Dimitrios Ntarlagiannis

On the estimation of specific surface per unit pore volume from induced polarization: A robust empirical relation fits multiple data sets

We analyze the relationship between induced polarization (IP) parameters and the specific surface area normalized to the pore volume ( Spor ) for an extensive sample database. We find that a single linear imaginary conductivity- Spor 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 (DD) to determine normalized chargeability ( mn ) , a global estimate of polarization magnitude from available spectral IP (SIP) data sets. A strong linear relationship between mn and Spor 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 mineral-fluid interface per unit Spor ” to explain this difference, whi...

On the relationship between induced polarization and surface area in metal-sand and clay-sand mixtures

Induced polarization (IP) measurements were conducted on saturated kaolinite-, iron-, and magnetitesand 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 ColeCole 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, nearlinear dependence on the ratio of surface area to pore volume (Sp) 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 Sp 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.

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

Spectral induced polarization and electrodic potential monitoring of microbially mediated iron sulfide transformations Yves Robert Personna, 1 Dimitrios Ntarlagiannis, 1,2 Lee Slater, 1 Nathan Yee, 3 Michael O’Brien, 1 and Susan Hubbard 4 Department of Earth and Environmental Sciences, Rutgers University, Newark, New Jersey, USA Nowat School of Planning, Architecture, and Civil Engineering, Queen’s University Belfast, Belfast, UK Department of Environmental Sciences, Rutgers University, New Brunswick, New Jersey, USA. Lawrence Berkeley National Laboratory, Earth Sciences Division, Berkeley, California, USA. [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 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 bisulfideion (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. 1. Introduction [2] Soil and groundwater contamination by acid-mine drainage, industrial sources, and government nuclear weapon programs pose threats to human health and the environ-ment. Such anthropogenic activities may deliver into the environment a variety of substances of significant toxicity, carcinogenicity and potential for bioaccumulation in living systems. Microbial driven remediation (bio-remediation) has attracted interest in recent years as an effective cleanup technology [Rittle et al., 1995; Schultze-Lametal., 1996; Drury, 1999; Ehrlich, 1999; Drzyzga et al., 2002]. Biore-mediation techniques can offer an efficient, safe and cost effective option for the removal of hazardous pollutants without production of hazardous byproducts [Providentietal., 1993; Ward et al., 2003]. However, observational methods that enable realtime,spatially accurate monitoring and assessment of biological processes at the field scale are lacking. [3] One successful remediation strategy involves common soilborne microorganisms, such as Desulfo vibriovulgaris (D.vulgaris) studied here, to mineralize toxic metals in solution [Lovley et al., 1993; Anderson et al., 2003]. Williams et al. [2005] and Ntarlagiannis et al. [2005] showed that electrical and acoustic geophysical methods are sensitive to the formation of insoluble precipitates, or biominerals often associated with such remediation strategies. They suggested that geophysical techniques could be employed to monitor such bioremediation strategies in situ. Others have demonstrated the potential of geophysics to elucidate system transformations occur- ring during bioremediation of hydrocarbon contaminants [Atekwana et al., 2000, 2004]. Werkema et al. [2003] showed that zones of microbial degradation coincided with elevated soil electrical conductivity whereas Abdel Aal et al. [2004] showed that microbial activity enhances

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

Pore-scale Spectral Induced Polarization (SIP) signatures associated with FeS biomineral transformations Lee Slater , Dirnitrios Ntarlagiannis *, Yves R. Personna and Susan Hubbard 1. Department of Earth & Environmental Sciences, Rutgers-Newark, New Jersey, USA 2. Lawrence Berkeley National Laboratory, Berkeley, California, U S A # Now at School of Planning, Architecture and Civil Engineering, Queens University Belfast, Belfast, U K Abstract We measured Spectral Induced Polarization (SIP) signatures in sand columns during (1) FeS biomineralization produced by sulfate reducing bacteria (D. 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.

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 0.006 gr 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.

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 (SIP) signatures of clayey soils containing toluene

We 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.

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.

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.

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.