René A. Rozendal

Towards practical implementation of bioelectrochemical wastewater treatment

Bioelectrochemical systems (BESs), such as microbial fuel cells (MFCs) and microbial electrolysis cells (MECs), are generally regarded as a promising future technology for the production of energy from organic material present in wastewaters. The current densities that can be generated with laboratory BESs now approach levels that come close to the requirements for practical applications. However, full-scale implementation of bioelectrochemical wastewater treatment is not straightforward because certain microbiological, technological and economic challenges need to be resolved that have not previously been encountered in any other wastewater treatment system. Here, we identify these challenges, provide an overview of their implications for the feasibility of bioelectrochemical wastewater treatment and explore the opportunities for future BESs.

Microbial electrosynthesis - revisiting the electrical route for microbial production.

Microbial electrocatalysis relies on microorganisms as catalysts for reactions occurring at electrodes. Microbial fuel cells and microbial electrolysis cells are well known in this context; both use microorganisms to oxidize organic or inorganic matter at an anode to generate electrical power or H2, respectively. The discovery that electrical current can also drive microbial metabolism has recently lead to a plethora of other applications in bioremediation and in the production of fuels and chemicals. Notably, the microbial production of chemicals, called microbial electrosynthesis, provides a highly attractive, novel route for the generation of valuable products from electricity or even wastewater. This Review addresses the principles, challenges and opportunities of microbial electrosynthesis, an exciting new discipline at the nexus of microbiology and electrochemistry.

Simultaneous nitrification, denitrification and carbon removal in microbial fuel cells

Microbial fuel cells (MFCs) can use nitrate as a cathodic electron acceptor, allowing for simultaneous removal of carbon (at the anode) and nitrogen (at the cathode). In this study, we supplemented the cathodic process with in situ nitrification through specific aeration, and thus obtained simultaneous nitrification and denitrification (SND) in the one half-cell. Synthetic wastewater containing acetate and ammonium was supplied to the anode; the effluent was subsequently directed to the cathode. The influence of oxygen levels and carbon/nitrogen concentrations and ratios on the system performances was investigated. Denitrification occurred simultaneously with nitrification at the cathode, producing an effluent with levels of nitrate and ammonium as low as 1.0+/-0.5 mg N L(-1) and 2.13+/-0.05 mg N L(-1), respectively, resulting in a nitrogen removal efficiency of 94.1+/-0.9%. The integration of the nitrification process into the cathode solves the drawback of ammonium losses due to diffusion between compartments in the MFC, as previously reported in a system operating with external nitrification stage. This work represents the first successful attempt to combine SND and organics oxidation while producing electricity in an MFC.

High Current Generation Coupled to Caustic Production Using a Lamellar Bioelectrochemical System

Recently, bioelectrochemical systems (BESs) have emerged as a promising technology for energy and product recovery from wastewaters. To become economically viable, BESs need to (i) reach sufficient turnover rates at scale and (ii) generate a product that offsets the investment costs within a reasonable time frame. Here we used a liter scale, lamellar BES to produce a caustic solution at the cathode. The reactor was operated as a three-electrode system, in which the anode potential was fixed and power was supplied over the reactor to allow spontaneous anodic current generation. In laboratory conditions, with acetate as electron donor in the anode, the system generated up to 1.05 A (at 1.77 V applied cell voltage, 1015 A m(-3) anode volume), and allowed for the production of caustic to 3.4 wt %, at an acetate to caustic efficiency of 61%. The reactor was subsequently operated on a brewery site, directly using effluent from the brewing process. Currents of up to 0.38 A were achieved within a six-week time frame. Considerable fluctuations over weekly periods were observed, due to operational parameter changes. This study is the first to demonstrate effective production of caustic at liter scale, using BESs both in laboratory and field conditions. It also shows that input of power can easily be justified by product value.

Nitrobenzene removal in bioelectrochemical systems.

Nitrobenzene occurs as a pollutant in wastewaters originating from numerous industrial and agricultural activities. It needs to be removed prior to discharge to sewage treatment works because of its high toxicity and persistence. In this study, we investigated the use of a bioelectrochemical system (BES) to remove nitrobenzene at a cathode coupled to microbial oxidation of acetate at an anode. Effective removal of nitrobenzene at rates up to 1.29 +/- 0.04 mol m(-3) TCC d(-1) (total cathodic compartment, TCC) was achieved with concomitant energy recovery. Correspondingly, the formation rate for the reduction product aniline was 1.14 +/- 0.03 mol m(-3) TCC d(-1). Nitrobenzene removal and aniline formation rates were significantly enhanced when the BES was supplied with power, reaching 8.57 +/- 0.03 and 6.68 +/- 0.03 mol m(-3) TCC d(-1), respectively, at an energy consumption of 17.06 +/- 0.16 W m(-3) TCC (current density at 59.5 A m(-3) TCC). Compared to those of conventional anaerobic biological methods for nitrobenzene removal, the required dosage of organic cosubstrate was significantly reduced in this system. Although aniline was always identified as the major product of nitrobenzene reduction at the cathode of BES in this study, the Coulombic efficiencies of nitrobenzene removal and aniline formation were dependent on the current density of the BES.

Effect of the type of ion exchange membrane on performance, ion transport, and pH in biocatalyzed electrolysis of wastewater

Previous studies have shown that the application of cation exchange membranes (CEMs) in bioelectrochemical systems running on wastewater can cause operational problems. In this paper the effect of alternative types of ion exchange membrane is studied in biocatalyzed electrolysis cells. Four types of ion exchange membranes are used: (i) a CEM, (ii) an anion exchange membrane (AEM), (iii) a bipolar membrane (BPM), and (iv) a charge mosaic membrane (CMM). With respect to the electrochemical performance of the four biocatalyzed electrolysis configurations, the ion exchange membranes are rated in the order AEM > CEM > CMM > BPM. However, with respect to the transport numbers for protons and/or hydroxyl ions (t(H/OH)) and the ability to prevent pH increase in the cathode chamber, the ion exchange membranes are rated in the order BPM > AEM > CMM > CEM.

Butler–Volmer–Monod model for describing bio-anode polarization curves

A kinetic model of the bio-anode was developed based on a simple representation of the underlying biochemical conversions as described by enzyme kinetics, and electron transfer reactions as described by the Butler-Volmer electron transfer kinetics. This Butler-Volmer-Monod model was well able to describe the measured bio-anode polarization curves. The Butler-Volmer-Monod model was compared to the Nernst-Monod model described the experimental data significantly better. The Butler-Volmer-Monod model has the Nernst-Monod model as its full electrochemically reversible limit. Contrary to the Nernst-Monod model, the Butler-Volmer-Monod model predicts zero current at equilibrium potential. Besides, the Butler-Volmer-Monod model predicts that the apparent Monod constant is dependent on anode potential, which was supported by experimental results.

Electrochemical oxidation of reverse osmosis concentrate on mixed metal oxide (MMO) titanium coated electrodes.

Reverse osmosis (RO) membranes have been successfully applied around the world for wastewater reuse applications. However, RO is a physical separation process, and besides the clean water stream (permeate) a reverse osmosis concentrate (ROC) is produced, usually representing 15-25% of the feed water flow and containing the organic and inorganic contaminants at higher concentrations. In this study, electrochemical oxidation was investigated for the treatment of ROC generated during the reclamation of municipal wastewater effluent. Using laboratory-scale two-compartment electrochemical systems, five electrode materials (i.e. titanium coated with IrO2-Ta2O5, RuO2-IrO2, Pt-IrO2, PbO2, and SnO2-Sb) were tested as anodes in batch mode experiments, using ROC from an advanced water treatment plant. The best oxidation performance was observed for Ti/Pt-IrO2 anodes, followed by the Ti/SnO2-Sb and Ti/PbO2 anodes. The effectiveness of the treatment appears to correlate with the formation of oxidants such as active chlorine (i.e. Cl2/HClO/ClO-). As a result, electro-generated chlorine led to the abundant formation of harmful by-products such as trihalomethanes (THMs) and haloacetic acids (HAAs), particularly at Ti/SnO2-Sb and Ti/Pt-IrO2 anodes. The highest concentration of total HAAs (i.e. 2.7 mg L(-1)) was measured for the Ti/SnO2-Sb electrode, after 0.55 Ah L(-1) of supplied specific electrical charge. Irrespective of the used material, electrochemical oxidation of ROC needs to be complemented by a polishing treatment to alleviate the release of halogenated by-products.

Electrochemical oxidation of trace organic contaminants in reverse osmosis concentrate using RuO2/IrO2-coated titanium anodes.

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru(0.7)Ir(0.3)O(2) electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA(254)), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m(-2) anode, and a batch reactor at J = 250 A m(-2). Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m(-3) ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA(254) during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH(2)Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA(254) removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m(-2) (i.e. Q ≥ 461.5 A h m(-3)) and 437.0 A h m(-3) (J = 250 A m(-2)), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m(-3) ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.

Biofilm stratification during simultaneous nitrification and denitrification (SND) at a biocathode.

The aeration of the cathode compartment of bioelectrochemical systems (BESs) was recently shown to promote simultaneous nitrification and denitrification (SND). This study investigates the cathodic metabolism under different operating conditions as well as the structural organization of the cathodic biofilm during SND. Results show that a maximal nitrogen removal efficiency of 86.9 ± 0.5%, and a removal rate of 3.39 ± 0.08 mg NL(-1)h(-1) could be achieved at a dissolved oxygen (DO) level of 5.73 ± 0.03 mg L(-1) in the catholyte. The DO levels used in this study are higher than the thresholds previously reported as detrimental for denitrification. Analysis of the cathodic half-cell potential during batch tests suggested the existence of an oxygen gradient within the biofilm while performing SND. FISH analysis corroborated this finding revealing that the structure of the biofilm included an outer layer occupied by putative nitrifying organisms, and an inner layer where putative denitrifying organisms were most dominant. To our best knowledge this is the first time that nitrifying and denitrifying microorganisms are simultaneously observed in a cathodic biofilm.