Hao-Yi Cheng

Efficient Reduction of Nitrobenzene to Aniline with a Biocatalyzed Cathode

Nitrobenzene (NB) is a toxic compound that is often found as a pollutant in the environment. The present removal strategies suffer from high cost or slow conversion rate. Here, we investigated the conversion of NB to aniline (AN), a less toxic endproduct that can easily be mineralized, using a fed-batch bioelectrochemical system with microbially catalyzed cathode. When a voltage of 0.5 V was applied in the presence of glucose, 88.2 ± 0.60% of the supplied NB (0.5 mM) was transformed to AN within 24 h, which was 10.25 and 2.90 times higher than an abiotic cathode and open circuit controlled experiment, respectively. AN was the only product detected during bioelectrochemical reduction of NB (maximum efficiency 98.70 ± 0.87%), whereas in abiotic conditions nitrosobenzene was observed as intermediate of NB reduction to AN (decreased efficiency to 73.75 ± 3.2%). When glucose was replaced by NaHCO(3), the rate of NB degradation decreased about 10%, selective transformation of NB to AN was still achieved (98.93 ± 0.77%). Upon autoclaving the cathode electrode, nitrosobenzene was formed as an intermediate, leading to a decreased AN formation efficiency of 71.6%. Cyclic voltammetry highlighted higher peak currents as well as decreased overpotentials for NB reduction at the biocathode. 16S rRNA based analysis of the biofilm on the cathode indicated that the cathode was dominated by an Enterococcus species closely related to Enterococcus aquimarinus.

Accelerated Reduction of Chlorinated Nitroaromatic Antibiotic Chloramphenicol by Biocathode

Chlorinated nitroaromatic antibiotic chloramphenicol (CAP) is a priority pollutant in wastewaters. A fed-batch bioelectrochemical system (BES) with biocathode with applied voltage of 0.5 V (served as extracellular electron donor) and glucose as intracellular electron donor was applied to reduce CAP to amine product (AMCl2). The biocathode BES converted 87.1 ± 4.2% of 32 mg/L CAP in 4 h, and the removal efficiency reached 96.0 ± 0.9% within 24 h. Conversely, the removal efficiency of CAP in BES with an abiotic cathode was only 73.0 ± 3.2% after 24 h. When the biocathode was disconnected (no electrochemical reaction but in the presence of microbial activities), the CAP removal rate was dropped to 62.0% of that with biocathode BES. Acetylation of one hydroxyl of CAP was noted exclusive in the biocatalyzed process, while toxic intermediates, hydroxylamino (HOAM), and nitroso (NO), from CAP reduction were observed only in the abiotic cathode BES. Electrochemical hydrodechlorination and dehalogenase were responsible for dechlorination of AMCl2 to AMCl in abiotic and microbial cathode BES, respectively. The cyclic voltammetry (CV) highlighted higher peak currents and lower overpotentials for CAP reduction at the biocathode compared with abiotic cathode. With the biocathode BES, antibacterial activity of CAP was completely removed and nitro group reduction combined with dechlorination reaction enhanced detoxication efficiency of CAP. The CAP cathodic transformation pathway was proposed based on intermediates analysis. Bacterial community analysis indicated that the dominate bacteria on the biocathode were belonging to α, β, and γ-Proteobacteria. The biocathode BES could serve as a potential treatment process for CAP-containing wastewater.

Microbial community structure and function of Nitrobenzene reduction biocathode in response to carbon source switchover

The stress of poised cathode potential condition and carbon source switchover for functional biocathode microbial community influences is poorly understood. Using high-throughput functional gene array (GeoChip v4.2) and Illumina 16S rRNA gene MiSeq sequencing, we investigated the phylogenetic and functional microbial community of the initial inoculum and biocathode for bioelectrochemical reduction of nitrobenzene to less toxic aniline in response to carbon source switchover (from organic glucose to inorganic bicarbonate). Selective transformation of nitrobenzene to aniline maintained in the bicarbonate fed biocathode although nitrobenzene reduction rate and aniline formation rate were significantly decreased compared to those of the glucose-fed biocathode. When the electrical circuit of the glucose-fed biocathode was disconnected, both rates of nitrobenzene reduction and of aniline formation were markedly decreased, confirming the essential role of an applied electric field for the enhancement of nitrobenzene reduction. The stress of poised cathode potential condition led to clear succession of microbial communities from the initial inoculum to biocathode and the carbon source switchover obviously changed the microbial community structure of biocathode. Most of the dominant genera were capable of reducing nitroaromatics to the corresponding aromatic amines regardless of the performance mode. Heterotrophic Enterococcus was dominant in the glucose-fed biocathode while autotrophic Paracoccus and Variovorax were dominant in the bicarbonate-fed biocathode. Relatively higher intensity of diverse multi-heme cytochrome c (putatively involved in electrons transfer) and carbon fixation genes was observed in the biocarbonate-fed biocathode, likely met the requirement of the energy conservation and maintained the nitrobenzene selective reduction capability after carbon source switchover. Extracellular pilin, which are important for biofilm formation and potential conductivity, had a higher gene abundance in the glucose-fed biocathode might explain the enhancement of electro-catalysis activity for nitrobenzene reduction with glucose supply. Dominant nitroaromatics-reducing or electrochemically active bacteria and diverse functional genes related to electrons transfer and nitroaromatics reduction were associated with nitrobenzene reduction efficiency of biocathode communities in response to carbon source switchover.

Azo dye removal in a membrane-free up-flow biocatalyzed electrolysis reactor coupled with an aerobic bio-contact oxidation reactor

Azo dyes that consist of a large quantity of dye wastewater are toxic and persistent to biodegradation, while they should be removed before being discharged to water body. In this study, Alizarin Yellow R (AYR) as a model azo dye was decolorized in a combined bio-system of membrane-free, continuous up-flow bio-catalyzed electrolysis reactor (UBER) and subsequent aerobic bio-contact oxidation reactor (ABOR). With the supply of external power source 0.5 V in the UBER, AYR decolorization efficiency increased up to 94.8±1.5%. Products formation efficiencies of p-phenylenediamine (PPD) and 5-aminosalicylic acid (5-ASA) were above 90% and 60%, respectively. Electron recovery efficiency based on AYR removal in cathode zone was nearly 100% at HRTs longer than 6 h. Relatively high concentration of AYR accumulated at higher AYR loading rates (>780 gm(-3) d(-1)) likely inhibited acetate oxidation of anode-respiring bacteria on the anode, which decreased current density in the UBER; optimal AYR loading rate for the UBER was 680 gm(-3) d(-1) (HRT 2.5 h). The subsequent ABOR further improved effluent quality. Overall the Chroma decreased from 320 times to 80 times in the combined bio-system to meet the textile wastewater discharge standard II in China.

Enhanced decolorization of azo dye in a small pilot-scale anaerobic baffled reactor coupled with biocatalyzed electrolysis system (ABR–BES): A design suitable for scaling-up

A four-compartment anaerobic baffled reactor (ABR) incorporated with membrane-less biocatalyzed electrolysis system (BES) was tested for the treatment of azo dye (alizarin yellow R, AYR) wastewater (AYR, 200 mg L(-1); glucose, 1000 mg L(-1)). The ABR-BES was operated without and with external power supply to examine AYR reduction process and reductive intermediates with different external voltages (0.3, 0.5 and 0.7 V) and hydraulic retention times (HRT: 8, 6 and 4h). The decolorization efficiency in the ABR-BES (8h HRT, 0.5 V) was higher than that in ABR-BES without electrolysis, i.e. 95.1 ± 1.5% versus 86.9 ± 6.3%. Incorporation of BES with ABR accelerated the consumption of VFAs (mainly acetate) and attenuated biogas (methane) production. Higher power supply (0.7 V) enhanced AYR decolorization efficiency (96.4 ± 1.8%), VFAs removal, and current density (24.1 Am(-3) TCV). Shorter HRT increased volumetric AYR decolorization rates, but decreased AYR decolorization efficiency.

Sediment microbial fuel cell with floating biocathode for organic removal and energy recovery

A sediment microbial fuel cell (SMFC) with three dimensional floating biocathode (FBC) was developed for the electricity generation and biodegradation of sediment organic matter in order to avoid negative effect of dissolved oxygen (DO) depletion in aqueous environments on cathode performance and search cost-effective cathode materials. The biocathode was made from graphite granules with microbial attachment to replace platinum (Pt)-coated carbon paper cathode in a laboratory-scale SMFC (3 L in volume) filled with river sediment (organic content 49±4 g·kg−1 dry weight). After start-up of 10 days, the maximum power density of 1.00W·m−3 (based on anode volume) was achieved. The biocathode was better than carbon paper cathode catalyzed by Pt. The attached biofilm on cathode enhanced power generation significantly. The FBC enhanced SMFC performance further in the presence aeration. The SMFC was continuously operated for an over 120-day period. Power generation peaked within 24 days, declined gradually and stabilized at a level of 1/6 peak power output. At the end, the sediment organic matter content near the anode was removed by 29% and the total electricity generated was equal to 0.251 g of chemical oxygen demand (COD) removed.

A membrane-free, continuously feeding, single chamber up-flow biocatalyzed electrolysis reactor for nitrobenzene reduction

A new bioelectrochemical system (BES), a membrane-free, continuous feeding up-flow biocatalyzed electrolysis reactor (UBER) was developed to reduce oxidative toxic chemicals to less- or non-toxic reduced form in cathode zone with oxidation of electron donor in anode zone. Influent was fed from the bottom of UBER and passed through cathode zone and then anode zone. External power source (0.5 V) was provided between anode and cathode to enhance electrochemical reactions. Granular graphite and carbon brush were used as cathode and anode, respectively. This system was tested for the reduction of nitrobenzene (NB) using acetate as electron donor and carbon source. The influent contained NB (50-200 mg L(-1)) and acetate (1000 mg L(-1)). NB was removed by up to 98% mainly in cathode zone. The anode potential maintained under -480 mV. The maximum NB removal rate was up to 3.5 mol m(-3) TV d(-1) (TV=total empty volume) and the maximum aniline (AN) formation rate was 3.06 mol m(-3) TV d(-1). Additional energy required was less than 0.075 kWh mol(-1)NB. The molar ratio of NB removed vs acetate consumed varied from 4.3 ± 0.4 to 2.3 ± 0.1 mol mol(-1). Higher influent phosphate or acetate concentration helped NB removal rate. NB could be efficiently reduced to AN as the power supplied of 0.3 V.

Polarity inversion of bioanode for biocathodic reduction of aromatic pollutants

The enrichment of specific pollutant-reducing consortium is usually required prior to the startup of biocathode bioelectrochemical system (BES) and the whole process is time consuming. To rapidly establish a non-specific functional biocathode, direct polar inversion from bioanode to biocathode is proposed in this study. Based on the diverse reductases and electron transfer related proteins of anode-respiring bacteria (ARB), the acclimated electrochemically active biofilm (EAB) may catalyze reduction of different aromatic pollutants. Within approximately 12 d, the acclimated bioanodes were directly employed as biocathodes for nitroaromatic nitrobenzene (NB) and azo dye acid orange 7 (AO7) reduction. Our results indicated that the established biocathode significantly accelerated the reduction of NB to aniline (AN) and AO7 to discolored products compared with the abiotic cathode and open circuit controls. Several microbes possessing capabilities of nitroaromatic/azo dye reduction and bidirectional electron transfer were maintained or enriched in the biocathode communities. Cyclic voltammetry highlighted the decreased over-potentials and enhanced electron transfer of biocathode as well as demonstrated the ARB Geobacter containing cytochrome c involved in the backward electron transfer from electrode to NB. This study offers new insights into the rapid establishment and modularization of functional biocathodes for the potential treatment of complicated electron acceptors-coexisting wastewaters.

Accelerated decolorization of azo dye Congo red in a combined bioanode-biocathode bioelectrochemical system with modified electrodes deployment.

In this study, BES with bioanode and biocathode was applied to decolorize an azo dye Congo red (CR). Results showed that the Congo red decolorization efficiency (CR-DE) within 23 h in a combined bioanode-biocathode single chamber BES was 98.3±1.3%, significantly higher than that of mixed solution in a dual chamber BES (67.2±3.5%) (P<0.005). Various electrodes deployments (horizontal, vertical and surrounding) in the combined bioanode-biocathode BES were further compared based on the decolorization performance and electrochemical characterization. Results indicated that CR-DE within 11h improved from 87.4±1.3% to 97.5±2.3%, meanwhile the internal resistance decreased from 236.6 to 42.2Ω as modifying the horizontal deployment to be a surrounding deployment. It proved that the combination of bioanode and biocathode with suitable electrodes deployment could accelerate the decolorization of azo dye Congo red, which would be great potential for the application of bioelectrochemical technology in azo dye wastewater treatment.

Improved azo dye decolorization in a modified sleeve-type bioelectrochemical system

Bioelectrochemical system (BES) that removes recalcitrant pollutant out of wastewater is of special interest for practice. This study modified the configuration of BES to be a sleeve-type with compact structure. Azo dye (acid orange 7, AO7) in the outer cathode chamber performed a complete decolorization by electrons supplied from acetate oxidized with electricigens in the inner anode chamber. The AO7 decolorization efficiency (DEAO7) was enhanced to be higher than 98% from 0.14 to 2.00 mM. Electrochemical impedance spectroscopy (EIS) analysis showed that the internal resistance of anode, cathode and the whole cell was 26.4, 38.3, and 64.6 Ω, respectively, indicating that the modified configuration with large area and small distance between anode and cathode can result in a lower internal resistance and higher decolorization performance. This is the first study for azo dye decolorization using sleeve-type configuration with highly efficient decolorization by abiotic cathode BES.