International audienceIn electrolyte-saturated sands, the reversible storage of electrical charges is responsible for a phase lag between the current (injected and retrieved by two current electrodes) and the electrical field recorded by two voltage electrodes. This phenomenon is called 'spectral induced polarization' in geophysics and can potentially be used to monitor salt tracer tests in shallow aquifers to infer their permeability and dispersivity tensors. We demonstrate analytically that the polarization of the inner part of the electrical triple layer coating the surface of the grains (named the Stern layer in electrochemistry) is consistent with available data. We also perform new experiments using silica sands saturated by NaCl and CaCl2 pore water solutions. The salinity dependence of quadrature conductivity can be modelled using an analytical solution of the triple layer model, which offers a simple way to interpret laboratory and field data. This analytical solution depends on the total site density of the mineral surface, the pH value and the sorption coefficient of the cation in the Stern layer. This model shows that both the specific surface conductivity of the Stern layer and the quadrature conductivity of the porous material depend on the conductivity of the pore water. The quadrature conductivity is becoming independent of the salinity above 1 S m−1. The parameters entering the analytical model are consistent with independent estimates from titration data and zeta potential measurements, which are two classical methods to characterize the electrical triple layer at the pore water mineral interface

Tremendous opportunities exist for enhancing water quality and improving aquatic habitat by actively managing urban water infrastructure to operate in conjunction with natural systems. The hyporheic zone (HZ) of streams, which is the area of active mixing between surface water and groundwater, is one such system that is overlooked by many water professionals, because the state of the science on this topic has not been transferred into practice. As a biogeochemically active zone, the HZ offers great potential to provide natural treatment of organic compounds, nutrients, and pathogens in urban streams, which are often strongly impacted by flow modifications and water pollution. Reliable treatment is most likely in streams in which the majority of flow occurs through the HZ, the flow is aerated, and sufficient residence times occur, which may be limited to specific channel morphologies and seasons. Integration of the HZ into stream management plans could also provide quality habitat in a landscape with increasingly depauperate biodiversity. Here, we review current knowledge on hydrological, chemical, and biological aspects of the HZ, with a focus on urban settings, and include a set of examples drawn from the literature of low-flow, effluent-dominated streams in which there is significant hyporheic flow and potential for contaminant attenuation. The HZ can be incorporated much more effectively into urban water management, including stream restoration efforts, by understanding the surface and subsurface features conducive to HZ flow and the water-quality and biodiversity improvements that can be gained in the HZ without posing unreasonable risk. The main barriers to implementation of HZ considerations include lack of information, absence of established metrics for evaluating success, small number of controlled HZ experiments in urban settings, and concern over risks to both public health and aquatic organisms. A combination of field studies, laboratory experiments, and model development that consider hydrological, chemical, and biological interactions in the HZ can overcome these barriers.

6p.International audienceIn electrolyte-saturated sands, the storage of electrical charges under an alternating electrical field (called "induced polarization") is responsible for a phase lag between the applied current and the resulting electrical field. Because a variety of polarization mechanisms exists in porous materials, the underlying physics of induced polarization is somehow unclear and the field data difficult to interpret quantitatively. Measurements at various pHs and salinities can be used to discriminate between different competing mechanisms at low frequencies (1 mHz-1 kHz) in porous media in the absence of electronic conductors. New experimental data point out that, in addition to the polarization of the Stern layer (the inner part of the electrical double layer coating the surface of the silica grains), there is another polarization mechanism possibly associated with a hopping process of the protons on the silica surface. We propose that such a process could follow a Grotthuss cooperation mechanism (as in ice) involving the bound water of the silica surface. Our data also rule out a mechanism based on the diffuse layer. The new polarization mechanism may be applied to quantifying induced-polarization data collected over acidic contaminant plumes

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At the Oak Ridge Integrated Field Research Challenge site, near Oak Ridge, Tennessee, the shallow saprolitic aquifer is contaminated by nitric acid, uranium, and metals originating from the former S3 settling ponds. To interpret low-frequency geophysical methods used to image contaminant plumes, we have characterized the petrophysical properties of three representative saprolite core samples. Their hydraulic conductivity ranges from [Formula: see text] to [Formula: see text] in agreement with field data. Complex conductivity measurements, in the frequency range of 1 mHz to 45 kHz, were performed with NaCl solutions with electrical conductivities in the range [Formula: see text] to [Formula: see text], a range representative of field conditions. The electrical conductivity data were well reproduced with a simple linear conductivity model between the saprolite conductivity and the pore water conductivity. The conductivity plots were used to estimate the formation factor (the cementation exponent was about [Formula: see text]) and the surface conductivity ([Formula: see text]). The magnitude of the surface conductivity depended on the degree of weathering and therefore on the amount of smectite and mixed layer (illite-smectite) clays present in the saprolite. The chargeability of the core samples was in the range of [Formula: see text] and is strongly dependent on the salinity. We also performed streaming potential measurements with the same pore fluid composition as that used for the complex conductivity measurements. We found an excess of movable electrical charges on the order of 100 to [Formula: see text] in agreement with previous investigations connecting the movable excess charge density to permeability. The zeta potential was in the range of [Formula: see text] to [Formula: see text] independent on the salinity. The electrical measurements were consistent with an average cation exchange capacity in the range of 1.4 to [Formula: see text] and a specific surface area on the order of 4000 to about 30,000 [Formula: see text].

At the Oak Ridge Integrated Field Research Challenge site, near Oak Ridge, Tennessee, contaminants from the former S-3 ponds have infiltrated the shallow saprolite for over 60 years. Two- and three-dimensional DC-resistivity tomography is used to characterize the number and location of the main contaminant plumes, which include high concentration of nitrate. These contaminant plumes have typically an electrical resistivity in the range 2–20 ohm-m while the background saprolite resistivity is in the range 60–120 ohm-m, so the difference of resistivity can be easily mapped using DC-resistivity tomography to locate the contaminant pathways. We develop a relationship to derive the in situ nitrate concentrations from the 3D resistivity tomograms accounting for the effect of surface conductivity. The footprint of the contamination upon the resistivity is found to be much stronger than the local variations associated with changes in the porosity and the clay content. With this method, we identified a total of five main plumes (termed CP1 to CP5). Plume CP2 corresponds to the main plume in terms of nitrate concentration (∼50,000 [Formula: see text]). We also used an active time constrained approach to perform time-lapse resistivity tomography over a section crossing the plumes CP1 and CP2. The sequence of tomograms is used to determine the changes in the nitrate concentrations associated with infiltration of fresh (meteoritic) water from a perched aquifer. This study highlights the importance of accounting for surface conductivity when characterizing plume distributions in clay-rich subsurface systems.

[1] We investigated magnetic susceptibility (MS) variations in hydrocarbon contaminated sediments. Our objective was to determine if MS can be used as an intrinsic bioremediation indicator due to the activity of ironreducing bacteria. A contaminated and an uncontaminated core were retrieved from a site contaminated with crude oil near Bemidji, Minnesota and subsampled for MS measurements. The contaminated core revealed enriched MS zones within the hydrocarbon smear zone, which is related to iron-reduction coupled to oxidation of hydrocarbon compounds and the vadose zone, which is coincident with a zone of methane depletion suggesting aerobic or anaerobic oxidation of methane is coupled to iron-reduction. The latter has significant implications for methane cycling. We conclude that MS can serve as a proxy for intrinsic bioremediation due to the activity of iron-reducing bacteria iron-reducing bacteria and for the application of geophysics to iron cycling studies. Citation: Mewafy, F. M., E. A.

Prior work has suggested that (carboxymethyl)-beta-cyclodextrin (CMCD) is capable of simultaneously enhancing the solubility of organics and metals, but sparse experimental data and no theoretical models have been published on this process. Preciously, a geochemical model for metal complexation by CMCD was formulated using PHREEQC on the basis of conditional stability constants measured in experiments using single-metal salts. In this study, the model is expanded to simultaneous metal and organic (perchloroethylene, PCE) complexation by CMCD. Experiments to verify the application of the formulation to mixed-waste systems were performed using solutions containing multiple metal ions (Pb, Sr, and Zn) and in a separate experiment introducing PCE with multiple metal ions. These experimental results show simultaneous solubility enhancement of metals and PCE. For solutions up to about 50 g/L CMCD, the model accurately predicted the simultaneous solubility enhancement for PCE, Pb, and Zn, while the difference between the measured and predicted Sr concentrations was accurate to within 15%. At CMCD concentrations greater than 50 g/L, the observed metal solubilities were greater than predicted (10% for Pb and Zn), probably due to the difficulty in accurately representing the activity and the effect on the ionic strength of functional groups on large organic molecules at higher concentrations.