Anaerobic digestion of sludge by different pretreatments: Changes of amino acids and microbial community

•Tryptophan protein, and aromatic protein I/II were the key identified proteins. •Cysteine was more correlated with methane production than other amino acids. •The presence of cysteine can promote methane production and degradation of VFAs. •The presence of cysteine can lower ORP and increase biomass activity. •Predominant Tissierella and Proteiniphilum were noted in pretreated sludge samples. Many studies have investigated the effects of different pretreatments on the performance of anaerobic digestion of sludge. However, the detailed changes of dissolved organic nitrogen, particularly the release behavior of proteins and the byproducts of protein hydrolysis-amino acids, are rarely known during anaerobic digestion of sludge by different pretreatments. Here we quantified the changes of three types of proteins and 17 types of amino acids in sludge samples solubilized by ultrasonic, thermal, and acid/alkaline pretreatments and their transformation during anaerobic digestion of sludge. Tryptophan protein, aromatic protein I, aromatic protein II, and cysteine were identified as the key dissolved organic nitrogen responsible for methane production during anaerobic digestion of sludge, regardless of the different pretreatment methods. Different from the depletion of other amino acids, cysteine was resistant to degradation after an incubation period of 30 days in all sludge samples. Meanwhile, the “cysteine and methionine metabolism (K00270)” was absent in all sludge samples by identifying 6755 Kyoto Encyclopedia of Genes and Genomes assignments of genes hits. Cysteine contributed to the generation of methane and the degradation of acetic, propionic, and n-butyric acids through decreasing oxidation-reduction potential and enhancing biomass activity. This study provided an alternative strategy to enhance anaerobic digestion of sludge through in situ production of cysteine.     

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.     

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.     

Product identification and toxicity change during oxidation of methotrexate by ferrate and permanganate in water

• Oxidation of methotrexate by high-valent metal-oxo species was first explored. • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0. • Ketonization and cleavage of peptide bond were two initial reaction pathways. • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals. • The less biodegradable products exhibited developmental and acute/chronic toxicity. Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M⁻¹ s⁻¹) than Mn(VII) (3.01 M⁻¹ s⁻¹) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.     

Nitrate removal to its fate in wetland mesocosm filled with sponge iron: Impact of influent COD/N ratio

• CW-Fe allowed a high-performance of NO₃^‒-N removal at the COD/N ratio of 0. • Higher COD/N resulted in lower chem-denitrification and higher bio-denitrification. • The application of s-Fe⁰ contributed to TIN removal in wetland mesocosm. • s-Fe⁰ changed the main denitrifiers in wetland mesocosm. Sponge iron (s-Fe⁰) is a porous metal with the potential to be an electron donor for denitrification. This study aims to evaluate the feasibility of using s-Fe⁰ as the substrate of wetland mesocosms. Here, wetland mesocosms with the addition of s-Fe⁰ particles (CW-Fe) and a blank control group (CW-CK) were established. The NO₃^‒-N reduction property and water quality parameters (pH, DO, and ORP) were examined at three COD/N ratios (0, 5, and 10). Results showed that the NO₃^‒-N removal efficiencies were significantly increased by 6.6 to 58.9% in the presence of s-Fe⁰. NH₄⁺-N was mainly produced by chemical denitrification, and approximately 50% of the NO₃^‒-N was reduced to NH₄⁺-N, at the COD/ratio of 0. An increase of the influent COD/N ratio resulted in lower chemical denitrification and higher bio-denitrification. Although chemical denitrification mediated by s-Fe⁰ led to an accumulation of NH₄⁺-N at COD/N ratios of 0 and 5, the TIN removal efficiencies increased by 4.5%‒12.4%. Moreover, the effluent pH, DO, and ORP values showed a significant negative correlation with total Fe and Fe (II) (P<0.01). High-throughput sequencing analysis indicated that Trichococcus (77.2%) was the most abundant microorganism in the CW-Fe mesocosm, while Thauera, Zoogloea, and Herbaspirillum were the primary denitrifying bacteria. The denitrifiers, Simplicispira, Dechloromonas, and Denitratisoma, were the dominant bacteria for CW-CK. This study provides a valuable method and an improved understanding of NO₃^‒-N reduction characteristics of s-Fe⁰ in a wetland mesocosm.     

Simultaneous Feammox and anammox process facilitated by activated carbon as an electron shuttle for autotrophic biological nitrogen removal

• The autotrophic nitrogen removal combining Feammox and Anammox was achieved. • Activated carbon can be used as an electron shuttle to enhance Feammox activity. • Fe(III) was reduced to Fe(II) and the secondary Fe(II) mineral (FeOOH) was obtained. • The iron-reducing bacteria and Anammox consortium was enriched simultaneously. Ferric iron reduction coupled with anaerobic ammonium oxidation (Feammox) is a novel ferric-dependent autotrophic process for biological nitrogen removal (BNR) that has attracted increasing attention due to its low organic carbon requirement. However, extracellular electron transfer limits the nitrogen transformation rate. In this study, activated carbon (AC) was used as an electron shuttle and added into an integrated autotrophic BNR system consisting of Feammox and anammox processes. The nitrogen removal performance, nitrogen transformation pathways and microbial communities were investigated during 194 days of operation. During the stable operational period (days 126–194), the total nitrogen (TN) removal efficiency reached 82.9%±6.8% with a nitrogen removal rate of 0.46±0.04 kg-TN/m³/d. The contributions of the Feammox, anammox and heterotrophic denitrification pathways to TN loss accounted for 7.5%, 89.5% and 3.0%, respectively. Batch experiments showed that AC was more effective in accelerating the Feammox rate than the anammox rate. X-ray photoelectron spectroscopy (XPS) analyses showed the presence of ferric iron (Fe(III)) and ferrous iron (Fe(II)) in secondary minerals. X-ray diffraction (XRD) patterns indicated that secondary iron species were formed on the surface of iron-AC carrier (Fe/AC), and Fe(III) was primarily reduced by ammonium in the Feammox process. The phyla Anaerolineaceae (0.542%) and Candidatus Magasanikbacteria (0.147%) might contribute to the Feammox process, and Candidatus Jettenia (2.10%) and Candidatus Brocadia (1.18%) were the dominative anammox phyla in the bioreactor. Overall, the addition of AC provided an effective way to enhance the autotrophic BNR process by integrating Feammox and anammox.     

Degradation of polyacrylamide (PAM) and methane production by mesophilic and thermophilic anaerobic digestion: Effect of temperature and concentration

• PAM degradation in thermophilic AD in comparison with mesophilic AD. • PAM degradation and its impact on thermophilic and mesophilic AD. • Enhanced methane yield in presence of PAM during thermophilic and mesophilic AD. • PAM degradation and microbial community analysis in thermophilic and mesophilic AD. Polyacrylamide (PAM) is generally employed in wastewater treatment processes such as sludge dewatering and therefore exists in the sludge. Furthermore, it degrades slowly and can deteriorate methane yield during anaerobic digestion (AD). The impact or fate of PAM in AD under thermophilic conditions is still unclear. This study mainly focuses on PAM degradation and enhanced methane production from PAM-added sludge during 15 days of thermophilic (55°C) AD compared to mesophilic (35°C) AD. Sludge and PAM dose from 10 to 50 g/kg TSS were used. The results showed that PAM degraded by 76% to 78% with acrylamide (AM) content of 0.2 to 3.3 mg/L in thermophilic AD. However, it degraded only 27% to 30% with AM content of 0.5 to 7.2 mg/L in mesophilic AD. The methane yield was almost 230 to 238.4 mL/g VSS on the 8th day in thermophilic AD but was 115.2 to 128.6 mL/g VSS in mesophilic AD. Mechanism investigation revealed that thermophilic AD with continuous stirring not only enhanced PAM degradation but also boosted the organics release from the sludge with added PAM and gave higher methane yield than mesophilic AD.     

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.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

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.     

The coupling of sand with ZVI/oxidants achieved proportional and highly efficient removal of arsenic

• Simply doping sands with ZVI achieved an even activation of ZVI by oxidants. • Sand doping facilitated proportional As trapping along the ZVI/oxidants column. • ZVI/sand/oxidants are highly efficient for arsenic removal. • ZVI/sand/oxidants reduced significantly the Fe²⁺ leaching and effluent turbidity. • More than 54% of arsenic was reduced to As(III) in ZVI/sand/oxidants system. The coupling of zero-valent iron (ZVI) with common oxidants has recently achieved very rapid and highly efficient removal of Heavy metals from wastewater. However, the uniform activation of ZVI throughout the column and the proportional removal of target contaminants are urgently required for the prevention of premature filter clogging and the extension of the effective column operational time. In this study, we successfully achieved this objective by simply doping granular sand with ZVI at appropriate weight ratios. When pure ZVI packed column was spiked with oxidants, the majority of As trapping occurred between the column inlet and the first sampling point. In a packed column with a 1:20 mixture of ZVI and sand, the average As removal efficiency was 36 (1st), 13.1 (2nd), 18.5 (3rd), 19.2 (4th) and 5.9% (5th outlet). The overall arsenic removal performance of the composite filling system of ZVI/sand was equally as efficient as that of the previous pure ZVI-packed system. Moreover, the leaching of Fe was significantly reduced with an increased sand ratio, resulting in clearer water with less turbidity. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that more than 54% of the arsenic was reduced to As(III). X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the extensive corrosion of the ZVI surface, which resulted in various species of iron oxyhydroxides responsible for the highly efficient sequester of arsenic through reduction, adsorption, and coprecipitation.     

A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4-Dichlorophenoxyacetic acid degradation

• A new pulsed switching peroxi-coagulation (PSPC) system was developed. • The EC_T for 2,4-D removal in the PSPC was lower than that in the EF. • The iron consumption for 2,4-D removal in the PSPC was lower than that in the PC. The aim of this study was to develop a new pulsed switching peroxi-coagulation system to control hydroxyl radical (?OH) production and to enhance 2,4-Dichlorophenoxyacetic acid (2,4-D) degradation. The system was constructed with a sacrifice iron anode, a Pt anode, and a gas diffusion cathode. Production of H₂O₂ and Fe²⁺ was controlled separately by time delayers with different pulsed switching frequencies. Under current densities of 5.0 mA/cm² (H₂O₂) and 0.5 mA/cm² (Fe²⁺), the ?OH production was optimized with the pulsed switching frequency of 1.0 s (H₂O₂):0.3 s (Fe²⁺) and the ratio of H₂O₂ to Fe²⁺ molar concentrations of 6.6. Under the optimal condition, 2,4-D with an initial concentration of 500 mg/L was completely removed in the system within 240 min. The energy consumption for the 2,4-D removal in the system was much lower than that in the electro-Fenton process (68±6 vs. 136±10 kWh/kg TOC). The iron consumption in the system was ~20 times as low as that in the peroxi-coagulation process (196±20 vs. 3940±400 mg/L) within 240 min. The system should be a promising peroxi-coagulation method for organic pollutants removal in wastewater.     

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.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.     

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.     

Enhanced methane production during long-term UASB operation at high organic loads as enabled by the immobilized Fungi

• Fungi enable the constant UASB operation even at OLR of 25.0 kg/(m³×d). • The COD removal of 85.9% and methane production of 5.6 m³/(m³×d) are achieved. • Fungi inhibit VFAs accumulation and favor EPS generation and sludge granulation. • Fungi enrich methanogenic archaea and promote methanogenic pathways. Anaerobic digestion is widely applied in organic wastewater treatment coupled with bioenergy production, and how to stabilize its work at the high organic loading rate (OLR) remains a challenge. Herein, we proposed a new strategy to address this issue via involving the synergetic role of the Aspergillus sydowii 8L-9-F02 immobilized beads (AEBs). A long-term (210-day) continuous-mode operation indicated that the upflow anaerobic sludge bed (UASB) reactor (R1, with AEBs added) could achieve the OLR as high as 25.0 kg/(m³×d), whereas the control reactor (R0, with AEBs free) could only tolerate the maximum OLR of 13.3 kg/(m³×d). Remarkably, much higher COD removal (85.9% vs 23.9%) and methane production (5.4 m³/(m³×d) vs 2.2 m³/(m³×d)) were achieved in R1 than R0 at the OLR of 25.0 kg/(m³×d). Such favorable effect results from the facts that fungi inhibit VFAs accumulation, favor the pH stabilization, promote the generation of more extracellular polymeric substance, and enhance the sludge granulation and settleability. Moreover, fungi may enhance the secretion of acetyl-coenzyme A, a key compound in converting organic matters to CO₂. In addition, fungi are favorable to enrich methanogenic archaea even at high OLR, improving the activity of acetate kinase and coenzyme F₄₂₀ for more efficient methanogenic pathway. This work may shed new light on how to achieve higher OLR and methane production in anaerobic digestion of wastewater.     

Deciphering the effect of sodium dodecylbenzene sulfonate on up-flow anaerobic sludge blanket treatment of synthetic sulfate-containing wastewater

• UASB reactor can work efficiently with high COD/SO₄^2- ratios when SDBS exists. • Outcome of the competition between SRB and MPA was affected by SDBS. • Presence of SDBS makes methanogens with H₂/CO₂ as a substrate dominant. • Microbial diversity decreases in the presence of SDBS. In this study, the effects of organic sulfur on anaerobic biological processes were investigated by operating two up-flow anaerobic sludge blanket (UASB) reactors with sodium dodecylbenzene sulfonate (SDBS) as a representative of organic sulfur. The results indicated that the specific methanogenic activity (SMA) and chemical oxygen demand (COD) removal efficiency of R2 (with SDBS added) were higher than those of R1 (without SDBS) when the COD/SO₄²⁻ ratio was above 5.0. However, when the COD/SO₄²⁻ ratio was lower than 5.0, the sulfate reduction efficiency of R2 was higher than that of R1. These results and the observed SDBS transformation efficiency in anaerobic reactors indicate that low concentrations of SDBS accelerate methane production and the continuous accumulation of SDBS does not weaken the reduction of sulfate. Similarly, the calculated electron flux for a COD/SO₄²⁻ ratio of 1.0 indicates that the utilization intensity of electrons by sulfate-reducing bacteria (SRB) in R2 was 36.48% higher than that of SRB in R1 and exceeded that of methane-producing archaea (MPA) under identical working conditions. Moreover, the addition of SDBS in R2 made sulfidogenesis the dominant reaction at low COD/SO₄²⁻, and Methanobacterium and Methanobrevibacter with H₂/CO₂ as the substrate and Desulfomicrobium were the dominant MPA and SRB, respectively. However, methanogenesis was still the dominant reaction in R1, and Methanosaeta with acetic acid as the substrate and Desulfovibrio were the dominant MPA and SRB, respectively.     

A review on sustainable reuse applications of Fenton sludge during wastewater treatment

• The sustainable approaches related to Fenton sludge reuse systems are summarized. • Degradation mechanism of Fenton sludge heterogeneous catalyst is deeply discussed. • The efficient utilization directions of Fenton sludge are proposed. The classical Fenton oxidation process (CFOP) is a versatile and effective application that is generally applied for recalcitrant pollutant removal. However, excess iron sludge production largely restricts its widespread application. Fenton sludge is a hazardous solid waste, which is a complex heterogeneous mixture with Fe(OH)₃, organic matter, heavy metals, microorganisms, sediment impurities, and moisture. Although studies have aimed to utilize specific Fenton sludge resources based on their iron-rich characteristics, few reports have fully reviewed the utilization of Fenton sludge. As such, this review details current sustainable Fenton sludge reuse systems that are applied during wastewater treatment. Specifically, coagulant preparation, the reuse of Fenton sludge as an iron source in the Fenton process and as a synthetic heterogeneous catalyst/adsorbent, as well as the application of the Fenton sludge reuse system as a heterogeneous catalyst for resource utilization. This is the first review article to comprehensively summarize the utilization of Fenton sludge. In addition, this review suggests future research ideas to enhance the cost-effectiveness, environmental sustainability, and large-scale feasibility of Fenton sludge applications.     

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.     

Effect of current density on groundwater arsenite removal performance using air cathode electrocoagulation

• With the same charge, current density had little effect on As(III) removal in ACEC. • ACEC had the lowest energy consumption compared with EC/O₂ or EC/N₂. • There was a trade-off relationship between energy consumption and removal time. • The ·OH concentration in ACEC was 1.5 times of that in the EC/O₂ system. Naturally occurring arsenic enrichment in groundwater poses a huge threat to human health. Air cathode electrocoagulation (ACEC) has recently been proposed to enhance As(III) oxidation and lower energy consumption. In this study, ACEC, EC/O₂ and EC/N₂ were evaluated with different current densities from 1 to 8 mA/cm² to investigate the effect on As(III) removal in different redox environments. Current density had no appreciable effect on arsenic removal efficiency given the same charge in ACEC because the concentration ratio of Fe/H₂O₂ under different current densities remained stable. However, in EC/O₂ and EC/N₂, As(III) removal was inhibited at higher current densities (4–8 mA/cm²), likely because more Fe(II) competed with As(III) for the oxidant, leading to less effective oxidation of As(III). In all EC systems, the ·OH units generated per power consumption reached the highest value at the lowest current density. Compared with other EC systems, the ACEC system showed lower energy consumption at all current densities due to the low energy consumption of the electrode reaction and more free radical generation. A lower current density saved more energy at the expense of time, showing the trade-off relationship between energy consumption and removal time. The operation costs for As(III) removal under optimal conditions were calculated as 0.028 $/m³ for ACEC, 0.030 $/m³ for EC/O₂, and 0.085 $/m³ for EC/N₂