Understanding how microorganisms influence the physical and chemical properties of the subsurface is hindered by our inability to observe microbial dynamics in real time and with high spatial resolution. Here, we investigate the use of noninvasive geophysical methods to monitor biomineralization at the laboratory scale during stimulated sulfate reduction under dynamic flow conditions. Alterations in sediment characteristics resulting from microbe-mediated sulfide mineral precipitation were concomitant with changes in complex resistivity and acoustic wave propagation signatures. The sequestration of zinc and iron in insoluble sulfides led to alterations in the ability of the pore fluid to conduct electrical charge and of the saturated sediments to dissipate acoustic energy. These changes resulted directly from the nucleation, growth, and development of nanoparticulate precipitates along grain surfaces and within the pore space. Scanning and transmission electron microscopy (SEM and TEM) confirmed the sulfides to be associated with cell surfaces, with precipitates ranging from aggregates of individual 3-5 nm nanocrystals to larger assemblages of up to 10-20 microm in diameter. Anomalies in the geophysical data reflected the distribution of mineral precipitates and biomass over space and time, with temporal variations in the signals corresponding to changes in the aggregation state of the nanocrystalline sulfides. These results suggest the potential for using geophysical techniques to image certain subsurface biogeochemical processes, such as those accompanying the bioremediation of metal-contaminated aquifers.

We analyze the relationship between induced polarization ͑IP͒ parameters and the specific surface area normalized to the pore volume ͑S por ͒ for an extensive sample database. We find that a single linear imaginary conductivity-S por relation holds across a range of single-frequency IP data sets composed of sandstones and unconsolidated sediments that lack an appreciable metallic mineral content. We also apply a recent approach defined as Debye decomposition ͑DD͒ to determine normalized chargeability ͑m n ͒, a global estimate of polarization magnitude from available spectral IP ͑SIP͒ data sets. A strong linear relationship between m n and S por is also found across multiple data sets. However, SIP model parameters determined for samples containing metallic minerals are approximately two orders of magnitude greater than for the model parameters estimated for the nonmetallic sample database. We propose a concept of "polarizability of the mineralfluid interface per unit S por " to explain this difference, which is supported by the observed dependence of IP parameters on fluid conductivity between sample types. We suggest that this linear IP-S por relation can be considered the IP equivalent of the classical Archie empirical relation. Whereas the Archie relation describes a power-law relation between electrical conductivity due to electrolytic conduction through the available interconnected pore volume, the IP-S por relation is an equivalent relation between mineral-fluid interfacial polarization and available pore surface area.

[1] We explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber-optic distributed temperature sensor (FO-DTS) monitoring, to improve the conceptual model for uranium transport within the Columbia River corridor at the Hanford 300 Area, Washington. We first inverted resistivity and induced polarization CWEI data sets for distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units was reconstructed. Variations in the depth to the interface between the overlying coarse-grained, high-permeability Hanford Formation and the underlying finer-grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, were resolved along ∼3 km of the river corridor centered on the 300 Area. Polarizability images were translated into lithologic images using established relationships between polarizability and surface area normalized to pore volume (S por ). The FO-DTS data recorded along 1.5 km of cable with a 1 m spatial resolution and 5 min sampling interval revealed subreaches showing (1) temperature anomalies (relatively warm in winter and cool in summer) and (2) a strong correlation between temperature and river stage (negative in winter and positive in summer), both indicative of reaches of enhanced surface water-groundwater exchange. The FO-DTS data sets confirm the hydrologic significance of the variability identified in the CWEI and reveal a pattern of highly focused exchange, concentrated at springs where the Hanford Formation is thickest. Our findings illustrate how the combination of CWEI and FO-DTS technologies can characterize surface water-groundwater exchange in a complex, coupled river-aquifer system.

[1] We investigated the sensitivity of low-frequency electrical measurements to microbeinduced metal sulfide precipitation. Three identical sand-packed monitoring columns were used; a geochemical column, an electrical column and a control column. In the first experiment, continuous upward flow of nutrients and metals in solution was established in each column. Cells of Desulfovibrio vulgaris (D. vulgaris) were injected into the center of the geochemical and electrical columns. Geochemical sampling and post-experiment destructive analysis showed that microbial induced sulfate reduction led to metal precipitation on bacteria cells, forming motile biominerals. Precipitation initially occurred in the injection zone, followed by chemotactic migration of D. vulgaris and ultimate accumulation around the nutrient source at the column base. Results from this experiment conducted with metals show (1) polarization anomalies, up to 14 mrad, develop at the bacteria injection and final accumulation areas, (2) the onset of polarization increase occurs concurrently with the onset of lactate consumption, (3) polarization profiles are similar to calculated profiles of the rate of lactate consumption, and (4) temporal changes in polarization and conduction correlate with a geometrical rearrangement of metal-coated bacterial cells. In a second experiment, the same biogeochemical conditions were established except that no metals were added to the flow solution. Polarization anomalies were absent when the experiment was replicated without metals in solution. We therefore attribute the polarization increase observed in the first experiment to a metal-fluid interfacial mechanism that develops as metal sulfides precipitate onto microbial cells and form biominerals. Temporal changes in polarization and conductivity reflect changes in (1) the amount of metal-fluid interfacial area, and (2) the amount of electronic conduction resulting from microbial growth, chemotactic movement and final coagulation. This polarization is correlated with the rate of microbial activity inferred from the lactate concentration gradient, probably via a common total metal surface area effect.

Induced polarization (IP) measurements were conducted on saturated kaolinite-, iron-, and magnetite-sand mixtures as a function of varying percentage weight of a mineral constituent: 0%–100% for iron and magnetite and 0%–32% for kaolinite. We determined the specific surface area for each mineral using nitrogen gas adsorption, where the porosity of each mixture was calculated from weight loss after drying. We fit a Cole-Cole model (Cole and Cole, 1941) to the electrical data obtained for the magnetite and iron mixtures. In contrast, the kaolinite mixtures showed a power-law dependence of phase-on frequency. The global polarization magnitude we obtained from the Cole-Cole modeling of the iron and magnetite mixtures displays a single, near-linear dependence on the ratio of surface area to pore volume ([Formula: see text]) calculated for the mixtures. A similar relationship is found using a local measure of polarization (imaginary conductivity at 1 Hz) for the clay-sand mixtures. The [Formula: see text] appears to be a critical parameter for determining IP in both metallic- and clay-containing soils. This result is not easily reconciled with traditional models of induced polarization.

[1] Time-lapse resistivity imaging is increasingly used to monitor hydrologic processes. Compared to conventional hydrologic measurements, surface time-lapse resistivity provides superior spatial coverage in two or three dimensions, potentially high-resolution information in time, and information in the absence of wells. However, interpretation of time-lapse electrical tomograms is complicated by the ever-increasing size and complexity of long-term, three-dimensional (3-D) time series conductivity data sets. Here we use 3-D surface time-lapse electrical imaging to monitor subsurface electrical conductivity variations associated with stage-driven groundwater-surface water interactions along a stretch of the Columbia River adjacent to the Hanford 300 near Richland, Washington, USA. We reduce the resulting 3-D conductivity time series using both time-series and time-frequency analyses to isolate a paleochannel causing enhanced groundwater-surface water interactions. Correlation analysis on the time-lapse imaging results concisely represents enhanced groundwater-surface water interactions within the paleochannel, and provides information concerning groundwater flow velocities. Time-frequency analysis using the Stockwell (S) transform provides additional information by identifying the stage periodicities driving groundwater-surface water interactions due to upstream dam operations, and identifying segments in time-frequency space when these interactions are most active. These results provide new insight into the distribution and timing of river water intrusion into the Hanford 300 Area, which has a governing influence on the behavior of a uranium plume left over from historical nuclear fuel processing operations.

We measured spectral induced polarization (SIP) signatures in sand columns during (1) FeS biomineralization produced by sulfate reducing bacteria (Desulfovibrio vulgaris) under anaerobic conditions, and (2) subsequent biomineral dissolution upon return to an aerobic state. The low‐frequency (0.1–10 Hz peak) relaxations produced during biomineralization can be modeled with a Cole‐Cole formulation, from which the evolution of the polarization magnitude and relaxation length scale can be estimated. We find that the modeled time constant is consistent with the polarizable elements being biomineral encrusted pores. Evolution of the model parameters is consistent with FeS surface area increases and pore‐size reduction during biomineral growth, and subsequent biomineral dissolution (FeS surface area decreases and pore expansion) upon return to the aerobic state. We conclude that SIP signatures are diagnostic of pore‐scale geometrical changes associated with FeS biomineralization by sulfate reducing bacteria.

[1] 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 Desulfovibrio vulgaris. 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 À ) sensitive silver-silver chloride (Ag-AgCl) electrodes ($À630 mV) were diagnostic of induced transitions between anaerobic iron sulfide forming conditions and aerobic conditions promoting iron sulfide dissolution. The SIP data showed $10 mrad 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 (S p ), 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.