Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

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.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Enhancement of the polynomial functions response surface model for real-time analyzing ozone sensitivity

• The calculation process and algorithm of response surface model (RSM) were enhanced. • The prediction errors of RSM in the margin and transition areas were greatly reduced. • The enhanced RSM was able to analyze O₃-NO_x-VOC sensitivity in real-time. • The O₃ formations were mainly sensitive to VOC, for the two case study regions. Quantification of the nonlinearities between ambient ozone (O₃) and the emissions of nitrogen oxides (NO_x) and volatile organic compound (VOC) is a prerequisite for an effective O₃ control strategy. An Enhanced polynomial functions Response Surface Model (Epf-RSM) with the capability to analyze O₃-NO_x-VOC sensitivities in real time was developed by integrating the hill-climbing adaptive method into the optimized Extended Response Surface Model (ERSM) system. The Epf-RSM could single out the best suited polynomial function for each grid cell to quantify the responses of O₃ concentrations to precursor emission changes. Several comparisons between Epf-RSM and pf-ERSM (polynomial functions based ERSM) were performed using out-of-sample validation, together with comparisons of the spatial distribution and the Empirical Kinetic Modeling Approach diagrams. The comparison results showed that Epf-RSM effectively addressed the drawbacks of pf-ERSM with respect to over-fitting in the margin areas and high biases in the transition areas. The O₃ concentrations predicted by Epf-RSM agreed well with Community Multi-scale Air Quality simulation results. The case study results in the Pearl River Delta and the north-western area of the Shandong province indicated that the O₃ formations in the central areas of both the regions were more sensitive to anthropogenic VOC in January, April, and October, while more NO_x-sensitive in July.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

Rapid and long-effective removal of broad-spectrum pollutants from aqueous system by ZVI/oxidants

• The coupling of oxidants with ZVI overcome the impedance of ZVI passive layer. • ZVI/oxidants system achieved fast and long-effective removal of contaminants. • Multiple mechanisms are involved in contaminants removal by ZVI/oxidant system. • ZVI/Oxidants did not change the reducing property of ORP in the fixed-bed system. Zero-valent iron (ZVI) technology has recently gained significant interest in the efficient sequestration of a wide variety of contaminants. However, surface passivation of ZVI because of its intrinsic passive layer would lead to the inferior reactivity of ZVI and its lower efficacy in contaminant removal. Therefore, to activate the ZVI surface cheaply, continuously, and efficiently is an important challenge that ZVI technology must overcome before its wide-scale application. To date, several physical and chemical approaches have been extensively applied to increase the reactivity of the ZVI surface toward the elimination of broad-spectrum pollutants. Nevertheless, these techniques have several limitations such as low efficacy, narrow working pH, eco-toxicity, and high installation cost. The objective of this mini-review paper is to identify the critical role of oxygen in determining the reactivity of ZVI toward contaminant removal. Subsequently, the effect of three typical oxidants (H₂O₂, KMnO₄, and NaClO) on broad-spectrum contaminants removal by ZVI has been documented and discussed. The reaction mechanism and sequestration efficacies of the ZVI/oxidant system were evaluated and reviewed. The technical basis of the ZVI/oxidant approach is based on the half-reaction of the cathodic reduction of the oxidants. The oxidants commonly used in the water treatment industry, i.e., NaClO, O₃, and H₂O₂, can be served as an ideal coupling electron receptor. With the combination of these oxidants, the surface corrosion of ZVI can be continuously driven. The ZVI/oxidants technology has been compared with other conventional technologies and conclusions have been drawn.     

Mechanisms for simultaneous ozonation of sulfamethoxazole and natural organic matters in secondary effluent from sewage treatment plant

• SMX was mainly degraded by hydrolysis, isoxazole oxidation and double-bond addition. • Isoxazole oxidation and bond addition products were formed by direct ozonation. • Hydroxylated products were produced by indirect oxidation. • NOM mainly affected the degradation of SMX by consuming ^•OH rather than O₃. • Inhibitory effect of NOM on SMX removal was related to the components’ aromaticity. Sulfamethoxazole (SMX) is commonly detected in wastewater and cannot be completely decomposed during conventional treatment processes. Ozone (O₃) is often used in water treatment. This study explored the influence of natural organic matters (NOM) in secondary effluent of a sewage treatment plant on the ozonation pathways of SMX. The changes in NOM components during ozonation were also analyzed. SMX was primarily degraded by hydrolysis, isoxazole-ring opening, and double-bond addition, whereas hydroxylation was not the principal route given the low maximum abundances of the hydroxylated products, with m/z of 269 and 287. The hydroxylation process occurred mainly through indirect oxidation because the maximum abundances of the products reduced by about 70% after the radical quencher was added, whereas isoxazole-ring opening and double-bond addition processes mainly depended on direct oxidation, which was unaffected by the quencher. NOM mainly affected the degradation of micropollutants by consuming ^•OH rather than O₃ molecules, resulting in the 63%–85% decrease in indirect oxidation products. The NOM in the effluent were also degraded simultaneously during ozonation, and the components with larger aromaticity were more likely degraded through direct oxidation. The dependences of the three main components of NOM in the effluent on indirect oxidation followed the sequence: humic-like substances>fluvic-like substances>protein-like substances. This study reveals the ozonation mechanism of SMX in secondary effluent and provides a theoretical basis for the control of SMX and its degradation products in actual water treatment.     

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.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Significant increase of assimilable organic carbon (AOC) levels in MBR effluents followed by coagulation,ozonation and combined treatments: Implications for biostability control of reclaimed water

• Annual AOCs in MBR effluents were stable with small increase in warmer seasons. • Significant increase in AOC levels of tertiary effluents were observed. • Coagulation in prior to ozonation can reduce AOC formation in tertiary treatment. • ∆UV₂₅₄ and SUVA can be surrogates to predict the AOC changes during ozonation. As water reuse development has increased, biological stability issues associated with reclaimed water have gained attention. This study evaluated assimilable organic carbon (AOC) in effluents from a full-scale membrane biological reactor (MBR) plant and found that they were generally stable over one year (125–216 µg/L), with slight increases in warmer seasons. After additional tertiary treatments, the largest increases in absolute and specific AOCs were detected during ozonation, followed by coagulation-ozonation and coagulation. Moreover, UV₂₅₄ absorbance is known to be an effective surrogate to predict the AOC changes during ozonation. Applying coagulation prior to ozonation of MBR effluents for removal of large molecules was found to reduce the AOC formation compared with ozonation treatment alone. Finally, the results revealed that attention should be paid to seasonal variations in influent and organic fraction changes during treatment to enable sustainable water reuse.     

Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

• Light irradiation increased the concentration of free radicals on HS. • The increased spin densities on HS readily returned back to the original value. • The “unstable” free radicals induced the formation of reactive radical species. • Reactive radicals’ concentration correlated strongly with EPFRs’ concentration. Environmentally persistent free radicals (EPFRs) in humic substances play an essential role in soil geochemical processes. Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments; however, the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear. In this study, humic acid, fulvic acid, and humin were extracted from peat soil and then in situ irradiated using simulated sunlight. Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time, the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau. After irradiation for 2h, the maximum spin density levels were up to 1.63 × 10¹⁷, 2.06 × 10¹⁷, and 1.77 × 10¹⁷ spins/g for the humic acid, fulvic acid, and humin, respectively. And the superoxide radicals increased to 1.05 × 10¹⁴–1.46 × 10¹⁴ spins/g while the alkyl radicals increased to 0.47 × 10¹⁴–1.76 × 10¹⁴ spins/g. The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions. Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species (R² = 0.65–0.98, p<0.05), which suggested that the newly produced EPFRs contributed to the formation of reactive radical species. Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.     

Enhanced hydrogen production in microbial electrolysis through strategies of carbon recovery from alkaline/thermal treated sludge

• High hydrogen yield is recovered from thermal-alkaline pretreated sludge. • Separating SFL by centrifugation is better than filtration for hydrogen recovery. • The cascaded bioconversion of complex substrates in MECs are studied. • Energy and electron efficiency related to substrate conversion are evaluated. The aim of this study was to investigate the biohydrogen production from thermal (T), alkaline (A) or thermal-alkaline (TA) pretreated sludge fermentation liquid (SFL) in a microbial electrolysis cells (MECs) without buffer addition. Highest hydrogen yield of 36.87±4.36 mgH₂/gVSS (0.026 m³/kg COD) was achieved in TA pretreated SFL separated by centrifugation, which was 5.12, 2.35 and 43.25 times higher than that of individual alkaline, thermal pretreatment and raw sludge, respectively. Separating SFL from sludge by centrifugation eliminated the negative effects of particulate matters, was more conducive for hydrogen production than filtration. The accumulated short chain fatty acid (SCFAs) after pretreatments were the main substrates for MEC hydrogen production. The maximum utilization ratio of acetic acid, propionic acid and n-butyric acid was 93.69%, 90.72% and 91.85%, respectively. These results revealed that pretreated WAS was highly efficient to stimulate the accumulation of SCFAs. And the characteristics and cascade bioconversion of complex substrates were the main factor that determined the energy efficiency and hydrogen conversion rate of MECs.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Performance of activated carbon coated graphite bipolar electrodes on capacitive deionization method for salinity reduction

• Graphite bipolar electrodes act as an appropriate bed for the CDI process. • Activated carbon Coating improves the application of the electrodes. • CDI is an environmentally friendly method to apply for brackish water. • Initial concentration is the most important parameter in the CDI method. • CDI process in a batch-mode setup needs more development. This research investigates a capacitive deionization method for salinity reduction in a batch reactor as a new approach for desalination. Reductions of cost and energy compared with conventional desalination methods are the significant advantages of this approach. In this research, experiments were performed with a pair of graphite bipolar electrodes that were coated with a one-gram activated carbon solution. After completing preliminary tests, the impacts of four parameters on electrical conductivity reduction, including (1) the initial concentration of feed solution, (2) the duration of the tests, (3) the applied voltage, and (4) the pH of the solution, were examined. The results show that the maximum efficiency of electrical conductivity reduction in this laboratory-scale reactor is about 55%. Furthermore, the effects of the initial concentration of feed solution are more significant than the other parameters. Thus, using the capacitive deionization method for water desalination with low and moderate salt concentrations (i.e., brackish water) is proposed as an affordable method. Compared with conventional desalination methods, capacitive deionization is not only more efficient but also potentially more environmentally friendly.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

Utilizing transparent and conductive SnO2 as electron mediator to enhance the photocatalytic performance of Z-scheme Si-SnO2-TiOx

• A novel Z-scheme Si-SnO₂-TiO_x with SnO₂ as electron mediator is first constructed. • Transparent and conductive SnO₂ can pass light through and promote charge transport. • V_O from SnO₂ and TiO_x improve photoelectrochemical performances. • Efficient photocatalytic degradations originate from the Z scheme construction. Z-scheme photocatalysts, with strong redox ability, have a great potential for pollutants degradation. However, it is challenging to construct efficient Z-scheme photocatalysts because of their poor interfacial charge separation. Herein, by employing transparent and conductive SnO₂ as electron mediator to pass light through and promote interfacial charge transportation, a novel Z-scheme photocatalyst Si-SnO₂-TiO_{x (1<x<2)} was constructed. The Z-scheme photocatalyst displayed an order of magnitude higher photocurrent density and a 4-fold increase in open-circuit potential compared to those of Si. Moreover, the onset potential shifted negatively for approximately 2.2 V. Benefiting from these advantages, this Z-scheme Si-SnO₂-TiO_x exhibited efficient photocatalytic performance toward phenol degradation and mineralization. 75% of the phenol was degraded without bias potential and 70% of the TOC was removed during phenol degradation. Other typical pollutants such as bisphenol A and atrazine could also be degraded without bias potential. Introducing a transparent and conductive electron mediator to construct Z-scheme photocatalyst gives a new sight to the improvement of photocatalytic performance in Z scheme.