Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII). • Pb(II) enhanced Mn(VII) oxidation performance over a wide pH range. • Pb(II) did not alter the pH-rate profile for contaminants oxidation by Mn(VII). • Mn(VII) alone cannot oxidize Pb(II) effectively at pH below 5.0. • Pb(III) plays important roles on enhancing Mn(VII) decontamination process. The permanganate (Mn(VII)) oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds. Nonetheless, only a few studies have been conducted to explore the role of the heavy metals (especially the redox-active ones) during the Mn(VII) oxidation process. In this study, taking Pb(II) as an example, its influence on the Mn(VII) decontamination performance has been extensively investigated. It was found that, with the presence of Pb(II), Mn(VII) could degrade diclofenac (DCF), 2,4-dichlorophenol, and aniline more effectively than without. For instance, over a wide pH range of 4.5–8.0, the dosing of 10 μmol/L Pb(II) accelerated the DCF removal rate from 0.006–0.25 min⁻¹ to 0.05–0.46 min⁻¹ with a promotion factor of 1.9–9.4. Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII) could react with Pb(II) to produce Mn(IV) and Pb(IV) at pH 6.0–8.0, further experiments revealed that Pb(II) did not exert its enhancing effect through promoting the generation of MnO₂, as the reactivity of MnO₂ was poor under the employed pH range. At pH below 5.0, it was interesting to find that, a negligible amount of MnO₂ was formed in the Mn(VII)/Pb(II) system in the absence of contaminants, while once MnO₂ was generated in the presence of contaminants, it could catalyze the Pb(II) oxidation to Pb(IV) by Mn(VII). Collectively, by highlighting the conversion process of Pb(II) to Pb(IV) by either Mn(VII) or MnO₂, the reactive Pb(III) intermediates were proposed to account for the Pb(II) enhancement effect.     

Comparison of different valent iron on anaerobic sludge digestion: Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

• ORP value from −278.71 to −379.80 mV showed indiscernible effects on methane yield. • Fe(II) and Fe(III) promoted more degradation of proteins and amino acids than Fe⁰. • The highest enrichment of Geobacter was noted in samples added with Fe⁰. • Cysteine was accumulated during iron enhanced anaerobic sludge digestion. • Both iron content and valence were important for methane production. This study compared effects of three different valent iron (Fe⁰, Fe(II) and Fe(III)) on enhanced anaerobic sludge digestion, focusing on the changes of oxidation reduction potential (ORP), dissolved organic nitrogen (DON), and microbial community. Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days (d), the maximum methane production rate of sludge samples dosed with respective Fe⁰, Fe(II) and Fe(III) at the same concentration showed indiscernible differences at each iron dose, regardless of the different iron valence. Moreover, their behavior in changes of ORP, DON and microbial community was different: (1) the addition of Fe⁰ made the ORP of sludge more negative, and the addition of Fe(II) and Fe(III) made the ORP of sludge less negative. However, whether being more or less negative, the changes of ORP may show unobservable effects on methane yield when it ranged from −278.71 to −379.80 mV; (2) the degradation of dissolved organic nitrogen, particularly proteins, was less efficient in sludge samples dosed with Fe⁰ compared with those dosed with Fe(II) and Fe(III) after an incubation period of 30 d. At the same dose of 160 mg/L iron, more cysteine was noted in sludge samples dosed with Fe(II) (30.74 mg/L) and Fe(III) (27.92 mg/L) compared with that dosed with Fe⁰ (21.75 mg/L); (3) Fe⁰ particularly promoted the enrichment of Geobacter, and it was 6 times higher than those in sludge samples dosed with Fe(II) and Fe(III) at the same dose of 160 mg/L iron.     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

Application of Fe(VI) in abating contaminants in water: State of art and knowledge gaps

• The properties of Fe(VI) were summarized. • Both the superiorities and the limitations of Fe(VI) technologies were discussed. • Methods to improve contaminants oxidation/disinfection by Fe(VI) were introduced. • Future research needs for the development of Fe(VI) technologies were proposed. The past two decades have witnessed the rapid development and wide application of Fe(VI) in the field of water de-contamination because of its environmentally benign character. Fe(VI) has been mainly applied as a highly efficient oxidant/disinfectant for the selective elimination of contaminants. The in situ generated iron(III) (hydr)oxides with the function of adsorption/coagulation can further increase the removal of contaminants by Fe(VI) in some cases. Because of the limitations of Fe(VI) per se, various modified methods have been developed to improve the performance of Fe(VI) oxidation technology. Based on the published literature, this paper summarized the current views on the intrinsic properties of Fe(VI) with the emphasis on the self-decay mechanism of Fe(VI). The applications of Fe(VI) as a sole oxidant for decomposing organic contaminants rich in electron-donating moieties, as a bi-functional reagent (both oxidant and coagulant) for eliminating some special contaminants, and as a disinfectant for inactivating microorganisms were systematically summarized. Moreover, the difficulties in synthesizing and preserving Fe(VI), which limits the large-scale application of Fe(VI), and the potential formation of toxic byproducts during Fe(VI) application were presented. This paper also systematically reviewed the important nodes in developing methods to improve the performance of Fe(VI) as oxidant or disinfectant in the past two decades, and proposed the future research needs for the development of Fe(VI) technologies.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

Exogenously applied oxalic acid assists in the phytoremediation of Mn by Polygonum pubescens Blume cultivated in three Mn-contaminated soils

• The OA supply significantly increased the water-extractable Mn in all soils. • All OA supply levels promoted plant growth in unexplored soil. • Low OA supply level promoted plant growth in explored and tailing soils. • OA amendment increased the Mn concentrations and total Mn in P. pubescens. • P. pubescens experienced less Mn stress in unexplored soil than in the other two soils. The current study evaluated the effects of oxalic acid (OA) application on the growth and Mn phytoremediation efficiency of Polygonum pubescens Blume cultivated in three different manganese (Mn)-contaminated soils sampled from an unexplored area (US), an explored area (ES) and a tailing area (TS) of the Ertang Mn mine, South China. The supplied levels of OA were 0 (control), 1 (low level), 3 (medium level), and 9 (high level) mmol/kg, referred to as CK, OA1, OA3 and OA9, respectively. The results revealed that the average water-extractable Mn concentrations US, ES and TS amended with OA increased by 214.13, 363.77 and 266.85%, respectively. All OA supply levels increased plant growth and Mn concentrations in US. The low OA supply level increased plant growth in ES and TS; however, contrasting results were found for the medium and high OA supply levels. Plant Mn concentrations and total Mn increased in ES and TS in response to all OA supply levels. Total Mn in the aerial parts increased by 81.18, 44.17 and 83.17% in US, ES and TS, respectively; the corresponding percentages for the whole plants were 81.53, 108.98 and 77.91%, respectively. The rate of ·O₂⁻ production and malondialdehyde (MDA) concentrations increased in response to OA amendment, especially the medium and high OA supply levels in ES and TS. In general, antioxidant enzymes might play a vital role in alleviating Mn stress in plants cultivated in US, while non-enzymatic antioxidants might be the main factor for plants cultivated in ES and TS.     

Fungal diversity and its mechanism of community shaping in the milieu of sanitary landfill

• Ascomycota was the predominant phylum in sanitary landfill fungal communities. • Saprophytic fungi may be of special importance in landfill ecology. • Both richness and diversity of fungal community were lower in leachate than refuse. • Physical habitat partly contributed to the geographic variance of fungal community. • NO₃⁻ was considered the most significant abiotic factor shaping fungal community. Land filling is the main method to dispose municipal solid waste in China. During the decomposition of organic waste in landfills, fungi play an important role in organic carbon degradation and nitrogen cycling. However, fungal composition and potential functions in landfill have not yet been characterized. In this study, refuse and leachate samples with different areas and depths were taken from a large sanitary landfill in Beijing to identify fungal communities in landfills. In high-throughput sequencing of ITS region, 474 operational taxonomic units (OTUs) were obtained from landfill samples with a cutoff level of 3% and a sequencing depth of 19962. The results indicates that Ascomycota, with the average relative abundance of 84.9%, was the predominant phylum in landfill fungal communities. At the genus level, Family Hypocreaceae unclassified (15.7%), Fusarium (9.9%) and Aspergillus (8.3%) were the most abundant fungi found in the landfill and most of them are of saprotrophic lifestyle, which plays a big role in nutrient cycling in ecosystem. Fungi existed both in landfilled refuse and leachate while both the richness and evenness of fungal communities were higher in the former. In addition, fungal communities in landfilled refuse presented geographic variances, which could be partly attributed to physical habitat properties (pH, dissolved organic carbon, volatile solid, NH₄⁺, NO₂⁻ and NO₃⁻), while NO₃⁻ was considered the most significant factor (p<0.05) in shaping fungal community.     

Integration of microbial reductive dehalogenation with persulfate activation and oxidation (Bio-RD-PAO) for complete attenuation of organohalides

•Bio-RD-PAO can effectively and extensively remove organohalides. •Bio-RD alone effectively dehalogenate the highly-halogenated organohalides. •PAO alone is efficient in degrading the lowly-halogenated organohalides. •The impacts of PAO on organohalide-respiring microbial communities remain elusive. •Bio-RD-PAO provides a promising solution for remediation of organohalide pollution. Due to the toxicity of bioaccumulative organohalides to human beings and ecosystems, a variety of biotic and abiotic remediation methods have been developed to remove organohalides from contaminated environments. Bioremediation employing organohalide-respiring bacteria (OHRB)-mediated microbial reductive dehalogenation (Bio-RD) represents a cost-effective and environmentally friendly approach to attenuate highly-halogenated organohalides, specifically organohalides in soil, sediment and other anoxic environments. Nonetheless, many factors severely restrict the implications of OHRB-based bioremediation, including incomplete dehalogenation, low abundance of OHRB and consequent low dechlorination activity. Recently, the development of in situ chemical oxidation (ISCO) based on sulfate radicals (SO₄^·−) via the persulfate activation and oxidation (PAO) process has attracted tremendous research interest for the remediation of lowly-halogenated organohalides due to its following advantages, e.g., complete attenuation, high reactivity and no selectivity to organohalides. Therefore, integration of OHRB-mediated Bio-RD and subsequent PAO (Bio-RD-PAO) may provide a promising solution to the remediation of organohalides. In this review, we first provide an overview of current progress in Bio-RD and PAO and compare their limitations and advantages. We then critically discuss the integration of Bio-RD and PAO (Bio-RD-PAO) for complete attenuation of organohalides and its prospects for future remediation applications. Overall, Bio-RD-PAO opens up opportunities for complete attenuation and consequent effective in situ remediation of persistent organohalide pollution.     

Hexavalent chromium in drinking water: Chemistry,challenges and future outlook on Sn(II)- and photocatalyst-based treatment

• Wide occurrence of Cr(VI) in US source drinking water. • A strong dependence of occurrence on groundwater sources. • Elucidate Redox and equilibrium chemistry of Cr(VI). • Sn(II)-based and TiO₂-based reductive treatments hold extreme promise. • Key challenges include residual waste, Cr(VI) re-generation and socioeconomic drivers. Chromium (Cr) typically exists in either trivalent and hexavalent oxidation states in drinking water, i.e., Cr(III) and Cr(VI), with Cr(VI) of particular concern in recent years due to its high toxicity and new regulatory standards. This Account presented a critical analysis of the sources and occurrence of Cr(VI) in drinking water in the United States, analyzed the equilibrium chemistry of Cr(VI) species, summarized important redox reaction relevant to the fate of Cr(VI) in drinking water, and critically reviewed emerging Cr(VI) treatment technologies. There is a wide occurrence of Cr(VI) in US source drinking water, with a strong dependence on groundwater sources, mainly due to naturally weathering of chromium-containing aquifers. Challenges regarding traditional Cr(VI) treatment include chemical cost, generation of secondary waste and inadvertent re-generation of Cr(VI) after treatment. To overcome these challenges, reductive Cr(VI) treatment technologies based on the application of stannous tin or electron-releasing titanium dioxide photocatalyst hold extreme promise in the future. To moving forward in the right direction, three key questions need further exploration for the technology implementation, including effective management of residual waste, minimizing the risks of Cr(VI) re-occurrence downstream of drinking water treatment plant, and promote the socioeconomic drivers for Cr(VI) control in the future.     

Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

New method for efficient control of hydrogen sulfide and methane in gravity sewers: Combination of NaOH and nitrite

• The combination of NaOH and nitrite was used to control harmful gas in sewers. • Hydrogen sulfide and methane in airspace were reduced by 96.01% and 91.49%. • Changes in sewage quality and greenhouse effect by chemical dosing were negligible. • The strong destructive effects on biofilm slowed down the recovery of harmful gases. • The cost of the method was only 3.92 × 10⁻³ $/m³. An innovative treatment method by the combination of NaOH and nitrite is proposed for controlling hydrogen sulfide and methane in gravity sewers and overcome the drawbacks of the conventional single chemical treatment. Four reactors simulating gravity sewers were set up to assess the effectiveness of the proposed method. Findings demonstrated hydrogen sulfide and methane reductions of about 96.01% and 91.49%, respectively, by the combined addition of NaOH and nitrite. The consumption of NaNO₂ decreased by 42.90%, and the consumption rate of NaOH also showed a downward trend. Compared with a single application of NaNO₂, the C/N ratio of wastewater was increased to about 0.61 mg COD/mg N. The greenhouse effect of intermediate N₂O and residual methane was about 48.80 gCO₂/m³, which is far lower than that of methane without control (260 gCO₂/m³). Biofilm was destroyed to prevent it from entering the sewage by the chemical additives, which reduced the biomass and inhibited the recovery of biofilm activity to prolong the control time. The sulfide production rate and sulfate reduction rate were reduced by 92.32% and 85.28%, respectively. Compared with conventional control methods, the cost of this new method was only 3.92 × 10⁻³ $/m³, which is potentially a cost-effective strategy for sulfide and methane control in gravity sewers.     

The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

Selective targeted adsorption and inactivation of antibiotic-resistant bacteria by Cr-loaded mixed metal oxides

• LDHs and MMOs was synthesized by ultrasound-assisted one-step co-precipitation. • MMOs performs the best for Cr(VI) and E. coli_NDM-1 simultaneous removal. • Possible antibacterial pathways of Cr-MMOs were proposed. Herein we provide a novel high-efficiency nanocomposite for bacterial capture based on mixed metal oxides (MMOs) with deleterious chromium properties. With both the layer structure of layered double hydroxides (LDHs) and the magnetic properties of Fe, MMOs enrich the location of ionic forms on the surface, providing a good carrier for adsorption of the heavy metal Cr(VI). The capacity for adsorption of Cr(VI) by MMOs can be as high as 98.80 mg/g. The prepared Cr(VI)-MMOs achieved extremely expeditious location of gram-negative antibiotic-resistant E. coli_NDM-1 by identifying lipid bilayers. Cr-MMOs with a Cr loading of 19.70 mg/g had the best bactericidal effect, and the concentration of E. coli_NDM-1 was decreased from ~10⁸ to ~10³ CFU/mL after 30 min of reaction. The binding of nitrogen and phosphorus hydrophilic groups to chromate generated realistic models for density functional theory (DFT) calculations. The specific selectivity of MMOs toward bacterial cells was improved by taking Cr(VI) as a transferable medium, thereby enhancing the antibacterial activity of Cr-MMOs. Under the combined action of chemical and physical reactions, Cr(VI)-MMOs achieved high capacity for inactivation of bacteria. Moreover, the metallic elements ratio in Cr-MMOs remained stable in their initial valence states after inactivation. This guaranteed high removal efficiency for both heavy metals and bacteria, allowing recycling of the adsorbent in practical applications.     

Redox reactions of iron and manganese oxides in complex systems

• Mechanisms of redox reactions of Fe- and Mn-oxides were discussed. • Oxidative reactions of Mn- and Fe-oxides in complex systems were reviewed. • Reductive reaction of Fe(II)/iron oxides in complex systems was examined. • Future research on examining the redox reactivity in complex systems was suggested. Conspectus Redox reactions of Fe- and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments. Due to experimental and analytical challenges associated with complex environments, there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems, and most of the studies so far have only focused on simple model systems. To bridge the gap between simple model systems and complex environmental systems, it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation. In this Account, we primarily focused on (1) the oxidative reactivity of Mn- and Fe-oxides and (2) the reductive reactivity of Fe(II)/iron oxides in complex model systems toward contaminant degradation. The effects of common metal ions such as Mn²⁺ , Ca²⁺, Ni²⁺, Cr³⁺ and Cu²⁺, ligands such as small anionic ligands and natural organic matter (NOM), and second metal oxides such as Al, Si and Ti oxides on the redox reactivity of the systems are briefly summarized.     

Sorption mechanisms of diphenylarsinic acid on natural magnetite and siderite: Evidence from sorption kinetics,sequential extraction and extended X-ray absorption fine-structure spectroscopy analysis

• DPAA sorption followed pseudo-secondary and intra-particle diffusion models. • Chemical bonding and intra-particle diffusion were dominant rate-limiting steps. • DPAA simultaneously formed inner- and outer-sphere complexes on siderite. • DPAA predominantly formed occluded inner-sphere complexes on magnetite. • Bidentate binuclear bond was identified for DPAA on siderite and magnetite. Diphenylarsinic acid (DPAA) is both the prime starting material and major metabolite of chemical weapons (CWs). Because of its toxicity and the widespread distribution of abandoned CWs in burial site, DPAA sorption by natural Fe minerals is of considerable interest. Here we report the first study on DPAA sorption by natural magnetite and siderite using macroscopic sorption kinetics, sequential extraction procedure (SEP) and microscopic extended X-ray absorption fine-structure spectroscopy (EXAFS). Our results show that the sorption pseudo-equilibrated in 60 minutes and that close to 50% and 20%–30% removal can be achieved for magnetite and siderite, respectively, at the initial DPAA concentrations of 4–100 mg/L. DPAA sorption followed pseudo-secondary and intra-particle diffusion kinetics models, and the whole process was mainly governed by intra-particle diffusion and chemical bonding. SEP and EXAFS results revealed that DPAA mainly formed inner-sphere complexes on magnetite (>80%), while on siderite it simultaneously resulted in outer-sphere and inner-sphere complexes. EXAFS analysis further confirmed the formation of inner-sphere bidentate binuclear corner-sharing complexes (²C) for DPAA. Comparison of these results with previous studies suggests that phenyl groups are likely to impact the sorption capacity and structure of DPAA by increasing steric hindrance or affecting the way the central arsenic (As) atom maintains charge balance. These results improve our knowledge of DPAA interactions with Fe minerals, which will help to develop remediation technology and predict the fate of DPAA in soil-water environments.