Overlooked competition and promotion effects in electrochemical oxidation of humic acid and ammonia in landfill leachate.

Electrochemical oxidation (EO) can effectively reduce the degree of humification and toxicity of landfill leachate by generating highly active oxidative species in situ. However, the selective and competitive oxidation of humic acid (HA) and ammonia (NH4+) and the role of different oxidative species during the EO process in complex aqueous conditions remain unclear. In this study, a nanostructured tin-antimony electrode (Ti/Sb-SnO2 NFs) was prepared and compared with three types of commercial electrodes (Ti/Ir-RuO2, Ti4O7, Ti/Sb-SnO2) in terms of electrochemical properties and electrocatalytic oxidation of HA and NH4+. The de-humification capacity, interactive effects of HA and NH4+ on each other's oxidation by different oxidative species, as well as the related oxidation byproducts were investigated. The differences in pollutant electrooxidation among the different electrodes were found to be insignificant. The presence of HA was found to be detrimental to NH4+ degradation while reducing the N2 conversion rate. Interestingly, NH4+ initially inhibited the degradation rates of HA while promoted the degradation and reduced the accumulation of organic chlorine during the later EO process. A proposed mechanism accounts for both competitive and promotional effects for simultaneous HA and NH4+ oxidation during the EO process.

Development of an electrochemical separation-Rhodopseudomonas palustris electrolysis cell-coupled system for resourceful treatment of mature leachate landfill.

Electrochemical technology is a promising technique for separating ammonia from mature landfill leachate. However, the accompanying migration and transformation of coexisting pollutants and strategies for further high-value resourceful utilization of ammonia have rarely received attention. In this study, an electrochemical separation-Rhodopseudomonas palustris electrolysis cell coupled system was initially constructed for efficient separation and conversion of nitrogen in mature landfill leachate to microbial protein with synchronously tracking the transport and conversion of coexisting heavy metals accompanying the process. The results revealed that ammonia concentration in the cathode increased from 40.3 to 49.8% with increasing the current density from 20 to 40 mA/cm2, with less than 3% of ammonia transformation to NO2--N and NO3--N. During ammonia separation, approximately 95% of HM-DOMs (Cr, Cu, Ni, Pb, and Zn) were released into the anolyte due to humus degradation and further diffused to the cathode. A significant correlation was observed between the releases of HM-DOMs. Cu-DOMs accounted for 70.2% of the total Cu content, which was the highest proportion among the heavy metals (HMs). Among the HMs in anolyte, 57.4% of Pb, 52.5% of Ni, and 50.6% of Zn diffused to the cathode, and most of the HMs were removed in the form of hydroxide precipitations due to heavy alkaline catholyte. Compared with the open-circuit condition, the utilization efficiency of NH4+-N in the R. palustris electrolysis cell increased by 445.1% with 47% and 50% increases in final NH4+-N conversion rate and R. palustris biomass, respectively, due to bio-electrochemical enhanced phototrophic metabolism and acid generation for buffering the strong alkalinity of the electrolyte to maintain suitable growth conditions for R. palustris.

Blind spots of universal primers and specific FISH probes for functional microbe and community characterization in EBPR systems.

Fluorescence in situ hybridization (FISH) and 16S rRNA gene amplicon sequencing are commonly used for microbial ecological analyses in biological enhanced phosphorus removal (EBPR) systems, the successful application of which was governed by the oligonucleotides used. We performed a systemic evaluation of commonly used probes/primers for known polyphosphate-accumulating organisms (PAOs) and glycogen-accumulating organisms (GAOs). Most FISH probes showed blind spots and covered nontarget bacterial groups. Ca. Competibacter probes showed promising coverage and specificity. Those for Ca. Accumulibacter are desirable in coverage but targeted out-group bacteria, including Ca. Competibacter, Thauera, Dechlorosoma, and some polyphosphate-accumulating Cyanobacteria. Defluviicoccus probes are good in specificity but poor in coverage. Probes targeting Tetrasphaera or Dechloromonas showed low coverage and specificity. Specifically, DEMEF455, Bet135, and Dech453 for Dechloromonas covered Ca. Accumulibacter. Special attentions are needed when using these probes to resolve the PAO/GAO phenotype of Dechloromonas. Most species-specific probes for Ca. Accumulibacter, Ca. Lutibacillus, Ca. Phosphoribacter, and Tetrasphaera are highly specific. Overall, 1.4% Ca. Accumulibacter, 9.6% Ca. Competibacter, 43.3% Defluviicoccus, and 54.0% Dechloromonas in the MiDAS database were not covered by existing FISH probes. Different 16S rRNA amplicon primer sets showed distinct coverage of known PAOs and GAOs. None of them covered all members. Overall, 520F-802R and 515F-926R showed the most balanced coverage. All primers showed extremely low coverage of Microlunatus (<36.0%), implying their probably overlooked roles in EBPR systems. A clear understanding of the strength and weaknesses of each probe and primer set is a premise for rational evaluation and interpretation of obtained community results.

Structural Fe(II)-induced generation of reactive oxygen species on magnetite surface for aqueous As(III) oxidation during oxygen activation.

Magnetite is a reductive Fe(II)-bearing mineral, and its reduction property is considered important for degradation of contaminants in groundwater and anaerobic subsurface environments. However, the redox condition of subsurface environments frequently changes from anaerobic to aerobic owing to natural and anthropogenic disturbances, generating reactive oxygen species (ROS) from the interaction between Fe(II)-bearing minerals and O2. Despite this, the mechanism of ROS generation induced by magnetite under aerobic conditions is poorly understood, which may play a crucial role in As(III) oxidation. Herein, we found that magnetite could activate O2 and induce the oxidative transformation of As(III) under aerobic conditions. As(III) oxidation was attributed to the ROS generated via structural Fe(II) within the magnetite octahedra oxygenation. The electron paramagnetic resonance and quenching tests confirmed that O2•-, H2O2, and •OH were produced by magnetite. Moreover, density function theory calculations combined with experiments demonstrated that O2•- was initially formed via single electron transfer from the structural Fe(II) to the adsorbed O2; O2•- was then converted to •OH and H2O2 via a series of free radical reactions. Among them, O2•-and H2O2 were the primary ROS responsible for As(III) oxidation, accounting for approximately 52 % and 19 % of As(III) oxidation. Notably, As(III) oxidation mainly occurred on the magnetite surface, and As was immobilized further within the magnetite structure. This study provides solid evidence regarding the role of magnetite in determining the fate and transformation of As in redox-fluctuating subsurface environments.

Boosting Ammonium Oxidation in Wastewater by the BiOCl-Functionalized Anode.

Mixed metal oxide (MMO) anodes are commonly used for electrochlorination of ammonium (NH4+) in wastewater treatment, but they suffer from low efficiency due to inadequate chlorine generation at low Cl- concentrations and sluggish reaction kinetics between free chlorine and NH4+ under acidic pH conditions. To address this challenge, we develop a straightforward wet chemistry approach to synthesize BiOCl-functionalized MMO electrodes using the MMO as an efficient Ohmic contact for electron transfer. Our study demonstrates that the BiOCl@MMO anode outperforms the pristine MMO anode, exhibiting higher free chlorine generation (24.6-60.0 mg Cl2 L-1), increased Faradaic efficiency (75.5 vs 31.0%), and improved rate constant of NH4+ oxidation (2.41 vs 0.76 mg L-1 min-1) at 50 mM Cl- concentration. Characterization techniques including electron paramagnetic resonance and in situ transient absorption spectra confirm the production of chlorine radicals (Cl• and Cl2•-) by the BiOCl/MMO anode. Laser flash photolysis reveals significantly higher apparent second-order rate constants ((4.3-4.9) × 106 M-1 s-1 at pH 2.0-4.0) for the reaction between NH4+ and Cl•, compared to the undetectable reaction between NH4+ and Cl2•-, as well as the slower reaction between NH4+ and free chlorine (102 M-1 s-1 at pH < 4.0) within the same pH range, emphasizing the significance of Cl• in enhancing NH4+ oxidation. Mechanistic studies provide compelling evidence of the capacity of BiOCl for Cl- adsorption, facilitating chlorine evolution and Cl• generation. Importantly, the BiOCl@MMO anode exhibits excellent long-term stability and high catalytic activity for NH4+-N removal in a real landfill leachate. These findings offer valuable insights into the rational design of electrodes to improve electrocatalytic NH4+ abatement, which holds great promise for wastewater treatment applications.

Strain-Engineering of Mesoporous Cs3 Bi2 Br9 /BiVO4 S-Scheme Heterojunction for Efficient CO2 Photoreduction.

Slow charge kinetics and unfavorable CO2 adsorption/activation strongly inhibit CO2 photoreduction. In this study, a strain-engineered Cs3 Bi2 Br9 /hierarchically porous BiVO4 (s-CBB/HP-BVO) heterojunction with improved charge separation and tailored CO2 adsorption/activation capability is developed. Density functional theory calculations suggest that the presence of tensile strain in Cs3 Bi2 Br9 can significantly downshift the p-band center of the active Bi atoms, which enhances the adsorption/activation of inert CO2 . Meanwhile, in situ irradiation X-ray photoelectron spectroscopy and electron spin resonance confirm that efficient charge transfer occurs in s-CBB/HP-BVO following an S-scheme with built-in electric field acceleration. Therefore, the well-designed s-CBB/HP-BVO heterojunction exhibits a boosted photocatalytic activity, with a total electron consumption rate of 70.63 µmol g-1 h-1 , and 79.66% selectivity of CO production. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy reveals that CO2 photoreduction undergoes a formaldehyde-mediated reaction process. This work provides insight into strain engineering to improve the photocatalytic performance of halide perovskite.

Magnetic anaerobic granular sludge for sequestration and immobilization of Pb.

The development of magnetic adsorbents with high capacity to capture heavy metals has been the subject of intense research, but the process usually involves costive synthesis steps. Here, we propose a green approach to obtaining a magnetic biohybrid through in situ grown anaerobic granular sludge (AGS) with the help of magnetite, constituting a promising adsorbent for sequestration and immobilization of Pb in aqueous solutions and soils. The resultant magnetite-embedded AGS (M-AGS) was not only capable of promoting methane production but also conducive to Pb adsorption because of the large surface area and abundant function groups. The uptake of Pb on M-AGS followed the pseudo-second order, having a maximum adsorption capacity of 197.8 mg gDS-1 at pH 5.0, larger than 159.7, 170.3, and 178.1 mg gDS-1 in relation to AGS, F-AGS (ferrihydrite-mediated), and H-AGS (hematite-mediated), respectively. Mechanistic investigations showed that Pb binding to M-AGS proceeds via surface complexation, mineral precipitation, and lattice replacement, which promotes heavy metal capture and stabilization. This was evident from the increased proportion of structural Pb sequestrated from the aqueous solution and the enhanced percentage of the residual fraction of Pb extracted from the contaminated soils.

Constructing Highly Active Metal Oxides for Toluene Degradation by Fenton Iron Mud Modulation.

Fenton iron mud (IM) is a hazardous solid waste produced by Fenton oxidation technology after treating industrial wastewater. Thus, it is necessary and challenging to develop a recycling technology to back-convert dangerous materials into useful products. Herein, we develop a sustainable approach to prepare highly active metal oxides via a solid-state grinding method. IM, as an amorphous material, can disperse and interact well with these supported metal oxides, boosting toluene degradation significantly. Among these IM-based catalysts, the catalyst 8% MnOx/IM-0.2VC exhibits the best performance (T100 = 290 °C), originating from the oxide-support interaction and optimal balance between low-temperature reducibility and oxygen vacancy concentration. In addition, in situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS) results expound that ring breakage is prone to occur on MnOx, and oxygen vacancies are beneficial to adsorb oxygen and activate oxygen species to boost toluene oxidation following the Mars-van Krevelen mechanism. This work advances a complete industrial hazardous waste recycling route to develop extremely active catalysts.

A coupled electrochemical process for schwertmannite recovery from acid mine drainage: Important roles of anodic reactive oxygen species and cathodic alkaline.

The increasing need for sustainable acid mine drainage (AMD) treatment has spurred much attention to strategic development of resource recovery. Along this line, we envisage that a coupled electrochemical system involving anodic Fe(II) oxidation and cathodic alkaline production will facilitate in situ synthesis of schwertmannite from AMD. Multiple physicochemical studies showed the successful formation of electrochemistry-induced schwertmannite, with its surface structure and chemical composition closely related to the applied current. A low current (e.g., 50 mA) led to the formation of schwertmannite having a small specific surface area (SSA) of 122.8 m2 g-1 and containing small amounts of -OH groups (formula Fe8O8(OH)4.49(SO4)1.76), whereas a large current (e.g., 200 mA) led to schwertmannite high in SSA (169.5 m2 g-1) and amounts of -OH groups (formula Fe8O8(OH)5.16(SO4)1.42). Mechanistic studies revealed that the reactive oxygen species (ROS)-mediated pathway, rather than the direct oxidation pathway, plays a dominant role in accelerating Fe(II) oxidation, especially at high currents. The abundance of •OH in the bulk solution, along with the cathodic production of OH-, were the key to obtaining schwertmannite with desirable properties. It was also found to function as a powerful sorbent in removal of arsenic species from the aqueous phase.

In Situ Reconstruction of Metal Oxide Cathodes for Ammonium Generation from High-Strength Nitrate Wastewater: Elucidating the Role of the Substrate in the Performance of Co3O4-x.

In situ electrochemical reconstruction is important for transition metal oxides explored as electrocatalysts for electrochemical nitrate reduction reactions (ENRRs). Herein, we report substantial performance enhancement of ammonium generation on Co, Fe, Ni, Cu, Ti, and W oxide-based cathodes upon reconstruction. Among them, the performance of a freestanding ER-Co3O4-x/CF (Co3O4 grown on Co foil subjected to electrochemical reduction) cathode was superior to its unreconstructed counterpart and other cathodes; e.g., an ammonium yield of 0.46 mmol h-1 cm-2, an ammonium selectivity of 100%, and a Faradaic efficiency of 99.9% were attained at -1.3 V in a 1400 mg L-1 NO3--N solution. The reconstruction behaviors were found to vary with the underlying substrate. The inert carbon cloth only acted as a supporting matrix for immobilizing Co3O4, without appreciable electronic interactions between them. A combination of physicochemical characterizations and theoretical modeling provided compelling evidence that the CF-promoted self-reconstruction of Co3O4 induced the evolution of metallic Co and the creation of oxygen vacancies, which promoted and optimized interfacial nitrate adsorption and water dissociation, thus boosting the ENRR performance. The ER-Co3O4-x/CF cathode performed well over wide ranges of pH and applied current and at high nitrate loadings, ensuring its high efficacy in treating high-strength real wastewater.

Photoinduced transformation of ferrihydrite in the presence of aqueous sulfite and its influence on the repartitioning of Cd.

The photoinduced transformation of ferrihydrite is an important process that can predict the geochemical cycle of Fe in anoxic environments as well as the fate of trace elements bonded to Fe minerals. We report that the photooxidation of sulfite by UV irradiation produces hydrated electrons (super-reductants), which significantly promote ferrihydrite reduction to Fe(II), and SO3•- (a moderate oxidant), enabling its further oxidation to more crystalline Fe(III) products. The experimental results show that the concentration of sulfite was key in influencing the rate and extent of surface-bound Fe(II) formation, which ultimately determined the distribution of individual products. For example, fitting of the Mössbauer spectroscopy data revealed that the relative abundances of mineral species after 8 h of treatment in the UV/sulfite systems were 41.9% lepidocrocite and 58.1% ferrihydrite at 2 mM SO32-; 41.8% goethite, 28.2% lepidocrocite, and 29.1% ferrihydrite at 5 mM SO32-; and 100% goethite at 10 mM SO32-. The combined results of the chemical speciation analysis and the Cd K-edge EXAFS characterization provided compelling evidence that Cd was firmly incorporated into the structure of newly formed minerals, particularly at high sulfite concentrations. These findings provide an understanding of the role of UV/sulfite in facilitating ferrihydrite transformation and promoting Cd stabilization in oxygen-deficit soils and aquatic environments.

A Bipolar Membrane-Integrated Electrochlorination Process for Highly Efficient Ammonium Removal in Mature Landfill Leachate: The Importance of ClO• Generation.

Electrochemical oxidation has been demonstrated to be a useful method for removing biorefractory organic pollutants in mature landfill leachate but suffers from low efficiency in eliminating ammonium because of its resistance to being oxidized by HO• or free chlorine (FC) at decreased pH. Here, we propose a new bipolar membrane-electrochlorination (BPM-EC) process to address this issue. We found that the BPM-EC system was significantly superior to both the undivided and divided reactors with monopolar membranes in terms of elevated rate of ammonium removal, attenuated generation of byproducts (e.g., nitrate and chloramines), increased Faradaic efficiency, and decreased energy consumption. Mechanistic studies revealed that the integration of BPM was helpful in creating alkaline environments in the vicinity of the anode, which facilitated production of surface-bound HO• and FC and eventually promoted in situ generation of ClO•, a crucial reactive species mainly responsible for accelerating ammonium oxidation and selective transformation to nitrogen. The efficacy of BPM-EC in treating landfill leachates with different ammonium concentrations was verified under batch and continuous-flow conditions. A kinetic model that incorporates the key parameters was developed, which can successfully predict the optimal number of BPM-EC reactors (e.g., 2 and 5 for leachates containing 589.4 ± 5.5 and 1258.1 ± 9.6 mg L-1 NH4+-N, respectively) necessary for complete removal of ammonium. These findings reveal that the BPM-EC process shows promise in treating ammonium-containing wastewater, with advantages that include effectiveness, adaptability, and flexibility.

Electrocoagulation coupled with electrooxidation for the simultaneous treatment of multiple pollutants in contaminated sediments.

In situ and simultaneous remediation of a variety of pollutants in sediments remains a challenge. In this study, we report that the combination of electrocoagulation (EC) and electrooxidation (EO) is efficient in the immobilization of phosphorus and heavy metals and in the oxidation of ammonium and toxic organic matter. The integrated mixed metal oxide (MMO)/Fe anode system allowed the facile removal of ammonium and phosphorus in the overlying water (99% of 10 mg/L NH4+-N and 95% of 10 mg/L P disappeared in 15 and 30 min, respectively). Compared with the controls of the single Fe anode and single MMO anode systems, the dual MMO/Fe anode system significantly improved the removal of phenanthrene and promoted the transition of Pb and Cu from the mobile species to the immobile species. The concentrations of Pb and Cu in the toxicity characteristic leaching procedure extracts were reduced by 99% and 97% after an 8 hr operation. Further tests with four real polluted samples indicated that substantial proportions of acid-soluble fraction Pb and Cu were reduced (30%-31% for Pb and 16%-23% for Cu), and the amounts of total organic carbon and NH4+-N decreased by 56%-71% and 32%-63%, respectively. It was proposed that the in situ electrogenerated Fe(II) at the Fe anode and the active oxygen/chlorine species at the MMO anode are conducive to outstanding performance in the co-treatment of multiple pollutants. The results suggest that the EC/EO method is a powerful technology for the in situ remediation of sediments contaminated with different pollutants.

Reactive species conversion into 1O2 promotes substantial inhibition of chlorinated byproduct formation during electrooxidation of phenols in Cl--laden wastewater.

The generation of chlorinated byproducts during the electrochemical oxidation (EO) of Cl--laden wastewater is a significant concern. We aim to propose a concept of converting reactive species (e.g., reactive chlorines and HO• resulting from electrolysis) into 1O2 via the addition of H2O2, which substantially alleviates chlorinated organic formation. When phenol was used as a model organic compound, the results showed that the H2O2-involving EO system outperformed the H2O2-absent system in terms of higher rate constants (5.95 × 10-2 min-1vs. 2.97 × 10-2 min-1) and a much lower accumulation of total organic chlorinated products (1.42 mg L-1vs. 8.18 mg L-1) during a 60 min operation. The rate constants of disappearance of a variety of phenolic compounds were positively correlated with the Hammett constants (σ), suggesting that the reactive species preferred oxidizing phenols with electron-rich groups. After the identification of 1O2 that was abundant in the bulk solution with the use of electron paramagnetic resonance and computational kinetic simulation, the routes of 1O2 generation were revealed. Despite the consensus as to the contribution of reaction between H2O2 and ClO- to 1O2 formation, we conclude that the predominant pathway is through H2O2 reaction with electrogenerated HO• or chlorine radicals (Cl• and Cl2•-) to produce O2•-, followed by self-combination. Density functional theory calculations theoretically showed the difficulty in forming chlorinated byproducts for the 1O2-initiated phenol oxidation in the presence of Cl-, which, by contrast, easily occurred for the Cl•-or HO•-initiated phenol reaction. The experiments run with real coking wastewater containing high-concentration phenols further demonstrated the superiority of the H2O2-involving EO system. The findings imply that this unique method for treating Cl--laden organic wastewater is expected to be widely adopted for generalizing EO technology for environmental applications.

Boosting the oxidative capacity of the Fe(0)/O2 system via an air-breathing cathode.

The corrosion of Fe(0) in the presence of O2 in nature can lead to the oxidation of organic compounds, but the efficiency is very limited. Herein, attempts were made to establish a galvanic system that separates the anodic Fe(0) oxidation reaction and the cathodic O2 reduction reaction using an air-breathing cathode. Compared with the chemical Fe(0)/O2 system, it exhibited a substantially higher capability of destroying a variety of pollutants, such as organic dyes (12 types), phenol, nitrobenzene, acetaminophen, phenol, and ethylenediaminetetraacetic acid. The degradation rate constant of a model dye (i.e., Rhodamine B) increased from 0.047 min-1 (chemical) to 1.412 min-1 (galvanic) under the passive air-breathing condition. The electric circuit design promoted Fe(0) dissolution to Fe(II) and triggered electron transfer that drives O2 reduction to H2O2, two important species responsible for the generation of HO• at high abundance. In addition, the galvanic Fe(0)/O2 system produces electricity while destroying pollutants. Tests with real Ni plating wastewater further demonstrated the capability of the system to oxidize complexed organics and phosphite. This study provides a new strategy for boosting the oxidative capacity of the Fe(0)/O2 system, which shows promise for acid wastewater treatment.

A co-doped oxygen reduction catalyst with FeCu promotes the stability of microbial fuel cells.

Air cathode microbial fuel cell (AC-MFC) cannot be used on a large scale because of its low oxygen reduction reaction (ORR) efficiency. Despite the fact that bimetallic catalysts can greatly enhance the oxygen reduction rate by regulating the electronic structure of the active site, the flaws of insufficient exposure of the active site and easy metal agglomeration limit its catalytic activity. Herein, we report on the preparation of a stable heteroatomic substrate using a copper material organic framework as a precursor, covered by Fe-based active sites. As a result of dipole-dipole interactions, the reduced product Fe2+ forms a weak Fe-O surface that is conducive to the adsorption of active substances. The presence of Fe0 enhances the electrical conductivity of the catalytic, thus promoting ORR efficiency. Through redox coupling, the D-band center of Fe at FeCu@CN is optimized and brought close to the Fermi level to facilitate electron transfer. Notably, FeCu@CN demonstrates a superior power density of 2796.23 ± 278.58 mW m-3, far exceeding that of Pt/C (1363.93 ± 102.56 mW m-3), in the application of microbial fuel cells (MFCs). Meanwhile, the MFC-loaded FeCu@CN maintains excellent stability and outstanding output voltage after 1000 h, which provides feasibility for large-scale application.

Minimizing toxic chlorinated byproducts during electrochemical oxidation of Ni-EDTA: Importance of active chlorine-triggered Fe(II) transition to Fe(IV).

The formation of chlorinated byproducts represents a significant threat to the quality of the effluent treated using electrochemical advanced oxidation processes (EAOPs), thus spurring investigation into alleviating their production. This study presents a new strategy to minimize the release of chlorinated intermediates during the electrochemical oxidation of Ni-EDTA by establishing a dual mixed metal oxide (MMO)/Fe anode system. The results indicate that the dual-anode system achieved a substantially higher rate (0.141 min-1) of Ni-EDTA destruction and accordingly allowed a more pronounced removal of aqueous Ni (from 39.85 to 0.63 mg L-1) after alkaline precipitation, compared with its single MMO anode (0.017 min-1 of Ni-EDTA removal, with 14.38 mg L-1 Ni remaining) and single Fe anode (insignificant Ni-EDTA removal, with 38.37 mg L-1 Ni remaining) counterparts. Compared to reactive chlorine species (RCS) produced from the single MMO anode system, Fe(IV) was in situ generated from the dual-anode system and was predominantly responsible for the attenuation of chlorinated byproducts and thus the decrease in the acute toxicity of the treated solution (evaluated using luminescent bacteria). The Fe(IV)-dominated dual-anode system also exhibited superior performance in removing multiple pollutants (including organic ligands, Ni, and phosphite) in the real electroless plating effluent. The findings suggest that the strategy for Fe(II) transition to Fe(IV) by active chlorine paves a new avenue for yielding less chlorinated products with lower toxicity when EAOPs are used to treat chloride-containing organic wastewater.

Extracellular polymeric substance induces biogenesis of vivianite under inorganic phosphate-free conditions.

Vivianite is often found in reducing environments rich in iron and phosphorus from organic debris degradation or phosphorus mineral dissolution. The formation of vivianite is essential to the geochemical cycling of phosphorus and iron elements in natural environments. In this study, extracellular polymeric substances (EPS) were selected as the source of phosphorus. Microcosm experiments were conducted to test the evolution of mineralogy during the reduction of polyferric sulfate flocs (PFS) by Shewanella oneidensis MR-1 (S. oneidensis MR-1) at EPS concentrations of 0, 0.03, and 0.3 g/L. Vivianite was found to be the secondary mineral in EPS treatment when there was no phosphate in the media. The EPS DNA served as the phosphorus source and DNA-supplied phosphate could induce the formation of vivianite. EPS impedes PFS aggregation, contains redox proteins and stores electron shuttle, and thus greatly promotes the formation of minerals and enhances the reduction of Fe(III). At EPS concentration of 0, 0.03, and 0.3 g/L, the produced HCl-extractable Fe(II) was 107.9, 111.0, and 115.2 mg/L, respectively. However, when the microcosms remained unstirred, vivianite can be formed without the addition of EPS. In unstirred systems, the EPS secreted by S. oneidensis MR-1 could agglomerate at some areas, resulting in the formation of vivianite in the proximity of microbial cells. It was found that vivianite can be generated biogenetically by S. oneidensis MR-1 strain and EPS may play a key role in iron reduction and concentrating phosphorus in the oligotrophic ecosystems where quiescent conditions prevail.

Anoxic oxidation of As(III) during Fe(II)-induced goethite recrystallization: Evidence and importance of Fe(IV) intermediate.

Under anoxic conditions, aqueous Fe(II) (Fe(II)aq)-induced recrystallization of iron (oxyhydr)oxides changes the speciation and geochemical cycle of trace elements in environments. Oxidation of trace element, i.e., As(III), driven by Fe(II)aq-iron (oxyhydr)oxides interactions under anoxic condition was observed previously, but the oxidative species and involved mechanisms are remained unknown. In the present study, we explored the formed oxidative intermediates during Fe(II)aq-induced recrystallization of goethite under anoxic conditions. The methyl phenyl sulfoxide-based probe experiment suggested the featured oxidation by Fe(IV) species in Fe(II)aq-goethite system. Both the Mössbauer spectra and X-ray absorption near edge structure spectroscopic evidenced the generation and quenching of Fe(IV) intermediate. It was proved that the interfacial electron exchange between Fe(II)aq and Fe(III) of goethite initiated the generation of Fe(IV). After transferring electrons to goethite, Fe(II)aq was transformed to labile Fe(III), which was then transformed to Fe(IV) via a proton-coupled electron transfer process. This highly reactive transient Fe(IV) could quickly react with reductive species, i.e. Fe(II) or As(III). Considering the ubiquitous occurrence of Fe(II)-iron (oxyhydr)oxides reactions under anoxic conditions, our findings are expected to provide new insight into the anoxic oxidative transformation processes of matters in non-surface environments on earth.

Evolution of biochemical processes in coking wastewater treatment: A combined evaluation of material and energy efficiencies and secondary pollution.

The application of advanced biological treatment technology results in improved coking wastewater (CW) effluent quality at lower material and energy input practiced by wastewater treatment plants. In wastewater treatment, the diversity of biological processes combinations affects the variety of microorganisms and biochemical reactions resulting in effluent quality. Four full-scale CW processes, anaerobic-anoxic-oxic (A/A/O), anoxic-oxic-hydrolytic-oxic (A/O/H/O), anoxic-oxic-oxic (A/O/O), and oxic-hydrolytic-oxic (O/H/O) were compared for their consumption of chemicals and energy, emissions of greenhouse gases, and excess sludge production. A new performance indicator combining the above mentioned parameters was proposed to comprehensively evaluate processes in capacity to CW. The O/H/O process showed stable and reliable operation with minimum chemicals cost and the average energy consumption, whereas A/A/O at its good performance in TN removal required a large amount of alkaline chemicals to maintain stability. Besides, a substantial addition of chemicals in A/A/O results in larger average amounts of inorganic sludge. Also, the A/A/O process with a single aerobic unit appeared to be incapable of energy saving when dealing with CW rich in nitrogen and poor in phosphorus. The process with dual aerobic units can achieve more complete carbon and nitrogen removal, which is related to the sequence of biochemical reactions. Diverse sequence combinations can create variation in HRT and DO, whereby contaminants proceed through distinct channels of degradation. In the comparative analysis of CWPIs, it could be seen that O/H/O is the biological treatment process with the least equivalent energy consumption input at present thus exhibiting promising application in CW treatment. The A/O/O and A/O/H/O combinations are good attempts of development; however, more energy-efficient operation modes have to be further investigated.