Cees N.J. Buisman

Stabilizing the baseline current of a microbial fuel cell-based biosensor through overpotential control under non-toxic conditions.

A MFC-based biosensor can act as online toxicity sensor. Electrical current is a direct linear measure for metabolic activity of electrochemically active microorganisms. Microorganisms gain energy from anodic overpotential and current strongly depends on anodic overpotential. Therefore control of anodic overpotential is necessary to detect toxic events and prevent false positive alarms. Anodic overpotential and thus current is influenced by anode potential, pH, substrate and bicarbonate concentrations. In terms of overpotential all factor showed a comparable effect, anode potential 1.2% change in current density per mV, pH 0.43%/mV, bicarbonate 0.75%/mV and acetate 0.8%/mV. At acetate saturation the maximum acetate conversion rate is reached and with that a constant bicarbonate concentration. Control of acetate and bicarbonate concentration can be less strict than control of anode potential and pH. Current density changes due to changing anode potential and pH are in the same order of magnitude as changes due to toxicity. Strict control of pH and anode potential in a small range is required. The importance of anodic overpotential control for detection of toxic compounds is shown. To reach a stable baseline current under nontoxic conditions a MFC-based biosensor should be operated at controlled anode potential, controlled pH and saturated substrate concentrations.

Feasibility Study on Electrochemical Impedance Spectroscopy for Microbial Fuel Cells: Measurement Modes & Data Validation

Electrochemical impedance spectroscopy (EIS) is in potential a powerful tool for the in depth analysis of microbial fuels cells (MFCs). To prevent the risk of drawing false conclusions from invalid EIS measurements we investigated the feasibility of this method on an MFC by checking: linearity, causality, stability and finiteness. EIS application under steady state conditions was partly feasible. For further application EIS on MFCs we recommend to: (1) use the constant anode or cathode potential measurement mode with a fast couple at the counter electrode; (2) record the polarization curve and measure at different amplitudes to check the linearity condition; (3) perform preliminary measurements to reveal measurement presets; (4) apply prolonged pretreatment to facilitate the stability criterion; (5) perform duplicate measurements to examine the stability; (6) use a broad frequency range to validate the finiteness criterion; (7) use a statistical based validation check based on the Kramers-Kronig transformation.

Low Substrate Loading Limits Methanogenesis and Leads to High Coulombic Efficiency in Bioelectrochemical Systems

A crucial aspect for the application of bioelectrochemical systems (BESs) as a wastewater treatment technology is the efficient oxidation of complex substrates by the bioanode, which is reflected in high Coulombic efficiency (CE). To achieve high CE, it is essential to give a competitive advantage to electrogens over methanogens. Factors that affect CE in bioanodes are, amongst others, the type of wastewater, anode potential, substrate concentration and pH. In this paper, we focus on acetate as a substrate and analyze the competition between methanogens and electrogens from a thermodynamic and kinetic point of view. We reviewed experimental data from earlier studies and propose that low substrate loading in combination with a sufficiently high anode overpotential plays a key-role in achieving high CE. Low substrate loading is a proven strategy against methanogenic activity in large-scale reactors for sulfate reduction. The combination of low substrate loading with sufficiently high overpotential is essential because it results in favorable growth kinetics of electrogens compared to methanogens. To achieve high current density in combination with low substrate concentrations, it is essential to have a high specific anode surface area. New reactor designs with these features are essential for BESs to be successful in wastewater treatment in the future.

X-Ray Diffraction of Iron Containing Samples: The Importance of a Suitable Configuration

X-ray diffraction (XRD) is a commonly used technology to identify crystalline phases. However, care must be taken with the combination of XRD configuration and sample. Copper (most commonly used radiation source) is a poor match with iron containing materials due to induced fluorescence. Magnetite and maghemite are analysed in different configurations using copper or cobalt radiation. Results show the effects of fluorescence repressing measures and the superiority of diffractograms obtained with cobalt radiation. Diffractograms obtained with copper radiation make incontestable phase identification often impossible. Cobalt radiation on the other hand yields high quality diffractograms, making phase identification straightforward.

Anwendung für organisch und anorganisch belastete Abwässer anderer Industriebereiche

Das Kapitel 7 beschaftigt sich mit der Anwendung anaerober Technologien bei organisch verschmutzen Abwassern aus der Zellstoff- und Papierindustrie sowie der Verarbeitung tierischer Nebenprodukte. Weiterhin werden Anlagen zur anaeroben Behandlung von anorganisch belasteten Abwassern aus der chemischen und pharmazeutischen Industrie behandelt. An diesem Kapitel haben 10 unterschiedliche Autoren aus der Praxis mitgewirkt, um die wesentlichen Aspekte der Anwendung berucksichtigen zu konnen und den Wert fur den praktischen Nutzer zu erhohen. Seit den 1980er-Jahren erfolgte ein vermehrter Einsatz anaerober Verfahren auch in der Papier- und Zellstoffindustrie. Am haufigsten wird das Verfahren bei den Herstellern von Verpackungspapieren aus Altpapier angewendet, insbesondere bei den Wellpappenrohpapieren, die mit geringen spezifischen Abwassermengen produziert werden konnen. Auch die Brudenkondensate aus der Eindampfung verbrauchter Kochsaure oder Ablauge aus der Zellstofferzeugung (EDA (Eindampfanlage)-Kondensate) eignen sich sehr gut fur die anaerobe Reinigung, die im Bereich der Sulfitzellstofferzeugung auch verbreitet technisch eingesetzt wird.

Chemical vs. Biological Crystals, all the Same?

Using microorganisms to mediate crystallisation of metals and minerals in open-culture bioreactors has potential to recover recyclable materials from dilute aqueous streams, but also to prevent their emission to the environment. Although this potential is already exploited in practice to some extent, biological crystallization for metal recovery is still largely a black box technology with limited understanding of the role of the microorganisms in the crystallization, and the differences with chemical crystallisation. Using biocrystallisation of scorodite (FeAsO4.2H2O) and sphalerite (ZnS) as examples we propose that the role of microorganisms strongly depends on established saturation state of the solution. For scorodite, microorganisms are used to exert control over the crystallization as their ferrous iron-oxidizing activity keeps the solution slightly oversaturated. Also, the oversaturation level is kept homogeneous because of continuous biological formation of the reactant ferrous iron throughout the solution. In continuous bioreactor experiments on which we reported previously, scorodite crystal sizes still increased after 72 days of bioreactor operation indicating that indeed crystal growth was favored over nucleation. On the other hand, in our experiments with zinc sulfide, crystallization proceeded in highly oversaturated solutions in a continuous sulfate reducing bioreactor fed with a zinc sulfate solution and H2/CO2 as electron donor and carbon source. The high oversaturation likely resulted in dominant primary nucleation in the bulk solution, with little or no control over crystal growth, even though agglomeration may still have occurred. This was exemplified by particle sizes which decreased in the bioreactor experiment and remained stable after already about 2 weeks of operation.

Immobilization of arsenic by a thermoacidophilic mixed culture with pyrite as energy source

Arsenic is an abundant element associated with a wide range of minerals and a major contaminant in metallurgical wastewater. For the immobilization of arsenic, iron arsenate in the very stable mineral scorodite (FeAsO4 2H2O) is the preferred route. Microorganisms of the natural iron cycle living at pH below 2 and high temperatures can conduct the oxidation of ferrous iron with oxygen, which is not feasible chemically at these extreme conditions. Remarkably, at similar acidic conditions and high temperature these microorganisms can also carry out the oxidation of arsenite (As(III)) to arsenate (As(V)). Using these intrinsic features of the microorganisms, we have investigated the role of a thermoacidophilic mixed culture in the oxidation of As(III) and precipitation of (As(V) in the form of scorodite from a synthetic wastewater containing 6.7mM of As(III) and 0.5%Wt pyrite as main iron Fe(II) source. The results indicate that As(III) was completely oxidized from the synthetic wastewater in the presence of pyrite and scorodite was formed only in presence of the mixed culture at a Fe/As:1.3. This is a combination of biological oxidation and biocrystallisation accomplished to the presence of pyrite not only as the main energy source for the microorganisms, but as catalyst in the As(III) oxidation reaction.

Recovery of Metals and Stabilization of Arsenic from (Bio-)Leaching Operations by Engineered Biological Processes

This paper focuses on the application of biotechnological stabilization of arsenic from (bio-) leaching operations. One of the latest applications of the Thioteq technology is arsenic immobilization. The Thioteq-scorodite biorecovery reactor is an aerobic system to immobilise arsenic in bio-scorodite crystals. In this patented process, biological arsenite oxidation, biological ferrous iron oxidation and crystallisation reactions are simultaneously taking place. Bio-scorodite crystals can be easily harvested by sedimentation due to their relative large size of up to 160 μm. This biogenic material is classified as non-hazardous due to its very low arsenic leaching rates. Furthermore, bioscorodite crystals resemble the colour, crystal morphology, iron and arsenic content, structural water of the mineral scorodite. The operational costs related to scorodite bio-crystallization can be reduced at least 50% compared to chemical precipitation because the use of biological reactions to induce the crystallization of scorodite and the good stability properties of the produced crystals. The Thioteq-scorodite process is a reliable cost effective solution to arsenic removal and immobilization by using biological processes. The stabilization of arsenic in the form of biologically produced scorodite is an attractive technology for the compact and safe immobilization of arsenic from medium to high concentrations of arsenic in acidic process streams.