An Anti-Scaling Strategy for Electrochemical Wastewater Treatment: Leveraging Tip-Enhanced Electric Fields.

Electrode scaling poses a critical barrier to the adoption of electrochemical processes in wastewater treatment, primarily due to electrode inactivation and increased internal reactor resistance. We introduce an antiscaling strategy using tip-enhanced electric fields to redirect scale-forming compounds (e.g., Mg(OH)2 and CaCO3) from the electrode-electrolyte interface to the bulk solution. Our study utilized Cu nanowires (Cu NW) with high-curvature nanostructures as the cathode, in contrast to Cu nanoparticles (Cu NP), Cu foil (CF), and Cu mesh (CM), to evaluate the electrochemical nitrate reduction reaction (NO3RR) performance in hard water conditions. The Cu NW/CF cathode demonstrated superior NO3RR efficiency, with an apparent rate constant (Kapp) of 1.04 h-1, significantly outperforming control electrodes under identical conditions (Kapp < 0.051 h-1). Through experimental and theoretical analysis, including COMSOL simulations, we show that the high-curvature design of Cu NW induced localized electric field enhancements, propelling OH- ions away from the electrode surface into the bulk solution, thus mitigating scale formation on the cathode. Testing with real nitrate-contaminated wastewater confirms that the Cu NW/CF cathode maintained excellent denitrification efficiency over a 60-day period. This study offers a promising perspective on preventing electrode scaling in electrochemical wastewater treatment, paving the way for more efficient and sustainable practices.

Trace Br- Inhibits Halogenated Byproduct Formation in Saline Wastewater Electrochemical Treatment.

The electrochemical technology provides a practical and viable solution to the global water scarcity issue, but it has an inherent challenge of generating toxic halogenated byproducts in treatment of saline wastewater. Our study reveals an unexpected discovery: the presence of a trace amount of Br- not only enhanced the electrochemical oxidation of organic compounds with electron-rich groups but also significantly reduced the formation of halogenated byproducts. For example, in the presence of 20 µM Br-, the oxidation rate of phenol increased from 0.156 to 0.563 min-1, and the concentration of total organic halogen decreased from 59.2 to 8.6 µM. Through probe experiments, direct electron transfer and HO• were ruled out as major contributors; transient absorption spectroscopy (TAS) and computational kinetic models revealed that trace Br- triggers a shift in the dominant reactive species from Cl2•- to Br2•-, which plays a key role in pollutant removal. Both TAS and electron paramagnetic resonance identified signals unique to the phenoxyl and carbon-centered radicals in the Br2•--dominated system, indicating distinct reaction mechanisms compared to those involving Cl2•-. Kinetic isotope experiments and density functional theory calculations confirmed that the interaction between Br2•- and phenolic pollutants follows a hydrogen atom abstraction pathway, whereas Cl2•- predominantly engages pollutants through radical adduct formation. These insights significantly enhance our understanding of bromine radical-involved oxidation processes and have crucial implications for optimizing electrochemical treatment systems for saline wastewater.

Carbon Nanotubes as Controllable Electric-Field-Induced Bipolar Electrodes for Efficient Water Purification.

Advanced oxidation processes (AOPs) are the most efficient water cleaning technologies, but their applications face critical challenges in terms of mass/electron transfer limitations and catalyst loss/deactivation. Bipolar electrochemistry (BPE) is a wireless technique that is promising for energy and environmental applications. However, the synergy between AOPs and BPE has not been explored. In this study, by combining BPE with AOPs, we develop a general approach of using carbon nanotubes (CNTs) as electric-field-induced bipolar electrodes to control electron transfer for efficient water purification. This approach can be used for permanganate and peroxide activation, with superior performances in the degradation of refractory organic pollutants and excellent durability in recycling and scale-up experiments. Theoretical calculations, in situ measurements, and physical experiments showed that an electric field could substantially reduce the energy barrier of electron transfer over CNTs and induce them to produce bipolar electrodes via electrochemical polarization or to form monopolar electrodes through a single particle collision effect with feeding electrodes. This approach can continuously provide activated electrons from one pole of bipolar electrodes and simultaneously achieve "self-cleaning" of catalysts through CNT-mediated direct oxidation from another pole of bipolar electrodes. This study provides a fundamental scientific understanding of BPE, expands its scope in the environmental field, and offers a general methodology for water purification.

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.

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.

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.

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.

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.

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.

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.

Self-Activated Ni Cathode for Electrocatalytic Nitrate Reduction to Ammonia: From Fundamentals to Scale-Up for Treatment of Industrial Wastewater.

Electrocatalytic reduction has recently received increasing attention as a method of converting waste nitrate into value-added ammonia, but most studies have focused on complex strategies of catalyst preparation and little has been done in the way of large-scale demonstrations. Herein, we report that in situ activation of a pristine Ni electrode, either on a lab scale or a pilot scale, is effective in facilitating nitrate reduction to ammonia, exhibiting extraordinarily high activity, selectivity, and stability. The self-activated Ni cathode has a robust capacity to reduce nitrate over a wide range of concentrations and achieves great conversion yield, NH4+-N selectivity, and Faradaic efficiency, respectively, 95.3, 95.5, and 64.4% at 200 mg L-1 NO3--N and 97.8, 97.1, and 90.4% at 2000 mg L-1 NO3--N, for example. Fundamental research indicates that Ni(OH)2 nanoparticles are formed on the Ni electrode surface upon self-activation, which play crucial roles in governing nitrate reduction reaction (NO3RR) through the atomic H*-mediated pathway and accordingly suppressing hydrogen evolution reaction. More importantly, the self-activated Ni(OH)2@Ni cathode can be easily scaled up to allow large volumes of real industrial wastewater to be processed, successfully transferring nitrate into ammonia with high yields and Faradaic efficiency. This study demonstrates a new, mild, and promising method of cleaning nitrate-laden wastewater that produces ammonia as a valuable byproduct.

Single-Atom Cu Catalysts for Enhanced Electrocatalytic Nitrate Reduction with Significant Alleviation of Nitrite Production.

Metallic Cu is a well-known electrocatalyst for nitrate reduction reaction (NO3 RR), but it suffers from relatively low activity, poor stability, and inducing nitrite accumulation during the long-term operation. Herein, it is found that Cu catalysts minimized at the single-atom level can overcome the limitations of bulk materials in NO3 RR. A metal-nitrogen-carbon (M-N-C) electrocatalyst composed of carbon nanosheets embedding isolated copper atoms coordinated with N, Cu-N-C-800, is synthesized by pyrolysis of a Cu-based metal-organic framework at 800 °C. In comparison with Cu nanoparticles and Cu plate-800, kinetic measurements show that the Cu-N-C-800 electrocatalyst is more active and stable and distinctly suppresses the release of nitrite intermediate into the solution. The combined results of experimental data and density functional theory calculations indicate that Cu bound with N (particularly Cu-N2 ) is the key to favorable adsorption of NO3 - and NO2 - . This strong binding is responsible for the enhanced rate of nitrate conversion to the end products of ammonia and nitrogen. These findings highlight the promise of single-atom Cu electrocatalysts for nitrate reduction with desirable performance.

Immobilization of Phosphatidylserine by Ethanol and Lysozyme on the Cell Surface for Evaluation of Apoptosis-Like Decay in Activated-Sludge Bacteria.

Accurate determination of microbial viability can be crucial in microbe-dominated biosystems. However, the identification of metabolic decay in bacterial cells can be elaborate and difficult. We sought to identify apoptosis-like bacterial processes by using annexin V-fluorescein isothiocyanate (FITC) (AVF), a probe typically used to stain phosphatidylserine (PS) on exposed cell membranes. The bacterial cell wall provides a barrier that is responsible for low efficiency of direct PS staining of decayed bacterial cells. This can be overcome by pretreatment of the bacteria with 70% ethanol, which fixates the bacteria and preserves the PS status, combined with lysozyme treatment to hydrolyze the cell wall. That treatment improved the efficiency of AVF staining considerably, as shown for pure strains of an Ochrobactrum sp. and a Micrococcus sp. Using this method, decayed bacterial cells (induced by starvation) were more strongly stained, indicating externalization of PS to a greater extent than seen for cells harvested at logarithmic growth. A multispecies microbial sludge was artificially decayed by heat treatment or alternating anoxic-oxic treatment, which also induced increased AVF staining, again presumably via decay-related PS externalization. The method developed proved to be efficient for identification of bacterial decay and has potential for the evaluation of multispecies bacterial samples from sources like soil matrix, bioaerosol, and activated sludge.IMPORTANCE Since the externalization of phosphatidylserine (PS) is considered a crucial characteristic of apoptosis, we sought to identify apoptosis-like decay in bacterial cells by PS staining using AVF. We show that this is possible, provided the bacteria are pretreated with ethanol plus lysozyme to remove a physical staining barrier and preserve the original, decay-related externalization of PS. Our work suggests that PS externalization occurs in starved bacteria and this can be quantified with AVF staining, providing a measure of bacterial decay. Since PS is the common component of the lipid bilayer in bacterial cell membranes, this approach also has potential for evaluation of cell decay of other bacterial species.

Fe2+/HClO Reaction Produces FeIVO2+: An Enhanced Advanced Oxidation Process.

The reaction between Fe2+ and HClO constitutes a promising advanced oxidation process (AOP) for removing pollutants from wastewater, and •OH has been considered the dominant reactive oxidant despite limited evidence for this. Herein, we demonstrate that the Fe2+/HClO reaction enables the production of FeIVO2+ rather than •OH in acid medium, a finding that is strongly supported by multiple lines of evidence. Both X-ray absorption near-edge structure spectroscopic tests and Mössbauer spectroscopic tests confirmed the appearance of FeIVO2+ as the reactive intermediate in the reaction between Fe2+ and HClO. The determination of FeIVO2+ generation was also derived from the methyl phenyl sulfoxide (PMSO)-based probe experiments with respect to the formation of PMSO2 without •OH adducts and the density functional theory studies according to the lower energy barrier for producing FeIVO2+ compared with •OH. A dual-anode electrolytic system was established for the in situ generation of Fe2+ and HClO that allows the production of FeIVO2+. The system exhibits an enhanced capacity for oxidizing a model pollutant (e.g., phosphite) from industrial wastewater, making it an attractive and promising AOP for the abatement of aqueous contaminants.

Discovering the Importance of ClO• in a Coupled Electrochemical System for the Simultaneous Removal of Carbon and Nitrogen from Secondary Coking Wastewater Effluent.

Inorganic constituents in real wastewater, such as halides and carbonates/bicarbonates, may have negative effects on the performance of electrochemical systems because of their capability of quenching HO•. However, we discovered that the presence of Cl- and HCO3- in an electrochemical system is conducive to the formation of ClO•, which plays an important role in promoting the simultaneous elimination of biorefractory organics and nitrogen in secondary coking wastewater effluent. The 6-h operation of the coupled electrochemical system (an undivided electrolytic cell with a PbO2/Ti anode and a Cu/Zn cathode) at a current density of 37.5 mA cm-2 allowed the removal of 87.8% of chemical oxygen demand (COD) and 86.5% of total nitrogen. The electron paramagnetic resonance results suggested the formation of ClO• in the system, and the probe experiments confirmed the predominance of ClO•, whose steady-state concentrations (8.08 × 10-13 M) were 16.4, 26.5, and 1609.5 times those of Cl2•- (4.92 × 10-14 M), HO• (3.05 × 10-14 M), and Cl• (5.02 × 10-16 M), respectively. The rate constant of COD removal and the Faradaic efficiency of anodic oxidation obtained with Cl- and HCO3- was linearly proportional to the natural logarithm of the ClO• concentration, and the specific energy consumption was inversely correlated to it, demonstrating the crucial role of ClO• in pollutant removal.

One-Step Treatment of Phosphite-Laden Wastewater: A Single Electrochemical Reactor Integrating Superoxide Radical-Induced Oxidation and Electrocoagulation.

Elimination of phosphite from water is more difficult than elimination of phosphate owing to its higher solubility and resistance to biotransformation. Herein, we report an efficient, facile, electrochemical method integrating electrooxdiation (EO) and electrocoagulation (EC) to treat phosphite-laden wastewater. The mechanistic studies demonstrate that in-situ-generated Fe2+ at an Fe anode can react with in-situ-generated O2 at a mixed metal oxide (MMO) anode, leading to formation of •O2-, a reactive species predominantly responsible for oxidation of phosphite to phosphate. The phosphate is immediately coagulated by Fe hydroxides that are formed due to the production of OH- at a stainless-steel cathode. The integrated EO/EC system enables a phosphite removal efficiency of 74.25% (MMO anode, 100 mA; Fe anode, 100 mA; reaction time, 60 min), a significantly higher efficiency rate than the rate obtained in the control experiments in the absence of an MMO anode (<23.41%) and the rate obtained with the chemical coagulation process (<5.03%). The quenching experiments with scavengers and electron spin resonance tests verify the pivotal role of •O2- in transformation of phosphite. Tests carried out with nickel-plating wastewater further demonstrate the superiority of this integrated system, as evidenced by efficient removal of phosphite and nickel from the solution.

Residual chemical oxygen demand (COD) fractionation in bio-treated coking wastewater integrating solution property characterization.

The refractory nature of residual COD in bio-treated coking wastewater (BTCW) creates barriers for its further treatment and reclamation. It is necessary to fractionate the residual COD in BTCW associated with characterization of solution properties. In this paper, a stepwise process composed of membrane filtration, coagulation, adsorption and ozonation was proposed to fractionate residual COD in the BTCW, in which the COD was stepwise reduced to near zero. In addition, the correlation between COD and water quality indexes as well as solution properties were discussed together with a safety assessment of the water quality. Results showed that the residual COD fractionation percentage contributed by suspended solids, colloids, dissolved organics and reductive inorganic substances in the BTCW was 43.7%, 22.1%, 26.2% and 4.9%, respectively. By stepwise fractionating of these substances, the residual COD was reduced from 168.8 to 5.2 mg L-1, and the UV254 value decreased from 1.90 to 0.15 cm-1. In addition, the particle size of the dominant substances contributing to the residual COD was smaller than 450 nm. Among these substances, the hydrophobic fraction accounted for 78.66% (in the term of TOC). Three-dimensional excitation-emission matrix (3D-EEM) analysis showed that hydrophobic neutral substances (HON) were the main fluorescence constituent in the BTCW, which was highly removable by adsorption. The residual COD after adsorption was mainly composed of reductive inorganic substances. Apart from pursuit of high COD removal rates, more emphasis should be given to the removal of toxic COD. Correlations were observed between the residual COD and water quality indicators as well as solution properties, providing a guideline for optimized removal of residual COD in the BTCW. In summary, these results gave a referential information about the nature of residual COD in the BTCW for the selection of advanced treatment technologies and the management of water quality safety.

Bioelectricity generation by wetland plant-sediment microbial fuel cells (P-SMFC) and effects on the transformation and mobility of arsenic and heavy metals in sediment.

Two wetland plant-sediment microbial fuel cell systems (PSM1 and PSM2) and one wetland sediment microbial fuel cell system (SM) were constructed to investigate their electricity production performance and the simultaneous migration and transformation of arsenic and heavy metals in sediment and overlying water, arsenic and heavy metals uptake by plants. The bioelectricity generation was monitored for 175 days, and sediment samples were collected at three time points (64, 125 and 200 days) for the analysis. The results showed that plants improved the efficiency of the electricity production by the fuel cell system. The average output voltage was: PSM1 (0.32 V) > PSM2 (0.28 V) > SM (0.24 V)(P ≤ 0.05).The electricity production of the electrodes and the introduction of plants affected the mobility and transformation of As, Zn and Cd in the sediment, which contributed to their stability in the sediment and reduced the release of these metals into the overlying water column. The bioelectricity production process affected the bioavailability of arsenic and heavy metals in the sediment and attenuated metal uptake by plants, which indicated the potential for remediation of arsenic and heavy metals pollution in sediment.

Metal-Carbon Hybrid Electrocatalysts Derived from Ion-Exchange Resin Containing Heavy Metals for Efficient Hydrogen Evolution Reaction.

Transition metal-carbon hybrids have been proposed as efficient electrocatalysts for hydrogen evolution reaction (HER) in acidic media. Herein, effective HER electrocatalysts based on metal-carbon composites are prepared by controlled pyrolysis of resin containing a variety of heavy metals. For the first time, Cr2 O3 nanoparticles of 3-6 nm in diameter homogeneously dispersed in the resulting porous carbon framework (Cr-C hybrid) is synthesized as efficient HER electrocatalyst. Electrochemical measurements show that Cr-C hybrids display a high HER activity with an onset potential of -49 mV (vs reversible hydrogen electrode), a Tafel slope of 90 mV dec(-1) , a large catalytic current density of 10 mA cm(-2) at -123 mV, and the prominent electrochemical durability. X-ray photoelectron spectroscopic measurements confirm that electron transfer occurs from Cr2 O3 into carbon, which is consistent with the reported metal@carbon systems. The obtained correlation between metals and HER activities may be exploited as a rational guideline in the design and engineering of HER electrocatalysts.

Patients with type 2 diabetes exhibit cognitive impairment with changes of metabolite concentration in the left hippocampus.

Type 2 diabetes mellitus (T2DM) is associated with cognitive dysfunction. Previous studies have reported the relationship between cerebral metabolite changes and glucose levels. However, the specific aspects of cognition that are affected by metabolic changes in T2DM- related cognitive impairment remain undetermined. In this study, 188 T2DM patients and 266 controls were recruited. Proton magnetic resonance spectra with a single voxel stimulated echo acquisition mode (STEAM) were acquired from the left hippocampus and the frontal lobe. Presence of T2DM negatively affected the scores of Mini-Mental State Examination (MMSE), sub-tests (i.e., attention and language) of MMSE, Montreal Cognitive Assessment (MoCA) according to the Beijing version, and sub-tests (i.e., visuospatial/executive reasoning, attention, and language) of MoCA, rather than the Wechsler Memory Scale - Revised in China (WMS-RC), and all memory sub-tests contained with the MMSE and MoCA frameworks. T2DM positively affected creatine and myoinositol peak areas from the left hippocampus, rather than metabolites in the left frontal lobe. Negative correlations were shown between the left hippocampal myoinositol levels and language scores, and between the left hippocampal creatine levels and visuospatial/executive scores in T2DM. These findings suggest that T2DM may be an independent risk factor for cognitive impairment. Further, the cognitive domains of visuospatial /executive reasoning, attention and language may be predominantly impaired in the early phases of T2DM-related cognitive impairment. In addition, left hippocampal myoinositol and creatine concentrations were associated with cognitive impairment in patients with T2DM.