolism, particularly in relation to ethanol oxidation, electron transfer, and MCCA synthesis. This was achieved through single-factor influence experiments and metagenomic analysis. The results showed that the addition of 1 g/gVSS NZVI achieved the highest MCCA yield (n-caproic acid + n-octanoic acid) at 2.02 g COD/L, which was 4.9 times higher than the control. This improvement in MCCA production induced by NZVI was attributed to several factors. Firstly, NZVI facilitated the oxidation of acetaldehyde, leading to its reduced accumulation in the system (from 18.4 % to 5.8 %), due to the optimized chemical environment created by NZVI corrosion, including near-neutral pH and a more reductive oxidation-reduction potential (ORP). Additionally, the inherent conductivity property of NZVI and the additional Fe ions released during corrosion improved the electron transfer efficiency between CEB. Lastly, both the composition of microbial communities and the abundance of unique enzyme genes confirmed the selective stimulation of NZVI on the reverse β-oxidation (RBO) pathway. These findings provide valuable insights into the role of NZVI in CEB metabolism and its potential application for enhancing MCCA production in CE bioreactors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The co-contamination of arsenic (As) and cadmium (Cd) in rice fields presents a global imperative for resolution. However, understanding the complex microbially driven geochemical processes and network connectivity crucial for As and Cd bioavailability under the frequent redox transitions in rice fields remains limited. Here, we conducted a series of microcosm experiments, using flooding and drainage, alongside fertilization treatments to emulate different redox environment in paddy soils. Soil As significantly reduced in drained conditions following applications of biochar or calcium-magnesium-phosphate (CMP) fertilizers by 26.3 % and 31.2 %, respectively, with concurrent decreases in Cd levels. Utilizing geochemical models, we identified the primary redox cycles dynamically altering during flooding (Fe and S cycles) and drainage (Fe, Mn, and N cycles). PLS-SEM elucidated 76 % and 61 % of the variation in Cd and As through Mn and N cycles. Functional genes implicated in multi-element cycles were analyzed, revealing a significantly higher abundance of assimilatory N reduction genes (nasA, nirA/B, narB) in drained soil, whereas an increase in ammonia-oxidizing genes (amoA/B) and a decrease in nitrate reduction to ammonium genes were observed after CMP fertilizer application. Biochar application led to significant enrichment of the substrate-binding protein of the Mn transport gene (mntC). Moreover, Fe transport genes were enriched after biochar or CMP application compared to drained soils. Among 40 high-quality metagenome-assembled genomes (MAGs), microbial predictors associated with low Cd and As contents across different treatments were examined. Bradyrhizobacea harbored abundant Mn and Fe III transport genes, while Nitrososphaeraceae carried nitrification-related genes. Two MAGs affiliated with Caulobacteraceae, carrying diverse Fe transport genes, were enriched in biochar-applied soils. Therefore, applying CMP fertilizer or biochar in aerobic rice fields can synergistically reduce the bioavailability of Cd and As by specifically enhancing the circulation of essential elements., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Serious arsenic (As) contaminations could commonly result from the oxidative dissolution of As-containing sulfide minerals, such as arsenopyrite (FeAsS). Pyrite (Py) and calcite (Cal) are two typically co-existing reactive minerals and represent different geological scenarios. Previous studies have shown that a high proportion of Py can generate a stronger galvanic effect and acid dissolution, thereby significantly promoting the release of arsenic. However, this conclusion overlooks calcite's antagonistic effect on the release of As in the natural environment. That antagonistic effect could remodel the linear relationship of pyrite on the oxidative dissolution of arsenopyrite, thus altering the environmental risk of As. We examined As release from arsenopyrite along a gradient of Py to Cal molar ratios (Py:Cal). The results showed that the lowest As release from arsenopyrite was surprisingly found in co-existing Py and Cal systems than in the singular Cal system, let alone in the singular Py system. This phenomenon indicated an interesting possibility of Py assistance to Cal inhibition of As release, though Py has always been regarded as a booster, also evidenced in this research, for As release from arsenopyrite. In singular systems of Py and Cal, As continued to be released for 60 days. However, in co-existing Py and Cal systems, As was released non-linearly in three stages over time: initial release (0-1 Day), immobilization (1-15 Days), and subsequent re-release (>15 Days). This is a new short-term natural attenuation stage for As, but over time, this stage gradually collapses. During the re-release stage (> 15 Days), a higher molar ratio of Py:Cal (increasing from 1:9 to 9:1) results in a lower rate constant k (mg·L -1 ·h -1 ) of As release (range from 0.0011 to 0.0002), and a higher abundance of secondary minerals formed (up to 26 mg/g goethite and hematite at Py: Cal=9:1). This demonstrates that increasing the Py:Cal molar ratio results in the formation of more secondary minerals which compensate for the higher potential antagonistic mechanisms generated by pyrites, such as acid dissolution and galvanic effect. These results explain the mechanisms of the high-risk characteristics of As both in acidic mine drainage and karst aquifers and discover the lowest risk in pyrite and calcite co-existing regions. Moreover, we emphasize that reactive minerals are important variables that can't be ignored in predicting As pollution in the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Microbes possessing electron transfer capabilities hold great promise for remediating subsurface contaminated by redox-active radionuclides such as technetium-99 ( 99 TcO 4 - ) through bio-transformation of soluble contaminants into their sparingly soluble forms. However, the practical application of this concept has been impeded due to the low electron transfer efficiency and long-term product stability under various biogeochemical conditions. Herein, we proposed and tested a pyrite-stimulated bio-immobilization strategy for immobilizing ReO 4 - (a nonradioactive analogue of 99 TcO 4 - ) using sulfate-reducing bacteria (SRB), with a focus on pure-cultured Desulfovibrio vulgaris. Pyrite acted as an effective stimulant for the bio-transformation of ReO 4 - , boosting the removal rate of ReO 4 - (50 mg/L) in a solution from 2.8 % (without pyrite) to 100 %. Moreover, the immobilized products showed almost no signs of remobilization during 168 days of monitoring. Dual lines of evidence were presented to elucidate the underlying mechanisms for the pyrite-enhanced bio-activity. Transcriptomic analysis revealed a global upregulation of genes associated with electron conductive cytochromes c network, extracellular tryptophan, and intracellular electron transfer units, leading to enhanced ReO 4 - bio-reduction. Spectroscopic analysis confirmed the long-term stability of the bio-immobilized products, wherein ReO 4 - is reduced to stable Re(IV) oxides and Re(IV) sulfides. This work provides a novel green strategy for remediation of radionuclides- or heavy metals-contaminated sites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Offshore aquaculture's explosive growth improves the public food chain while also unavoidably adding new pollutants to the environment. Consequently, the protection of coastal marine eco-systems depends on the efficient treatment of wastewater from marine aquaculture. For the sulfamethazine (SMZ) of representative sulfonamides and total organic pollutants removal utilizing in-situ high salinity, this work has established an inventive and systematic treatment process coupled with iron-electrode electrochemical and ultrafiltration. Additionally, the activated dithionite (DTN) was being used in the electrochemical and ultrafiltration processes with electricity/varivalent iron (Fe II /Fe III ) and ceramic membrane (CM), respectively, indicated by the notations DTN@iron-electrode/EO-CM. Quenching experiments and ESR detection have identified plenty of reactive species including SO 4 ·- , ·OH, 1 O 2 , and O 2 ·- , for the advanced treatment. In addition, the mass spectrometry (MS) and the Gaussian simulation calculation for these primary reaction sites revealed the dominate SMZ degradation mechanisms, including cleavage of S-N bond, hydroxylation, and Smile-type rearrangement in DTN@iron-electrode/EO process. The DTN@iron-electrode/EO effluent also demonstrated superior membrane fouling mitigation in terms of the CM process, owing to its higher specific flux. XPS and SEM confirmed the reducing membrane fouling, which showed the formation of a loose and porous cake layer. This work clarified diverse reactive species formation and detoxification with DTN@iron-electrode/EO system and offers a sustainable and efficient process for treating tailwater from coastal aquaculture., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this study, a UV-driven photocatalytic activation of peroxymonosulfate (PMS) system was constructed using bimetallic metal-organic frameworks to degrade pharmaceuticals and personal care products (PPCPs). Mn-MIL-53(Fe) was successfully synthesised by adjusting the doping ratio of Mn using solvothermal method. The removal of ibuprofen (IBP) by UV/Mn-MIL-53(Fe)/PMS process was as high as 79.7% in 30 min with a Mn doping ratio of 1.0 (molar ratio of Mn to Fe), and the reaction rate constant was 26.9% higher than undoped. Mn-MIL-53(Fe) had been systematically characterized in terms of its physical structure, microscopic morphology, surface functional groups and photoelectric properties. The mechanism investigation revealed that the cycling of Mn and Fe accelerated the rate of electron transfer in the system, which significantly increased the activation efficacy of PMS to generate more hydroxyl and sulfate radicals for IBP degradation. A total of 13 transformation products were detected during the degradation of IBP by the UV/Mn-MIL-53(Fe)/PMS process. Theoretical calculations were used to predict the sites on the IBP molecule that were vulnerable to attack, and four possible degradation pathways were deduced. The excellent stability and efficient catalytic properties of Mn-MIL-53(Fe) provided a promising solution to the problem of water treatment contaminated with PPCPs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Fenton/Fenton-like reaction induced chemical dynamic therapy (CDT) has been widely recognized in tumor therapy. Due to the low efficiency of conversion from high-valent metal ions (M ( n +1)+ ) to low-valent ions (M n + ) in the Fenton/Fenton-like catalytic process, enhancing the conversion efficiency safely and effectively would create a great opportunity for the clinical application of CDT. In the study, a universal nanoreactor (NR) consisting of liposome (Lip), tumor cell membrane (CM), and bis(2,4,5-trichloro-6-carboxyphenyl) oxalate (CPPO) is developed to tackle this challenge. The CPPO was first discovered to decompose under weak acidity and H 2 O 2 conditions to generate carboxylic acids (R'COOH) and alcohols (R'OH) with reducibility, which will reduce M ( n +1)+ to M n + and magnify the effect of CDT. Furthermore, glucose oxidase (GOx) was introduced to decompose glucose in tumor and generate H 2 O 2 and glucose acid, which promote the degradation of CPPO, further strengthening the efficiency of CDT, leading to a butterfly effect. This demonstrated that the butterfly effect triggered by NR and GOx encourages Fenton/Fenton-like reactions of Fe 3 O 4 and MoS 2 , thereby enhancing the tumor inhibition effect. The strategy of combining GOx and CPPO to strengthen the Fenton/Fenton-like reaction is a universal strategy, which provides a new and interesting perspective for CPPO in the application of CDT, reflecting the exquisite integration of Fenton chemistry and catalytic medicine., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Given the potential dangers of thiram to food safety, constructing a facile sensor is significantly critical. Herein, we presented a colorimetric sensor based on glutathione‑iron hybrid (GSH-Fe) nanozyme for specific and stable detection of thiram. The GSH-Fe nanozyme exhibits good peroxidase-mimicking activity with comparable Michaelis constant (K m  = 0.551 mM) to the natural enzyme. Thiram pesticides can specifically limit the catalytic activity of GSH-Fe nanozyme via surface passivation, causing the change of colorimetric signal. It is worth mentioning that the platform was used to prepare a portable hydrogel kit for rapid qualitative monitoring of thiram. Coupling with an image-processing algorithm, the colorimetric image of the hydrogel reactor is converted into the data information for accurate quantification of thiram with a detection limit of 0.3 μg mL -1 . The sensing system has good selectivity and high stability, with recovery rates in fruit juice samples ranging from 92.4% to 106.9%., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study developed a novel process named sulfidated zero-valent iron/peroxymonosulfate/visible light irradiation (S-mZVI/PMS/vis) for enhanced organic pollutant degradation. The S-mZVI/PMS/vis process exhibited remarkable catalytic activity, achieving a 99.6% rhodamine B (RhB) removal within 10 min. The degradation rate constant of RhB by the S-mZVI/PMS/vis process was found to be 6.49 and 79.84 times higher than that by the S-mZVI/PMS and PMS/vis processes, respectively. Furthermore, the S-mZVI/PMS/vis process worked efficiently across a wide pH range (3.0-9.0), and the result of five-cycle experiments demonstrated the excellent reusability and stability of S-mZVI. Radical quenching tests and electron paramagnetic resonance analysis indicated that ·O 2 - , 1 O 2 , and h +  significantly contributed to the degradation of RhB through the S-mZVI/PMS/vis process. The visible light irradiation increased the Fe 2+ concentration, improved the Fe 3+ /Fe 2+ cycle, and consequently enhanced the PMS decomposition, reactive species production, and RhB degradation. This work offers a promising strategy to highly efficiently activate PMS for organic pollutants elimination from aqueous solutions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Doping with nitrogen atoms can improve the catalytic activity of activated carbon cathodes in electro-Fenton systems, but currently there is a lack of understanding of the catalytic mechanism, which limits the further development of high-performance activated carbon cathodes. Here, a multi-scale exploration was conducted using density functional theory and experimental methods to investigate the mechanism of different nitrogen doping types promoting the redox performance of activated carbon cathodes and the degradation of phenol. The density functional theory results indicate that the introduction of nitrogen atoms enhances the binding ability between carbon substrates and oxygen-containing substances, promotes the localization of surrounding electrons, and makes it easier for O 2 to bind with protons and catalyze the hydrogenation reaction of *OOH. Due to its weak binding ability with oxygen-containing substances, AC is difficult to form H 2 O 2 , resulting in a tendency towards the 4e - ORR pathway. The binding energy between graphite-N carbon substrate and pyridine-N carbon substrate with *OOH is closer to the volcano top, so graphite n and pyridine n can better promote the selectivity of activated carbon for 2e-ORR. In addition, the calculation results also indicate that pyrrole-N and graphite-N are more capable of catalyzing the reaction energy barrier between ·OH and phenol. Finally, the simulation results were used to guide the modification of nitrogen doped activated carbon and experimental verification was carried out. The degradation results of phenol confirmed the efficient synergistic effect between different types of nitrogen doping, and the NAC-800 electrode exhibited efficient and stable characteristics. This work provides a guiding strategy for further developing stable and highly selective activated carbon cathode materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

The FeOCl-based photo-Fenton heterojunction catalyst holds great promise for effective water pollution treatment. A novel heterojunction FeOCl/MOF-In 2 S 3 (F/M-I) was fabricated by coating hollow MOF-In 2 S 3 nanoflowers onto the surface of FeOCl. Under the optimal conditions, the maximum photo-Fenton degradation rate constants of FeOCl/MOF-In 2 S 3 for oxytetracycline (OTC) within 20 min is 0.88192 L mg -1 ·min -1 , which are 3.2 and 2.5 times that of pure FeOCl (0.27357 L mg -1 ·min -1 ) and MOF-In 2 S 3 (0.35222 L mg -1 ·min -1 ). Density functional theory (DFT) results confirm that the electron-rich nature of MOF-In 2 S 3 accelerates the cycle between Fe (III)/Fe (II)of FeOCl, promoting H 2 O 2 adsorption by FeOCl/MOF-In 2 S 3 and generating more hydroxyl radicals (·OH) for pollutant degradation. Based on the results of DFT, combined with the results of the reactive oxidation species scavenger (ROSs), electron paramagnetic resonance (EPR) and Mott-Schottky curves, the separation and transfer behavior of photoexcited charges in FeOCl/MOF-In 2 S 3 heterojunction and the possible photocatalytic degradation mechanism were investigated. Finally, a Z-scheme heterostructure is proposed to elucidate the catalytic mechanism. This study provides a new perspective on designing and synthesizing semiconductor materials for water treatment by photo-Fenton catalysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

In this study, bimetallic Cu-Fe nanoparticles were synthesized using the green approach with Piper betle leaves, and the removal efficiency of one of the pharmaceutical compounds, Atorvastatin, was investigated. UV, SEM, FTIR, EDAX, particle size, and zeta potential measurements were used to confirm nanoparticle fabrication. The removal efficiency of Atorvastatin (10 mg/L) by bimetallic Cu-Fe nanoparticles was 67% with a contact time of 30 min at pH 4, the adsorbent dosage of 0.2 g/L, and stirring at 100 rpm. Piper betle bimetallic Cu-Fe nanoparticles have demonstrated excellent stability, reusability, and durability, even after being reused five times. Furthermore, the synthesized bimetallic Cu-Fe nanoparticles demonstrated remarkable antimicrobial properties against gram-negative strains such as Escherichia coli and Klebsiella pneumoniae, gram-positive strains such as Staphylococcus aureus and Bacillus subtilis, and fungi such as Aspergillus niger. In addition, the antioxidant properties of the synthesized bimetallic Cu-Fe nanoparticles were assessed using the DPPH radical scavenging assay. The results indicated that the nanoparticles had good antioxidant activity. Thus, using Piper betle extract to make Cu-Fe nanoparticles made the procedure less expensive, chemical-free, and environmentally friendly, and the synthesized bimetallic Cu-Fe nanoparticles helped remove the pharmaceutical compound Atorvastatin from wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Co-pyrolysis is a promising technology for industrial organic waste to utilize their unique resource and energy properties for efficient conversion into valuable products. This study was the first time to characterize the co-pyrolysis of waste textiles with Ca-rich industrial sludge and Fe-rich industrial sludge on a laboratory-scale fixed bed. The properties, mechanisms, gas, oil and carbon production were investigated as a function of temperature and mixing type. Co-pyrolysis increased the total weight loss from 50.05 % to 69.81 % for Ca-rich industrial sludge mixed with 50 % waste textiles and from 49.13 % to 70.01 % for Fe-rich industrial sludge mixed with 50 % waste textiles. The activation energy of co-pyrolysis was approximately 50 % lower compared to the pyrolysis of waste textiles alone. The optimal reaction model for the different reaction stages for all samples was three diffusion (D3). Co-pyrolysis resulted in lower CO and CO 2 emission temperatures of about 25-110 °C and produced more short-chain organic compounds (C < 10). Co-pyrolysis produced more aldehydes and ketones organics. Moreover, co-pyrolysis char exhibited an elevated level of fatty alkyl side chains and bridge branching, as well as higher degrees of aromatization and stability. This study offers valuable insights into the potential application of pyrolysis for the management of Ca/Fe-rich industrial sludge and waste textiles, thereby serving as a basis for future utilization endeavors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Recently, photocatalysis combined peroxydisulfate activation under visible light (PC-PDS/Vis) was developed as a promising technology for removing antibiotics in water. Herein, Mn doped FeOOH (Mn-FeOOH) nanoclusters were grown in-situ on the surface of graphitic carbon nitride nanosheets (CNNS) using a wet chemical method, which served as a visible-light-driven photocatalyst for peroxydisulfate (PDS) activation. Photovoltaic property characterizations revealed that Mn-FeOOH/CNNS owned superior light capture ability and carrier separation efficiency. According to DFT calculations, the synergistic effect between Mn and Fe species was proved to enhance the adsorption and activation of PDS. 99.7% of tetracycline (TC) was rapidly removed in 50 min in the PC-PDS/Vis system. In addition, Mn-FeOOH/CNNS exhibited high recycling stability with low iron leaching, attributed to the interaction between Mn-FeOOH clusters and carbon species. Quenching experiments and electron spin resonance (ESR) tests unveiled that • O 2 - played a significant role in TC removal, while • OH and SO 4 •- acted as additional roles contributing to the overall process. These findings given a new strategy for antibiotics degradation by photocatalysis, offering deeper insights for the advancement of sustainable and cutting-edge wastewater treatment technologies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

We describe a non-chromatographic, ligand-free platform for the efficient purification of recombinant human lactoferrin (LF). The platform consists of a [metal:chelator] complex precipitate in the presence of osmotically active polyethylene glycol 6000 (PEG-6000). Purification is achieved in three stages. Following formation of the complex, LF is captured under neutral conditions by the aggregated complexes (Step I), a washing step follows (Step II) and then, (Step III) LF is extracted in pure form with 100 mM tribasic Na citrate buffer (pH 7). Of the four complexes investigated, [bathophenanthroline (batho) 3 :Fe 2+ ] was determined to be the most efficient. LF is recovered with high yield (∼90%, by densitometry) and purity (≥97%, by SDS polyacrylamide gel electrophoresis (SDS-PAGE)) from an artificial contamination background comprising E. coli lysate proteins. Purified LF is demonstrated to be monomeric by dynamic light scattering (DLS); to preserve its native secondary structure by circular dichroism (CD) spectroscopy; and, as apo-LF, to efficiently inhibit bacterial growth. Process yield is not affected by a 45-fold increase in LF concentration from 0.2 to 9 mg/mL. We provide evidence that protein capture relies on [cation:π] interactions between the lysine and arginine residues of LF with the fully aromatic [(batho) 3 :Fe 2+ ] complexes. The use of [metal:chelator] complex aggregates is demonstrated to provide an economical and efficient avenue for LF purification., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Peroxidase-like (POD-like) as a kind of new Fenton-like catalyst can effectively activate H 2 O 2 to degrade organic pollutants in water, but improving the catalytic activity and stability of POD-like remains a challenging task. Here, we synthesized a novel dual single-atom nanoenzyme (DSAzyme) FeMn/N-CNTs with Fe-N 4 and Mn-N 4 bimetallic single-atom active centers by mimicking the active centers of natural enzymes and taking advantage of the synergistic effect between the dual metals. FeMn/N-CNTs DSAzyme showed significantly enhanced POD-like activity compared to monometallic-loaded Fe/N-CNTs and Mn/N-CNTs. Within the FeMn/N-CNTs/H 2 O 2 system, bisphenol A (BPA) could be removed 100 % within 20 min. DFT calculations show that Mn-N 4 in FeMn/N-CNTs can readily adsorb negatively charged BPA molecules and capture electrons. Meanwhile, Fe-N 4 sites can easily adsorb H 2 O 2 molecules, leading to their activation and splitting into strongly oxidizing hydroxyl radicals (·OH). Throughout this process, electrons are continuously recycled in BPA → Mn-N 4 → Fe-N 4 → H 2 O 2 , effectively promoting the regeneration of Fe 2+ . Practical studies on wastewater and cycling experiments have demonstrated the great potential of this method for remediating water environments., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Basalt fiber (BF) with modification of iron (Fe-MBF) and calcium (Ca-MBF) were filled into constructed wetland-microbial fuel cell (CW-MFC) for innovative comparison of improved performance under perfluorooctanoic acid (PFOA) exposure. More enhancement on nitrogen and phosphorus removal was observed by Fe-MBF than Ca-MBF, with significant increase of ammonium (NH 4 + -N) removal by 3.36-5.66 % (p < 0.05) compared to control, even under PFOA stress. Markedly higher removal efficiency of PFOA by 4.76-8.75 % (p < 0.05) resulted from Fe-MBF, compared to Ca-MBF and control BF groups. Besides, superior electrochemical performance was found in Fe-MBF group, with maximum power density 28.65 % higher than control. Fe-MBF caused higher abundance of dominant microbes on electrodes ranged from phylum to family. Meanwhile, ammonia oxidizing bacteria like Nitrosomonas was more abundant in Fe-MBF group, which was positively correlated to NH 4 + -N and total nitrogen removal. Some other functional genera involved in denitrification and phosphorus-accumulation were enriched by Fe-MBF on electrodes and MBF carrier, including Dechloromonas, Candidatus&#95;Competibacter, and Pseudomonas. Additionally, there were more biomarkers in Fe-MBF group, like Pseudarcobacter and Acidovorax, conducive to nitrogen and iron cycling. Most functional genes of nitrogen, carbon, and sulfur metabolisms were up-regulated with Fe-MBF filling, causing improvement on nitrogen removal., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Iron-based catalysts for peroxymonosulfate (PMS) activation hold considerable potential in water treatment. However, the slow conversion of Fe(III) to Fe(II) restricts its large-scale application. Herein, an iron phosphate tungsten boride composite (FePO 4 /WB) was synthesized by a simple hydrothermal method to facilitate the Fe(III)/Fe(II) redox cycle and realize the efficient degradation of neonicotinoid insecticides (NEOs). Based on electron paramagnetic resonance (EPR) characterization, scavenging experiments, chemical probe approaches, and quantitative tests, both radicals (HO • and SO 4 ⋅- ) and non-radicals ( 1 O 2 and Fe(IV)) were produced in the FePO 4 /WB-PMS system, with relative contributions of 3.02 %, 3.58 %, 6.24 %, and 87.16 % to the degradation of imidacloprid (IMI), respectively. Mechanistic studies revealed that tungsten boride (WB) promoted the reduction of FePO 4 , and the generated Fe(II) dominantly activated PMS through a two-electron transfer to form Fe(IV), while a minority of Fe(II) engaged in a one-electron transfer with PMS to produce SO 4 ⋅- , HO • , and 1 O 2 . In addition, four degradation pathways of NEOs were proposed by analyzing the byproducts using UPLC-Q-TOF-MS/MS. Besides, seed germination experiments revealed the biotoxicity of NEOs was significantly reduced after degradation via the FePO 4 /WB-PMS system. Meanwhile, the recycling experiments and continuous flow reactor experiments showed that FePO 4 /WB exhibited high stability. Overall, this study provided a new perspective on water remediation by Fenton-like reaction. ENVIRONMENTAL IMPLICATION: Neonicotinoids (NEOs) are a type of insecticide used widely around the world. They've been found in many aquatic environments, raising concerns about their possible negative effects on the environment and health. Iron-based catalysts for peroxymonosulfate (PMS) activation hold great promise for water purification. However, the slow conversion of Fe(III) to Fe(II) restricts its large-scale application. Herein, iron phosphate tungsten boride composite (FePO 4 /WB) was synthesized by a simple hydrothermal method to facilitate the Fe(III)/Fe(II) redox cycle and realize the efficient degradation of NEOs. The excellent stability and reusability provided a great prospect for water remediation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Neonicotinoids pose significant environmental risks due to their widespread use, persistence, and challenges in elimination. This study explores the effectiveness of Fe/Mn biochar in enhancing the removal efficiency of neonicotinoids in recirculating constructed wetlands (RCWs). Results demonstrated that incorporating Fe/Mn biochar into RCWs significantly improved the removal of COD, NH 4 + -N, TN, TP, imidacloprid (IMI), and acetamiprid (ACE). However, the simultaneous presence of IMI and ACE in the RCWs hindered the elimination of NH 4 + -N, TN, and TP from wastewater. The enhanced removal of nutrients and pollutants by Fe/Mn biochar was attributed to its promotion of carbon, nitrogen, and phosphorus cycling in RCWs, along with its facilitation of the adsorption and biodegradation of IMI and ACE. Metagenomics analysis demonstrated that Fe/Mn biochar altered the structure and diversity of microbial communities in RCWs. A total of 17 biodegradation genes (BDGs) and two pesticide degradation genes (PDGs) were identified within RCWs, with Fe/Mn biochar significantly increasing the abundance of BDGs such as cytochrome P450. The potential host genera for these BDGs/PDGs were identified as Betaproteobacteria, Acidobacteria, Nitrospiraceae, Gemmatimonadetes, and Bacillus. This study offers valuable insights into how Fe/Mn biochar enhances pesticide removal and its potential application in constructed wetland systems for treating pesticide-contaminated wastewater., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. No interests to declare., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ball-milled plastic char supported nano zero-valent iron (nZVI@BMPC) and their application combined with anaerobic sludge for microbial dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) were investigated. The XRD and FTIR analysis proved composition of zero valent states of iron, and the BET and SEM analysis showed that nZVI was uniformly distributed on the surface of BMPC. Successive addition of 1000 mg/L sodium lactate and nZVI@BMPC enhanced the acclamation of anaerobic sludge and resulted in the degradation of 4-CP within 80 days. The acclimated consortium with nZVI@BMPC completely degraded 2,4,6-TCP into CH 4 and CO 2 , and the key dechlorination route was through 4-CP dechlorinaion and mineralization. The degradation rate of 2,4,6-TCP with nZVI@BMPC was 0.22/d, greater than that without nZVI@BMPC. The dechlorination efficiency was enhanced in the Fe 2+ /Fe 3+ system controlled by nZVI@BMPC and iron-reducing bacteria. Metagenomic analysis result showed that the dominant de-chlorinators were Chloroflexi sp., Desulfovibrio, and Pseudomonas, which could directly degrade 2,4,6-TCP to 4-CP, especially, Chloroflexi bacterium could concurrently be used to mineralize 4-CP. The relative abundance of the functional genes cprA, acoA, acoB, and tfdB increased significantly in the presence of the nZVI@BMPC. This study provides a new strategy can be a good alternative for possible application in groundwater remediation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Extracellular electron transfer was essential for degrading recalcitrant pollutants by anaerobic digestion (AD). Therefore, existing studies improved AD efficiency by enhancing the electron transfer from microbes-to-pollutants or inter-microbes. This study synthesized a novel Fe, N co-doped biochar (Fe, N-BC), which could enhance both the microbes-to-pollutants and inter-microbes electron transfer in AD. Detailed characterization data indicated that Fe, N-BC has an ordered mesoporous structure, high specific surface area (463.46 m 2 /g), and abundant redox functional groups (Fe 2+ /Fe 3+ , pyrrolic-N), which translate into excellent biocompatibility and electrochemical properties of Fe, N-BC. By adding Fe, N-BC, the stability and efficiency of the medium-temperature AD system in the treatment of methyl orange (MO) wastewater were improved: obtained a high degradation efficiency of MO (96.8 %) and enhanced the methane (CH 4 ) production by 65 % compared to the control group. Meanwhile, Fe, N-BC reduced the accumulation of volatile fatty acids in the AD system, and the activity of anaerobic granular sludge electron transport system and coenzyme F 420 was enhanced. In addition, Fe, N-BC showed positive enrichment of azo dyes decolorization bacteria (Georgenia) and direct interspecies electron transfer (DIET) synergistic partners (Syntrophobacter, Methanosarcina). Overall, the rapid degradation of MO and enhanced CH 4 production in AD systems by Fe, N-BC is associated with enhancing two electronic pathways, i.e., microbes to MO and DIET between syntrophic bacteria and methanogenic archaea. This study introduced an enhanced "two-pathways of electron transfer" theory, realized by Fe, N-BC. These findings provided new insights into the interactions within AD systems and offer strategies for enhancing their performance with recalcitrant pollutants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Low-dosage nitrate pollutants can contribute to eutrophication in surface water bodies, such as lakes and reservoirs. This study employed assembled denitrifying bacterial-fungal communities as bio-denitrifiers, in combination with zero-valent iron (ZVI), to treat micro-polluted water. Immobilized bacterial-fungal mixed communities (IBFMC) reactors demonstrated their ability to reduce nitrate and organic carbon by over 43.2 % and 53.7 %, respectively. Compared to IBFMC reactors, IBFMC combined with ZVI (IBFMC@ZVI) reactors exhibited enhanced removal efficiencies for nitrate and organic carbon, reaching the highest of 31.55 % and 17.66 %, respectively. The presence of ZVI in the IBFMC@ZVI reactors stimulated various aspects of microbial activity, including the metabolic processes, electron transfer system activities, abundance of functional genes and enzymes, and diversity and richness of microbial communities. The contents of adenosine triphosphate and electron transfer system activities enhanced more than 5.6 and 1.43 folds in the IBFMC@ZVI reactors compared with IBFMC reactors. Furthermore, significant improvement of crucial genes and enzyme denitrification chains was observed in the IBFMC@ZVI reactors. Iron played a central role in enhancing microbial diversity and activity, and promoting the supply, and transfer of inorganic electron donors. This study presents an innovative approach for applying denitrifying bacterial-fungal communities combined with iron enhancing efficient denitrification in micro-polluted water., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Developing the efficient nanozymes for reactive oxygen species (ROS)-mediated highly potent tumor catalytic therapy has become a great challenge. In this study, we prepared the DNA-Fe, -FeAg, and -FeCuAg nanocluster (NCs) using the G-/C-rich single-stranded DNA (ssDNA) templates. The steady-state kinetic and the catalytic performances and mechanisms of DNA-metal NCs were first systematically investigated. The results indicated that c-kit-TBA-Fe, c-kit-TBA-FeAg, and c-kit-TBA-FeCuAg NCs exhibited the high peroxidase-like activity. All of three types of NCs presented the higher affinity to the substrate TMB and better storage stability at 4 °C than horseradish peroxidase (HRP). Moreover, c-kit-TBA-FeAg and c-kit-TBA-FeCuAg NCs presented the 6.7- and 4.7-fold stronger affinity to TMB than c-kit-TBA-Fe, respectively. However, the maximum reaction rate (V max ) of c-kit-TBA-FeCuAg NCs with H 2 O 2 was the largest, which promoted the generation of much more • OH in the reaction system. More importantly, c-kit-TBA-FeCuAg NCs were able to deplete largely the intracellular GSH and thus generate lots of endogenous ROS in HeLa cells, thereby exhibiting the significant and specific in vitro cancer cells toxicity. Therefore, c-kit-TBA-FeCuAg NCs, with peroxidase-like activity and glutathione (GSH) consumption ability, hold the ROS-based promising therapeutic effects for cancer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Facing complex and variable emerging antibiotic pollutants, the traditional development of functional materials is a "trial-and-error" process based on physicochemical principles, where laborious steps and long timescales make it difficult to accelerate technical breakthroughs. Notably, natural biomolecular coronas derived from highly tolerant organisms under significant contamination scenarios can be used in conjunction with nanotechnology to tackling emerging contaminants of concern. Here, super worms ( Tubifex tubifex ) with high pollutant tolerance were integrated with nano-zero valent iron (nZVI) to effectively reduce the content of 17 antibiotics in wastewater within 7 d. Inspired by the synergistic remediation, nZVI-augmented worms were constructed as biological nanocomposites. Neither nZVI (0.3 to 3 g/L) nor worms (10 4 to 10 5 per liter) alone efficiently degraded florfenicol (FF, as a representative antibiotic), while their composite removed 87% of FF (3 μmol/L). Under antibiotic exposure, biomolecules secreted by worms formed a corona on and modified the nZVI particle surface, enabling the nano-bio interface greater functionality, including responsiveness, enrichment, and reduction. Mechanistically, FF exposure activated glucose-alanine cycle pathways that synthesize organic acids and amines as major metabolites, which were assembled into vesicles and secreted, thereby interacting with nZVI in a biologically response design strategy. Lactic acid and urea formed hydrogen bonds with FF, enriched analyte presence at the heterogeneous interface. Succinic and lactic acids corroded the nZVI passivation layer and promoted electron transfer through surface conjugation. This unique strategy highlights biomolecular coronas as a complex resource to augment nano-enabled technologies and will provide shortcuts for rational manipulation of nanomaterial surfaces with coordinated multifunctionalities., Competing Interests: Competing interests statement:The authors declare no competing interest.

Metal-organic frameworks (MOFs) have shown promise in enhancing the stability of biomolecules. Herein, biliverdin (BVD), a photoacoustic (PA) and fluorescent agent, was immobilized within the pores of NH 2 -MIL-101 (Fe) (FeMOFs) and on the surface of CuBTC crystallites (CuMOFs). MOFs were found to enhance the fluorescence emission and quench the PA intensity of biliverdin. Fluorescence and PA studies, in tandem with DFT simulations, demonstrated that the spectral interactions between MOFs and BVD resulted from interactions between biliverdin and the MOF pores and surfaces in addition to alterations in the HOMO-LUMO energy gap. The MOF internal structure of the MOF played a role in BVD loading, with the FeMOFs enabling greater BVD encapsulation, while CuMOF interactions with BVD primarily took place on the MOF surface. The role of these surface vs pore interactions in the release of biliverdin was explored. This study demonstrates that the effects of the MOF internal structure, surface interactions, and energy interactions should be taken into consideration for biomolecule loading in MOFs.

This study delves into the formation of ferryl ions (Fe(IV)) within the Fe(II)/peroxydisulfate (PDS) process, a pivotal reaction in advanced oxidation processes (AOPs) aimed at organic pollutant removal. Our findings challenge the conventional view that Fe(IV) predominantly forms through oxygen transfer from PDS to Fe(II), revealing that sulfate radicals (SO 4 •- ) play a crucial role in Fe(IV) generation. By employing competitive kinetics, the second-order rate constant for Fe(III) oxidation by SO 4 •- was quantified as 4.58 × 10 8 M -1 s -1 . Factors such as the probe compound concentration, chloride presence, and iron species influence Fe(IV) generation, all of which were systematically evaluated. Additionally, the study explores Fe(IV) formation in various Fe(II)-activated AOPs, demonstrating that precursors like peroxymonosulfate and H 2 O 2 can also directly oxidize Fe(II) to Fe(IV). Through experimental data, kinetic modeling, and oxygen-18 labeling experiments, this research offers a comprehensive understanding of the Fe(II)/PDS system, facilitating the optimization of AOPs for pollutant degradation. Finally, introducing HSO 3 - was proposed to shift the Fe(II)/PDS process from Fe(IV)-dominated to SO 4 •- -dominated mechanisms, thereby enhancing pollutant removal efficiencies.

Textile wastewater, laden with persistent dyes and non-biodegradable organics, poses a challenge for treatment in common effluent treatment plants (CETPs) using conventional methods. Pre-treatment of textile effluents is essential to ensure compatibility with CETPs. The present study employed three-dimensional (3D) aluminum and graphite electrodes for a sequential electro-coagulation and electro-Fenton (EC + EF) process. An experimental plan of 25 experiments was constructed using Taguchi method. The combination resulted in high removal efficiencies: 99.91% for color, 93.20% for chemical oxygen demand (COD), and 91.75% for total organic carbon (TOC) for the operating parameters; for EC, current density (J): 20 mA/cm 2 , time (t): 45 min, speed of rotation (N): 55 rpm; and for EF, current density (J): 25 mA/cm 2 , time (t): 50 min, iron concentration: 40 mg/L. Post-treatment, the wastewater exhibited an enhanced biodegradability index of 0.875, rendering it suitable for CETPs. There was an increase of 11% in the total energy consumption when energy spent during rotation and aeration at the time of EC and EF, respectively, were considered. This energy increases the cost and is not accounted for, in previous research. The energy consumption in kWh per g of COD removed at optimum condition for the hybrid treatment was 0.0314, which is lower than the energy consumption by other electrochemical processes employing plate electrodes. This indicates that 3D electrodes are more energy efficient than plate electrodes. PRACTITIONER POINTS: Hybrid electrochemical processes can be used as pre-treatment method for textile effluents. Three-dimensional electrodes improve removal rates with lower energy consumption. Significant color, COD, and TOC abatement were noted post-hybrid treatment of textile wastewater. Biodegradability of the textile effluent improves after the hybrid treatment., (© 2024 Water Environment Federation.)

Boiled lotus rhizome discs (BLRDs), as common processed products of lotus rhizome, have gained increasing attention from consumers and food manufacturers. However, the blue pigment formed during boiling affects its appearance and reduces the appetite of BLRDs. In this study, the effects of polyphenols and iron contents on blue pigment formation in BLRDs in different regions and months were investigated. Results revealed that blue variation was more serious in March and April of the second year in Wuhan, and polyphenols and iron contents in these two months were significantly higher than those in other months. Then, UPLC and UV-Vis analysis showed that polyphenols causing the formation of blue pigment in BLRDs were L-dopa, gallocatechin, catechin, epigallocatechin, chlorogenic acid and epicatechin, among which L-dopa (52.450 mg/100 g in fresh lotus rhizome (FLR)) and gallocatechin (36.210 mg/100 g in FLR) possessed the greatest effect. Moreover, the ESI-Q-TOF-MS analysis of L-dopa-iron chelate and gallocatechin-iron chelate suggested that the blue pigment of BLRDs was mainly in the form of bis-complexes under boiling conditions. The study on formation mechanism of blue pigment in BLRDs can provide a reference for lotus rhizome processing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Zero-valent iron (ZVI) applied to the remediation of contaminated groundwater (GW) in situ, especially using engineered permeable reactive barriers (PRBs), has been proven to be an effective reactive material. However, many of ZVI brands do not represent tailored reagents specifically regarding destroying pollutants in GW. Thus, their reactivity towards certain contaminants in GW may vary significantly in a wide range even with different production batches of the same ZVI brand. This issue has rarely been known and consequently not addressed to a higher extend so far. Therefore, this study implemented extensive, long-term column experiments followed by short-term batch experiments for chlorinated volatile organic compounds (cVOCs) degradation for developing a semi-empirical test methodology to thoroughly resolve this pivotal issue by achieving an improved quality assurance guidance regarding proper field-scale emplacement of different ZVI brands and their production batches. The results showed that during column experiments perchloroethylene (PCE) led to a significant degradation up to a certain period but sulfate-reducing microorganisms enhanced the dehalogenation and led approximately to 100 % PCE removal. However, the efficacy varied for different ZVI brands, i.e., Gotthart Maier (GM) and Sponge Iron (Responge®). Furthermore, it could be shown that it might even vary among different production batches of the same ZVI brand. It was also observed that evolution of sulfate-reducing microorganisms may improve the efficacy of PCE degradation vastly that occur at different intensities with different ZVI brands and their respective production batches over time. Further, comparing comprehensive long-term column (k obs  = 0.0488 1/h) and short-term batch experiments (k obs = 0.07794 1/h) as well as refined kinetic analyses (k obs  = 0.0424 1/h) clearly prove that an appropriate guidance protocol for successful full-scale in situ remediation is required for properly select the right ZVI brand and production batch before it is loaded to a PRB in the field., Competing Interests: Declaration of competing interest The authors declared that they have no known competing financial interests or personal relationships, which seem to affect the work reported in this article. We declare that we have no human participants, human data, or human issues. We do not have any individual person's data in any form. The authors declare no competing interests., (Copyright © 2024. Published by Elsevier Ltd.)

This study evaluates the effectiveness of microalgal-based carbon-encapsulated iron nanoparticles (ME-nFe) in the removal of pharmaceutical compounds (PhACs) from water solutions and real municipal effluent at a laboratory scale. The investigated PhACs were chosen to represent different classes of synthetic drugs: antibiotics, anti-inflammatory drugs, antihypertensives, antiepileptics, neuroprotectors, and antidepressants. The adsorbent material was produced through hydrothermal carbonization (225 °C for 3 h), using microalgae grown on wastewater as the carbon source. ME-nFe showed heterogeneity in terms of porosity (with both abundance of macro and mesopores), a total pore volume of 0.65 mL g -1 , a specific surface area of 117 m 2  g -1 and a total iron content of 40%. Laboratory scale adsorption tests (1 g L -1 of nanoparticles with 2 min contact time) showed high removal for the most hydrophobic compounds. Removal efficiencies were high (over 98%) for Irbesartan, Ofloxacin and Diclofenac, promising (over 65-80%) for Clarithromycin, Fluoxetine, Lamotrigine and Metoprolol, but low for Gabapentin-Lactam and Propyphenazone (<20%). Electrostatic interactions between the drugs and the surface of the nanoparticles may account for the observed data, although additional removal mechanisms cannot be ruled out., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Due to the bioavailability and movement of antimony in trophic web, the overexploitation of antimony mine resulted in antimony contamination that harmed the ecology nearby, raising concerns for public health. Whereas, most researches focused on the removal of antimony in the aqueous instead of the immobilization of antimony in the soil. Herein, the immobilized performance of biochar (BC) loaded with nano zero-valent iron (nZVI-BC) on antimony in the soil near the smelting area was researched through pot experiments for the first time, and its stabilization mechanism on antimony was investigated by valent state variation of antimony. The results demonstrated that BC restricted the cation exchange capacity and catalase activity in the soil, while nZVI-BC had a favorable and negative impact on two variables, respectively. The nZVI-BC showed more stable immobilization capacity on antimony over time than BC, whose exchangeable speciation only marginally rose (2%-6%), although the exchangeable speciation of antimony fell both from 15% to 2% after adding the BC and nZVI-BC, The electron attraction force between nZVI-BC and antimony was also intensified owing to the oxidation-reduction process, which was considered as the stabilizing principle of nZVI-BC on antimony in soil. Furthermore, the decreased bioaccumulation factor for the perennial ryegrass (0.46-0.21) and Galinsoga parviflora Cav. (0.26-0.17) stated that the BC effectively mitigated the bioaccumulation risk of antimony., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Bioleaching and Fenton technology are commonly used preconditioning techniques for sludge dewatering. This study compared the dewatering mechanisms of different conditioning technologies. The results showed that bound water, specific resistance to filtration (SRF), and capillary suction time decreased from 3.95 g/g, 6.16 × 10 12  m/kg, and 130.6 s to 3.15 g/g, 2.81 × 10 11  m/kg, and 33 s, respectively, under combined treatment condition. Moreover, the free radicals, including ·OH, O 2 - ·and Fe (Ⅳ), further damaged the cell structure, thus increasing the concentration of DNA in the S-EPS layer. This intense degradation sludge particle size decreased by 15.6% and significantly increased zeta potential. Under the combined technology, the α-helix and β-sheet decreased by 42.2% and 56.5%, respectively, destabilizing the spatial structure of proteins and promoting the release of bound water. In addition, the combined technology decreased (Ala/Lys) ratio in the TB-EPS layer by 67.6%, indicating the weakening of protein water-holding capacity. Moreover, the conversion of oxygen-containing compounds to nonpolar hydrocarbons increased the hydrophobicity of the sludge under a combined treatment, thus enhancing dewatering performance., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Fenton-conditioning is commonly used to improve dewatering ability for municipal biological sludge, however, its application in industries is scarce. In this study, biochar (FT-BC) was successfully synthesized from a Fenton-conditioned landfill leachate biological sludge under oxygen-limited. As compared to the corresponding blank and poly ferric-pretreated biochars (BC and PF-BC), moderate Fenton conditioning of the sludge could enable good removal performance for Cr (Ⅵ) by FT-BC. It was found that the oxygen central free radicals (OCFRs) on the biochar surface was intensively promoted due to Fenton electrophilic addition of ·OH onto the oxygen-containing functional groups in biomass. The amounts of OCFRs correlated positively well with the removal efficiency, indicating these persistent free radicals (PFRs)would mainly responsible for the reductive immobilization of Cr(VI)on the FT-BC surface. This study is expected to provide a new method for reclamation of industrial biological sludges with poor agglomeration by introducing simple Fenton pre-conditioning., Competing Interests: Declaration of competing interest The authors have no competing interests to declare that are relevant to the content of this article., (Copyright © 2024. Published by Elsevier Ltd.)

With fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), this study evaluated the performance of zero-valent iron (ZVI) enhanced anammox process for treating fulvic acids (FA)-containing wastewater and investigated the fate of dissolved organic nitrogen (DON) at the molecular level. The results showed that ZVI increased the total organic carbon (TOC) removal rate of the anammox system by approximately 10% and reduced the organic matter fluorescence intensity by 21%. Specifically, microbial humic-like C1 and terrestrial humic-like C4 components were preferentially degraded by ZVI among the fluorescence components (C1-C4). Moreover, ZVI significantly altered the transformation pathways of DON molecules in anammox. The number of precursors molecular formulas increased from 1617 to 2002, attributed to the elimination of high molecular weight (MW) (>500 Da) molecules. Specifically, DON molecules with high O/C were degraded under the effect of ZVI, while some high MW were resisted. The original products generated from anammox consortia metabolism and FA degradation underwent secondary reactions with ZVI, thereby decreased the O/C of products molecular formulas. Furthermore, anammox process was subjected to the most carboxylic acid reaction, including decarboxylation and reduction of carboxylic acids. For CHON molecules, a significant number of reactions involving the reduction of nitro groups contributed to the reduction of wastewater toxicity, which improved the overall performance., Competing Interests: Declaration of competing interest I acknowledge that I have consulted the Guide for Authors and have prepared the manuscript in compliance with the Publishing Policy as described in the Guide for Authors. This manuscript has not been published or presented elsewhere in part or in entirety and is not under consideration by another journal. This study is the original work of the authors, and all authors mutually agree that it should be submitted to your journal. We have read and understood your journal's policies, and we believe that neither the manuscript nor the study violates any of these. There are no conflicts of interest to declare., (Copyright © 2024. Published by Elsevier Ltd.)

The adsorption layer system has shown great potential as a cost-effective and practical strategy for the recycling and management of excavated rocks containing potentially toxic elements (PTEs). Although this system has been employed in various civil engineering projects throughout Japan, its long-term performance to immobilize PTEs has rarely been investigated. This study aims to evaluate the effectiveness of the adsorption layer system applied in an actual road embankment approximately 11 years after construction. The embankment system is comprised of a layer of excavated arsenic (As)-bearing mudstone built on top of a bottom adsorption layer mixed with an iron (Fe)-based adsorbent. Collection of undisturbed sample was carried out by implementing borehole drilling surveys on the embankment. Batch leaching experiments using deionized water and hydrochloric acid were conducted to evaluate the water-soluble and acid-leachable concentrations of As, Fe, and other coexisting ions. The leaching of As from the mudstone layer was likely induced by As desorption from Fe-oxides/oxyhydroxides naturally present under alkaline conditions, including the oxidation of framboidal pyrite, which was identified as a potential source of As. This was supported by electron probe microanalyzer (EPMA) observations showing the presence of trace amounts of As in framboidal pyrite crystals. Arsenic leached from the mudstone layer was then immobilized by Fe oxyhydroxides found in the adsorption layer. Based on geochemical modeling and X-ray photoelectron spectroscopy (XPS) results, leached As predominantly existed as the negatively charged HAsO 4 2- oxyanion, which is readily sequestered by Fe oxyhydroxides. Moreover, the effectiveness of the adsorption layer was assessed and its lifetime was estimated, and the results revealed it still possessed enough capacity to adsorb As released from mudstone in the foreseeable future. This prediction utilized the maximum potential amount of As that could leach from the excavated rock layer with time., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

An iron-retrofitted anaerobic baffled reactor (ABR) system was developed for the effective treatment of rural wastewater with reduced maintenance demand and aeration costs. Average removal efficiencies of chemical oxygen demand, total nitrogen and total phosphorus of 99.4%, 62.7% and 92.6% were achieved respectively, when the ABR system was operating at steady state. With effective bioreduction of Fe III in the anaerobic chambers, phosphorus was immobilized in the sludge as vivianite, the sole phosphorus-carrying mineral. The Fe III in the recirculated sludge induced Feammox in the ABR reactor, contributing 14.8% to total nitrogen removal. Biophase separation and enrichment of microorganisms associated with iron and nitrogen transformations were observed in the system after Fe dosing, which enhanced the removal of pollutants. The coupling of Feammox and vivianite crystallization to remove nitrogen and phosphorus in an iron-retrofitted ABR would appear to be a promising technology for rural wastewater treatment., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Xiang Cheng reports financial support was provided by National Key Research and Development Program of China. Xiang Cheng reports financial support was provided by Natural Science Foundation of China. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)