Results for “subsurface diffusion” — Page 9

DOE OSTI2023

Recent Developments in Hydrogeologic Applications for Strain Tensor Analyses

Changes in fluid pressure deform porous media and this effect occurs in a variety of hydrogeologic processes, from the change in storage during pumping or injection to fluctuations in water levels caused by barometric pressure. We have developed instruments for measuring small strains in porous media, and we have used the resulting strain data to evaluate well testing, hydraulic fracturing, manual loading at the ground surface, and ambient hydrologic processes, like rainfall and evaporation. A particularly important application is the use of strain tensor data measured at shallow depths to analyze well tests or hydraulic fractures conducted at much greater depths. An early demonstration of this technique was conducted at the North Avant Field north of Tulsa, Oklahoma, where Pennsylvanian sandstone creates a confined aquifer and oil reservoir at a depth of 530m. We have showed that the strains caused by injecting into the aquifer could be measured at a depth of 30m and used to evaluate the properties of the aquifer. We recently expanded the array of strainmeters at the North Avant Field by deploying three more instruments at shallow depth (30m) along with a deep instrument at 520m depth in the winter, 2021. The deep instrument is deployed in shale caprock slightly above the aquifer. To our knowledge, the deep strainmeter at the North Avant Field is the deepest strainmeter ever deployed and this required refining methods originally developed for shallow deployments. The instrument was lowered to depth on oil field tubing and cemented in place using techniques and materials developed for use in oil wells. Optical fiber used to communicate with the instrument was cemented in the annulus on the outside of tubing. This is significant because the techniques we used could readily be extended to greater depth, suggesting that strainmeters can be deployed over a wide range of depths for monitoring critical subsurface processes. For example, it suggests that strainmeters could be deployed through the caprock to monitor for leaks from underlying CO2 storage reservoirs. The strainmeter array at the North Avant Field has been used to characterize deformation during a series of injection tests in the spring and summer, 2021. All the new strainmeters respond to pumping, and the strainmeters we installed earlier also responded. To our knowledge, this is the first application of well testing in a deep aquifer that was monitored by an array of strainmeters—our earlier work used strainmeters at a single location. We are currently analyzing the strain data using an analytical solution, a proxy-based Bayesian inversion algorithm, and other methods. Strainmeter data has also been used to characterize periodic pumping tests by us and Riley Blais. A periodically varying pumping rate causes both hydraulic head and strain signals that vary with the same period as the pumping. The peaks and troughs of the head in monitoring wells lag behind the peaks and troughs of the head in the pumping well, and this lag time increases with distance from the pumping well. The lag time of the pressure and the distance to the monitoring well can be used in a simple analysis to estimate the hydraulic diffusivity of the aquifer. The lag time determined from strain data can be used to estimate aquifer properties using the same analysis that works for the pressure only for strain data measured at particular locations. That is because the strain field in a confining unit advances upward, laterally and then downward even though the pressure in the underlying aquifer only advances laterally, according to our recent simulations. We have field data showing that a small periodic signal superimposed on an injection rate at the North Avant Field will create a periodic strain signal at shallow strainmeters. The field data and the recent simulations suggest that including a periodic component to injection or pumping and then monitoring the resulting strain signal could be a way to monitor the subsurface.

Murdoch, Larry↗

DOE OSTI2023

Recent Developments in Hydrogeologic Applications for Strain Tensor Analyses

Changes in fluid pressure deform porous media and this effect occurs in a variety of hydrogeologic processes, from the change in storage during pumping or injection to fluctuations in water levels caused by barometric pressure. We have developed instruments for measuring small strains in porous media, and we have used the resulting strain data to evaluate well testing, hydraulic fracturing, manual loading at the ground surface, and ambient hydrologic processes, like rainfall and evaporation. A particularly important application is the use of strain tensor data measured at shallow depths to analyze well tests or hydraulic fractures conducted at much greater depths. An early demonstration of this technique was conducted at the North Avant Field north of Tulsa, Oklahoma, where Pennsylvanian sandstone creates a confined aquifer and oil reservoir at a depth of 530m. We have showed that the strains caused by injecting into the aquifer could be measured at a depth of 30m and used to evaluate the properties of the aquifer. We recently expanded the array of strainmeters at the North Avant Field by deploying three more instruments at shallow depth (30m) along with a deep instrument at 520m depth in the winter, 2021. The deep instrument is deployed in shale caprock slightly above the aquifer. To our knowledge, the deep strainmeter at the North Avant Field is the deepest strainmeter ever deployed and this required refining methods originally developed for shallow deployments. The instrument was lowered to depth on oil field tubing and cemented in place using techniques and materials developed for use in oil wells. Optical fiber used to communicate with the instrument was cemented in the annulus on the outside of tubing. This is significant because the techniques we used could readily be extended to greater depth, suggesting that strainmeters can be deployed over a wide range of depths for monitoring critical subsurface processes. For example, it suggests that strainmeters could be deployed through the caprock to monitor for leaks from underlying CO2 storage reservoirs. The strainmeter array at the North Avant Field has been used to characterize deformation during a series of injection tests in the spring and summer, 2021. All the new strainmeters respond to pumping, and the strainmeters we installed earlier also responded. To our knowledge, this is the first application of well testing in a deep aquifer that was monitored by an array of strainmeters—our earlier work used strainmeters at a single location. We are currently analyzing the strain data using an analytical solution, a proxy-based Bayesian inversion algorithm, and other methods. Strainmeter data has also been used to characterize periodic pumping tests by us and Riley Blais. A periodically varying pumping rate causes both hydraulic head and strain signals that vary with the same period as the pumping. The peaks and troughs of the head in monitoring wells lag behind the peaks and troughs of the head in the pumping well, and this lag time increases with distance from the pumping well. The lag time of the pressure and the distance to the monitoring well can be used in a simple analysis to estimate the hydraulic diffusivity of the aquifer. The lag time determined from strain data can be used to estimate aquifer properties using the same analysis that works for the pressure only for strain data measured at particular locations. That is because the strain field in a confining unit advances upward, laterally and then downward even though the pressure in the underlying aquifer only advances laterally, according to our recent simulations. We have field data showing that a small periodic signal superimposed on an injection rate at the North Avant Field will create a periodic strain signal at shallow strainmeters. The field data and the recent simulations suggest that including a periodic component to injection or pumping and then monitoring the resulting strain signal could be a way to monitor the subsurface.

Murdoch, Larry↗

DOE OSTI2025

Joint state-parameter estimation for the reduced fracture model via the united filter

Here, in this paper, we introduce an effective United Filter method for jointly estimating the solution state and physical parameters in flow and transport problems within fractured porous media. Fluid flow and transport in fractured porous media are critical in subsurface hydrology, geophysics, and reservoir geomechanics. Reduced fracture models, which represent fractures as lower-dimensional interfaces, enable efficient multi-scale simulations. However, reduced fracture models also face accuracy challenges due to modeling errors and uncertainties in physical parameters such as permeability and fracture geometry. To address these challenges, we propose a United Filter method, which integrates the Ensemble Score Filter (EnSF) for state estimation with the Direct Filter for parameter estimation. EnSF, based on a score-based diffusion model framework, produces ensemble representations of the state distribution without deep learning. Meanwhile, the Direct Filter, a recursive Bayesian inference method, estimates parameters directly from state observations. The United Filter combines these methods iteratively: EnSF estimates are used to refine parameter values, which are then fed back to improve state estimation. Numerical experiments demonstrate that the United Filter method surpasses the state-of-the-art Augmented Ensemble Kalman Filter, delivering more accurate state and parameter estimation for reduced fracture models. This framework also provides a robust and efficient solution for PDE-constrained inverse problems with uncertainties and sparse observations.

Bayesian inference↗

DOE OSTI2024

Forecasting fluid-injection induced seismicity to choose the best injection strategy for safety and efficiency

Induced seismicity poses a challenge to the development of Enhanced Geothermal Systems (EGS). Improving monitoring and forecasting techniques is essential to mitigate induced seismicity and thereby fostering a positive perception of EGS projects among local authorities and population. Induced seismicity is the result of complex and coupled thermo-hydro-mechanical-chemical mechanisms. Injection flux and pressure are crucial controlling parameters for both hydraulic stimulation and circulation protocols. We develop a methodology combining a hydro-mechanical model with a seismicity rate model to estimate the magnitude and frequency of mainshocks and aftershocks induced by fluid injection. We apply the methodology to the case of the Basel EGS (2006, Switzerland) to compare the effects of progressive, cyclic and constant injections on the mechanical response of discrete faults. Results from the coupled hydro-mechanical models show that the pore pressure diffusion and consequent enhancement of fault permeability are limited to the vicinity of the injection well during cyclic injection. Additionally, constant injection induces seismicity from the start of the injection but enhances the permeability of most of the faults within a shorter duration, inducing less post-injection seismicity. The methodology can be adapted to any numerical model and allows new projects to be developed by anticipating the safest injection protocol. This article is part of the theme issue ‘Induced seismicity in coupled subsurface systems’.

58 GEOSCIENCES↗

DOE OSTI2024

Climate forcing controls on carbon terrestrial fluxes during shale weathering

Climate influences near-surface biogeochemical processes and thereby determines the partitioning of carbon dioxide (CO 2 ) in shale, and yet the controls on carbon (C) weathering fluxes remain poorly constrained. Using a dataset that characterizes biogeochemical responses to climate forcing in shale regolith, we implement a numerical model that describes the effects of water infiltration events, gas exchange, and temperature fluctuations on soil respiration and mineral weathering at a seasonal timescale. Our modeling approach allows us to quantitatively disentangle the controls of transient climate forcing and biogeochemical mechanisms on C partitioning. We find that ~3% of soil CO 2 (1.02 mol C/m 2 /y) is exported to the subsurface during large infiltration events. Here, net atmospheric CO 2 drawdown primarily occurs during spring snowmelt, governs the aqueous C exports (61%), and exceeds the CO 2 flux generated by pyrite and petrogenic organic matter oxidation (~0.2 mol C/m 2 /y). We show that shale CO 2 consumption results from the temporal coupling between soil microbial respiration and carbonate weathering. This coupling is driven by the impacts of hydrologic fluctuations on fresh organic matter availability and CO 2 transport to the weathering front. Diffusion-limited transport of gases under transient hydrological conditions exerts an important control on CO 2 (g) egress patterns and thus must be considered when inferring soil CO 2 drawdown from the gas phase composition. Our findings emphasize the importance of seasonal climate forcing in shaping the net contribution of shale weathering to terrestrial C fluxes and suggest that warmer conditions could reduce the potential for shale weathering to act as a CO 2 sink.

58 GEOSCIENCES↗

DOE OSTI2026

Geologic stress modulates fluid mixing at fracture intersections

Fracture intersections are critical links that enable flow and transport in subsurface fracture networks, and their behavior strongly influences fluid mixing in a network. Although all subsurface fractures are subjected to geological stress, we lack a fundamental understanding of how fracture intersection geometry evolves under stress and how these changes influence fluid mixing. Here, we combine 3D printing, 3D X-ray tomographic imaging, and 3D pore-scale numerical simulations to reveal stress-induced changes in intersection geometry and their impact on mixing. Mixing is found to be strongly affected by partial closure of an intersection under stress. As an intersection closes, the void area for fluid flow and diffusion decreases leading to substantial deviations between conventional mixing models and full pore-scale modeling. To address this, we propose a modified mixing model that accounts for intersection deformation, which is essential for accurate modeling of solute transport and mixing through fracture networks.

15 GEOTHERMAL ENERGY↗

DOE OSTI2024

Toward a Universal Model of Hyporheic Exchange and Nutrient Cycling in Streams

In this paper we demonstrate that several ubiquitous hyporheic exchange mechanisms can be represented simply as a one-dimensional diffusion process, where the diffusivity decays exponentially with depth into the streambed. Based on a meta-analysis of 106 previously published laboratory measurements of hyporheic exchange (capturing a range of bed morphologies, hydraulic conditions, streambed properties, and experimental approaches) we find that the reference diffusivity and mixing length-scale are functions of the permeability Reynolds Number and Schmidt Number. These dimensionless numbers, in turn, can be estimated for a particular stream from the median grain size of the streambed and the stream's depth, slope, and temperature. Application of these results to a seminal study of nitrate removal in 72 headwater streams across the United States, reveals: (a) streams draining urban and agricultural landscapes have a diminished capacity for in-stream and in-bed mixing along with smaller subsurface storage zones compared to streams draining reference landscapes; (b) under steady-state conditions nitrate uptake in the streambed is primarily biologically controlled; and (c) median reaction timescales for nitrate removal in the hyporheic zone are 0.5 and 20 hr for uptake by assimilation and denitrification, respectively. While further research is needed, the simplicity and extensibility of the framework described here should facilitate cross-disciplinary discussions and inform reach-scale studies of pollutant fate and transport and their scale-up to watersheds and beyond.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Operational and geological controls of coupled poroelastic stressing and pore-pressure accumulation along faults: Induced earthquakes in Pohang, South Korea

Coupled poroelastic stressing and pore-pressure accumulation along pre-existing faults in deep basement contribute to recent occurrence of seismic events at subsurface energy exploration sites. Our coupled fluid-flow and geomechanical model describes the physical processes inducing seismicity corresponding to the sequential stimulation operations in Pohang, South Korea. Simulation results show that prolonged accumulation of poroelastic energy and pore pressure along a fault can nucleate seismic events larger than M w 3 even after terminating well operations. In particular the possibility of large seismic events can be increased by multiple-well operations with alternate injection and extraction that can enhance the degree of pore-pressure diffusion and subsequent stress transfer through a rigid and low-permeability rock to the fault. This study demonstrates that the proper mechanistic model and optimal well operations need to be accounted for to mitigate unexpected seismic hazards in the presence of the site-specific uncertainty such as hidden/undetected faults and stress regime.

58 GEOSCIENCES↗

NASA NTRS1995

Oxygenic Photosynthesis and the Oxidation State of Mars

The oxidation state of the Earth's surface is one of the most obvious indications of the effect of life on this planet. The surface of Mars is highly oxidized, as evidenced by its red color, but the connection to life is less apparent. Two possibilities can be considered. First, the oxidant may be photochemically produced in the atmosphere. In this case the fundamental source of O2 is the loss of H2 to space and the oxidant produced is H2O2. This oxidant would accumulate on the surface and thereby destroy any organic material and other reductants to some depth. Recent models suggest that diffusion limits this depth to a few meters. An alternative source of oxygen is biological oxygen production followed by sequestration of organic material in sediments - as on the Earth. In this case, the net oxidation of the surface was determined billions of years ago when Mars was a more habitable planet and oxidative conditions could persist to great depths, over 100 m. Below this must be a compensating layer of biogenic organic material. Insight into the nature of past sources of oxidation on Mars will require searching for organics in the martian subsurface and sediments.

Hartman, Hyman↗

NASA NTRS1989

Ballistic-electron-emission microscopy of subsurface defects at the Au-GaAs(100) interface

The application of ballistic-electron-emission microscopy (BEEM) to a study of the influence of GaAs(100) substrate conditions on the formation of a multidefect structure at the Au-GaAs(100) Schottky barrier interface is described. Interfaces prepared on both melt-grown GaAs(100) wafer substrates and MBF-deposited GaAs(100) buffer layers are considered. As a comparison to the study of Au-GaAs(100) interfaces, BEEM imaging is performed on Au-Si(100) interfaces. It is noted that Au-GaAs(100) interface formation is relatively insensitive to the effects of substrate surface condition and substrate bulk defect density, and that the combination of BEEM imaging and BEEM spectroscopy indicates that the heterogeneous interface defects are the result of diffusion between the Schottky barrier electrodes.

Hecht, M. H.↗

DOE OSTI2023

Energetics of silicon in the bulk and near surfaces of tungsten: a first-principles study

Abstract Siliconization of the tokamak walls is a candidate method to improve plasma confinement in fusion tokamaks containing tungsten plasma facing components (W PFCs). To understand the interactions of silicon (Si) with W, the Si behavior in bulk W, and near three low-index W surfaces ((100), (110) and (111)) has been investigated using first-principles density functional theory. In bulk W, Si interstitial atoms have a low solution ability and high mobility, and Si atoms can be strongly trapped by W vacancies. The interaction between two Si adatoms is responsible for the stability of adatom superstructures on W surfaces, consistent with previous experimental observation (Tsong and Casanova 1981 Phys. Rev. Lett. 47 113). Although the coverage dependence of Si adsorption and diffusion energetics on surfaces is related to surface orientation, the W(110) surface has lower Si adsorption affinity and higher Si diffusivity than either the W(111) or W(100) surfaces. The most stable Si adatom superstructure on W surfaces is: square c(2 × 2) pattern on W(100) covered with 0.5 ML Si; rectangular c(4 × 2) pattern on W(110) with 0.25 ML Si; and rhombus p(1 × 1) pattern on W(111) with 1 ML Si. The coverage dependence of Si mobility on/toward W surfaces is generally related to the stability of the Si superstructures as a function of coverage on each surface. Interestingly, Si adatoms prefer to transport below the surface and into W subsurface by an exchange mechanism with W atoms, indicating the likelihood of epitaxial growth of W silicide layers on W surfaces during the operation of W PFCs.

Yang, L. (ORCID:0000000322166071)↗

DOE OSTI2023

Effect of Formation Heterogeneity on CO 2 Dissolution in Subsurface Porous Media

Dissolution trapping is one of the most dominant mechanisms for the secure storage of CO 2 injected in porous subsurface formations saturated with brine. This trapping mechanism is enhanced by convective mixing, which occurs due to the gravitational instability between the different fluid layers in the aquifer. The reservoir permeability also plays a crucial role in the dissolution rate and overall fluid flow dynamics during the density-driven convection in porous media. Herein this study investigates the role of complex heterogeneity, i.e., irregular permeability distribution in CO 2 dissolution, using a novel experimental approach to create medium permeability heterogeneity in Hele–Shaw cells. Complex subsurface transport phenomena such as a preferential dissolution path, CO 2 sweep efficiency, changes in finger morphology, and CO 2 concentration distribution are visualized by creating heterogeneous media. Experimental results showed that reservoir permeability heterogeneity causes significant channeling effects and poor sweep efficiency. A scaling relationship between average finger growth rate (Gr) and permeability (k) was obtained as Gr [m s –1 ] = 266.8k [m 2 ] + 1.20 × 10 –6 . Furthermore, the mass of CO 2 dissolved is calculated using the spectrophotometric method to characterize the convective instability. The convective flux was analyzed by comparing the experimental dissolution flux with the theoretical diffusion flux, calculating a maximum Sherwood number of 6.8. The study’s findings improve the current understanding of the CO 2 convection morphology in heterogeneous media, allowing better assessment of long-term CO 2 storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Surface Hydroxyls of Imogolite Nanotubes Drive Distinct Structures and Mobility Differentiation of Nanoconfined Water

Abstract Nanoconfined fluids, particularly water, govern subsurface geochemistry, yet the molecular-level mechanisms by which mineral surfaces dictate confined water structure and mobility remain poorly resolved. Here, we combine solution- and solid-state proton (1H) NMR spectroscopy, NMR relaxometry, modulated-gradient spin–echo (MGSE) NMR diffusometry, infrared spectroscopy, and molecular dynamics simulations to demonstrate that surface hydroxyls drive the structural and dynamic differentiation of water in imogolite nanotubes. In saturated suspensions, we observe the coexistence of distinct water 1H environments, each exhibiting significantly reduced mobility, which we attribute to strong interactions with the imogolite surfaces. As more mobile water is removed, long-range water diffusivity in the fibrous solid samples slows to 1.6 × 10–10 m2·s–1 while local fluctuations increase to 3.4 × 10–8 m2·s–1, indicating a significant increase in molecular restriction through surface interactions. Together, our experiments reveal three coexisting populations with varied structures and mobilities, all distinct from liquid bulk water. We resolve a persistent solid-like interfacial layer strongly bound to surface hydroxyls, characterized by an unusually short T2 (<1 ms), and a very close effective 1H–1H distance of ∼1.55 Å between water and the inner-surface silanol group. An inner-core population occupying the inner cavity exhibits an intermediate dynamic regime with restricted axial diffusion, while outer-surface water associated with aluminum hydroxyls retains relatively higher mobility. These results experimentally substantiate a hierarchy of water populations in imogolite and show how surface chemistry dictates the structures and dynamics of confined water.

Fleming, Xander B. [Earth and Environmental Scienc↗

NASA NTRS1984

Morphology of fresh craters on Ganymede and the origin of pedestal craters

Properties of the planetary surface and subsurface can affect the morphology of impact craters. A mechanism was proposed to explain pedestal craters and domed floors within fresh craters on Ganymede. Voyager 1 and 2 images with resolutions = to or 3.2 km/lp were examined and 523 fresh craters were identified. For each crater, the rim and ejecta diameters were measured, and the crater was characterized by ejecta class(es), interior features, floor morphology and target terrain. Of the craters examined, 97 show moderate to prominent doming of the crater floor; 340 craters have continuous ejecta which terminates in a scarp pedestal craters, of which 86 (25%) have a high albedo diffuse deposit beyond the pedestal.

Horner, V. M.↗

DOE OSTI2026

Development Fiber Optic Distributed System for Direct Detection of Subsurface Gases Leakages

Carbon, natural gas, and hydrogen gas storage is an emerging solution to safeguard us against pollution, support goals of negative carbon emission, and protect sources of renewable energy. Properly constructed storage wells provide a virtually impervious barrier to any unintended subsurface transmission. The ability to ensure the long-term integrity of such wells is vital to the success of any storage operation and be successful in the public eyes. Therefore, robust monitoring of any gas migration into the subsurface is highly sought. A fiber-optic distributed chemical sensor (DCS) enables monitoring of long-term well integrity along its depth, ensuring the success of any storage operation and bolsters public acceptance of the safety of the reservoir via leak early detection. The same technique can be applied to gas monitoring in pipeline networks and nuclear stockpile monitoring applications. Fiber based Raman spectroscopy enables DCS, as optical fibers can be deployed in virtually any environment and relay spectroscopic information over long distances back to the user. Hollow core fibers (HCF) make excellent DCSs as the air core of the fiber allows gas from the environment to diffuse into the core, which interacts with the laser signal that is carried in the air core. This work builds upon the previous LDRD project, Fiber Optic System for Direct Detection of Carbon Dioxide Leakage in Carbon Storage Wells (21-FS-003), in which the feasibility of Raman spectroscopy detection of Carbon Dioxide (CO2) in HCF detection was demonstrated. We mitigated the risk of this DCS technology by establishing and completing five objectives. The first objective was to model and optically characterize HCF uptake of CO2, establishing the relationship between HCF length, gas diffusion time, detectable gas concentration, and measured Raman intensity. In objective two, we developed a fiber core drilling recipe to enable additional diffusion ports in the fiber core and established a method for maintaining fiber strength and integrity post drilling. Objective three characterized the drilled fibers against the undrilled fibers, establishing the differences in the gas mechanics and optical properties and provided parameters to iterate the drilling process. In objective four, a fusion splicing technique was developed to join the HCF to conventional single-mode fibers, localizing the gas detection point at the drilled HCF hole, emulating a DCS. Lastly, objective five was the testing of the sensor in Edgar Mines at Colorado School of Mines on a CO2 pipeline with a simulated leak, to showcase the ability to detect CO2 leaks. This capstone result showed CO2 leak detection in < 10 minutes, raising the technology readiness level of HCF segments as deployable DCS.

organic↗

DOE OSTI2022

Versatile soil gas concentration and isotope monitoring: optimization and integration of novel soil gas probes with online trace gas detection

Abstract. Gas concentrations and isotopic signatures can unveil microbial metabolisms and their responses to environmental changes in soil. Currently, few methods measure in situ soil trace gases such as the products of nitrogen and carbon cycling or volatile organic compounds (VOCs) that constrain microbial biochemical processes like nitrification, methanogenesis, respiration, and microbial communication. Versatile trace gas sampling systems that integrate soil probes with sensitive trace gas analyzers could fill this gap with in situ soil gas measurements that resolve spatial (centimeters) and temporal (minutes) patterns. We developed a system that integrates new porous and hydrophobic sintered polytetrafluoroethylene (sPTFE) diffusive soil gas probes that non-disruptively collect soil gas samples with a transfer system to direct gas from multiple probes to one or more central gas analyzer(s) such as laser and mass spectrometers. Here, we demonstrate the feasibility and versatility of this automated multiprobe system for soil gas measurements of isotopic ratios of nitrous oxide (δ18O, δ15N, and the 15N site preference of N2O), methane, carbon dioxide (δ13C), and VOCs. First, we used an inert silica matrix to challenge probe measurements under controlled gas conditions. By changing and controlling system flow parameters, including the probe flow rate, we optimized recovery of representative soil gas samples while reducing sampling artifacts on subsurface concentrations. Second, we used this system to provide a real-time window into the impact of environmental manipulation of irrigation and soil redox conditions on in situ N2O and VOC concentrations. Moreover, to reveal the dynamics in the stable isotope ratios of N2O (i.e., 14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O), we developed a new high-precision laser spectrometer with a reduced sample volume demand. Our integrated system – a tunable infrared laser direct absorption spectrometry (TILDAS) in parallel with Vocus proton transfer reaction mass spectrometry (PTR-MS), in line with sPTFE soil gas probes – successfully quantified isotopic signatures for N2O, CO2, and VOCs in real time as responses to changes in the dry–wetting cycle and redox conditions. Broadening the collection of trace gases that can be monitored in the subsurface is critical for monitoring biogeochemical cycles, ecosystem health, and management practices at scales relevant to the soil system.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Spectral induced polarization monitoring of induced calcite precipitation in subsurface sediments

Co-precipitation of contaminants within the crystalline structure of calcite is a promising natural attenuation or remedial technology being considered at contaminated sites. We explore the sensitivity of the spectral induced polarization (SIP) method to induced calcite precipitation in natural sediments as a path forward to non-invasively monitor these sites. We performed time-lapse column experiments using phased (I-IV) injections over 40 days on natural sediments from the Hanford Site (Washington State, USA). In the phased injections, abiotic calcite precipitation was induced and confirmed to have occurred. Previous work in glass beads and homogeneous sand was limited to high frequency detection of calcite, however in this work we observed the development of two polarization mechanisms, one at high frequency (>100 Hz) and one at low frequency (< 100 Hz). Based on the characteristic frequencies from the SIP high and low frequency regimes, characteristic length scales (L) were computed where the adsorption mode of Na+ versus Ca2+ was compared by using diffusion coefficients corresponding to Na+ versus an arithmetically averaged value for Na+ and Ca2+. Using the diffusion coefficient of Na+, the high frequency L was found to correlate well with the size of the calcite crystals. The low frequency L correlated well with the individual natural sediment grain sizes within the columns. During late experimental times (day 36 and 40), the characteristic low frequency in two of the experimental columns shifted to lower frequencies (<0.001 Hz) which may signify SIP sensitivity of the formed calcite with the sediment grains. In field applications, the development of a low frequency polarization length scale to monitor calcite precipitation is promising for field monitoring applications, however further laboratory work needs to be performed to examine the SIP sensitivity of calcite formation in the presence of to natural sediments

calcium carbonate, calcite, precipitation, spectra↗

NASA NTRS2008

Development of Eddy Current Techniques for Detection of Deep Fatigue Cracks in Multi-Layer Airframe Components

Thick, multi-layer aluminum structure has been widely used in aircraft design in critical wing splice areas. The multi-layer structure generally consists of three or four aluminum layers with different geometry and varying thickness, which are held together with fasteners. The detection of cracks under fasteners with ultrasonic techniques in subsurface layers away from the skin is impeded primarily by interlayer bonds and faying sealant condition. Further, assessment of such sealant condition is extremely challenging in terms of complexity of structure, limited access, and inspection cost. Although Eddy current techniques can be applied on in-service aircraft from the exterior of the skin without knowing sealant condition, the current eddy current techniques are not able to detect defects with wanted sensitivity. In this work a series of low frequency eddy current probes have been designed, fabricated and tested for this application. A probe design incorporating a shielded magnetic field sensor concentrically located in the interior of a drive coil has been employed to enable a localized deep diffusion of the electromagnetic field into the part under test. Due to the required low frequency inspections, probes have been testing using a variety of magnetic field sensors (pickup coil, giant magneto-resistive, anisotropic magneto-resistive, and spin-dependent tunneling). The probe designs as well as capabilities based upon a target inspection for sub-layer cracking in an airframe wing spar joint is presented.

Wincheski, Russell A.↗