Marika E. Kokko

Electricity generation from tetrathionate in microbial fuel cells by acidophiles

Inorganic sulfur compounds, such as tetrathionate, are often present in mining process and waste waters. The biodegradation of tetrathionate was studied under acidic conditions in aerobic batch cultivations and in anaerobic anodes of two-chamber flow-through microbial fuel cells (MFCs). All four cultures originating from biohydrometallurgical process waters from multimetal ore heap bioleaching oxidized tetrathionate aerobically at pH below 3 with sulfate as the main soluble metabolite. In addition, all cultures generated electricity from tetrathionate in MFCs at pH below 2.5 with ferric iron as the terminal cathodic electron acceptor. The maximum current and power densities during MFC operation and in the performance analysis were 79.6 mA m(-2) and 13.9 mW m(-2) and 433 mA m(-2) and 17.6 mW m(-2), respectively. However, the low coulombic efficiency (below 5%) indicates that most of the electrons were directed to other processes, such as aerobic oxidation of tetrathionate and unmeasured intermediates. The microbial community analysis revealed that the dominant species both in the anolyte and on the anode electrode surface of the MFCs were Acidithiobacillus spp. and Ferroplasma spp. This study provides a proof of concept that tetrathionate serves as electron donor for biological electricity production in the pH range of 1.2-2.5.

Arsenic removal from acidic solutions with biogenic ferric precipitates

Treatment of acidic solution containing 5g/L of Fe(II) and 10mg/L of As(III) was studied in a system consisting of a biological fluidized-bed reactor (FBR) for iron oxidation, and a gravity settler for iron precipitation and separation of the ferric precipitates. At pH 3.0 and FBR retention time of 5.7h, 96-98% of the added Fe(II) precipitated (99.1% of which was jarosite). The highest iron oxidation and precipitation rates were 1070 and 28mg/L/h, respectively, and were achieved at pH 3.0. Subsequently, the effect of pH on arsenic removal through sorption and/or co-precipitation was examined by gradually decreasing solution pH from 3.0 to 1.6 (feed pH). At pH 3.0, 2.4 and 1.6, the highest arsenic removal efficiencies obtained were 99.5%, 80.1% and 7.1%, respectively. As the system had ferric precipitates in excess, decreased arsenic removal was likely due to reduced co-precipitation at pH<2.4. As(III) was partially oxidized to As(V) in the system. In shake flask experiments, As(V) sorbed onto jarosite better than As(III). Moreover, the sorption capacity of biogenic jarosite was significantly higher than that of synthetic jarosite. The developed bioprocess simultaneously and efficiently removes iron and arsenic from acidic solutions, indicating potential for mining wastewater treatment.

Long-term stability of bioelectricity generation coupled with tetrathionate disproportionation.

To prevent uncontrolled acidification of the environment, reduced inorganic sulfur compounds (RISCs) can be bioelectrochemically removed from water streams. The long-term stability of bioelectricity production from tetrathionate (S4O6(2-)) was studied in highly acidic conditions (pH<2.5) in two-chamber fed-batch microbial fuel cells (MFCs). The maximum current density was improved from previously reported 80mAm(-2) to 225mAm(-2) by optimizing the external resistance. The observed reaction products of tetrathionate disproportionation were sulfate and elemental sulfur. In long-term run, stable electricity production was obtained for over 700days with the average current density of 150mAm(-2). The internal resistance of the MFC decreased over time and no biofouling was observed. This study shows that tetrathionate is an efficient substrate also for long-term bioelectricity production.

The effect of anode potential on bioelectrochemical and electrochemical tetrathionate degradation

The effect of poised anode potential on electricity production and tetrathionate degradation was studied in two-chamber flow-through electrochemical (ES) and bioelectrochemical systems (BES). The minimum anode potential (vs. Ag/AgCl) for positive current generation was 0.3V in BES and 0.5V in the abiotic ES. The anode potential required to obtain average current density above 70mAm-2 was 0.4V in BES and above 0.7V in ES. ES provided higher coulombic efficiency, but the average tetrathionate degradation rate remained significantly higher in BES (above 110mgL-1d-1) than in the abiotic ES (below 35mgL-1d-1). This study shows that at anode potentials below 0.7V, the electrochemical tetrathionate degradation is only efficient with microbial catalyst and that significantly higher tetrathionate degradation rates can be obtained with bioelectrochemical systems than with electrochemical systems at the tested anode potentials.

Anaerobes in Bioelectrochemical Systems

In bioelectrochemical systems (BES), the catalytic activity of anaerobic microorganisms generates electrons at the anode which can be used, for example, for the production of electricity or chemical compounds. BES can be used for various purposes, including wastewater treatment, production of electricity, fuels and chemicals, biosensors, bioremediation, and desalination. Electrochemically active microorganisms are widely present in the environment and they can be found, in sediment, soil, compost, wastewaters and their treatment plants. Exoelectrogens are microorganisms capable of donating electrons to anode electrode or accepting electrons from cathode electrode and are mainly responsible for current generation or use in BES. However, current generation from fermentable substrates often requires the presence of electrochemically inactive microorganisms that break down complex substrates into metabolites which can be further utilized by exoelectrogens. The growth and electron transfer efficiency of anaerobes depend on several parameters, such as system architecture, electrode material and porosity, electrode potential and external resistance, pH, temperature, substrate concentration, organic loading rate, and ionic strength. In this chapter, the principles and microbiology of bioelectrochemical systems as well as selective factors for exoelectrogens are reviewed. The anaerobic microorganisms and their electron transfer mechanisms at the anode and cathode are described and future aspects are briefly discussed.

Anaerobic digestion of 30−100-year-old boreal lake sedimented fibre from the pulp industry: Extrapolating methane production potential to a practical scale

Since the 1980s, the pulp and paper industry in Finland has resulted in the accumulation of fibres in lake sediments. One such site in Lake Näsijärvi contains approximately 1.5 million m3 sedimented fibres. In this study, the methane production potential of the sedimented fibres (on average 13% total solids (TS)) was determined in batch assays. Furthermore, the methane production from solid (on average 20% TS) and liquid fractions of sedimented fibres after solid-liquid separation was studied. The sedimented fibres resulted in fast methane production and high methane yields of 250 ± 80 L CH4/kg volatile solids (VS). The main part (ca. 90%) of the methane potential was obtained from the solid fraction of the sedimented fibres. In addition, the VS removal from the total and solid sedimented fibres was high, 61-65% and 63-78%, respectively. The liquid fraction also contained a large amount of organics (on average 8.8 g COD/L), treatment of which also has to be considered. The estimations of the methane production potentials in the case area showed potential up to 40 million m3 of methane from sedimented fibres.

Remediation of sedimented fiber originating from pulp and paper industry: Laboratory scale anaerobic reactor studies and ideas of scaling up

Anaerobic treatment of sedimented fibers collected from bottom of a bay that had been receiving pulp and paper mill wastewater for about 70 years were studied for the first time in semi-continuously fed continuously stirred tank reactors (CSTR). Anaerobic treatment of the fiber sediment was shown to be feasible, without dilution and with nitrogen and buffer supplement, at organic loading rates (OLR) up to 2.5 kg VS/m3d and hydraulic retention times (HRT) of 60 d resulting in methane yields of 201 ± 18 L CH4/kg VS. Co-digestion of sedimented fiber with sewage sludge at an OLR of 1.5 kg VS/m3d and HRT of 20 d resulted in a methane production of 246 ± 10 L CH4/kg VS. The techno-economic feasibility of mono and co-digestion process together with several case dependent factors such as maximum operable OLR, digestate utilization needs to be evaluated before making further conclusions for larger scale remediation applications.