Monitoring microbial sulfate reduction in porous media using multi-purpose electrodes

[1] There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS−) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (σ″) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes

Monitoring microbial sulfate reduction in porous media using multipurpose electrodes

[1] There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS−) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (σ″) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes

FINAL REPORT: Adopting Biophysics Methods in Pursuit of Biogeophysical Research: Advancing the Measurement and Modeling of Electrical Signatures of Microbe-Mineral Transformations Impacting Contaminant Transport

This exploratory project involved laboratory experiments to investigate three hypotheses: (H1) Physics-based modeling of low-frequency dispersions (henceforth referred to as alpha) measured in broadband dielectric spectroscopy (DS) data can quantify pore-scale geometric changes impacting contaminant transport resulting from biomineralization; (H2) Physics-based modeling of high-frequency dispersions (henceforth referred to as beta) measured in broadband dielectric spectroscopy data can quantify rates of mineral growth in/on the cell wall; (H3) Application of this measurement and modeling approach can enhance geophysical interpretation of bioremediation experiments conducted at the RIFLE IFC by providing constraints on bioremediation efficiency (biomass concentration, mineral uptake within the cell wall, biomineralization rate). We tested H1 by performing DS measurements (alpha and beta range) on iron (Fe) particles of dimensions similar to microbial cells, dispersed within agar gels over a range of Fe concentrations. We have tested the ability of the physics-based modeling to predict volume concentrations of the Fe particles by assuming that the Fe particles are polarizable inclusions within an otherwise nonpolarizable medium. We evaluated the smallest volume concentration that can be detected with the DS method. Similar experiments and modeling have been performed on the sulfate-reducing bacteria D. vulgaris. Synchrotron x-ray absorption measurements were conducted to determine the local structure of biominerals coatings on D. vulgaris which were grown in the presence of different Fe concentrations. We imaged the mineral growth on cell wall using SEM. We used dielectric spectroscopy to differentiate between iron sulfide precipitates of biotic and abiotic nature. Biotic measurements were made on D. vulgaris bacteria grown in the presence of different concentrations of iron to form different thicknesses of iron sulfide precipitates around themselves and abiotic measurements were made on different concentrations of pyrrhotite particles suspended in agar. Results show a decrease in dielectric permittivity as a function of frequency for biotic minerals and an opposite trend is observed for abiotic minerals. Our results suggest that dielectric spectroscopy offers a noninvasive and fast approach for distinguishing between abiotic and biotic mineral precipitates

Microbial Nanowires: Is the Subsurface Hardwired ?

The Earth\u27s shallow subsurface results from integrated biological, geochemical, and physical processes. Methods are sought to remotely assess these interactive processes, especially those catalysed by micro-organisms. Using saturated sand columns and the metal reducing bacterium Shewanella oneidensis MR-1, we show that electrically conductive appendages called bacterial nanowires are directly associated with electrical potentials. No significant electrical potentials were detectable in columns inoculated with mutant strains that produced non-conductive appendages. Scanning electron microscopy imaging revealed a network of nanowires linking cells-cells and cells to mineral surfaces, hardwiring the entire length of the column. We hypothesize that the nanowires serve as conduits for transfer of electrons from bacteria in the anaerobic part of the column to bacteria at the surface that have access to oxygen, akin to a biogeobattery. These results advance understanding of the mechanisms of electron transport in subsurface environments and of how microorganisms cycle geologic material and share energy

Electrodic voltages in the presence of dissolved sulfide: Implications for monitoring natural microbial activity

Abstract There is growing interest in the development of new monitoring strategies for obtaining spatially extensive data diagnostic of microbial processes occurring in the earth. Open-circuit potentials arising from variable redox conditions in the fluid local-to-electrode surfaces (electrodic potentials) were recorded for a pair of silver-silver chloride electrodes in a column experiment, whereby a natural wetland soil containing a known community of sulfate reducers was continuously fed with a sulfate-rich nutrient medium. Measurements were made between five electrodes equally spaced along the column and a reference electrode placed on the column inflow. The presence of a sulfate reducing microbial population, coupled with observations of decreasing sulfate levels, formation of black precipitate (likely iron sulfide),elevated solid phase sulfide, and a characteristic sulfurous smell, suggest microbial-driven sulfate reduction (sulfide generation) in our column. Based on the known sensitivity of a silver electrode to dissolved sulfide concentration, we interpret the electrodic potentials approaching 700mV recorded in this experiment as an indicator of the bisulfide (HS−) concentration gradients in the column. The measurement of the spatial and temporal variation in these electrodic potentials provides a simple and rapid method for monitoring patterns of relative HS− concentration that are indicative of the activity of sulfate-reducing bacteria. Our measurements have implications both for the autonomous monitoring of anaerobic microbial processes in the subsurface and the performance of self-potential electrodes, where it is critical to isolate, and perhaps quantify, electrochemical interfaces contributing to observed potentials

Field-Scale Observations of a Transient Geobattery Resulting from Natural Attenuation of a Crude Oil Spill

We present evidence of a geobattery associated with microbial degradation of a mature crude oil spill. Self-potential measurements were collected using a vertical array of nonpolarizing electrodes, starting at the land surface and passing through the smear zone where seasonal water table fluctuations have resulted in the coating of hydrocarbons on the aquifer solids. These passive electrical potential measurements exhibit a dipolar pattern associated with a current source. The anodic and cathodic reactions of this natural battery occur below and above the smear zone, respectively. The smear zone is characterized by high magnetic susceptibility values associated with the precipitation of semiconductive magnetic iron phase minerals as a by-product of biodegradation, facilitating electron transfer between the anode and the cathode. This geobattery response appears to have a transient nature, changing on a monthly scale, probably resulting from chemical and physical changes in subsurface conditions such as water table fluctuations

Magnetic Susceptibility As a Proxy for Investigating Microbially Mediated Iron Reduction

We investigated magnetic susceptibility (MS) variations in hydrocarbon contaminated sediments. Our objective was to determine if MS can be used as an intrinsic bioremediation indicator due to the activity of iron-reducing bacteria. A contaminated and an uncontaminated core were retrieved from a site contaminated with crude oil near Bemidji, Minnesota and subsampled for MS measurements. The contaminated core revealed enriched MS zones within the hydrocarbon smear zone, which is related to iron-reduction coupled to oxidation of hydrocarbon compounds and the vadose zone, which is coincident with a zone of methane depletion suggesting aerobic or anaerobic oxidation of methane is coupled to iron-reduction. The latter has significant implications for methane cycling. We conclude that MS can serve as a proxy for intrinsic bioremediation due to the activity of iron-reducing bacteria iron-reducing bacteria and for the application of geophysics to iron cycling studies

Electrical Resistivity Imaging for Long-Term Autonomous Monitoring of Hydrocarbon Degradation: Lessons from the Deepwater Horizon Oil Spill

Conceptual models for the geophysical responses associated with hydrocarbon degradation suggest that the long-term evolution of an oil plume will result in a more conductive anomaly than the initial contamination. In response to the Deepwater Horizon (DH) oil spill into the Gulf of Mexico in 2010, an autonomous resistivity monitoring system was deployed on Grand Terre, Louisiana, in an attempt to monitor natural degradation processes in hydrocarbon-impacted beach sediments of this island. A 48-electrode surface array with a 0.5-m spacing was installed to obtain twice-daily images of the resistivity structure of the shallow subsurface impacted by oil. Over the course of approximately 18 months, we observed a progressive decrease in the resistivity of the DH spill-impacted region. Detailed analysis of pixel/point resistivity variation within the imaged area showed that long-term decreases in resistivity were largely associated with the DH-impacted sediments. A microbial diversity survey revealed the presence of hydrocarbon-degrading organisms throughout the test site. However, hydrocarbon degradation activity was much higher in the DH-impacted locations compared to nonimpacted locations, suggesting the presence of active hydrocarbon degraders, supporting biodegradation processes. The results of this long-term monitoring experiment suggested that resistivity might be used to noninvasively monitor the long-term degradation of crude oil spills