Enhanced chlorobenzene removal by internal magnetic field through initial cell adhesion and biofilm formation.

Magnetic fields (MF) have been proven efficient in bioaugmentation, and the internal MFs have become competitive because they require no configuration, despite their application in waste gas treatment remaining largely unexplored. In this study, we firstly developed an intensity-regulable bioaugmentation with internal MF for gaseous chlorobenzene (CB) treatment with modified packing in batch bioreactors, and the elimination capacity increased by up to 26%, surpassing that of the external MF. Additionally, the microbial affinity to CB and the packing surface was enhanced, which was correlated with the ninefold increased secreted ratio of proteins/polysaccharides, 43% promoted cell surface hydrophobicity, and half reduced zeta potential. Furthermore, the dehydrogenase content was promoted over 3 times, and CB removal steadily increased with the rising intensity indicating enhanced biofilm activity and reduced CB bioimpedance; this was further supported by kinetic analysis, which resulted in improved cell adhesive ability and biological utilisation of CB. The results introduced a novel concept of adjustable magnetic bioaugmentation and provided technical support for industrial waste gas treatments. KEY POINTS: • Regulable magnetic bioaugmentation was developed to promote 26% chlorobenzene removal • Chlorobenzene mineralisation was enhanced under the magnetic field • Microbial adhesion was promoted through weakening repulsive forces.

Mechanisms of Active Substances in a Dielectric Barrier Discharge Reactor: Species Determination, Interaction Analysis, and Contribution to Chlorobenzene Removal.

Several typical active substances (•NO, •NO2, H2O2, O3, •OH, and O2-•), directly or indirectly play dominant roles during dielectric barrier discharge (DBD) reaction. This study measured these active substances and removed them by using radical scavengers, such as catalase, superoxide dismutase, carboxy-PTIO (c-PTIO), tert-butanol (TBA), and MnO2 in different reaction atmospheres (air, N2, and O2). The mechanism for chlorobenzene (CB) removal by plasma in air atmosphere was also investigated. The production of O═NOO-• generated by •NO took around 75% of the total production of O═NOO-•. Removing •NO increased the O3 amount by about 80% likely because of the mutual inhibition between O3 and reactive nitrogen species in or out of the discharge area. The quantitative comparison of •OH and H2O2 revealed that the formation of •OH was 3.06-4.65 times that of H2O2 in these reaction atmospheres. Calculation results showed that approximately 1.61% of H2O was used for O3 generation. Ionization patterns affected the form of solid deposits during the removal of CB in N2 and O2 atmospheres caused by Penning ionization and thermal radiation tendencies, respectively. Correlation analysis results suggested the macroscopic synergistic or inhibitory effects happened among these active substances. A zero-dimensional reaction kinetics model was adopted to analyze the reactions during the formation of active substances in DBD, and the results showed good consistency with experiments. The interactions of each active substance were clarified. Finally, a response surface method model was developed to predict CB removal by the DBD plasma process. Stepwise regression analysis results showed that CB removal was affected by the contents of different active substances in air, N2 atmosphere, and O2 atmosphere, respectively: O2-•, •OH, and O3; H2O2, O═NOO-•, and O3; •OH and O3.

A Novel Dual-Stage Phase Separation Process for CO2 Absorption into a Biphasic Solvent with Low Energy Penalty.

An amine-based biphasic solvent is promising to cut down the energy penalty of CO2 capture. However, the high viscosity of the CO2-enriched solvent retards its industrial application. This work proposed a novel dual-stage phase separation process using a triethylenetetramine and 2-(diethylamino)ethanol blend as a biphasic solvent, which separates a certain proportion of CO2-enriched phase during CO2 absorption to reduce its viscosity. Experimental results showed that the proposed dual-stage phase separation process improved the phase separation behavior and effectively enhanced the absorption rate by 49% at 50 °C, when 50 vol % CO2-enriched phase was separated at 0.3 mol mol-1. Kinetic analysis showed that the absorption rate was mainly controlled by liquid-side mass transfer. The regeneration heat of the dual-stage phase separation process cut down the energy penalty by 33% compared with the monoethanolamine-based process. Compared with the conventional biphasic solvent-based process, the heat duty was further declined by 8%. The 1H nuclear magnetic resonance analysis showed that the dual-stage phase separation process could effectively control the generation of absorption products and intensify the interphase migration of tertiary amines.

Phase Splitting Agent Regulated Biphasic Solvent for Efficient CO2 Capture with a Low Heat Duty.

A biphasic solvent features high absorption capacity and low heat duty for CO2 capture. Phase separation behavior is essential to cut down energy penalty. Four phase splitting agents with different hydrophobicities, such as 1,3-dimethyl-2-imidazolidinone (DMI), 1-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide, and sulfolane, were dosed to biphasic solvents, triethylenetetramine and 2-(diethylamino)ethanol. Experimental results revealed that they can tune the phase separation behavior during CO2 absorption. Generally, under the same CO2 loading, the volume ratio of the rich phase increased with their hydrophobicity (log P), which accounts for over 50%. Moreover, their influences on absorption capacity, kinetics, and thermodynamics were also investigated. After dosing NMP, the heat duty was decreased by 22%. Furthermore, a phase splitting agent with a positive log P was more conducive to reducing the heat duty, and one with a negative log P enhanced the absorption rate. With DMI, the absorption rate was 114% higher than that of MEA at rich loading. The 13C NMR analysis showed that the agents were not involved in CO2 absorption and did not affect the reaction mechanism. Furthermore, quantum calculation was used to verify the reaction mechanism, confirming that the phase splitting agent increases the reaction equilibrium constant and makes it proceed more thoroughly.

Novel Biphasic Solvent with Tunable Phase Separation for CO2 Capture: Role of Water Content in Mechanism, Kinetics, and Energy Penalty.

The biphasic solvent-based absorption process has been regarded as a promising alternative to the monoethanolamine (MEA)-based process because of its high absorption capacity, phase separation behavior, and potential for conserving energy for CO2 capture. A trade-off between the absorption capacity and phase separation ratio is critical for developing an advanced biphasic solvent. Typically, water content in the biphasic solvent can be manipulated to tune the phase separation behavior. To explore the relationship between water content and phase separation behavior, an inert organic solvent, 1-methyl-2-pyrrolidinone, was added as a substitute for water in a biphasic solvent, specifically a triethylenetetramine (TETA) and 2-(diethylamino)ethanol (DEEA) blend. Moreover, the water content-kinetics and thermodynamics relationships were also evaluated. Experimental results revealed that reducing the water content was beneficial for phase separation but adverse for adsorption capacity. Kinetic analysis indicated that the water content did not significantly affect the rate of CO2 absorption at a rich loading. Furthermore, the regeneration heat decreased with the water content. The regeneration heat of TETA-DEEA with a water content of 20 wt % was almost 50% less than that of MEA solution. 13C nuclear magnetic resonance analysis revealed that the water content did not affect the reaction mechanism between CO2 and amines.

Piscinibacter caeni sp. nov., isolated from activated sludge.

A yellowish-pigmented bacterial strain, designated as MQ-18T, was isolated from a sample of activated sludge collected from a pharmaceutical factory in Zhejiang, China. The strain was characterized through a polyphasic taxonomy approach. 16S rRNA gene sequence analysis demonstrated that strain MQ-18T showed high similarities to Piscinibacter defluvii SH-1T (99.7 %) and Piscinibacter aquaticus IMCC1728T (98.4 %), thereby suggesting that it belongs to the genus Piscinibacter. The DNA-DNA relatedness values of this strain to strains SH-1T and IMCC1728T were only 35.4 and 33.3 %, respectively. Cells of MQ-18T were Gram-negative, aerobic, motile, rod-shaped and non-spore forming. This strain exhibited growth at 25-37 °C (optimum: 30 °C) in the presence of 0-3.0 % (w/v) NaCl (optimum, 0 % NaCl) and at pH 5.0-8.0 (pH 7.0). The predominant fatty acids were C12 : 0 (5.5 %), C16 : 0 (33.7 %), summed feature 3 (C16 : 1ω7c and/or C16 : 1ω6c; 38.5 %), and summed feature 4 (anteiso-C17 : 1 B and/or iso C17 : 1 I; 11.6 %). The main quinone type was ubiquinone-8, and the major polyamines were cadaverine and putrescine. The major polar lipid profile consisted of diphosphatidylglycerol, phosphatidylglycerol and phosphatidylethanolamine. The DNA G+C content was 70.1 mol%. On the basis of its phylogenetic, phenotypic and physiological characteristics, strain MQ-18T is considered to represent a novel species of the genus Piscinibacter, for which the name Piscinibacter caeni sp. nov. is proposed. The type strain is MQ-18T (CCTCC AB 2017223T=JCM 32138T).

Carbonic Anhydrase Enzyme-MOFs Composite with a Superior Catalytic Performance to Promote CO2 Absorption into Tertiary Amine Solution.

Carbonic anhydrase (CA) enzyme-based absorption technology for CO2 capture has been intensively investigated. The main issue related to this novel technology is the activity and stability of the CA enzyme under the typical flue gas conditions. To address this issue, CA enzymes were embedded into zeolitic imidazolate framework (ZIF-L) nanoparticles to synthesize a novel CA/ZIF-L-1 composite. The composite exhibited a superior apparent catalytic activity (1.5 times higher) for CO2 absorption compared with their free counterparts, which was due to the synergistic enhancement of CO2 adsorption by support ZIF-L and enzymatic catalysis. The analyses of Fourier transform infrared spectroscopy and circular dichroism revealed that the CA enzyme's secondary structure was not significantly varied during the CA/ZIF-L-1 preparation, resulting in a high enzyme activity retention. Moreover, the CA/ZIF-L-1 possessed a high thermal stability and reusability due to the structural rigidity and confinement of ZIF-L scaffolds. Compared with the free enzyme, its thermal stability was improved by approximately 100% at 40 °C. After six cycles of reuse, CA/ZIF-L-1 still retained a relative activity of 134%. Therefore, the CA/ZIF-L-1 can be a good candidate to promote the CO2 capture in industrial application.

Comparative investigation on a hexane-degrading strain with different cell surface hydrophobicities mediated by starch and chitosan.

Bioremediation usually exhibits low removal efficiency toward hexane because of poor water solubility, which limits the mass transfer rate between the substrate and microorganism. This work aimed to enhance the hexane degradation rate by increasing cell surface hydrophobicity (CSH) of the degrader, Pseudomonas mendocina NX-1. The CSH of P. mendocina NX-1 was manipulated by treatment with starch and chitosan solution of varied concentrations, reaching a maximum hydrophobicity of 52%. The biodegradation of hexane conformed to the Haldane inhibition model, and the maximum degradation rate (ν max) of the cells with 52% CSH was 0.72 mg (mg cell)-1·h-1 in comparison with 0.47 mg (mg cell)-1·h-1 for cells with 15% CSH. The production of CO2 by high CSH cells was threefold higher than that by cells at 15% CSH within 30 h, and the cumulative rates of O2 consumption were 0.16 and 0.05 mL/h, respectively. High CSH was related to low negative charge carried by the cell surface and probably reduced the repulsive electrostatic interactions between hexane and microorganisms. The FT-IR spectra of cell envelopes demonstrated that the methyl chain was inversely proportional to increasing CSH values, but proteins exhibited a positive effect to CSH enhancement. The ratio of extracellular proteins and polysaccharides increased from 0.87 to 3.78 when the cells were treated with starch and chitosan, indicating their possible roles in increased CSH.

Characterization and Genome Analysis of a Nicotine and Nicotinic Acid-Degrading Strain Pseudomonas putida JQ581 Isolated from Marine.

The presence of nicotine and nicotinic acid (NA) in the marine environment has caused great harm to human health and the natural environment. Therefore, there is an urgent need to use efficient and economical methods to remove such pollutants from the environment. In this study, a nicotine and NA-degrading bacterium-strain JQ581-was isolated from sediment from the East China Sea and identified as a member of Pseudomonas putida based on morphology, physio-biochemical characteristics, and 16S rDNA gene analysis. The relationship between growth and nicotine/NA degradation suggested that strain JQ581 was a good candidate for applications in the bioaugmentation treatment of nicotine/NA contamination. The degradation intermediates of nicotine are pseudooxynicotine (PN) and 3-succinoyl-pyridine (SP) based on UV, high performance liquid chromatography, and liquid chromatography-mass spectrometry analyses. However, 6-hydroxy-3-succinoyl-pyridine (HSP) was not detected. NA degradation intermediates were identified as 6-hydroxynicotinic acid (6HNA). The whole genome of strain JQ581 was sequenced and analyzed. Genome sequence analysis revealed that strain JQ581 contained the gene clusters for nicotine and NA degradation. This is the first report where a marine-derived Pseudomonas strain had the ability to degrade nicotine and NA simultaneously.

Structural effects of provincial digital economy on carbon emissions within China: A multi-region input-output based structural decomposition analysis.

The digital economy, serving as a new engine to boost China's economic growth, inevitably affects carbon emissions given both its green features and its potential demands for energy inputs. To investigate the province-level impacts of the digital economy on carbon emissions, this study splits the digital industry from the multi-regional input-output table, and adopts a downscale structural decomposition analysis to reveal the technological, structural, and scale effects of the digital economy on carbon emissions. The results show that: (1) the expansion of digital economy increased 186.3 Mt of carbon emissions at the aggregate level during the investigated period (2012-2017) and that, therefore, the direct structural effects of the digital economy played a leading role in emission reduction (-156 Mt); (2) in terms of heterogeneity, most provinces presented a U distribution with the structural mitigation effect at the bottom and highly-developed provinces generated significant negative spillover effects; (3) from a regional coordination perspective, digital production achieved greater carbon emission reductions in the eastern and western areas of the country, while the northeastern and central regions gained environmental benefits via digital applications. The main conclusions thus enhance existent understanding of China's digital economy and low-carbon development, and the paper also proffers corresponding policy recommendations, e.g., accelerating the convergence of digital economy and traditional industries to promote carbon emissions reduction.

Metagenomics revealing biomolecular insights into the enhanced toluene removal and electricity generation in PANI@CNT bioanode.

Microbial fuel cells (MFCs) have significant potential for environmental remediation and energy recycling directly from refractory aromatic hydrocarbons. To boost the capacities of toluene removal and the electricity production in MFCs, this study constructed a polyaniline@carbon nanotube (PANI@CNT) bioanode with a three-dimensional framework structure. Compared with the control bioanode based on graphite sheet, the PANI@CNT bioanode increased the output voltage and toluene degradation kinetics by 2.27-fold and 1.40-fold to 0.399 V and 0.60 h-1, respectively. Metagenomic analysis revealed that the PANI@CNT bioanode promoted the selective enrichment of Pseudomonas, with the dual functions of degrading toluene and generating exogenous electrons. Additionally, compelling genomic evidence elucidating the relationship between functional genes and microorganisms was found. It was interesting that the genes derived from Pseudomonas related to extracellular electron transfer, tricarboxylic acid cycle, and toluene degradation were upregulated due to the existence of PANI@CNT. This study provided biomolecular insights into key genes and related microorganisms that effectively facilitated the organic pollutant degradation and energy recovery in MFCs, offering a novel alternative for high-performance bioanode.

Electro-stimulated biodegradation of dimethyl disulfide: Insights from biofilm spatial structure and key functional genes.

As a typical sulfur-containing volatile organic compound, dimethyl disulfide (DMDS) is known for its high toxicity and resistance to degradation, necessitating efficient control in environmental media. To address the limitations of biological treatment in degradation capacity, this study employs electro-stimulation to promote DMDS elimination by a porous polyaniline@carbon nanotube bioanode developed on graphite sheet (PANI@CNT/GS). Compared with the unmodified GS bioanode, the PANI@CNT/GS bioanode demonstrates significant advantages in biofilm activity, redox property, and DMDS degradation efficiency. Kinetics analysis shows that the maximum degradation rate of the PANI@CNT/GS bioanode was 0.60 mM h-1, which is 1.36 times higher than that of the control. Characterization results reveal that the highly active biofilms in PANI@CNT/GS bioanode possess 1.40 times the amount of living cells and a 12.5% increase in thickness, contributing to the notable enhancement in DMDS degradation capacity. Additionally, functional gene annotation indicates that the PANI@CNT/GS electrode facilitates the motility and activity of microbial cells and enriches the genes encoding key enzymes involved in DMDS metabolism. This work validates the feasibility of electro-stimulation for enhancing DMDS degradation and further provides in-depth insights into the process intensification mechanism from the perspectives of biofilm spatial structure and key functional genes.

Enhanced 1,2-dichloroethane removal using g-C3N4/Blue TiO2 nanotube array photoanode in microbial photoelectrochemical cells.

The compound 1,2-dichloroethane (1,2-DCA), a persistent and ubiquitous pollutant, is often found in groundwater and can strongly affect the ecological environment. However, the extreme bio-impedance of C-Cl bonds means that a high energy input is needed to drive biological dechlorination. Biotechnology techniques based on microbial photoelectrochemical cell (MPEC) could potentially convert solar energy into electricity and significantly reduce the external energy inputs currently needed to treat 1,2-DCA. However, low electricity-generating efficiency at the anode and sluggish bioreaction kinetics at the cathode limit the application of MPEC. In this study, a g-C3N4/Blue TiO2-NTA photoanode was fabricated and incorporated into an MPEC for 1,2-DCA removal. Optimal performance was achieved when Blue TiO2 nanotube arrays (Blue TiO2-NTA) were loaded with graphitic carbon nitride (g-C3N4) 10 times. The photocurrent density of the g-C3N4/Blue TiO2-NTA composite electrode was 2.48-fold higher than that of the pure Blue TiO2-NTA electrode under light irradiation. Furthermore, the MPEC equipped with g-C3N4/Blue TiO2-NTA improved 1,2-DCA removal efficiency by 45.21% compared to the Blue TiO2-NTA alone, which is comparable to that of a microbial electrolysis cell. In the modified MPEC, the current efficiency reached 69.07% when the light intensity was 150 mW cm-2 and the 1,2-DCA concentration was 4.4 mM. The excellent performance of the novel MPEC was attributed to the efficient direct electron transfer process and the abundant dechlorinators and electroactive bacteria. These results provide a sustainable and cost-effective strategy to improve 1,2-DCA treatment using a biocathode driven by a photoanode.

Effective anaerobic treatment of fresh leachate from MSW incineration plant and dynamic characteristics of microbial community in granular sludge.

We investigated the treatment of fresh leachate from municipal solid waste incineration plants with high-strength organics using a lab-scale expanded granular sludge bed (EGSB) reactor. The reactor was operated at a mesophilic temperature (33 °C) for 118 days. The influent chemical oxygen demand (COD) of the leachate gradually increased to over 70,000 mg/L, and the organic loading rate increased to 18 kg COD/(m(3) day). An average COD removal efficiency of 86.7 % was achieved when the reactor was fed with raw leachate, which suggests the feasibility of the EGSB process for leachate treatment. The microbial communities in the sludge from the reactor during the trial operation were constructed by denaturing gradient gel electrophoresis, clone libraries, and real-time quantitative polymerase chain reaction. The dominant group for archaea was Methanosaeta, with 68.4 % proportion at the start of the operation, and then changed to Methanosarcina, with a proportion of 62.3 %, after 118 days of operation. The dominant group of eubacteria was confirmed to be Firmicutes throughout the operation process, with the proportion increasing from >50 to 81.2 %. Almost all the operational taxonomic units of Firmicutes belonged to the order Clostridiales, with characteristic spore formation. The microbial diversity of the population was low under raw leachate as feed in the reactor. The dynamics of the microbial community in the anaerobic granular sludge was discussed relating with the operating status of the EGSB reactor.

Coupling Ni-Cu atomic pair to promote CO2 electroreduction with near-unity CO selectivity.

The electrocatalytic reduction of CO2 towards CO is one of the most desirable routines to reduce atmospheric CO2 concentration and maintain a global carbon balance. In this work, a novel porous NiCu-embedded ZIF-derived N-doped carbon nanoparticle (NiCu@NCNPs) catalyst has been identified as an active, highly selective, stable, and cost-effective catalyst in CO2 reduction. A CO selectivity as high as 100% has been achieved on NiCu@NCNPs which is the highest reported to date. The particle current density of CO on NiCu@NCNPs is around 15 mA cm-2 under the optimized potential at -0.9 V vs. RHE. The NiCu@NCNPs electrode also exhibits excellent stability during the five sequential CO2 electroreduction experiments. The superior catalytic performance of NiCu@NCNPs in CO2RR can be related to its microstructure with high electrochemical surface area and low electron transfer resistance. Furthermore, a kinetic analysis has shown the formation of intermediate *COOH is the rate-determining step in CO2RR towards CO. According to the results of density functional theory (DFT) calculations, a low Gibbs-free energy change (∆G) for the rate-determining step leads to the enhanced catalytic performance of CO2RR on NiCu@NCNPs.

Dibenzothiophene Removal from Fuel Oil by Metal-Organic Frameworks: Performance and Kinetics.

Desulfurization of organic sulfur in the fuel oil is essential to cut down the emission of sulfur dioxide, which is a major precursor of the acid rain and PM2.5. Currently, hydrodesulfurization is regarded as a state-of-art technology for the desulfurization of fuel oil. However, due to the stringent legislation of the fuel oil, the deep desulfurization technology is urgent to be developed. Adsorptive desulfurization method is promising due to the high selectivity and easy operation. The development of efficient adsorbent is important to advance this technology into industrial application. In this work, the five types of metal-organic frameworks (MOFs), including Cu-BTC, UMCM-150, MIL-101(Cr), UIO-66, and Cu-ABTC were synthesized for the adsorption of dibenzothiophene (DBT), a typical organic sulfur compound in the fuel oil. The experimental results revealed that the adsorption capacity of the five MOFs followed the order of Cu-ABTC, UMCM-150, Cu-BTC, MIL-101(Cr), and UIO-66, which adsorption capacities were 46.2, 34.2, 28.3, 26.3, and 22.0 mgS/g, respectively. The three types of Cu-based MOFs such as Cu-ABTC, UMCM-150, and Cu-BTC outperformed the Cr-based MOFs, MIL-101, and Zr-based MOFs, UIO-66. Since the surface area and pore volumes of the Cu-based MOFs were not the greatest among the tested five MOFs, the physical properties of the MOFs were not the only limited factor for the DBT adsorption. The π-complexation between DBT and linkers/metal in the MOFs was also important. Kinetic analysis showed that the DBT adsorption onto the five tested MOFs follows the pseudo-second-order kinetics, confirming that the chemical π-complexation was also contributed to the DBT adsorption. Furthermore, the operation parameters such as oil-adsorbent ratio, initial sulfur concentration and adsorption temperature for the DBT adsorption onto Cu-ABTC were optimized to be 100:1 g/g, 1000 mgS/L and 30 °C, respectively. This work can provide some insights into the development of efficient adsorbent for the organic sulfur adsorption.

BiOI-SnO2 Heterojunction Design to Boost Visible-Light-Driven Photocatalytic NO Purification.

The efficient, stable, and selective photocatalytic conversion of nitric oxide (NO) into harmless products such as nitrate (NO3-) is greatly desired but remains an enormous challenge. In this work, a series of BiOI/SnO2 heterojunctions (denoted as X%B-S, where X% is the mass portion of BiOI compared with the mass of SnO2) were synthesized for the efficient transformation of NO into harmless NO3-. The best performance was achieved by the 30%B-S catalyst, whose NO removal efficiency was 96.3% and 47.2% higher than that of 15%B-S and 75%B-S, respectively. Moreover, 30%B-S also exhibited good stability and recyclability. This enhanced performance was mainly caused by the heterojunction structure, which facilitated charge transport and electron-hole separation. Under visible light irradiation, the electrons gathered in SnO2 transformed O2 to ·O2- and ·OH, while the holes generated in BiOI oxidized H2O to produce ·OH. The abundantly generated ·OH, ·O2-, and 1O2 species effectively converted NO to NO- and NO2-, thus promoting the oxidation of NO to NO3-. Overall, the heterojunction formation between p-type BiOI and n-type SnO2 significantly reduced the recombination of photo-induced electron-hole pairs and promoted the photocatalytic activity. This work reveals the critical role of heterojunctions during photocatalytic degradation and provides some insight into NO removal.

Performance and Mechanisms of Sulfidated Nanoscale Zero-Valent Iron Materials for Toxic TCE Removal from the Groundwater.

Trichloroethylene (TCE) is one of the most widely distributed pollutants in groundwater and poses serious risks to the environment and human health. In this study, sulfidated nanoscale zero-valent iron (S-nZVI) materials with different Fe/S molar ratios were synthesized by one-step methods. These materials degraded TCE in groundwater and followed a pathway that did not involve the production of toxic byproducts such as dichloroethenes (DCEs) and vinyl chloride (VC). The effects of sulfur content on TCE dechlorination by S-nZVI were thoroughly investigated in terms of TCE-removal efficiency, H2 evolution, and reaction rate. X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) characterizations confirmed Fe(0) levels in S-nZVI were larger than for zero-valent iron (nZVI). An Fe/S molar ratio of 10 provided the highest TCE-removal efficiencies. Compared with nZVI, the 24-h TCE removal efficiencies of S-nZVI (Fe/S = 10) increased from 30.2% to 92.6%, and the Fe(0) consumed during a side-reaction of H2 evolution dropped from 77.0% to 12.8%. This indicated the incorporation of sulfur effectively inhibited H2 evolution and allowed more Fe(0) to react with TCE. Moreover, the pseudo-first-order kinetic rate constants of S-nZVI materials increased by up to 485% compared to nZVI. In addition, a TCE degradation was proposed based on the variation of detected degradation products. Noting that acetylene, ethylene, and ethane were detected rather than DCEs and VC confirmed that TCE degradation followed ß-elimination with acetylene as the intermediate. These results demonstrated that sulfide modification significantly enhanced nZVI performance for TCE degradation, minimized toxic-byproduct formation, and mitigated health risks. This work provides some insight into the remediation of chlorinated-organic-compound-contaminated groundwater and protection from secondary pollution during remediation by adjusting the degradation pathway.

Flavin mononucleotide-stimulated microbial fuel cell for efficient gaseous toluene abatement.

Chemical park is regarded as a major contributor of VOCs emissions in China. Currently, a green and safe technology, microbial fuel cells (MFCs), is being developed for the VOCs abatement. Noting that effective electron transfer is critical to the MFC performance. In this work, flavin mononucleotide (FMN) was dosed as an electron shuttle to improve the removal of the typical toxic VOCs, toluene. The experimental results revealed that the performance of toluene removal and power generation were accelerated with the dosage of 0.2-2 µM FMN. With the addition of 1 µM FMN, the removal efficiency, the maximum output voltage and the coulombic efficiency of MFC were increased by 18.4%, 64.4% and 56.3%, respectively. However, a further increase in FMN concentration to 2 µM caused a reduction in the removal efficiency and coulombic efficiency. The images of scanning electron microscopy and confocal laser scanning microscopy showed that the presence of FMN greatly promoted the microbial growth and its activity. Furthermore, microbial community analysis also implied that the moderate dosage of FMN (0.2-1 µM) was beneficial for the growth of the typical exoelectrogens, Geobacter sp., and thus the coulombic efficiency was increased. In addition, an electron transfer pathway involving in cytochrome b, OMCs, cytochrome c, and MtrA was proposed based on the cyclic voltammetry analysis. This work will provide a fundamental theoretical support for its application of toxic VOCs abatement from the chemical park.

Superior dimethyl disulfide degradation in a microbial fuel cell: Extracellular electron transfer and hybrid metabolism pathways.

To enhance the biological degradation of volatile organic sulfur compounds, a microbial fuel cell (MFC) system with superior activity is developed for dimethyl disulfide (DMDS) degradation. The MFC achieves a removal efficiency near 100% within 6 h (initial concentration: 90 mg L-1) and a maximum biodegradation rate constant of 0.743 mM h-1. The DMDS removal load attains 2.684 mmol h-1 L-1, which is 6.18-2440 times the loads of conventional biodegradation processes reported. Meanwhile, the maximum power density output and corresponding current density output are 5.40 W m-3 and 40.6 A m-3, respectively. The main mechanism of extracellular electron transfer is classified as mediated electron transfer, supplemented by direct transfer. Furthermore, the mass balance analysis indicates that methanethiol, S0, S2-, SO42-, HCHO, and CO2 are the main intermediate and end products involved in the hybrid metabolism pathway of DMDS. Overall, these findings may offer basic information for bioelectrochemical degradation of DMDS and facilitate the application of MFC in waste gas treatment. ENVIRONMENTAL IMPLICATION: Dimethyl disulfide (DMDS), which features poor solubility, odorous smell, and refractory property, is a typical pollutant emitted from the petrochemical industry. For the first time, we develop an MFC system for DMDS degradation. The superior DMDS removal load per unit reactor volume is 6.18-2440 times those of conventional biodegradation processes in literature. Both the electron transfer route and the hybrid metabolism pathway of DMDS are cleared in this work. Overall, these findings give an in-depth understanding of the bioelectrochemical DMDS degradation mechanism and provide an efficient alternative for DMDS removal.