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Title: Quantifying Microbe-Mineral Interactions Leading to Remotely Detectable Induced Polarization Signals (Final Project Report)

The objective of this project was to investigate controls on induced polarization responses in porous media. The approach taken in the project was to compare electrical measurements made on mineral surfaces with atomic force microscopy (AFM) techniques to observations made at the column-scale using traditional spectral induced polarization measurements. In the project we evaluated a number of techniques for investigating the surface properties of materials, including the development of a new AFM measurement protocol that utilizes an external electric field to induce grain-scale polarizations that can be probed using a charged AFM tip. The experiments we performed focused on idealized systems (i.e., glass beads and silica gel) where we could obtain the high degree of control needed to understand how changes in the pore environment, which are determined by biogeochemical controls in the subsurface, affect mechanisms contributing to complex electrical conductivity, i.e., conduction and polarization, responses. The studies we performed can be classified into those affecting the chemical versus physical properties of the grain surface and pore space. Chemical alterations of the surface focused on evaluating how changes in pore fluid pH and ionic composition control surface conduction. These were performed as column flow through experiments where the pore fluidmore » was exchanged in a column of silica gel. Given that silica gel has a high surface area due to internal grain porosity, high-quality data could be obtained where the chemical influences on the surface are clearly apparent and qualitatively consistent with theories of grain (i.e., Stern layer) polarization controlled by electrostatic surface sorption processes (i.e., triple layer theory). Quantitative fitting of the results by existing process-based polarization models (e.g., Leroy et al., 2008) has been less successful, however, due to what we have attributed to differences between existing models developed for spherical grains versus the actual geometry associated with the nano-pores in the silica gel, though other polarization processes, e.g., proton hopping along the surface (Skold et al., 2013), may also be a contributing factor. As an alternative model-independent approach to confirming the link between surface sorption and SIP we initiated a study that will continue (unfunded) beyond the completion of this project to independently measure the accumulation of gamma emitting isotopes on the silica gel during the SIP monitoring experiments. Though our analyses of the project data are ongoing, our preliminary analyses are generally supportive of the grain (Stern layer) polarization theory of SIP. Experiments focused on evaluating the impact of physical modifications of the medium on polarization included etching and biotic and abiotic facilitated precipitation of carbonate and iron oxides to alter the roughness and electrical conductivity of the surfaces. These experiments were performed for both silica gel and glass beads, the latter of which lacked the interior porosity and high surface area of the silica gel. The results appear to be more nuanced that the chemical modifications of the system. In general, however, it was found that deposition of iron oxides and etching had relatively minimal or negative impacts on the polarization response of the medium, whereas carbonate coatings increased the polarization response. These results were generally consistent with changes in surface charge observed via AFM. Abiotic and biotic column flow through experiments demonstrated that precipitation of carbonate within the medium significantly impacted the real and imaginary conductivity over time in a manner generally consistent with the carbonate precipitation as observed from the batch grain coating experiments. Biotic effects were not observed to provide distinctly different signatures, but may have contributed to differences in the rate of changes observed with SIP. AFM was used in a variety of different ways to investigate the grain surfaces throughout the course of the project. Standard imaging methods were used to evaluate surface roughness and charge density, which showed that these data could provide qualitative insights about consistency between surface trends and the electrical behavior at the column scale (for the case of glass beads). Polarization and conductive force microscopy (PCFM) measurements were developed by the original project PI (Treavor Kendall), which illustrated the importance of the initial few monolayers of water on the mineral surface for producing surface conductivity. The technique allowed for initial local estimates of complex electrical conductivity on mineral surfaces, but could not be pursued after Kendall left the project due to phase locking limitations with the AFM instrument at Clemson and an inability to perform measurements in solution, which limited their value for linking the measurements to column-scale SIP responses. As a result, co-PI Dean developed a new methodology for making AFM measurements within an externally applied electric field. In this method, the charged tip of an AFM probe is brought within the proximity of a polarization domain while an external electric field is applied to the sample. The premise of the approach is that the tip will be attracted to or rebound from charge accumulations on the surface, which allow for detection of the local polarization response. Initial experiments showed promise in terms of the general trends of responses observed, though we have not yet been able to develop a quantitative interpretation technique that can be applied to predicting column scale responses.« less
 [1] ;  [1] ;  [2]
  1. Clemson University
  2. Rutgers University
Publication Date:
OSTI Identifier:
Report Number(s):
DOE Contract Number:
Resource Type:
Technical Report
Research Org:
Clemson University
Sponsoring Org:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States