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

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

Spectral induced polarization and electrodic potential monitoring of microbially mediated iron sulfide transformations

Stimulated sulfate-reduction is a bioremediation technique utilized for the sequestration of heavy metals in the subsurface.We performed laboratory column experiments to investigate the geoelectrical response of iron sulfide transformations by Desulfo vibriovulgaris. Two geoelectrical methods, (1) spectral induced polarization (SIP), and (2) electrodic potential measurements, were investigated. Aqueous geochemistry (sulfate, lactate, sulfide, and acetate), observations of precipitates (identified from electron microscopy as iron sulfide), and electrodic potentials on bisulfide ion (HS) sensitive silver-silver chloride (Ag-AgCl) electrodes (630 mV) were diagnostic of induced transitions between an aerobic iron sulfide forming conditions and aerobic conditions promoting iron sulfide dissolution. The SIP data showed 10m rad anomalies during iron sulfide mineralization accompanying microbial activity under an anaerobic transition. These anomalies disappeared during iron sulfide dissolution under the subsequent aerobic transition. SIP model parameters based on a Cole-Cole relaxation model of the polarization at the mineral-fluid interface were converted to (1) estimated biomineral surface area to pore volume (Sp), and (2) an equivalent polarizable sphere diameter (d) controlling the relaxation time. The temporal variation in these model parameters is consistent with filling and emptying of pores by iron sulfide biofilms, as the system transitions between anaerobic (pore filling) and aerobic (pore emptying) conditions. The results suggest that combined SIP and electrodic potential measurements might be used to monitor spatiotemporal variability in microbial iron sulfide transformations in the field

Centimeter-long electron transport in marine sediments via conductive minerals

© 2015 International Society for Microbial Ecology All rights reserved. Centimeter-long electron conduction through marine sediments, in which electrons derived from sulfide in anoxic sediments are transported to oxygen in surficial sediments, may have an important influence on sediment geochemistry. Filamentous bacteria have been proposed to mediate the electron transport, but the filament conductivity could not be verified and other mechanisms are possible. Surprisingly, previous investigations have never actually measured the sediment conductivity or its basic physical properties. Here we report direct measurements that demonstrate centimeter-long electron flow through marine sediments, with conductivities sufficient to account for previously estimated electron fluxes. Conductivity was lost for oxidized sediments, which contrasts with the previously described increase in the conductivity of microbial biofilms upon oxidation. Adding pyrite to the sediments significantly enhanced the conductivity. These results suggest that the role of conductive minerals, which are more commonly found in sediments than centimeter-long microbial filaments, need to be considered when modeling marine sediment biogeochemistry

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface