Importance of subsurface water for hydrological response during storms in a post-wildfire bedrock landscape.

Wildfire alters the hydrologic cycle, with important implications for water supply and hazards including flooding and debris flows. In this study we use a combination of electrical resistivity and stable water isotope analyses to investigate the hydrologic response during storms in three catchments: one unburned and two burned during the 2020 Bobcat Fire in the San Gabriel Mountains, California, USA. Electrical resistivity imaging shows that in the burned catchments, rainfall infiltrated into the weathered bedrock and persisted. Stormflow isotope data indicate that the amount of mixing of surface and subsurface water during storms was similar in all catchments, despite higher streamflow post-fire. Therefore, both surface runoff and infiltration likely increased in tandem. These results suggest that the hydrologic response to storms in post-fire environments is dynamic and involves more surface-subsurface exchange than previously conceptualized, which has important implications for vegetation regrowth and post-fire landslide hazards for years following wildfire.

Post-remediation geophysical assessment: Investigating long-term electrical geophysical signatures resulting from bioremediation at a chlorinated solvent contaminated site.

There is a growing need to assess long-term impacts of active remediation strategies on treated aquifers. A variety of biogeochemical alterations can result from interactions of the amendment with the aquifer, conceivably leading to a geophysical signal associated with the long-term alteration of an aquifer. This concept of post-remediation geophysical assessment was investigated in a shallow, chlorinated solvent-contaminated aquifer six to eight years after amendment delivery. Surface resistivity imaging and cross-borehole resistivity and induced polarization (IP) imaging were performed on a transect that spanned treated and untreated zones of the aquifer. Established relationships between IP parameters and surface electrical conductivity were used to predict vertical profiles of electrolytic conductivity and surface conductivity from the inverted cross-borehole images. Aqueous geochemistry data, along with natural gamma and magnetic susceptibility logs, were used to constrain the interpretation. The electrical conductivity structure determined from surface and borehole imaging was foremost controlled by the electrolytic conductivity of the interconnected pore space, being linearly related to fluid specific conductance. The electrolytic conductivity (and thus the conductivity images alone) did not discriminate between treated and untreated zones of the aquifer. In contrast, inverted phase angles and surface conductivities did discriminate between treated and untreated zones of the aquifer, with the treated zone being up to an order of magnitude more polarizable in places. Supporting aqueous chemistry and borehole logging datasets indicate that this geophysical signal from the long-term impact of the remediation on the aquifer is most likely associated with the formation of polarizable, dispersed iron sulfide minerals.

Geophysical methods for monitoring soil stabilization processes.

Soil stabilization involves methods used to turn unconsolidated and unstable soil into a stiffer, consolidated medium that could support engineered structures, alter permeability, change subsurface flow, or immobilize contamination through mineral precipitation. Among the variety of available methods carbonate precipitation is a very promising one, especially when it is being induced through common soil borne microbes (MICP - microbial induced carbonate precipitation). Such microbial mediated precipitation has the added benefit of not harming the environment as other methods can be environmentally detrimental. Carbonate precipitation, typically in the form of calcite, is a naturally occurring process that can be manipulated to deliver the expected soil strengthening results or permeability changes. This study investigates the ability of spectral induced polarization and shear-wave velocity for monitoring calcite driven soil strengthening processes. The results support the use of these geophysical methods as soil strengthening characterization and long term monitoring tools, which is a requirement for viable soil stabilization projects. Both tested methods are sensitive to calcite precipitation, with SIP offering additional information related to long term stability of precipitated carbonate. Carbonate precipitation has been confirmed with direct methods, such as direct sampling and scanning electron microscopy (SEM). This study advances our understanding of soil strengthening processes and permeability alterations, and is a crucial step for the use of geophysical methods as monitoring tools in microbial induced soil alterations through carbonate precipitation.

Evidence of Coupled Carbon and Iron Cycling at a Hydrocarbon-Contaminated Site from Time Lapse Magnetic Susceptibility.

Conventional characterization and monitoring of hydrocarbon (HC) pollution is often expensive and time-consuming. Magnetic susceptibility (MS) has been proposed as an inexpensive, long-term monitoring proxy of the degradation of HC. We acquired repeated down hole MS logging data in boreholes at a HC-contaminated field research site in Bemidji, MN, USA. The MS data were analyzed in conjunction with redox conditions and iron availability within the source zone to better assess whether MS can serve as a proxy for monitoring HC contamination in unconsolidated sediments. The MS response at the site diminished during the sampling period, which was found to coincide with depletion of solid phase iron in the source zone. Previous geochemical observations and modeling at the site suggest that the most likely cause of the decrease in MS is the transformation of magnetite to siderite, coupled with the exhaustion of ferrihydrite. Although the temporal MS response at this site gives valuable field-scale evidence for changing conditions of iron cycling and stability of iron minerals it does not provide a simple proxy for long-term monitoring of biodegradation of hydrocarbons in the smear zone.

Specific polarizability of sand-clay mixtures with varying ethanol concentration.

We utilise a concept of specific polarizability (c s ), represented as the ratio of mineral-fluid interface polarization per pore-normalised surface area S p , to demonstrate the influence of clay-organic interaction on complex conductivity measurements. Complex conductivity measurements were performed on kaolinite- and illite-sand mixtures as a function of varying ethanol (EtOH) concentration (10% and 20% v/v). The specific surface area of each clay type and Ottawa sand was determined by nitrogen-gas-adsorption Brunauer-Emmett-Teller method. We also calculated the porosity and saturation of each mixture based on weight loss of dried samples. Debye decomposition, a phenomenological model, was applied to the complex conductivity data to determine normalised chargeability (m n ). Specific polarizability estimates from previous complex conductivity measurements for bentonite-sand mixtures were compared with our dataset. The c s for all sand-clay mixtures decreased as the EtOH concentration increased from 0% to 10% to 20% v/v. We observe similar c s responses to EtOH concentration for all sand-clay mixtures. Analysis of variance with a level of significance α = 0.05 suggests that the suppression in c s responses with increasing EtOH concentration was statistically significant for all sand-clay mixtures. On the other hand, real conductivity showed only 10% to 20% v/v changes with increasing EtOH concentration. The c s estimates reflect the sensitivity of complex conductivity measurements to alteration in surface chemistry at available surface adsorption sites for different clay types, likely resulting from ion exchange at the clay surface and associated with kinetic reactions in the electrical double layer of the clay-water-EtOH media. Our results indicate a much larger influence of specific surface area and ethanol concentration on clay-driven polarization relative to changes in clay mineralogy.

Imaging Pathways in Fractured Rock Using Three-Dimensional Electrical Resistivity Tomography.

Major challenges exist in delineating bedrock fracture zones because these cause abrupt changes in geological and hydrogeological properties over small distances. Borehole observations cannot sufficiently capture heterogeneity in these systems. Geophysical techniques offer the potential to image properties and processes in between boreholes. We used three-dimensional cross borehole electrical resistivity tomography (ERT) in a 9 m (diameter) × 15 m well field to capture high-resolution flow and transport processes in a fractured mudstone contaminated by chlorinated solvents, primarily trichloroethylene. Conductive (sodium bromide) and resistive (deionized water) injections were monitored in seven boreholes. Electrode arrays with isolation packers and fluid sampling ports were designed to enable acquisition of ERT measurements during pulsed tracer injections. Fracture zone locations and hydraulic pathways inferred from hydraulic head drawdown data were compared with electrical conductivity distributions from ERT measurements. Static ERT imaging has limited resolution to decipher individual fractures; however, these images showed alternating conductive and resistive zones, consistent with alternating laminated and massive mudstone units at the site. Tracer evolution and migration was clearly revealed in time-lapse ERT images and supported by in situ borehole vertical apparent conductivity profiles collected during the pulsed tracer test. While water samples provided important local information at the extraction borehole, ERT delineated tracer migration over spatial scales capturing the primary hydrogeological heterogeneity controlling flow and transport. The fate of these tracer injections at this scale could not have been quantified using borehole logging and/or borehole sampling methods alone.

Evaluation of Surface Sorption Processes Using Spectral Induced Polarization and a (22)Na Tracer.

We investigate mechanisms controlling the complex electrical conductivity of a porous media using noninvasive spectral induced polarization (SIP) measurements of a silica gel during a pH dependent surface adsorption experiment. Sorption of sodium on silica gel surfaces was monitored as the pH of a column was equilibrated at 5.0 and then successively raised to 6.5 and 8.0, but the composition of the 0.01 M NaCl solution was otherwise unchanged. SIP measurements show an increase in the imaginary conductivity of the sample (17.82 ± 0.07 µS/cm) in response to the pH change, interpreted as deprotonation of silanol groups on the silica gel surface followed by sorption of sodium cations. Independent measurements of Na(+) accumulation on grain surfaces performed using a radioactive (22)Na tracer support the interpretation of pH-dependent sorption as a dominant process controlling the electrical properties of the silica gel (R(2) = 0.99) and confirms the importance of grain polarization (versus membrane polarization) in influencing SIP measurements of silicate minerals. The number of surface sorption sites estimated by fitting a mechanistic, triple-layer model for the complex conductivity to the SIP data (13.22 × 10(16) sites/m(2)) was 2.8 times larger than that estimated directly by a (22)Na mass balance (5.13 × 10(16) sites/m(2)), suggesting additional contributions to polarization exist.

Complex resistivity signatures of ethanol biodegradation in porous media.

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability (m), normalized chargeability (m(n)) and time constant (τ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real (σ') and imaginary (σ″) conductivity, phase (ϕ) and apparent formation factor (F(app)). Unlike the control columns, a substantial decrease in σ' and increase in F(app) occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in σ' is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~9 mrad) and σ″ (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m(n) were consistent with temporal changes in ϕ and σ″ responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Complex resistivity signatures of ethanol in sand-clay mixtures.

We performed complex resistivity (CR) measurements on laboratory columns to investigate changes in electrical properties as a result of varying ethanol (EtOH) concentration (0% to 30% v/v) in a sand-clay (bentonite) matrix. We applied Debye decomposition, a phenomenological model commonly used to fit CR data, to determine model parameters (time constant: τ, chargeability: m, and normalized chargeability: mn). The CR data showed a significant (P≤0.001) time-dependent variation in the clay driven polarization response (~12 mrad) for 0% EtOH concentration. This temporal variation probably results from the clay-water reaction kinetics trending towards equilibrium in the sand-clay-water system. The clay polarization is significantly suppressed (P≤0.001) for both measured phase (ϕ) and imaginary conductivity (σ″) with increasing EtOH concentration. Normalized chargeability consistently decreases (by up to a factor of ~2) as EtOH concentration increases from 0% to 10% and 10 to 20%, respectively. We propose that such suppression effects are associated with alterations in the electrical double layer (EDL) at the clay-fluid interface due to (a) strong EtOH adsorption on clay, and (b) complex intermolecular EtOH-water interactions and subsequent changes in ionic mobility on the surface in the EDL. Changes in the CR data following a change of the saturating fluid from EtOH 20% to plain water indicate strong hysteresis effects in the electrical response, which we attribute to persistent EtOH adsorption on clay. Our results demonstrate high sensitivity of CR measurements to clay-EtOH interactions in porous media, indicating the potential application of this technique for characterization and monitoring of ethanol contamination in sediments containing clays.

Laboratory SIP signatures associated with oxidation of disseminated metal sulfides.

Oxidation of metal sulfide minerals is responsible for the generation of acidic waters rich in sulfate and metals. When associated with the oxidation of sulfide ore mine waste deposits the resulting pore water is called acid mine drainage (AMD); AMD is a known environmental problem that affects surface and ground waters. Characterization of oxidation processes in-situ is challenging, particularly at the field scale. Geophysical techniques, spectral induced polarization (SIP) in particular, may provide a means of such investigation. We performed laboratory experiments to assess the sensitivity of the SIP method to the oxidation mechanisms of common sulfide minerals found in mine waste deposits, i.e., pyrite and pyrrhotite, when the primary oxidant agent is dissolved oxygen. We found that SIP parameters, e.g., phase shift, the imaginary component of electrical conductivity and total chargeability, decrease as the time of exposure to oxidation and oxidation degree increase. This observation suggests that dissolution-depletion of the mineral surface reduces the capacitive properties and polarizability of the sulfide minerals. However, small increases in the phase shift and imaginary conductivity do occur during oxidation. These transient increases appear to correlate with increases of soluble oxidizing products, e.g., Fe(2+) and Fe(3+) in solution; precipitation of secondary minerals and the formation of a passivating layer to oxidation coating the mineral surface may also contribute to these increases. In contrast, the real component of electrical conductivity associated with electrolytic, electronic and interfacial conductance is sensitive to changes in the pore fluid chemistry as a result of the soluble oxidation products released (Fe(2+) and Fe(3+)), particularly for the case of pyrrhotite minerals.

Electrical signatures of ethanol-liquid mixtures: implications for monitoring biofuels migration in the subsurface.

Ethanol (EtOH), an emerging contaminant with potential direct and indirect environmental effects, poses threats to water supplies when spilled in large volumes. A series of experiments was directed at understanding the electrical geophysical signatures arising from groundwater contamination by ethanol. Conductivity measurements were performed at the laboratory scale on EtOH-water mixtures (0 to 0.97 v/v EtOH) and EtOH-salt solution mixtures (0 to 0.99 v/v EtOH) with and without a sand matrix using a conductivity probe and a four-electrode electrical measurement over the low frequency range (1-1000 Hz). A Lichtenecker-Rother (L-R) type mixing model was used to simulate electrical conductivity as a function of EtOH concentration in the mixture. For all three experimental treatments increasing EtOH concentration resulted in a decrease in measured conductivity magnitude (|σ|). The applied L-R model fitted the experimental data at concentration ≤0.4v/v EtOH, presumably due to predominant and symmetric intermolecular (EtOH-water) interaction in the mixture. The deviation of the experimental |σ| data from the model prediction at higher EtOH concentrations may be associated with hydrophobic effects of EtOH-EtOH interactions in the mixture. The |σ| data presumably reflected changes in relative strength of the three types of interactions (water-water, EtOH-water, and EtOH-EtOH) occurring simultaneously in EtOH-water mixtures as the ratio of EtOH to water changed. No evidence of measurable polarization effects at the EtOH-water and EtOH-water-mineral interfaces over the investigated frequency range was found. Our results indicate the potential for using electrical measurements to characterize and monitor EtOH spills in the subsurface.

Geophysical imaging of stimulated microbial biomineralization.

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.