Geophysical signatures of soil AFFF contamination from spectral induced polarization and low field nuclear magnetic resonance methods.

Few field methods are available for characterizing source zones impacted with aqueous film forming foam (AFFF). Non-invasive geophysical characterization of AFFF source zone contamination in situ could assist with the delineation and characterization of these sites, allowing for more informed sampling regimes aimed at quantifying subsurface poly- and perfluoroalkyl substances (PFAS) contamination. We present initial results from the investigation of the sensitivity of two existing surface and borehole-deployable geophysical technologies, spectral induced polarization (SIP), and low field nuclear magnetic resonance (NMR), to soils impacted with AFFF. To investigate the sensitivity of these methods to AFFF-impacted soil, bench-scale column experiments were conducted on samples consisting of natural and synthetic soils and groundwater. While our findings do not show strong evidence of NMR sensitivity to soil PFAS contamination, we do find evidence that SIP has sufficient sensitivity to detect sorption of AFFF constituents (including PFAS) to soils. This finding is based on evidence that AFFF constituents associated with the pore surface produce a measurable polarization response in both freshly impacted synthetic soils and in soils historically impacted with AFFF. Our findings encourage further exploration of the SIP method as a technology for characterizing contaminant concentrations across AFFF source zones.

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.

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.

Scenario Evaluator for Electrical Resistivity Survey Pre-modeling Tool.

Geophysical tools have much to offer users in environmental, water resource, and geotechnical fields; however, techniques such as electrical resistivity imaging (ERI) are often oversold and/or overinterpreted due to a lack of understanding of the limitations of the techniques, such as the appropriate depth intervals or resolution of the methods. The relationship between ERI data and resistivity is nonlinear; therefore, these limitations depend on site conditions and survey design and are best assessed through forward and inverse modeling exercises prior to field investigations. In this approach, proposed field surveys are first numerically simulated given the expected electrical properties of the site, and the resulting hypothetical data are then analyzed using inverse models. Performing ERI forward/inverse modeling, however, requires substantial expertise and can take many hours to implement. We present a new spreadsheet-based tool, the Scenario Evaluator for Electrical Resistivity (SEER), which features a graphical user interface that allows users to manipulate a resistivity model and instantly view how that model would likely be interpreted by an ERI survey. The SEER tool is intended for use by those who wish to determine the value of including ERI to achieve project goals, and is designed to have broad utility in industry, teaching, and research.

An overview of geophysical technologies appropriate for characterization and monitoring at fractured-rock sites.

Geophysical methods are used increasingly for characterization and monitoring at remediation sites in fractured-rock aquifers. The complex heterogeneity of fractured rock poses enormous challenges to groundwater remediation professionals, and new methods are needed to cost-effectively infer fracture and fracture-zone locations, orientations and properties, and to develop conceptual site models for flow and transport. Despite the potential of geophysical methods to "see" between boreholes, two issues have impeded the adoption of geophysical methods by remediation professionals. First, geophysical results are commonly only indirectly related to the properties of interest (e.g., permeability) to remediation professionals, and qualitative or quantitative interpretation is required to convert geophysical results to hydrogeologic information. Additional demonstration/evaluation projects are needed in the site remediation literature to fully transfer geophysical methods from research to practice. Second, geophysical methods are commonly viewed as inherently risky by remediation professionals. Although it is widely understood that a given method may or may not work at a particular site, the reasons are not always clear to end users of geophysical products. Synthetic modeling tools are used in research to assess the potential of a particular method to successfully image a target, but these tools are not widely used in industry. Here, we seek to advance the application of geophysical methods to solve problems facing remediation professionals with respect to fractured-rock aquifers. To this end, we (1) provide an overview of geophysical methods applied to characterization and monitoring of fractured-rock aquifers; (2) review case studies showcasing different geophysical methods; and (3) discuss best practices for method selection and rejection based on synthetic modeling and decision support tools.

The emergence of hydrogeophysics for improved understanding of subsurface processes over multiple scales.

A review of the emergence and development of hydrogeophysicsOutline of emerging techniques in hydrogeophysicsPresentation of future opportunities in hydrogeophysics.

Hydraulic anisotropy characterization of pneumatic-fractured sediments using azimuthal self potential gradient.

The pneumatic fracturing technique is used to enhance the permeability and porosity of tight unconsolidated soils (e.g. clays), thereby improving the effectiveness of remediation treatments. Azimuthal self potential gradient (ASPG) surveys were performed on a compacted, unconsolidated clay block in order to evaluate their potential to delineate contaminant migration pathways in a mechanically-induced fracture network. Azimuthal resistivity (ARS) measurements were also made for comparative purposes. Following similar procedures to those used in the field, compressed kaolinite sediments were pneumatically fractured and the resulting fracture geometry characterized from strike analysis of visible fractures combined with strike data from optical borehole televiewer (BHTV) imaging. We subsequently injected a simulated treatment (electrolyte/dye) into the fractures. Both ASPG and ARS data exhibit anisotropic geoelectric signatures resulting from the fracturing. Self potentials observed during injection of electrolyte are consistent with electrokinetic theory and previous laboratory results on a fracture block model. Visual (polar plot) analysis and linear regression of cross plots show ASPG lobes are correlated with azimuths of high fracture strike density, evidence that the ASPG anisotropy is a proxy measure of hydraulic anisotropy created by the pneumatic fracturing. However, ARS data are uncorrelated with fracture strike maxima and resistivity anisotropy is probably dominated by enhanced surface conduction along azimuths of weak 'starter paths' formed from pulverization of the clay and increases in interfacial surface area. We find the magnitude of electrokinetic SP scales with the applied N2 gas pressure gradient (DeltaPN2) for any particular hydraulically-active fracture set and that the positive lobe of the ASPG anomaly indicates the flow direction within the fracture network. These findings demonstrate the use of ASPG in characterizing the effectiveness of (1) pneumatic fracturing and (2) defining likely flow directions of remedial treatments in unconsolidated sediments and rock.

Low frequency electrical properties of corroded iron barrier cores.

We investigated the electrical signatures of iron corrosion and mineral precipitation in angle cores from an Fe(0) barrier installation in operation for eight years. The real and imaginary parts of the complex electrical conductivity measured between 0.1 and 1000 Hz were 2-10 times higher (varying between cores) in the reacted zone at the upgradient edge of the barrier relative to less altered locations inside the barrier. Scanning electron microscopy identified iron surface alteration with the thickest corrosion rinds closest to the upgradient soil/iron interface. Surface area of iron minerals was also greatest at the upgradient interface, gradually decreasing into the cores. X-ray diffractometry identified precipitation of iron oxide/hydroxide, carbonate minerals, iron sulfide, as well as green rusts, with mineral complexity decreasing away from the interface. The electrical measurements correlate very well with the solid-phase analyses, and they verify that electrical methods could be used to assess or monitor iron corrosion and mineral precipitation occurring in Fe(0) barriers.

Effect of precipitation on low frequency electrical properties of zerovalent iron columns.

We conducted column studies to investigate the application of a noninvasive electrical method to monitor precipitation in Fe0 columns using (a) Na2SO4 (0.01 M, dissolved oxygen (DO) = 8.8 ppm), and (b) Na2CO3 (0.01 M, DO = 2.3 ppm) solutions. An increase in complex conductivity terms (maximum 40% in sulfate column and 23% in carbonate column) occurred over 25 days. Scanning electron microscopy (SEM) identified mineral surface alteration, with greater changes in the high DO sulfate column relative to the low DO carbonate column. X-ray diffractometry (XRD) identified reduced amounts of hematite/maghemite in both columns, precipitation of goethite/akaganeite in the sulfate column, and precipitation of siderite in the carbonate column. Nitrogen adsorption measurements showed increases in specific surface area of iron minerals (27.5% for sulfate column and 8.2% for carbonate column). As variations in electrolytic conductivity and porosity were minimal, electrical changes are attributed to (1) higher complex interfacial conductivity due to increased surface area and mineralogical alteration and (2) increased electronic conduction due to enhanced electron transfer across the iron-fluid interface. Our results show that electrical measurements are a proxy indicator of Fe0 surface alteration.

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.