Spectral Induced Polarization Signals Research Articles

The Relative Importance of Saturated Silica Sand Interfacial and Pore Fluid Geochemistry on the Spectral Induced Polarization Response

AbstractAdsorption at the solid‐pore fluid interface is a key mechanism controlling the mobility of nutrients and contaminants in subsurface soils and sediments. The spectral induced polarization (SIP) method has been shown to be sensitive to the quantity and type of adsorbed ions. Extending previous results, we investigated the relevance of pH, solution conductivity, and ion type on the SIP response of saturated silica sand. We also performed adsorption experiments to evaluate whether adsorption plays a relevant role on the effect of saturating solution conductivity and pH. Given their environmental relevance and different electrochemical characteristics, we focused on exploring the influence of Cu2+ and Na+ adsorption on the SIP signature. The adsorption results confirm the expected and modeled pH influence on the adsorption of both Cu2+ and Na+. The measured quadrature conductivity spectra indicate that pH and solution conductivity control the electrical double layer electrochemical state and its capacitive behavior. On the contrary, no appreciable SIP signal changes are associated with ion substitution. The adsorption experiments highlight low values of site occupancy for Na and Cu, which suggests that the effects of pH and fluid conductivity are unrelated to their control on the ion adsorption. We interpret the solution conductivity as a proxy for ionic strength. The relative importance of pH and solution conductivity over ion type helps to further constrain the interpretation of SIP results in field geochemical and biogeochemical characterization and monitoring.

The effect of organic acid on the spectral-induced polarization response of soil

In spectral-induced polarization (SIP) studies of sites contaminated by organic hydrocarbons, it was shown that biodegradation by-products in general, and organic acids in particular, significantly alter the SIP signature of the subsurface. Still a systematic study that considers the effect of organic acid on the physicochemical and electrical (SIP) properties of the soil is missing. The goal of this work is to relate between the effect of organic acid on the physicochemical properties of the soil, and the soil electrical properties. To do so, we measured the temporal changes of the soil chemical (ion content) and electrical (low-frequency SIP) properties in response to influx of organic acid at different concentrations, gradually altering the soil pH. Our results show that organic acid reduces the soil pH, enhances mineral weathering and consequently reduces both the in-phase and quadrature conductivity. At the pH range where mineral weathering is most significant (pH 6–4.5) a negative linear relation between the soil pH and the soil formation factor was found, suggesting that mineral weathering changes the pore space geometry and hence affecting the in-phase electrical conductivity. In addition, we attribute the reduction in the quadrature conductivity to an exchange process between the natural cation adsorbed on the mineral surface and hydronium, and to changes in the width of the pore bottleneck that results from the mineral weathering. Overall, our results allow a better understanding of the SIP signature of soil undergoing acidification process in general and as biodegradation process in particular.

On the spectral induced polarization signature of soil organic matter

Although often composing a non-negligible fraction of soil cation exchange capacity (CEC), the impact of soil organic matter (OM) on the electrical properties of soil has not been thoroughly investigated. In this research the impact of soil OM on the spectral induced polarization (SIP) signature of soil was investigated. Electrical and chemical measurements for two experiments using the same soil, one with calcium as the dominant cation and the other with sodium, with different concentration of OM were performed. Our results show that despite the high CEC of OM, a decrease in polarization and an increase in relaxation time with increasing concentration of OM is observed. For the soil with calcium as the dominant cation, the decreases in polarization and the increase in relaxation time were stronger. We explain these non-trivial results by accounting for the interactions between the OM and the soil minerals. We suggest that the formation of organo-mineral complexes reduce ionic mobility, explaining both the decrease in polarization and the increase in relaxation time. These results demonstrate the important role of OM on SIP response of soil, and call for a further research in order to establish a new polarization model that will include the impact of OM on soil polarization.

The effect of free-phase NAPL on the spectral induced polarization signature of variably saturated soil

[1] In this study, the influence of a free phase nonaqueous phase liquid (NAPL), decane, on the soil's SIP signature was experimentally investigated. The complex electrical conductivity was determined using the SIP measurement system and compared between two main treatment types: clean and decane contaminated. Complementary chemical and temporal measurements were conducted. The results show a clear decrease in the imaginary part of the complex conductivity for the decane contaminated soil. Moreover, a shift of the relaxation frequency was observed for the contaminated soil. Our chemical analysis suggests that there was no change in the chemical composition of the Stern layer, and clearly, the grain size distribution did not change as well. Therefore, these results are attributed to membrane polarization. The decane addition to the unsaturated porous media changes the pore-scale liquid phase distribution, thus affecting membrane polarization. Further, the electrical signature is a time-related process associated with liquid phase arrangement time. The findings of this study can enable a better understanding of the SIP response for soils contaminated with free-phase organic compounds.

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.

Spectral induced polarization signature of soil contaminated by organic pollutant: Experiment and modeling

The spectral induced polarization (SIP) signature of soil contaminated with organic pollutant was studied. Using a flow column experiment, the effect of crystal violet (CV, a polar organic pollutant) on the temporal change of the SIP response over a broad frequency range (1 mHz to 45 KHz) was determined. Complimentary measurements were used to determine the effect of CV on the chemical composition of both the pore water and the solid surface. In addition, analysis of the experimental results was carried out by using both chemical complexation and induced polarization models. Our results shows that adsorption of CV to the mineral surface resulted in release of inorganic ions to the soil solution, increasing the solution electrical conductivity and therefore also the real part of the complex conductivity. Despite the increase in the real part of the complex conductivity, the imaginary part of the complex conductivity decreased with increasing concentration of adsorbed CV. Using the Revil induced polarization model, we were able to show that the contribution of the adsorbed CV to the polarization of the soil is negligible, and that the main process affecting the polarization is the decrease in the density of the inorganic surface species. The results of this study can be used to better interpret SIP signature of soils contaminated by organic compounds.

A new model for the spectral induced polarization signature of bacterial growth in porous media

The complex conductivity of porous materials and colloidal suspensions comprises two components: an in‐phase conductivity associated with electromigration of the charge carriers and a quadrature conductivity associated with the reversible storage of the charges at some polarization length scales. We developed a quantitative model to investigate the frequency domain induced polarization response of suspensions of bacteria and bacteria growth in porous media. Induced polarization of bacteria (α polarization) is related to the properties of the electrical double layer of the bacteria. Surface conductivity and α polarization are due to the Stern layer of counterions occurring in a brush of polymers coating the surface of the bacteria. These phenomena can be related to their cation exchange capacity. The mobility of the counterions in this Stern layer is found to be very small (4.7 × 10−10 m2 s−1 V−1 at 25°C). This implies a very low relaxation frequency for the αpolarization of the bacteria cells (typically around 0.1–5 Hz), in agreement with experimental observations. This new model can be coupled to reactive transport modeling codes in which the evolution of bacterial populations are usually described by Monod kinetics. We show that the growth rate and endogenous decay coefficients of bacteria in a porous sand can be inferred nonintrusively from time‐lapse frequency domain induced polarization data.

Spectral Induced Polarization (SIP) signatures of clayey soils containing toluene

ABSTRACTWe performed laboratory experiments to investigate the sensitivity of the Spectral Induced Polarization (SIP) method to toluene contamination in clayey soils. We used mixtures of quartzitic sand and montmorillonite as soil samples, artificially contaminated with varying amounts of toluene. Care was taken to quantify the experimental uncertainty resulting from packing since such effects must be quantified if variations in SIP signatures between samples are to be reliably interpreted in terms of the effects of hydrocarbon concentration. The SIP response of all samples following addition of toluene was monitored for a period of 40 days following sample preparation. Stepwise regression was used to examine the statistical significance of correlations between (i) clay content and (ii) toluene concentration and SIP parameters. Both single‐frequency real and imaginary conductivity measurements, along with the integral chargeability, normalized chargeability, DC conductivity and time constant obtained from a Debye decomposition fitting, were examined in this regression analysis.The SIP measurements show a clear time dependence following sample preparation, indicating that samples containing toluene may take significant time to reach an equilibrium electrical response. SIP measurements are significantly related to toluene content shortly after sample preparation, when the expected dependence of SIP on clay concentration is apparently suppressed. However, for the state of electrical equilibrium after 40 days (interpreted to indicate surface chemistry at equilibrium) there is no significant relation between SIP measurements and toluene content; instead SIP measurements are then significantly correlated with clay concentration. The total chargeability, normalized chargeability and relaxation time obtained from the Debye decomposition show no correlation with toluene content, indicating that this procedure, which likely integrates over multiple mechanisms, may not be suitable for understanding relationships between SIP and hydrocarbon contamination. We find only small low‐frequency polarization signals observed in relation to toluene concentration (2 mrad at 0.01 Hz), which initially decreases the interfacial polarization. Unlike earlier works, our results do not support the use of the SIP method as a tool for monitoring toluene contamination in clay soils.

Spectral Induced Polarization Signatures of Hydroxide Adsorption and Mineral Precipitation in Porous Media

The spectral induced polarization (SIP) technique is a promising approach for delineating subsurface physical and chemical property changes in a minimally invasive manner. To facilitate the understanding of position and chemical properties of reaction fronts that involve mineral precipitation in porous media, we investigated spatiotemporal variations in complex conductivity during evolution of urea hydrolysis and calcite precipitation reaction fronts within a silica gel column. The real and imaginary parts of complex conductivity were shown to be sensitive to changes in both solution chemistry and calcium carbonate precipitation. Distinct changes in imaginary conductivity coincided with increased hydroxide ion concentration during urea hydrolysis. In a separate experiment focused on the effect of hydroxide concentration on interfacial polarization of silica gel and well-sorted sand, we found a significant dependence of the polarization response on pH changes of the solution. We propose a conceptual model describing hydroxide ion adsorption behavior in silica gel and its control on interfacial polarizability. Our results demonstrate the utility of SIP for noninvasive monitoring of reaction fronts, and indicate its potential for quantifying geochemical processes that control the polarization responses of porous media at larger spatial scales in the natural environment.

The effect of NAPL on the electrical properties of unsaturated porous media

SUMMARY The spectral induced polarization signature of porous media contaminated with non-aqueous phase liquid (NAPL) was studied. Using an accurate measurement system, the complex electrical conductivity of unsaturated porous media contaminated with either diesel fuel or motor oil at a constant water saturation was determined. Counter intuitively, the results show that replacing air with NAPL increases the real part of the complex conductivity of unsaturated porous media. We interpret the results in terms of electrochemical polarization, and suggest that polar compounds contained in the NAPL adsorb to the mineral surface leading to release of inorganic ions to the pore water, which affects both the fluid and surface conductivity. In addition, we observed a decrease in the polarization followed by further addition of NAPL, which we relate to a lower mobility of the adsorbed polar compound. This study allows a better understanding of the electrical signature of NAPL contaminated porous media, especially in variably saturated conditions.

Spectral induced polarization signatures of abiotic FeS precipitation

In recent years, geophysical methods have been shown to be sensitive to microbial-induced mineralization processes. The spectral induced-polarization (SIP) method appears to be very promising for monitoring mineralization and microbial processes. With this work, we study the links of mineralization and SIP signals, in the absence of microbial activity. We recorded the SIP response during abiotic FeS precipitation. We show that the SIP signals are diagnostic of FeS mineralization and can be differentiated from SIP signals from biomineralization processes. More specifically, the imaginary conductivity shows almost linear dependence on the amount of FeS precipitating out of solution, above the threshold value [Formula: see text] under our experimental conditions. This research has direct implications for the use of the SIP method as a monitoring and decision-making tool for sustainable remediation of metals in contaminated soils and groundwater.

Pore‐scale spectral induced polarization signatures associated with FeS biomineral transformations

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.