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A crucial step in the formation of mono-aminoboranes (R2N-BH2) from the corresponding imine-BH3 adducts, under mild reaction conditions, is the 1,3-hydride shift. We offer experimental and theoretical insights into this...

In biofilm electrode reactors (BER), good nitrate removal performance can be achieved through cooperation of heterotrophic and hydrogen autotrophic denitrification under low carbon/nitrogen conditions. In this study, we proposed a more multifunctional composite cathode, which combine immobilized anthraquinone-2,6-disulphonic disodium salt (AQDS) with polypyrrole (PPy) by electrochemical polymerization-doping method. The nitrate removal performance in BER with PPy/AQDS composite cathode was obviously improved, the nitrate removal rate (4.96 mg/L·h) was almost 2.0 times higher than the control BER system, and relatively stabled nitrate removal efficiency (≥90.0%) was also achieved even as the COD/N of 2.50. Compared with the bare graphite felt, PPy/AQDS coating cathode showed much better electrocatalytic activities, which was more advantageous for in situ production of H

Effective treatment and utilization of sludge contribute to achieve conventional carbon emission reduction and resource recovery, which is of great significance to realize carbon neutralization of WWTPs. Sludge carbonization derived biochar has attracted more interest because of high potential as catalytic materials. Therein, sludge-derived electrode exhibits a promising potential in the case of sludge utilization for electrocatalysis, however, electrocatalytic performance of the already reported sludge-derived electrode is unsatisfactory due to insufficient active sites. In this study, an efficient Pd/sludge-biochar loaded foam nickel (Pd-SAC@Ni) was successfully fabricated using simple pyrolysis and solidification method, and exhibited remarkable electrocatalytic performance for 4-chlorophenol (4-CP) degradation. Furthermore, the morphology, element distribution and crystal composition were characterized by SEM, EDS, XPS and XRD. The Pd-SAC@Ni electrode exhibited superior electrocatalytic performance than Ni, SAC@Ni, Pd-Ni electrodes. The reduction rate of 98.9% was achieved at current density of 5 mA cm

Although there exists a variety of different catalysts for hydroboration of organic substrates such as aldehydes, ketones, imines, nitriles etc., recent evidence suggests that tetra-coordinate borohydride species, formed by activation, redistribution, or decomposition of boron reagents, are the true hydride donors. We then proposed that Me2S-BH3 could also act as a hydride donor for the reduction of various imines, as similar compounds have been observed to reduce carbonyl substrates. This boron reagent was shown to be an effective and chemoselective hydroboration reagent for a wide variety of imines.

4-Hydroxybenzoic acid (HBA) is commonly found at high concentrations in waste streams generated by the thermochemical conversion of lignocellulosic biomass to bio-oils and biofuels. The objective of this study was to systematically assess the biotransformation of HBA in the bioanode of a microbial electrolysis cell (MEC) for the production of renewable cathodic H2. A mixed, denitrifying culture, enriched with HBA as the sole electron donor, was used as the anode inoculum. MEC electrochemical performance, H2 yield, HBA biotransformation pathways and products, and the bioanode suspended and biofilm microbial communities were examined. In the absence of nitrate, 60%-100% HBA was converted to phenol, which persisted, resulting in very limited exoelectrogenesis. Under nitrate-reducing conditions, complete HBA degradation was achieved in the MEC bioanode with very low phenol production, resulting in the production of cathodic H2. The predominant bacterial genus in the MEC bioanode (relative abundance 33.4%-41.9%) was the denitrifier Magnetospirillum, which uses the benzoyl-CoA pathway to degrade aromatic compounds. Geobacter accounted for 5.9-7.8% of the MEC bioanode community. Thus, active nitrate reduction in the MEC bioanode led to complete HBA degradation, resulting in a higher extent of exoelectrogenesis and cathodic H2 production. The results of this study provide mechanistic insights into a productive use of HBA and other phenolic compounds typically found in waste streams resulting from the thermochemical conversion of lignocellulosic biomass to biofuels.

Hexavalent chromium (Cr(VI)) may inhibit denitrification in biological wastewater treatment systems, and the inhibited denitrification process is difficult to recover in a short time. This study explored Cr(VI) cascade impact (20–125 mg L−1) on denitrification and developed one nontoxic biological accelerant (combination of L -cysteine, flavin adenine dinucleotide, biotin and cytokinin) for denitrification recovery. The results showed that NO3−-N removal efficiency decreased from 75.7% to 21.5% when Cr(VI) concentration increased from 80 to 125 mg L−1. Addition of accelerant could effectively promote the removal of NO3--N, and observably reduce the recovery time (42 T) compared with natural recovery (63 T). Furthermore, the main site of Cr(VI) reduction and Cr(III) immobilization was located in the intercellular compartment of the biofilm. Microbes produced more tightly bound extracellular polymeric substances (TB-EPS) to protect them from toxicity under the low Cr(VI) concentrations, while low EPS was secreted when Cr(VI) concentration was higher than 60 mg L−1. Compared to natural recovery system, bio-accelerant addition was beneficial to the recovery of denitrifiers activities, especially for the bacteria containing nirS gene. The results facilitated an understanding of Cr(VI) impact on denitrification, and the proposed bio-accelerant can be potentially applied to heavy metal shock-loading emergency situations.

Pyridine contamination poses a significant threat to human and environmental health. Due to the presence of nitrogen atom in the pyridine ring, the pi bond electrons are attracted toward it and make difficult for pyridine treatment with biological and chemical methods. In this study, coupling Fenton treatment with different biological process was designed to enhance pyridine biotransformation and further mineralization. After Fenton oxidation process optimized, pretreated pyridine was evaluated under three biological (anaerobic, aerobic and microaerobic) operating conditions. Under optimum Fenton oxidation, pyridine (30–75%) and TOC (5–25%) removal efficiencies were poor. Biological process alone also showed insignificant removal efficiency, particularly anaerobic (pyridine = 8.2%; TOC = 5.3%) culturing condition. However, combining Fenton pretreatment with biological process increased pyridine (93–99%) and TOC (87–93%) removals, suggesting that hydroxyl radical generated during Fenton oxidation enhanced pyridine hydroxylation and further mineralization in the biological (aerobic > microaerobic > anaerobic) process. Intermediates were analyzed with UPLC-MS and showed presence of maleic acid, pyruvic acid, glutaric dialdehyde, succinic semialdehyde and 4-formylamino-butyric acid. High-throughput sequencing analysis also indicated that Proteobacteria (35–43%) followed by Chloroflexi (10.6–24.3%) and Acidobacteria (8.0–29%) were the dominant phyla detected in the three biological treatment conditions. Co-existence of dominant genera under aerobic/microaerobic (Nitrospira > Dokdonella > Caldilinea) and anaerobic (Nitrospira > Caldilinea > Longilinea) systems most probably play significant role in biotransformation of pyridine and its intermediate products. Overall, integrating Fenton pretreatment with different biological process is a promising technology for pyridine treatment, especially the combined system enhanced anaerobic (>10 times) microbial pyridine biotransformation activity.

Monoaromatic compounds (MACs) are typical refractory organic pollutants which are existing widely in various environments. Biodegradation strategies are benign while the key issue is the sustainable supply of electron acceptors/donors. Bioelectrochemical system (BES) shows great potential in this field for providing continuous electrons for MACs degradation. Phenol and BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) can utilize anode to enhance oxidative degradation, while chlorophenols, nitrobenzene and antibiotic chloramphenicol (CAP) can be efficiently reduced to less-toxic products by the cathode. However, there still have several aspects need to be improved including the scale, electricity output and MACs degradation efficiency of BES. This review provides a comprehensive summary on the BES degradation of MACs, and discusses the advantages, future challenges and perspectives for BES development. Instead of traditional expensive dual-chamber configurations for MACs degradation, new single-chamber membrane-less reactors are cost-effective and the hydrogen generated from cathodes may promote the anode degradation. Electrode materials are the key to improve BES performance, approaches to increase the biofilm enrichment and conductivity of materials have been discussed, including surface modification as well as composition of carbon and metal-based materials. Besides, the development and introduction of functional microbes and redox mediators, participation of sulfur/hydrogen cycling may further enhance the BES versatility. Some critical parameters, such as the applied voltage and conductivity, can also affect the BES performance, which shouldn’t be overlooked. Moreover, sequential cathode-anode cascaded mode is a promising strategy for MACs complete mineralization.

BACKGROUND: A biofilm‐electrode reactor (BER) was developed on the basis of hydrogenotrophic denitrification. The BER can be strengthened by adding organic matter, and the nitrate removal will be enhanced by a combination of heterotrophic and autotrophic denitrification. Denitrification in a biological system can be affected by operating parameters, and the microbial community and functional genes can be changed at the same time. In this study, the effect of hydraulic retention time (HRT) and current on the denitrification of a low chemical oxygen demand to nitrogen ratio (COD/N), saline wastewater in a continuous‐flow BER was evaluated and compared to a conventional biofilm reactor (BR). RESULTS: The highest extent of nitrate removal was obtained at the optimum HRT (8 h) and current (10 mA). Low levels of ammonia (0.5–4 mg L⁻¹), produced through dissimilatory nitrate reduction to ammonia (DNRA), were observed. Quantitative real‐time polymerase chain reaction analysis revealed that the proportion of nirS‐type denitrifiers (3.75–8.30%) exceeded nirK‐type denitrifiers (0.24–0.90%) in both BR and BER. The genera of T78, Paracoccus and Azoarcus were identified as the dominant denitrifying bacteria in the BER. The cooperative activity of nitrate, nitrite and nitrous oxide reductase is necessary to reduce nitrate to dinitrogen in the denitrification process. The highest ratio of nosZ/nir genes in the bacterial community was 0.25 when the applied current was 10 mA. CONCLUSION: Compared to other denitrification reactors, the BER is more effective to treat low‐COD/N, saline wastewater with short HRT and low current. © 2018 Society of Chemical Industry

A dicyclic-type electrode-based biofilm-electrode reactor (BER) was investigated for simultaneous removal of nitrate and Cr(VI). In the absence of Cr(VI), almost complete denitrification of 50 mg/L NO3−–N was achieved at a very low C/N ratio of 0.8 with the optimal current of 50 mA. Cr(VI) was removed by biological reduction and co-precipitation when Cr(VI) was taken as the only electron acceptor, and the removal efficiencies of Cr(VI) were 99.8%. In the coexistent system of nitrate and Cr(VI), nitrate removal was the result of the cooperation of hydrogenotrophic denitrification and heterotrophic denitrification. The methanol and H2 were also used as electron donors for biological reduction Cr(VI). The denitrification process was slightly inhibited by 1.00 mg/L Cr(VI) and 94.15% removal efficiency was achieved at current = 50 mA and HRT = 8 h. The present results show that the biofilm-electrode reactor is an effective way to simultaneous remove co-contaminants.

A dicyclic-type electrode based biofilm electrode reactor (BER) was developed for advanced nitrate removal from saline municipal wastewater. The denitrification efficiency was evaluated with a synthetic feed (NO3−-N, 20 mg L−1) under different salinity and COD to nitrogen ratios (COD/N). As the salinity increased from 0% to 1.0%, the denitrification performance of both the traditional biofilm reactor (BR) and BER was inhibited; however, the BER showed better adaptation and ability to recover. The BER achieved a high nitrate removal efficiency (≥90%) at a salinity of 1.0% and a low COD/N of 2.5 (theoretical stoichiometric 2.86 ignoring microbial growth). The abundance of Methylotenera mobilis in BR and Clostridium sticklandii in BER was higher than in the initial sludge sample used as inoculum. Likewise, the abundance of napA, nirS and nosZ genes increased as the COD/N further decreased. Under high salinity stress, the BER had a higher denitrification efficiency and the consumption of the organic carbon source (i.e., methanol) was reduced compared to BR. The cooperation between heterotrophic and autotrophic denitrifiers in the BER system provides a more efficient and feasible solution for nitrate removal from saline municipal wastewater.

The transient hexavalent chromium (Cr(VI)) shock may directly inhibit the denitrification process of municipal wastewater treatment plants (WWTPs), which is difficult to recover in a short time. This study developed four nontoxic bio-promoters (combination of L -cysteine, flavin adenine dinucleotide (FAD), biotin, cytokinin and different redox mediators) to quickly restore the denitrification performance after high-loading Cr(VI) suppressing. After feeding with 100 mg/L of Cr(VI) for 42 cycles (T, 4 h), the removal efficiency of nitrate was reduced by 85.00%, and nitrite was accumulated simultaneously. The denitrification performance was recovered quickly with the addition of bio-promoters, introducing redox mediators showed noticeable superiority on the bio-inhibition release. Compared with sodium humate and riboflavin, the AQDS induced bio-promoter achieved the best nitrate removal recovery performance within only 28 T, and the recovery rate was 2.16 times faster than the natural recovery. Microbial analysis showed that Cr(VI) specially inhibited napA-type denitrifiers, and the OTU numbers sharply dropped by 48.74%. Redox mediators induced bio-promoters could effectively recover the abundance of napA-type and nirS-type denitrifying microorganisms, which was consistent with the change of nitrate removal efficiency. This study offers a cost-effective approach to deal with Cr(VI) shock problem, which may promote the development of bio-promoters for WWTPs.

A spiral fiber based biofilm reactor was developed to remove nitrate and chromate simultaneously. The denitrification and Cr(VI) removal efficiency was evaluated with synthetic groundwater (NO3--N=50mg/L) under different Cr(VI) concentrations (0-1.0mg/L), carbon nitrogen ratios (C/N) (0.8-1.2), hydraulic retention times (HRT) (2-16h) and initial pHs (4-10). Nitrate and Cr(VI) were completely removed without nitrite accumulation when the Cr(VI) concentration was lower than 0.4mg/L. As Cr(VI) up to 1.0mg/L, the system was obviously inhibited, but it recovered rapidly within 6days due to the strong adaption and domestication of microorganisms in the biofilm reactor. The results demonstrated that high removal efficiency of nitrate (≥99%) and Cr(VI) (≥95%) were achieved at lower C/N=0.9, HRT=8h, initial pH=7, and Cr(VI)=1.0mg/L. The technology proposed in present study can be alternative for simultaneous removal of co-contaminants in groundwater.

A breathable, biodegradable, antibacterial, and self-powered skin is developed., Mimicking the comprehensive functions of human sensing via electronic skins (e-skins) is highly interesting for the development of human-machine interactions and artificial intelligences. Some e-skins with high sensitivity and stability were developed; however, little attention is paid to their comfortability, environmental friendliness, and antibacterial activity. Here, we report a breathable, biodegradable, and antibacterial e-skin based on all-nanofiber triboelectric nanogenerators, which is fabricated by sandwiching silver nanowire (Ag NW) between polylactic-co-glycolic acid (PLGA) and polyvinyl alcohol (PVA). With micro-to-nano hierarchical porous structure, the e-skin has high specific surface area for contact electrification and numerous capillary channels for thermal-moisture transfer. Through adjusting the concentration of Ag NW and the selection of PVA and PLGA, the antibacterial and biodegradable capability of e-skins can be tuned, respectively. Our e-skin can achieve real-time and self-powered monitoring of whole-body physiological signal and joint movement. This work provides a previously unexplored strategy for multifunctional e-skins with excellent practicability.

Wastewater treatment plants (WWTPs) are designed to eliminate pollutants and alleviate environmental pollution resulting from human activities. However, the construction and operation of WWTPs consume resources, emit greenhouse gases (GHGs) and produce residual sludge, thus require further optimization. WWTPs are complex to control and optimize because of high non-linearity and variation. This study used a novel technique, multi-agent deep reinforcement learning (MADRL), to simultaneously optimize dissolved oxygen (DO) and chemical dosage in a WWTP. The reward function was specially designed from life cycle perspective to achieve sustainable optimization. Five scenarios were considered: baseline, three different effluent quality and cost-oriented scenarios. The result shows that optimization based on LCA has lower environmental impacts compared to baseline scenario, as cost, energy consumption and greenhouse gas emissions reduce to 0.890 CNY/m3-ww, 0.530 kWh/m3-ww, 2.491 kg CO2-eq/m3-ww respectively. The cost-oriented control strategy exhibits comparable overall performance to the LCA-driven strategy since it sacrifices environmental benefits but has lower cost as 0.873 CNY/m3-ww. It is worth mentioning that the retrofitting of WWTPs based on resources should be implemented with the consideration of impact transfer. Specifically, LCA-SW scenario decreases 10 kg PO4-eq in eutrophication potential compared to the baseline within 10 days, while significantly increases other indicators. The major contributors of each indicator are identified for future study and improvement. Last, the authors discussed that novel dynamic control strategies required advanced sensors or a large amount of data, so the selection of control strategies should also consider economic and ecological conditions. In a nutshell, there are still limitations of this work and future studies are required.

Carbon coated stainless-steel (SS) electrode has been suggested to be a powerful composite electrode with high conductivity, excellent biocompatibility and good mechanical strength, which is promising for scaling up the bioelectrochemical systems (BESs). However, the already reported carbon coating methods were independent on the production of SS material. Additional steps and investment of equipment for carbon coating are costly, and the industrialization of these carbon coating processes remains challenging. In this study, we report an industrializable carbon coating approach that was embedded into the production line of the SS wire, which was realized through a wire-drawing process with graphite emulsion as the lubricant and carbon source. We found the slide of SS wire through the dies was essential for the graphite coating in terms of loading amount and stability. When the graphite coated SS wire was prepared as the anode and operated in a BESs, the current density reached 1.761 ± 0.231 mA cm−2, which was 20 times higher than that without graphite coating. Biomass analysis was then conducted, confirming the superior bioelectrochemical performance was attributed to the improvement of biocompatibility by the graphite coating layer. Furthermore, graphite coating by the wire-drawing process was systematically compared with the existing methods, which showed a comparable or even better bioelectrochemical performance but with extremely low cost (0.036 $·m−2) and seconds level of the time consumption. Overall, this study offers a cost-effective and industrializable approach to preparing graphite coated SS electrode, which may open up great opportunities to promote the development of BESs at large scale.

High salinity suppresses denitrification by inhibiting microorganism activities. The shift of microbial community and denitrification functional genes under salinity gradient was systematically investigated in a biofilm electrode reactor (BER) and biofilm reactor (BR) systems. Denitrification efficiency of both BER and BR was not significantly inhibited during the period of low salinity (0–2.0%). As the salinity increased to 2.5%, BER could overcome the impact of high salinity and maintained a relatively stable denitrification performance, and the effluent NO3−-N was lower than 1.5 mg/L. High salinity (>2.5%) impoverished microbial diversity and altered the microbial community in both BER and BR. However, two genera Methylophaga and Methyloexplanations were enriched in BER due to electrochemical stimulation, which can tolerate high salinity (>3.0%). The relative abundance of Methylophaga in BER was almost 10 times as much as in BR. Paracoccus is a hydrogen autotrophic denitrifier, which was obviously inhibited with 1.0% NaCl. The hetertrophic denitrifiers were primarily responsible for the nitrate removal in the BER compared to the autotrophic denitrifiers. The abundance and proportion of denitrifying functional genes confirmed that main denitrifiers shift to salt-tolerant species (nirK-type denitrifiers) to reduce the toxic effects. The napA (2.2 × 108 to 6.5 × 108 copies/g biofilm) and nosZ (2.2 × 107 to 4.4 × 107 copies/g biofilm) genes were more abundant in BER compared to BR's, which was attributed to the enrichment of Methylophaga alcalica and Methyloversatilis universalis FAM5 in the BER. The results proved that BER had greater denitrification potential under high salinity (>2.0%) stress at the molecular level.

The collaborative and mutually reinforcing phosphorus removal in domestic wastewater in a sponge iron and microorganisms system was studied through a laboratory and a pilot scale experiment. The results showed that the total phosphorus concentration of the effluent of less than 0.5 mg/L could be achieved. The results also support that the biochemical reaction accelerated the iron electrochemical corrosion. As a driving force, iron bacteria strengthened the chemical oxidation of Fe(II) to Fe(III). The chemical precipitation of Fe(III) is the main form of phosphorus removal. In addition, there exists adsorption phosphorus removal by phosphate-accumulating organisms. The mechanism of the enhanced phosphorus removal by microbial-collaborating sponge iron was thus proposed.

Differing from municipal wastewater, rural wastewater in salinization areas is characterized with arbitrary discharge and high concentration of salt, COD, nitrogen and phosphorus, which would cause severe deterioration of rivers and lakes. To overcome the limits of traditional biological processes, a spiral fiber based salinity-persistent Sequencing Biofilm Batch Reactor (SBBR) was developed and investigated with synthetic rural wastewater (COD = 500 mg/L, NH4+-N = 50 mg/L, TP = 6 mg/L) under different salinity (0.0–10.0 g/L of NaCl). Results indicated that a quick start-up could be achieved in 15 days, along with sufficient biomass up to 7275 mg/L. During operating period, the removal of COD, NH4+-N, TN was almost not disturbed by salt varying from 0.0 to 10.0 g/L with stable efficiency reaching 92%, 82% and 80%, respectively. Although TP could be removed at high efficiency of 90% in low salinity conditions (from 0.0 to 5.0 g/L of NaCl), it was seriously inhibited due to nitrite accumulation and reduction of Phosphorus Accumulating Organisms (PAOs) after addition of 10.0 g/L of salt. The behavior proposed in this study will provide theoretical foundation and guidance for application of SBBR in saline rural wastewater treatment.