Xue-Fei Sun

Nano-structured manganese oxide as a cathodic catalyst for enhanced oxygen reduction in a microbial fuel cell fed with a synthetic wastewater

Microbial fuel cells (MFCs) provide new opportunities for the simultaneous wastewater treatment and electricity generation. Enhanced oxygen reduction capacity of cost-effective metal-based catalysts in an air cathode is essential for the scale-up and commercialization of MFCs in the field of wastewater treatment. We demonstrated that a nano-structured MnO(x) material, prepared by an electrochemically deposition method, could be an effective catalyst for oxygen reduction in an MFC to generate electricity with the maximum power density of 772.8 mW/m(3) and remove organics when the MFC was fed with an acetate-laden synthetic wastewater. The nano-structured MnO(x) with the controllable size and morphology could be readily obtained with the electrochemical deposition method. Both morphology and manganese oxidation state of the nano-scale catalyst were largely dependent on the electrochemical preparation process, and they governed its catalytic activity and the cathodic oxygen reduction performance of the MFC accordingly. Furthermore, cyclic voltammetry (CV) performed on each nano-structured material suggests that the MnO(x) nanorods had an electrochemical activity towards oxygen reduction reaction via a four-electron pathway in a neutral pH solution. This work provides useful information on the facile preparation of cost-effective cathodic catalysts in a controllable way for the single-chamber air-cathode MFC for wastewater treatment.

Sorption and detoxification of chromium(VI) by aerobic granules functionalized with polyethylenimine.

This study describes the modification of aerobic granules by grafting polyethylenimine (PEI) for simultaneous sorption and detoxification of Cr(VI). After modification, the uptake capacity of modified aerobic granules (MAG) showed about 401.5 mg/g at pH 5.5 and increased by 274% compared to the control. Adsorption experiments were carried out as a function of contact time, pH and concentration of Cr(VI). It was found that the equilibrium sorption can be attained within 3 h and the process obeys the Redlich-Peterson isotherm model. The adsorption process is a function of pH of the solution, with the greater adsorption at pH 5.2. The interaction characteristics between the Cr and MAG were elucidated by applying FTIR and XPS analyses. FTIR results showed that the -NH2 groups in the sorbent are involved in the adsorption process. XPS results verified the presence of Cr(III) on the MAG surface in the pH range 1.5-8.5, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption.

Spectroscopic study of Zn2+ and Co2+ binding to extracellular polymeric substances (EPS) from aerobic granules.

The interacting mechanisms of metallic cations (Zn2+ and Co2+) to active chemical groups on the extracellular polymeric substances (EPS) of the aerobic granules, including loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS), were examined by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. For Zn2+ and Co2+, LB-EPS showed stronger binding properties than TB-EPS and the process of them was described well by the Langmuir isotherm. Compared to the single-metal system, binary-metal addition induced competitive binding between the Zn2+ and Co2+ with reduction of the maximal binding capacity for both EPS. The main chemical groups involved in the interactions between contaminants were apparently alcohol, carboxyl and amino. These groups were part of the EPS structural polymers, namely, polysaccharides, proteins, and hydrocarbon-like products. When biosorption and flocculation occurred at the same time, the LB-EPS were used not only as chelate sorbents but also as flocculants to further enhance their sorption capacity.

Enhanced Cu(II) and Cr(VI) biosorption capacity on poly(ethylenimine) grafted aerobic granular sludge

The biosorption characteristics of cations and anions from aqueous solution using polyethylenimine (PEI) modified aerobic granules were investigated. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis exhibit the presence of PEI on the granule surface. Compared with the raw granule, the modified aerobic granules with PEI showed a significant increase in sorption capacity for both metal ions. The monolayer biosorption capacity of granules for Cu(II) and Cr(VI) ions was found to be 71.239 and 348.125mg/g. The optimum solution pH for adsorption of Cu(II) and Cr(VI) from aqueous solutions was found to be 6 and 5.2, respectively. The biosorption data fitted better with the Redlich-Peterson isotherm model. FTIR showed chemical interactions occurred between the metal ions and the amide groups of PEI on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption.

Integration of a microbial fuel cell with activated sludge process for energy-saving wastewater treatment: Taking a sequencing batch reactor as an example†

In the research and application of microbial fuel cell (MFC), how to incorporate MFCs into current wastewater infrastructure is an importance issue. Here, we report a novel strategy of integrating an MFC into a sequencing batch reactor (SBR) to test the energy production and the chemical oxygen demand (COD) removal. The membrane‐less biocathode MFC is integrated with the SBR to recover energy from the aeration in the form of electricity and thus reduce the SBR operation costs. In a lab‐scale integrated SBR‐MFC system, the maximum power production of the MFC was 2.34 W/m3 for one typical cycle and the current density reached up to 14 A/m3. As a result, the MFC contributed to the 18.7% COD consumption of the integrated system and also recovered energy from the aeration tank with a volume fraction of only 12% of the SBR. Our strategy provides a feasible and effective energy‐saving and ‐recovering solution to upgrade the existing activated sludge processes. Biotechnol. Bioeng. 2011; 108:1260–1267.

Aerobic granulation for nitrogen removal via nitrite in a sequencing batch reactor and the emission of nitrous oxide.

In this study, the granulation of nitrifying-denitrifying via nitrite process in a sequencing batch reactor (SBR) as well as N(2)O emission patterns was investigated. After 60 days of operation, 0.8 mm granules were obtained, and partial nitrification was achieved after NH(4)(+)-N was raised to 350 mg/L. Fluorescence In-Situ Hybridization (FISH) analysis indicated that a fairly large proportion of ammonia-oxidizing bacteria (AOB) was close to the surface but nitrite-oxidizing bacteria (NOB) were rarely found. Batch experiments showed that 64.0% of NH(4)(+)-N in influent was transformed into NO(2)(-)-N, which showed the granules had excellent partial nitrification ability. Inhibition of free ammonia (FA) and limited DO diffusion within granules may contribute to the development and stabilization of partial nitrification. This process did not simultaneously lead to increased N(2)O production. N(2)O emissions at the anoxic and aerobic phases were 0.06 and 13.13 mg N(2)O/cycle, respectively.

Competitive biosorption of zinc(II) and cobalt(II) in single- and binary-metal systems by aerobic granules.

The biosorption process for removal of cobalt(II) and zinc(II) by aerobic granules was characterized. Single component and binary equimolar systems were studied at different pH values. The equilibrium was well described by Redlich-Peterson adsorption isotherm. The maximal adsorption capacity of the granules, in single systems (55.25 mg g(-1) Co; 62.50 mg g(-1) Zn) compared with binary systems (54.05 mg g(-1) Co; 56.50 mg g(-1) Zn) showed reduction in the accumulation of these metals onto aerobic granules. The kinetic modelling of metal sorption by granules has been carried out using Lagergren equations. The regression analysis of pseudo second-order equation gave a higher R(2) value, indicating that chemisorption involving valent forces through the sharing or exchange of electrons between sorbent and sorbate may be the rate limiting step. The initial biosorption rate indicated that aerobic granules can adsorb Co(II) more rapidly than Zn(II) from aqueous solutions. Meanwhile, FTIR and XPS analyses revealed that chemical functional groups (e.g., alcoholic and carboxylate) on aerobic granules would be the active binding sites for biosorption of Co(II) and Zn(II).

Enhancement of acidic dye biosorption capacity on poly(ethylenimine) grafted anaerobic granular sludge

Developing a novel biosorbent with high capacity is crucial to remove dyes from waters in an efficient way. This study demonstrated that porous anaerobic granular sludge could be grafted with polyethylenimine (PEI), which definitely improved the sorption capacity towards Acid Red 18 (AR18) removal. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) study revealed that the PEI modification introduced a large number of amino groups on the surface of sludge, and the amino groups played an important role in the adsorption of dye molecule. Analysis of sorption data using a Boyd plot confirms the film diffusion was the rate-limiting step. The equilibrium data were well fitted Langmuir model, with a maximum AR18 uptake of 520.52 mg/g. Removal of AR18 decreased with the increasing pH and the maximum color removal was observed at pH 2.0. The sorption energy calculated from Dubinin-Radushkevich isotherm was found to be less than 8 for the biosorption of AR 18, which suggested that the biosorption processes of dye molecule onto modified anaerobic granules could be taken place by physical adsorption. Various thermodynamic parameters, such as ΔG(0), ΔH(0) and ΔS(0), were also calculated, which indicated that the present system was spontaneous and endothermic process.

Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches

The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV–visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation–emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces.

Fluoride adsorption on carboxylated aerobic granules containing Ce(III)

Aerobic granules (AG) were carboxylated and Ce(III) was incorporated to obtain modified granuels (Ce(III)-MAG) for removal of fluoride from aqueous solutions. The Ce(III)-MAG was characterized by SEM, FTIR, XRD and pH(pzc), and the introduction of carboxyl groups and Ce(III) was confirmed. The adsorption capacity of Ce(III)-MAG for fluoride was 45.80 mg/g at neutral pH, an increase of 359% compared to the capacity of pristine AG. Adsorption was highest at pH range of 3.0-5.0. A positive effect on fluoride removal in the order of K(+) ≈ Mg(2+) > Ca(2+) > Na(+) and a negative effect in the order of NO(3)(-) > Cl(-) > SO(4)(2-) > HCO(3)(-) > PO(4)(3-) was observed. Fluoride adsorption followed the Redlich-Peterson model and the pseudo-first order model with correlation factors of 0.999 and 0.950, respectively. Ce(III)-MAG held up to 790 bed volumes and the effluent fluoride concentration remained below 1.0mg/L (influent fluoride 10mg/L).