Nano Pd doped Ni foam electrode stimulated electrochemical reduction of tetrabromobisphenol A: Optimization strategies and function mechanism.

Tetrabromobisphenol A (TBBPA), a hazardous and persistent flame retardant, has been widely detected in the natural aquatic system. The acceleration of reductive debromination (rate-limiting process) is vital during the decomposition and detoxification of TBBPA. This study achieved superior TBBPA electrochemical reductive debromination performance by nano Pd doped Ni foam electrode (4.8 times higher than Ni foam electrode). The optimal TBBPA reductive debromination performance was obtained under -1.2 V of cathode potential, 1.2 wt% of Pd loading, 10 mg L-1 of TBBPA and 100 mM of Na2SO4 as the electrolyte solution. UPLC-QTOF-MS verified that Br atoms in TBBPA were removed sequentially to form bisphenol A as the major product. Most TBBPA was reductively debrominated by atomic H* through indirect hydrodebromination, evidenced by the atomic H* quenching test. The higher solution conductivity and appropriate TBBPA concentration would contribute to the debromination efficiency. Excessive H2 generation whether by over negative potential or H atom richness electrolyte largely disturbed the reaction process and restricted the debromination. The improved generation of reductant (H*)adsPd was the most significant, while excessive Pd loading would make aggregation and limit the debromination efficiency. The study confirmed the optimization strategies of conditions for Pd/Ni foam electrode and revealed the related function mechanism for stimulating TBBPA electrochemical reduction, giving suggestions for the efficient removal of TBBPA in the aquatic environment.

Influence on denitrifying community performance by the long-term exposure to sulfamethoxazole and chlortetracycline in the continuous-flow EGSB reactors.

The response of the denitrification community to long-term antibiotic exposure requires further investigation. Here, the significantly altered denitrifying community structure and function were observed by continuous exposure to 1 mg/L sulfamethoxazole (SMZ) or chlortetracycline (CTC) for 180 d in the expanded granular sludge bed reactors. Thaurea, positively correlated with SMZ and NO3- removal efficiency (NrE), was highly enriched in the SMZ-added reactor, while, Comamons and Acinetobacter were largely inhibited. The acute inhibited and then gradual-recovered NrE (87.17-90.38 %) was observed with highly expressed narG, indicating the adaptability of Thaurea to SMZ. However, the abundance of Thaurea and Comamonas greatly decreased, while Melioribacter and Acinetobacter were largely enriched in the CTC-added reactor. CTC created more serious and continuous inhibition of NO3- reduction (NrE of 64.53-66.95 %), with lowly expressed narG. Improved NO2- reduction capacity was observed in both reactors (70.16-95.42 %) with highly expressed nirS and nosZ, revealing the adaptability of NO2- reduction populations to antibiotics.

Biodegradation and metabolism of tetrabromobisphenol A in microbial fuel cell: Behaviors, dynamic pathway and the molecular ecological mechanism.

Tetrabromobisphenol A (TBBPA) has aroused widespread pollution in industrial wastewater. Microbial fuel cell (MFC) was proved powerful in organics degradation and simultaneous resource recovery during wastewater treatment. However, the TBBPA biotransformation potential, pathway and the related molecular mechanism remain poorly understood. In this study, the enhanced degradation and detoxification performance of TBBPA in MFC anode was confirmed, evidenced by the shorter degradation period (2.3 times shorter) and less generation of bisphenol A. UPLC-QTOF-MS analysis verified TBBPA metabolism went through reductive debromination, hydrolytic debromination, oxidative ring cleavage and o-methylation. Accompanied with those biochemical processes, the metabolites underwent dynamic changes. The distinctly decreased abundance and fewer interactions with other functional genera for the potential reductive dehalogenators (Pseudomonas, etc.) possibly led to the suppressed reductive debromination (5.1%) in the closed bioanode. Otherwise, the more abundant potential function bacteria with more collaborated interrelations, including hydrolytic dehalogenators (Acinetobacter, etc.), aromatics degrading bacteria (Geobacter, Holophaga, etc.) and electroactive bacteria (Geobacter, Desulfovibrio, etc.) made great sense to the enhanced hydrolytic debromination and detoxification of TBBPA. This study revealed that MFC anode was beneficial to TBBPA degradation and provided theoretical support for the decomposition and transformation of micro-pollutants in the municipal sewage treatment coupled with MFC process.

Microbial fuel cell-upflow biofilter coupling system for deep denitrification and power recovery: Efficiencies, bacterial succession and interactions.

The excess organic carbon is often added to meet denitrification requirements during municipal wastewater treatment, resulting in the carbon waste and increased risk of secondary pollution. In this study, microbial fuel cell (MFC) was coupled with an up-flow denitrification biofilter (BF), and the long-term performances of denitrification and power output were investigated under the different carbon source concentration. With sodium acetate (NaAc) of 600 mg/L and 300 mg/L, the favorable denitrification efficiencies were obtained (98.60%) and the stable current output was maintained (0.44 mÃ0.48 mA). By supplying NaAc of 150 mg/L, the high denitrification efficiency remained in a high range (89.31%) and the current output maintained at 0.12 mA, while, the denitrification efficiency dropped to 71.34% without coupling MFC. Electron balance analysis indicated that both nitrate removal and electron recovery efficiencies were higher in MFC-BF than that in BF, verifying the improved denitrification and carbon utilization performance. Coupling MFC significantly altered the bacterial community structure and composition, and while, the diversified abundance and distribution of bacterial genera were observed at the different locations. Compared with BF, the more exoelectrogenic genera (Desulfobacterium, Trichococcus) and genera holding both denitrifying and electrogenic functions (Dechloromonas, Geobacter) were found dominated in MFC-BF. Instead, the dominating genera in BF were Dechloromonas, Desulfomicrobium, Acidovorax and etc. By coupling MFC, the more complex and diversified network and the closer interaction relationships between the dominant potential functional genera were found. The study provides a feasible approach to effectively improve the denitrification efficiency and organic carbon recovery for deep denitrification process.

Selective stress of antibiotics on microbial denitrification: Inhibitory effects, dynamics of microbial community structure and function.

Antibiotics commonly exist in municipal, livestock and industrial wastewaters. However, the response of key microbiota performance in wastewater treatment plants to antibiotic exposure lacks systematic research. In this study, the short-term acute stress of four commonly used antibiotics (sulfamethoxazole, chlortetracycline, ciprofloxacin, and amoxicillin) on microbial denitrification performance was systematically investigated. All tested antibiotics exhibited the inhibitory effects in varying degrees by repeated addition for six cycles. The nitrate removal efficiencies (NrE) decreased to 7.98-26.80%, accompanied by the significant decrease of the expressed narG gene, by exposure to sulfamethoxazole, chlortetracycline or amoxicillin. Nitrite reduction was inhibited more severely than nitrate reduction, which was further verified by the low- or non-expressed nirS and nosZ genes. Furthermore, a higher antibiotic concentration made stronger inhibitory effect. Except for chlortetracycline, 2.09-6.80 times decrease of k value was commonly observed as concentration increased from 10 to 50 or 100 mg L-1. Even in a short period (24 h), antibiotics largely decreased the abundance of the dominant denitrifying bacterial genera (Thauera, Comamonas, etc.), while, some unclassified populations (Labrenzia, Longilinea, etc.) were enriched. This study provides theoretical researches on the microbial denitrification behaviors influenced by exposure to different antibiotics.

Efficient treatment of alizarin yellow R contained wastewater in an electrostimulated anaerobic-oxic integrated system.

An electrostimulated anaerobic-oxic integrated system was constructed for treating alizarin yellow R (AYR) containing wastewater. In electro-stimulated anaerobic unit, AYR decolorization efficiency improved from 51.2% to 96.6%. Two amination metabolites, p-phenylenediamine and 5-aminosalicylic acid, went through oxidation, ammonification and mineralization in oxic unit. Electro-stimulation promoted denitrification and COD removal efficiencies by 15.5% and 8.6%, respectively. A 20% improved nitrification efficiency was observed in oxic unit, due to elimination of AYR toxicity inhibition. No corrosion of heat-treated stainless steel occurred during the 60 days of continuous operation. Electrons sunk in denitrification and decolorization accounted for 34.4-36.8% of those released from COD removal, and 7.3% increase of removed nitrogen in nitrogenous compounds (AYR, nitrate and ammonia) was found. Electro-stimulated anaerobic unit predominated with fermentation and denitrification genera (Propionispira, Rhodocyclus, etc.) and aboundance of electro-active decolorization genus (Desulfovibrio, etc.) increased. Ammonia-oxidizing genus, Comamonas, was the most abundant in aerobic unit. Compared to the suspension, the electrostimulation could increased the abundance of electro-active genera in cathodic biofilm. This study revealed the feasibility of applying electro-stimulation and the conversion laws of nitrogenous organics in secondary bio-treatment system for treating toxic nitrogenous organics-contained wastewater.

Palladium/iron nanoparticles stimulate tetrabromobisphenol a microbial reductive debromination and further mineralization in sediment.

Tetrabromobisphenol A (TBBPA) has aroused serious pollution in surface sediment. To date, whether and how iron-based nanoparticles could stimulate TBBPA in situ anaerobic biodegradation in sediment remains poorly understood. In this study, the distinctly enhanced TBBPA degradation activity with the rate constant k improved 4.7 times by fed with Pd/Fe nanoparticles (0.412 g L-1 dosage, 0.5 wt% Pd loading) was observed. TBBPA degradation first went through reductive dehalogenation with bisphenol A (BPA) as the metabolites, and after the addition of Pd/Fe nanoparticles, BPA was further degraded to 4-(allene)phenol and 2,2-bis(4-hydroxyphenyl) propanoic acid via UPLC-QTOF-MS analysis, suggesting the complete detoxification potential. By the addition of Pd/Fe nanoparticles, the large amount of H2 production (560 times higher) and the significant inhibition of methane generation facilitated the metabolism of potential reductive dehalogenators (Desulfovibrio, Clostridium, etc.), demonstrated by their increased ecological abundance and the tighter cooperative interrelations between each other. Meanwhile, the addition of Pd/Fe nanoparticles largely promoted the ecological abundance of Fe(III) reducing and aromatics degrading bacteria (Bacillus, Cryptanaerobacter, etc.), resulting in BPA further degradation. The bacterial ecological network further revealed that the potential BPA degrading bacteria shared the more positive interactions with the potential dehalogenators in the presence of Pd/Fe nanoparticles. The study firstly revealed the addition of Pd/Fe nanoparticles obviously enhanced the respiratory metabolic activities and cooperative interrelations of reductive dehalogenators and BPA degraders, which gives suggestions for in situ remediation and detoxification of BFRs in contaminated sediment.

Recirculation ratio regulates denitrifying sulfide removal and elemental sulfur recovery by altering sludge characteristics and microbial community composition in an EGSB reactor.

Expanded granular sludge blanket (EGSB) is regarded as a promising reactor to carry out denitrifying sulfide removal (DSR) and elemental sulfur (S0) recovery. Although the recirculation ratio is an essential parameter for EGSB reactors, how it impacts the DSR process remains poorly understood. Here, three lab-scale DSR-EGSB reactors were established with the different recirculation ratios (3:1, 6:1 and 9:1) to evaluate the corresponding variations in pollutant removal, S0 recovery, anaerobic granular sludge (AGS) characteristics and microbial community composition. It was found that an intermediate recirculation ratio (6:1) could facilitate long-term reactor stability. Adequate recirculation ratio could enhance S0 recovery, but an excessive recirculation ratio (9:1) was likely to cause AGS fragmentation and biomass loss. The S0 desorbed more from sludge at higher recirculation ratios, probably due to the enhanced hydraulic disturbance caused by the increased recirculation ratios. At the low recirculation ratio (3:1), S0 accumulation as inorganic suspended solids in AGS led to a decrease in VSS/TSS ratio and mass transfer efficiency. Although typical denitrifying and sulfide-oxidizing bacteria (e.g., Azoarcus, Thauera and Arcobacter) were predominant in all conditions, facultative and heterotrophic functional bacteria (e.g., Azoarcus and Thauera) were more adaptable to higher recirculation ratios than autotrophs (e.g., Arcobacter, Thiobacillus and Vulcanibacillus), which was conducive to the formation of bacterial aggregates to response to the increased recirculation ratio. The study revealed recirculation ratio regulation significantly impacted the DSR-EGSB reactor performance by altering AGS characteristics and microbial community composition, which provides a novel strategy to improve DSR performance and S0 recovery.

Accelerated microbial reductive dechlorination of 2,4,6-trichlorophenol by weak electrical stimulation.

Microbial reductive dechlorination of chlorinated aromatics frequently suffers from the long dechlorination period and the generation of toxic metabolites. Biocathode bioelectrochemical systems were verified to be effective in the degradation of various refractory pollutants. However, the electrochemical and microbial related working mechanisms for bio-dechlorination by electro-stimulation remain poorly understood. In this study, we reported the significantly improved 2,4,6-trichlorophenol dechlorination activity through the weak electro-stimulation (cathode potential of -0.36 V vs. SHE), as evidenced by the 3.1 times higher dechlorination rate and the complete dechlorination ability with phenol as the end dechlorination product. The high reductive dechlorination rate (20.8 µM/d) could be maintained by utilizing electrode as an effective electron donor (coulombic efficiency of 82.3 ±â€¯4.8%). Cyclic voltammetry analysis of the cathodic biofilm gave the direct evidences of the cathodic respiration with the improved and positive-shifted reduction peaks of 2,4,6-TCP, 2,4-DCP and 4-CP. The optimal 2,4,6-TCP reductive dechlorination rate (24.2 µM/d) was obtained when a small amount of lactate (2 mM) was added, and the generation of H2 and CH4 were accompanied due to the biological fermentation and methanogenesis. The electrical stimulation significantly altered the cathodic biofilm structure and composition with some potential dechlorinators (like Acetobacterium) predominated. The microbial interactions in the ecological network of cathodic biofilm were more simplified than the planktonic community. However, some potential dechlorinators (Acetobacterium, Desulfovibrio, etc.) shared more positive interactions. The co-existence and possible cooperative relationships between potential dechlorinators and fermenters (Sedimentibacter, etc.) were revealed. Meanwhile, the competitive interrelations between potential dechlorinators and methanogens (Methanomassiliicoccus) were found. In the network of plankton, the fermenters and methanogens possessed the more positive interrelations. Electro-stimulation at the cathodic potential of -0.36 V selectively enhanced the dechlorination function, while it showed little influence on either fermentation or methanogenesis process. The study gave suggestions for the enhanced bioremediation of chlorinated aromatics, in views of the electro-stimulation capacity, efficiency and microbial interrelations related microbial mechanism.

Identification of biofilm formation and exoelectrogenic population structure and function with graphene/polyanliline modified anode in microbial fuel cell.

Improving anode configuration with polymer or nanomaterial modification is promising for enhancing microbial fuel cell performance. However, how anode modification affects biofilm development and electrogenic function remains poorly understood. In this study, the carbon cloth anode modified with polyaniline and reduced graphene oxide was successfully fabricated which obtained the highest power output. Accelerated electrogenic biofilm formation and the better electrogenic bacterial colonization based on the superior material properties (preferable electrochemical characteristics, the film-like structure and the more activated sites) were observed with the in situ biofilm development monitoring. The acclimation time was 2.4 times shorter with graphene and polyaniline modified anode than the bare one when inoculated with wastewater. Biofilm structure and function analysis show that Geobacter is the most predominant with the abundance as high as 81.4%, and meanwhile, electrogenesis related outer-surface octaheme c-type cytochrome omcZ is highly expressed in the modified anode. The anode modified with graphene and polyaniline favors Geobacter colonization, accelerates electrogenic biofilm formation and improves omcZ expression level, eventually leading to the improved performance of microbial fuel cell. The study for the first time reveals the impacts on biofilm development and microbial function by anode modification, which will better guide the potential application of microbial fuel cell for wastewater recovery.