Bioelectrochemical stability improvement by Ce-N modified carbon-based cathode in high-salt stress and mechanism research.

Although microbial fuel cells (MFCs) have potential for high-salt wastewater treatment, their application is limited by poor salt tolerance, deactivation and unstable catalytic performance. This study designed Ce-C, N-C, and Ce-N modified activated carbon (Ce-N-C) based on the catalytic mechanism and salt tolerance performance of Ce and N elements to address these limitations. With activated carbon (AC) as the control, this study analyzed the stability of the four cathodes under different salinity environments using norfloxacin (NOR) as a probe to assess the effect of cathodes and salinity on MFC degradation performance. After three months, comparing with other three cathodes, the Ce-N-C cathode demonstrated superior and stable electrochemical and power generation performance. In particular, the advantages of Ce-N-C in high-salt (600 mM NaCl) environment is more significant than no-salt or low-salt. The potential of Ce-N-C-End at current density of 0 was 14.0% higher than AC-End, and the power density of the MFC with Ce-N-C cathode was 105.7 mW/m2, which was 3.1 times higher than AC. Also, the stability of NOR removal under the function of Ce-N-C improved with the increase of NaCl concentration or operation time. The CeO2(111) crystal form, N-Ce-O bond and pyridine N might be the key factors in improving the catalytic performance and salt tolerance of the Ce-N modified carbon-based cathode using XPS and XRD analysis.

Electroactive microorganisms synthesizing iron sulfide nanoparticles for enhanced hexavalent chromium removal in microbial fuel cells.

Microbial fuel cells (MFCs) have been considered a promising technology for Cr6+ removal, but they are limited by Cr6+-reducing biocathodes with low extracellular electron transfer (EET) and poor microbial activity. In this study, three kinds of nano-FeS hybridized electrode biofilms, obtained through synchronous biosynthesis (Sy-FeS), sequential biosynthesis (Se-FeS) and cathode biosynthesis (Ca-FeS), were applied as biocathodes for Cr6+ removal in MFCs. The Ca-FeS biocathode exhibited the best performance due to the superior properties of biogenic nano-FeS (e.g., more synthetic amount, smaller particle size, better dispersion). The MFC with the Ca-FeS biocathode achieved the highest power density (42.08 ± 1.42 mW/m2) and Cr6+ removal efficiency (99.18 ± 0.1 %), which were 1.42 and 2.08 times as high as those of the MFC with the normal biocathode, respectively. The synergistic effects of nano-FeS and microorganisms enhanced the bioelectrochemical reduction of Cr6+, first realizing deep reduction of Cr6+ to Cr0 in biocathode MFCs. This significantly alleviated the cathode passivation caused by Cr3+ deposition. In addition, the hybridized nano-FeS as "armor" layers protected the microbes from toxic attack by Cr6+, improving the biofilm physiological activity and extracellular polymeric substances (EPS) secretion. The hybridized nano-FeS as "electron bridges" facilitated the microbial community to form a balanced, stable and syntrophic ecological structure. This study proposes a novel strategy through the cathode in-situ biosynthesis of nanomaterials to fabricate hybridized electrode biofilms with enhanced EET and microbial activity for toxic pollutant treatment in bioelectrochemical systems.

Improved performance of Cr(vi)-reducing microbial fuel cells by nano-FeS hybridized biocathodes.

Biocathode microbial fuel cells (MFCs) show promise for Cr(vi)-contaminated wastewater treatment. However, biocathode deactivation and passivation caused by highly toxic Cr(vi) and nonconductive Cr(iii) deposition limit the development of this technology. A nano-FeS hybridized electrode biofilm was fabricated by simultaneously feeding Fe and S sources into the MFC anode. This bioanode was then reversed as the biocathode to treat Cr(vi)-containing wastewater in a MFC. The MFC obtained the highest power density (40.75 ± 0.73 mW m-2) and Cr(vi) removal rate (3.99 ± 0.08 mg L-1 h-1), which were 1.31 and 2.00 times those of the control, respectively. The MFC also maintained high stability for Cr(vi) removal in three consecutive cycles. These improvements were due to synergistic effects of nano-FeS with excellent properties and microorganisms in the biocathode. The mechanisms were: (1) the accelerated electron transfer mediated by nano-FeS 'electron bridges' strengthened bioelectrochemical reactions, firstly realizing deep reduction of Cr(vi) to Cr(0) and thus effectively alleviating cathode passivation; (2) nano-FeS as 'armor' layers improved cellular viability and extracellular polymeric substance secretion; (3) the biofilm selectively enriched a diversity of bifunctional bacteria for electrochemical activity and Cr(vi) removal. This study provides a new strategy to obtain electrode biofilms for sustainable treatment of heavy metal wastewater.

N-acyl-homoserine lactones in extracellular polymeric substances from sludge for enhanced chloramphenicol-degrading anode biofilm formation in microbial fuel cells.

Exploring an efficient acclimation strategy to obtain robust bioanodes is of practical significance for antibiotic wastewater treatment by bioelectrochemical systems (BESs). This study investigated the effects of two acclimation conditions on chloramphenicol (CAP)-degrading anode biofilm formation in microbial fuel cells (MFCs). The one was continuously added the extracellular polymeric substances (EPS) extracted from anaerobic sludge and increasing concentrations of CAP after the first start-up phase, while the other was added the EPS-1 (N-acyl-homoserine lactones, namely AHLs were extracted from the EPS) at the same conditions. The results demonstrated that AHLs in the sludge EPS played a crucial role for enhanced CAP-degrading anode biofilm formation in MFCs. The AHL-regulation could not only maintain stable voltage outputs but also significantly accelerate CAP removal in the EPS MFC. The maximum voltage of 653.83 mV and CAP removal rate of 1.21 ± 0.05 mg/L·h were attained from the EPS MFC at 30 mg/L of CAP, which were 0.84 and 1.57 times higher than those from the EPS-1 MFC, respectively. These improvements were largely caused by the thick and 3D structured biofilm, strong and homogeneous cell viability throughout the biofilm, and high protein/polysaccharide ratio along with more conductive contents in the biofilm EPS. Additionally, AHLs facilitated the formation of a biofilm with rich biodiversity and balanced bacterial proportions, leading to more beneficial mutualism among different functional bacteria. More bi-functional bacteria (for electricity generation and antibiotic resistance/degradation) were specifically enriched by AHLs as well. These findings provide quorum sensing theoretical knowledge and practical instruction for rapid antibiotic-degrading electrode biofilm acclimation in BESs.

The fate of anaerobic syntrophy in anaerobic digestion facing propionate and acetate accumulation.

How the acetate and propionate accumulation impact anaerobic syntrophy during methane formation is not well understood. To investigate such effect, continuous acetate (35 g/L), propionate (11.25 g/L) and bicarbonate (30 g/L) supplementation were used during mesophilic anaerobic digestion. The high throughput sequencing (16S rRNA and mcrA), Real-Time quantitative PCR, and stable carbon isotope fingerprinting were applied to investigate the structure and activity of microbial community members. The results demonstrated that the abundance of syntrophic acetate oxidizing bacteria exhibited a gradual decrease coupled with heavier stable carbon isotopic signature of methane (δ 13CH4) in the three reagents impacted reactors. The increased acetate and propionate concentrations exerted negative influence on biogas production but the relatively stable hydrogenotrophic methanogens together with syntrophic acetate/propionate oxidizing bacteria kept the stable methane formation facing acetate and propionate accumulation. The functional genes copy number of the hydrogenotrophic Methanocellaceae and Methanomicrobiaceae correlated significantly with δ 13CH4 (R2 > 0.74), but only the abundance of Methanocellaceae fitted well with δ 13CH4 (p < 0.05). The δ 13CH4 signatures can predict methanogenesis, as it directly reflects the main methanogenic pathway; yet, further investigation of isotope fractionation in acetate/propionate coupled with δ 13CH4 is needed. Collectively, these results provide deep insight into anaerobic syntrophy and reveal changes of synergistic relationships, both of which may contribute to the stability of biogas reactors.

A novel core-shell Fe@Co nanoparticles uniformly modified graphite felt cathode (Fe@Co/GF) for efficient bio-electro-Fenton degradation of phenolic compounds.

In this study, a core-shell Fe@Co nanoparticles uniformly modified graphite felt (Fe@Co/GF) was fabricated as the cathode by one-pot self-assembly strategy for the degradation of vanillic acid (VA), syringic acid (SA), and 4-hydroxybenzoic acid (HBA) in the Bio-Electro-Fenton (BEF) system. The Fe@Co/GF cathode showed dual advantages with excellent electrochemical performance and catalytic reactivity not only due to the high electron transfer efficiency but also the synergistic redox cycles between Fe and Co species, both of which significantly enhanced the in situ generation of H2O2 and hydroxyl radicals (OH) to 152.40 µmol/L and 138.48 µmol/L, respectively. In this case, the degradation rates of VA, SA, and HBA reached 100, 94.32, and 100%, respectively, within 22 h. Representatively, VA was degraded and ultimately mineralized via demethylation, decarboxylation and ring-opening reactions. This work provided a promising approach for eliminating typical recalcitrant organic pollutants generated by the pre-treatment of lignocellulose resources.

Coordinated response of Au-NPs/rGO modified electroactive biofilms under phenolic compounds shock: Comprehensive analysis from architecture, composition, and activity.

Electroactive biofilms (EABs) can be integrated with conductive nanomaterials to boost extracellular electron transfer (EET) for achieving efficient waste treatment and energy conversion in bioelectrochemical systems. However, the in situ nanomaterial-modified EABs of mixed-culture, and their response under environmental stress are rarely revealed. Here, two nanocatalyst-decorated EABs were established by self-assembled Au nanoparticles-reduced graphene oxide (Au-NPs/rGO) in mixed-biofilms with different maturities, then their multi-property were analyzed under long-term phenolic shock. Results showed that the power density of Au-NPs/rGO decorated EABs was significantly enhanced by 28.66-42.82% due to the intensified EET pathways inside biofilms. Meanwhile, the electrochemical and catalytic performance of EABs were controllably regulated by 0.3-3.0 g/L phenolic compounds, which, however, resulted in differential alterations in their architecture, composition, and viability. EABs originated with higher maturity displayed more compact structure, lower thickness (110 µm), higher biomass (8.67 mg/cm2) and viability (0.85-0.91), endowing it better antishock ability to phenolic compounds. Phenolic-shock also induced the heterogeneous distribution of extracellular polymeric substances in terms of both spatial and bonding degrees of the decorated EABs, which could be regarded as an active response to strike a balance between self-protection and EET under environmental pressure. Our findings provide a broader understanding of microbe-electrode interactions in the micro-ecology interface and improve their performance in the removal of complex contaminants for sustainable remediation and new-energy development.

Biosynthesized iron sulfide nanoparticles by mixed consortia for enhanced extracellular electron transfer in a microbial fuel cell.

The bioanode of mixed consortia was for the first time used to in-situ synthesize iron sulfide nanoparticles in a microbial fuel cell (MFC) over a long-term period (46 days). These poorly crystalline nanoparticles with an average size of 29.97 ± 7.1 nm, comprising of FeS and FeS2, significantly promoted extracellular electron transfer and thus the electricity generation of the MFC. A maximum power density of 519.00 mW/m2 was obtained from the MFC, which was 1.92 times as high as that of the control. The cell viability was promoted by a small amount of iron sulfide nanoparticles but inhibited by the thick nanoparticle "shell" covered on the bacterial cells. Some electroactive and sulfur reducing bacteria (eg. Enterobacteriaceae, Desulfovibrio, and Geobacter) were specifically enriched on the anode. This study provides a novel insight for improving the performance of bioelectrochemical systems through in-situ sustainable nanomaterials biofabrication by mixed consortia.

Temperature regulations impose positive influence on the biomethane potential versus digesting modes treating agricultural residues.

Temperature regulations (mesophilic/thermophilic) and digesting modes (mono-/co-digestion) play key roles in the biomethane potential of anaerobic digestion, but limited research focus on the synergetic effects on microbial interconnections of the biomethane process. In this study, the pineapple and maize residues under different operations were monitored by batch biogas assays and 16S high-throughput sequencing to explore: 1) biomethane potential regarding different operations, 2) microbial communities in different treated reactors, and 3) significant factors determine microbial distribution. Results showed that the co-digestion had higher methanogenic abundance and biomethane production (~3300 mLn) versus mono-digestion under mesophilic condition. To the thermophilic condition, the co-digestion had less methanogenic abundance but more biomethane production (~5000 mLn). Statistical evidence uncovered that the Clostridiaceae and Thermoanaerobacteraceae dominated pathways linked closely with methanogenesis which may contribute the more biomethane production in the thermophilic condition. This study demonstrated the temperature regulations drove rare taxa as major contributors for biomethane production.

Effects of copper salts on performance, antibiotic resistance genes, and microbial community during thermophilic anaerobic digestion of swine manure.

This study investigated methane production and ARGs reduction during thermophilic AD of swine manure with the addition of different Cu salts (cupric sulfate, cupric glycinate, and the 1:1 mixture of these two salts). Results showed methane production was increased by 28.78% through adding mixed Cu salts. The mixed Cu group effectively reduced total ARGs abundance by 26.94%, suggesting mixed Cu salts did not promote the potential ARGs risk. The positive effects of mixed Cu salts on AD performance and ARGs removal might be ascribed to the low bioavailability. Microbial community analysis indicated the highest abundances of Clostridia_MBA03 and Methanobacterium in the mixed Cu group might cause the increased methane production. Spearman's rank correlation analysis elucidated the succession in microbial community induced by environmental factors was the main driver for shaping ARGs profiles. Thus, mixed Cu salts could be an alternative to replace the inorganic Cu salt in animal feed additives.

Positive effects of concomitant heavy metals and their reduzates on hexavalent chromium removal in microbial fuel cells.

Cr(vi) laden wastewaters generally comprise a range of multiple heavy metals such as Au(iii) and Cu(ii) with great toxicity. In the present study, cooperative cathode modification by biogenic Au nanoparticles (BioAu) reduced from aqueous Au(iii) and in situ Cu(ii) co-reduction were investigated for the first time to enhance Cr(vi) removal in microbial fuel cells (MFCs). With the co-existence of Cu(ii) in the catholyte, the MFC with carbon cloth modified with nanocomposites of multi-walled carbon nanotubes blended with BioAu (BioAu/MWCNT) obtained the highest Cr(vi) removal rate (4.07 ± 0.01 mg L-1 h-1) and power density (309.34 ± 17.65 mW m-2), which were 2.73 and 3.30 times as high as those for the control, respectively. The enhancements were caused by BioAu/MWCNT composites and deposited reduzates of Cu(ii) on the cathode surface, which increased the adsorption capacity, electronic conductivity and electrocatalytic activity of the cathode. This study provides an alternative approach for efficiently remediating co-contamination of multiple heavy metals and simultaneous bioenergy recovery.

Effects of amino-modified biofilm carriers on biogas production in the anaerobic digestion of corn straw.

This paper studied the property of three different biofilm carriers added into the anaerobic digestion systems, a granular activated carbon, a polyacrylonitrile, and a polyacrylonitrile modified with diethylenetriamine (PAN-NH2). The PAN-NH2 system kept the maximum biogas and methane production, which were 42.69% and 37.29% higher than the control system, respectively. The value of pH and chemical oxygen demand, the content of total solid and volatile solid, volatile fatty acids concentration, coenzyme F420 concentration, and microbial community analysis were investigated during the anaerobic digestion process. The PAN-NH2 system had the highest removal efficiency of the pollutants and regulated the pH of the system better than other systems. The result of high-throughput sequencing analysis showed that the addition of biofilm carriers and mediation with amino-groups adjusted system pH and improved biogas and CH4 production by reducing the relative abundance of bacteria in the hydrolysis/acidogenesis stages. Methanosarcina gradually replaced other methanogens during the experimental runs and was the dominant methanogen at the end of the anaerobic digestion process.

Anaerobic biodegradation of pyrene by Klebsiella sp. LZ6 and its proposed metabolic pathway.

Pyrene is one of the polycyclic aromatic hydrocarbons, which are a potential threat to ecosystems due to their mutagenicity, carcinogenicity, and teratogenicity. In this study, several bacteria were isolated from oil contaminated sludge and their capacity to biodegrade pyrene was investigated. Of these bacteria, the monoculture strain LZ6 showed the highest pyrene anaerobic biodegradation rate of 33% after 30 days when the initial concentration was 50 mg/L, and was identified as Klebsiella sp. LZ6 by morphological observation, the GENIII technology of Biolog, and 16S rDNA gene sequence analysis. The influence of various culture parameters on the biodegradation of pyrene were evaluated, and Klebsiella sp. LZ6 all showed the high degradation rate at an inoculum of 10-20% (v/v), pH 6.0-8.4, temperature 30-38°C, and initial pyrene concentration of 50-150 mg/L. The intermediate metabolites of the anaerobic biodegradation were analyzed by GC-MS. Several metabolites were identified, such as pyrene, 4,5-dihydro-, phenanthrene, dibenzo-p-dioxin, and 4-hydroxycinnamate acid. The anaerobic metabolic pathway for the degradation of pyrene was inferred by the products. It seems that pyrene was first reduced to pyrene,4,5-dihydro- by the adding of two hydrogen atoms, and then the carbon-carbon bond cleavage at saturated carbon atoms generated phenanthrene.

Odor emission and microbial community succession during biogas residue composting covered with a molecular membrane.

A membrane-covered composting system was used to investigate the odor emission and microbial community succession during biogas residue composting. Results showed that in comparison with the control (CK) group, the NH3 and H2S emissions outside the membrane of the membrane-covered (CT) group decreased by 58.64% and 38.13%, respectively. The nitrogen preservation rate of the CT group was increased by 17.27% in comparison with the CK group. Moreover, the ammonium nitrogen and nitrate nitrogen contents of the CT group were 37.68% and 11.77% higher than those of the CK group, respectively. Microbial analysis showed that the average abundance and co-occurrence rate of ammonification bacteria dominated by Pseudomonas and Bacillus in the CT group were lower than those in the CK group, and the abundance of anaerobic sulfate-reducing bacteria (SRB) dominated by Desulfovibrio in the CT group was higher than that in the CK group.

Effect of one step temperature increment from mesophilic to thermophilic anaerobic digestion on the linked pattern between bacterial and methanogenic communities.

Process fluctuation caused by temperature modification of anaerobic digestion is routinely monitored via operational parameters, such as pH and gas production, but these parameters are lagging on microbial community performance. In this study, 13C isotope fractionation in CH4 and CO2 of biogas together with microbial community dynamics were applied to evaluate process stability in response to temperature increment. Results showed that the weakening correlated links between Firmicutes affiliated families and Methanomicrobiaceae were found regarding temperature increase. In contrast, Methanosarcinaceae and Methanobacteriaceae strengthened their links with multiple bacterial groups. This suggests that the 13C isotope fractionation in CH4 can predict the collapse of certain microbial interconnections and process instability, the new reinforced microbial links directly reflect the microbial community redundancy for maintaining function of syntrophic populations.

Degradation of phenolic compounds with simultaneous bioelectricity generation in microbial fuel cells: Influence of the dynamic shift in anode microbial community.

This study evaluated the feasibility of microbial fuel cells (MFCs) for simultaneous electricity generation and degradation of phenolic compounds. The voltage generation was inhibited by 36.18-63.90%, but the degradation rate increased by 146.15-392.31% when the initial concentration of syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) increased from 0.3 to 3.0 g/L. The collaboration among the functional microbes significantly enhanced the degradation rate of parent compounds and their intermediates in MFCs systems, while the accumulated intermediates severely inhibited their complete mineralization in fermentative systems. High-throughput sequencing showed that the growth of fermentative bacteria prevailed, but electrogenic bacteria were inhibited in the anode microbial community (AMC) under high concentrations of phenolic compounds (3.0 g/L). These findings provide a better understanding of the dynamic shift and synergy effects of the AMC to evaluate its potential for the treatment of phenolic-containing wastewater.

Enhanced Bio-Electro-Fenton degradation of phenolic compounds based on a novel Fe-Mn/Graphite felt composite cathode.

Phenolic compounds are problematic byproducts generated from lignocellulose pretreatment. In this study, the feasibility degradation of syringic acid (SA), vanillic acid (VA), and 4-hydroxybenzoic acid (HBA) by Bio-Electro-Fenton (BEF) system with a novel Fe-Mn/graphite felt (Fe-Mn/GF) composite cathode were investigated. The nano-scale Fe-Mn multivalent composite catalyst with core shell structure distributed more evenly on GF surface to form a catalyst layer with higher oxygen reduction reaction performance. Accordingly, the maximum power density generated with Fe-Mn/GF cathode was 48.1% and 238.9% higher than Fe/GF and GF respectively, which further enhanced the in situ generation of H2O2 due to the superiority of nano-scale core shell structure and synergistic effect of Fe and Mn species. The degradation efficiency of the three phenolic compounds in the BEF system could reached 100% after optimization of influencing parameters. Furthermore, a possible SA degradation pathway by BEF process in the present system was proposed based on the detected intermediates. These results demonstrated an efficient approach for the degradation of phenolic compounds derived from lignocellulose hydrolysates.

Increased fermentative adenosine production by gene-targeted Bacillus subtilis mutation.

Adenosine, which is produced mainly by microbial fermentation, plays an important role in the therapy of cardiovascular disease and has been widely used as an antiarrhythmic agent. In this study, guanosine 5'-monophosphate (GMP) synthetase gene (guaA) was inactivated by gene-target manipulation to increase the metabolic flux from inosine 5'-monophosphate (IMP) to adenosine in B. subtilis A509. The resulted mutant M3-3 showed an increased adenosine production from 7.40 to 10.45 g/L, which was further enhanced to a maximum of 14.39 g/L by central composite design. As the synthesis of succinyladenosine monophosphate (sAMP) from IMP catalysed by adenylosuccinate synthetase (encoded by purA gene) is the rate-limiting step in adenosine synthesis, the up-regulated transcription level of purA was the potential underlying mechanism for the increased adenosine production. This work demonstrated a practical strategy for breeding B. subtilis strains for industrial nucleoside production.

A Facultative Electroactive Chromium(VI)-Reducing Bacterium Aerobically Isolated From a Biocathode Microbial Fuel Cell.

A facultative electroactive bacterium, designated strain H, was aerobically isolated from the biocathode of a hexavalent chromium (Cr(VI))-reducing microbial fuel cell (MFC). Strain H is Gram-positive and rod shaped (1-3 µm length). 16S rRNA gene analysis suggested that this strain (accession number MH782060) belongs to the genus Bacillus and shows maximum similarity to Bacillus cereus whose electrochemical activity has never previously been reported. Moreover, this strain showed efficient Cr(VI)-reducing ability in both heterotrophic (aerobic LB broth) and autotrophic (anaerobic MFC cathode) environments. Cr(VI) removal reached 50.6 ± 1.8% after 20 h in LB broth supplemented with Cr(VI) (40 mg/L). The strain H biocathode significantly improved the performance of the Cr(VI)-reducing MFC, achieving a maximum power density of 31.80 ± 1.06 mW/m2 and Cr(VI) removal rate of 2.56 ± 0.10 mg/L-h, which were 1.26 and 1.75 times higher than those of the MFC with the sterile control cathode, respectively. This study offers a novel Gram-positive Bacillus sp. strain for Cr(VI) removal in MFCs, and shows a facile aerobic isolation method could be used to screen facultative electroactive bacteria.

Anode modification by biogenic gold nanoparticles for the improved performance of microbial fuel cells and microbial community shift.

In this study, carbon cloth anodes were modified using biogenic gold nanoparticles (BioAu) and nanohybrids of multi-walled carbon nanotubes blended with BioAu (BioAu/MWCNT) to improve the performance of microbial fuel cells (MFCs). The results demonstrated that BioAu modification significantly enhanced the electricity generation of MFCs. In particular, BioAu/MWCNT nanohybrids as the modifier displayed a better performance. The MFC with the BioAu/MWCNT electrode had the shortest start-up time (6.74 d) and highest power density (178.34 ±â€¯4.79 mW/m2), which were 141.69% shorter and 56.11% higher compared with those of the unmodified control, respectively. These improvements were attributed to the excellent electrocatalytic activity and strong affinity towards exoelectrogens of the BioAu/MWCNT nanohybrids on the electrode. High throughput sequencing analysis indicated that the relative abundance of electroactive bacteria in the biofilm community, mostly from the classes of Gammaproteobacteria and Negativicutes, increased after anode modification.