Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

DOE PAGES

Garza, Alejandro J.; Bell, Alexis T.; Head-Gordon, Martin

2018-01-17

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer inmore » deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.« less

QM/MD studies on graphene growth from small islands on the Ni(111) surface

NASA Astrophysics Data System (ADS)

Jiao, Menggai; Song, Wei; Qian, Hu-Jun; Wang, Ying; Wu, Zhijian; Irle, Stephan; Morokuma, Keiji

2016-01-01

Quantum chemical molecular dynamics simulations of graphene growth from small island precursors in different carbon nucleation densities on the Ni(111) surface at high temperatures have been conducted. The results indicate that small islands are not static, i.e. lateral diffusion and vertical fluctuation are frequently observed. In the case of low carbon nucleation density, carbon atoms or small carbon patches diffuse and attach to the edge of the nuclei to expand the size of the growing carbon network. The growth of graphene precursors is accompanied by the corresponding changes in the bonding of nickel atoms with the precipitation of subsurface carbon atoms. This is because the carbon-carbon interaction is stronger than the nickel-carbon interaction. In the case of high carbon nucleation densities, the dominant ripening mechanism depends on different growth stages. In the initial stage, the coalescence of carbon islands takes place via the Smoluchowski ripening mechanism. In the later stage the Smoluchowski ripening process is damped owing to the higher diffusion barrier of larger clusters and the restriction of movement by self-assembled nickel step edges. The cross-linking mechanism eventually takes over by the coalescence of extended polyyne chains between graphene islands. In either case, the Ostwald ripening process is not found in our molecular dynamics simulations due to the stability of carbon-carbon bonds within the islands. These investigations should be instructive to the control of graphene growth in experiments.Quantum chemical molecular dynamics simulations of graphene growth from small island precursors in different carbon nucleation densities on the Ni(111) surface at high temperatures have been conducted. The results indicate that small islands are not static, i.e. lateral diffusion and vertical fluctuation are frequently observed. In the case of low carbon nucleation density, carbon atoms or small carbon patches diffuse and attach to the edge of the nuclei to expand the size of the growing carbon network. The growth of graphene precursors is accompanied by the corresponding changes in the bonding of nickel atoms with the precipitation of subsurface carbon atoms. This is because the carbon-carbon interaction is stronger than the nickel-carbon interaction. In the case of high carbon nucleation densities, the dominant ripening mechanism depends on different growth stages. In the initial stage, the coalescence of carbon islands takes place via the Smoluchowski ripening mechanism. In the later stage the Smoluchowski ripening process is damped owing to the higher diffusion barrier of larger clusters and the restriction of movement by self-assembled nickel step edges. The cross-linking mechanism eventually takes over by the coalescence of extended polyyne chains between graphene islands. In either case, the Ostwald ripening process is not found in our molecular dynamics simulations due to the stability of carbon-carbon bonds within the islands. These investigations should be instructive to the control of graphene growth in experiments. Electronic supplementary information (ESI) available: There are two movies showing the simulation process and they are provided in separate files. Movie S1 is the evolution of QM/MD simulations of the growth of graphene from one C13 on the Ni(111) surface for trajectory D@C13. Movie S2 is the evolution of QM/MD simulations of the growth of graphene from two C13 species on the Ni(111) surface for trajectory C@2C13. Fig. S1 shows the optimized geometries of C13-G and C13-H on the Ni(111) surface. Fig. S2 is the final structures of trajectories A-J@C13 following 400 ps QM/MD simulation for the Ni(111) + C13 system. Fig. S3 is the final structures of trajectories A-J@2C13 following 350 ps QM/MD simulation for the Ni(111) + 2C13 system. Fig. S4 shows average polygonal carbon ring populations formed during graphene growth from the Ni(111) + C13 and Ni(111) + 2C13 systems. Fig. S5 shows the averaged δ value of the C13 clusters and the nickel catalyst in the Ni(111) + C13 and Ni(111) + 2C13 systems. Fig. S6 depicts the total Mermin free energy as a function of simulation time in the Ni(111) + 2C13 system. See DOI: 10.1039/c5nr07680c

Diffusion of Radionuclides in Concrete and Soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mattigod, Shas V.; Wellman, Dawn M.; Bovaird, Chase C.

2012-04-25

One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Such concrete encasement would contain and isolate the waste packages from the hydrologic environment and would act as an intrusion barrier. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion and move into the surrounding subsurface environment. Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability ofmore » the surrounding soil to retard radionuclide migration. The objective of our study was to measure the diffusivity of Re, Tc and I in concrete containment and the surrounding vadose zone soil. Effects of carbonation, presence of metallic iron, and fracturing of concrete and the varying moisture contents in soil on the diffusivities of Tc and I were evaluated.« less

Diffusion and aggregation of subsurface radiation defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Martynovich, E. F.; Stupak, A. P.; Runets, L. P.

2015-09-01

Lithium fluoride nanocrystals were irradiated by gamma rays at a temperature below the temperature corresponding to the mobility of anion vacancies. The kinetics of the aggregation of radiation-induced defects in subsurface layers of nanocrystals during annealing after irradiation was elucidated. The processes that could be used to determine the activation energy of the diffusion of anion vacancies were revealed. The value of this energy in subsurface layers was obtained. For subsurface layers, the concentrations ratio of vacancies and defects consisting of one vacancy and two electrons was found. The factors responsible for the differences in the values of the activation energies and concentration ratios in subsurface layers and in the bulk of the crystals were discussed.

Empirical relation between carbonate porosity and thermal maturity: an approach to regional porosity prediction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmoker, J.W.

1984-11-01

Data indicate that porosity loss in subsurface carbonate rocks can be empirically represented by the power function, theta = a (TTI) /SUP b/ , where theta is regional porosity, TTI is Lopatin's time-temperature index of thermal maturity, the exponent, b, equals approximately -0.372, and the multiplier, a, is constant for a given data population but varies by an order of magnitude overall. Implications include the following. 1. The decrease of carbonate porosity by burial diagenesis is a maturation process depending exponentially on temperature and linearly on time. 2. The exponent, b, is essentially independent of the rock matrix, and maymore » reflect rate-limiting processes of diffusive transport. 3. The multiplying coefficient, a, incorporates the net effect on porosity of all depositional and diagenetic parameters. Within constraints, carbonate-porosity prediction appears possible on a regional measurement scale as a function of thermal maturity. Estimation of carbonate porosity at the time of hydrocarbon generation, migration, or trapping also appears possible.« less

Organic and Inorganic Carbon in the Rio Tinto (Spain) Deep Subsurface System: a Possible Model for Subsurface Carbon and Lithoautotrophs on Mars.

NASA Astrophysics Data System (ADS)

Bonaccorsi, R.; Stoker, C. R.; MARTE Science Team

2007-12-01

The subsurface is the key environment for searching for life on planets lacking surface life. Subsurface ecosystems are of great relevance to astrobiology including the search for past/present life on Mars. Conditions on the Martian surface do not support biological activity but the subsurface might preserve organics and host subsurface life [1]. A key requirement for the analysis of subsurface samples on Mars is the ability to characterize organic vs. inorganic carbon pools. This information is needed to determine if the sample contains organic material of biological origin and/ or to establish if pools of inorganic carbon can support subsurface biospheres. The Mars Analog Rio Tinto Experiment (MARTE) performed deep drilling of cores i.e., down to 165-m depth, in a volcanically-hosted-massive-sulfide deposit at Rio Tinto, Spain, which is considered an important analog of the Sinus Meridiani site on Mars. Results from MARTE suggest the existence of a relatively complex subsurface life including aerobic and anaerobic chemoautotrophs, and strict anaerobic methanogens sustained by Fe and S minerals in anoxic conditions, which is an ideal model analog for a deep subsurface Martian environment. We report here on the distribution of organic (C-org: 0.01-0.3Wt% and inorganic carbon (IC = 0.01-7.0 Wt%) in a subsurface rock system including weathered/oxidized i.e., gossan, and unaltered pyrite stockwork. Cores were analyzed from 3 boreholes (BH-4, BH-7, and BH-8) that penetrated down to a depth of ~165 m into massive sulfide. Nearsurface phyllosilicate rich-pockets contain the highest amounts of organics (0.3Wt%) [2], while the deeper rocks contain the highest amount of carbonates. Assessing the amount of C pools available throughout the RT subsurface brings key insight on the type of trophic system sustaining its microbial ecosystem (i.e., heterotrophs vs. autotrophs) and the biogeochemical relationships that characterize a new type of subsurface biosphere at RT. This potentially novel biosphere on Earth could be used as a model to test for extant and extinct life on Mars. Furthermore, having found carbonates in an hyperacidic system (pH ~2.3) brings new insights on the possible occurrence of deep carbonates deposits under low-pH condition on Mars. [1] Boston, P.J., et al., 1992. Icarus 95,300-308; Bonaccorsi, Stoker and Sutter, 2007 Accepted with review in Astrobiology.

Fracture Mechanics Analyses of Subsurface Defects in Reinforced Carbon-Carbon Joggles Subjected to Thermo-Mechanical Loads

NASA Technical Reports Server (NTRS)

Knight, Norman F., Jr.; Raju, Ivatury S.; Song, Kyongchan

2011-01-01

Coating spallation events have been observed along the slip-side joggle region of the Space Shuttle Orbiter wing-leading-edge panels. One potential contributor to the spallation event is a pressure build up within subsurface voids or defects due to volatiles or water vapor entrapped during fabrication, refurbishment, or normal operational use. The influence of entrapped pressure on the thermo-mechanical fracture-mechanics response of reinforced carbon-carbon with subsurface defects is studied. Plane-strain simulations with embedded subsurface defects are performed to characterize the fracture mechanics response for a given defect length when subjected to combined elevated-temperature and subsurface-defect pressure loadings to simulate the unvented defect condition. Various subsurface defect locations of a fixed-length substrate defect are examined for elevated temperature conditions. Fracture mechanics results suggest that entrapped pressure combined with local elevated temperatures have the potential to cause subsurface defect growth and possibly contribute to further material separation or even spallation. For this anomaly to occur, several unusual circumstances would be required making such an outcome unlikely but plausible.

Translucent Radiosity: Efficiently Combining Diffuse Inter-Reflection and Subsurface Scattering.

PubMed

Sheng, Yu; Shi, Yulong; Wang, Lili; Narasimhan, Srinivasa G

2014-07-01

It is hard to efficiently model the light transport in scenes with translucent objects for interactive applications. The inter-reflection between objects and their environments and the subsurface scattering through the materials intertwine to produce visual effects like color bleeding, light glows, and soft shading. Monte-Carlo based approaches have demonstrated impressive results but are computationally expensive, and faster approaches model either only inter-reflection or only subsurface scattering. In this paper, we present a simple analytic model that combines diffuse inter-reflection and isotropic subsurface scattering. Our approach extends the classical work in radiosity by including a subsurface scattering matrix that operates in conjunction with the traditional form factor matrix. This subsurface scattering matrix can be constructed using analytic, measurement-based or simulation-based models and can capture both homogeneous and heterogeneous translucencies. Using a fast iterative solution to radiosity, we demonstrate scene relighting and dynamically varying object translucencies at near interactive rates.

Diffusing, side-firing, and radial delivery laser balloon catheters for creating subsurface thermal lesions in tissue

NASA Astrophysics Data System (ADS)

Chang, Chun-Hung; Fried, Nathaniel M.

2016-02-01

Infrared lasers have been used in combination with applied cooling methods to preserve superficial skin layers during cosmetic surgery. Similarly, combined laser irradiation and tissue cooling may also allow development of minimally invasive laser therapies beyond dermatology. This study compares diffusing, side-firing, and radial delivery laser balloon catheter designs for creation of subsurface lesions in tissue, ex vivo, using a near-IR laser and applied contact cooling. An Ytterbium fiber laser with 1075 nm wavelength delivered energy through custom built 18 Fr (6-mm-OD) balloon catheters incorporating either 10-mm-long diffusing fiber tip, 90 degree side-firing fiber, or radial delivery cone mirror, through a central lumen. A chilled solution was flowed through a separate lumen into 9-mm-diameter balloon to keep probe cooled at 7°C. Porcine liver tissue samples were used as preliminary tissue model for immediate observation of thermal lesion creation. The diffusing fiber produced subsurface thermal lesions measuring 49.3 +/- 10.0 mm2 and preserved 0.8 +/- 0.1 mm of surface tissue. The side-firing fiber produced subsurface thermal lesions of 2.4 +/- 0.9 mm2 diameter and preserved 0.5 +/- 0.1 mm of surface tissue. The radial delivery probe assembly failed to produce subsurface thermal lesions, presumably due to the small effective spot diameter at the tissue surface, which limited optical penetration depth. Optimal laser power and irradiation time measured 15 W and 100 s for diffusing fiber and 1.4 W and 20 s, for side-firing fiber, respectively. Diffusing and side-firing laser balloon catheter designs provided subsurface thermal lesions in tissue. However, the divergent laser beam in both designs limited the ability to preserve a thicker layer of tissue surface. Further optimization of laser and cooling parameters may be necessary to preserve thicker surface tissue layers.

Biogenic Carbon on Mars: A Subsurface Chauvinistic Viewpoint

NASA Astrophysics Data System (ADS)

Onstott, T. C.; Lau, C. Y. M.; Magnabosco, C.; Harris, R.; Chen, Y.; Slater, G.; Sherwood Lollar, B.; Kieft, T. L.; van Heerden, E.; Borgonie, G.; Dong, H.

2015-12-01

A review of 150 publications on the subsurface microbiology of the continental subsurface provides ~1,400 measurements of cellular abundances down to 4,800 meter depth. These data suggest that the continental subsurface biomass is comprised of ~1016-17 grams of carbon, which is higher than the most recent estimates of ~1015 grams of carbon (1 Gt) for the marine deep biosphere. If life developed early in Martian history and Mars sustained an active hydrological cycle during its first 500 million years, then is it possible that Mars could have developed a subsurface biomass of comparable size to that of Earth? Such a biomass would comprise a much larger fraction of the total known Martian carbon budget than does the subsurface biomass on Earth. More importantly could a remnant of this subsurface biosphere survive to the present day? To determine how sustainable subsurface life could be in isolation from the surface we have been studying subsurface fracture fluids from the Precambrian Shields in South Africa and Canada. In these environments the energetically efficient and deeply rooted acetyl-CoA pathway for carbon fixation plays a central role for chemolithoautotrophic primary producers that form the base of the biomass pyramid. These primary producers appear to be sustained indefinitely by H2 generated through serpentinization and radiolytic reactions. Carbon isotope data suggest that in some subsurface locations a much larger population of secondary consumers are sustained by the primary production of biogenic CH4 from a much smaller population of methanogens. These inverted biomass and energy pyramids sustained by the cycling of CH4 could have been and could still be active on Mars. The C and H isotopic signatures of Martian CH4 remain key tools in identifying potential signatures of an extant Martian biosphere. Based upon our results to date cavity ring-down spectroscopic technologies provide an option for making these measurements on future rover missions.

High CO2 subsurface environment enriches for novel microbial lineages capable of autotrophic carbon fixation

NASA Astrophysics Data System (ADS)

Probst, A. J.; Jerett, J.; Castelle, C. J.; Thomas, B. C.; Sharon, I.; Brown, C. T.; Anantharaman, K.; Emerson, J. B.; Hernsdorf, A. W.; Amano, Y.; Suzuki, Y.; Tringe, S. G.; Woyke, T.; Banfield, J. F.

2015-12-01

Subsurface environments span the planet but remain little understood from the perspective of the capacity of the resident organisms to fix CO2. Here we investigated the autotrophic capacity of microbial communities in range of a high-CO2 subsurface environments via analysis of 250 near-complete microbial genomes (151 of them from distinct species) that represent the most abundant organisms over a subsurface depth transect. More than one third of the genomes belonged to the so-called candidate phyla radiation (CPR), which have limited metabolic capabilities. Approximately 30% of the community members are autotrophs that comprise 70% of the microbiome with metabolism likely supported by sulfur and nitrogen respiration. Of the carbon fixation pathways, the Calvin Benson Basham Cycle was most common, but the Wood-Ljungdhal pathway was present in the greatest phylogenetic diversity of organisms. Unexpectedly, one organism from a novel phylum sibling to the CPR is predicted to fix carbon by the reverse TCA cycle. The genome of the most abundant organism, an archaeon designated "Candidatus Altiarchaeum hamiconexum", was also found in subsurface samples from other continents including Europe and Asia. The archaeon was proven to be a carbon fixer using a novel reductive acetyl-CoA pathway. These results provide evidence that carbon dioxide is the major carbon source in these environments and suggest that autotrophy in the subsurface represents a substantial carbon dioxide sink affecting the global carbon cycle.

Finding the best windows: An apparent environmental threshold determines which diffuse flows are dominated by subsurface microbes

NASA Astrophysics Data System (ADS)

Olins, H. C.; Rogers, D.; Scholin, C. A.; Preston, C. J.; Vidoudez, C.; Ussler, W.; Pargett, D.; Jensen, S.; Roman, B.; Birch, J. M.; Girguis, P. R.

2014-12-01

Hydrothermal vents are hotspots of microbial primary productivity often described as "windows into the subsurface biosphere." High temperature vents have received the majority of research attention, but cooler diffuse flows are as, if not more, important a source of heat and chemicals to the overlying ocean. We studied patterns of in situ gene expression and co-registered geochemistry in order to 1) describe the diversity and physiological poise of active microbial communities that span thermal and geochemical gradients from active diffuse flow to background vent field seawater, and 2) determine to what extent seawater or subsurface microbes were active throughout this environment. Analyses of multiple metatranscriptomes from 5 geochemically distinct sites (some from samples preserved in situ) show that proximate diffuse flows showed strikingly different transcription profiles. Specifically, caldera background and some diffuse flows were similar, both dominated by seawater-derived Gammaproteobacteria despite having distinct geochemistries. Intra-field community shows evidence of increased primary productivity throughout the entire vent field and not just at individual diffuse flows. In contrast, a more spatially limited, Epsilonproteobacteria-dominated transcription profile from the most hydrothermally-influenced diffuse flow appeared to be driven by the activity of vent-endemic microbes, likely reflecting subsurface microbial activity. We suggest that the microbial activity within many diffuse flow vents is primarily attributable to seawater derived Gammaproteobacterial sulfur oxidizers, while in certain other flows vent-endemic Epsilonproteobactiera are most active. These data reveal a diversity in microbial activity at diffuse flows that has not previously been recognized, and reshapes our thinking about the relative influence that different microbial communities may have on local processes (such as primary production) and potentially global biogeochemical cycles.

The Role of Subsurface Properties on Transport of Water and Trace Gases: 1D Simulations at Selected Mars Landing Sites.

NASA Astrophysics Data System (ADS)

Karatekin, O.; Gloesener, E.; Dehant, V. M. A.

2017-12-01

In this work, water ice stability and water vapour transport through porous martian subsurface are studied using a 1D diffusive model. The role of adsorption on water transfer in martian conditions is investigated as well as the range of parameters that have the largest effect on gas transport. In addition, adsorption kinetics is considered to examine its influence on the water vapor exchange between the subsurface and the atmosphere. As methane has been detected in the martian atmosphere, the subsurface model is then used to study methane diffusion in the CH4/CO2/H2O system from variable depths under the surface. The results of subsurface gas transport at selected locations/landing sites are shown and implications for present/future observations are discussed.

Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials

NASA Astrophysics Data System (ADS)

Ayral-Cinar, Derya; Demond, Avery H.

2017-12-01

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18 months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed.

A new solar cycle model including meridional circulation

NASA Technical Reports Server (NTRS)

Wang, Y.-M.; Sheeley, N. R., Jr.; Nash, A. G.

1991-01-01

A kinematic model is presented for the solar cycle which includes not only the transport of magnetic flux by supergranular diffusion and a poleward bulk flow at the sun's surface, but also the effects of turbulent diffusion and an equatorward 'return flow' beneath the surface. As in the earlier models of Babcock and Leighton, the rotational shearing of a subsurface poloidal field generates toroidal flux that erupts at the surface in the form of bipolar magnetic regions. However, such eruptions do not result in any net loss of toroidal flux from the sun (as assumed by Babcock and Leighton); instead, the large-scale toroidal field is destroyed both by 'unwinding' as the local poloidal field reverses its polarity, and by diffusion as the toroidal flux is transported equatorward by the subsurface flow and merged with its opposite hemisphere counterpart. The inclusion of meridional circulation allows stable oscillations of the magnetic field, accompanied by the equatorward progression of flux eruptions, to be achieved even in the absence of a radial gradient in the angular velocity. An illustrative case in which a subsurface flow speed of order 1 m/s and subsurface diffusion rate of order 10 sq km/s yield 22-yr oscillations in qualitative agreement with observations.

Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials.

PubMed

Ayral-Cinar, Derya; Demond, Avery H

2017-12-01

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13 C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed. Copyright © 2017. Published by Elsevier B.V.

Elastic stress transfer as a diffusive process due to aseismic fault slip in response to fluid injection

NASA Astrophysics Data System (ADS)

Viesca, R. C.

2015-12-01

Subsurface fluid injection is often followed by observations of an enlarging cloud of microseismicity. The cloud's diffusive growth is thought to be a direct response to the diffusion of elevated pore fluid pressure reaching pre-stressed faults, triggering small instabilities; the observed high rates of this growth are interpreted to reflect a relatively high permeability of a fractured subsurface [e.g., Shapiro, GJI 1997]. We investigate an alternative mechanism for growing a microseismic cloud: the elastic transfer of stress due to slow, aseismic slip on a subset of the pre-existing faults in this damaged subsurface. We show that the growth of the slipping region of the fault may be self-similar in a diffusive manner. While this slip is driven by fluid injection, we show that, for critically stressed faults, the apparent diffusion of this slow slip may quickly exceed the poroelastically driven diffusion of the elevated pore fluid pressure. Under these conditions, microseismicity can be first triggered by the off-fault stress perturbation due to the expanding region of slip on principal faults. This provides an alternative interpretation of diffusive growth rates in terms of the subsurface stress state rather than an enhanced hydraulic diffusivity. That such aseismic slip may occur, outpace fluid diffusion, and in turn trigger microseismic events, is also suggested by on- and near-fault observations in past and recently reported fluid injection experiments [e.g., Cornet et al., PAGEOPH 1997; Guglielmi et al., Science 2015]. The model of injection-induced slip assumes elastic off-fault behavior and a fault strength determined by the product of a constant friction coefficient and the local effective normal stress. The sliding region is enlarged by the pore pressure increase resolved on the fault plane. Remarkably, the rate of self-similar expansion may be determined by a single parameter reflecting both the initial stress state and the magnitude of the pore pressure increase.

Manipulation of subsurface carbon nanoparticles in Bi 2 Sr 2 CaCu 2 O 8 + δ using a scanning tunneling microscope

DOE PAGES

Stollenwerk, A. J.; Hurley, N.; Beck, B.; ...

2015-03-19

In this study, we present evidence that subsurface carbon nanoparticles in Bi₂Sr₂CaCu₂O 8+δ can be manipulated with nanometer precision using a scanning tunneling microscope. High resolution images indicate that most of the carbon particles remain subsurface after transport observable as a local increase in height as the particle pushes up on the surface. Tunneling spectra in the vicinity of these protrusions exhibit semiconducting characteristics with a band gap of approximately 1.8 eV, indicating that the incorporation of carbon locally alters the electronic properties near the surface.

Can Surface Seeps Elucidate Carbon Cycling in Terrestrial Subsurface Ecosystems in Ophiolite-hosted Serpentinizing Fluids?

NASA Astrophysics Data System (ADS)

Meyer-Dombard, D. R.; Cardace, D.; Woycheese, K. M.; Vallalar, B.; Arcilla, C. A.

2017-12-01

Serpentinization in ophiolite-hosted regimes produces highly reduced, high pH fluids that are often characterized as having copious H2 and CH4 gas, little/no inorganic carbon, and limited electron acceptors. Subsurface microbial biomes shift as deeply-sourced fluids reach the oxygenated surface environment, where organisms capable of metabolizing O2 thrive (Woycheese et al., 2015). The relationship, connection, and communication between surface expressions (such as fluid seeps) and the subsurface biosphere is still largely unexplored. Our work in the Zambales and Palawan ophiolites (Philippines) defines surface habitats with geochemistry, targeted culturing efforts, and community analysis (Cardace et al., 2015; Woycheese et al., 2015). Fluids in the spring sources are largely `typical' and fall in the pH range of 9-11.5 with measurable gas escaping from the subsurface (H2 and CH4 > 10uM, CO2 > 1 mM; Cardace et al., 2015). Outflow channels extend from the source pools. These surface data encourage prediction of the subsurface metabolic landscape. To understand how carbon cycling in the subsurface and surface environments might be related, we focus on community analysis, culturing, and the geochemical context of the ecosystem. Shotgun metagenomic analyses indicate carbon cycling is reliant on methanogenesis, acetogenesis, sulfate reduction, and H2 and CH4 oxidation. Methyl coenzyme M reductase, and formylmethanofuran dehydrogenase were detected, and relative abundance increased near the near-anoxic spring source. In this tropical climate, cellulose is also a likely carbon source, possibly even in the subsurface. Enrichment cultures [pH 8-12] and strains [pH 8-10] from Zambales springs show degradation of cellulose and production of cellulase. DIC, DOC, and 13C of solid substrates show mixed autotrophic/heterotrophic activity. Results indicate a metabolically flexible surface community, and suggest details about carbon cycling in the subsurface.

Subsurface characterization of methane production and oxidation from a New Hampshire wetland.

PubMed

Shoemaker, J K; Schrag, D P

2010-06-01

We measured the carbon isotopic composition of pore water carbon dioxide from Sallie's Fen, a New Hampshire poor fen. The isotope profiles are used in combination with a one-dimensional diffusion-reaction model to calculate rates of methane production, oxidation and transport over an annual cycle. We show how the rates vary with depth over a seasonal cycle, with methane produced deeper during the winter months and at progressively shallower depths into the summer season. The rates of methane production, constrained by the measured delta(13)C(dic) profiles, cannot explain high methane emission during the summer. We suggest that much of the methane produced during this time comes either from the unsaturated peat, or from the top 1-3 cm of saturated peat where episodic exchange with the atmosphere makes it invisible to our method.

Constraining the subsoil carbon source to cave-air CO2 and speleothem calcite in central Texas

NASA Astrophysics Data System (ADS)

Bergel, Shelly J.; Carlson, Peter E.; Larson, Toti E.; Wood, Chris T.; Johnson, Kathleen R.; Banner, Jay L.; Breecker, Daniel O.

2017-11-01

Canonical models for speleothem formation and the subsurface carbon cycle invoke soil respiration as the dominant carbon source. However, evidence from some karst regions suggests that belowground CO2 originates from a deeper, older source. We therefore investigated the carbon sources to central Texas caves. Drip-water chemistry of two caves in central Texas implies equilibration with calcite at CO2 concentrations (PCO2_sat) higher than the maximum CO2 concentrations observed in overlying soils. This observation suggests that CO2 is added to waters after they percolate through the soils, which requires a subsoil carbon source. We directly evaluate the carbon isotope composition of the subsoil carbon source using δ13C measurements on cave-air CO2, which we independently demonstrate has little to no contribution from host rock carbon. We do so using the oxidative ratio, OR, defined as the number of moles of O2 consumed per mole of CO2 produced during respiration. However, additional belowground processes that affect O2 and CO2 concentrations, such as gas-water exchange and/or diffusion, may also influence the measured oxidative ratio, yielding an apparent OR (ORapparent). Cave air in Natural Bridge South Cavern has ORapparent values (1.09 ± 0.06) indistinguishable from those expected for respiration alone (1.08 ± 0.06). Pore space gases from soils above the cave have lower values (ORapparent = 0.67 ± 0.05) consistent with respiration and gas transport by diffusion. The simplest explanation for these observations is that cave air in NB South is influenced by respiration in open-system bedrock fractures such that neither diffusion nor exchange with water influence the composition of the cave air. The radiocarbon activities of NB South cave-air CO2 suggest the subsoil carbon source is hundreds of years old. The calculated δ13C values of the subsoil carbon source are consistent with tree-sourced carbon (perhaps decomposing root matter), the δ13C values of which have shifted during industrialization due to changes in the δ13C values and concentrations of atmospheric CO2. Seasonal variations in PCO2_sat in most of the drip waters suggest that these waters exchange with ventilated bedrock fractures in the epikarst, implying that the subsoil CO2 source contributes carbon to speleothems.

Point-of-care instrument for monitoring tissue health during skin graft repair

NASA Astrophysics Data System (ADS)

Gurjar, R. S.; Seetamraju, M.; Zhang, J.; Feinberg, S. E.; Wolf, D. E.

2011-06-01

We have developed the necessary theoretical framework and the basic instrumental design parameters to enable mapping of subsurface blood dynamics and tissue oxygenation for patients undergoing skin graft procedures. This analysis forms the basis for developing a simple patch geometry, which can be used to map by diffuse optical techniques blood flow velocity and tissue oxygenation as a function of depth in subsurface tissue.skin graft, diffuse correlation analysis, oxygen saturation.

Transport of Chemical Vapors from Subsurface Sources to Atmosphere as Affected by Shallow Subsurface and Atmospheric Conditions

NASA Astrophysics Data System (ADS)

Rice, A. K.; Smits, K. M.; Hosken, K.; Schulte, P.; Illangasekare, T. H.

2012-12-01

Understanding the movement and modeling of chemical vapor through unsaturated soil in the shallow subsurface when subjected to natural atmospheric thermal and mass flux boundary conditions at the land surface is of importance to applications such as landmine detection and vapor intrusion into subsurface structures. New, advanced technologies exist to sense chemical signatures at the land/atmosphere interface, but interpretation of these sensor signals to make assessment of source conditions remains a challenge. Chemical signatures are subject to numerous interactions while migrating through the unsaturated soil environment, attenuating signal strength and masking contaminant source conditions. The dominant process governing movement of gases through porous media is often assumed to be Fickian diffusion through the air phase with minimal or no quantification of other processes contributing to vapor migration, such as thermal diffusion, convective gas flow due to the displacement of air, expansion/contraction of air due to temperature changes, temporal and spatial variations of soil moisture and fluctuations in atmospheric pressure. Soil water evaporation and interfacial mass transfer add to the complexity of the system. The goal of this work is to perform controlled experiments under transient conditions of soil moisture, temperature and wind at the land/atmosphere interface and use the resulting dataset to test existing theories on subsurface gas flow and iterate between numerical modeling efforts and experimental data. Ultimately, we aim to update conceptual models of shallow subsurface vapor transport to include conditionally significant transport processes and inform placement of mobile sensors and/or networks. We have developed a two-dimensional tank apparatus equipped with a network of sensors and a flow-through head space for simulation of the atmospheric interface. A detailed matrix of realistic atmospheric boundary conditions was applied in a series of experiments. Water saturation, capillary pressure, air and soil temperature, and relative humidity were continuously monitored. Aqueous TCE was injected into the tank below the water table and allowed to volatilize. TCE concentration exiting the tank head space was measured through interval sampling by direct injection into a gas chromatograph. To quantify the transient concentration of TCE vapor in the soil pore space a novel use of Solid Phase Micro-Extraction (SPME) was developed. Results from our numerical simulations were compared with the experimental data, which demonstrated the importance of considering the interaction of the atmosphere with the subsurface in conceptualization and numerical model development. Results also emphasize that soil saturation and transient sorption have a significant effect on vapor transport through the vadose zone. Follow-up tests and detailed analyses are still underway. Additional applications of this work include carbon sequestration leakage, methane contamination in the shallow subsurface and environmental impact of hydraulic fracturing.

[Effects of intensive management on soil C and N pools and soil enzyme activities in Moso bamboo plantations.

PubMed

Yang, Meng; Li, Yong Fu; Li, Yong Chun; Xiao, Yong Heng; Yue, Tian; Jiang, Pei Kun; Zhou, Guo Mo; Liu, Juan

2016-11-18

In order to elucidate the effects of intensive management on soil carbon pool, nitrogen pool, enzyme activities in Moso bamboo (Phyllostachys pubescens) plantations, we collected soil samples from the soil surface (0-20 cm) and subsurface (20-40 cm) layers in the adjacent Moso bamboo plantations with extensive and intensive managements in Sankou Township, Lin'an City, Zhejiang Province. We determined different forms of C, N and soil invertase, urease, catalase and acid phosphatase activities. The results showed that long-term intensive management of Moso bamboo plantations significantly decreased the content and storage of soil organic carbon (SOC), with the SOC storage in the soil surface and subsurface layers decreased by 13.2% and 18.0%, respectively. After 15 years' intensive management of Masoo bamboo plantations, the contents of soil water soluble carbon (WSOC), hot water soluble carbon (HWSOC), microbial carbon (MBC) and readily oxidizable carbon (ROC) were significantly decreased in the soil surface and subsurface layers. The soil N storage in the soil surface and subsurface layers in intensively managed Moso bamboo plantations increased by 50.8% and 36.6%, respectively. Intensive management significantly increased the contents of nitrate-N (NO 3 - -N) and ammonium-N (NH 4 + -N), but decreased the contents of water-soluble nitrogen (WSON) and microbial biomass nitrogen (MBN). After 15 years' intensive management of Masoo bamboo plantations, the soil invertase, urease, catalase and acid phosphatase activities in the soil surface layer were significantly decreased, the soil acid phosphatase activity in the soil subsurface layer were significantly decreased, and other enzyme activities in the soil subsurface layer did not change. In conclusion, long-term intensive management led to a significant decline of soil organic carbon storage, soil labile carbon and microbial activity in Moso bamboo plantations. Therefore, we should consider the use of organic fertilizer in the intensive mana-gement process for the sustainable management of Moso bamboo plantations in the future.

Modeling Deuterium Release from Plasma Implanted Surfaces

NASA Astrophysics Data System (ADS)

Grossman, A. A.; Doerner, R.; Hirooka, Y.; Luckhardt, S. C.; Sze, F. C.

1997-11-01

When energetic ions or atoms of hydrogen isotopes interact with a solid surface, they may either be reflected or they may be implanted, a slowing down process within the subsurface layer of the energetic particles to thermal velocities. Subsequent interactions of the thermalized particles are those of diffusion and trapping within the material and the possibility of re-emission from the solid via desorption. The diffusion equation and its boundary conditions govern the transport of this thermalized hydrogen within the material. Diffusivities obey an Arrhenius law over as much as fourteen orders of magnitude for the temperature range of interest for a fusion reactor first wall and divertor plate. Using TMAP4, a variety of diffusion models are set up for comparison with experiments on PISCES which involve implantation and desorption of deuterium from beryllium, tungsten, carbon and boron carbide. The parameters and characteristics of the models which give the closest fit to the experimental data are reported. At the high fluences of these experiments, it is necessary to take into account saturation effects during implantation using a separate implantation layer with thickness given by TRIM and a higher trapping to lattice ratio than in the bulk in order to model the experimental data.

Growth of microorganisms in Martian-like shallow subsurface conditions: laboratory modelling

NASA Astrophysics Data System (ADS)

Pavlov, A. K.; Shelegedin, V. N.; Vdovina, M. A.; Pavlov, A. A.

2010-01-01

Low atmospheric pressures on Mars and the lack of substantial amounts of liquid water were suggested to be among the major limiting factors for the potential Martian biosphere. However, large amounts of ice were detected in the relatively shallow subsurface layers of Mars by the Odyssey Mission and when ice sublimates the water vapour can diffuse through the porous surface layer of the soil. Here we studied the possibility for the active growth of microorganisms in such a vapour diffusion layer. Our results showed the possibility of metabolism and the reproduction of non-extremophile terrestrial microorganisms (Vibrio sp.) under very low (0.01-0.1 mbar) atmospheric pressures in a Martian-like shallow subsurface regolith.

Carbon mineralization in surface and subsurface soils in a subtropical mixed forest in central China

NASA Astrophysics Data System (ADS)

Liu, F.; Tian, Q.

2014-12-01

About a half of soil carbon is stored in subsurface soil horizons, their dynamics have the potential to significantly affect carbon balancing in terrestrial ecosystems. However, the main factors regulating subsurface soil carbon mineralization are poorly understood. As affected by mountain humid monsoon, the subtropical mountains in central China has an annual precipitation of about 2000 mm, which causes strong leaching of ions and nutrition. The objectives of this study were to monitor subsurface soil carbon mineralization and to determine if it is affected by nutrient limitation. We collected soil samples (up to 1 m deep) at three locations in a small watershed with three soil layers (0-10 cm, 10-30 cm, below 30 cm). For the three layers, soil organic carbon (SOC) ranged from 35.8 to 94.4 mg g-1, total nitrogen ranged from 3.51 to 8.03 mg g-1, microbial biomass carbon (MBC) ranged from 170.6 to 718.4 μg g-1 soil. We measured carbon mineralization with the addition of N (100 μg N/g soil), P (50 μg P/g soil), and liable carbon (glucose labeled by 5 atom% 13C, at five levels: control, 10% MBC, 50% MBC, 100% MBC, 200% MBC). The addition of N and P had negligible effects on CO2 production in surface soil layers; in the deepest soil layer, the addition of N and P decreased CO2 production from 4.32 to 3.20 μg C g-1 soil carbon h-1. Glucose addition stimulated both surface and subsurface microbial mineralization of SOC, causing priming effects. With the increase of glucose addition rate from 10% to 200% MBC, the primed mineralization rate increased from 0.19 to 3.20 μg C g-1 soil carbon h-1 (fifth day of glucose addition). The magnitude of priming effect increased from 28% to 120% as soil layers go deep compare to the basal CO2 production (fifth day of 200% MBC glucose addition, basal CO2 production rate for the surface and the deepest soil was 11.17 and 2.88 μg C g-1 soil carbon h-1). These results suggested that the mineralization of subsurface carbon is more sensitive to nutrient addition, and carbon mineralization in this layer is likely limited by carbon availability. Thus, any changes in environment conditions (global warming, nitrogen deposition, precipitation pattern change etc.) that affect the distribution of fresh carbon in soil profiles could then stimulate the release of deep soil carbon.

Influences of bicarbonate on processes of enamel subsurface remineralization and demineralization: assessment using micro-Raman spectroscopy and transverse microradiography.

PubMed

Kuramochi, Erika; Iizuka, Junko; Mukai, Yoshiharu

2016-12-01

In the present study, we investigated, using micro-Raman spectroscopy (Raman) and transverse microradiography, the influence of bicarbonate [sodium hydrogen carbonate (NaHCO 3 )] on the effects of carbonate ions in the mineral phase during demineralization (acid resistance test) of subsurface lesions. Baseline lesions were created by demineralizing bovine enamel, and specimens were then exposed to remineralization solutions containing 0, 5, or 50 mM bicarbonate. Acid resistance tests were performed on remineralized and sound enamel specimens. Raman spectra showed that carbonate and phosphate were incorporated into both surface layers and lesion bodies during remineralization in the presence of bicarbonate. Moreover, the presence of bicarbonate did not affect the rates of remineralization, although the average mineral profiles of remineralized enamel differed from those of sound enamel after acid resistance tests. Raman analyses enabled close evaluation of site-specific characteristics of carbonate and phosphate in subsurface lesions. In conclusion, incorporation of carbonate and phosphate ions into enamel subsurface lesions during remineralization does not affect the magnitude of remineralization or acid resistance. © 2016 Eur J Oral Sci.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsigabu Gebrehiwet; James R. Henriksen; Luanjing Guo

Multi-component mineral precipitation in porous, subsurface environments is challenging to simulate or engineer when in situ reactant mixing is controlled by diffusion. In contrast to well-mixed systems, the conditions that favor mineral precipitation in porous media are distributed along chemical gradients, which evolve spatially due to concurrent mineral precipitation and modification of solute transport in the media. The resulting physical and chemical characteristics of a mixing/precipitation zone are a consequence of coupling between transport and chemical processes, and the distinctive properties of individual chemical systems. We examined the spatial distribution of precipitates formed in “double diffusion” columns for two chemicalmore » systems, calcium carbonate and calcium phosphate. Polyacrylamide hydrogel was used as a low permeability, high porosity medium to maximize diffusive mixing and minimize pressure- and density-driven flow between reactant solutions. In the calcium phosphate system, multiple, visually dense and narrow bands of precipitates were observed that were reminiscent of previously reported Liesegang patterns. In the calcium carbonate system, wider precipitation zones characterized by more sparse distributions of precipitates and a more open channel structure were observed. In both cases, formation of precipitates inhibited, but did not necessarily eliminate, continued transport and mixing of the reactants. A reactive transport model with fully implicit coupling between diffusion, chemical speciation and precipitation kinetics, but where explicit details of nucleation processes were neglected, was able to qualitatively simulate properties of the precipitation zones. The results help to illustrate how changes in the physical properties of a precipitation zone depend on coupling between diffusion-controlled reactant mixing and chemistry-specific details of precipitation kinetics.« less

Clays and Carbonates in a Groundwater-Fed 3.8 Ga Martian Lake: Insights to Subsurface Habitability on Mars

NASA Technical Reports Server (NTRS)

Michalski, Joseph; Niles, Paul

2015-01-01

On Earth, the deep biosphere remains a largely unexplored, but clearly important carbon reservoir. Results from some uplifted central peaks in craters on Mars indicate that substantial carbon was also present at depth and might have helped sustain a deep biosphere. In fact, many factors relevant to deep biosphere habitability are more favorable on Mars than on Earth (e.g. porosity of the crust, geothermal gradient). Future exploration of Mars should include landing sites where materials have been exhumed from depth by meteor impact or basins where subsurface fluids have emerged, carrying clues to subsurface habitability. One of the most astrobiologically interesting sites on Mars McLaughlin Crater, a 93 km-diameter impact crater that formed approximately 4 b.y. ago. On the floor of the crater is a stratigraphic section of subhorizontal, layered sedimentary rocks with strong spectroscopic evidence for Fe-rich clay minerals and Mg-rich carbonates, which we interpret as ancient lacustrine deposits. The fluids that formed these materials likely originated in the subsurface, based on the paucity of channels leading into the crater basin and the fact that this is one of the deepest basins on Mars - a good candidate to have experienced upwelling of subsurface fluids. Therefore, the deposits within McLaughlin crater provide insight into subsurface processes on Mars. In this presentation, we will discuss the habitability of the martian subsurface as well as the geology of McLaughlin Crater and the possibility to detect biomarkers at that site with a future landed mission.

Geochemical and microbiological responses to oxidant introduction into reduced subsurface sediment from the Hanford 300 Area, Washington.

PubMed

Percak-Dennett, Elizabeth M; Roden, Eric E

2014-08-19

Pliocene-aged reduced lacustrine sediment from below a subsurface redox transition zone at the 300 Area of the Hanford site (southeastern Washington) was used in a study of the geochemical response to introduction of oxygen or nitrate in the presence or absence of microbial activity. The sediments contained large quantities of reduced Fe in the form of Fe(II)-bearing phyllosilicates, together with smaller quantities of siderite and pyrite. A loss of ca. 50% of 0.5 M HCl-extractable Fe(II) [5-10 mmol Fe(II) L(-1)] and detectable generation of sulfate (ca. 0.2 mM, equivalent to 10% of the reduced inorganic sulfur pool) occurred in sterile aerobic reactors. In contrast, no systematic loss of Fe(II) or production of sulfate was observed in any of the other oxidant-amended sediment suspensions. Detectable Fe(II) accumulation and sulfate consumption occurred in non-sterile oxidant-free reactors. Together, these results indicate the potential for heterotrophic carbon metabolism in the reduced sediments, consistent with the proliferation of known heterotrophic taxa (e.g., Pseudomonadaceae, Burkholderiaceae, and Clostridiaceae) inferred from 16S rRNA gene pyrosequencing. Microbial carbon oxidation by heterotrophic communities is likely to play an important role in maintaining the redox boundary in situ, i.e., by modulating the impact of downward oxidant transport on Fe/S redox speciation. Diffusion-reaction simulations of oxygen and nitrate consumption coupled to solid-phase organic carbon oxidation indicate that heterotrophic consumption of oxidants could maintain the redox boundary at its current position over millennial time scales.

Lattice Boltzmann-Based Approaches for Pore-Scale Reactive Transport

DOE PAGES

Yoon, Hongkyu; Kang, Qinjun; Valocchi, Albert J.

2015-07-29

Here an important geoscience and environmental applications such as geologic carbon storage, environmental remediation, and unconventional oil and gas recovery are best understood in the context of reactive flow and multicomponent transport in the subsurface environment. The coupling of chemical and microbiological reactions with hydrological and mechanical processes can lead to complex behaviors across an enormous range of spatial and temporal scales. These coupled responses are also strongly influenced by the heterogeneity and anisotropy of the geologic formations. Reactive transport processes can change the pore morphology at the pore scale, thereby leading to nonlinear interactions with advective and diffusive transport,more » which can strongly influence larger-scale properties such as permeability and dispersion.« less

Spatially resolved, diffuse reflectance imaging for subsurface pattern visualization toward development of a lensless imaging platform: phantom experiments

NASA Astrophysics Data System (ADS)

Schelkanova, Irina; Pandya, Aditya; Saiko, Guennadi; Nacy, Lidia; Babar, Hannan; Shah, Duoaud; Lilge, Lothar; Douplik, Alexandre

2016-01-01

A portable, spatially resolved, diffuse reflectance lensless imaging technique based on the charge-coupled device or complementary metal-oxide semiconductor sensor directly coupled to the fiber optic bundle is proposed for visualization of subsurface structures such as superficial microvasculature in the epithelium. We discuss an experimental method for emulating a lensless imaging setup via raster scanning a single fiber-optic cable over a microfluidic phantom containing periodic hemoglobin absorption contrast. To evaluate the ability of the technique to recover information about the subsurface linear structures, scattering layers formed of the Sylgard® 184 Silicone Elastomer and titanium dioxide were placed atop the microfluidic phantom. Thickness of the layers ranged from 0.2 to 0.7 mm, and the values of the reduced scattering coefficient (μs‧) were between 0.85 and 4.25 mm-1. The results demonstrate that fiber-optic, lensless platform can be used for two-dimensional imaging of absorbing inclusions in diffuse reflectance mode. In these experiments, it was shown that diffuse reflectance imaging can provide sufficient spatial sampling of the phantom for differentiation of 30 μm structural features of the embedded absorbing pattern inside the scattering media.

The Importance of Subsurface Production for Carbon Export - Evidence from Past Oceans

NASA Astrophysics Data System (ADS)

Kemp, A. E. S.

2016-02-01

The maxim of the geological concept of uniformitarianism is "the present is the key to the past", but in the context of our temporally and spatially minimal observational record of modern ocean biogeochemical processes, ancient ocean sediments may provide critical evidence of the key species involved in carbon flux. Specifically, laminated marine sediments that preserve the seasonal flux cycle represent "palaeo-sediment traps" that vastly expand our knowledge of the operations of the marine biological carbon pump. Several key subsurface-dwelling diatom taxa, hitherto thought to be biogeochemically insignificant, are dominant components of ancient marine sediments. For example, the sapropels and equivalent horizons that have accumulated in the Mediterranean over the past 5 million years, contain abundant rhizosolenid and hemiaulid diatoms. These deposits contain the highest concentrations of organic carbon and there is extensive evidence that this was produced by subsurface production in a deep chlorophyll maximum. The highly stratified conditions that led to this subsurface production and carbon flux are in contrast to prevailing views that have held upwelling systems as those with the highest potential for export in the global ocean. Similarly, studies of ancient "greenhouse" periods such as the Cretaceous, with highly stratified oceans and which are potential analogues for future climate change, show evidence for extensive subsurface production. Together with emerging evidence from stratified regions of the modern ocean, such as the subtropical gyres, insights from these ancient oceans suggest that a reappraisal is required of current views on key phytoplankton producers and their role the operation of the marine biological carbon pump.

Geochemistry, faunal composition and trophic structure in reducing sediments on the southwest South Georgia margin

NASA Astrophysics Data System (ADS)

Bell, James B.; Aquilina, Alfred; Woulds, Clare; Glover, Adrian G.; Little, Crispin T. S.; Reid, William D. K.; Hepburn, Laura E.; Newton, Jason; Mills, Rachel A.

2016-09-01

Despite a number of studies in areas of focused methane seepage, the extent of transitional sediments of more diffuse methane seepage, and their influence upon biological communities is poorly understood. We investigated an area of reducing sediments with elevated levels of methane on the South Georgia margin around 250 m depth and report data from a series of geochemical and biological analyses. Here, the geochemical signatures were consistent with weak methane seepage and the role of sub-surface methane consumption was clearly very important, preventing gas emissions into bottom waters. As a result, the contribution of methane-derived carbon to the microbial and metazoan food webs was very limited, although sulfur isotopic signatures indicated a wider range of dietary contributions than was apparent from carbon isotope ratios. Macrofaunal assemblages had high dominance and were indicative of reducing sediments, with many taxa common to other similar environments and no seep-endemic fauna, indicating transitional assemblages. Also similar to other cold seep areas, there were samples of authigenic carbonate, but rather than occurring as pavements or sedimentary concretions, these carbonates were restricted to patches on the shells of Axinulus antarcticus (Bivalvia, Thyasiridae), which is suggestive of microbe-metazoan interactions.

Geochemistry, faunal composition and trophic structure in reducing sediments on the southwest South Georgia margin

PubMed Central

Aquilina, Alfred; Woulds, Clare; Glover, Adrian G.; Little, Crispin T. S.; Hepburn, Laura E.; Newton, Jason; Mills, Rachel A.

2016-01-01

Despite a number of studies in areas of focused methane seepage, the extent of transitional sediments of more diffuse methane seepage, and their influence upon biological communities is poorly understood. We investigated an area of reducing sediments with elevated levels of methane on the South Georgia margin around 250 m depth and report data from a series of geochemical and biological analyses. Here, the geochemical signatures were consistent with weak methane seepage and the role of sub-surface methane consumption was clearly very important, preventing gas emissions into bottom waters. As a result, the contribution of methane-derived carbon to the microbial and metazoan food webs was very limited, although sulfur isotopic signatures indicated a wider range of dietary contributions than was apparent from carbon isotope ratios. Macrofaunal assemblages had high dominance and were indicative of reducing sediments, with many taxa common to other similar environments and no seep-endemic fauna, indicating transitional assemblages. Also similar to other cold seep areas, there were samples of authigenic carbonate, but rather than occurring as pavements or sedimentary concretions, these carbonates were restricted to patches on the shells of Axinulus antarcticus (Bivalvia, Thyasiridae), which is suggestive of microbe–metazoan interactions. PMID:27703692

Modeling experimental stable isotope results from CO2 adsorption and diffusion experiments

NASA Astrophysics Data System (ADS)

Larson, T. E.

2012-12-01

Transport of carbon dioxide through porous media can be affected by diffusion, advection and adsorption processes. Developing new tools to understand which of these processes dominates migration of CO2 or other gases in the subsurface is important to a wide range of applications including CO2 storage. Whereas advection rates are not affected by isotope substitution in CO2, adsorption and diffusion constants are. For example, differences in the binary diffusion constant calculated between C12O2-He and C13O2-He results in a carbon isotope fractionation whereby the front of the chromatographic peak is enriched in carbon-12 and the tail of the peak is enriched in carbon-13. Interestingly, adsorption is shown to have an opposite, apparent inverse affect whereby the lighter isotopologues of CO2 are preferentially retained by the chromatographic column and the heavier isotopologues are eluted first. This apparent inverse chromatographic effect has been ascribed to Van der Waals dispersion forces. Smaller molar volumes of the heavier isotopologues resulting from increased bond strength (shorter bond length) effectively decreases Van der Waals forces in heavier isotopologues compared to lighter isotopologues. Here we discuss the possible application of stable isotope values measured across chromatographic peaks to differentiate diffusion-dominated from adsorption-dominated transport processes for CO2. Separate 1-dimensional flow-through columns were packed with quartz and illite, and one remained empty. Dry helium was used as a carrier gas. Constant flow rate, temperature and column pressure were maintained. After background CO2 concentrations were minimized and constant, a sustained pulse of CO2 was injected at the head of the column and the effluent was sampled at 4 minute intervals for CO2 concentration, and carbon and oxygen isotope ratios. The quartz-sand packed and empty columns resulted in similar trends in concentration and isotope ratios whereby CO2 concentrations steadily increased and became constant after two pore volumes of CO2 flushed through the column. Carbon and oxygen isotope values of the front of the peak (first pore volume) are 2‰ and 5‰ lower than the injected CO2 values, respectively. These results are fit very well using a mass transfer model that only includes binary diffusion between CO2 and helium that account for isotope substitution in the reduced mass coefficient. In contrast to these diffusion-dominated systems, CO2 break through curves from the illite packed column show strong adsorption effects that include a +180‰ increase in the carbon isotope ratio at the front of the peak followed by a 20‰ decrease. Up to 20 pore volumes of CO2 were flushed through the column before the carbon and oxygen isotope values stabilized to their starting values. These adsorption effects cannot be modeled using mass isotope effects alone, and instead must include additional parameters such as volume effects. These results demonstrate the importance of understanding the isotopic effects of CO2 in different substrates, and potentially offers a tracer tool that can be used to quantify surface area, transport distance, and surface reactivity of CO2. Additional applications may include more affectively determining transfer rates of CO2 across low permeability zones.

Significant contribution of Archaea to extant biomass in marine subsurface sediments.

PubMed

Lipp, Julius S; Morono, Yuki; Inagaki, Fumio; Hinrichs, Kai-Uwe

2008-08-21

Deep drilling into the marine sea floor has uncovered a vast sedimentary ecosystem of microbial cells. Extrapolation of direct counts of stained microbial cells to the total volume of habitable marine subsurface sediments suggests that between 56 Pg (ref. 1) and 303 Pg (ref. 3) of cellular carbon could be stored in this largely unexplored habitat. From recent studies using various culture-independent techniques, no clear picture has yet emerged as to whether Archaea or Bacteria are more abundant in this extensive ecosystem. Here we show that in subsurface sediments buried deeper than 1 m in a wide range of oceanographic settings at least 87% of intact polar membrane lipids, biomarkers for the presence of live cells, are attributable to archaeal membranes, suggesting that Archaea constitute a major fraction of the biomass. Results obtained from modified quantitative polymerase chain reaction and slot-blot hybridization protocols support the lipid-based evidence and indicate that these techniques have previously underestimated archaeal biomass. The lipid concentrations are proportional to those of total organic carbon. On the basis of this relationship, we derived an independent estimate of amounts of cellular carbon in the global marine subsurface biosphere. Our estimate of 90 Pg of cellular carbon is consistent, within an order of magnitude, with previous estimates, and underscores the importance of marine subsurface habitats for global biomass budgets.

Exploring Microbial Life in Oxic Sediments Underlying Oligotrophic Ocean Gyres

NASA Astrophysics Data System (ADS)

Ziebis, W.; Orcutt, B.; Wankel, S. D.; D'Hondt, S.; Szubin, R.; Kim, J. N.; Zengler, K.

2015-12-01

Oxygen, carbon and nutrient availability are defining parameters for microbial life. In contrast to organic-rich sediments of the continental margins, where high respiration rates lead to a depletion of O2 within a thin layer at the sediment surface, it was discovered that O2 penetrates several tens of meters into organic-poor sediments underlying oligotrophic ocean gyres. In addition, nitrate, another important oxidant, which usually disappears rapidly with depth in anoxic sediments, tends to accumulate above seawater concentrations in the oxic subsurface, reflecting the importance of nitrogen cycling processes, including both nitrification and denitrification. Two IODP drilling expeditions were vital for exploring the nature of the deep subsurface beneath oligotrophic ocean gyres, expedition 329 to the South Pacific Gyre (SPG) and expedition 336 to North Pond, located on the western flank of the Mid-Atlantic ridge beneath the North Atlantic Gyre. Within the ultra-oligotrophic SPG O2 penetrates the entire sediment column from the sediment-water interface to the underlying basement to depths of > 75 m. At North Pond, a topographic depression filled with sediment and surrounded by steep basaltic outcrops, O2 penetrates deeply into the sediment (~ 30 m) until it eventually becomes depleted. O2 also diffuses upward into the sediment from seawater circulating within the young crust underlying the sediment, resulting in a deep oxic layer several meters above the basalt. Despite low organic carbon contents microbial cells persist throughout the entire sediment column within the SPG (> 75 m) and at North Pond, albeit at low abundances. We explored the nature of the subsurface microbial communities by extracting intact cells from large volumes of sediment obtained from drill cores of the two expeditions. By using CARD-FiSH, amplicon (16s rRNA) and metagenome sequencing we shed light on the phylogenetic and functional diversity of the elusive communities residing in the deep oxic sediments of these two different areas. Given the global extent of this oxic subsurface studies of the diversity and metabolic potential of its biome, together with the analyses of porewater geochemical and isotopic composition, are beginning to reveal its role in global biogeochemical cycles.

Prediction of future subsurface temperatures in Korea

NASA Astrophysics Data System (ADS)

Lee, Y.; Kim, S. K.; Jeong, J.; SHIN, E.

2017-12-01

The importance of climate change has been increasingly recognized because it has had the huge amount of impact on social, economic, and environmental aspect. For the reason, paleoclimate change has been studied intensively using different geological tools including borehole temperatures and future surface air temperatures (SATs) have been predicted for the local areas and the globe. Future subsurface temperatures can have also enormous impact on various areas and be predicted by an analytical method or a numerical simulation using measured and predicted SATs, and thermal diffusivity data of rocks. SATs have been measured at 73 meteorological observatories since 1907 in Korea and predicted at same locations up to the year of 2100. Measured SATs at the Seoul meteorological observatory increased by about 3.0 K from the year of 1907 to the present. Predicted SATs have 4 different scenarios depending on mainly CO2 concentration and national action plan on climate change in the future. The hottest scenario shows that SATs in Korea will increase by about 5.0 K from the present to the year of 2100. In addition, thermal diffusivity values have been measured on 2,903 rock samples collected from entire Korea. Data pretreatment based on autocorrelation analysis was conducted to control high frequency noise in thermal diffusivity data. Finally, future subsurface temperatures in Korea were predicted up to the year of 2100 by a FEM simulation code (COMSOL Multiphysics) using measured and predicted SATs, and thermal diffusivity data in Korea. At Seoul, the results of predictions show that subsurface temperatures will increase by about 5.4 K, 3.0 K, 1.5 K, and 0.2 K from the present to 2050 and then by about 7.9 K, 4.8 K, 2.5 K, and 0.5 K to 2100 at the depths of 10 m, 50 m, 100 m, and 200 m, respectively. We are now proceeding numerical simulations for subsurface temperature predictions for 73 locations in Korea.

Flow and Transport in Complex Microporous Carbonates as a Consequence of Separation of Scales

NASA Astrophysics Data System (ADS)

Bijeljic, B.; Raeini, A. Q.; Lin, Q.; Blunt, M. J.

2017-12-01

Some of the most important examples of flow and transport in complex pore structures are found in subsurface applications such as contaminant hydrology, carbon storage and enhanced oil recovery. Carbonate rock structures contain most of the world's oil reserves, considerable amount of water reserves, and potentially hold a storage capacity for carbon dioxide. However, this type of pore space is difficult to represent due to complexities associated with a wide range of pore sizes and variation in connectivity which poses a considerable challenge for quantitative predictions of transport across multiple scales.A new concept unifying X-ray tomography experiment and direct numerical simulation has been developed that relies on full description flow and solute transport at the pore scale. Differential imaging method (Lin et al. 2016) provides rich information in microporous space, while advective and diffusive mass transport are simulated on micro-CT images of pore-space: Navier-Stokes equations are solved for flow in the image voxels comprising the pore space, streamline-based simulation is used to account for advection, and diffusion is superimposed by random walk.Quantitative validation has been done on analytical solutions for diffusion and by comparing the model predictions versus the experimental NMR measurements in the dual porosity beadpack. Furthermore, we discriminate signatures of multi-scale transport behaviour for a range of carbonate rock (Figure 1), dependent on the heterogeneity of the inter- and intra-grain pore space, heterogeneity in the flow field, and the mass transfer characteristics of the porous media. Finally, we demonstrate the predictive capabilities of the model through an analysis that includes a number of probability density functions flow and transport (PDFs) measures of non-Fickian transport on the micro-CT i935mages. In complex porous media separation of scales exists, leading to flow and transport signatures that need to be described by multiple functions with distinct flow field and transport characteristics. Reference: Lin, Q., Al-Khulaifi Y., Blunt, M.J. and Bijeljic B. (2016). Advances in Water Resources, 96, 306-322, doi:10.1016/j.advwatres.2016.08.002.

The origin of anomalous transport in porous media - is it possible to make a priori predictions?

NASA Astrophysics Data System (ADS)

Bijeljic, Branko; Blunt, Martin

2013-04-01

Despite the range of significant applications of flow and solute transport in porous rock, including contaminant migration in subsurface hydrology, geological storage of carbon-dioxide and tracer studies and miscible displacement in oil recovery, even the qualitative behavior in the subsurface is uncertain. The non-Fickian nature of dispersive processes in heterogeneous porous media has been demonstrated experimentally from pore to field scales. However, the exact relationship between structure, velocity field and transport has not been fully understood. Advances in X ray imaging techniques made it possible to accurately describe structure of the pore space, helping predict flow and anomalous transport behaviour using direct simulation. This is demonstrated by simulating solute transport through 3D images of rock samples, with resolutions of a few microns, representing geological media of increasing pore-scale complexity: a sandpack, a sandstone, and a carbonate. A novel methodology is developed that predicts solute transport at the pore scale by using probability density functions of displacement (propagators) and probability density function of transit time between the image voxels, and relates it to probability density function of normalized local velocity. A key advantage is that full information on velocity and solute concentration is retained in the models. The methodology includes solving for Stokes flow by Open Foam, solving for advective transport by the novel streamline simulation method, and superimposing diffusive transport diffusion by the random walk method. It is shown how computed propagators for beadpack, sandstone and carbonate depend on the spread in the velocity distribution. A narrow velocity distribution in the beadpack leads to the least anomalous behaviour where the propagators rapidly become Gaussian; the wider velocity distribution in the sandstone gives rise to a small immobile concentration peak, and a large secondary mobile peak moving at approximately the average flow speed; in the carbonate with the widest velocity distribution the stagnant concentration peak is persistent, while the emergence of a smaller secondary mobile peak is observed, leading to a highly anomalous behavior. This defines different generic nature of non-Fickian transport in the three media and quantifies the effect of pore structure on transport. Moreover, the propagators obtained by the model are in a very good agreement with the propagators measured on beadpack, Bentheimer sandstone and Portland carbonate cores in nuclear magnetic resonance experiments. These findings demonstrate that it is possible to make a priori predictions of anomalous transport in porous media. The importance of these findings for transport in complex carbonate rock micro-CT images is discussed, classifying them in terms of degree of anomalous transport that can have an impact at the field scale. Extensions to reactive transport will be discussed.

Microbial production and oxidation of methane in deep subsurface

NASA Astrophysics Data System (ADS)

Kotelnikova, Svetlana

2002-10-01

The goal of this review is to summarize present studies on microbial production and oxidation of methane in the deep subterranean environments. Methane is a long-living gas causing the "greenhouse" effect in the planet's atmosphere. Earlier, the deep "organic carbon poor" subsurface was not considered as a source of "biogenic" methane. Evidence of active methanogenesis and presence of viable methanogens including autotrophic organisms were obtained for some subsurface environments including water-flooded oil-fields, deep sandy aquifers, deep sea hydrothermal vents, the deep sediments and granitic groundwater at depths of 10 to 2000 m below sea level. As a rule, the deep subterranean microbial populations dwell at more or less oligotrophic conditions. Molecular hydrogen has been found in a variety of subsurface environments, where its concentrations were significantly higher than in the tested surface aquatic environments. Chemolithoautotrophic microorganisms from deep aquifers that could grow on hydrogen and carbon dioxide can act as primary producers of organic carbon, initiating heterotrophic food chains in the deep subterranean environments independent of photosynthesis. "Biogenic" methane has been found all over the world. On the basis of documented occurrences, gases in reservoirs and older sediments are similar and have the isotopic character of methane derived from CO 2 reduction. Groundwater representing the methanogenic end member are characterized by a relative depletion of dissolved organic carbon (DOC) in combination with an enrichment in 13C in inorganic carbon, which is consistent with the preferential reduction of 12CO 2 by autotrophic methanogens or acetogens. The isotopic composition of methane formed via CO 2 reduction is controlled by the δ13C of the original CO 2 substrate. Literature data shows that CH 4 as heavy as -40‰ or -50‰ can be produced by the microbial reduction of isotopically heavy CO 2. Produced methane may be oxidized microbially to carbon dioxide. Microbial methane oxidation is a biogeochemical process that limits the release of methane, a greenhouse gas from anaerobic environments. Anaerobic methane oxidation plays an important role in marine sediments. Similar processes may take place in deep subsurface and thus fuel the deep microbial community. Organisms or consortia responsible for anaerobic methane oxidation have not yet been cultured, although diverse aerobic methanotrophs have been isolated from a variety of underground niches. The presence of aerobic methanotrophs in the anoxic subsurface remains to be explained. The presence of methane in the deep subsurface have been shown all over the world. The flux of gases between the deep subsurface and the atmosphere is driven by the concentration gradient from depth to the atmosphere. However, methane is consumed by methanotrophs on the way of its evolution in oxidized environments and is transformed to organic form, available for further microbial processing. When the impact of subsurface environments to global warming is estimated, it is necessary to take into account the activity of methane-producing Archaea and methane-oxidizing biofilters in groundwater. Microbial production and oxidation of methane is involved in the carbon cycle in the deep subsurface environments.

Enhanced truncated-correlation photothermal coherence tomography with application to deep subsurface defect imaging and 3-dimensional reconstructions

NASA Astrophysics Data System (ADS)

Tavakolian, Pantea; Sivagurunathan, Koneswaran; Mandelis, Andreas

2017-07-01

Photothermal diffusion-wave imaging is a promising technique for non-destructive evaluation and medical applications. Several diffusion-wave techniques have been developed to produce depth-resolved planar images of solids and to overcome imaging depth and image blurring limitations imposed by the physics of parabolic diffusion waves. Truncated-Correlation Photothermal Coherence Tomography (TC-PCT) is the most successful class of these methodologies to-date providing 3-D subsurface visualization with maximum depth penetration and high axial and lateral resolution. To extend the depth range and axial and lateral resolution, an in-depth analysis of TC-PCT, a novel imaging system with improved instrumentation, and an optimized reconstruction algorithm over the original TC-PCT technique is developed. Thermal waves produced by a laser chirped pulsed heat source in a finite thickness solid and the image reconstruction algorithm are investigated from the theoretical point of view. 3-D visualization of subsurface defects utilizing the new TC-PCT system is reported. The results demonstrate that this method is able to detect subsurface defects at the depth range of ˜4 mm in a steel sample, which exhibits dynamic range improvement by a factor of 2.6 compared to the original TC-PCT. This depth does not represent the upper limit of the enhanced TC-PCT. Lateral resolution in the steel sample was measured to be ˜31 μm.

Adsorption, dissociation and diffusion of hydrogen on the ZrCo surface and subsurface: A comprehensive study using first principles approach

NASA Astrophysics Data System (ADS)

Chattaraj, D.; Kumar, Nandha; Ghosh, Prasenjit; Majumder, C.; Dash, Smruti

2017-11-01

With increasing demand for hydrogen economy driven world, the fundamental research of hydrogen-metal interactions has gained momentum. In this work we report a systematic theoretical study of the stability of different surfaces of intermetallic ZrCo that is a possible candidate as a getter bed for tritium. Our first principles ab initio thermodynamic calculations predict that amongst the (100), (110) and (111) surfaces, the stoichiometric (110) surface is the most stable one over a wide range of Co chemical potential. We have also studied adsorption, dissociation and diffusion of hydrogen on the (110) surface. On the basis of total energy, it is seen that adsorption of molecular hydrogen (H2) on the surface is much weaker than atomic hydrogen. The H2 decomposition on ZrCo surface can easily take place and the dissociation barrier is calculated to be 0.70 eV. The strength of binding of H atom on the surface is more or less independent of surface coverage till 1.0 ML of H. The thermodynamic stability of atomic H adsorbed on the surface, in subsurface and bulk decreases from surface to bulk to subsurface. Though the H atoms are mobile on the surface, their diffusion to the subsurface involves a barrier of about 0.79 eV.

Discontinuities Characteristics of the Upper Jurassic Arab-D Reservoir Equivalent Tight Carbonates Outcrops, Central Saudi Arabia

NASA Astrophysics Data System (ADS)

Abdlmutalib, Ammar; Abdullatif, Osman

2017-04-01

Jurassic carbonates represent an important part of the Mesozoic petroleum system in the Arabian Peninsula in terms of source rocks, reservoirs, and seals. Jurassic Outcrop equivalents are well exposed in central Saudi Arabia and which allow examining and measuring different scales of geological heterogeneities that are difficult to collect from the subsurface due to limitations of data and techniques. Identifying carbonates Discontinuities characteristics at outcrops might help to understand and predict their properties and behavior in the subsurface. The main objective of this study is to identify the lithofacies and the discontinuities properties of the upper Jurassic carbonates of the Arab D member and the Jubaila Formation (Arab-D reservoir) based on their outcrop equivalent strata in central Saudi Arabia. The sedimentologic analysis revealed several lithofacies types that vary in their thickness, abundances, cyclicity and vertical and lateral stacking patterns. The carbonates lithofacies included mudstone, wackestone, packstone, and grainstone. These lithofacies indicate deposition within tidal flat, skeletal banks and shallow to deep lagoonal paleoenvironmental settings. Field investigations of the outcrops revealed two types of discontinuities within Arab D Member and Upper Jubaila. These are depositional discontinuities and tectonic fractures and which all vary in their orientation, intensity, spacing, aperture and displacements. It seems that both regional and local controls have affected the fracture development within these carbonate rocks. On the regional scale, the fractures seem to be structurally controlled by the Central Arabian Graben System, which affected central Saudi Arabia. While, locally, at the outcrop scale, stratigraphic, depositional and diagenetic controls appear to have influenced the fracture development and intensity. The fracture sets and orientations identified on outcrops show similarity to those fracture sets revealed in the upper Jurassic carbonates in the subsurface which suggest inter-relationships. Therefore, the integration of discontinuities characteristics revealed from the Arab-D outcrop with subsurface data might help to understand and predict discontinuity properties and patterns of the Arab-D reservoir in the subsurface.

Subsurface North Atlantic warming as a trigger of rapid cooling events: evidences from the Early Pleistocene (MIS 31-19)

NASA Astrophysics Data System (ADS)

Hernández-Almeida, I.; Sierro, F.-J.; Cacho, I.; Flores, J.-A.

2014-10-01

Subsurface water column dynamics in the subpolar North Atlantic were reconstructed in order to improve the understanding of the cause of abrupt IRD events during cold periods of the Early Pleistocene. We used Mg / Ca-based temperatures of deep-dwelling (Neogloboquadrina pachyderma sinistral) planktonic foraminifera and paired Mg / Ca-δ18O measurements to estimate the subsurface temperatures and δ18O of seawater at Site U1314. Carbon isotopes on benthic and planktonic foraminifera from the same site provide information about the ventilation and water column nutrient gradient. Mg / Ca-based temperatures and δ18O of seawater suggest increased temperatures and salinities during ice-rafting, likely due to enhanced northward subsurface transport of subtropical waters during periods of AMOC reduction. Planktonic carbon isotopes support this suggestion, showing coincident increased subsurface ventilation during deposition of ice-rafted detritus (IRD). Warm waters accumulated at subsurface would result in basal warming and break-up of ice-shelves, leading to massive iceberg discharges in the North Atlantic. Release of heat and salt stored at subsurface would help to restart the AMOC. This mechanism is in agreement with modelling and proxy studies that observe a subsurface warming in the North Atlantic in response to AMOC slowdown during the MIS3.

Vadose Zone as a Potential Carbon Source: a Look at Seasonal Spikes in Hyporheic Zone pCO2

NASA Astrophysics Data System (ADS)

Brandes, J.

2016-12-01

Connections between soils, terrestrial streams and the atmosphere are not yet thoroughly understood as contributing factors to the global carbon budget. We collected data from an undisturbed soil column adjacent to a small stream in a forested watershed in the H. J. Andrews Experimental Forest in the Western Cascades of Oregon in the United States. Our data includes: CO2 (ppm); temperature (oC); depth below water table (m); and soil moisture (cm3/cm3) and spans approximately one year. We are analyzing the data using the gradient method and have observed distinct seasonal patterns which may support previous research describing temporal processes. We can expect to see changing soil moisture characteristics which may promote either vertical CO2 diffusion out of the surface or vertical/lateral advection into subsurface flow. We hypothesize that there is flushing of soil CO2 into the hyporheic zone during precipitation events following soil CO2 buildup.

Subsurface North Atlantic warming as a trigger of rapid cooling events: evidence from the early Pleistocene (MIS 31-19)

NASA Astrophysics Data System (ADS)

Hernández-Almeida, I.; Sierro, F.-J.; Cacho, I.; Flores, J.-A.

2015-04-01

Subsurface water column dynamics in the subpolar North Atlantic were reconstructed in order to improve the understanding of the cause of abrupt ice-rafted detritus (IRD) events during cold periods of the early Pleistocene. We used paired Mg / Ca and δ18O measurements of Neogloboquadrina pachyderma (sinistral - sin.), deep-dwelling planktonic foraminifera, to estimate the subsurface temperatures and seawater δ18O from a sediment core from Gardar Drift, in the subpolar North Atlantic. Carbon isotopes of benthic and planktonic foraminifera from the same site provide information about the ventilation and water column nutrient gradient. Mg / Ca-based temperatures and seawater δ18O suggest increased subsurface temperatures and salinities during ice-rafting, likely due to northward subsurface transport of subtropical waters during periods of weaker Atlantic Meridional Overturning Circulation (AMOC). Planktonic carbon isotopes support this suggestion, showing coincident increased subsurface ventilation during deposition of IRD. Subsurface accumulation of warm waters would have resulted in basal warming and break-up of ice-shelves, leading to massive iceberg discharges in the North Atlantic. The release of heat stored at the subsurface to the atmosphere would have helped to restart the AMOC. This mechanism is in agreement with modelling and proxy studies that observe a subsurface warming in the North Atlantic in response to AMOC slowdown during Marine Isotope Stage (MIS) 3.

The genome of Geobacter bemidjiensis, exemplar for the subsurface clade of Geobacter species that predominate in Fe(III)-reducing subsurface environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aklujkar, Muktak; Young, Nelson D; Holmes, Dawn

2010-01-01

Background. Geobacter species in a phylogenetic cluster known as subsurface clade 1 are often the predominant microorganisms in subsurface environments in which Fe(III) reduction is the primary electron-accepting process. Geobacter bemidjiensis, a member of this clade, was isolated from hydrocarbon-contaminated subsurface sediments in Bemidji, Minnesota, and is closely related to Geobacter species found to be abundant at other subsurface sites. This study examines whether there are significant differences in the metabolism and physiology of G. bemidjiensis compared to non-subsurface Geobacter species. Results. Annotation of the genome sequence of G. bemidjiensis indicates several differences in metabolism compared to previously sequenced non-subsurfacemore » Geobacteraceae, which will be useful for in silico metabolic modeling of subsurface bioremediation processes involving Geobacter species. Pathways can now be predicted for the use of various carbon sources such as propionate by G. bemidjiensis. Additional metabolic capabilities such as carbon dioxide fixation and growth on glucose were predicted from the genome annotation. The presence of different dicarboxylic acid transporters and two oxaloacetate decarboxylases in G. bemidjiensis may explain its ability to grow by disproportionation of fumarate. Although benzoate is the only aromatic compound that G. bemidjiensis is known or predicted to utilize as an electron donor and carbon source, the genome suggests that this species may be able to detoxify other aromatic pollutants without degrading them. Furthermore, G. bemidjiensis is auxotrophic for 4-aminobenzoate, which makes it the first Geobacter species identified as having a vitamin requirement. Several features of the genome indicated that G. bemidjiensis has enhanced abilities to respire, detoxify and avoid oxygen. Conclusion. Overall, the genome sequence of G. bemidjiensis offers surprising insights into the metabolism and physiology of Geobacteraceae in subsurface environments, compared to non-subsurface Geobacter species, such as the ability to disproportionate fumarate, more efficient oxidation of propionate, enhanced responses to oxygen stress, and dependence on the environment for a vitamin requirement. Therefore, an understanding of the activity of Geobacter species in the subsurface is more likely to benefit from studies of subsurface isolates such as G. bemidjiensis than from the non-subsurface model species studied so far.« less

Diffusion of hydrogen interstitials in the near-surface region of Pd(111) under the influence of surface coverage and external static electric fields

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanco-Rey, M.; Donostia International Physics Center; Tremblay, J. C.

2015-04-21

Past scanning tunneling microscopy (STM) experiments of H manipulation on Pd(111), at low temperature, have shown that it is possible to induce diffusion of surface species as well as of those deeply buried under the surface. Several questions remain open regarding the role of subsurface site occupancies. In the present work, the interaction potential of H atoms with Pd(111) under various H coverage conditions is determined by means of density functional theory calculations in order to provide an answer to two of these questions: (i) whether subsurface sites are the final locations for the H impurities that attempt to emergemore » from bulk regions, and (ii) whether penetration of the surface is a competing route of on-surface diffusion during depletion of surface H on densely covered Pd(111). We find that a high H coverage has the effect of blocking resurfacing of H atoms travelling from below, which would otherwise reach the surface fcc sites, but it hardly alters deeper diffusion energy barriers. Penetration is unlikely and restricted to high occupancies of hcp hollows. In agreement with experiments, the Pd lattice expands vertically as a consequence of H atoms being blocked at subsurface sites, and surface H enhances this expansion. STM tip effects are included in the calculations self-consistently as an external static electric field. The main contribution to the induced surface electric dipoles originates from the Pd substrate polarisability. We find that the electric field has a non-negligible effect on the H-Pd potential in the vicinity of the topmost Pd atomic layer, yet typical STM intensities of 1-2 VÅ{sup −1} are insufficient to invert the stabilities of the surface and subsurface equilibrium sites.« less

Comparison of precursor infiltration into polymer thin films via atomic layer deposition and sequential vapor infiltration using in-situ quartz crystal microgravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padbury, Richard P.; Jur, Jesse S., E-mail: jsjur@ncsu.edu

Previous research exploring inorganic materials nucleation behavior on polymers via atomic layer deposition indicates the formation of hybrid organic–inorganic materials that form within the subsurface of the polymer. This has inspired adaptations to the process, such as sequential vapor infiltration, which enhances the diffusion of organometallic precursors into the subsurface of the polymer to promote the formation of a hybrid organic–inorganic coating. This work highlights the fundamental difference in mass uptake behavior between atomic layer deposition and sequential vapor infiltration using in-situ methods. In particular, in-situ quartz crystal microgravimetry is used to compare the mass uptake behavior of trimethyl aluminummore » in poly(butylene terephthalate) and polyamide-6 polymer thin films. The importance of trimethyl aluminum diffusion into the polymer subsurface and the subsequent chemical reactions with polymer functional groups are discussed.« less

Active Marine Subsurface Bacterial Population Composition in Low Organic Carbon Environments from IODP Expedition 320

NASA Astrophysics Data System (ADS)

Shepard, A.; Reese, B. K.; Mills, H. J.; IODP Expedition 320 Shipboard Science Party

2011-12-01

The marine subsurface environment contains abundant and active microorganisms. These microbial populations are considered integral players in the marine subsurface biogeochemical system with significance in global geochemical cycles and reservoirs. However, variations in microbial community structure, activity and function associated with the wide-ranging sedimentary and geochemical environments found globally have not been fully resolved. Integrated Ocean Drilling Program Expedition 320 recovered sediments from site U1332. Two sampling depths were selected for analysis that spanned differing lithological units in the sediment core. Sediments were composed of mostly clay with zeolite minerals at 8 meters below sea floor (mbsf). At 27 mbsf, sediments were composed of alternating clayey radiolarian ooze and nannofossil ooze. The concentration of SO42- had little variability throughout the core and the concentration of Fe2+ remained close to, or below, detection limits (0.4 μM). Total organic carbon content ranged from a low of 0.03 wt% to a high of 0.07 wt% between 6 and 30 mbsf providing an opportunity to evaluate marine subsurface microbial communities under extreme electron donor limiting conditions. The metabolically active fraction of the bacterial population was isolated by the extraction and amplification of 16S ribosomal RNA. Pyrosequencing of 16S rRNA transcripts and subsequent bioinformatic analyses provided a robust data set (15,931 total classified sequences) to characterize the community at a high resolution. As observed in other subsurface environments, the overall diversity of active bacterial populations decreased with depth. The population shifted from a diverse but evenly distributed community at approximately 8 mbsf to a Firmicutes dominated population at 27 mbsf (80% of sequences). A total of 95% of the sequences at 27 mbsf were grouped into three genera: Lactobacillus (phylum Firmicutes) at 80% of the total sequences, Marinobacter (phylum Proteobacteria) at 8%, and Formosa (phylum Bacteroidetes) at 7%. These lineages support a paradigm suggesting the importance of fermentation in the subsurface. However, this study extends the predicted range for fermentation below the shallow subsurface and into organic carbon limited marine sediments. Other previously characterized subsurface active populations from environments with higher organic carbon concentrations do not show similar levels of reduced diversity or predominance of fermentative populations. This study further emphasizes the spatial variability of microbial populations in the deep subsurface and highlights the need for continued exploration.

Measurement of effective air diffusion coefficients for trichloroethene in undisturbed soil cores.

PubMed

Bartelt-Hunt, Shannon L; Smith, James A

2002-06-01

In this study, we measure effective diffusion coefficients for trichloroethene in undisturbed soil samples taken from Picatinny Arsenal, New Jersey. The measured effective diffusion coefficients ranged from 0.0053 to 0.0609 cm2/s over a range of air-filled porosity of 0.23-0.49. The experimental data were compared to several previously published relations that predict diffusion coefficients as a function of air-filled porosity and porosity. A multiple linear regression analysis was developed to determine if a modification of the exponents in Millington's [Science 130 (1959) 100] relation would better fit the experimental data. The literature relations appeared to generally underpredict the effective diffusion coefficient for the soil cores studied in this work. Inclusion of a particle-size distribution parameter, d10, did not significantly improve the fit of the linear regression equation. The effective diffusion coefficient and porosity data were used to recalculate estimates of diffusive flux through the subsurface made in a previous study performed at the field site. It was determined that the method of calculation used in the previous study resulted in an underprediction of diffusive flux from the subsurface. We conclude that although Millington's [Science 130 (1959) 100] relation works well to predict effective diffusion coefficients in homogeneous soils with relatively uniform particle-size distributions, it may be inaccurate for many natural soils with heterogeneous structure and/or non-uniform particle-size distributions.

Effect of Carbon in the Dielectric Fluid and Workpieces on the Characteristics of Recast Layers Machined by Electrical Discharge Machining

NASA Astrophysics Data System (ADS)

Muttamara, Apiwat; Kanchanomai, Chaosuan

2016-06-01

Electrical discharge machining (EDM) is a popular non-traditional machining technique that is usually performed in kerosene. Carbon from the kerosene is mixed into the recast layer during EDM, increasing its hardness. EDM can be performed in deionized water, which causes decarburization. We studied the effects of carbon in the dielectric fluid and workpiece on the characteristics of recast layers. Experiments were conducted using gray cast iron and mild steel workpieces in deionized water or kerosene under identical operating conditions. Scanning electron microscopy revealed that the recast layer formed on gray iron was rougher than that produced on mild steel. Moreover, the dispersion of graphite flakes in the gray iron seemed to cause subsurface cracks, even when EDM was performed in deionized water. Dendritic structures and iron carbides were found in the recast layer of gray iron treated in deionized water. Kerosene caused more microcracks to form and increased surface roughness compared with deionized water. The microcrack length per unit area of mild steel treated in deionized water was greater than that treated in kerosene, but the cracks formed in kerosene were wider. The effect of the diffusion of carbon during cooling on the characteristics of the recast layer was discussed.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

Active fungi amidst a marine subsurface RNA paleome

NASA Astrophysics Data System (ADS)

Orsi, W.; Biddle, J.; Edgcomb, V.

2012-12-01

The deep marine subsurface is a vast habitat for microbial life where cells may live on geologic timescales. Since extracellular DNA in sediments may be preserved on long timescales, ribosomal RNA (rRNA) is suggested to be a proxy for the active fraction of a microbial community in the subsurface. During an investigation of eukaryotic 18S rRNA signatures by amplicon pyrosequencing, metazoan, plant, and diatom rRNA signatures were recovered from marine sediments up to 2.7 million years old, suggesting that rRNA may be much more stable than previously considered in the marine subsurface. This finding confirms the concept of a paleome, extending it to include rRNA. Within the same dataset, unique profiles of fungi were found across a range of marine subsurface provinces exhibiting statistically significant correlations with total organic carbon (TOC), sulfide, and dissolved inorganic carbon (DIC). Sequences from metazoans, plants and diatoms showed different correlation patterns, consistent with a depth-controlled paleome. The fungal correlations with geochemistry allow the inference that some fungi are active and adapted for survival in the marine subsurface. A metatranscriptomic analysis of fungal derived mRNA confirms that fungi are metabolically active and utilize a range of organic and inorganic substrates in the marine subsurface.

Exploration of diffuse and discrete sources of acid mine drainage to a headwater mountain stream in Colorado, USA

USGS Publications Warehouse

Johnston, Allison; Runkel, Robert L.; Navarre-Sitchler, Alexis; Singha, Kamini

2017-01-01

We investigated the impact of acid mine drainage (AMD) contamination from the Minnesota Mine, an inactive gold and silver mine, on Lion Creek, a headwater mountain stream near Empire, Colorado. The objective was to map the sources of AMD contamination, including discrete sources visible at the surface and diffuse inputs that were not readily apparent. This was achieved using geochemical sampling, in-stream and in-seep fluid electrical conductivity (EC) logging, and electrical resistivity imaging (ERI) of the subsurface. The low pH of the AMD-impacted water correlated to high fluid EC values that served as a target for the ERI. From ERI, we identified two likely sources of diffuse contamination entering the stream: (1) the subsurface extent of two seepage faces visible on the surface, and (2) rainfall runoff washing salts deposited on the streambank and in a tailings pile on the east bank of Lion Creek. Additionally, rainfall leaching through the tailings pile is a potential diffuse source of contamination if the subsurface beneath the tailings pile is hydraulically connected with the stream. In-stream fluid EC was lowest when stream discharge was highest in early summer and then increased throughout the summer as stream discharge decreased, indicating that the concentration of dissolved solids in the stream is largely controlled by mixing of groundwater and snowmelt. Total dissolved solids (TDS) load is greatest in early summer and displays a large diel signal. Identification of diffuse sources and variability in TDS load through time should allow for more targeted remediation options.

MuSET, A High Precision Logging Sensor For Downhole Spontaneous Electrical Potential.

NASA Astrophysics Data System (ADS)

Pezard, P. A.; Gautier, S.; Le Borgne, T.; Deltombe, J.

2008-12-01

MuSET has been designed by ALT and CNRS in the context of the EC ALIANCE research project. It is based on an existing multi-parameter borehole fluid sensor (p, T, Cw, pH, Eh) built by ALT. The new downhole geophysical tool aims to measure subsurface spontaneous electrical potentials (SP) in situ with great precision (< µV). For this, the device includes an unpolazirable Pb/PbCl2 electrode referred to a similar one at surface. Initial field testing in Montpellier (Languedoc, France), Ploemeur (Brittany, France) and Campos (Mallorca, Spain) took advantage of the set of field sites developed as part of ALIANCE then as part of the environmental research observatory (ORE) network for hydrogeology "H+". While Cretaceous marly limestone at Lavalette (Montpellier) proved to be almost exclusively the source of membrane potential, the clay-starved Miocene reefal carbonates of Campos generate a signal dominated by electrokinetic potential. This signal is generated due to nearby agricultural pumping, and associated strong horizontal flow. At the top of the salt to fresh water transtion, a discrepancy between the SP signal and the absence of vertical flow measured with a heat-pulse flowmeter hints at a capacity to detect the "fluid-junction", diffusion potential. At Ploemeur, the altered granite found in the vicinity of faults and fractures is also the source of a SP signal, mostly surface related while most fractures appear to be closed. In all, the MuSET demonstrates a capacity to identify several subsurface sources of natural electrical potential such as diffusion ones (membrane potential in the presence of clays, fickean processes due to pore fluid salinity gradients), or else the electrokinetic potential with pore fluid pressure gradients. While spontaneous electrical currents often loop out of the borehole, MuSET might be used as a radial electrical flowmeter once the diffusion components taken into account.

Abiotic vs biological sources and fates of organic compounds in a low temperature continental serpentinizing system

NASA Astrophysics Data System (ADS)

Robinson, K.; Noble, S. M.; Shock, E.

2016-12-01

Serpentinization is likely the most common water-rock reaction in our solar system. During this process ultramafic silicates are hydrated, a calcium hydroxide solution is formed, and H2O is reduced to H2 coupled to the oxidation of Fe2+ to Fe3+. The resulting hyper-alkaline, reduced conditions generate thermodynamic drives for numerous carbon compound reactions, including the precipitation of various carbonate minerals and the reduction of inorganic carbonate to organic carbon. Testing the extent to which these thermodynamic drives lead to observable results led to the present study of the flow and transformations of carbon through the active continental serpentinizing system at the Samail Ophiolite in the Sultanate of Oman. Water samples were collected from shallow groundwater (representing system input), hyper-alkaline seeps (system output), boreholes (system intermediate), and surface fluid mixing zones, and analyzed for concentrations of dissolved inorganic carbon (DIC + δ13C), organic carbon (+ δ13C), formate, acetate, H2, methane (+ δ13C), ethane, and an accompanying suite of other geochemical solutes. These analyses indicate that the vast majority of DIC in these serpentinizing fluids precipitates in the subsurface as carbonate minerals; however, a significant amount of DIC is converted into organic acids and light hydrocarbons and expelled at the surface in hyper-alkaline seeps. Based on thermodynamic calculations, it seems most likely that formate last equilibrated with dolomite (CaMg[CO3]2) in the subsurface, acetate last equilibrated with calcite (CaCO3) near the surface, and methane and ethane last equilibrated in a distinct carbon-limited region of the subsurface. As for the fates of these compounds, energetic calculations reveal that a combination of oxidative, reductive, and fermentative metabolisms are thermodynamically favorable. Indeed, δ13C trends record microbial methane oxidation at the surface and cannot rule out methane as biologically sourced from the subsurface.

An innovative wood-chip-framework substrate used as slow-release carbon source to treat high-strength nitrogen wastewater.

PubMed

Li, Huai; Chi, Zifang; Yan, Baixing; Cheng, Long; Li, Jianzheng

2017-01-01

Removal of nitrogen in wastewater before discharge into receiving water courses is an important consideration in treatment systems. However, nitrogen removal efficiency is usually limited due to the low carbon/nitrogen (C/N) ratio. A common solution is to add external carbon sources, but amount of liquid is difficult to determine. Therefore, a combined wood-chip-framework substrate (with wood, slag and gravel) as a slow-release carbon source was constructed in baffled subsurface-flow constructed wetlands to overcome the problem. Results show that the removal rate of ammonia nitrogen (NH 4 + -N), total nitrogen (TN) and chemical oxygen demand (COD) could reach 37.5%-85%, 57.4%-86%, 32.4%-78%, respectively, indicating the combined substrate could diffuse sufficient oxygen for the nitrification process (slag and gravel zone) and provide carbon source for denitrification process (wood-chip zone). The nitrification and denitrification were determined according to the location of slag/gravel and wood-chip, respectively. Nitrogen removal was efficient at the steady phase before a shock loading using slag-wood-gravel combined substrate because of nitrification-denitrification process, while nitrogen removal was efficient under a shock loading with wood-slag-gravel combined substrate because of ANAMMOX process. This study provides a new idea for wetland treatment of high-strength nitrogen wastewater. Copyright © 2016. Published by Elsevier B.V.

Microbial Communities and Organic Matter Composition in Surface and Subsurface Sediments of the Helgoland Mud Area, North Sea

PubMed Central

Oni, Oluwatobi E.; Schmidt, Frauke; Miyatake, Tetsuro; Kasten, Sabine; Witt, Matthias; Hinrichs, Kai-Uwe; Friedrich, Michael W.

2015-01-01

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30–530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments. PMID:26635758

Homogenization of Electromagnetic and Seismic Wavefields for Joint Inverse Modeling

NASA Astrophysics Data System (ADS)

Newman, G. A.; Commer, M.; Petrov, P.; Um, E. S.

2011-12-01

A significant obstacle in developing a robust joint imaging technology exploiting seismic and electromagnetic (EM) wave fields is the resolution at which these different geophysical measurements sense the subsurface. Imaging of seismic reflection data is an order of magnitude finer in resolution and scale compared to images produced with EM data. A consistent joint image of the subsurface geophysical attributes (velocity, electrical conductivity) requires/demands the different geophysical data types be similar in their resolution of the subsurface. The superior resolution of seismic data results from the fact that the energy propagates as a wave, while propagation of EM energy is diffusive and attenuates with distance. On the other hand, the complexity of the seismic wave field can be a significant problem due to high reflectivity of the subsurface and the generation of multiple scattering events. While seismic wave fields have been very useful in mapping the subsurface for energy resources, too much scattering and too many reflections can lead to difficulties in imaging and interpreting seismic data. To overcome these obstacles a formulation for joint imaging of seismic and EM wave fields is introduced, where each data type is matched in resolution. In order to accomplish this, seismic data are first transformed into the Laplace-Fourier Domain, which changes the modeling of the seismic wave field from wave propagation to diffusion. Though high frequency information (reflectivity) is lost with this transformation, several benefits follow: (1) seismic and EM data can be easily matched in resolution, governed by the same physics of diffusion, (2) standard least squares inversion works well with diffusive type problems including both transformed seismic and EM, (3) joint imaging of seismic and EM data may produce better starting velocity models critical for successful reverse time migration or full waveform imaging of seismic data (non transformed) and (4) possibilities to image across multiple scale lengths, incorporating different types of geophysical data and attributes in the process. Important numerical details of 3D seismic wave field simulation in the Laplace-Fourier domain for both acoustic and elastic cases will also be discussed.

Biofilm-induced calcium carbonate precipitation: application in the subsurface

NASA Astrophysics Data System (ADS)

Phillips, A. J.; Eldring, J.; Lauchnor, E.; Hiebert, R.; Gerlach, R.; Mitchell, A. C.; Esposito, R.; Cunningham, A. B.; Spangler, L.

2012-12-01

We have investigated mitigation strategies for sealing high permeability regions, like fractures, in the subsurface. This technology has the potential to, for example, improve the long-term security of geologically-stored carbon dioxide (CO2) by sealing fractures in cap rocks or to mitigate leakage pathways to prevent contamination of overlying aquifers from hydraulic fracturing fluids. Sealing technologies using low-viscosity fluids are advantageous since they potentially reduce the necessary injection pressures and increase the radius of influence around injection wells. In this technology, aqueous solutions and suspensions are used to promote microbially-induced mineral precipitation which can be applied in subsurface environments. To this end, a strategy was developed to twice seal a hydraulically fractured, 74 cm (2.4') diameter Boyles Sandstone core, collected in North-Central Alabama, with biofilm-induced calcium carbonate (CaCO3) precipitates under ambient pressures. Sporosarcina pasteurii biofilms were established and calcium and urea containing reagents were injected to promote saturation conditions favorable for CaCO3 precipitation followed by growth reagents to resuscitate the biofilm's ureolytic activity. Then, in order to evaluate this process at relevant deep subsurface pressures, a novel high pressure test vessel was developed to house the 74 cm diameter core under pressures as high as 96 bar (1,400 psi). After determining that no impact to the fracture permeability occurred due to increasing overburden pressure, the fractured core was sealed under subsurface relevant pressures relating to 457 meters (1,500 feet) below ground surface (44 bar (650 psi) overburden pressure). After fracture sealing under both ambient and subsurface relevant pressure conditions, the sandstone core withstood three times higher well bore pressure than during the initial fracturing event, which occurred prior to biofilm-induced CaCO3 mineralization. These studies suggest biofilm-induced CaCO3 precipitation technologies may potentially seal and strengthen high permeability regions or fractures (either natural or induced) in the subsurface. Novel high pressure test vessel to investigate biogeochemical processes under relevant subsurface scales and pressures.

The role microbial sulfate reduction in the direct mediation of sedimentary authigenic carbonate precipitation

NASA Astrophysics Data System (ADS)

Turchyn, A. V.; Walker, K.; Sun, X.

2016-12-01

The majority of modern deep marine sediments are bathed in water that is undersaturated with respect to calcium carbonate. However, within marine sediments changing chemical conditions, driven largely by the microbial oxidation of organic carbon in the absence of oxygen, lead to supersaturated conditions and drive calcium carbonate precipitation. This sedimentary calcium carbonate is often called `authigenic carbonate', and is found in the form of cements and disseminated crystals within the marine sedimentary pile. As this precipitation of this calcium carbonate is microbially mediated, identifying authigenic carbonate within the geological record and understanding what information its geochemical and/or isotopic signature may hold is key for understanding its importance and what information it may contain past life. However, the modern controls on authigenic carbonate precipitation remain enigmatic because the myriad of microbially mediated reactions occurring within sediments both directly and indirectly impact the proton balance. In this submission we present data from 25 ocean sediment cores spanning the globe where we explore the deviation from the stoichiometrically predicted relationships among alkalinity, calcium and sulfate concentrations. In theory for every mol of organic carbon reduced by sulfate, two mol of alkalinity is produced, and to precipitate subsurface calcium carbonate one mol of calcium is used to consume two mol of alkalinity. We use this data with a model to explore changes in carbonate saturation state with depth below the seafloor. Alkalinity changes in the subsurface are poorly correlated with changes in calcium concentrations, however calcium concentrations are directly and tightly coupled to changes in sulfate concentrations in all studied sites. This suggests a direct role for sulfate reducing bacteria in the precipitation of subsurface carbonate cements.

Abnormal growth kinetics of h-BN epitaxial monolayer on Ru(0001) enhanced by subsurface Ar species

NASA Astrophysics Data System (ADS)

Wei, Wei; Meng, Jie; Meng, Caixia; Ning, Yanxiao; Li, Qunxiang; Fu, Qiang; Bao, Xinhe

2018-04-01

Growth kinetics of epitaxial films often follows the diffusion-limited aggregation mechanism, which shows a "fractal-to-compact" morphological transition with increasing growth temperature or decreasing deposition flux. Here, we observe an abnormal "compact-to-fractal" morphological transition with increasing growth temperature for hexagonal boron nitride growth on the Ru(0001) surface. The unusual growth process can be explained by a reaction-limited aggregation (RLA) mechanism. Moreover, introduction of the subsurface Ar atoms has enhanced this RLA growth behavior by decreasing both reaction and diffusion barriers. Our work may shed light on the epitaxial growth of two-dimensional atomic crystals and help to control their morphology.

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir: Microbial life in the deep carbonated biosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freedman, Adam J. E.; Tan, BoonFei; Thompson, Janelle R.

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected super-critical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO 2- water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four membersmore » of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. In conclusion, the existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling.« less

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir: Microbial life in the deep carbonated biosphere

DOE PAGES

Freedman, Adam J. E.; Tan, BoonFei; Thompson, Janelle R.

2017-05-02

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected super-critical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO 2- water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four membersmore » of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. In conclusion, the existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling.« less

Transport of Carbon Tetrachloride in a Fractured Vadose Zone due to Atmospheric Pressure Fluctuations, Diffusion, and Vapor Density

NASA Astrophysics Data System (ADS)

McCray, J. E.; Downs, W.; Falta, R. W.; Housley, T.

2005-12-01

DNAPL sources of carbon tetrachloride (CT) vapors are of interest at the Radioactive Waste Management Complex (RWMC) at the Idaho National Engineering and Environmental Laboratory (INEEL). The site is underlain by thick fractured basalt that includes sedimentary interbeds, each are a few meters thick. Daily atmospheric pressure fluctuations serve as driving forces for CT vapor transport in the subsurface. Other important transport processes for vapor movement include gas-phase diffusion and density-driven transport. The objective of this research is to investigate the influence and relative importance of these processes on gaseous transport of CT. Gas pressure and vapor concentration measurements were conducted at various depths in two wells. A numerical multiphase flow model (TOUGH2), calibrated to field pressure data, is used to conduct sensitivity analyses to elucidate the importance of the different transport mechanisms. Results show that the basalt is highly permeable to vertical air flow. The pressure dampening occurs mainly in the sedimentary interbeds. Model-calibrated permeability values for the interbeds are similar to those obtained in a study by the U.S. Geological Survey for shallow sediments, and an order of magnitude higher than column-scale values obtained by previous studies conducted by INEEL scientists. The transport simulations indicate that considering the effect of barometric pressure changes is critical to simulating transport of pollutants in the vadose zone above the DNAPL source. Predicted concentrations can be orders of magnitude smaller than actual concentrations if the effect is not considered. Below the DNAPL vapor source, accounting for density and diffusion alone would yield acceptable results provided that a 20% error in concentrations are acceptable, and that simulating concentrations trends (and not actual concentrations) is the primary goal.

Integrated Coupling of Surface and Subsurface Flow with HYDRUS-2D

NASA Astrophysics Data System (ADS)

Hartmann, Anne; Šimůnek, Jirka; Wöhling, Thomas; Schütze, Niels

2016-04-01

Describing interactions between surface and subsurface flow processes is important to adequately define water flow in natural systems. Since overland flow generation is highly influenced by rainfall and infiltration, both highly spatially heterogeneous processes, overland flow is unsteady and varies spatially. The prediction of overland flow needs to include an appropriate description of the interactions between the surface and subsurface flow. Coupling surface and subsurface water flow is a challenging task. Different approaches have been developed during the last few years, each having its own advantages and disadvantages. A new approach by Weill et al. (2009) to couple overland flow and subsurface flow based on a generalized Richards equation was implemented into the well-known subsurface flow model HYDRUS-2D (Šimůnek et al., 2011). This approach utilizes the one-dimensional diffusion wave equation to model overland flow. The diffusion wave model is integrated in HYDRUS-2D by replacing the terms of the Richards equation in a pre-defined runoff layer by terms defining the diffusion wave equation. Using this approach, pressure and flux continuity along the interface between both flow domains is provided. This direct coupling approach provides a strong coupling of both systems based on the definition of a single global system matrix to numerically solve the coupled flow problem. The advantage of the direct coupling approach, compared to the loosely coupled approach, is supposed to be a higher robustness, when many convergence problems can be avoided (Takizawa et al., 2014). The HYDRUS-2D implementation was verified using a) different test cases, including a direct comparison with the results of Weill et al. (2009), b) an analytical solution of the kinematic wave equation, and c) the results of a benchmark test of Maxwell et al. (2014), that included several known coupled surface subsurface flow models. Additionally, a sensitivity analysis evaluating the effects of various model parameters on simulated overland flow (while considering or neglecting the effects of subsurface flow) was carried out to verify the applicability of the model to different problems. The model produced reasonable results in describing the diffusion wave approximation and its interactions with subsurface flow processes. The model could handle coupled surface-subsurface processes for conditions involving runoff generated by infiltration excess, saturation excess, or run-on, as well as a combination of these runoff generating processes. Several standard features of the HYDRUS 2D model, such as root water uptake and evaporation from the soil surface, as well as evaporation from runoff layer, can still be considered by the new model. The code required relatively small time steps when overland flow was active, resulting in long simulation times, and sometimes produced poor mass balance. The model nevertheless showed potential to be a useful tool for addressing various issues related to irrigation research and to natural generation of overland flow at the hillslope scale. Maxwell, R., Putti, M., Meyerhoff, S., Delf, J., Ferguson, I., Ivanov, V., Kim, J., Kolditz, O., Kollet, S., Kumar, M., Lopez, S., Niu, J., Paniconi, C., Park, Y.-J., Phanikumar, M., Shen, C., Sudicky, E., and Sulis, M. (2014). Surface-subsurface model intercomparison: A first set of benchmark results to diagnose integrated hydrology and feedbacks. Water Resourc. Res., 50:1531-1549. Šimůnek, J., van Genuchten, M. T., and Šejna, M. (2011). The HYDRUS Software Package for Simulating Two- and Three-Dimensional Movement of Water, Heat, and Multiple Solutes in Variably-Saturated Media. Technical Manual, Version 2.0, PC Progress, Prague, Czech Republic. Takizawa, K., Bazilevs Y., Tezduyar, T. E., Long, C.C., Marsden, A. L. and Schjodt.K., Patient-Specific Cardiovascular Fluid Mechanics Analysis with the ST and ALE-VMS Method in Idelsohn, S. R. (2014). Numerical Simulations of Coupled Problems in Engineering. Springer. Weill, S., Mouche, E., and Patin, J. (2009). A generalized Richards equation for surface/subsurface flow modelling. Journal of Hydrology, 366:9-20.

An Isopycnal Box Model with predictive deep-ocean structure for biogeochemical cycling applications

NASA Astrophysics Data System (ADS)

Goodwin, Philip

2012-07-01

To simulate global ocean biogeochemical tracer budgets a model must accurately determine both the volume and surface origins of each water-mass. Water-mass volumes are dynamically linked to the ocean circulation in General Circulation Models, but at the cost of high computational load. In computationally efficient Box Models the water-mass volumes are simply prescribed and do not vary when the circulation transport rates or water mass densities are perturbed. A new computationally efficient Isopycnal Box Model is presented in which the sub-surface box volumes are internally calculated from the prescribed circulation using a diffusive conceptual model of the thermocline, in which upwelling of cold dense water is balanced by a downward diffusion of heat. The volumes of the sub-surface boxes are set so that the density stratification satisfies an assumed link between diapycnal diffusivity, κd, and buoyancy frequency, N: κd = c/(Nα), where c and α are user prescribed parameters. In contrast to conventional Box Models, the volumes of the sub-surface ocean boxes in the Isopycnal Box Model are dynamically linked to circulation, and automatically respond to circulation perturbations. This dynamical link allows an important facet of ocean biogeochemical cycling to be simulated in a highly computationally efficient model framework.

The Importance of pH, Oxygen, and Bitumen on the Oxidation and Precipitation of Fe(III)-(oxy)hydroxides during Hydraulic Fracturing of Oil/Gas Shales

NASA Astrophysics Data System (ADS)

Jew, A. D.; Dustin, M. K.; Harrison, A. L.; Joe-Wong, C. M.; Thomas, D.; Maher, K.; Brown, G. E.; Bargar, J.

2016-12-01

Due to the rapid growth of hydraulic fracturing in the United States, understanding the cause for the rapid production drop off of new wells over the initial months of production is paramount. One possibility for the production decrease is pore occlusion caused by the oxidation of Fe(II)-bearing phases resulting in Fe(III) precipitates. To understand the release and fate of Fe in the shale systems, we reacted synthesized fracture fluid at 80oC with shale from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.). A variety of wet chemical and synchrotron-based techniques (XRF mapping and x-ray absorption spectroscopy) were used to understand Fe release and solid phase Fe speciation. Solution pH was found to be the greatest factor for Fe release. Carbonate-poor Barnett and Marcellus shale showed rapid Fe release into solution followed by a plateau or significant drop in Fe concentrations indicating mineral precipitation. Conversely, in high carbonate shales, Eagle Ford and Green River, no Fe was detected in solution indicating fast Fe oxidation and precipitation. For all shale samples, bulk Fe EXAFS data show that a significant amount of Fe in the shales is bound directly to organic carbon. Throughout the course of the experiments inorganic Fe(II) phases (primarily pyrite) reacted while Fe(II) bound to C showed no indication of reaction. On the micron scale, XRF mapping coupled with μ-XANES spectroscopy showed that at pH < 4.0, Fe(III) bearing phases precipitated as diffuse surface precipitates of ferrihydrite, goethite, and magnetite away from Fe(II) point sources. In near circum-neutral pH systems, Fe(III)-bearing phases (goethite and hematite) form large particles 10's of μm's in diameter near Fe(II) point sources. Idealized systems containing synthesized fracturing fluid, dissolved ferrous chloride, and bitumen showed that bitumen released during reaction with fracturing fluids is capable of oxidizing Fe(II) to Fe(III) at pH's 2.0 and 7.0. This indicates that bitumen can play a large role in Fe oxidation and speciation in the subsurface. This work shows that shale mineralogy has a significant impact on the morphology and phases of Fe(III) precipitates in the subsurface which in turn can significantly impact subsurface solution flow.

SORPTION OF VOLATILE ORGANIC SOLVENTS FROM AQUEOUS SOLUTION ONTO SUBSURFACE SOLIDS

EPA Science Inventory

Sorption isotherms for tetrachloroethene on low-carbon subsurface core samples were linear to equilibrium solution concentrations of 2 mg L−1. Concentrations above this value produced pronounced curvature in the sorption isotherms. Sorption of tetrachloroethene, benzene, trichlor...

2500 high-quality genomes reveal that the biogeochemical cycles of C, N, S and H are cross-linked by metabolic handoffs in the terrestrial subsurface

NASA Astrophysics Data System (ADS)

Anantharaman, K.; Brown, C. T.; Hug, L. A.; Sharon, I.; Castelle, C. J.; Shelton, A.; Bonet, B.; Probst, A. J.; Thomas, B. C.; Singh, A.; Wilkins, M.; Williams, K. H.; Tringe, S. G.; Beller, H. R.; Brodie, E.; Hubbard, S. S.; Banfield, J. F.

2015-12-01

Microorganisms drive the transformations of carbon compounds in the terrestrial subsurface, a key reservoir of carbon on earth, and impact other linked biogeochemical cycles. Our current knowledge of the microbial ecology in this environment is primarily based on 16S rRNA gene sequences that paint a biased picture of microbial community composition and provide no reliable information on microbial metabolism. Consequently, little is known about the identity and metabolic roles of the uncultivated microbial majority in the subsurface. In turn, this lack of understanding of the microbial processes that impact the turnover of carbon in the subsurface has restricted the scope and ability of biogeochemical models to capture key aspects of the carbon cycle. In this study, we used a culture-independent, genome-resolved metagenomic approach to decipher the metabolic capabilities of microorganisms in an aquifer adjacent to the Colorado River, near Rifle, CO, USA. We sequenced groundwater and sediment samples collected across fifteen different geochemical regimes. Sequence assembly, binning and manual curation resulted in the recovery of 2,542 high-quality genomes, 27 of which are complete. These genomes represent 1,300 non-redundant organisms comprising both abundant and rare community members. Phylogenetic analyses involving ribosomal proteins and 16S rRNA genes revealed the presence of up to 34 new phyla that were hitherto unknown. Less than 11% of all genomes belonged to the 4 most commonly represented phyla that constitute 93% of all currently available genomes. Genome-specific analyses of metabolic potential revealed the co-occurrence of important functional traits such as carbon fixation, nitrogen fixation and use of electron donors and electron acceptors. Finally, we predict that multiple organisms are often required to complete redox pathways through a complex network of metabolic handoffs that extensively cross-link subsurface biogeochemical cycles.

An Evaluation of Subsurface Microbial Activity Conditional to Subsurface Temperature, Porosity, and Permeability at North American Carbon Sequestration Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, B.; Mordensky, S.; Verba, Circe

Several nations, including the United States, recognize global climate change as a force transforming the global ecosphere. Carbon dioxide (CO 2) is a greenhouse gas that contributes to the evolving climate. Reduction of atmospheric CO 2 levels is a goal for many nations and carbon sequestration which traps CO 2 in the Earth’s subsurface is one method to reduce atmospheric CO 2 levels. Among the variables that must be considered in developing this technology to a national scale is microbial activity. Microbial activity or biomass can change rock permeability, alter artificial seals around boreholes, and play a key role inmore » biogeochemistry and accordingly may determine how CO 2 is sequestered underground. Certain physical parameters of a reservoir found in literature (e.g., temperature, porosity, and permeability) may indicate whether a reservoir can host microbial communities. In order to estimate which subsurface formations may host microbes, this report examines the subsurface temperature, porosity, and permeability of underground rock formations that have high potential to be targeted for CO 2 sequestration. Of the 268 North American wellbore locations from the National Carbon Sequestration Database (NATCARB; National Energy and Technology Laboratory, 2015) and 35 sites from Nelson and Kibler (2003), 96 sequestration sites contain temperature data. Of these 96 sites, 36 sites have temperatures that would be favorable for microbial survival, 48 sites have mixed conditions for supporting microbial populations, and 11 sites would appear to be unfavorable to support microbial populations. Future studies of microbe viability would benefit from a larger database with more formation parameters (e.g. mineralogy, structure, and groundwater chemistry), which would help to increase understanding of where CO 2 sequestration could be most efficiently implemented.« less

Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

USGS Publications Warehouse

Molins, S.; Mayer, K.U.

2007-01-01

The two‐way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate‐rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

Impact of Moisture Content and Grain Size on Hydrocarbon Diffusion in Porous Media

NASA Astrophysics Data System (ADS)

McLain, A. A.; Ho, C. K.

2001-12-01

Diffusion of hydrocarbon vapors in porous media can play an important role in our ability to characterize subsurface contaminants such as trichloroethylene (TCE). For example, traditional monitoring methods often rely on direct sampling of contaminated soils or vapor. These samples may be influenced by the diffusion of vapors away from the contaminant source term, such as non-aqueous-phase TCE liquid. In addition, diffusion of hydrocarbon vapors can also impact the migration and dispersion of the contaminant in the subsurface. Therefore, understanding the diffusion rates and vapor transport processes of hydrocarbons in variably-saturated, heterogeneous porous media will assist in the characterization and detection of these subsurface contaminants. The purpose of this study was to investigate the impact of soil heterogeneity and water-moisture content on the diffusion processes for TCE. A one-dimensional column experiment was used to monitor the rates of vapor diffusion through sand. Experiments were performed with different average water-moisture contents and different grain sizes. On one end of the column, a reservoir cap is used to encase the TCE, providing a constant vapor boundary condition while sealing the end. The other end of the column contains a novel microchemical sensor. The sensor employs a polymer-absorption resistor (chemiresistor) that reversibly swells and increases in resistance when exposed to hydrocarbons. Once calibrated, the chemiresistors can be used to passively monitor vapor concentrations. This unique method allows the detection of in-situ vapor concentrations without disturbing the local environment. Results are presented in the form of vapor-concentration breakthrough curves as detected by the sensor. The shape of the breakthrough curve is dependent on several key parameters, including the length of the column and parameters (e.g., water-moisture content and grain-size) that affect the effective diffusion coefficient of TCE in air. Comparisons are made between theoretical and observed breakthrough curves to evaluate the diffusion of TCE and other relevant physical processes (e.g., air-water partitioning of TCE). The relative impact of water-moisture content and grain size on the diffusion of TCE vapor in porous media is also addressed. The authors thank Bob Hughes, who developed the chemiresistor sensors, and Chad Davis, who assisted with the calibrations. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL85000.

Late diagenetic indicators of buried oil and gas

USGS Publications Warehouse

Donovan, Terrence J.; Dalziel, Mary C.

1977-01-01

At least three hydrocarbon seepage mechanisms are interpreted to operate over oil and gas fields. These are: (1) effusion ofh ydrocarbons through inadequate caprocks and along faults and fractures, (2) low-molecular-weight hydrocarbons dissolved in water moving vertically through capping shales as a result of a hydrodynamic or chemical potential drive, and (3) diffusion of gases dissolved in water. Combinations of these mechanisms may also occur. Seeping hydrocarbons are oxidized near the earth's surface, and the resulting carbon dioxide reacts with water producing bicarbonate ions, which combine with calcium and magnesium dissolved in ground waters to yield isotopically distinctive pore-filling carbonate cements and surface rocks. The passage of hydrocarbons and associated compounds such as hydrogen sulfide through surface rocks causes a reducing environment and consequent reduction, mobilization, and loss of iron from iron-bearing minerals commonly resulting in a discoloration. Other metals such as manganese are also mobilized and redistributed. These changes in the physical and chemical properties of surface rocks correlate with the subsurface distribution of petroleum, and potentially can be detected from both airborne and spaceborne platforms.

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir

PubMed Central

Freedman, Adam J.E.; Tan, BoonFei

2017-01-01

Summary Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected supercritical (sc) CO2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO2 reservoirs, which serve as analogs for the long‐term fate of sequestered scCO2, harbor a ‘deep carbonated biosphere’ with carbon cycling potential. We sampled subsurface fluids from scCO2‐water separators at a natural scCO2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four members of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO2 and N2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. The existence of a microbial ecosystem associated with the McElmo Dome scCO2 reservoir indicates that potential impacts of the deep biosphere on CO2 fate and transport should be taken into consideration as a component of GCS planning and modelling. PMID:28229521

Subsurface flow pathway dynamics in the active layer of coupled permafrost-hydrogeological systems under seasonal and annual temperature variability.

NASA Astrophysics Data System (ADS)

Frampton, Andrew

2017-04-01

There is a need for improved understanding of the mechanisms controlling subsurface solute transport in the active layer in order to better understand permafrost-hydrological-carbon feedbacks, in particular with regards to how dissolved carbon is transported in coupled surface and subsurface terrestrial arctic water systems under climate change. Studying solute transport in arctic systems is also relevant in the context of anthropogenic pollution which may increase due to increased activity in cold region environments. In this contribution subsurface solute transport subject to ground surface warming causing permafrost thaw and active layer change is studied using a physically based model of coupled cryotic and hydrogeological flow processes combined with a particle tracking method. Changes in subsurface water flows and solute transport travel times are analysed for different modelled geological configurations during a 100-year warming period. Results show that for all simulated cases, the minimum and mean travel times increase non-linearly with warming irrespective of geological configuration and heterogeneity structure. The timing of the start of increase in travel time depends on heterogeneity structure, combined with the rate of permafrost degradation that also depends on material thermal and hydrogeological properties. These travel time changes are shown to depend on combined warming effects of increase in pathway length due to deepening of the active layer, reduced transport velocities due to a shift from horizontal saturated groundwater flow near the surface to vertical water percolation deeper into the subsurface, and pathway length increase and temporary immobilization caused by cryosuction-induced seasonal freeze cycles. The impact these change mechanisms have on solute and dissolved substance transport is further analysed by integrating pathway analysis with a Lagrangian approach, incorporating considerations for both dissolved organic and inorganic carbon releases. Further model development challenges are also highlighted and discussed, including coupling between subsurface and surface runoff, soil deformations, as well as site applications and larger system scales.

Contents and composition of organic matter in subsurface soils affected by land use and soil mineralogy

NASA Astrophysics Data System (ADS)

Ellerbrock, Ruth H.; Kaiser, Michael

2010-05-01

Land use and mineralogy affect the ability of surface as well as subsurface soils to sequester organic carbon and their contribution to mitigate the greenhouse effect. This study aimed to investigate the long-term impact of land use (i.e., arable and forest) and soil mineralogy on contents and composition of soil organic matter (SOM) from subsurface soils. Seven soils different in mineralogy (Albic and Haplic Luvisol, Colluvic and Haplic Regosol, Haplic and Vertic Cambisol, Haplic Stagnosol) were selected within Germany. Soil samples were taken from forest and adjacent arable sites. First, particulate and water soluble organic matter were separated from the subsurface soil samples. From the remaining solid residues the OM(PY) fractions were separated, analyzed for its OC content (OCPY) and characterized by FTIR spectroscopy. For the arable subsurface soils multiple regression analyses indicate significant positive relationships between the soil organic carbon contents and the contents of i) exchangeable Ca and oxalate soluble Fe, and Alox contents. Further for the neutral arable subsurface soils the contents OCPY weighted by its C=O contents were found to be related to the contents of Ca indicating interactions between OM(PY) and Ca cations. For the forest subsurface soils (pH <5) the OCPY contents were positively related with the contents of Na-pyrophosphate soluble Fe and Al. For the acidic forest subsurface soils such findings indicate interactions between OM(PY) and Fe3+ and Al3+ cations. The effects of land use and soil mineralogy on contents and composition of SOM and OM(PY) will be discussed.

Interplay between microorganisms and geochemistry in geological carbon storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Altman, Susan J.; Kirk, Matthew Fletcher; Santillan, Eugenio-Felipe U.

Researchers at the Center for Frontiers of Subsurface Energy Security (CFSES) have conducted laboratory and modeling studies to better understand the interplay between microorganisms and geochemistry for geological carbon storage (GCS). We provide evidence of microorganisms adapting to high pressure CO 2 conditions and identify factors that may influence survival of cells to CO 2 stress. Factors that influenced the ability of cells to survive exposure to high-pressure CO 2 in our experiments include mineralogy, the permeability of cell walls and/or membranes, intracellular buffering capacity, and whether cells live planktonically or within biofilm. Column experiments show that, following exposure tomore » acidic water, biomass can remain intact in porous media and continue to alter hydraulic conductivity. Our research also shows that geochemical changes triggered by CO 2 injection can alter energy available to populations of subsurface anaerobes and that microbial feedbacks on this effect can influence carbon storage. Our research documents the impact of CO 2 on microorganisms and in turn, how subsurface microorganisms can influence GCS. Furthermore, we conclude that microbial presence and activities can have important implications for carbon storage and that microorganisms should not be overlooked in further GCS research.« less

Interplay between microorganisms and geochemistry in geological carbon storage

DOE PAGES

Altman, Susan J.; Kirk, Matthew Fletcher; Santillan, Eugenio-Felipe U.; ...

2016-02-28

Researchers at the Center for Frontiers of Subsurface Energy Security (CFSES) have conducted laboratory and modeling studies to better understand the interplay between microorganisms and geochemistry for geological carbon storage (GCS). We provide evidence of microorganisms adapting to high pressure CO 2 conditions and identify factors that may influence survival of cells to CO 2 stress. Factors that influenced the ability of cells to survive exposure to high-pressure CO 2 in our experiments include mineralogy, the permeability of cell walls and/or membranes, intracellular buffering capacity, and whether cells live planktonically or within biofilm. Column experiments show that, following exposure tomore » acidic water, biomass can remain intact in porous media and continue to alter hydraulic conductivity. Our research also shows that geochemical changes triggered by CO 2 injection can alter energy available to populations of subsurface anaerobes and that microbial feedbacks on this effect can influence carbon storage. Our research documents the impact of CO 2 on microorganisms and in turn, how subsurface microorganisms can influence GCS. Furthermore, we conclude that microbial presence and activities can have important implications for carbon storage and that microorganisms should not be overlooked in further GCS research.« less

Transport diffusion in deformed carbon nanotubes

NASA Astrophysics Data System (ADS)

Feng, Jiamei; Chen, Peirong; Zheng, Dongqin; Zhong, Weirong

2018-03-01

Using non-equilibrium molecular dynamics and Monte Carlo methods, we have studied the transport diffusion of gas in deformed carbon nanotubes. Perfect carbon nanotube and various deformed carbon nanotubes are modeled as transport channels. It is found that the transport diffusion coefficient of gas does not change in twisted carbon nanotubes, but changes in XY-distortion, Z-distortion and local defect carbon nanotubes comparing with that of the perfect carbon nanotube. Furthermore, the change of transport diffusion coefficient is found to be associated with the deformation factor. The relationship between transport diffusion coefficient and temperature is also discussed in this paper. Our results may contribute to understanding the mechanism of molecular transport in nano-channel.

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 STORAGE

EPA Science Inventory

The paper discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of the...

KINETIC CONTROL OF OXIDATION STATE AT THERMODYNAMICALLY BUFFERED POTENTIALS IN SUBSURFACE WATERS

EPA Science Inventory

Dissolved oxygen (DO) and organic carbon (Corg) are among the highest- and lowest-potential reactants, respectively, of redox couples in natural waters. When DO and Corg are present in subsurface settings, other couples are drawn toward potentials imposed by them, generating a b...

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 SEQUESTRATION

EPA Science Inventory

The chapter discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of t...

Mineral storage of CO2/H2S gas mixture injection in basaltic rocks

NASA Astrophysics Data System (ADS)

Clark, D. E.; Gunnarsson, I.; Aradottir, E. S.; Oelkers, E. H.; Sigfússon, B.; Snæbjörnsdottír, S. Ó.; Matter, J. M.; Stute, M.; Júlíusson, B. M.; Gíslason, S. R.

2017-12-01

Carbon capture and storage is one solution to reducing CO2 emissions in the atmosphere. The long-term geological storage of buoyant supercritical CO2 requires high integrity cap rock. Some of the risk associated with CO2 buoyancy can be overcome by dissolving CO2 into water during its injection, thus eliminating its buoyancy. This enables injection into fractured rocks, such as basaltic rocks along oceanic ridges and on continents. Basaltic rocks are rich in divalent cations, Ca2+, Mg2+ and Fe2+, which react with CO2 dissolved in water to form stable carbonate minerals. This possibility has been successfully tested as a part of the CarbFix CO2storage pilot project at the Hellisheiði geothermal power plant in Iceland, where they have shown mineralization occurs in less than two years [1, 2]. Reykjavik Energy and the CarbFix group has been injecting a mixture of CO2 and H2S at 750 m depth and 240-250°C since June 2014; by 1 January 2016, 6290 tons of CO2 and 3530 tons of H2S had been injected. Once in the geothermal reservoir, the heat exchange and sufficient dissolution of the host rock neutralizes the gas-charged water and saturates the formation water respecting carbonate and sulfur minerals. A thermally stable inert tracer was also mixed into the stream to monitor the subsurface transport and to assess the degree of subsurface carbonation and sulfide precipitation [3]. Water and gas samples have been continuously collected from three monitoring wells and geochemically analyzed. Based on the results, mineral saturation stages have been defined. These results and tracer mass balance calculations are used to evaluate the rate and magnitude of CO2 and H2S mineralization in the subsurface, with indications that mineralization of carbon and sulfur occurs within months. [1] Gunnsarsson, I., et al. (2017). Rapid and cost-effective capture and subsurface mineral storage of carbon and sulfur. Manuscript submitted for publication. [2] Matter, J., et al. (2016). Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions. Science 352 (6291), 1312-1314. [3] Snæbjörnsdottír, S.O., et al. (2017). The chemistry and saturation states of subsurface fluids during the in-situ mineralisation of CO2 and H2S at the CarbFix site in SW-Iceland. International Journal of Greenhouse Gas Control 58, 87-102.

Macrosegregation in aluminum alloy ingot cast by the semicontinuous direct chill method

NASA Technical Reports Server (NTRS)

Yu, H.; Granger, D. A.

1984-01-01

A theoretical model of the semicontinuous DC casting method is developed to predict the positive segregation observed at the subsurface and the negative segregation commonly found at the center of large commercial-size aluminum alloy ingot. Qualitative analysis of commercial-size aluminum alloy semicontinuous cast direct chill (DC) ingot is carried out. In the analysis, both positive segregation in the ingot subsurface and negative segregation at the center of the ingot are examined. Ingot subsurface macrosegregation is investigated by considering steady state casting of a circular cross-section binary alloy ingot. Nonequilibrium solidification is assumed with no solid diffusion, constant equilibrium partition ratio, and constant solid density.

National assessment of geologic carbon dioxide storage resources: methodology implementation

USGS Publications Warehouse

Blondes, Madalyn S.; Brennan, Sean T.; Merrill, Matthew D.; Buursink, Marc L.; Warwick, Peter D.; Cahan, Steven M.; Corum, Margo D.; Cook, Troy A.; Craddock, William H.; DeVera, Christina A.; Drake II, Ronald M.; Drew, Lawrence J.; Freeman, P.A.; Lohr, Celeste D.; Olea, Ricardo A.; Roberts-Ashby, Tina L.; Slucher, Ernie R.; Varela, Brian A.

2013-01-01

In response to the 2007 Energy Independence and Security Act, the U.S. Geological Survey (USGS) conducted a national assessment of potential geologic storage resources for carbon dioxide (CO2). Storage of CO2 in subsurface saline formations is one important method to reduce greenhouse gas emissions and curb global climate change. This report provides updates and implementation details of the assessment methodology of Brennan and others (2010, http://pubs.usgs.gov/of/2010/1127/) and describes the probabilistic model used to calculate potential storage resources in subsurface saline formations.

Concentration-Discharge Relationships, Nested Reaction Fronts, and the Balance of Oxidative and Acid-Base Weathering Fluxes in an Alpine Catchment, East River, Colorado

NASA Astrophysics Data System (ADS)

Winnick, M.; Carroll, R. W. H.; Williams, K. H.; Maxwell, R. M.; Maher, K.

2016-12-01

Although important for solute production and transport, the varied interactions between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the headwaters of the East River, CO, a high-elevation shale-dominated catchment system in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with well-defined clockwise hysteresis, indicating the mobilization and depletion of DOC in the upper soil horizons and highlighting the importance of shallow flowpaths through the snowmelt period. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both carbonic acid and sulfuric acid derived from oxidation of pyrite in the shale bedrock. Sulfuric acid weathering in the deep subsurface dominates during base flow conditions when waters have infiltrated below the hypothesized pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during the snowmelt period as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This increase in CO2(aq) at the expense of HCO3- results in outgassing of CO2 when waters equilibrate to surface conditions, and reduces the export of carbon and alkalinity from the East River by roughly 33% annually. Future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering therefore have the capacity to substantially alter the cycling of carbon in the East River catchment. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

Snowmelt controls on concentration-discharge relationships and the balance of oxidative and acid-base weathering fluxes in an alpine catchment, East River, Colorado: ACID-BASE VERSUS OXIDATIVE WEATHERING FLUXES

DOE PAGES

Winnick, Matthew J.; Carroll, Rosemary W. H.; Williams, Kenneth H.; ...

2017-03-01

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flowpaths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyritemore » oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during baseflow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flowpaths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO 2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. In conclusion, future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.« less

Stochastic theory of photon flow in homogeneous and heterogeneous anisotropic biological and artificial material

NASA Astrophysics Data System (ADS)

Miller, Steven D.

1995-05-01

Standard Monte Carlo methods used in photon diffusion score absorbed photons or statistical weight deposited within voxels comprising a mesh. An alternative approach to a stochastic description is considered for rapid surface flux calculations and finite medias. Matrix elements are assigned to a spatial lattice whose function is to score vector intersections of scattered photons making transitions into either the forward or back solid angle half spaces. These complete matrix elements can be related to the directional fluxes within the lattice space. This model differentiates between ballistic, quasi-ballistic, and highly diffuse photon contributions, and effectively models the subsurface generation of a scattered light flux from a ballistic source. The connection between a path integral and diffusion is illustrated. Flux perturbations can be effectively illustrated for tissue-tumor-tissue and for 3 layer systems with strong absorption in one or more layers. For conditions where the diffusion theory has difficulties such as strong absorption, highly collimated sources, small finite volumes, and subsurface regions, the computation time of the algorithm is rapid with good accuracy and compliments other description of photon diffusion. The model has the potential to do computations relevant to photodynamic therapy (PDT) and analysis of laser beam interaction with tissues.

Effects of carbon on phosphorus diffusion in SiGe:C and the implications on phosphorus diffusion mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yiheng; Xia, Guangrui; Yasuda, Hiroshi

2014-10-14

The use of carbon (C) in SiGe base layers is an important approach to control the base layer dopant phosphorus (P) diffusion and thus enhance PNP heterojunction bipolar transistor (HBT) performance. This work quantitatively investigated the carbon impacts on P diffusion in Si₀.₈₂Ge₀.₁₈:C and Si:C under rapid thermal anneal conditions. The carbon molar fraction is up to 0.32%. The results showed that the carbon retardation effect on P diffusion is less effective for Si₀.₈₂Ge₀.₁₈:C than for Si:C. In Si₀.₈₂Ge₀.₁₈:C, there is an optimum carbon content at around 0.05% to 0.1%, beyond which more carbon incorporation does not retard P diffusionmore » any more. This behavior is different from the P diffusion behavior in Si:C and the B in Si:C and low Ge SiGe:C, which can be explained by the decreased interstitial-mediated diffusion fraction f{sub I}{sup P,SiGe} to 95% as Ge content increases to 18%. Empirical models were established to calculate the time-averaged point defect concentrations and effective diffusivities as a function of carbon and was shown to agree with previous studies on boron, phosphorus, arsenic and antimony diffusion with carbon.« less

Modeling of Near-Surface Leakage and Seepage of CO2 for Risk Characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oldenburg, Curtis M.; Unger, Andre A.J.

2004-02-18

The injection of carbon dioxide (CO2) into deep geologic carbon sequestration sites entails risk that CO2 will leak away from the primary storage formation and migrate upwards to the unsaturated zone from which it can seep out of the ground. We have developed a coupled modeling framework called T2CA for simulating CO2 leakage and seepage in the subsurface and in the atmospheric surface layer. The results of model simulations can be used to calculate the two key health, safety, and environmental (HSE) risk drivers, namely CO2 seepage flux and nearsurface CO2 concentrations. Sensitivity studies for a subsurface system with amore » thick unsaturated zone show limited leakage attenuation resulting in correspondingly large CO2 concentrations in the shallow subsurface. Large CO2 concentrations in the shallow subsurface present a risk to plant and tree roots, and to humans and other animals in subsurface structures such as basements or utility vaults. Whereas CO2 concentrations in the subsurface can be high, surfacelayer winds reduce CO2 concentrations to low levels for the fluxes investigated. We recommend more verification and case studies be carried out with T2CA, along with the development of extensions to handle additional scenarios such as calm conditions, topographic effects, and catastrophic surface-layer discharge events.« less

SUBSURFACE PROPERTY RIGHTS: IMPLICATIONS FOR GEOLOGIC CO2 SEQUESTRATION (PRESENTATION)

EPA Science Inventory

The paper discusses subsurface property rights as they apply to geologic sequestration (GS) of carbon dioxide (CO2). GS projects inject captured CO2 into deep (greater than ~1 km) geologic formations for the explicit purpose of avoiding atmospheric emission of CO2. Because of the...

An important atomic process in the CVD growth of graphene: Sinking and up-floating of carbon atom on copper surface

NASA Astrophysics Data System (ADS)

Li, Yingfeng; Li, Meicheng; Gu, TianSheng; Bai, Fan; Yu, Yue; Trevor, Mwenya; Yu, Yangxin

2013-11-01

By density functional theory (DFT) calculations, the early stages of the growth of graphene on copper (1 1 1) surface are investigated. At the very first time of graphene growth, the carbon atom sinks into subsurface. As more carbon atoms are adsorbed nearby the site, the sunken carbon atom will spontaneously form a dimer with one of the newly adsorbed carbon atoms, and the formed dimer will up-float on the top of the surface. We emphasize the role of the co-operative relaxation of the co-adsorbed carbon atoms in facilitating the sinking and up-floating of carbon atoms. In detail: when two carbon atoms are co-adsorbed, their co-operative relaxation will result in different carbon-copper interactions for the co-adsorbed carbon atoms. This difference facilitates the sinking of a single carbon atom into the subsurface. As a third carbon atom is co-adsorbed nearby, it draws the sunken carbon atom on top of the surface, forming a dimer. Co-operative relaxations of the surface involving all adsorbed carbon atoms and their copper neighbors facilitate these sinking and up-floating processes. This investigation is helpful for the deeper understanding of graphene synthesis and the choosing of optimal carbon sources or process.

ENVIRONMENTAL RESEARCH BRIEF: CHARACTERIZATION OF ORGANIC MATTER IN SOIL AND AQUIFER SOLIDS

EPA Science Inventory

The focus of this work was the evaluation of analytical methods to determine and characterize fractions of subsurface organic matter. Major fractions of total organic carbon (TOC) include: particulate organic carbon (POC) in aquifer material, dissolved organic carbon (DOC) and ...

Detection of Subsurface Material Separation in Shuttle Orbiter Slip-Side Joggle Region of the Wing Leading Edge using Infrared Imaging Data from Arc Jet Tests

NASA Technical Reports Server (NTRS)

Daryabeigi, Kamran; Walker, Sandra P.

2009-01-01

The objective of the present study was to determine whether infrared imaging (IR) surface temperature data obtained during arc-jet tests of Space Shuttle Orbiter s reinforced carbon-carbon (RCC) wing leading edge panel slip-side joggle region could be used to detect presence of subsurface material separation, and if so, to determine when separation occurs during the simulated entry profile. Recent thermostructural studies have indicated thermally induced interlaminar normal stress concentrations at the substrate/coating interface in the curved joggle region can result in local subsurface material separation, with the separation predicted to occur during approach to peak heating during reentry. The present study was an attempt to determine experimentally when subsurface material separations occur. A simplified thermal model of a flat RCC panel with subsurface material separation was developed and used to infer general surface temperature trends due to the presence of subsurface material separation. IR data from previously conducted arc-jet tests on three test specimens were analyzed: one without subsurface material separation either pre or post test, one with pre test separation, and one with separation developing during test. The simplified thermal model trend predictions along with comparison of experimental IR data of the three test specimens were used to successfully infer material separation from the arc-jet test data. Furthermore, for the test specimen that had developed subsurface material separation during the arc-jet tests, the initiation of separation appeared to occur during the ramp up to the peak heating condition, where test specimen temperature went from 2500 to 2800 F.

Subsurface Oxygen in Oxide-Derived Copper Electrocatalysts for Carbon Dioxide Reduction

DOE PAGES

Eilert, Andre; Cavalca, Filippo; Roberts, F. Sloan; ...

2016-12-16

Copper electrocatalysts derived from an oxide have shown extraordinary electrochemical properties for the carbon dioxide reduction reaction (CO 2RR). Using in situ ambient pressure X-ray photoelectron spectroscopy and quasi in situ electron energy-loss spectroscopy in a transmission electron microscope, we show that there is a substantial amount of residual oxygen in nanostructured, oxide-derived copper electrocatalysts but no residual copper oxide. On the basis of these findings in combination with density functional theory simulations, we propose that residual subsurface oxygen changes the electronic structure of the catalyst and creates sites with higher carbon monoxide binding energy. If such sites are stablemore » under the strongly reducing conditions found in CO 2RR, these findings would explain the high efficiencies of oxide-derived copper in reducing carbon dioxide to multicarbon compounds such as ethylene.« less

Microbial potential for carbon and nutrient cycling in a geogenic supercritical carbon dioxide reservoir.

PubMed

Freedman, Adam J E; Tan, BoonFei; Thompson, Janelle R

2017-06-01

Microorganisms catalyze carbon cycling and biogeochemical reactions in the deep subsurface and thus may be expected to influence the fate of injected supercritical (sc) CO 2 following geological carbon sequestration (GCS). We hypothesized that natural subsurface scCO 2 reservoirs, which serve as analogs for the long-term fate of sequestered scCO 2 , harbor a 'deep carbonated biosphere' with carbon cycling potential. We sampled subsurface fluids from scCO 2 -water separators at a natural scCO 2 reservoir at McElmo Dome, Colorado for analysis of 16S rRNA gene diversity and metagenome content. Sequence annotations indicated dominance of Sulfurospirillum, Rhizobium, Desulfovibrio and four members of the Clostridiales family. Genomes extracted from metagenomes using homology and compositional approaches revealed diverse mechanisms for growth and nutrient cycling, including pathways for CO 2 and N 2 fixation, anaerobic respiration, sulfur oxidation, fermentation and potential for metabolic syntrophy. Differences in biogeochemical potential between two production well communities were consistent with differences in fluid chemical profiles, suggesting a potential link between microbial activity and geochemistry. The existence of a microbial ecosystem associated with the McElmo Dome scCO 2 reservoir indicates that potential impacts of the deep biosphere on CO 2 fate and transport should be taken into consideration as a component of GCS planning and modelling. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Kinetic Monte Carlo (kMC) simulation of carbon co-implant on pre-amorphization process.

PubMed

Park, Soonyeol; Cho, Bumgoo; Yang, Seungsu; Won, Taeyoung

2010-05-01

We report our kinetic Monte Carlo (kMC) study of the effect of carbon co-implant on the pre-amorphization implant (PAL) process. We employed BCA (Binary Collision Approximation) approach for the acquisition of the initial as-implant dopant profile and kMC method for the simulation of diffusion process during the annealing process. The simulation results implied that carbon co-implant suppresses the boron diffusion due to the recombination with interstitials. Also, we could compare the boron diffusion with carbon diffusion by calculating carbon reaction with interstitial. And we can find that boron diffusion is affected from the carbon co-implant energy by enhancing the trapping of interstitial between boron and interstitial.

Toward the existence of ultrafast diffusion paths in Cu with a gradient microstructure: Room temperature diffusion of Ni

NASA Astrophysics Data System (ADS)

Wang, Z. B.; Lu, K.; Wilde, G.; Divinski, S.

2008-09-01

Room temperature diffusion of Ni63 in Cu with a gradient microstructure prepared by surface mechanical attrition treatment (SMAT) was investigated by applying the radiotracer technique. The results reveal significant penetration of Ni into the nanostructured layer. The relevant diffusivity is higher than that along the conventional high-angle grain boundaries by about six orders of magnitude. This behavior is associated with a higher energy state of internal interfaces produced via plastic deformation. The diffusivity in the top surface layer is somewhat smaller than that in the subsurface layer. This fact is related to nanotwin formation in the former during SMAT.

Researchers Mine Information from Next-Generation Subsurface Flow Simulations

DOE PAGES

Gedenk, Eric D.

2015-12-01

A research team based at Virginia Tech University leveraged computing resources at the US Department of Energy's (DOE's) Oak Ridge National Laboratory to explore subsurface multiphase flow phenomena that can't be experimentally observed. Using the Cray XK7 Titan supercomputer at the Oak Ridge Leadership Computing Facility, the team took Micro-CT images of subsurface geologic systems and created two-phase flow simulations. The team's model development has implications for computational research pertaining to carbon sequestration, oil recovery, and contaminant transport.

Enhanced groundwater recharge rates and altered recharge sensitivity to climate variability through subsurface heterogeneity

PubMed Central

Hartmann, Andreas; Gleeson, Tom; Wagener, Thorsten

2017-01-01

Our environment is heterogeneous. In hydrological sciences, the heterogeneity of subsurface properties, such as hydraulic conductivities or porosities, exerts an important control on water balance. This notably includes groundwater recharge, which is an important variable for efficient and sustainable groundwater resources management. Current large-scale hydrological models do not adequately consider this subsurface heterogeneity. Here we show that regions with strong subsurface heterogeneity have enhanced present and future recharge rates due to a different sensitivity of recharge to climate variability compared with regions with homogeneous subsurface properties. Our study domain comprises the carbonate rock regions of Europe, Northern Africa, and the Middle East, which cover ∼25% of the total land area. We compare the simulations of two large-scale hydrological models, one of them accounting for subsurface heterogeneity. Carbonate rock regions strongly exhibit “karstification,” which is known to produce particularly strong subsurface heterogeneity. Aquifers from these regions contribute up to half of the drinking water supply for some European countries. Our results suggest that water management for these regions cannot rely on most of the presently available projections of groundwater recharge because spatially variable storages and spatial concentration of recharge result in actual recharge rates that are up to four times larger for present conditions and changes up to five times larger for potential future conditions than previously estimated. These differences in recharge rates for strongly heterogeneous regions suggest a need for groundwater management strategies that are adapted to the fast transit of water from the surface to the aquifers. PMID:28242703

Enhanced Groundwater Recharge Rates and Altered Recharge Sensitivity to Climate Variability Through Subsurface Heterogeneity

NASA Technical Reports Server (NTRS)

Hartmann, Andreas; Gleeson, Tom; Wada, Yoshihide; Wagener, Thorsten

2017-01-01

Our environment is heterogeneous. In hydrological sciences, the heterogeneity of subsurface properties, such as hydraulic conductivities or porosities, exerts an important control on water balance. This notably includes groundwater recharge, which is an important variable for efficient and sustainable groundwater resources management. Current large-scale hydrological models do not adequately consider this subsurface heterogeneity. Here we show that regions with strong subsurface heterogeneity have enhanced present and future recharge rates due to a different sensitivity of recharge to climate variability compared with regions with homogeneous subsurface properties. Our study domain comprises the carbonate rock regions of Europe, Northern Africa, and the Middle East, which cover 25 of the total land area. We compare the simulations of two large-scale hydrological models, one of them accounting for subsurface heterogeneity. Carbonate rock regions strongly exhibit karstification, which is known to produce particularly strong subsurface heterogeneity. Aquifers from these regions contribute up to half of the drinking water supply for some European countries. Our results suggest that water management for these regions cannot rely on most of the presently available projections of groundwater recharge because spatially variable storages and spatial concentration of recharge result in actual recharge rates that are up to four times larger for present conditions and changes up to five times larger for potential future conditions than previously estimated. These differences in recharge rates for strongly heterogeneous regions suggest a need for groundwater management strategies that are adapted to the fast transit of water from the surface to the aquifers.

Modelling deuterium release from tungsten after high flux high temperature deuterium plasma exposure

NASA Astrophysics Data System (ADS)

Grigorev, Petr; Matveev, Dmitry; Bakaeva, Anastasiia; Terentyev, Dmitry; Zhurkin, Evgeny E.; Van Oost, Guido; Noterdaeme, Jean-Marie

2016-12-01

Tungsten is a primary candidate for plasma facing materials for future fusion devices. An important safety concern in the design of plasma facing components is the retention of hydrogen isotopes. Available experimental data is vast and scattered, and a consistent physical model of retention of hydrogen isotopes in tungsten is still missing. In this work we propose a model of non-equilibrium hydrogen isotopes trapping under fusion relevant plasma exposure conditions. The model is coupled to a diffusion-trapping simulation tool and is used to interpret recent experiments involving high plasma flux exposures. From the computational analysis performed, it is concluded that high flux high temperature exposures (T = 1000 K, flux = 1024 D/m2/s and fluence of 1026 D/m2) result in generation of sub-surface damage and bulk diffusion, so that the retention is driven by both sub-surface plasma-induced defects (bubbles) and trapping at natural defects. On the basis of the non-equilibrium trapping model we have estimated the amount of H stored in the sub-surface region to be ∼10-5 at-1, while the bulk retention is about 4 × 10-7 at-1, calculated by assuming the sub-surface layer thickness of about 10 μm and adjusting the trap concentration to comply with the experimental results for the integral retention.

Development of a Carbon Sequestration Visualization Tool using Google Earth Pro

NASA Astrophysics Data System (ADS)

Keating, G. N.; Greene, M. K.

2008-12-01

The Big Sky Carbon Sequestration Partnership seeks to prepare organizations throughout the western United States for a possible carbon-constrained economy. Through the development of CO2 capture and subsurface sequestration technology, the Partnership is working to enable the region to cleanly utilize its abundant fossil energy resources. The intent of the Los Alamos National Laboratory Big Sky Visualization tool is to allow geochemists, geologists, geophysicists, project managers, and other project members to view, identify, and query the data collected from CO2 injection tests using a single data source platform, a mission to which Google Earth Pro is uniquely and ideally suited . The visualization framework enables fusion of data from disparate sources and allows investigators to fully explore spatial and temporal trends in CO2 fate and transport within a reservoir. 3-D subsurface wells are projected above ground in Google Earth as the KML anchor points for the presentation of various surface subsurface data. This solution is the most integrative and cost-effective possible for the variety of users in the Big Sky community.

Final Technical Report: Viral Infection of Subsurface Microorganisms and Metal/Radionuclide Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, Karrie A.; Bender, Kelly S.; Li, Yusong

Microbially mediated metabolisms have been identified as a significant factor either directly or indirectly impacting the fate and transport of heavy metal/radionuclide contaminants. To date microorganisms have been isolated from contaminated environments. Examination of annotated finished genome sequences of many of these subsurface isolates from DOE sites, revealed evidence of prior viral infection. To date the role that viruses play influencing microbial mortality and the resulting community structure which directly influences biogeochemical cycling in soils and sedimentary environments remains poorly understood. The objective of this exploratory study was to investigate the role of viral infection of subsurface bacteria and themore » formation of contaminant-bearing viral particles. This objective was approached by examining the following working hypotheses: (i) subsurface microorganisms are susceptible to viral infections by the indigenous subsurface viral community, and (ii) viral surfaces will adsorb heavy metals and radionuclides. Our results have addressed basic research needed to accomplish the BER Long Term Measure to provide sufficient scientific understanding such that DOE sites would be able to incorporate coupled physical, chemical and biological processes into decision making for environmental remediation or natural attenuation and long-term stewardship by establishing viral-microbial relationships on the subsequent fate and transport of heavy metals and radionuclides. Here we demonstrated that viruses play a significant role in microbial mortality and community structure in terrestrial subsurface sedimentary systems. The production of viral-like particles within subsurface sediments in response to biostimulation with dissolved organic carbon and a terminal electron acceptor resulted in the production of viral-like particles. Organic carbon alone did not result in significant viral production and required the addition of a terminal electron acceptor (nitrate), indicating that nutrients are not limiting viral production, but rather substrates that can be converted into energy for host metabolism. Our results also revealed that cell abundance was not correlated to the mineralization of organic carbon, but rather viruses were positively correlated with carbon mineralization. This is a result of viral-mediated cell lysis and demonstrates that viruses are sensitive indicators of microbial activity. Viruses as an indicator of microbial activity was not unique to batch culture studies as results obtained from an in situ field experiment conducted at the DOE Old Rifle Field site. This study revealed that viral abundance increased in response to the injection of oxygenated groundwater and influx of dissolved organic carbon whereas cell abundance changes were minimal. However, the extent to which viral-mediated cell lysis alters organic matter pools subsequently influencing microbial community structure and biogeochemical function remains a critical question in subsurface biogeochemical cycling. The production of significant numbers of viruses in groundwater has implications for nanoparticulate metal as well as carbon transport in groundwater. We have demonstrated that the virus surface is reactive and will adsorb heavy metals. Thus viruses can promote colloidal contaminant mobility. Interestingly, the presence of heavy metals has a positive effect on infectivity of the phage, increasing phage infection which could lead to further production of viruses. Together, the results indicate that the sorption of metals to the surface of viruses could not only contribute to nanoparticulate metal as well as carbon transport but could also enhance infectivity further contributing to cell lysis which could subsequently influence biogeochemical cycling. As more viruses infect host microbial populations the high concentration of metals would enhance infection, resulting in cell lysis, and decreasing the metabolically active host population while yielding greater numbers of viruses capable of transporting contaminats. Additional studies will be necessary to further establish the potential relationship(s) between viruses, cells, carbon, and metals/radionuclides to provide sufficient scientific understanding to incorporate coupled physical, chemical, and biological processes into agent based and reactive transport models.« less

Research Performed at NETL on the Subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

Deep below our feet, lies the unique and complex world of the subsurface. A world that is improving the lives of Americans and brimming with the potential to generate even greater benefits through NETL research. NETL research supports industry by improving resource extraction while also helping to make carbon storage safe and more effective.

Metagenomic Evidence for H2 Oxidation and H2 Production by Serpentinite-Hosted Subsurface Microbial Communities

PubMed Central

Brazelton, William J.; Nelson, Bridget; Schrenk, Matthew O.

2012-01-01

Ultramafic rocks in the Earth’s mantle represent a tremendous reservoir of carbon and reducing power. Upon tectonic uplift and exposure to fluid flow, serpentinization of these materials generates copious energy, sustains abiogenic synthesis of organic molecules, and releases hydrogen gas (H2). In order to assess the potential for microbial H2 utilization fueled by serpentinization, we conducted metagenomic surveys of a marine serpentinite-hosted hydrothermal chimney (at the Lost City hydrothermal field) and two continental serpentinite-hosted alkaline seeps (at the Tablelands Ophiolite, Newfoundland). Novel [NiFe]-hydrogenase sequences were identified at both the marine and continental sites, and in both cases, phylogenetic analyses indicated aerobic, potentially autotrophic Betaproteobacteria belonging to order Burkholderiales as the most likely H2-oxidizers. Both sites also yielded metagenomic evidence for microbial H2 production catalyzed by [FeFe]-hydrogenases in anaerobic Gram-positive bacteria belonging to order Clostridiales. In addition, we present metagenomic evidence at both sites for aerobic carbon monoxide utilization and anaerobic carbon fixation via the Wood–Ljungdahl pathway. In general, our results point to H2-oxidizing Betaproteobacteria thriving in shallow, oxic–anoxic transition zones and the anaerobic Clostridia thriving in anoxic, deep subsurface habitats. These data demonstrate the feasibility of metagenomic investigations into novel subsurface habitats via surface-exposed seeps and indicate the potential for H2-powered primary production in serpentinite-hosted subsurface habitats. PMID:22232619

Metagenomic evidence for h(2) oxidation and h(2) production by serpentinite-hosted subsurface microbial communities.

PubMed

Brazelton, William J; Nelson, Bridget; Schrenk, Matthew O

2012-01-01

Ultramafic rocks in the Earth's mantle represent a tremendous reservoir of carbon and reducing power. Upon tectonic uplift and exposure to fluid flow, serpentinization of these materials generates copious energy, sustains abiogenic synthesis of organic molecules, and releases hydrogen gas (H(2)). In order to assess the potential for microbial H(2) utilization fueled by serpentinization, we conducted metagenomic surveys of a marine serpentinite-hosted hydrothermal chimney (at the Lost City hydrothermal field) and two continental serpentinite-hosted alkaline seeps (at the Tablelands Ophiolite, Newfoundland). Novel [NiFe]-hydrogenase sequences were identified at both the marine and continental sites, and in both cases, phylogenetic analyses indicated aerobic, potentially autotrophic Betaproteobacteria belonging to order Burkholderiales as the most likely H(2)-oxidizers. Both sites also yielded metagenomic evidence for microbial H(2) production catalyzed by [FeFe]-hydrogenases in anaerobic Gram-positive bacteria belonging to order Clostridiales. In addition, we present metagenomic evidence at both sites for aerobic carbon monoxide utilization and anaerobic carbon fixation via the Wood-Ljungdahl pathway. In general, our results point to H(2)-oxidizing Betaproteobacteria thriving in shallow, oxic-anoxic transition zones and the anaerobic Clostridia thriving in anoxic, deep subsurface habitats. These data demonstrate the feasibility of metagenomic investigations into novel subsurface habitats via surface-exposed seeps and indicate the potential for H(2)-powered primary production in serpentinite-hosted subsurface habitats.

An Optimal Centralized Carbon Dioxide Repository for Florida, USA

PubMed Central

Poiencot, Brandon; Brown, Christopher

2011-01-01

For over a decade, the United States Department of Energy, and engineers, geologists, and scientists from all over the world have investigated the potential for reducing atmospheric carbon emissions through carbon sequestration. Numerous reports exist analyzing the potential for sequestering carbon dioxide at various sites around the globe, but none have identified the potential for a statewide system in Florida, USA. In 2005, 83% of Florida’s electrical energy was produced by natural gas, coal, or oil (e.g., fossil fuels), from power plants spread across the state. In addition, only limited research has been completed on evaluating optimal pipeline transportation networks to centralized carbon dioxide repositories. This paper describes the feasibility and preliminary locations for an optimal centralized Florida-wide carbon sequestration repository. Linear programming optimization modeling is used to plan and route an idealized pipeline network to existing Florida power plants. Further analysis of the subsurface geology in these general locations will provide insight into the suitability of the subsurface conditions and the available capacity for carbon sequestration at selected possible repository sites. The identification of the most favorable site(s) is also presented. PMID:21695024

An optimal centralized carbon dioxide repository for Florida, USA.

PubMed

Poiencot, Brandon; Brown, Christopher

2011-04-01

For over a decade, the United States Department of Energy, and engineers, geologists, and scientists from all over the world have investigated the potential for reducing atmospheric carbon emissions through carbon sequestration. Numerous reports exist analyzing the potential for sequestering carbon dioxide at various sites around the globe, but none have identified the potential for a statewide system in Florida, USA. In 2005, 83% of Florida's electrical energy was produced by natural gas, coal, or oil (e.g., fossil fuels), from power plants spread across the state. In addition, only limited research has been completed on evaluating optimal pipeline transportation networks to centralized carbon dioxide repositories. This paper describes the feasibility and preliminary locations for an optimal centralized Florida-wide carbon sequestration repository. Linear programming optimization modeling is used to plan and route an idealized pipeline network to existing Florida power plants. Further analysis of the subsurface geology in these general locations will provide insight into the suitability of the subsurface conditions and the available capacity for carbon sequestration at selected possible repository sites. The identification of the most favorable site(s) is also presented.

New Insights on Subsurface Imaging of Carbon Nanotubes in Polymer Composites via Scanning Electron Microscopy

NASA Technical Reports Server (NTRS)

Zhao, Minhua; Ming, Bin; Kim, Jae-Woo; Gibbons, Luke J.; Gu, Xiaohong; Nguyen, Tinh; Park, Cheol; Lillehei, Peter T.; Villarrubia, J. S.; Vladar, Andras E.;

Murt user`s guide: A hybrid Lagrangian-Eulerian finite element model of multiple-pore-region solute transport through subsurface media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gwo, J.P.; Jardine, P.M.; Yeh, G.T.

Matrix diffusion, a diffusive mass transfer process,in the structured soils and geologic units at ORNL, is believe to be an important subsurface mass transfer mechanism; it may affect off-site movement of radioactive wastes and remediation of waste disposal sites by locally exchanging wastes between soil/rock matrix and macropores/fractures. Advective mass transfer also contributes to waste movement but is largely neglected by researchers. This report presents the first documented 2-D multiregion solute transport code (MURT) that incorporates not only diffusive but also advective mass transfer and can be applied to heterogeneous porous media under transient flow conditions. In this report, theoreticalmore » background is reviewed and the derivation of multiregion solute transport equations is presented. Similar to MURF (Gwo et al. 1994), a multiregion subsurface flow code, multiplepore domains as suggested by previous investigators (eg, Wilson and Luxmoore 1988) can be implemented in MURT. Transient or steady-state flow fields of the pore domains can be either calculated by MURF or by modelers. The mass transfer process is briefly discussed through a three-pore-region multiregion solute transport mechanism. Mass transfer equations that describe mass flux across pore region interfaces are also presented and parameters needed to calculate mass transfer coefficients detailed. Three applications of MURT (tracer injection problem, sensitivity analysis of advective and diffusive mass transfer, hillslope ponding infiltration and secondary source problem) were simulated and results discussed. Program structure of MURT and functions of MURT subroutiness are discussed so that users can adapt the code; guides for input data preparation are provided in appendices.« less

Hydrogeological controls on spatial patterns of groundwater discharge in peatlands

NASA Astrophysics Data System (ADS)

Hare, Danielle K.; Boutt, David F.; Clement, William P.; Hatch, Christine E.; Davenport, Glorianna; Hackman, Alex

2017-11-01

Peatland environments provide important ecosystem services including water and carbon storage, nutrient processing and retention, and wildlife habitat. However, these systems and the services they provide have been degraded through historical anthropogenic agricultural conversion and dewatering practices. Effective wetland restoration requires incorporating site hydrology and understanding groundwater discharge spatial patterns. Groundwater discharge maintains wetland ecosystems by providing relatively stable hydrologic conditions, nutrient inputs, and thermal buffering important for ecological structure and function; however, a comprehensive site-specific evaluation is rarely feasible for such resource-constrained projects. An improved process-based understanding of groundwater discharge in peatlands may help guide ecological restoration design without the need for invasive methodologies and detailed site-specific investigation. Here we examine a kettle-hole peatland in southeast Massachusetts historically modified for commercial cranberry farming. During the time of our investigation, a large process-based ecological restoration project was in the assessment and design phases. To gain insight into the drivers of site hydrology, we evaluated the spatial patterning of groundwater discharge and the subsurface structure of the peatland complex using heat-tracing methods and ground-penetrating radar. Our results illustrate that two groundwater discharge processes contribute to the peatland hydrologic system: diffuse lower-flux marginal matrix seepage and discrete higher-flux preferential-flow-path seepage. Both types of groundwater discharge develop through interactions with subsurface peatland basin structure, often where the basin slope is at a high angle to the regional groundwater gradient. These field observations indicate strong correlation between subsurface structures and surficial groundwater discharge. Understanding these general patterns may allow resource managers to more efficiently predict and locate groundwater seepage, confirm these using remote sensing technologies, and incorporate this information into restoration design for these critical ecosystems.

Extraction of Seabed/Subsurface Features in a Potential CO2 Sequestration Site in the Southern Baltic Sea, Using Wavelet Transform of High-resolution Sub-Bottom Profiler Data

NASA Astrophysics Data System (ADS)

Tegowski, J.; Zajfert, G.

2014-12-01

Carbon Capture & Storage (CCS) efficiently prevents the release of anthropogenic CO2 into the atmosphere. We investigate a potential site in the Polish Sector of the Baltic Sea (B3 field site), consisting in a depleted oil and gas reservoir. An area ca. 30 x 8 km was surveyed along 138 acoustic transects, realised from R/V St. Barbara in 2012 and combining multibeam echosounder, sidescan sonar and sub-bottom profiler. Preparation of CCS sites requires accurate knowledge of the subsurface structure of the seafloor, in particular deposit compactness. Gas leaks in the water column were monitored, along with the structure of upper sediment layers. Our analyses show the shallow sub-seabed is layered, and quantified the spatial distribution of gas diffusion chimneys and seabed effusion craters. Remote detection of gas-containing surface sediments can be rather complex if bubbles are not emitted directly into the overlying water and thus detectable acoustically. The heterogeneity of gassy sediments makes conventional bottom sampling methods inefficient. Therefore, we propose a new approach to identification, mapping, and monitoring of potentially gassy surface sediments, based on wavelet analysis of echo signal envelopes of a chirp sub-bottom profiler (EdgeTech SB-0512). Each echo envelope was subjected to wavelet transformation, whose coefficients were used to calculate wavelet energies. The set of echo envelope parameters was input to fuzzy logic and c-means algorithms. The resulting classification highlights seafloor areas with different subsurface morphological features, which can indicate gassy sediments. This work has been conducted under EC FP7-CP-IP project No. 265847: Sub-seabed CO2 Storage: Impact on Marine Ecosystems (ECO2).

Spatially Explicit Simulation of Mesotopographic Controls on Peatland Hydrology and Carbon Fluxes

NASA Astrophysics Data System (ADS)

Sonnentag, O.; Chen, J. M.; Roulet, N. T.

2006-12-01

A number of field carbon flux measurements, paleoecological records, and model simulations have acknowledged the importance of northern peatlands in terrestrial carbon cycling and methane emissions. An important parameter in peatlands that influences both net primary productivity, the net gain of carbon through photosynthesis, and decomposition under aerobic and anaerobic conditions, is the position of the water table. Biological and physical processes involved in peatland carbon dynamics and their hydrological controls operate at different spatial scales. The highly variable hydraulic characteristics of the peat profile and the overall shape of the peat body as defined by its surface topography at the mesoscale (104 m2) are of major importance for peatland water table dynamics. Common types of peatlands include bogs with a slightly domed centre. As a result of the convex profile, their water supply is restricted to atmospheric inputs, and water is mainly shed by shallow subsurface flow. From a modelling perspective the influence of mesotopographic controls on peatland hydrology and thus carbon balance requires that process-oriented models that examine the links between peatland hydrology, ecosystem functioning, and climate must incorporate some form of lateral subsurface flow consideration. Most hydrological and ecological modelling studies in complex terrain explicitly account for the topographic controls on lateral subsurface flow through digital elevation models. However, modelling studies in peatlands often employ simple empirical parameterizations of lateral subsurface flow, neglecting the influence of peatlands low relief mesoscale topography. Our objective is to explicitly simulate the mesotopographic controls on peatland hydrology and carbon fluxes using the Boreal Ecosystem Productivity Simulator (BEPS) adapted to northern peatlands. BEPS is a process-oriented ecosystem model in a remote sensing framework that takes into account peatlands multi-layer canopy through vertically stratified mapped leaf area index. Model outputs are validated against multi-year measurements taken at an eddy-covariance flux tower located within Mer Bleue bog, a typical raised bog near Ottawa, Ontario, Canada. Model results for seasonal water table dynamics and evapotranspiration at daily time steps in 2003 are in good agreement with measurements with R2=0.74 and R2=0.79, respectively, and indicate the suitability of our pursued approach.

Microbial Metagenomics Reveals Climate-Relevant Subsurface Biogeochemical Processes.

PubMed

Long, Philip E; Williams, Kenneth H; Hubbard, Susan S; Banfield, Jillian F

2016-08-01

Microorganisms play key roles in terrestrial system processes, including the turnover of natural organic carbon, such as leaf litter and woody debris that accumulate in soils and subsurface sediments. What has emerged from a series of recent DNA sequencing-based studies is recognition of the enormous variety of little known and previously unknown microorganisms that mediate recycling of these vast stores of buried carbon in subsoil compartments of the terrestrial system. More importantly, the genome resolution achieved in these studies has enabled association of specific members of these microbial communities with carbon compound transformations and other linked biogeochemical processes-such as the nitrogen cycle-that can impact the quality of groundwater, surface water, and atmospheric trace gas concentrations. The emerging view also emphasizes the importance of organism interactions through exchange of metabolic byproducts (e.g., within the carbon, nitrogen, and sulfur cycles) and via symbioses since many novel organisms exhibit restricted metabolic capabilities and an associated extremely small cell size. New, genome-resolved information reshapes our view of subsurface microbial communities and provides critical new inputs for advanced reactive transport models. These inputs are needed for accurate prediction of feedbacks in watershed biogeochemical functioning and their influence on the climate via the fluxes of greenhouse gases, CO2, CH4, and N2O. Copyright © 2016 Elsevier Ltd. All rights reserved.

Trajectories of Microbial Community Function in Response to Accelerated Remediation of Subsurface Metal Contaminants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Firestone, Mary

Objectives of proposed research were to; Determine if the trajectories of microbial community composition and function following organic carbon amendment can be related to, and predicted by, key environmental determinants; Assess the relative importance of the characteristics of the indigenous microbial community, sediment, groundwater, and concentration of organic carbon amendment as the major determinants of microbial community functional response and bioremediation capacity; and Provide a fundamental understanding of the microbial community ecology underlying subsurface metal remediation requisite to successful application of accelerated remediation and long-term stewardship of DOE-IFC sites.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.; Henson, Neil J.; Devanathan, Ram; Schwantes, Jon M.; Reilly, Dallas D.

2018-04-01

In this work we used ab initio molecular dynamics within the framework of density functional theory and the projector-augmented wave method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activation energy for carbon was nearly twice that of uranium: 0.55 ± 0.03 eV for carbon compared to 0.32 ± 0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.

Carbon diffusion in solid iron as function of pressure and temperature

NASA Astrophysics Data System (ADS)

Stagno, V.; Crispin, K. L.; Fei, Y.

2012-12-01

The knowledge of carbon diffusion in metallic iron is of importance for both industrial and geological applications. In industry the diffusion properties of carbon apply to the massive production of steel through carburizing and galvanization processes at high temperature with the aim to improve the hardness and rust resistance of such materials. In geoscience the diffusion of carbon in metallic phases at high pressure and temperature is important for determining the rate of reactions and crystal growth of carbide phases likely coexisting with mantle silicates. Due to a small atomic radius, carbon is expected to dissolve by interstitial diffusion in solid metals. However, to date there are no experimental data available to understand the role that pressure plays on the mobilization of carbon through solid iron. Further, for light elements such as carbon or sulfur the activation energy is assumed to be lower than in case of lattice diffusion. However, with increasing pressure the activation volume must be taken into account to better understand diffusion processes at the atomic scale. We performed experiments using multianvil and piston cylinder devices at pressures between 1.5 and 6 GPa and temperature of 700-1200°C. Experiments were carried out using cylindrical glassy carbon sandwiched between layers of pure iron rods of known thickness enclosed in MgO capsule. Analytical techniques included FE-SEM for textural observation and accurate analyses of the interface between layers, while concentration profiles were measured using the electron microprobe with an optimized standardization procedure. Concentration profiles of carbon in iron were computed to determine the diffusion coefficients based on Fick's second law formulation assuming isotropic one dimension diffusion. Preliminary results confirm the positive temperature dependence of the diffusion coefficient for carbon widely discussed in literature. However, our results also show that a significant increase in pressure is required to affect the mobility of carbon through metallic iron by almost the same order of magnitude as cooling. The variation of the diffusion coefficient as function of temperature and pressure will be used to determine the activation energy and volume. It is known that the stability of carbide phases in the Earth's interior is mainly governed by the local Fe/C ratios. In the case of enriched mantle model, for instance, carbon in form of diamond will coexist with Fe7C3 for small amounts of metallic iron. In contrast, this would imply that at low carbon contents (<50 ppm) typical of a depleted mantle source, and at oxygen fugacity conditions lower than EMOD buffer, the transport of carbon will likely occur by diffusion through the coexisting metal phase. Results from this study will improve our understanding on the transport of carbon by diffusion at conditions of the Earth's interior and will provide new thermodynamic data to explain the fractionation of carbon by diffusion in other planetary bodies.

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna; Gregory, Kelvin B.; Lowry, Gregorgy V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 22 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2 exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Impact of CO 2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO 2 Leakage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Gregory, Kelvin B.; Lowry, Gregory V.

Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO 2) emissions to the atmosphere. During this process, CO 2 is injected as super critical carbon dioxide (SC-CO 2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO 2 in subsurface geologic formations could unintentionally lead to CO 2 leakage into overlying freshwater aquifers. Introduction of CO 2 into these subsurface environments will greatly increase the CO 2 concentration and will create CO 2 concentration gradients that drivemore » changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO 2 gradients will impact these communities. The overarching goal of this project is to understand how CO 2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO 2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO 2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO 2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO 2 injection/leakage plume where CO 2 concentrations are highest. At CO 2 exposures expected downgradient from the CO 2 plume, selected microorganisms emerged as dominant in the CO 2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site-dependent results suggest a limited ability to predict the emerging dominant species for other CO 2-exposed environments. This study improves the understanding of how a subsurface microbial community may respond to conditions expected from GCS and CO 2 leakage. This is the first step for understanding how a CO 2-altered microbial community may impact injectivity, permanence of stored CO 2, and subsurface water quality. Future work with microbial communities from new subsurface sites would increase the current understanding of this project. Additionally, incorporation of metagenomic methods would increase understanding of potential microbial processes that may be prevalent in CO 2 exposed environments.« less

Volatile Emissions from Hot Spring Basin, Yellowstone National Park, USA

NASA Astrophysics Data System (ADS)

Werner, C.; Hurwitz, S.; Bergfeld, D.; Evans, W. C.; Lowenstern, J. B.; Jaworowski, C.; Heasler, H.

2007-12-01

The flux and composition of magmatic volatiles were characterized for Hot Spring Basin (HSB), Yellowstone National Park, in August 2006. Diffuse fluxes of CO2 (228 sites) from thermal soil were elevated, with a population distribution similar to that of other acid-sulfate areas in Yellowstone. Thus the estimated diffuse emission rate at HSB is proportionately larger than other areas due to its large area, and could be as high as 1000 td-1 CO2. The diffuse flux of H2S was only above detection limits at 20 of the 31 sites measured. The estimated diffuse H2S emission rate was ~ 4 td-1. Good correlation exists between the log of CO2 flux and shallow soil temperatures, indicating linked steam and gas upflow in the subsurface. The correlation between CO2 and H2S fluxes is weak, and the CO2 / H2S diffuse flux ratio was higher than in fumarolic ratios of CO2 to H2S. This suggests that various reactions, e.g., native sulfur deposition, act to remove H2S from the original gas stream in the diffuse low- temperature environment. Dissolved sulfate flux through Shallow Creek, which drains part of HSB, was ~ 4 td-1. Comparing dissolved sulfate flux to estimates of primary emission of H2S based on fumarolic gas geochemistry gives first order estimates of the sulfur consumed in surficial or subsurface mineral deposition. Total C and S outputs from HSB are comparable to other active volcanic systems.

Reactive Transport Modeling of Induced Calcite Precipitation Reaction Fronts in Porous Media Using A Parallel, Fully Coupled, Fully Implicit Approach

NASA Astrophysics Data System (ADS)

Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.; Fox, D. T.; Fujita, Y.

2010-12-01

Inducing mineral precipitation in the subsurface is one potential strategy for immobilizing trace metal and radionuclide contaminants. Generating mineral precipitates in situ can be achieved by manipulating chemical conditions, typically through injection or in situ generation of reactants. How these reactants transport, mix and react within the medium controls the spatial distribution and composition of the resulting mineral phases. Multiple processes, including fluid flow, dispersive/diffusive transport of reactants, biogeochemical reactions and changes in porosity-permeability, are tightly coupled over a number of scales. Numerical modeling can be used to investigate the nonlinear coupling effects of these processes which are quite challenging to explore experimentally. Many subsurface reactive transport simulators employ a de-coupled or operator-splitting approach where transport equations and batch chemistry reactions are solved sequentially. However, such an approach has limited applicability for biogeochemical systems with fast kinetics and strong coupling between chemical reactions and medium properties. A massively parallel, fully coupled, fully implicit Reactive Transport simulator (referred to as “RAT”) based on a parallel multi-physics object-oriented simulation framework (MOOSE) has been developed at the Idaho National Laboratory. Within this simulator, systems of transport and reaction equations can be solved simultaneously in a fully coupled, fully implicit manner using the Jacobian Free Newton-Krylov (JFNK) method with additional advanced computing capabilities such as (1) physics-based preconditioning for solution convergence acceleration, (2) massively parallel computing and scalability, and (3) adaptive mesh refinements for 2D and 3D structured and unstructured mesh. The simulator was first tested against analytical solutions, then applied to simulating induced calcium carbonate mineral precipitation in 1D columns and 2D flow cells as analogs to homogeneous and heterogeneous porous media, respectively. In 1D columns, calcium carbonate mineral precipitation was driven by urea hydrolysis catalyzed by urease enzyme, and in 2D flow cells, calcium carbonate mineral forming reactants were injected sequentially, forming migrating reaction fronts that are typically highly nonuniform. The RAT simulation results for the spatial and temporal distributions of precipitates, reaction rates and major species in the system, and also for changes in porosity and permeability, were compared to both laboratory experimental data and computational results obtained using other reactive transport simulators. The comparisons demonstrate the ability of RAT to simulate complex nonlinear systems and the advantages of fully coupled approaches, over de-coupled methods, for accurate simulation of complex, dynamic processes such as engineered mineral precipitation in subsurface environments.

Genome-to-Watershed Predictive Understanding of Terrestrial Environments

NASA Astrophysics Data System (ADS)

Hubbard, S. S.; Agarwal, D.; Banfield, J. F.; Beller, H. R.; Brodie, E.; Long, P.; Nico, P. S.; Steefel, C. I.; Tokunaga, T. K.; Williams, K. H.

2014-12-01

Although terrestrial environments play a critical role in cycling water, greenhouse gasses, and other life-critical elements, the complexity of interactions among component microbes, plants, minerals, migrating fluids and dissolved constituents hinders predictive understanding of system behavior. The 'Sustainable Systems 2.0' project is developing genome-to-watershed scale predictive capabilities to quantify how the microbiome affects biogeochemical watershed functioning, how watershed-scale hydro-biogeochemical processes affect microbial functioning, and how these interactions co-evolve with climate and land-use changes. Development of such predictive capabilities is critical for guiding the optimal management of water resources, contaminant remediation, carbon stabilization, and agricultural sustainability - now and with global change. Initial investigations are focused on floodplains in the Colorado River Basin, and include iterative model development, experiments and observations with an early emphasis on subsurface aspects. Field experiments include local-scale experiments at Rifle CO to quantify spatiotemporal metabolic and geochemical responses to O2and nitrate amendments as well as floodplain-scale monitoring to quantify genomic and biogeochemical response to natural hydrological perturbations. Information obtained from such experiments are represented within GEWaSC, a Genome-Enabled Watershed Simulation Capability, which is being developed to allow mechanistic interrogation of how genomic information stored in a subsurface microbiome affects biogeochemical cycling. This presentation will describe the genome-to-watershed scale approach as well as early highlights associated with the project. Highlights include: first insights into the diversity of the subsurface microbiome and metabolic roles of organisms involved in subsurface nitrogen, sulfur and hydrogen and carbon cycling; the extreme variability of subsurface DOC and hydrological controls on carbon and nitrogen cycling; geophysical identification of floodplain hotspots that are useful for model parameterization; and GEWaSC demonstration of how incorporation of identified microbial metabolic processes improves prediction of the larger system biogeochemical behavior.

Short-lived radium isotopes on the Scotian Shelf: Unique distribution and tracers of cross-shelf CO2 and nutrient transport

NASA Astrophysics Data System (ADS)

Burt, William; Thomas, Helmuth

2013-04-01

Radium (Ra) isotopes have become a common tool for investigating mixing rates on continental shelves, and more recently have been used to quantify the release of dissolved compounds enriched in pore-waters into the water column. We present results from Ra sampling of the Scotian Shelf region of the Canadian northwestern Atlantic Ocean, which reveal cross-shelf Ra distributions that are unique compared to other coastal regions. We explain the observations of lower 224Ra activities near the coast, relatively high activities at large distances offshore (>100km), and gradients in both offshore and onshore directions by inferring the regional geomorphology, as well as shelf bathymetry and circulation patterns. Ra gradients are used to calculate individual estimates of eddy diffusion in both the cross-shelf (KX) and vertical (KZ) directions using 1-D eddy diffusion models. Enhanced vertical mixing above offshore banks allows for Ra enrichments in offshore surface waters, while horizontal dispersion of this bank-related signal can transport Ra off the shelf break in surface waters, and towards the shore beneath the surface mixed layer. Similar onshore gradients in CO2 and nutrient species combined with Ra-derived KX values can yield onshore carbon and nutrient fluxes in subsurface waters, which in turn supply the CO2 outgassing from the Scotian Shelf. Our results thus provide constraints for cross-shelf transports of carbon and nutrients on the Scotian Shelf in order to guide mass balance or model based budget approaches in future studies.

A Forest of Sub-1.5-nm-wide Single-Walled Carbon Nanotubes over an Engineered Alumina Support

NASA Astrophysics Data System (ADS)

Yang, Ning; Li, Meng; Patscheider, Jörg; Youn, Seul Ki; Park, Hyung Gyu

2017-04-01

A precise control of the dimension of carbon nanotubes (CNTs) in their vertical array could enable many promising applications in various fields. Here, we demonstrate the growth of vertically aligned, single-walled CNTs (VA-SWCNTs) with diameters in the sub-1.5-nm range (0.98 ± 0.24 nm), by engineering a catalyst support layer of alumina via thermal annealing followed by ion beam treatment. We find out that the ion beam bombardment on the alumina allows the growth of ultra-narrow nanotubes, whereas the thermal annealing promotes the vertical alignment at the expense of enlarged diameters; in an optimal combination, these two effects can cooperate to produce the ultra-narrow VA-SWCNTs. According to micro- and spectroscopic characterizations, ion beam bombardment amorphizes the alumina surface to increase the porosity, defects, and oxygen-laden functional groups on it to inhibit Ostwald ripening of catalytic Fe nanoparticles effectively, while thermal annealing can densify bulk alumina to prevent subsurface diffusion of the catalyst particles. Our findings contribute to the current efforts of precise diameter control of VA-SWCNTs, essential for applications such as membranes and energy storage devices.

Influence of surface vacancy defects on the carburisation of Fe 110 surface by carbon monoxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakrabarty, Aurab, E-mail: aurab.chakrabarty@qatar.tamu.edu; Bouhali, Othmane; Mousseau, Normand

Adsorption and dissociation of gaseous carbon monoxide (CO) on metal surfaces is one of the most frequently occurring processes of carburisation, known as primary initiator of metal dusting corrosion. Among the various factors that can significantly influence the carburisation process are the intrinsic surface defects such as single surface vacancies occurring at high concentrations due to their low formation energy. Intuitively, adsorption and dissociation barriers of CO are expected to be lowered in the vicinity of a surface vacancy, due to the strong attractive interaction between the vacancy and the C atom. Here the adsorption energies and dissociation pathways ofmore » CO on clean and defective Fe 110 surface are explored by means of density functional theory. Interestingly, we find that the O adatom, resulting from the CO dissociation, is unstable in the electron-deficit neighbourhood of the vacancy due to its large electron affinity, and raises the barrier of the carburisation pathway. Still, a full comparative study between the clean surface and the vacancy-defected surface reveals that the complete process of carburisation, starting from adsorption to subsurface diffusion of C, is more favourable in the vicinity of a vacancy defect.« less

The carbon count of 2000 years of rice cultivation.

PubMed

Kalbitz, Karsten; Kaiser, Klaus; Fiedler, Sabine; Kölbl, Angelika; Amelung, Wulf; Bräuer, Tino; Cao, Zhihong; Don, Axel; Grootes, Piet; Jahn, Reinhold; Schwark, Lorenz; Vogelsang, Vanessa; Wissing, Livia; Kögel-Knabner, Ingrid

2013-04-01

More than 50% of the world's population feeds on rice. Soils used for rice production are mostly managed under submerged conditions (paddy soils). This management, which favors carbon sequestration, potentially decouples surface from subsurface carbon cycling. The objective of this study was to elucidate the long-term rates of carbon accrual in surface and subsurface soil horizons relative to those of soils under nonpaddy management. We assessed changes in total soil organic as well as of inorganic carbon stocks along a 2000-year chronosequence of soils under paddy and adjacent nonpaddy management in the Yangtze delta, China. The initial organic carbon accumulation phase lasts much longer and is more intensive than previously assumed, e.g., by the Intergovernmental Panel on Climate Change (IPCC). Paddy topsoils accumulated 170-178 kg organic carbon ha(-1) a(-1) in the first 300 years; subsoils lost 29-84 kg organic carbon ha(-1) a(-1) during this period of time. Subsoil carbon losses were largest during the first 50 years after land embankment and again large beyond 700 years of cultivation, due to inorganic carbonate weathering and the lack of organic carbon replenishment. Carbon losses in subsoils may therefore offset soil carbon gains or losses in the surface soils. We strongly recommend including subsoils into global carbon accounting schemes, particularly for paddy fields. © 2012 Blackwell Publishing Ltd.

Equatorial ground ice on Mars: Steady-state stability

NASA Technical Reports Server (NTRS)

Mellon, Michael T.; Jakosky, Bruce M.; Postawko, Susan E.

1993-01-01

Current Martian equatorial surface temperatures are too warm for water ice to exist at the surface for any appreciable length of time before subliming into the atmosphere. Subsurface temperatures are generally warmer still and, despite the presence of a diffusive barrier of porous regolith material, it has been shown by Smoluchowski, Clifford and Hillel, and Fanale et al. that buried ground ice will also sublime and be lost to the atmosphere in a relatively short time. We investigate the behavior of this subliming subsurface ice and show that it is possible for ice to maintain at a steady-state depth, where sublimation and diffusive loss to the atmosphere is balanced by resupply from beneath by diffusion and recondensation of either a deeper buried ice deposits or ground water. We examine the behavior of equatorial ground ice with a numercial time-marching molecular diffusion model. In our model we allow for diffusion of water vapor through a porous regolith, variations in diffusivity and porosity with ice content, and recondensation of sublimed water vapor. A regolith containing considerable amounts of ice can still be very porous, allowing water vapor to diffuse up from deeper within the ice layer where temperatures are warmer due to the geothermal gradient. This vapor can then recondense nearer to the surface where ice had previously sublimed and been lost to the atmosphere. As a result we find that ice deposits migrate to find a steady-state depth, which represents a balance between diffusive loss to the atmosphere through the overlying porous regolith and diffusive resupply through a porous icy regolith below. This depth depends primarily on the long-term mean surface temperature and the nature of the geothermal gradient, and is independent of the ice-free porosity and the regolith diffusivity. Only the rate of loss of ground ice depends on diffusive properties.

Carbon diffusion in molten uranium: an ab initio molecular dynamics study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garrett, Kerry E.; Abrecht, David G.; Kessler, Sean H.

In this work we used ab initio molecular dynamics (AIMD) within the framework of density functional theory (DFT) and the projector-augmented wave (PAW) method to study carbon diffusion in liquid uranium at temperatures above 1600 K. The electronic interactions of carbon and uranium were described using the local density approximation (LDA). The self-diffusion of uranium based on this approach is compared with literature computational and experimental results for liquid uranium. The temperature dependence of carbon and uranium diffusion in the melt was evaluated by fitting the resulting diffusion coefficients to an Arrhenius relationship. We found that the LDA calculated activationmore » energy for carbon was nearly twice that of uranium: 0.55±0.03 eV for carbon compared to 0.32±0.04 eV for uranium. Structural analysis of the liquid uranium-carbon system is also discussed.« less

Influence of hydrological, biogeochemical and temperature transients on subsurface carbon fluxes in a flood plain environment

DOE PAGES

Arora, Bhavna; Spycher, Nicolas F.; Steefel, Carl I.; ...

2016-02-12

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Modelmore » simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO 2 partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe +2 and S -2 oxidation) to match locally-observed high CO 2 concentrations above reduced zones. Observed seasonal variations in CO 2 concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m -2 d -1, while including water table variations resulted in an overall decrease in the simulated fluxes. We thus conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations.« less

Influence of hydrological, biogeochemical and temperature transients on subsurface carbon fluxes in a flood plain environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arora, Bhavna; Spycher, Nicolas F.; Steefel, Carl I.

2016-02-01

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Modelmore » simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO2 partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe?2 and S-2 oxidation) to match locally-observed high CO2 concentrations above reduced zones. Observed seasonal variations in CO2 concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m-2 d-1, while including water table variations resulted in an overall decrease in the simulated fluxes. We conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations.« less

Complete suppression of boron transient-enhanced diffusion and oxidation-enhanced diffusion in silicon using localized substitutional carbon incorporation

NASA Astrophysics Data System (ADS)

Carroll, M. S.; Chang, C.-L.; Sturm, J. C.; Büyüklimanli, T.

1998-12-01

In this letter, we show the ability, through introduction of a thin Si1-x-yGexCy layer, to eliminate the enhancement of enhanced boron diffusion in silicon due to an oxidizing surface or ion implant damage. This reduction of diffusion is accomplished through a low-temperature-grown thin epitaxial Si1-x-yGexCy layer which completely filters out excess interstitials introduced by oxidation or ion implant damage. We also quantify the oxidation-enhanced diffusion (OED) and transient-enhanced diffusion (TED) dependence on substitutional carbon level, and further report both the observation of carbon TED and OED, and its dependence on carbon levels.

On the effects of subsurface parameters on evaporite dissolution (Switzerland)

NASA Astrophysics Data System (ADS)

Zidane, Ali; Zechner, Eric; Huggenberger, Peter; Younes, Anis

2014-05-01

Uncontrolled subsurface evaporite dissolution could lead to hazards such as land subsidence. Observed subsidences in a study area of Northwestern Switzerland were mainly due to subsurface dissolution (subrosion) of evaporites such as halite and gypsum. A set of 2D density driven flow simulations were evaluated along 1000 m long and 150 m deep 2D cross sections within the study area that is characterized by tectonic horst and graben structures. The simulations were conducted to study the effect of the different subsurface parameters that could affect the dissolution process. The heterogeneity of normal faults and its impact on the dissolution of evaporites is studied by considering several permeable faults that include non-permeable areas. The mixed finite element method (MFE) is used to solve the flow equation, coupled with the multipoint flux approximation (MPFA) and the discontinuous Galerkin method (DG) to solve the diffusion and the advection parts of the transport equation.

Pressure pumping of carbon dioxide from soil

Treesearch

E. S. Takle; J. R. Brandle; R. A. Schmidt; R. Garcia; I. V. Litvina; G. Doyle; X. Zhou; Q. Hou; C. W. Rice; W. J. Massman

2000-01-01

Recent interest in atmospheric increases in carbon dioxide have heightened the need for improved accuracy in measurements of fluxes of carbon dioxide from soils. Diffusional movement has long been considered the dominant process by which trace gases move from the subsurface source to the surface, although there has been some indication that atmospheric pressure...

Subsurface damage detection in non-ferrous systems using 3D synchronous magnetic inspection

NASA Astrophysics Data System (ADS)

Gray, David; Berry, David

2018-04-01

Prime Photonics is developing a non-destructive inspection (NDI) technology, 3-D synchronous magnetic imaging system (3-D SMIS), that uses synchronous detection of magnetic signatures resulting from ultrasonic excitation to measure both surface and subsurface flaws in conductive structures. 3-D SMIS is showing promise in a wide range of NDI/NDE uses including characterizing surface-breaking cracks in ferrous and non-ferrous materials, locating and characterizing subsurface cracks within nonferrous conductive materials (Ti 6-4 and carbon fiber composites), and characterization of subsurface residual stresses. The technology offers a non-contact, high resolution inspection technique that does not require austere environments, and can accommodate non-planar specimen geometries.

Serpentinization and Synthesis: Can abiotic and biotic non-volatile organic molecules be identified in the subsurface of the Atlantis Massif?

NASA Astrophysics Data System (ADS)

Hickok, K.; Nguyen, T.; Orcutt, B.; Fruh-Green, G. L.; Wanamaker, E.; Lang, S. Q.

2016-12-01

The high concentrations of hydrogen created during serpentinization can promote the formation of abiotic organic carbon molecules such as methane, formate, short chain hydrocarbons and, in laboratory experiments, larger molecules containing up to 32 carbon atoms. Subsurface archaeal and bacterial communities can use these reduced compounds for metabolic energy. International Ocean Discovery Project Expedition 357 drilled into the Atlantis Massif with the goals of investigating carbon cycling and the presence of life in a zone of active serpentinization. The expedition recovered multiple rock lithologies including gabbros, basalts, carbonate sands, and serpentinites. A subset of these samples are being analyzed to determine if non-volatile organic molecules are produced abiotically in serpentinizing environments and to identify `hot spots' of microbial life in the subsurface. Rock samples of contrasting representative lithologies are being analyzed for the presence of n-alkanes and fatty acids. Preliminary results have so far indicated the presence of alkanes in some samples. The isotopic (13C, 2H) characteristics of these compounds are being compared to a suite of oils, greases, and drilling fluids used during sample collection to distinguish in situ abiotic and biotic signatures from contaminant compounds. Other initial results have shown the efficacy of various sample-handling procedures designed to reduce surface contamination. This study will contribute to the overall understanding of the role serpentinization plays in the global carbon cycle and its implications for pre-biotic chemistry.

Physical and chemical controls on habitats for life in the deep subsurface beneath continents and ice

PubMed Central

Parnell, John; McMahon, Sean

2016-01-01

The distribution of life in the continental subsurface is likely controlled by a range of physical and chemical factors. The fundamental requirements are for space to live, carbon for biomass and energy for metabolic activity. These are inter-related, such that adequate permeability is required to maintain a supply of nutrients, and facies interfaces invite colonization by juxtaposing porous habitats with nutrient-rich mudrocks. Viable communities extend to several kilometres depth, diminishing downwards with decreasing porosity. Carbon is contributed by recycling of organic matter originally fixed by photosynthesis, and chemoautotrophy using crustal carbon dioxide and methane. In the shallow crust, the recycled component predominates, as processed kerogen or hydrocarbons, but abiotic carbon sources may be significant in deeper, metamorphosed crust. Hydrogen to fuel chemosynthesis is available from radiolysis, mechanical deformation and mineral alteration. Activity in the subcontinental deep biosphere can be traced through the geological record back to the Precambrian. Before the colonization of the Earth's surface by land plants, a geologically recent event, subsurface life probably dominated the planet's biomass. In regions of thick ice sheets the base of the ice sheet, where liquid water is stable and a sediment layer is created by glacial erosion, can be regarded as a deep biosphere habitat. This environment may be rich in dissolved organic carbon and nutrients accumulated from dissolving ice, and from weathering of the bedrock and the sediment layer. PMID:26667907

Development of a 1 x N Fiber Optic Sensor Array for Carbon Sequestration Site Monitoring

DOE Office of Scientific and Technical Information (OSTI.GOV)

Repasky, Kevin

2014-02-01

A fiber sensor array for sub-surface CO 2 concentrations measurements was developed for monitoring geologic carbon sequestration sites. The fiber sensor array uses a single temperature tunable distributed feedback (DFB) laser operating with a nominal wavelength of 2.004 μm. Light from this DFB laser is direct to one of the 4 probes via an in-line 1 x 4 fiber optic switch. Each of the 4 probes are buried and allow the sub-surface CO 2 to enter the probe through Millipore filters that allow the soil gas to enter the probe but keeps out the soil and water. Light from themore » DFB laser interacts with the CO 2 before it is directed back through the in-line fiber optic switch. The DFB laser is tuned across two CO 2 absorption features where a transmission measurement is made allowing the CO 2 concentration to be retrieved. The fiber optic switch then directs the light to the next probe where this process is repeated allowing sub-surface CO 2 concentration measurements at each of the probes to be made as a function of time. The fiber sensor array was deployed for fifty-eight days beginning June 19, 2012 at the Zero Emission Research Technology (ZERT) field site where sub-surface CO 2 concentrations were monitored. Background measurements indicate the fiber sensor array can monitor background levels as low as 1,000 parts per million (ppm). A thirty four day sub-surface release of 0.15 tones CO 2/day began on July 10, 2012. The elevated subsurface CO 2 concentration was easily detected by each of the four probes with values ranging to over 60,000 ppm, a factor of greater than 6 higher than background measurements. The fiber sensor array was also deploy at the Big Sky Carbon Sequestration Partnership (BSCSP) site in north-central Montana between July 9th and August 7th, 2013 where background measurements were made in a remote sequestration site with minimal infrastructure. The project provided opportunities for two graduate students to participate in research directly related to geologic carbon sequestration. Furthermore, commercialization of the technology developed is being pursued with five different companies via the Department of energy SBIR/STTR program« less

Diffuse degassing at Longonot volcano, Kenya: Implications for CO2 flux in continental rifts

NASA Astrophysics Data System (ADS)

Robertson, Elspeth; Biggs, Juliet; Edmonds, Marie; Clor, Laura; Fischer, Tobias P.; Vye-Brown, Charlotte; Kianji, Gladys; Koros, Wesley; Kandie, Risper

2016-11-01

Magma movement, fault structures and hydrothermal systems influence volatile emissions at rift volcanoes. Longonot is a Quaternary caldera volcano located in the southern Kenyan Rift, where regional extension controls recent shallow magma ascent. Here we report the results of a soil carbon dioxide (CO2) survey in the vicinity of Longonot volcano, as well as fumarolic gas compositions and carbon isotope data. The total non-biogenic CO2 degassing is estimated at < 300 kg d- 1, and is largely controlled by crater faults and fractures close to the summit. Thus, recent volcanic structures, rather than regional tectonics, control fluid pathways and degassing. Fumarolic gases are characterised by a narrow range in carbon isotope ratios (δ13C), from - 4.7‰ to - 6.4‰ (vs. PDB) suggesting a magmatic origin with minor contributions from biogenic CO2. Comparison with other degassing measurements in the East African Rift shows that records of historical eruptions or unrest do not correspond directly to the magnitude of CO2 flux from volcanic centres, which may instead reflect the current size and characteristics of the subsurface magma reservoir. Interestingly, the integrated CO2 flux from faulted rift basins is reported to be an order of magnitude higher than that from any of the volcanic centres for which CO2 surveys have so far been reported.

Utilizing Diffusion Theory to predict carbon dioxide concentration in an indoor environment

NASA Astrophysics Data System (ADS)

Kramer, Andrew R.

This research details a new method of relating sources of carbon dioxide to carbon dioxide concentration in a room operating in a reduced ventilation mode by utilizing Diffusion Theory. The theoretical basis of this research involved solving Fick's Second Law of Diffusion in spherical coordinates for a source of carbon dioxide flowing at a constant rate and located in the center of an impermeable spherical boundary. The solution was developed using a Laplace Transformation. A spherical diffusion test chamber was constructed and used to validate and benchmark the developed theory. The method was benchmarked by using Dispersion Coefficients for large carbon dioxide flow rates due to diffusion induced convection. The theoretical model was adapted to model a room operating with restricted ventilation in the presence of a known, constant source of carbon dioxide. The room was modeled as a sphere of volume equal to the room and utilized a Dispersion Coefficient that is consistent with published values. The developed Diffusion Model successfully predicted the spatial concentration of carbon dioxide in a room operating in a reduced ventilation mode in the presence of a source of carbon dioxide. The flow rates of carbon dioxide that were used in the room are comparable to the average flow rate of carbon dioxide from a person during quiet breathing, also known as the Tidal Breathing. This indicates the Diffusion Model developed from this research has the potential to correlate carbon dioxide concentration with static occupancy levels which can lead to energy savings through a reduction in air exchange rates when low occupancy is detected.

Physically-Based Models for the Reflection, Transmission and Subsurface Scattering of Light by Smooth and Rough Surfaces, with Applications to Realistic Image Synthesis

NASA Astrophysics Data System (ADS)

He, Xiao Dong

This thesis studies light scattering processes off rough surfaces. Analytic models for reflection, transmission and subsurface scattering of light are developed. The results are applicable to realistic image generation in computer graphics. The investigation focuses on the basic issue of how light is scattered locally by general surfaces which are neither diffuse nor specular; Physical optics is employed to account for diffraction and interference which play a crucial role in the scattering of light for most surfaces. The thesis presents: (1) A new reflectance model; (2) A new transmittance model; (3) A new subsurface scattering model. All of these models are physically-based, depend on only physical parameters, apply to a wide range of materials and surface finishes and more importantly, provide a smooth transition from diffuse-like to specular reflection as the wavelength and incidence angle are increased or the surface roughness is decreased. The reflectance and transmittance models are based on the Kirchhoff Theory and the subsurface scattering model is based on Energy Transport Theory. They are valid only for surfaces with shallow slopes. The thesis shows that predicted reflectance distributions given by the reflectance model compare favorably with experiment. The thesis also investigates and implements fast ways of computing the reflectance and transmittance models. Furthermore, the thesis demonstrates that a high level of realistic image generation can be achieved due to the physically -correct treatment of the scattering processes by the reflectance model.

Turbidite carbon distribution by Ramped PyrOx, Astoria Canyon

NASA Astrophysics Data System (ADS)

Childress, L. B.; Galy, V.; McNichol, A. P.

2017-12-01

The magnitude and nature of carbon preserved in marine sediments can be affected by long-term processes such as climate change and tectonic transport; preservation of carbon can also be affected by short-term, episodic disturbances such as storm events, landslides, and earthquakes. In margins with active canyons, these systems can be efficient burial networks for carbon. The downslope displacement and reorganization of sediment and associated organic carbon (OC) during turbidite formation alters oxygen diffusion and the potential for aerobic oxidation, thereby modifying the redox geochemistry of the sediment package. Generally termed as a `burn-down', reactions at the subsurface oxidation front are linked to a loss of OC preservation within turbidite sequences. Still debated is the source of the OC residual within `burn-down' events, primarily whether the preserved material is dominated by terrestrial or marine components. To better understand the significance of canyon systems and turbidite deposits in the transport, preservation, and `burn-down' of organic carbon, samples from these systems can be studied using the Ramped PyrOx (RPO) technique. Whereas bulk radiocarbon measurements are unsuitable within turbidite deposits, RPO is well suited for characterizing the distribution of carbon sources within a turbidite interval. To complement RPO analyses, OC and N content, stable carbon isotope composition, gamma ray attenuation bulk density, computerized tomography, and magnetic susceptibility were determined. The turbidite systems of the Cascadia Subduction Zone have been extensively studied in relation to the Holocene paleoseismic record. Gravity cores collected in 2011 aboard the R/V Wecoma capture turbidite deposits in Astoria Canyon and demonstrate characteristics of `burn down' intervals. RPO data from within a 15 cm turbidite interval indicate minimal variation in reactivity structure, stable carbon isotope values and radiocarbon age, suggesting a shared source of sediment input. Such similarities imply minimal source-selective OC alteration and are consistent with a singular event (e.g. - flood) associated with late Holocene warm interval influence on the Columbia River Basin.

Experimental measurements of the SP response to concentration and temperature gradients in sandstones with application to subsurface geophysical monitoring

NASA Astrophysics Data System (ADS)

Leinov, E.; Jackson, M. D.

2014-09-01

Exclusion-diffusion potentials arising from temperature gradients are widely neglected in self-potential (SP) surveys, despite the ubiquitous presence of temperature gradients in subsurface settings such as volcanoes and hot springs, geothermal fields, and oil reservoirs during production via water or steam injection. Likewise, with the exception of borehole SP logging, exclusion-diffusion potentials arising from concentration gradients are also neglected or, at best, it is assumed that the diffusion potential dominates. To better interpret these SP sources requires well-constrained measurements of the various coupling terms. We report measurements of thermoelectric and electrochemical exclusion-diffusion potentials across sandstones saturated with NaCl brine and find that electrode effects can dominate the measured voltage. After correcting for these, we find that Hittorf transport numbers are the same within experimental error regardless of whether ion transport occurs in response to temperature or concentration gradients over the range of NaCl concentration investigated that is typical of natural systems. Diffusion potentials dominate only if the pore throat radius is more than approximately 4000 times larger than the diffuse layer thickness. In fine-grained sandstones with small pore throat diameter, this condition is likely to be met only if the saturating brine is of relatively high salinity; thus, in many cases of interest to earth scientists, exclusion-diffusion potentials will comprise significant contributions from both ionic diffusion through, and ionic exclusion from, the pore space of the rock. However, in coarse-grained sandstones, or sandstones saturated with high-salinity brine, exclusion-diffusion potentials can be described using end-member models in which ionic exclusion is neglected. Exclusion-diffusion potentials in sandstones depend upon pore size and salinity in a complex way: they may be positive, negative, or zero depending upon sandstone rock texture (expressed here by the pore radius r) and salinity.

Subsurface Environment Sampler for Improved In Situ Characterization of Subsurface Microbial Communities

NASA Astrophysics Data System (ADS)

Barnhart, E. P.; Ruppert, L. F.; Orem, W. H.; McIntosh, J. C.; Cunningham, A. B.; Fields, M. W.; Hiebert, R.; Hyatt, R.

2016-12-01

There is an increasing threat that deep aquifers, an important drinking water resource, may be contaminated by the extraction and transport of fossil fuels. This threat increases the need for improved groundwater monitoring and the ability to predict the extent to which microbial activity may remediate such contamination. The characterization of subsurface microbial communities could provide an ideal biomonitoring tool for the assessment of subsurface contamination due to prokaryotes environmental ubiquity, rapidity of response to environmental perturbation and the important role they play in hydrocarbon degradation and bioremediation. New DNA sequencing technologies provide the opportunity to cost-effectively identify the vast subsurface microbial ecosystem, but use of this new technology is restricted due to issues with sampling. Prior subsurface microbiology studies have relied on core samples that are expensive to obtain hard to collect aseptically and/or ground water samples that do not reflect in situ microbial densities or activities. The development of down-well incubation of sterile sediment with a Diffusive Microbial Sampler (DMS) has emerged as an alternative method to sample subsurface microbial communities that minimizes cost and contamination issues associated with traditional methods. We have designed a Subsurface Environment Sampler with a DMS module that could enable the anaerobic transport of the in situ microbial community from the field for laboratory bioremediation studies. This sampler could provide an inexpensive and standard method for subsurface microbial sampling which would make this tool useful for Federal, State, private and local agencies interested in monitoring contamination or the effectiveness of bioremediation activities in subsurface aquifers.

Thermal etching of silver: Influence of rolling defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ollivier, M., E-mail: o.maelig@imperial.ac.uk

2016-08-15

Silver is well known to be thermally etched in an oxygen-rich atmosphere and has been extensively studied in the laboratory to understand thermal etching and to limit its effect when this material is used as a catalyst. Yet, in many industrial applications the surface of rolled silver sheets is used without particular surface preparation. Here, it is shown by combining FIB-tomography, FIB-SIMS and analytical SEM that the kinetics of thermal etch pitting are significantly faster on rolled Ag surfaces than on polished surfaces. This occurs due to range of interacting phenomena including (i) the reaction of subsurface carbon-contamination with dissolvedmore » oxygen to form pores that grow to intersect the surface, (ii) surface reconstruction around corrosion pits and surface scratches, and (iii) sublimation at low pressure and high temperature. A method to identify subsurface pores is developed to show that the pores have (111) and (100) internal facets and may be filled with a gas coming from the chemical reaction of oxygen and carbon contamination. - Highlights: Thermal etching of industrial silver sheets vs. polished silver sheets Effect of annealing atmosphere on the thermal etching of silver: surface and subsurface characterization Link between etch pitting and defects induced by rolling. FIB-tomography coupled with EBSD for determining crystal planes of the facets of subsurface pores. FIB-SIMS characterization to probe the gas confined inside subsurface pores.« less

Improved measurement of extracellular enzymatic activities in subsurface sediments using competitive desorption treatment

NASA Astrophysics Data System (ADS)

Hoarfrost, Adrienne; Snider, Rachel; Arnosti, Carol

2017-02-01

Extracellular enzymatic activities initiate microbially-driven heterotrophic carbon cycling in subsurface sediments. While measurement of hydrolytic activities in sediments is fundamental to our understanding of carbon cycling, these measurements are often technically difficult due to sorption of organic substrates to the sediment matrix. Most methods that measure hydrolysis of organic substrates in sediments rely on recovery of a fluorophore or fluorescently-labeled target substrate from a sediment incubation. The tendency for substrates to sorb to sediments results in lower recovery of an added substrate, and can result in data that are unusable or difficult to interpret. We developed a treatment using competitive desorption of a fluorescently-labeled, high molecular weight organic substrate that improves recovery of the labeled substrate from sediment subsamples. Competitive desorption treatment improved recovery of the fluorescent substrate by a median of 66%, expanded the range of sediments for which activity measurements could be made, and was effective in sediments from a broad range of geochemical contexts. More reliable measurements of hydrolytic activities in sediments will yield usable and more easily interpretable data from a wider range of sedimentary environments, enabling better understanding of microbially-catalyzed carbon cycling in subsurface environments.

Linking Metabolism, Elemental Cycles, and Environmental Conditions in the Deep Biosphere: Growth of a Model Extremophile, Archaeoglobus fulgidus, Under High-Pressure Conditions

NASA Astrophysics Data System (ADS)

Oliver, G. C. M.; Cario, A.; Rogers, K. L.

2015-12-01

A majority of Earth's biosphere is hosted in subsurface environments where global-scale biogeochemical and energy cycles are driven by diverse microbial communities that operate on and are influenced by micro-scale environmental variables. While the subsurface hosts a variety of geochemical and geothermal conditions, elevated pressures are common to all subsurface ecosystems. Understanding how microbes adapt to and thrive in high-pressure environments is essential to linking microbial subsurface processes with global-scale cycles. Here we are using a model extremophile, Archaeoglobus fulgidus, to determine how elevated pressures affect the growth, metabolism, and physiology of subsurface microorganisms. A. fulgidus cycles carbon and sulfur via heterotrophic and autotrophic sulfate reduction in various high temperature and high-pressure niches including shallow marine vents, deep-sea hydrothermal vents, and deep oil reservoirs. Here we report the results of A. fulgidus growth experiments at optimum temperature, 83°C, and pressures up to 600 bars. Exponential growth was observed over the entire pressure range, though growth rates were diminished at 500 and 600 bars compared to ambient pressure experimental controls. At pressures up to 400 bars, cell density yields and growth rates were at least as high as ambient pressure controls. Elevated pressures and extended incubation times stimulated cell flocculation, a common stress response in this strain, and cellular morphology was affected at pressures exceeding 400 bars. These results suggest that A. fulgidus continues carbon, sulfur and energy cycling unaffected by elevated pressures up to 400 bars, representing a variety of subsurface environments. The ability of subsurface organisms to drive biogeochemical cycles at elevated pressures is a critical link between the surface and subsurface biospheres and understanding how species-scale processes operate under these conditions is a vital part of global-scale biogeochemical models.

Bacterial carbon utilization in vertical subsurface flow constructed wetlands.

PubMed

Tietz, Alexandra; Langergraber, Günter; Watzinger, Andrea; Haberl, Raimund; Kirschner, Alexander K T

2008-03-01

Subsurface vertical flow constructed wetlands with intermittent loading are considered as state of the art and can comply with stringent effluent requirements. It is usually assumed that microbial activity in the filter body of constructed wetlands, responsible for the removal of carbon and nitrogen, relies mainly on bacterially mediated transformations. However, little quantitative information is available on the distribution of bacterial biomass and production in the "black-box" constructed wetland. The spatial distribution of bacterial carbon utilization, based on bacterial (14)C-leucine incorporation measurements, was investigated for the filter body of planted and unplanted indoor pilot-scale constructed wetlands, as well as for a planted outdoor constructed wetland. A simple mass-balance approach was applied to explain the bacterially catalysed organic matter degradation in this system by comparing estimated bacterial carbon utilization rates with simultaneously measured carbon reduction values. The pilot-scale constructed wetlands proved to be a suitable model system for investigating microbial carbon utilization in constructed wetlands. Under an ideal operating mode, the bulk of bacterial productivity occurred within the first 10cm of the filter body. Plants seemed to have no significant influence on productivity and biomass of bacteria, as well as on wastewater total organic carbon removal.

Ecology, physiology, and phylogeny of deep subsurface Sphingomonas sp.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fredrickson, Jim K.; Balkwill, David L.; Romine, Margaret F.

Several new species of the genus Sphingomonas including S. aromaticivorans, S. stygia, and S. subterranea that have the capacity for degrading a broad range of aromatic compounds including toluene, naphthalene, xylenes, p-cresol, fluorene, biphenyl, and dibenzothiophene, were isolated from deeply-buried (>200 m) sediments of the US Atlantic coastal plain (ACP). In S. aromaticivorans F199, many of the genes involved in the catabolism of these aromatic compounds are encoded on a 184-kb conjugative plasmid; some of the genes involved in aromatic catabolism are plasmid-encoded in the other strains as well. Members of the genus Sphingomonas were common among aerobic heterotrophic bacteriamore » cultured from ACP sediments and have been detected in deep subsurface environments elsewhere. The major source of organic carbon for heterotrophic metabolism in ACP deep aquifers is lignite that originated from plant material buried with the sediments. We speculate that the ability of the subsurface Sphingomonas strains to degrade a wide array of aromatic compounds represents an adaptation for utilization of sedimentary lignite. These and related subsurface Sphingomonas spp may play an important role in the transformation of sedimentary organic carbon in the aerobic and microaerobic regions of the deep aquifers of the ACP.« less

Ecology, physiology, and phylogeny of deep subsurface Sphingomonas sp.

PubMed

Fredrickson, J K; Balkwill, D L; Romine, M F; Shi, T

1999-10-01

Several new species of the genus Sphingomonas including S. aromaticivorans, S. stygia, and S. subterranea that have the capacity for degrading a broad range of aromatic compounds including toluene, naphthalene, xylenes, p-cresol, fluorene, biphenyl, and dibenzothiophene, were isolated from deeply-buried (>200 m) sediments of the US Atlantic coastal plain (ACP). In S. aromaticivorans F199, many of the genes involved in the catabolism of these aromatic compounds are encoded on a 184-kb conjugative plasmid; some of the genes involved in aromatic catabolism are plasmid-encoded in the other strains as well. Members of the genus Sphingomonas were common among aerobic heterotrophic bacteria cultured from ACP sediments and have been detected in deep subsurface environments elsewhere. The major source of organic carbon for heterotrophic metabolism in ACP deep aquifers is lignite that originated from plant material buried with the sediments. We speculate that the ability of the subsurface Sphingomonas strains to degrade a wide array of aromatic compounds represents an adaptation for utilization of sedimentary lignite. These and related subsurface Sphingomonas spp may play an important role in the transformation of sedimentary organic carbon in the aerobic and microaerobic regions of the deep aquifers of the ACP.

Carbon dioxide fluid-flow modeling and injectivity calculations

USGS Publications Warehouse

Burke, Lauri

2011-01-01

These results were used to classify subsurface formations into three permeability classifications for the probabilistic calculations of storage efficiency and containment risk of the U.S. Geological Survey geologic carbon sequestration assessment methodology. This methodology is currently in use to determine the total carbon dioxide containment capacity of the onshore and State waters areas of the United States.

Physical and Biological Carbon Isotope Fractionation in Methane During Gas-Push-Pull-Tests

NASA Astrophysics Data System (ADS)

Gonzalez-Gil, G.; Schroth, M. H.; Gomez, K.; Zeyer, J.

2005-12-01

Stable isotope analyses have become a common tool to assess microbially-mediated processes in subsurface environments. We investigated if stable carbon isotope analysis can be used as a tool to complement gas push-pull tests (GPPTs), a novel technique that was recently developed and tested for the in-situ quantification of CH4 oxidation in soils. During a GPPT a gas mixture containing CH4, O2 and nonreactive tracer gases is injected into the soil, where CH4 is oxidized by indigenous microorganisms. Thereafter, a blend of injected gas mixture and soil air is extracted from the same location, and CH4 oxidation is quantified from an analysis of extracted CH4 and tracer gases. To assess the magnitude of physical isotope fractionation due to molecular diffusion during GPPTs, we conducted laboratory experiments in the absence of microbial activity in a 1m-high, 1m-diameter tank filled with dry sand. During the GPPTs' extraction phase, the isotopic composition of methane was analyzed. Results indicated strong carbon isotope fractionation (>20 per mil) during GPPTs. To assess the combined effect of physical and biological isotope fractionation, numerical simulations of GPPTs were conducted in which microbial CH4 isotope fractionation was simulated using first-order rate constants and microbial kinetic isotope fractionation factors previously reported for methane oxidation in landfill environments. Results of these simulations indicated that for small CH4 oxidation rates, overall isotope fractionation in CH4 is dominated by physical fractionation. Conversely, for high CH4 oxidation rates, overall fractionation is dominated by biological fractionation. Thus, CH4 isotope fractionation data alone from a single GPPT cannot be used to assess microbial CH4 oxidation. However, biological fractionation may be quantified if physical fractionation due to diffusion is known. This can be achieved by conducting two sequential GPPTs, with microbial activity being inhibited in the second test.

Understanding the Geometry of Connected Fracture Flow with Multiperiod Oscillatory Hydraulic Tests.

PubMed

Sayler, Claire; Cardiff, Michael; Fort, Michael D

2018-03-01

An understanding of the spatial and hydraulic properties of fast preferential flow pathways in the subsurface is necessary in applications ranging from contaminant fate and transport modeling to design of energy extraction systems. One method for the characterization of fracture properties over interwellbore scales is Multiperiod Oscillatory Hydraulic (MOH) testing, in which the aquifer response to oscillatory pressure stimulations is observed. MOH tests were conducted on isolated intervals of wells in siliciclastic and carbonate aquifers in southern Wisconsin. The goal was to characterize the spatial properties of discrete fractures over interwellbore scales. MOH tests were conducted on two discrete fractured intervals intersecting two boreholes at one field site, and a nest of three piezometers at another field site. Fracture diffusivity estimates were obtained using analytical solutions that relate diffusivity to observed phase lag and amplitude decay. In addition, MOH tests were used to investigate the spatial extent of flow using different conceptual models of fracture geometry. Results indicated that fracture geometry at both field sites can be approximated by permeable two-dimensional fracture planes, oriented near-horizontally at one site, and near-vertically at the other. The technique used on MOH field data to characterize fracture geometry shows promise in revealing fracture network characteristics important to groundwater flow and transport. © 2017, National Ground Water Association.

Post-injection Multiphase Flow Modeling and Risk Assessments for Subsurface CO2 Storage in Naturally Fractured Reservoirs

NASA Astrophysics Data System (ADS)

Jin, G.

2015-12-01

Subsurface storage of carbon dioxide in geological formations is widely regarded as a promising tool for reducing global atmospheric CO2 emissions. Successful geologic storage for sequestrated carbon dioxides must prove to be safe by means of risk assessments including post-injection analysis of injected CO2 plumes. Because fractured reservoirs exhibit a higher degree of heterogeneity, it is imperative to conduct such simulation studies in order to reliably predict the geometric evolution of plumes and risk assessment of post CO2injection. The research has addressed the pressure footprint of CO2 plumes through the development of new techniques which combine discrete fracture network and stochastic continuum modeling of multiphase flow in fractured geologic formations. A subsequent permeability tensor map in 3-D, derived from our preciously developed method, can accurately describe the heterogeneity of fracture reservoirs. A comprehensive workflow integrating the fracture permeability characterization and multiphase flow modeling has been developed to simulate the CO2plume migration and risk assessments. A simulated fractured reservoir model based on high-priority geological carbon sinks in central Alabama has been employed for preliminary study. Discrete fracture networks were generated with an NE-oriented regional fracture set and orthogonal NW-fractures. Fracture permeability characterization revealed high permeability heterogeneity with an order of magnitude of up to three. A multiphase flow model composed of supercritical CO2 and saline water was then applied to predict CO2 plume volume, geometry, pressure footprint, and containment during and post injection. Injection simulation reveals significant permeability anisotropy that favors development of northeast-elongate CO2 plumes, which are aligned with systematic fractures. The diffusive spreading front of the CO2 plume shows strong viscous fingering effects. Post-injection simulation indicates significant upward lateral spreading of CO2 resulting in accumulation of CO2 directly under the seal unit because of its buoyancy and strata-bound vertical fractures. Risk assessment shows that lateral movement of CO2 along interconnected fractures requires widespread seals with high integrity to confine the injected CO2.

Evidence for iron-sulfate coupling in salt marsh sediments

NASA Astrophysics Data System (ADS)

Mills, Jennifer; Antler, Gilad; Turchyn, Alexandra

2014-05-01

Organic carbon burial in shallow marine sediments represents an important net sink in the global carbon cycle. Microbially mediated oxidation of organic matter in oxic, suboxic, and anoxic sediments however, prevents the ultimate burial of organic carbon and its removal from the surface of the planet. Although the subsurface transformations of organic carbon have been studied extensively, an enigmatic question remains: when organic matter is deposited, what determines whether it will be buried, reoxidized, or undergo methanogenesis? One hypothesis is that the sulfur cycle, due to the abundance of sulfate in many surface environments, dominates the subsurface oxidation or other fate of organic carbon. However, it has also been suggested that iron may in turn play a key role in determining the behavior of the sulfur cycle. To better understand the controls on these processes, we are using stable isotope and geochemical techniques to explore the microbially mediated oxidation of organic carbon in salt marsh sediments in North Norfolk, UK. In these sediments there is a high supply of organic carbon, iron, and sulfate (from diurnal tidal cycles). Thus these environments may provide insight into the nature of interactions between the carbon, iron, and sulfur cycles. A series of sampling missions was undertaken in the autumn and winter of 2013-2014. In subsurface fluid samples we observe very high ferrous iron concentrations (>1mM), indicative of extended regions of iron reduction (to over 30cm depth). Within these zones of iron reduction we would predict no sulfate reduction, and as expected δ34Ssulfate remains unchanged with depth. However, δ18Osulfate exhibits significant enrichments of up to 5 permil. This decoupling in the sulfur and oxygen isotopes of sulfate is suggestive of a sulfate recycling process in which sulfate is reduced to an intermediate sulfur species and subsequently reoxidized to sulfate. Taken together, these data suggest that microbial assemblages in these salt marsh sediments facilitate a cryptic cycling of sulfur, potentially mediated by iron species in the zone of iron reduction.

Atmospheric volatilization and distribution of (Z)- and (E)-1,3-dichloropropene in field beds with and without plastic covers.

PubMed

Thomas, John E; Allen, L Hartwell; McCormack, Leslie A; Vu, Joseph C; Dickson, Donald W; Ou, Li-Tse

2004-01-01

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5-20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.

The pore space scramble

NASA Astrophysics Data System (ADS)

Gormally, Alexandra; Bentham, Michelle; Vermeylen, Saskia; Markusson, Nils

2015-04-01

Climate change and energy security continue to be the context of the transition to a secure, affordable and low carbon energy future, both in the UK and beyond. This is reflected in for example, binding climate policy targets at the EU level, the introduction of renewable energy targets, and has also led to an increasing interest in Carbon Capture and Storage (CCS) technology with its potential to help mitigate against the effects of CO2 emissions from fossil fuel burning. The UK has proposed a three phase strategy to integrate CCS into its energy system in the long term focussing on off-shore subsurface storage (DECC, 2014). The potential of CCS therefore, raises a number of challenging questions and issues surrounding the long-term storage of CO2 captured and injected into underground spaces and, alongside other novel uses of the subsurface, contributes to opening a new field for discussion on the governance of the subsurface. Such 'novel' uses of the subsurface have lead to it becoming an increasingly contested space in terms of its governance, with issues emerging around the role of ownership, liability and property rights of subsurface pore space. For instance, questions over the legal ownership of pore space have arisen with ambiguity over the legal standpoint of the surface owner and those wanting to utilise the pore space for gas storage, and suggestions of whether there are depths at which legal 'ownership' becomes obsolete (Barton, 2014). Here we propose to discuss this 'pore space scramble' and provide examples of the competing trajectories of different stakeholders, particularly in the off-shore context given its priority in the UK. We also propose to highlight the current ambiguity around property law of pore space in the UK with reference to approaches currently taken in different national contexts. Ultimately we delineate contrasting models of governance to illustrate the choices we face and consider the ethics of these models for the common good. Barton, B (2014) The Common Law of Subsurface Activity: General Principle and Current Problems. In: Zillman, D.N., McHarg, A., Barrera-Hernandez, L., Bradbrook., A. (Eds), The Law of Energy Underground: Understanding new developments in subsurface production, transmission, and storage. Oxford University Press, Croydon, pp. 21-36. DECC (2014) Next steps in CCS: Policy Scoping Document - Developing an approach for the next phase of Carbon Capture and Storage projects in the UK. HM Government.

The stratigraphic record of Khawr Al Maqta, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Lokier, S. W.; Herrmann, S.

2012-04-01

Well-constrained modern depositional analogues are vital to the development of accurate geological reservoir models. The development of realistic hydrocarbon reservoir models requires the application of high-precision, well-constrained outcrop and sub-surface data sets with accurately-documented facies geometries and depositional sequence architectures. The Abu Dhabi coastline provides the best modern analogue for the study of ramp-style carbonate depositional facies akin to those observed in the sub-surface reservoirs of the United Arab Emirates (UAE). However, all previous studies have relied on temporally limited surface datasets. This study employed thirty five shallow subsurface cores spanning the width of the Khawr Al Maqta - the narrow shallow tidal channel that separates Abu Dhabi Island from the mainland. The cores were taken over a transect measuring 1.2 km in length by 50 m wide thus providing a high-resolution record of sub-surface facies geometries in a stratigraphically complex setting. Geometries in these Pleistocene to Holocene facies are complex with interdigitating, laterally heterogeneous carbonate, siliciclastic and evaporite units represented throughout the area of the study. Carbonate facies range from molluscan rudstones to marls and are all indicative of deposition in a shallow, relatively low energy marine setting akin to that seen in the environs of Abu Dhabi Island today. Texturally mature quartz sands occur as thin lenses and as thin cross bedded or laminated horizons up to twenty five centimetres thick. Glauconitic mudstones are common and locally exhibit evidence of rootlets and desiccation cracks. Evaporites are present in the form of gypsum occurring as isolated crystals and nodules or as massive chicken-wire units in excess of three metres thick. All of these textures are consistent with evaporite development in the shallow subsurface. Early, shallow-burial diagenesis has been important. Bioclasts are pervasively leached throughout the stratigraphic sequence thereby resulting in a significant enhancement in porosity in the carbonate lithologies. This pervasive mouldic porosity is locally occluded by the precipitation of gypsum cements. The displacive precipitation of significant quantities of gypsum has resulted in the deformation of primary sedimentary structures. This complex sequence of mixed carbonate-siliciclastic-evaporite lithofacies is interpreted to record repeated episodes of flooding and sub-aerial exposure associated with the waxing and waning of the Pleistocene ice-sheets. During periods of relative sea-level fall carbonate sequences entered the meteoric realm with the consequent dissolution of unstable bioclasts. Transgression and reflooding once again isolated Abu Dhabi Island from the mainland, thus permitting the precipitation of shallow-water carbonate lithofacies. During sea-level highstands the north-westerly Shamal wind transported carbonate sediments into the lee-of the island resulting in the south-easterly shore-wards development of a tombolo. However, the strong tidal currents of the Khawr Al Maqta prevented final connection to the mainland, thus ensuring the isolation of Abu Dhabi until the subsequent regression.

A hydrogen-based subsurface microbial community dominated by methanogens

USGS Publications Warehouse

Chapelle, F.H.; O'Neil, Kyle; Bradley, P.M.; Methe, B.A.; Ciufo, S.A.; Knobel, L.L.; Lovley, D.R.

2002-01-01

The search for extraterrestrial life may be facilitated if ecosystems can be found on Earth that exist under conditions analogous to those present on other planets or moons. It has been proposed, on the basis of geochemical and thermodynamic considerations, that geologically derived hydrogen might support subsurface microbial communities on Mars and Europa in which methanogens form the base of the ecosystem1-5. Here we describe a unique subsurface microbial community in which hydrogen-consuming, methane-producing Archaea far outnumber the Bacteria. More than 90% of the 16s ribosomal DNA sequences recovered from hydrothermal waters circulating through deeply buried igneous rocks in Idaho are related to hydrogen-using methanogenic microorganisms. Geochemical characterization indicates that geothermal hydrogen, not organic carbon, is the primary energy source for this methanogen-dominated microbial community. These results demonstrate that hydrogen-based methanogenic communities do occur in Earth's subsurface, providing an analogue for possible subsurface microbial ecosystems on other planets.

Biologically-initiated rock crust on sandstone: Mechanical and hydraulic properties and resistance to erosion

NASA Astrophysics Data System (ADS)

Slavík, Martin; Bruthans, Jiří; Filippi, Michal; Schweigstillová, Jana; Falteisek, Lukáš; Řihošek, Jaroslav

2017-02-01

Biocolonization on sandstone surfaces is known to play an important role in rock disintegration, yet it sometimes also aids in the protection of the underlying materials from rapid erosion. There have been few studies comparing the mechanical and/or hydraulic properties of the BIRC (Biologically-Initiated Rock Crust) with its subsurface. As a result, the overall effects of the BIRC are not yet well understood. The objective of the present study was to briefly characterize the BIRC from both the mineralogical and biological points of view, and especially to quantify the effect of the BIRC upon the mechanical and hydraulic properties of friable sandstone. The mineralogical investigation of a well-developed BIRC showed that its surface is enriched in kaolinite and clay- to silt-sized quartz particles. Total organic carbon increases with the age of the BIRC. Based on DNA sequencing and microscopy, the BIRC is formed by various fungi, including components of lichens and green algae. Using the method of drilling resistance, by measuring tensile strength, and based on water jet testing, it was determined that a BIRC is up to 12 times less erodible and has 3-35 times higher tensile strength than the subsurface friable sandstone. Saturated hydraulic conductivity of the studied BIRC is 15-300 times lower than the subsurface, and was measured to also decrease in capillary water absorption (2-33 times). Water-vapor diffusion is not significantly influenced by the presence of the BIRC. The BIRC thus forms a hardened surface which protects the underlying material from rain and flowing water erosion, and considerably modifies the sandstone's hydraulic properties. Exposing the material to calcination (550 °C), and experiments with the enzyme zymolyase indicated that a major contribution to the surface hardening is provided by organic matter. In firmer sandstones, the BIRC may still considerably decrease the rate of weathering, as it is capable of providing cohesion to strongly weathered (and disintegrated) sandstone surfaces. However, only a near-surface zone of the sandstone is stabilized by the BIRC, and additional sources of stabilization (gravity-induced stress, inorganic cement, etc.) contribute to the resistance of the subsurface zone of sandstone exposures.

INTERLABORATORY METHODS COMPARISON FOR THE TOTAL ORGANIC CARBON ANALYSIS OF AQUIFER MATERIALS

EPA Science Inventory

The total organic carbon (TOC) content of aquifer materials has been found to have significant effects on the movement of pollutants in the subsurface environment. Accurate quantification of TOC is therefore of great im- portance to research in groundwater contamination. However,...

Sampling Soil CO2 for Isotopic Flux Partitioning: Non Steady State Effects and Methodological Biases

NASA Astrophysics Data System (ADS)

Snell, H. S. K.; Robinson, D.; Midwood, A. J.

2014-12-01

Measurements of δ13C of soil CO2 are used to partition the surface flux into autotrophic and heterotrophic components. Models predict that the δ13CO2 of the soil efflux is perturbed by non-steady state (NSS) diffusive conditions. These could be large enough to render δ13CO2 unsuitable for accurate flux partitioning. Field studies sometimes find correlations between efflux δ13CO2 and flux or temperature, or that efflux δ13CO2 is not correlated as expected with biological drivers. We tested whether NSS effects in semi-natural soil were comparable with those predicted. We compared chamber designs and their sensitivity to changes in efflux δ13CO2. In a natural soil mesocosm, we controlled temperature to generate NSS conditions of CO2 production. We measured the δ13C of soil CO2 using in situ probes to sample the subsurface, and dynamic and forced-diffusion chambers to sample the surface efflux. Over eight hours we raised soil temperature by 4.5 OC to increase microbial respiration. Subsurface CO2 concentration doubled, surface efflux became 13C-depleted by 1 ‰ and subsurface CO2 became 13C-enriched by around 2 ‰. Opposite changes occurred when temperature was lowered and CO2 production was decreasing. Different chamber designs had inherent biases but all detected similar changes in efflux δ13CO2, which were comparable to those predicted. Measurements using dynamic chambers were more 13C-enriched than expected, probably due to advection of CO2 into the chamber. In the mesocosm soil, δ13CO2 of both efflux and subsurface was determined by physical processes of CO2 production and diffusion. Steady state conditions are unlikely to prevail in the field, so spot measurements of δ13CO2 and assumptions based on the theoretical 4.4 ‰ diffusive fractionation will not be accurate for estimating source δ13CO2. Continuous measurements could be integrated over a period suitable to reduce the influence of transient NSS conditions. It will be difficult to disentangle biologically driven changes in soil δ13CO2 from physical controls, particularly as they occur on similar timescales and are driven by the same environmental variables, such as temperature, moisture and daylight.

Enhanced Carbon Diffusion in Austenitic Stainless Steel Carburized at Low Temperature

NASA Astrophysics Data System (ADS)

Ernst, F.; Avishai, A.; Kahn, H.; Gu, X.; Michal, G. M.; Heuer, A. H.

2009-08-01

Austenitic stainless steel AISI 316L was carburized by a novel, low-temperature gas-phase process. Using a calibrated scanning Auger microprobe (SAM) analysis of cross-sectional specimens under dynamic sputtering, we determined the fraction-depth profile of carbon. The profile is concave—very different from the shape expected for concentration-independent diffusion—and indicates a carbide-free solid solution with carbon levels up to 15 at. pct and a case depth of ≈30 μm. A Boltzmann-Matano analysis with a careful evaluation of the stochastic and potential systematic errors indicates that increasing levels of carbon significantly enhance carbon diffusion. For the highest carbon level observed (15 at. pct), the carbon diffusion coefficient is more than two orders of magnitude larger than in dilute solution. The most likely explanation for this strong increase is that carbon-induced local expansion of metal-metal atom distances, observed as an expansion of the lattice parameter, reduces the activation energy for carbon diffusion.

Subsurface conditions in hydrothermal vents inferred from diffuse flow composition, and models of reaction and transport

NASA Astrophysics Data System (ADS)

Larson, B. I.; Houghton, J. L.; Lowell, R. P.; Farough, A.; Meile, C. D.

2015-08-01

Chemical gradients in the subsurface of mid-ocean ridge hydrothermal systems create an environment where minerals precipitate and dissolve and where chemosynthetic organisms thrive. However, owing to the lack of easy access to the subsurface, robust knowledge of the nature and extent of chemical transformations remains elusive. Here, we combine measurements of vent fluid chemistry with geochemical and transport modeling to give new insights into the under-sampled subsurface. Temperature-composition relationships from a geochemical mixing model are superimposed on the subsurface temperature distribution determined using a heat flow model to estimate the spatial distribution of fluid composition. We then estimate the distribution of Gibb's free energies of reaction beneath mid oceanic ridges and by combining flow simulations with speciation calculations estimate anhydrite deposition rates. Applied to vent endmembers observed at the fast spreading ridge at the East Pacific Rise, our results suggest that sealing times due to anhydrite formation are longer than the typical time between tectonic and magmatic events. The chemical composition of the neighboring low temperature flow indicates relatively uniform energetically favorable conditions for commonly inferred microbial processes such as methanogenesis, sulfate reduction and numerous oxidation reactions, suggesting that factors other than energy availability may control subsurface microbial biomass distribution. Thus, these model simulations complement fluid-sample datasets from surface venting and help infer the chemical distribution and transformations in subsurface flow.

Isolated molecular dopants in pentacene observed by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Ha, Sieu D.; Kahn, Antoine

2009-11-01

Doping is essential to the control of electronic structure and conductivity of semiconductor materials. Whereas doping of inorganic semiconductors is well established, doping of organic molecular semiconductors is still relatively poorly understood. Using scanning tunneling microscopy, we investigate, at the molecular scale, surface and subsurface tetrafluoro-tetracyanoquinodimethane p -dopants in the prototypical molecular semiconductor pentacene. Surface dopants diffuse to pentacene vacancies and appear as negatively charged centers, consistent with the standard picture of an ionized acceptor. Subsurface dopants, however, have the effect of a positive charge, evidence that the donated hole is localized by the parent acceptor counterion, in contrast to the model of doping in inorganic semiconductors. Scanning tunneling spectroscopy shows that the electron potential energy is locally lowered near a subsurface dopant feature, in agreement with the localized hole model.

CO2 snow depth and subsurface water-ice abundance in the northern hemisphere of Mars.

PubMed

Mitrofanov, I G; Zuber, M T; Litvak, M L; Boynton, W V; Smith, D E; Drake, D; Hamara, D; Kozyrev, A S; Sanin, A B; Shinohara, C; Saunders, R S; Tretyakov, V

2003-06-27

Observations of seasonal variations of neutron flux from the high-energy neutron detector (HEND) on Mars Odyssey combined with direct measurements of the thickness of condensed carbon dioxide by the Mars Orbiter Laser Altimeter (MOLA) on Mars Global Surveyor show a latitudinal dependence of northern winter deposition of carbon dioxide. The observations are also consistent with a shallow substrate consisting of a layer with water ice overlain by a layer of drier soil. The lower ice-rich layer contains between 50 and 75 weight % water, indicating that the shallow subsurface at northern polar latitudes on Mars is even more water rich than that in the south.

Study on nitrogen removal enhanced by shunt distributing wastewater in a constructed subsurface infiltration system under intermittent operation mode.

PubMed

Li, Yinghua; Li, Haibo; Sun, Tieheng; Wang, Xin

2011-05-15

Subsurface wastewater infiltration system is an efficient and economic technology in treating small scattered sewage. The removal rates are generally satisfactory in terms of COD, BOD(5), TP and SS removal; while nitrogen removal is deficient in most of the present operating SWIS due to the different requirements for the presence of oxygen for nitrification and denitrification processes. To study the enhanced nitrogen removal technologies, two pilot subsurface wastewater infiltration systems were constructed in a village in Shenyang, China. The filled matrix was a mixture of 5% activated sludge, 65% brown soil and 30% coal slag in volume ratio for both systems. Intermittent operation mode was applied in to supply sufficient oxygen to accomplish the nitrification; meanwhile sewage was supplemented as the carbon source to the lower part in to denitrify. The constructed subsurface wastewater infiltration systems worked successfully under wetting-drying ratio of 1:1 with hydraulic loading of 0.081 m(3)/(m(2)d) for over 4 months. Carbon source was supplemented with shunt ratio of 1:1 and shunt position at the depth of 0.5m. The experimental results showed that intermittent operation mode and carbon source supplementation could significantly enhance the nitrogen removal efficiency with little influence on COD and TP removal. The average removal efficiencies for NH(3)-N and TN were 87.7 ± 1.4 and 70.1 ± 1.0%, increased by 12.5 ± 1.0 and 8.6 ± 0.7%, respectively. Copyright © 2011 Elsevier B.V. All rights reserved.

Photosynthesis below the surface in a cryptic microbial mat

NASA Astrophysics Data System (ADS)

Rothschild, Lynn J.; Giver, Lorraine J.

2002-10-01

The discovery of subsurface communities has encouraged speculation that such communities might be present on planetary bodies exposed to harsh surface conditions, including the early Earth. While the astrobiology community has focused on the deep subsurface, near-subsurface environments are unique in that they provide some protection while allowing partial access to photosynthetically active radiation. Previously we identified near-surface microbial communities based on photosynthesis. Here we assess the productivity of such an ecosystem by measuring in situ carbon fixation rates in an intertidal marine beach through a diurnal cycle, and find them surprisingly productive. Gross fixation along a transect (99×1 m) perpendicular to the shore was highly variable and depended on factors such as moisture and mat type, with a mean of ~41 mg C fixed m[minus sign]2 day[minus sign]1. In contrast, an adjacent well-established cyanobacterial mat dominated by Lyngbya aestuarii was ~12 times as productive (~500 mg C fixed m[minus sign]2 day[minus sign]1). Measurements made of the Lyngbya mat at several times per year revealed a correlation between total hours of daylight and gross daily production. From these data, annual gross fixation was estimated for the Lyngbya mat and yielded a value of ~1.3×105 g m[minus sign]2 yr[minus sign]1. An analysis of pulse-chase data obtained in the study in conjunction with published literature on similar ecosystems suggests that subsurface interstitial mats may be an overlooked endogenous source of organic carbon, mostly in the form of excreted fixed carbon.

Collective diffusion in carbon nanotubes: Crossover between one dimension and three dimensions

NASA Astrophysics Data System (ADS)

Chen, Pei-Rong; Xu, Zhi-Cheng; Gu, Yu; Zhong, Wei-Rong

2016-08-01

Using non-equilibrium molecular dynamics and Monte Carlo methods, we study the collective diffusion of helium in carbon nanotubes. The results show that the collective diffusion coefficient (CDC) increases with the dimension of the channel. The collective diffusion coefficient has a linear relationship with the temperature and the concentration. There exist a ballistic transport in short carbon nanotubes and a diffusive transport in long carbon nanotubes. Fick’s law has an invalid region in the nanoscale channel. Project supported by the National Natural Science Foundation of China (Grant Nos. 11004082 and 11291240477), the Natural Science Foundation of Guangdong Province, China (Grant No. 2014A030313367), and the Fundamental Research Funds for the Central Universities, Jinan University (Grant No. 11614341).

First principles study of intrinsic defects in hexagonal tungsten carbide

NASA Astrophysics Data System (ADS)

Kong, Xiang-Shan; You, Yu-Wei; Xia, J. H.; Liu, C. S.; Fang, Q. F.; Luo, G.-N.; Huang, Qun-Ying

2010-11-01

The characteristics of intrinsic defects are important for the understanding of self-diffusion processes, mechanical strength, brittleness, and plasticity of tungsten carbide, which are present in the divertor of fusion reactors. Here, we use first-principles calculations to investigate the stability of point defects and their complexes in tungsten carbide. Our results confirm that the defect formation energies of carbon are much lower than that of tungsten and reveal the carbon vacancy to be the dominant defect in tungsten carbide. The C sbnd C dimer configuration along the dense a direction is the most stable configuration of carbon interstitial defect. The results of carbon defect diffusion show that the carbon vacancy stay for a wide range of temperature because of extremely high diffusion barriers, while carbon interstitial migration is activated at lower temperatures for its considerably lower activation energy. Both of them prefer to diffusion in carbon basal plane.

Thermally Stable and Electrically Conductive, Vertically Aligned Carbon Nanotube/Silicon Infiltrated Composite Structures for High-Temperature Electrodes.

PubMed

Zou, Qi Ming; Deng, Lei Min; Li, Da Wei; Zhou, Yun Shen; Golgir, Hossein Rabiee; Keramatnejad, Kamran; Fan, Li Sha; Jiang, Lan; Silvain, Jean-Francois; Lu, Yong Feng

2017-10-25

Traditional ceramic-based, high-temperature electrode materials (e.g., lanthanum chromate) are severely limited due to their conditional electrical conductivity and poor stability under harsh circumstances. Advanced composite structures based on vertically aligned carbon nanotubes (VACNTs) and high-temperature ceramics are expected to address this grand challenge, in which ceramic serves as a shielding layer protecting the VACNTs from the oxidation and erosive environment, while the VACNTs work as a conductor. However, it is still a great challenge to fabricate VACNT/ceramic composite structures due to the limited diffusion of ceramics inside the VACNT arrays. In this work, we report on the controllable fabrication of infiltrated (and noninfiltrated) VACNT/silicon composite structures via thermal chemical vapor deposition (CVD) [and laser-assisted CVD]. In laser-assisted CVD, low-crystalline silicon (Si) was quickly deposited at the VACNT subsurfaces/surfaces followed by the formation of high-crystalline Si layers, thus resulting in noninfiltrated composite structures. Unlike laser-assisted CVD, thermal CVD activated the precursors inside and outside the VACNTs simultaneously, which realized uniform infiltrated VACNT/Si composite structures. The growth mechanisms for infiltrated and noninfiltrated VACNT/ceramic composites, which we attributed to the different temperature distributions and gas diffusion mechanism in VACNTs, were investigated. More importantly, the as-farbicated composite structures exhibited excellent multifunctional properties, such as excellent antioxidative ability (up to 1100 °C), high thermal stability (up to 1400 °C), good high velocity hot gas erosion resistance, and good electrical conductivity (∼8.95 Sm -1 at 823 K). The work presented here brings a simple, new approach to the fabrication of advanced composite structures for hot electrode applications.

A locally conservative stabilized continuous Galerkin finite element method for two-phase flow in poroelastic subsurfaces

NASA Astrophysics Data System (ADS)

Deng, Q.; Ginting, V.; McCaskill, B.; Torsu, P.

2017-10-01

We study the application of a stabilized continuous Galerkin finite element method (CGFEM) in the simulation of multiphase flow in poroelastic subsurfaces. The system involves a nonlinear coupling between the fluid pressure, subsurface's deformation, and the fluid phase saturation, and as such, we represent this coupling through an iterative procedure. Spatial discretization of the poroelastic system employs the standard linear finite element in combination with a numerical diffusion term to maintain stability of the algebraic system. Furthermore, direct calculation of the normal velocities from pressure and deformation does not entail a locally conservative field. To alleviate this drawback, we propose an element based post-processing technique through which local conservation can be established. The performance of the method is validated through several examples illustrating the convergence of the method, the effectivity of the stabilization term, and the ability to achieve locally conservative normal velocities. Finally, the efficacy of the method is demonstrated through simulations of realistic multiphase flow in poroelastic subsurfaces.

Regolith-atmosphere exchange of water in Mars' recent past

NASA Astrophysics Data System (ADS)

Steele, Liam J.; Balme, Matthew R.; Lewis, Stephen R.

2017-03-01

We investigate the exchange of water vapour between the regolith and atmosphere of Mars, and how it varies with different orbital parameters, atmospheric dust contents and surface water ice reservoirs. This is achieved through the coupling of a global circulation model (GCM) and a regolith diffusion model. GCM simulations are performed for hundreds of Mars years, with additional one-dimensional simulations performed for 50 kyr. At obliquities ɛ =15∘ and 30°, the thermal inertia and albedo of the regolith have more control on the subsurface water distribution than changes to the eccentricity or solar longitude of perihelion. At ɛ =45∘ , atmospheric water vapour abundances become much larger, allowing stable subsurface ice to form in the tropics and mid-latitudes. The circulation of the atmosphere is important in producing the subsurface water distribution, with increased water content in various locations due to vapour transport by topographically-steered flows and stationary waves. As these circulation patterns are due to topographic features, it is likely the same regions will also experience locally large amounts of subsurface water at different epochs. The dustiness of the atmosphere plays an important role in the distribution of subsurface water, with a dusty atmosphere resulting in a wetter water cycle and increased stability of subsurface ice deposits.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

New insights into the nation's carbon storage potential

USGS Publications Warehouse

Warwick, Peter D.; Zhu, Zhi-Liang

2012-01-01

Carbon sequestration is a method of securing carbon dioxide (CO2) to prevent its release into the atmosphere, where it contributes to global warming as a greenhouse gas. Geologic storage of CO2 in porous and permeable rocks involves injecting high-pressure CO2 into a subsurface rock unit that has available pore space. Biologic carbon sequestration refers to both natural and anthropogenic processes by which CO2 is removed from the atmosphere and stored as carbon in vegetation, soils, and sediments.

Migration of carbon dioxide included micro-nano bubble water in porous media and its monitoring

NASA Astrophysics Data System (ADS)

Takemura, T.; Hamamoto, S.; Suzuki, K.; Koichi, O.

2017-12-01

The distributed CO2 storage is the small scale storage and its located near the emission areas. In the distributed CO2 storage, the CO2 is neutralized by sediment and underground water in the subsurface region (300-500m depth). Carbon dioxide (CO2) included micro-nano bubbles is one approach in neutralizing CO2 and sediments by increasing CO2 volume per unit volume of water and accelerating the chemical reaction. In order to design underground treatment for CO2 gas in the subsurface, it is required to elucidate the behavior of CO2 included micro-nano bubbles in the water. In this study, we carried out laboratory experiment using the soil tank, and measure the amount of leakage of CO2 gas at the surface. In addition, the process of migration of carbon dioxide included micro-nano bubble was monitored by the nondestructive method, wave velocity and resistivity.

Reconstructing a hydrogen-driven microbial metabolic network in Opalinus Clay rock.

PubMed

Bagnoud, Alexandre; Chourey, Karuna; Hettich, Robert L; de Bruijn, Ino; Andersson, Anders F; Leupin, Olivier X; Schwyn, Bernhard; Bernier-Latmani, Rizlan

2016-10-14

The Opalinus Clay formation will host geological nuclear waste repositories in Switzerland. It is expected that gas pressure will build-up due to hydrogen production from steel corrosion, jeopardizing the integrity of the engineered barriers. In an in situ experiment located in the Mont Terri Underground Rock Laboratory, we demonstrate that hydrogen is consumed by microorganisms, fuelling a microbial community. Metagenomic binning and metaproteomic analysis of this deep subsurface community reveals a carbon cycle driven by autotrophic hydrogen oxidizers belonging to novel genera. Necromass is then processed by fermenters, followed by complete oxidation to carbon dioxide by heterotrophic sulfate-reducing bacteria, which closes the cycle. This microbial metabolic web can be integrated in the design of geological repositories to reduce pressure build-up. This study shows that Opalinus Clay harbours the potential for chemolithoautotrophic-based system, and provides a model of microbial carbon cycle in deep subsurface environments where hydrogen and sulfate are present.

Reconstructing a hydrogen-driven microbial metabolic network in Opalinus Clay rock

PubMed Central

Bagnoud, Alexandre; Chourey, Karuna; Hettich, Robert L.; de Bruijn, Ino; Andersson, Anders F.; Leupin, Olivier X.; Schwyn, Bernhard; Bernier-Latmani, Rizlan

2016-01-01

The Opalinus Clay formation will host geological nuclear waste repositories in Switzerland. It is expected that gas pressure will build-up due to hydrogen production from steel corrosion, jeopardizing the integrity of the engineered barriers. In an in situ experiment located in the Mont Terri Underground Rock Laboratory, we demonstrate that hydrogen is consumed by microorganisms, fuelling a microbial community. Metagenomic binning and metaproteomic analysis of this deep subsurface community reveals a carbon cycle driven by autotrophic hydrogen oxidizers belonging to novel genera. Necromass is then processed by fermenters, followed by complete oxidation to carbon dioxide by heterotrophic sulfate-reducing bacteria, which closes the cycle. This microbial metabolic web can be integrated in the design of geological repositories to reduce pressure build-up. This study shows that Opalinus Clay harbours the potential for chemolithoautotrophic-based system, and provides a model of microbial carbon cycle in deep subsurface environments where hydrogen and sulfate are present. PMID:27739431

Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

2018-03-01

Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

Development of anomaly detection models for deep subsurface monitoring

NASA Astrophysics Data System (ADS)

Sun, A. Y.

2017-12-01

Deep subsurface repositories are used for waste disposal and carbon sequestration. Monitoring deep subsurface repositories for potential anomalies is challenging, not only because the number of sensor networks and the quality of data are often limited, but also because of the lack of labeled data needed to train and validate machine learning (ML) algorithms. Although physical simulation models may be applied to predict anomalies (or the system's nominal state for that sake), the accuracy of such predictions may be limited by inherent conceptual and parameter uncertainties. The main objective of this study was to demonstrate the potential of data-driven models for leakage detection in carbon sequestration repositories. Monitoring data collected during an artificial CO2 release test at a carbon sequestration repository were used, which include both scalar time series (pressure) and vector time series (distributed temperature sensing). For each type of data, separate online anomaly detection algorithms were developed using the baseline experiment data (no leak) and then tested on the leak experiment data. Performance of a number of different online algorithms was compared. Results show the importance of including contextual information in the dataset to mitigate the impact of reservoir noise and reduce false positive rate. The developed algorithms were integrated into a generic Web-based platform for real-time anomaly detection.

Modeling the suppression of boron transient enhanced diffusion in silicon by substitutional carbon incorporation

NASA Astrophysics Data System (ADS)

Ngau, Julie L.; Griffin, Peter B.; Plummer, James D.

2001-08-01

Recent work has indicated that the suppression of boron transient enhanced diffusion (TED) in carbon-rich Si is caused by nonequilibrium Si point defect concentrations, specifically the undersaturation of Si self-interstitials, that result from the coupled out-diffusion of carbon interstitials via the kick-out and Frank-Turnbull reactions. This study of boron TED reduction in Si1-x-yGexCy during 750 °C inert anneals has revealed that the use of an additional reaction that further reduces the Si self-interstitial concentration is necessary to describe accurately the time evolved diffusion behavior of boron. In this article, we present a comprehensive model which includes {311} defects, boron-interstitial clusters, a carbon kick-out reaction, a carbon Frank-Turnbull reaction, and a carbon interstitial-carbon substitutional (CiCs) pairing reaction that successfully simulates carbon suppression of boron TED at 750 °C for anneal times ranging from 10 s to 60 min.

Phylogenetic and Functional Diversity of Microbial Communities Associated with Subsurface Sediments of the Sonora Margin, Guaymas Basin

PubMed Central

Vigneron, Adrien; Cruaud, Perrine; Roussel, Erwan G.; Pignet, Patricia; Caprais, Jean-Claude; Callac, Nolwenn; Ciobanu, Maria-Cristina; Godfroy, Anne; Cragg, Barry A.; Parkes, John R.; Van Nostrand, Joy D.; He, Zhili; Zhou, Jizhong; Toffin, Laurent

2014-01-01

Subsurface sediments of the Sonora Margin (Guaymas Basin), located in proximity of active cold seep sites were explored. The taxonomic and functional diversity of bacterial and archaeal communities were investigated from 1 to 10 meters below the seafloor. Microbial community structure and abundance and distribution of dominant populations were assessed using complementary molecular approaches (Ribosomal Intergenic Spacer Analysis, 16S rRNA libraries and quantitative PCR with an extensive primers set) and correlated to comprehensive geochemical data. Moreover the metabolic potentials and functional traits of the microbial community were also identified using the GeoChip functional gene microarray and metabolic rates. The active microbial community structure in the Sonora Margin sediments was related to deep subsurface ecosystems (Marine Benthic Groups B and D, Miscellaneous Crenarchaeotal Group, Chloroflexi and Candidate divisions) and remained relatively similar throughout the sediment section, despite defined biogeochemical gradients. However, relative abundances of bacterial and archaeal dominant lineages were significantly correlated with organic carbon quantity and origin. Consistently, metabolic pathways for the degradation and assimilation of this organic carbon as well as genetic potentials for the transformation of detrital organic matters, hydrocarbons and recalcitrant substrates were detected, suggesting that chemoorganotrophic microorganisms may dominate the microbial community of the Sonora Margin subsurface sediments. PMID:25099369

Effect of Iron and Carbonation of the Diffusion of Iodine and Rhenium in Waste Encasement Concrete and Soil Fill Material under Hydraulically Unsaturated Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wellman, Dawn M.; Parker, Kent E.; Powers, Laura

2008-07-31

Assessing long-term performance of Category 3 cement wasteforms and accurate prediction for radionuclide encasement requires knowledge of the radionuclide-cement interactions and mechanisms of retention (i.e. sorption or precipitation). A set of sediment-concrete half-cell diffusion experiments was conducted under unsaturated conditions (4% and 7% by weight moisture content) using carbonated and non-carbonated concrete-soil half-cells. Results indicate the behavior of rhenium and iodine release was comparable within a given half-cell test. Diffusivity in soil is a function of moisture content; a 3% increase in moisture content affords a one to two order of magnitude increase in diffusivity. Release of iodine and rheniummore » was 1 to 3 orders of magnitude less from non-carbonated, relative to carbonated, concrete monoliths. Inclusion of iron in non-carbonate monoliths resulted in the lowest concrete diffusivity values for both iodine and rhenium. This suggests that in the presence of iron, iodine and rhenium are converted to reduced species, which are less soluble and better retained within the concrete monolith. The release of iodine and rhenium was greatest from iron-bearing, carbonated concrete monoliths, suggesting carbonation negates the effect of iron on the retention of iodine and rhenium within concrete monoliths. This is likely due to enhanced formation of microcracks in the presence of iron, which provide preferential paths for contaminant migration. Although the release of iodine and rhenium were greatest from carbonated concrete monoliths containing iron, the migration of iodine and rhenium within a given half-cell is dependent on the moisture content, soil diffusivity, and diffusing species.« less

Heat transfer, diffusion, and evaporation

NASA Technical Reports Server (NTRS)

Nusselt, Wilhelm

1954-01-01

Although it has long been known that the differential equations of the heat-transfer and diffusion processes are identical, application to technical problems has only recently been made. In 1916 it was shown that the speed of oxidation of the carbon in iron ore depends upon the speed with which the oxygen of the combustion air diffuses through the core of gas surrounding the carbon surface. The identity previously referred to was then used to calculate the amount of oxygen diffusing to the carbon surface on the basis of the heat transfer between the gas stream and the carbon surface. Then in 1921, H. Thoma reversed that procedure; he used diffusion experiments to determine heat-transfer coefficients. Recently Lohrisch has extended this work by experiment. A technically very important application of the identity of heat transfer and diffusion is that of the cooling tower, since in this case both processes occur simultaneously.

Laboratory Experiments to Evaluate Matrix Diffusion of Dissolved Organic Carbon Carbon-14 in Southern Nevada Fractured-rock Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hershey, Ronald L.; Fereday, Wyatt

Dissolved inorganic carbon (DIC) carbon-14 ( 14C) is used to estimate groundwater ages by comparing the DIC 14C content in groundwater in the recharge area to the DIC 14C content in the downgradient sampling point. However, because of chemical reactions and physical processes between groundwater and aquifer rocks, the amount of DIC 14C in groundwater can change and result in 14C loss that is not because of radioactive decay. This loss of DIC 14C results in groundwater ages that are older than the actual groundwater ages. Alternatively, dissolved organic carbon (DOC) 14C in groundwater does not react chemically with aquifermore » rocks, so DOC 14C ages are generally younger than DIC 14C ages. In addition to chemical reactions, 14C ages may also be altered by the physical process of matrix diffusion. The net effect of a continuous loss of 14C to the aquifer matrix by matrix diffusion and then radioactive decay is that groundwater appears to be older than it actually is. Laboratory experiments were conducted to measure matrix diffusion coefficients for DOC 14C in volcanic and carbonate aquifer rocks from southern Nevada. Experiments were conducted using bromide (Br-) as a conservative tracer and 14C-labeled trimesic acid (TMA) as a surrogate for groundwater DOC. Outcrop samples from six volcanic aquifers and five carbonate aquifers in southern Nevada were used. The average DOC 14C matrix diffusion coefficient for volcanic rocks was 2.9 x 10 -7 cm 2/s, whereas the average for carbonate rocks was approximately the same at 1.7 x 10 -7 cm 2/s. The average Br- matrix diffusion coefficient for volcanic rocks was 10.4 x 10 -7 cm 2/s, whereas the average for carbonate rocks was less at 6.5 x 10 -7 cm 2/s. Carbonate rocks exhibited greater variability in DOC 14C and Br- matrix diffusion coefficients than volcanic rocks. These results confirmed, at the laboratory scale, that the diffusion of DOC 14C into southern Nevada volcanic and carbonate aquifers is slower than DIC 14C. Because of the apparent sorption of 14C-labeled TMA in the experiments, matrix diffusion coefficients are likely even lower. The reasons for the higher than expected Br-/ 14C-labeled TMA are unknown. Because the molecular size of TMA is on the low end of the range in molecular size for typical humic substances, the matrix diffusion coefficients for the 14C-labeled TMA likely represent close to the maximum diffusion rates for DOC 14C in the volcanic and carbonate aquifers in southern Nevada.« less

Acidification of subsurface coastal waters enhanced by eutrophication

EPA Science Inventory

Uptake of fossil-fuel carbon dioxide (CO2) from the atmosphere has acidified the surface ocean by ~0.1 pH units and driven down the carbonate saturation state. Ocean acidification is a threat to marine ecosystems and may alter key biogeochemical cycles. Coastal oceans have also b...

A HIERARCHICAL MODELING FRAMEWORK FOR GEOLOGICAL STORAGE OF CARBON DIOXIDE

EPA Science Inventory

Carbon Capture and Storage, or CCS, is likely to be an important technology in a carbonconstrained world. CCS will involve subsurface injection of massive amounts of captured CO₂, on a scale that has not previously been approached. The unprecedented scale of t...

Efforts to estimate pesticide degradation rates in subsurface ...

EPA Pesticide Factsheets

When pesticides are used in real-world settings, the objective is to be effective in pest eradication at the site of application, but also it is desired that the pesticide have minimal persistence and mobility as it migrates away from the application site. At the site of application, sorption on soil and surface-soil degradation rates both factor into the pesticides' persistence. But once it migrates to the subsurface vadose zone and/or aquifers, subsurface degradation rate is a factor as well. Unfortunately, numerous soil properties that might affect pesticide degradation rate vary by orders of magnitude in the subsurface environment, both spatially and temporally, e.g., organic-carbon concentration, oxygen concentration, redox conditions, pH and soil mineralogy. Consequently, estimation of subsurface pesticide degradation rates and, in tum, pesticide persistence and mobility in the environment, has remained a challenge. To address this intransigent uncertainty, we surveyed peer-reviewed literature to identify > 100 data pairs in which investigators reported pesticide degradation rates in both surface and subsurface soils, using internally consistent experimental methods. These > 100 data pairs represented >30 separate pesticides. When the > 100 subsurface half-lives were plotted against surface half-lives, a limiting line could be defined for which all subsurface half-lives but three fe ll below the line. Of the three data points plotting above the limiting li

Bacterial communities associated with subsurface geochemical processes in continental serpentinite springs.

PubMed

Brazelton, William J; Morrill, Penny L; Szponar, Natalie; Schrenk, Matthew O

2013-07-01

Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats.

Bacterial Communities Associated with Subsurface Geochemical Processes in Continental Serpentinite Springs

PubMed Central

Morrill, Penny L.; Szponar, Natalie; Schrenk, Matthew O.

2013-01-01

Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats. PMID:23584766

Effects of dilute substitutional solutes on interstitial carbon in α-Fe: Interactions and associated carbon diffusion from first-principles calculations

NASA Astrophysics Data System (ADS)

Liu, Peitao; Xing, Weiwei; Cheng, Xiyue; Li, Dianzhong; Li, Yiyi; Chen, Xing-Qiu

2014-07-01

By means of first-principles calculations coupled with the kinetic Monte Carlo simulations, we have systematically investigated the effects of dilute substitutional solutes on the behaviors of carbon in α-Fe. Our results uncover the following. (i) Without the Fe vacancy the interactions between most solutes and carbon are repulsive due to the strain relief, whereas Mn has a weak attractive interaction with its nearest-neighbor carbon due to the local ferromagnetic coupling effect. (ii) The presence of the Fe vacancy results in attractive interactions of all the solutes with carbon. In particular, the Mn-vacancy pair shows an exceptionally large binding energy of -0.81 eV with carbon. (iii) The alloying addition significantly impacts the atomic-scale concentration distributions and chemical potential of carbon in the Fe matrix. Among them, Mn and Cr increase the carbon chemical potential, whereas Al and Si reduce it. (iv) Within the dilute scale of the alloying solution, the solute concentration- and temperature-dependent carbon diffusivities demonstrate that Mn has a little impact on the carbon diffusion, whereas Cr (Al or Si) remarkably retards the carbon diffusion. Our results provide a certain implication for better understanding the experimental observations related with the carbon solubility limit, carbon microsegregation, and carbide precipitations in the ferritic steels.

A High-Resolution Multitechniques Approach to Characterize Bio-Organo-Mineral Associations Within Rock Samples: Tracking Biological vs Abiotic Processes? Towards a Better Understanding of the Deep Carbon Cycle.

NASA Astrophysics Data System (ADS)

Pisapia, C.

2015-12-01

Among all elements, carbon plays one of the major roles for the sustainability of life on Earth. Past considerations of the carbon cycle have mainly focused on surface processes occurring at the atmosphere, oceans and shallow crustal environments. By contrast, little is known about the Deep Carbon cycle whereas both geochemical and biological processes may induce organic carbon production and/or consumption at depth. Indeed, the nowadays-recognized capability of geochemical processes such as serpentinization to generate abiotic organic compounds as well as the existence of a potentially important intraterrestrial life raises questions about the limit of biotic/abiotic carbon on Earth's deep interior and how it impacts global biogeochemical cycles. It is then mandatory to increase our knowledge on the nature and extent of carbon reservoirs along with their sources, sinks and fluxes in the subsurface. This implies to be able to finely characterize organomineral associations within crustal rocks although it might be hampered by the scarceness and heterogeneous micrometric spatial distribution of organic molecules in natural rocks. We then developed an in situ analytical strategy based on the combination of high-resolution techniques to track organic molecules at the pore level in natural rocks and to determine their biological or abiotic origin. We associated classical high-resolution techniques and synchrotron-based imaging techniques in order to characterize their nature and localization (SEM/TEM, coupled CLSM/Raman spectroscopy, Tof-SIMS) along with their 3D-distribution relatively to mineral phases (S-FTIR, S-DeepUV, XANES, Biphoton microscopy). The effectiveness of this approach to shed light on the speciation and nature of carbon in subsurface environments will be illustrated through the study of (i) subsurface ecosystems and abiotic organic carbon within ultramafic rocks of the oceanic lithosphere as putative analogs for the nature and functioning of primitive ecosystems on Earth and of (ii) ecosystems inhabiting Archean craton and potentially playing a role in punk-rock karstification processes and rocks weathering.

Patterns and drivers of bacterial α- and β-diversity across vertical profiles from surface to subsurface sediments.

PubMed

Luna, Gian Marco; Corinaldesi, Cinzia; Rastelli, Eugenio; Danovaro, Roberto

2013-10-01

We investigated the patterns and drivers of bacterial α- and β-diversity, along with viral and prokaryotic abundance and the carbon production rates, in marine surface and subsurface sediments (down to 1 m depth) in two habitats: vegetated sediments (seagrass meadow) and non-vegetated sediments. Prokaryotic abundance and production decreased with depth in the sediment, but cell-specific production rates and the virus-to-prokaryote ratio increased, highlighting unexpectedly high activity in the subsurface. The highest diversity was observed in vegetated sediments. Bacterial β-diversity between sediment horizons was high, and only a minor number of taxa was shared between surface and subsurface layers. Viruses significantly contributed to explain α- and β-diversity patterns. Despite potential limitations due to the only use of fingerprinting techniques, this study indicates that the coastal subsurface host highly active and diversified bacterial assemblages, that subsurface cells are more active than expected and that viruses promote β-diversity and stimulate bacterial metabolism in subsurface layers. The limited number of taxa shared between habitats, and between surface and subsurface sediment horizons, suggests that future investigations of the shallow subsurface will provide insights into the census of bacterial diversity, and the comprehension of the patterns and drivers of prokaryotic diversity in marine ecosystems. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

Sources of fatty acids in Lake Michigan surface microlayers and subsurface waters

NASA Astrophysics Data System (ADS)

Meyers, Philip A.; Owen, Robert M.

1980-11-01

Fatty acid and organic carbon contents have been measured in the particulate and dissolved phases of surface microlayer and subsurface water samples collected from Lake Michigan. Concentrations are highest close to fluvial sources and lowest in offshore areas, yet surface/subsurface fractionation is lowest near river mouths and highest in open lake locations. These gradients plus accompanying fatty acid compositional changes indicate that river-borne organic materials are important constituents of coastal Lake Michigan microlayers and that sinking and turbulent resuspension of particulates affect surface film characteristics. Lake neuston and plankton contribute organic components which partially replace potamic materials removed by sinking.

Application of Carbonate Reservoir using waveform inversion and reverse-time migration methods

NASA Astrophysics Data System (ADS)

Kim, W.; Kim, H.; Min, D.; Keehm, Y.

2011-12-01

Recent exploration targets of oil and gas resources are deeper and more complicated subsurface structures, and carbonate reservoirs have become one of the attractive and challenging targets in seismic exploration. To increase the rate of success in oil and gas exploration, it is required to delineate detailed subsurface structures. Accordingly, migration method is more important factor in seismic data processing for the delineation. Seismic migration method has a long history, and there have been developed lots of migration techniques. Among them, reverse-time migration is promising, because it can provide reliable images for the complicated model even in the case of significant velocity contrasts in the model. The reliability of seismic migration images is dependent on the subsurface velocity models, which can be extracted in several ways. These days, geophysicists try to obtain velocity models through seismic full waveform inversion. Since Lailly (1983) and Tarantola (1984) proposed that the adjoint state of wave equations can be used in waveform inversion, the back-propagation techniques used in reverse-time migration have been used in waveform inversion, which accelerated the development of waveform inversion. In this study, we applied acoustic waveform inversion and reverse-time migration methods to carbonate reservoir models with various reservoir thicknesses to examine the feasibility of the methods in delineating carbonate reservoir models. We first extracted subsurface material properties from acoustic waveform inversion, and then applied reverse-time migration using the inverted velocities as a background model. The waveform inversion in this study used back-propagation technique, and conjugate gradient method was used in optimization. The inversion was performed using the frequency-selection strategy. Finally waveform inversion results showed that carbonate reservoir models are clearly inverted by waveform inversion and migration images based on the inversion results are quite reliable. Different thicknesses of reservoir models were also described and the results revealed that the lower boundary of the reservoir was not delineated because of energy loss. From these results, it was noted that carbonate reservoirs can be properly imaged and interpreted by waveform inversion and reverse-time migration methods. This work was supported by the Energy Resources R&D program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Knowledge Economy (No. 2009201030001A, No. 2010T100200133) and the Brain Korea 21 project of Energy System Engineering.

Quantification of the effect of temperature gradients in soils on subsurface radon signal

NASA Astrophysics Data System (ADS)

Haquin, Gustavo; Ilzycer, Danielle; Kamai, Tamir; Zafrir, Hovav; Weisbrod, Noam

2017-04-01

Temperature gradients that develop in soils due to atmospheric temperature cycles are factors of primary importance in determining the rates and directions of subsurface gas flow. Models including mechanisms of thermal convection and thermal diffusion partially explain the impact of temperature gradients on subsurface radon transport. However, the overall impact of temperature gradients on subsurface radon transport is still not well understood. A laboratory setup was designed and built to experimentally investigate the influence of temperature gradients on radon transport under well controlled conditions. A 60 cm diameter and 120 cm tall column was thermally insulated except from the atmosphere-soil interface, such that it was constructed to simulate field conditions where temperature gradients in soils are developed following atmospheric temperature cycles. The column was filled with fine grinded phosphate rock which provided the porous media with radon source. Radon in soil-air was continuously monitored using NaI gamma detectors positioned at different heights along the column. Soil temperature, differential pressure, and relative humidity were monitored along the column. Experiments based on steep and gradual stepwise changes in ambient temperature were conducted. Absolute changes on radon levels in the order of 10-30% were measured at temperature gradients of up to ±20oC/m. Results showed a non-linear correlation between the temperature gradient and the subsurface radon concentration. An asymmetric relationship between the radon concentration and the temperature gradients for ΔT>0 and ΔT<0 was also observed. Laboratory simulations of the time- and depth-dependent temperature wave functions with frequencies ranged from a daily cycle to few days were performed. In response to the harmonic temperature behaviour radon oscillations at similar frequencies were detected correspondingly. In this work a quantitative relationship between radon and temperature gradients will be presented for cases beyond the classical conditions for thermal convection and thermal diffusion.

The double-edged effects of annealing MgO underlayers on the efficient synthesis of single-wall carbon nanotube forests.

PubMed

Tsuji, Takashi; Hata, Kenji; Futaba, Don N; Sakurai, Shunsuke

2017-11-16

Recently, the millimetre-scale, highly efficient synthesis of single-wall carbon nanotube (SWCNT) forests from Fe catalysts has been reported through the annealing of the magnesia (MgO) underlayer. Here, we report the double-edged effects of underlayer annealing on the efficiency and structure of the SWCNT forest synthesis through a temperature-dependent examination. Our results showed that the efficiency of the SWCNT forests sharply increased with increased underlayer annealing temperatures from 600 °C up to 900 °C due to a temperature-dependent structural modification, characterized by increased grain size and reduced defects, of the MgO underlayer. Beyond this temperature, the SWCNT fraction also decreased as a result of further structural modification of the MgO underlayer. This exemplifies the double-edged effects of annealing. Specifically, for underlayer annealing below 600 °C, the catalyst subsurface diffusion was found to limit the growth efficiency, and for excessively high underlayer annealing temperatures (>900 °C), catalyst coalescence/ripening led to the formation of double-wall carbon nanotubes. As a result, three distinct regions of synthesis were observed: (i) a "low yield" region below a threshold temperature (∼600 °C); (ii) an "increased yield" region from 600 to 900 °C, and (iii) a "saturation" region above 900 °C. The efficient SWCNT forest synthesis could only occur within a specific annealing temperature window as a result of this double-edged effects of underlayer annealing.

Calculation of thermal conductivity, thermal diffusivity and specific heat capacity of sedimentary rocks using petrophysical well logs

NASA Astrophysics Data System (ADS)

Fuchs, Sven; Balling, Niels; Förster, Andrea

2015-12-01

In this study, equations are developed that predict for synthetic sedimentary rocks (clastics, carbonates and evapourates) thermal properties comprising thermal conductivity, specific heat capacity and thermal diffusivity. The rock groups are composed of mineral assemblages with variable contents of 15 major rock-forming minerals and porosities of 0-30 per cent. Petrophysical properties and their well-logging-tool-characteristic readings were assigned to these rock-forming minerals and to pore-filling fluids. Relationships are explored between each thermal property and other petrophysical properties (density, sonic interval transit time, hydrogen index, volume fraction of shale and photoelectric absorption index) using multivariate statistics. The application of these relations allows computing continuous borehole profiles for each rock thermal property. The uncertainties in the prediction of each property vary depending on the selected well-log combination. Best prediction is in the range of 2-8 per cent for the specific heat capacity, of 5-10 per cent for the thermal conductivity, and of 8-15 for the thermal diffusivity, respectively. Well-log derived thermal conductivity is validated by laboratory data measured on cores from deep boreholes of the Danish Basin, the North German Basin, and the Molasse Basin. Additional validation of thermal conductivity was performed by comparing predicted and measured temperature logs. The maximum deviation between these logs is <3 °C. The thermal-conductivity calculation allowed an evaluation of the depth range in which the palaeoclimatic effect on the subsurface temperature field can be observed in the North German Basin. This effect reduces the surface heat-flow density by 25 mW m-2.

How CO2 Leakage May Impact the Role of Geologic Carbon Storage in Climate Mitigation

NASA Astrophysics Data System (ADS)

Peters, C. A.; Deng, H.; Bielicki, J. M.; Fitts, J. P.; Oppenheimer, M.

2014-12-01

Among CCUS technologies (Carbon Capture Utilization and Sequestration), geological storage of CO2 has a large potential to mitigate greenhouse gas emissions, but confidence in its deployment is often clouded by the possibility and cost of leakage. In this study, we took the Michigan sedimentary basin as an example to investigate the monetized risks associated with leakage, using the Risk Interference of Subsurface CO2 Storage (RISCS) model. The model accounts for spatial heterogeneity and variability of hydraulic properties of the subsurface system and permeability of potential leaking wells. In terms of costs, the model quantifies the financial consequences of CO2 escaping back to the atmosphere as well as the costs incurred if CO2 or brine leaks into overlying formations and interferes with other subsurface activities or resources. The monetized leakage risks derived from the RISCS model were then used to modify existing cost curves by shifting them upwards and changing their curvatures. The modified cost curves were used in the integrated assessment model - GCAM (Global Change Assessment Model), which provides policy-relevant results to help inform the potential role of CCUS in future energy systems when carbon mitigation targets and incentives are in place. The results showed that the extent of leakage risks has a significant effect on the extent of CCUS deployment. Under more stringent carbon mitigation policies such as a high carbon tax, higher leakage risks can be afforded and incorporating leakage risks will have a smaller impact on CCUS deployment. Alternatively, if the leakage risks were accounted for by charging a fixed premium, similar to how the risk of nuclear waste disposal is treated, the contribution of CCUS in mitigating climate change varies, depending on the value of the premium.

Carbon diffusion in bulk hcp zirconium: A multi-scale approach

NASA Astrophysics Data System (ADS)

Xu, Y.; Roques, J.; Domain, C.; Simoni, E.

2016-05-01

In the framework of the geological repository of the used fuel claddings of pressurized water reactor, carbon behavior in bulk zirconium is studied by periodic Density Functional Theory calculations. The C interstitial sites were investigated and it was found that there are two possible carbon interstitial sites: a distorted basal tetragonal site and an octahedral site. There are four types of possible atomic jumps between them. After calculating the migration energies, the attempt frequencies and the jump probabilities for each possible migration path, kinetic Monte Carlo (KMC) simulations were performed to simulate carbon diffusion at the macroscopic scale. The results show that carbon diffusion in pure Zr bulk is extremely limited at the storage temperature (50 °C). Since there are defects in Zr bulk, in a second step, the effect of atomic vacancy was studied and it was proved that vacancies cannot increase carbon diffusion.

C Diffusion in Fe: Isotope Effects and Other Complexities

NASA Astrophysics Data System (ADS)

Watson, E. B.; Muller, T.; Trail, D.; Van Orman, J. A.; Papineau, D.

2011-12-01

Carbon is a minor but significant component of iron meteorites, and probably also of planetary cores, including that of Earth. Given the dynamical nature of core-forming processes, C diffusion in the metal phase may play a role in C equilibration between Fe-Ni metal and silicate, carbide or oxide at some stage. Despite its relevance to steel-making, C diffusion in Fe is not well characterized over the range of conditions of interest in planetary bodies, and the likelihood of an isotope mass effect on C diffusion has not been explored. The prospect of incomplete diffusive equilibration of carbon in Fe-Ni raises the possibility that carbon isotopes might be fractionated by diffusion during core formation and evolution-perhaps to an extent that could affect the C isotope ratio of the bulk silicate Earth. Here we report results of preliminary experiments addressing the isotopic mass effect on C diffusion in Fe. Initial low-pressure experiments were conducted by placing a layer of ^{13}C-enriched graphite ( 20% ^{13}C) at the end of a high-purity, polycrystalline Fe cylinder in a silica glass container. These diffusion couples were run in a piston-cylinder apparatus at 1.5 GPa and 1000-1100^{o}C for several hours, and the resulting C-uptake profiles in the Fe cylinders were measured by EPMA and SIMS. In traverses moving away from the original C-Fe interface, total carbon decreases monotonically and becomes significantly lighter, indicating that ^{12}C diffuses faster than ^{13}C. Preliminary estimates of β in the relative isotope diffusivity relation D_{1}/D_{2} = [M_{2}/M_{1}]^{β} (where D is diffusivity and M is mass of isotopes 1 and 2) suggest values as high as 0.5, corresponding to predictions for gaseous diffusion. Isotope mass effects approaching this magnitude have been observed previously for diffusion in metals, and are expected to be highest for interstitial diffusion. Such a high β value will lead to major C isotope fractionation in some partial equilibration scenarios in planets and meteorite parent bodies. Caution is warranted at this point, however, because D_{carbon} is sensitive to carbon concentration, complicating quantification of the isotope effect.

Carbon chain abundance in the diffuse interstellar medium

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Hudgins, D. M.; Bauschlicher, C. W. Jr; Langhoff, S. R.

1999-01-01

Thanks to the mid-IR sensitivities of the ISO and IRTS orbiting spectrometers it is now possible to search the diffuse interstellar medium for heretofore inaccessible molecular emission. In view of the recent strong case for the presence of C(7-) (Kirkwood et al. 1998, Tulej et al. 1998),and the fact that carbon chains possess prominent infrared active modes in a very clean portion of the interstellar spectrum, we have analyzed the IRTS spectrum of the diffuse interstellar medium for the infrared signatures of these species. Theoretical and experimental infrared band frequencies and absolute intensities of many different carbon chain species are presented. These include cyanopolyynes, neutral and anionic linear carbon molecules, and neutral and ionized, even-numbered, hydrogenated carbon chains. We show that--as a family--these species have abundances in the diffuse ISM on the order of 10(-10) with respect to hydrogen, values consistent with their abundances in dense molecular clouds. Assuming an average length of 10 C atoms per C-chain implies that roughly a millionth of the cosmically available carbon is in the form of carbon chains and that carbon chains can account for a few percent of the visible to near-IR diffuse interstellar band (DIB) total equivalent width (not DIB number).

Carbonate precipitation under bulk acidic conditions as a potential biosignature for searching life on Mars

NASA Astrophysics Data System (ADS)

Fernández-Remolar, David C.; Preston, Louisa J.; Sánchez-Román, Mónica; Izawa, Matthew R. M.; Huang, L.; Southam, Gordon; Banerjee, Neil R.; Osinski, Gordon R.; Flemming, Roberta; Gómez-Ortíz, David; Prieto Ballesteros, Olga; Rodríguez, Nuria; Amils, Ricardo; Darby Dyar, M.

2012-10-01

Recent observations of carbonate minerals in ancient Martian rocks have been interpreted as evidence for the former presence of circumneutral solutions optimal for carbonate precipitation. Sampling from surface and subsurface regions of the low-pH system of Río Tinto has shown, unexpectedly, that carbonates can form under diverse macroscopic physicochemical conditions ranging from very low to neutral pH (1.5-7.0). A multi-technique approach demonstrates that carbonate minerals are closely associated with microbial activity. Carbonates occur in the form of micron-size carbonate precipitates under bacterial biofilms, mineralization of subsurface colonies, and possible biogenic microstructures including globules, platelets and dumbbell morphologies. We propose that carbonate precipitation in the low-pH environment of Río Tinto is a process enabled by microbially-mediated neutralization driven by the reduction of ferric iron coupled to the oxidation of biomolecules in microbially-maintained circumneutral oases, where the local pH (at the scale of cells or cell colonies) can be much different than in the macroscopic environment. Acidic conditions were likely predominant in vast regions of Mars over the last four billion years of planetary evolution. Ancient Martian microbial life inhabiting low-pH environments could have precipitated carbonates similar to those observed at Río Tinto. Preservation of carbonates at Río Tinto over geologically significant timescales suggests that similarly-formed carbonate minerals could also be preserved on Mars. Such carbonates could soon be observed by the Mars Science Laboratory, and by future missions to the red planet.

Quantification of microbial activity in subsurface environments using a hydrogenase enzyme assay

NASA Astrophysics Data System (ADS)

Adhikari, R. R.; Nickel, J.; Kallmeyer, J.

2012-04-01

The subsurface biosphere is the largest microbial ecosystem on Earth. Despite its large size and extensive industrial exploitation, very little is known about the role of microbial activity in the subsurface. Subsurface microbial activity plays a fundamental role in geochemical cycles of carbon and other biologically important elements. How the indigenous microbial communities are supplied with energy is one of the most fundamental questions in subsurface research. It is still an enigma how these communities can survive with such recalcitrant carbon over geological time scales. Despite its usually very low concentration, hydrogen is an important element in subsurface environments. Heterotrophic and chemoautotrophic microorganisms use hydrogen in their metabolic pathways; they either obtain protons from the radiolysis of water and/or cleavage of hydrogen generated by the alteration of basaltic crust, or they dispose of protons by formation of water. Hydrogenase (H2ase) is a ubiquitous intracellular enzyme that catalyzes the interconversion of molecular hydrogen and/or water into protons and electrons. The protons are used for the synthesis of ATP, thereby coupling energy-generating metabolic processes to electron acceptors such as carbon dioxide or sulfate. H2ase activity can therefore be used as a measure for total microbial activity as it targets a key metabolic compound rather than a specific turnover process. Using a highly sensitive tritium assay we measured H2ase enzyme activity in the organic-rich sediments of Lake Van, a saline, alkaline lake in eastern Turkey and in marine subsurface sediments of the Barents Sea. Additionally, sulfate reduction rates (SRRs) were measured to compare the results of the H2ase enzyme assay with the quantitatively most important electron acceptor process. H2ase activity was found at all sites, measured values and distribution of activity varied widely with depth and between sites. At the Lake Van sites H2ase activity ranged from ca. 20 mmol H2 cm-3 d-1 close to the sediment-water interface to 0.5 mmol H2 cm-3 d-1 at a depth of 0.8 m. In samples from the Barents Sea H2ase activity ranged between 0.1 to 2.5 mmol H2 cm-3 d-1 down to a depth of 1.60 m. At all sites the SRR profile followed the H2ase activity profile until SRR declined to values close to the minimum detection limit (~10 pmol cm-3 d-1). H2ase activity increased again after SRR declined, indicating that other microbial processes are becoming quantitatively more important. The H2ase and SRR data show that our assay has a potential to become a valuable tool to measure total subsurface microbial activity.

Advances in Multiphase Flow and Transport in the Subsurface Environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Xiaoqing; Finsterle, Stefan; Zhang, Keni

Multiphase flow and transport processes in the subsurface environment are extremely important in a number of industrial and environmental applications at various spatial and temporal scales. Thus, it is necessary to identify, understand, and predict these processes to improve the production of conventional and unconventional oil and gas, to increase the safety of geological sequestration of carbon dioxide and nuclear waste disposal, and to make remediation of contaminated aquifers more effective.

Advances in Multiphase Flow and Transport in the Subsurface Environment

DOE PAGES

Shi, Xiaoqing; Finsterle, Stefan; Zhang, Keni; ...

2018-03-04

Multiphase flow and transport processes in the subsurface environment are extremely important in a number of industrial and environmental applications at various spatial and temporal scales. Thus, it is necessary to identify, understand, and predict these processes to improve the production of conventional and unconventional oil and gas, to increase the safety of geological sequestration of carbon dioxide and nuclear waste disposal, and to make remediation of contaminated aquifers more effective.

Aerobic Denitrification as an Innovative Method for In-Situ Biological Remediation of Contaminated Subsurface Sites

DTIC Science & Technology

1989-01-01

presumed subsurface conditon; * more rapid mineralization of organics and secondary metabolites ; * decrease in the biochemical oxygen demand and the...additon of nitrate would result in the more rapid mineralization of organic carbon and secondary metabolites . This was illustrated in this study with...and water. The list is far from complete. Many denitrifying species, such as those from the genera Moraxella and Achromobacter , are commonly found in

Heterotrophic Archaea dominate sedimentary subsurface ecosystems off Peru

PubMed Central

Biddle, Jennifer F.; Lipp, Julius S.; Lever, Mark A.; Lloyd, Karen G.; Sørensen, Ketil B.; Anderson, Rika; Fredricks, Helen F.; Elvert, Marcus; Kelly, Timothy J.; Schrag, Daniel P.; Sogin, Mitchell L.; Brenchley, Jean E.; Teske, Andreas; House, Christopher H.; Hinrichs, Kai-Uwe

2006-01-01

Studies of deeply buried, sedimentary microbial communities and associated biogeochemical processes during Ocean Drilling Program Leg 201 showed elevated prokaryotic cell numbers in sediment layers where methane is consumed anaerobically at the expense of sulfate. Here, we show that extractable archaeal rRNA, selecting only for active community members in these ecosystems, is dominated by sequences of uncultivated Archaea affiliated with the Marine Benthic Group B and the Miscellaneous Crenarchaeotal Group, whereas known methanotrophic Archaea are not detectable. Carbon flow reconstructions based on stable isotopic compositions of whole archaeal cells, intact archaeal membrane lipids, and other sedimentary carbon pools indicate that these Archaea assimilate sedimentary organic compounds other than methane even though methanotrophy accounts for a major fraction of carbon cycled in these ecosystems. Oxidation of methane by members of Marine Benthic Group B and the Miscellaneous Crenarchaeotal Group without assimilation of methane–carbon provides a plausible explanation. Maintenance energies of these subsurface communities appear to be orders of magnitude lower than minimum values known from laboratory observations, and ecosystem-level carbon budgets suggest that community turnover times are on the order of 100–2,000 years. Our study provides clues about the metabolic functionality of two cosmopolitan groups of uncultured Archaea. PMID:16505362

Applying linear discriminant analysis to predict groundwater redox conditions conducive to denitrification

NASA Astrophysics Data System (ADS)

Wilson, S. R.; Close, M. E.; Abraham, P.

2018-01-01

Diffuse nitrate losses from agricultural land pollute groundwater resources worldwide, but can be attenuated under reducing subsurface conditions. In New Zealand, the ability to predict where groundwater denitrification occurs is important for understanding the linkage between land use and discharges of nitrate-bearing groundwater to streams. This study assesses the application of linear discriminant analysis (LDA) for predicting groundwater redox status for Southland, a major dairy farming region in New Zealand. Data cases were developed by assigning a redox status to samples derived from a regional groundwater quality database. Pre-existing regional-scale geospatial databases were used as training variables for the discriminant functions. The predictive accuracy of the discriminant functions was slightly improved by optimising the thresholds between sample depth classes. The models predict 23% of the region as being reducing at shallow depths (<15 m), and 37% at medium depths (15-75 m). Predictions were made at a sub-regional level to determine whether improvements could be made with discriminant functions trained by local data. The results indicated that any gains in predictive success were offset by loss of confidence in the predictions due to the reduction in the number of samples used. The regional scale model predictions indicate that subsurface reducing conditions predominate at low elevations on the coastal plains where poorly drained soils are widespread. Additional indicators for subsurface denitrification are a high carbon content of the soil, a shallow water table, and low-permeability clastic sediments. The coastal plains are an area of widespread groundwater discharge, and the soil and hydrology characteristics require the land to be artificially drained to render the land suitable for farming. For the improvement of water quality in coastal areas, it is therefore important that land and water management efforts focus on understanding hydrological bypassing that may occur via artificial drainage systems.

Vertical Profiling of Soil Vapor Concentrations Using a New Passive Diffusion Sampler at a UST Site

EPA Science Inventory

Understanding the transport of volatile contaminants in soil gas, particularly those associated with underground storage tanks (USTs), requires a detailed knowledge about the depth-dependent distribution of chemical species in the subsurface. Traditional monitoring wells generall...

[Distribution and enrichment characteristics of organic carbon and total nitrogen in mollisols under long-term fertilization].

PubMed

Xu, Xiang-ru; Luo, Kun; Zhou, Bao-ku; Wang, Jing-kuan; Zhang, Wen-ju; Xu, Ming-gang

2015-07-01

The characteristics and changes of soil organic carbon (SOC) and total nitrogen (TN) in different size particles of soil under different agricultural practices are the basis for better understanding soil carbon sequestration of mollisols. Based on a 31-year long-term field experiment located at the Heilongjiang Academy of Agricultural Sciences (Harbin) , soil samples under six treatments were separated by size-fractionation method to explore changes and distribution of SOC and TN in coarse sand, fine sand, silt and clay from the top layer (0-20 cm) and subsurface layer (20-40 cm). Results showed that long-term application of manure (M) increased the percentages of SOC and TN in coarse sand and clay size fractions. In the top layer, application of nitrogen, phosphorus and potassium fertilizers combined with manure (NPKM) increased the percentages of SOC and TN in coarse sand by 191.3% and 179.3% compared with the control (CK), whereas M application increased the percentages of SOC and TN in clay by 45% and 47% respectively. For subsurface layers, the increase rates of SOC and TN in corresponding parts were lower than that in top layer. In the surface and subsurface layers, the percentages of SOC storage in silt size fraction accounted for 42%-63% and 48%-54%, TN storage accounted for 34%-59% and 41%-47%, respectively. The enrichment factors of SOC and TN in coarse sand and clay fractions of surface layers increased significantly under the treatments with manure. The SOC and TN enrichment factors were highest in the NPKM, being 2.30 and 1.88, respectively, while that in the clay fraction changed little in the subsurface layer.

Ground-based Remote Sensing for Quantifying Subsurface and Surface Co-variability to Scale Arctic Ecosystem Functioning

NASA Astrophysics Data System (ADS)

Oktem, R.; Wainwright, H. M.; Curtis, J. B.; Dafflon, B.; Peterson, J.; Ulrich, C.; Hubbard, S. S.; Torn, M. S.

2016-12-01

Predicting carbon cycling in Arctic requires quantifying tightly coupled surface and subsurface processes including permafrost, hydrology, vegetation and soil biogeochemistry. The challenge has been a lack of means to remotely sense key ecosystem properties in high resolution and over large areas. A particular challenge has been characterizing soil properties that are known to be highly heterogeneous. In this study, we exploit tightly-coupled above/belowground ecosystem functioning (e.g., the correlations among soil moisture, vegetation and carbon fluxes) to estimate subsurface and other key properties over large areas. To test this concept, we have installed a ground-based remote sensing platform - a track-mounted tram system - along a 70 m transect in the ice-wedge polygonal tundra near Barrow, Alaska. The tram carries a suite of near-surface remote sensing sensors, including sonic depth, thermal IR, NDVI and multispectral sensors. Joint analysis with multiple ground-based measurements (soil temperature, active layer soil moisture, and carbon fluxes) was performed to quantify correlations and the dynamics of above/belowground processes at unprecedented resolution, both temporally and spatially. We analyzed the datasets with particular focus on correlating key subsurface and ecosystem properties with surface properties that can be measured by satellite/airborne remote sensing over a large area. Our results provided several new insights about system behavior and also opens the door for new characterization approaches. We documented that: (1) soil temperature (at >5 cm depth; critical for permafrost thaw) was decoupled from soil surface temperature and was influenced strongly by soil moisture, (2) NDVI and greenness index were highly correlated with both soil moisture and gross primary productivity (based on chamber flux data), and (3) surface deformation (which can be measured by InSAR) was a good proxy for thaw depth dynamics at non-inundated locations.

Dissolved organic carbon loading from the field to watershed scale in tile-drained landscapes

USDA-ARS?s Scientific Manuscript database

Dissolved organic carbon (DOC) is an integral part to the functioning of aquatic ecosystems; yet, there is a paucity of data on DOC delivery and management in tile-drained agricultural headwater watersheds. The objective of this study was to quantify the contribution of subsurface tile drains to wat...

The Effect of Moisture on Carbon Fiber Reinforced Epoxy Composites. 1. Diffusion

DTIC Science & Technology

1976-09-27

II i NSWC/WOL/’r 76-7 0 00 WHITE OAK LABORATORY THE EFFECT OF MOISTURE ON CARBON FIBER REINFORCED EPOXY COMPOSITES I DIFFUSION 0 BY Joseph M. AugI 27...Effect of Moisture on Carbon Fiber’ Reinorcd EoxyComposites. onZI j , l Joseph M./Augll - lan E./egr ,. E RORMING ORGANIZATION NAME AND ADDRESS 10...Diffusion Carbon fiber composite* 20. A bf AACT (Ceedhlua on rverse side it meosemp &W idmtl’ 5 bl eek mmbeet) Mathematical models are suggested for

Nde of Frp Wrapped Columns Using Infrared Thermography

NASA Astrophysics Data System (ADS)

Halabe, Udaya B.; Dutta, Shasanka Shekhar; GangaRao, Hota V. S.

2008-02-01

This paper investigates the feasibility of using Infrared Thermography (IRT) for detecting debonds in Fiber Reinforced Polymer (FRP) wrapped columns. Laboratory tests were conducted on FRP wrapped concrete cylinders of size 6″×12″ (152.4 mm×304.8 mm) in which air-filled and water-filled debonds of various sizes were placed underneath the FRP wraps. Air-filled debonds were made by cutting plastic sheets into the desired sizes whereas water-filled debonds were made by filling water in custom made polyethylene pouches. Both carbon and glass fiber reinforced wraps were considered in this study. Infrared tests were conducted using a fully radiometric digital infrared camera which was successful in detecting air-filled as well as water-filled subsurface debonds. In addition to the laboratory testing, two field trips were made to Moorefield, West Virginia for detecting subsurface debonds in FRP wrapped timber piles of a railroad bridge using infrared testing. The results revealed that infrared thermography can be used as an effective nondestructive evaluation tool for detecting subsurface debonds in structural components wrapped with carbon or glass reinforced composite fabrics.

Quantification of mine-drainage inflows to Little Cottonwood Creek, Utah, using a tracer-injection and synoptic-sampling study

USGS Publications Warehouse

Kimball, B.; Runkel, R.; Gerner, L.

2001-01-01

Historic mining in Little Cottonwood Canyon in Utah has left behind many mine drainage tunnels that discharge water to Little Cottonwood Creek. To quantify the major sources of mine drainage to the stream, synoptic sampling was conducted during a tracer injection under low flow conditions (September 1998). There were distinct increases in discharge downstream from mine drainage and major tributary inflows that represented the total surface and subsurface contributions. The chemistry of stream water determined from synoptic sampling was controlled by the weathering of carbonate rocks and mine drainage inflows. Buffering by carbonate rocks maintained a high pH throughout the study reach. Most of the metal loading was from four surface-water inflows and three subsurface inflows. The main subsurface inflow was from a mine pool in the Wasatch Tunnel. Natural attenuation of all the metals resulted in the formation of colloidal solids, sorption of some metals, and accumulation onto the streambed. The deposition on the streambed could contribute to chronic toxicity for aquatic organisms. Information from the study will help to make decisions about environmental restoration.

In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

DOE PAGES

Alam, Todd M.; Osborn Popp, Thomas M.

2016-06-04

High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

Influence of Wind Pressure on the Carbonation of Concrete

PubMed Central

Zou, Dujian; Liu, Tiejun; Du, Chengcheng; Teng, Jun

2015-01-01

Carbonation is one of the major deteriorations that accelerate steel corrosion in reinforced concrete structures. Many mathematical/numerical models of the carbonation process, primarily diffusion-reaction models, have been established to predict the carbonation depth. However, the mass transfer of carbon dioxide in porous concrete includes molecular diffusion and convection mass transfer. In particular, the convection mass transfer induced by pressure difference is called penetration mass transfer. This paper presents the influence of penetration mass transfer on the carbonation. A penetration-reaction carbonation model was constructed and validated by accelerated test results under high pressure. Then the characteristics of wind pressure on the carbonation were investigated through finite element analysis considering steady and fluctuating wind flows. The results indicate that the wind pressure on the surface of concrete buildings results in deeper carbonation depth than that just considering the diffusion of carbon dioxide. In addition, the influence of wind pressure on carbonation tends to increase significantly with carbonation depth. PMID:28793462

Influence of Wind Pressure on the Carbonation of Concrete.

PubMed

Zou, Dujian; Liu, Tiejun; Du, Chengcheng; Teng, Jun

2015-07-24

Carbonation is one of the major deteriorations that accelerate steel corrosion in reinforced concrete structures. Many mathematical/numerical models of the carbonation process, primarily diffusion-reaction models, have been established to predict the carbonation depth. However, the mass transfer of carbon dioxide in porous concrete includes molecular diffusion and convection mass transfer. In particular, the convection mass transfer induced by pressure difference is called penetration mass transfer. This paper presents the influence of penetration mass transfer on the carbonation. A penetration-reaction carbonation model was constructed and validated by accelerated test results under high pressure. Then the characteristics of wind pressure on the carbonation were investigated through finite element analysis considering steady and fluctuating wind flows. The results indicate that the wind pressure on the surface of concrete buildings results in deeper carbonation depth than that just considering the diffusion of carbon dioxide. In addition, the influence of wind pressure on carbonation tends to increase significantly with carbonation depth.

Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

NASA Astrophysics Data System (ADS)

Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

2012-04-01

Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of diffuse agrochemical pollutants in a relatively simple hydrological system. The simulated shifts in isotopic signals are within a range that could be detected with current isotope analytics. Concentrations in the stream vary significantly only for a short period during and after intense rainfall events. In contrast, CSIA values reveal longer response times such that isotopic shifts are likely to be detected in samples with a coarser temporal resolution. Rainfall events which result in fast lateral subsurface transport from the pollution source to the stream can be separated from those that lead to pollution migration through deeper subsurface zones with much longer travel times. Two-dimensional CSIA highlights an increasing importance of the oxic reaction in the topsoil during the wetter period of the year. In order to examine to which extent CSIA is applicable for more complex hydrological systems, it is projected to simulate isotope fractionation in a 3-dimensional catchment featuring additional processes such as migration from several pollution sources or in-stream degradation.

Exploring the Deep Biosphere in Ophiolite-hosted Systems: What Can Metabolic Processes in Surface Seeps Tell Us About Subsurface Ecosystems in Serpentinizing Fluids?

NASA Astrophysics Data System (ADS)

Meyer-Dombard, D. R.; Cardace, D.; Woycheese, K. M.; Vallalar, B.; Casar, C.; Simon, A.; Arcilla, C. A.

2016-12-01

Serpentinization in the subsurface produces highly reduced, high pH fluids that provide microbial habitats. It is assumed that these deep subsurface fluids contain copious H2 and CH4 gas, little/no inorganic carbon, and limited electron acceptors. As serpentinized fluids reach the oxygenated surface environment, microbial biomes shift and organisms capable of metabolizing O2 thrive (Woycheese et al., 2015). However, the relationship of microbial communities found in surface expressions of serpentinizing fluids to the subsurface biosphere is still a target of exploration. Our work in the Zambales ophiolite (Philippines) defines surface microbial habitats with geochemistry, targeted culturing efforts, and community analysis (Cardace et al., 2015; Woycheese et al., 2015). Springs range from pH 9-11.5, and contain 0.06-2 ppm DO, 0-3.7 ppm sulfide, 30-800 ppm silica. Gases include H2 and CH4 > 10uM, CO2 > 1 mM, and trace amounts of CO. These surface data allow prediction of the subsurface metabolic landscape. For example, Cardace et al., (2015) predicted that metabolism of iron is important in both biospheres. Growth media were designed to target iron reduction yielding heterotrophic and autotrophic iron reducers at high pH. Reduced iron minerals were produced in several cultures (Casar et al., sub.), and isolation efforts are underway. Shotgun metagenomic analysis shows the metabolic capacity for methanogenesis, suggesting microbial origins for some CH4 present. The enzymes methyl coenzyme M reductase, and formylmethanofuran dehydrogenase were detected, and relative abundance increased near the near-anoxic spring source. The metagenomes indicate carbon cycling at these sites is reliant on methanogenesis, acetogenesis, sulfate reduction, and H2 and CH4 oxidation. In this tropical climate, cellulose is also a likely carbon source; cellulose degrading isolates have been obtained. These results indicate a metabolically flexible community at the surface where serpentinizing fluids are expressed. The next step is to understand what these surface systems might tell us about the subsurface biosphere. References: Cardace et al., 2015 Frontiers in Extreme Microbiology 6: doi: 10.3389/fmicb.2015.00010 Woycheese et al., 2015 Frontiers in Extreme Microbiology 6: doi: 10.3389/fmicb.2015.00044

Serpentinization-Influenced Groundwater Harbors Extremely Low Diversity Microbial Communities Adapted to High pH

PubMed Central

Twing, Katrina I.; Brazelton, William J.; Kubo, Michael D. Y.; Hyer, Alex J.; Cardace, Dawn; Hoehler, Tori M.; McCollom, Tom M.; Schrenk, Matthew O.

2017-01-01

Serpentinization is a widespread geochemical process associated with aqueous alteration of ultramafic rocks that produces abundant reductants (H2 and CH4) for life to exploit, but also potentially challenging conditions, including high pH, limited availability of terminal electron acceptors, and low concentrations of inorganic carbon. As a consequence, past studies of serpentinites have reported low cellular abundances and limited microbial diversity. Establishment of the Coast Range Ophiolite Microbial Observatory (California, U.S.A.) allowed a comparison of microbial communities and physicochemical parameters directly within serpentinization-influenced subsurface aquifers. Samples collected from seven wells were subjected to a range of analyses, including solute and gas chemistry, microbial diversity by 16S rRNA gene sequencing, and metabolic potential by shotgun metagenomics, in an attempt to elucidate what factors drive microbial activities in serpentinite habitats. This study describes the first comprehensive interdisciplinary analysis of microbial communities in hyperalkaline groundwater directly accessed by boreholes into serpentinite rocks. Several environmental factors, including pH, methane, and carbon monoxide, were strongly associated with the predominant subsurface microbial communities. A single operational taxonomic unit (OTU) of Betaproteobacteria and a few OTUs of Clostridia were the almost exclusive inhabitants of fluids exhibiting the most serpentinized character. Metagenomes from these extreme samples contained abundant sequences encoding proteins associated with hydrogen metabolism, carbon monoxide oxidation, carbon fixation, and acetogenesis. Metabolic pathways encoded by Clostridia and Betaproteobacteria, in particular, are likely to play important roles in the ecosystems of serpentinizing groundwater. These data provide a basis for further biogeochemical studies of key processes in serpentinite subsurface environments. PMID:28298908

Genomic evidence for the Wood-Ljungdahl pathway for carbon fixation in warm basaltic ocean crust

NASA Astrophysics Data System (ADS)

Smith, A. R.; Fisk, M. R.; Mueller, R.; Colwell, F. S.; Mason, O. U.; Popa, R.

2016-12-01

Microbial life in the deep suboceanic aquifer can harness geochemical energy resulting from water-rock reactions and contribute to carbon cycling in the ocean via primary production, or chemosynthesis. Iron-bearing minerals such as olivine in oceanic crust can produce molecular hydrogen, small molecular weight hydrocarbons, and hydrogen sulfide as they react with seawater. Although this generally occurs in serpentinizing systems at very high temperatures deep in the subsurface, it has also been hypothesized to drive the subseafloor microbial ecosystems present in shallower basaltic aquifers. We present genome-based evidence for chemolithoautotrophic microbes present on the surface of olivine incubated in Juan de Fuca Ridge basaltic ocean crust for a 4-year period. These metagenome-derived genomes show dominant taxa capable of using both branches of the Wood-Ljungdahl pathway for carbon fixation and energy generation. This pathway uses molecular hydrogen potentially derived from the olivine surface as it reacts with seawater and CO2 which is inherent to seawater. These taxa were not reported from aquifer fluid samples, but have been found only in association with mineral surfaces in this study location. Most taxa in this simple community are distant relatives of cultured taxa; therefore this genome information is crucial to understanding how the subseafloor aquifer community is structured, how it obtains energy, how it cycles carbon, and gives us keys to help cultivate these organisms in the laboratory. Our findings also support the Subsurface Lithoautotrophic Microbial Ecosystem (SLiME) hypothesis and have implications for understanding life on early Earth and the potential for life in the Martian subsurface.

Serpentinization-Influenced Groundwater Harbors Extremely Low Diversity Microbial Communities Adapted to High pH.

PubMed

Twing, Katrina I; Brazelton, William J; Kubo, Michael D Y; Hyer, Alex J; Cardace, Dawn; Hoehler, Tori M; McCollom, Tom M; Schrenk, Matthew O

2017-01-01

Serpentinization is a widespread geochemical process associated with aqueous alteration of ultramafic rocks that produces abundant reductants (H 2 and CH 4 ) for life to exploit, but also potentially challenging conditions, including high pH, limited availability of terminal electron acceptors, and low concentrations of inorganic carbon. As a consequence, past studies of serpentinites have reported low cellular abundances and limited microbial diversity. Establishment of the Coast Range Ophiolite Microbial Observatory (California, U.S.A.) allowed a comparison of microbial communities and physicochemical parameters directly within serpentinization-influenced subsurface aquifers. Samples collected from seven wells were subjected to a range of analyses, including solute and gas chemistry, microbial diversity by 16S rRNA gene sequencing, and metabolic potential by shotgun metagenomics, in an attempt to elucidate what factors drive microbial activities in serpentinite habitats. This study describes the first comprehensive interdisciplinary analysis of microbial communities in hyperalkaline groundwater directly accessed by boreholes into serpentinite rocks. Several environmental factors, including pH, methane, and carbon monoxide, were strongly associated with the predominant subsurface microbial communities. A single operational taxonomic unit (OTU) of Betaproteobacteria and a few OTUs of Clostridia were the almost exclusive inhabitants of fluids exhibiting the most serpentinized character. Metagenomes from these extreme samples contained abundant sequences encoding proteins associated with hydrogen metabolism, carbon monoxide oxidation, carbon fixation, and acetogenesis. Metabolic pathways encoded by Clostridia and Betaproteobacteria, in particular, are likely to play important roles in the ecosystems of serpentinizing groundwater. These data provide a basis for further biogeochemical studies of key processes in serpentinite subsurface environments.

Structure of peat soils and implications for biogeochemical processes and hydrological flow

NASA Astrophysics Data System (ADS)

Rezanezhad, F.; McCarter, C. P. R.; Gharedaghloo, B.; Kleimeier, C.; Milojevic, T.; Liu, H.; Weber, T. K. D.; Price, J. S.; Quinton, W. L.; Lenartz, B.; Van Cappellen, P.

2017-12-01

Permafrost peatlands contain globally important amounts of soil organic carbon and play major roles in global water, nutrient and biogeochemical cycles. The structure of peatland soils (i.e., peat) are highly complex with unique physical and hydraulic properties; where significant, and only partially reversible, shrinkage occurs during dewatering (including water table fluctuations), compression and/or decomposition. These distinct physical and hydraulic properties controls water flow, which in turn affect reactive and non-reactive solute transport (such as, sorption or degradation) and biogeochemical functions. Additionally, peat further attenuates solute migration through molecular diffusion into the inactive pores of Sphagnum dominated peat. These slow, diffusion-limited solute exchanges between the pore regions may give rise to pore-scale chemical gradients and heterogeneous distributions of microbial habitats and activity in peat soils. Permafrost peat plateaus have the same essential subsurface characteristics as other widely organic soil-covered peatlands, where the hydraulic conductivity is related to the degree of decomposition and soil compression. Increasing levels of decomposition correspond with a reduction of effective pore diameter and consequently restrict water and solute flow (by several orders of magnitude in hydraulic conductivity between the ground surface and a depth of 50 cm). In this presentation, we present the current knowledge of key physical and hydraulic properties related to the structure of globally available peat soils and discuss their implications for water storage, flow and the migration of solutes.

Kinetics of dodecanoic acid adsorption from caustic solution by activated carbon.

PubMed

Pendleton, Phillip; Wu, Sophie Hua

2003-10-15

This study examines the influences of adsorbent porosity and surface chemistry and of carbon dosage on dodecanoic acid adsorption kinetics from aqueous and 2 M NaOH solutions as batch adsorption processes. Both adsorbents are steam-activated carbons prepared from either coconut or coal precursors. Prior to use the adsorbents were washed in deionized water or 2 M NaOH. Mass transfer coefficients and effective overall diffusion coefficients indicate a minor contribution from adsorbent porosity. In contrast, high surface oxygen content impedes transport to and into the adsorbent structure. Carbon dosage shows a proportional increase in transport coefficients with increasing mass; these coefficients are constant when normalized per unit mass. Neither water nor NaOH treatment of the adsorbents has a significant influence on dodecanoic acid adsorption kinetics. Molecular and Knudsen diffusion coefficients are defined to demonstrate that the overall effective diffusion coefficient values and the diffusion process are controlled by surface diffusion.

The thermal impact of subsurface building structures on urban groundwater resources - A paradigmatic example.

PubMed

Epting, Jannis; Scheidler, Stefan; Affolter, Annette; Borer, Paul; Mueller, Matthias H; Egli, Lukas; García-Gil, Alejandro; Huggenberger, Peter

2017-10-15

Shallow subsurface thermal regimes in urban areas are increasingly impacted by anthropogenic activities, which include infrastructure development like underground traffic lines as well as industrial and residential subsurface buildings. In combination with the progressive use of shallow geothermal energy systems, this results in the so-called subsurface urban heat island effect. This article emphasizes the importance of considering the thermal impact of subsurface structures, which commonly is underestimated due to missing information and of reliable subsurface temperature data. Based on synthetic heat-transport models different settings of the urban environment were investigated, including: (1) hydraulic gradients and conductivities, which result in different groundwater flow velocities; (2) aquifer properties like groundwater thickness to aquitard and depth to water table; and (3) constructional features, such as building depths and thermal properties of building structures. Our results demonstrate that with rising groundwater flow velocities, the heat-load from building structures increase, whereas down-gradient groundwater temperatures decrease. Thermal impacts on subsurface resources therefore have to be related to the permeability of aquifers and hydraulic boundary conditions. In regard to the urban settings of Basel, Switzerland, flow velocities of around 1 md -1 delineate a marker where either down-gradient temperature deviations or heat-loads into the subsurface are more relevant. Furthermore, no direct thermal influence on groundwater resources should be expected for aquifers with groundwater thicknesses larger 10m and when the distance of the building structure to the groundwater table is higher than around 10m. We demonstrate that measuring temperature changes down-gradient of subsurface structures is insufficient overall to assess thermal impacts, particularly in urban areas. Moreover, in areas which are densely urbanized, and where groundwater flow velocities are low, appropriate measures for assessing thermal impacts should specifically include a quantification of heat-loads into the subsurface which result in a more diffuse thermal contamination of urban groundwater resources. Copyright © 2017 Elsevier B.V. All rights reserved.

A comparative study of authigenic carbonates from mussel and tubeworm environments: Implications for discriminating the effects of tubeworms

NASA Astrophysics Data System (ADS)

Feng, Dong; Cordes, Erik E.; Roberts, Harry H.; Fisher, Charles R.

2013-05-01

The Gulf of Mexico hydrocarbon seeps are often populated by dense mussel beds and tubeworm aggregations, as well as exposed authigenic carbonate outcrops. Previous studies suggest the activity of mussels and tubeworms could influence the sediment geochemistry of their habitats, resulting in variations in the stable carbon isotopes of the associated carbonates. However, this conclusion was based on the analyses of samples from a single site. To better understand whether there are consistent differences in the geochemical environments of mussels and tubeworms, mineralogical and stable isotopic compositions of authigenic carbonates from mussel and tubeworm environments from four seep sites were analyzed. The studied sites span a depth range of 1200 m to 2800 m on the northern Gulf of Mexico continental slope. We found that carbonate samples from tubeworm environments were more prone to contain aragonite whereas carbonates from mussel environments were more likely to have calcite. This finding supports the hypothesis that vestimentiferans release sulfate across their roots into the pore waters of the surrounding sediments, a process that could generate a locally sulfate-enriched environment that favors the precipitation of aragonite instead of calcite. Moreover, the δ13C values of tubeworm carbonates are generally lighter than that of mussel carbonates from the same site, which is consistent with the fact that tubeworms are fueling extra subsurface methane oxidation through the release of sulfate into the sediment. Such a process, consequently, enriches the subsurface dissolved inorganic carbon pool with light carbon derived from the seeping hydrocarbons. Taken together, our data suggest that tubeworms could produce a carbon isotope shift that is sufficient to influence the sediment geochemistry of their immediate area, and that this impact is reflected in the associated authigenic carbonates.

Paleokarst processes in the Eocene limestones of the Pyramids Plateau, Giza, Egypt

NASA Astrophysics Data System (ADS)

El Aref, M. M.; Refai, E.

The Eocene limestones of the Pyramids plateau are characterized by landforms of stepped terraced escarpment and karst ridges with isolated hills. The carbonate country rocks are also dominated by minor surface, surface to subsurface and subsurface solution features associated with karst products. The systematic field observations eludicate the denudation trend of the minor solution features and suggest the origin of the regional landscapes. The lithologic and structural characters of the limestone country rocks comprise the main factors controlling the surface and subsurface karst evolution. The development of the karst features and the associated sediments in the study area provides information on the paleohydrolic, chemical and climatic environments involved in the origin of the karstification.

Controlling Fluid Flow in the Subsurface through Ureolysis-Controlled Mineral Precipitation

NASA Astrophysics Data System (ADS)

Gerlach, R.; Phillips, A. J.; Cunningham, A. B.; Spangler, L.

2016-12-01

In situ urea hydrolysis has been used by us successfully to manipulate the carbonate alkalinity and control the precipitation of carbonate minerals. Urea hydrolysis can be promoted using microbial cells, enzymes or thermal energy. This technology can be used to mitigate leakage pathways, seal fractures or control fluid transport in the subsurface in hydrocarbon production, enhanced geothermal energy storage, carbon sequestration, nuclear waste disposal, etc. We have completed two field demonstrations of the urea hydrolysis-controlled in situ mineral precipitation technology. The first demonstration showed fracture sealing was possible in a sandstone formation approx. 1120' below ground surface (bgs) and that the fracture had increased resistance to re-fracturing after mineralization treatment. The second field demonstration was performed in a well with an identified channel in the cement near the wellbore at approx. 1020' bgs. The in situ mineralization treatment resulted in reduced pressure decay during shut in periods and reduced injectivity. In addition, a noticeable difference was observed in the solids percentage in the ultrasonic imaging logs before and after biomineralization treatment. The presentation will summarize and put into context the field and our recent laboratory research focusing on permeability manipulation using the in situ ureolysis-driven mineralization technology under ambient and subsurface pressure conditions. We have demonstrated permeability reductions of 3-6 orders of magnitude in 100 µm to 4mm gaps between shale, sandstone and cement/steel interfaces.

Quantum fluctuations increase the self-diffusive motion of para-hydrogen in narrow carbon nanotubes.

PubMed

Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Furmaniak, Sylwester

2011-05-28

Quantum fluctuations significantly increase the self-diffusive motion of para-hydrogen adsorbed in narrow carbon nanotubes at 30 K comparing to its classical counterpart. Rigorous Feynman's path integral calculations reveal that self-diffusive motion of para-hydrogen in a narrow (6,6) carbon nanotube at 30 K and pore densities below ∼29 mmol cm(-3) is one order of magnitude faster than the classical counterpart. We find that the zero-point energy and tunneling significantly smoothed out the free energy landscape of para-hydrogen molecules adsorbed in a narrow (6,6) carbon nanotube. This promotes a delocalization of the confined para-hydrogen at 30 K (i.e., population of unclassical paths due to quantum effects). Contrary the self-diffusive motion of classical para-hydrogen molecules in a narrow (6,6) carbon nanotube at 30 K is very slow. This is because classical para-hydrogen molecules undergo highly correlated movement when their collision diameter approached the carbon nanotube size (i.e., anomalous diffusion in quasi-one dimensional pores). On the basis of current results we predict that narrow single-walled carbon nanotubes are promising nanoporous molecular sieves being able to separate para-hydrogen molecules from mixtures of classical particles at cryogenic temperatures. This journal is © the Owner Societies 2011

Atomistic simulations of carbon diffusion and segregation in liquid silicon

NASA Astrophysics Data System (ADS)

Luo, Jinping; Alateeqi, Abdullah; Liu, Lijun; Sinno, Talid

2017-12-01

The diffusivity of carbon atoms in liquid silicon and their equilibrium distribution between the silicon melt and crystal phases are key, but unfortunately not precisely known parameters for the global models of silicon solidification processes. In this study, we apply a suite of molecular simulation tools, driven by multiple empirical potential models, to compute diffusion and segregation coefficients of carbon at the silicon melting temperature. We generally find good consistency across the potential model predictions, although some exceptions are identified and discussed. We also find good agreement with the range of available experimental measurements of segregation coefficients. However, the carbon diffusion coefficients we compute are significantly lower than the values typically assumed in continuum models of impurity distribution. Overall, we show that currently available empirical potential models may be useful, at least semi-quantitatively, for studying carbon (and possibly other impurity) transport in silicon solidification, especially if a multi-model approach is taken.

Stratigraphy and Structure of the Subsurface Cambrian and Ordovician Carbonates of New York.

ERIC Educational Resources Information Center

Rickard, Lawrence V.

This publication presents a description of 137 wells in New York State and adjacent parts of Pennsylvania. Correlations with surface exposures are established. Maps and cross sections display the thickness, structure, and stratigraphic relationships of the carbonates described. A paleogeologic map of New York State at the end of the Early…

Reconstructing a hydrogen-driven microbial metabolic network in Opalinus Clay rock

DOE PAGES

Bagnoud, Alexandre; Chourey, Karuna; Hettich, Robert L.; ...

2016-10-14

A significant fraction (~ 20%) of microbial life is found in the terrestrial deep subsurface, yet the metabolic processes extant in those environments are poorly understood. Here we show that H 2, injected into the Opalinus Clay formation in a borehole located 300 meters below the surface, fuels a community of microorganisms with interconnected metabolisms. Metagenomic binning and metaproteomic analysis reveal a complete carbon cycle, driven by autotrophic hydrogen oxidizers. Dead biomass from these organisms is a substrate for a fermenting bacterium that produces acetate as a product. In turn, complete oxidizer heterotrophic sulfate- reducing bacteria utilize acetate and oxidizemore » it to CO 2, closing the cycle. This metabolic reconstruction sheds light onto a hydrogen-driven carbon cycle, and a sunlight-independent ecosystem in the deep subsurface.« less

Basin-Scale Leakage Risks from Geologic Carbon Sequestration: Impact on Carbon Capture and Storage Energy Market Competitiveness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Catherine; Fitts, Jeffrey; Wilson, Elizabeth

This three-year project, performed by Princeton University in partnership with the University of Minnesota and Brookhaven National Laboratory, examined geologic carbon sequestration in regard to CO{sub 2} leakage and potential subsurface liabilities. The research resulted in basin-scale analyses of CO{sub 2} and brine leakage in light of uncertainties in the characteristics of leakage processes, and generated frameworks to monetize the risks of leakage interference with competing subsurface resources. The geographic focus was the Michigan sedimentary basin, for which a 3D topographical model was constructed to represent the hydrostratigraphy. Specifically for Ottawa County, a statistical analysis of the hydraulic properties ofmore » underlying sedimentary formations was conducted. For plausible scenarios of injection into the Mt. Simon sandstone, leakage rates were estimated and fluxes into shallow drinking-water aquifers were found to be less than natural analogs of CO{sub 2} fluxes. We developed the Leakage Impact Valuation (LIV) model in which we identified stakeholders and estimated costs associated with leakage events. It was found that costs could be incurred even in the absence of legal action or other subsurface interference because there are substantial costs of finding and fixing the leak and from injection interruption. We developed a model framework called RISCS, which can be used to predict monetized risk of interference with subsurface resources by combining basin-scale leakage predictions with the LIV method. The project has also developed a cost calculator called the Economic and Policy Drivers Module (EPDM), which comprehensively calculates the costs of carbon sequestration and leakage, and can be used to examine major drivers for subsurface leakage liabilities in relation to specific injection scenarios and leakage events. Finally, we examined the competiveness of CCS in the energy market. This analysis, though qualitative, shows that financial incentives, such as a carbon tax, are needed for coal combustion with CCS to gain market share. In another part of the project we studied the role of geochemical reactions in affecting the probability of CO{sub 2} leakage. A basin-scale simulation tool was modified to account for changes in leakage rates due to permeability alterations, based on simplified mathematical rules for the important geochemical reactions between acidified brines and caprock minerals. In studies of reactive flows in fractured caprocks, we examined the potential for permeability increases, and the extent to which existing reactive transport models would or would not be able to predict it. Using caprock specimens from the Eau Claire and Amherstburg, we found that substantial increases in permeability are possible for caprocks that have significant carbonate content, but minimal alteration is expected otherwise. We also found that while the permeability increase may be substantial, it is much less than what would be predicted from hydrodynamic models based on mechanical aperture alone because the roughness that is generated tends to inhibit flow.« less

Stimulation of Microbially Mediated Arsenic Release in Bangladesh Aquifers by Young Carbon Indicated by Radiocarbon Analysis of Sedimentary Bacterial Lipids.

PubMed

Whaley-Martin, K J; Mailloux, B J; van Geen, A; Bostick, B C; Silvern, R F; Kim, C; Ahmed, K M; Choudhury, I; Slater, G F

2016-07-19

The sources of reduced carbon driving the microbially mediated release of arsenic to shallow groundwater in Bangladesh remain poorly understood. Using radiocarbon analysis of phospholipid fatty acids (PLFAs) and potential carbon pools, the abundance and carbon sources of the active, sediment-associated, in situ bacterial communities inhabiting shallow aquifers (<30 m) at two sites in Araihazar, Bangladesh, were investigated. At both sites, sedimentary organic carbon (SOC) Δ(14)C signatures of -631 ± 54‰ (n = 12) were significantly depleted relative to dissolved inorganic carbon (DIC) of +24 ± 30‰ and dissolved organic carbon (DOC) of -230 ± 100‰. Sediment-associated PLFA Δ(14)C signatures (n = 10) at Site F (-167‰ to +20‰) and Site B (-163‰ to +21‰) were highly consistent and indicated utilization of carbon sources younger than the SOC, likely from the DOC pool. Sediment-associated PLFA Δ(14)C signatures were consistent with previously determined Δ(14)C signatures of microbial DNA sampled from groundwater at Site F indicating that the carbon source for these two components of the subsurface microbial community is consistent and is temporally stable over the two years between studies. These results demonstrate that the utilization of relatively young carbon sources by the subsurface microbial community occurs at sites with varying hydrology. Further they indicate that these young carbon sources drive the metabolism of the more abundant sediment-associated microbial communities that are presumably more capable of Fe reduction and associated release of As. This implies that an introduction of younger carbon to as of yet unaffected sediments (such as those comprising the deeper Pleistocene aquifer) could stimulate microbial communities and result in arsenic release.

THE INTERPLAY BETWEEN GEOCHEMICAL REACTIONS AND ADVECTION-DISPERSION IN CONTAMINANT TRANSPORT AT A URANIUM MILL TAILINGS SITE

EPA Science Inventory

It is well known that the fate and transport of contaminants in the subsurface are controlled by complex processes including advection, dispersion-diffusion, and chemical reactions. However, the interplay between the physical transport processes and chemical reactions, and their...

Evaluation of a New Passive Diffusion Sampler for Improving the Calibration of Models to Evaluate Vapor Movement at UST Sites

EPA Science Inventory

Understanding transport of volatile contaminants in soil gas and ground water, particularly those associated with underground storage tanks (USTs), requires a detailed knowledge about the depth-dependent distribution of chemical species in the subsurface. A risk assessment of th...

A New Passive Diffusion Sampler for Improving the Calibration of Models to Evaluate Vapor Movement at UST Sites

EPA Science Inventory

Understanding transport of volatile contaminants in soil gas and ground water, particularly those associated with underground storage tanks (USTs), requires a detailed knowledge about the depthdependent distribution of chemical species in the subsurface. A risk assessment of the...

PERFORMANCE OF A NEW PASSIVE DIFFUSION SAMPLER FOR MONITORING BENZENE IN EITHER SOIL GAS OR GROUND WATER

EPA Science Inventory

Understanding transport of volatile contaminants in soil gas and ground water, particularly those associated with underground storage tanks, requires a detailed knowledge about the depth-dependent distribution of chemical species in the subsurface. A risk assessment of the moveme...

Method of making carbon fiber-carbon matrix reinforced ceramic composites

NASA Technical Reports Server (NTRS)

Williams, Brian (Inventor); Benander, Robert (Inventor)

2007-01-01

A method of making a carbon fiber-carbon matrix reinforced ceramic composite wherein the result is a carbon fiber-carbon matrix reinforcement is embedded within a ceramic matrix. The ceramic matrix does not penetrate into the carbon fiber-carbon matrix reinforcement to any significant degree. The carbide matrix is a formed in situ solid carbide of at least one metal having a melting point above about 1850 degrees centigrade. At least when the composite is intended to operate between approximately 1500 and 2000 degrees centigrade for extended periods of time the solid carbide with the embedded reinforcement is formed first by reaction infiltration. Molten silicon is then diffused into the carbide. The molten silicon diffuses preferentially into the carbide matrix but not to any significant degree into the carbon-carbon reinforcement. Where the composite is intended to operate between approximately 2000 and 2700 degrees centigrade for extended periods of time such diffusion of molten silicon into the carbide is optional and generally preferred, but not essential.

Integrating spatial and temporal oxygen data to improve the quantification of in situ petroleum biodegradation rates.

PubMed

Davis, Gregory B; Laslett, Dean; Patterson, Bradley M; Johnston, Colin D

2013-03-15

Accurate estimation of biodegradation rates during remediation of petroleum impacted soil and groundwater is critical to avoid excessive costs and to ensure remedial effectiveness. Oxygen depth profiles or oxygen consumption over time are often used separately to estimate the magnitude and timeframe for biodegradation of petroleum hydrocarbons in soil and subsurface environments. Each method has limitations. Here we integrate spatial and temporal oxygen concentration data from a field experiment to develop better estimates and more reliably quantify biodegradation rates. During a nine-month bioremediation trial, 84 sets of respiration rate data (where aeration was halted and oxygen consumption was measured over time) were collected from in situ oxygen sensors at multiple locations and depths across a diesel non-aqueous phase liquid (NAPL) contaminated subsurface. Additionally, detailed vertical soil moisture (air-filled porosity) and NAPL content profiles were determined. The spatial and temporal oxygen concentration (respiration) data were modeled assuming one-dimensional diffusion of oxygen through the soil profile which was open to the atmosphere. Point and vertically averaged biodegradation rates were determined, and compared to modeled data from a previous field trial. Point estimates of biodegradation rates assuming no diffusion ranged up to 58 mg kg(-1) day(-1) while rates accounting for diffusion ranged up to 87 mg kg(-1) day(-1). Typically, accounting for diffusion increased point biodegradation rate estimates by 15-75% and vertically averaged rates by 60-80% depending on the averaging method adopted. Importantly, ignoring diffusion led to overestimation of biodegradation rates where the location of measurement was outside the zone of NAPL contamination. Over or underestimation of biodegradation rate estimates leads to cost implications for successful remediation of petroleum impacted sites. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Diffusion of Cd and Te adatoms on CdTe(111) surfaces: A computational study using density functional theory

NASA Astrophysics Data System (ADS)

Naderi, Ebadollah; Nanavati, Sachin; Majumder, Chiranjib; Ghaisas, S. V.

2015-01-01

CdTe is one of the most promising semiconductor for thin-film based solar cells. Here we report a computational study of Cd and Te adatom diffusion on the CdTe (111) A-type (Cd terminated) and B-type (Te terminated) surfaces and their migration paths. The atomic and electronic structure calculations are performed under the DFT formalism and climbing Nudge Elastic Band (cNEB) method has been applied to evaluate the potential barrier of the Te and Cd diffusion. In general the minimum energy site on the surface is labeled as Aa site. In case of Te and Cd on B-type surface, the sub-surface site (a site just below the top surface) is very close in energy to the A site. This is responsible for the subsurface accumulation of adatoms and therefore, expected to influence the defect formation during growth. The diffusion process of adatoms is considered from Aa (occupied) to Aa (empty) site at the nearest distance. We have explored three possible migration paths for the adatom diffusion. The adatom surface interaction is highly dependent on the type of the surface. Typically, Te interaction with both type (5.2 eV for A-type and 3.8 eV for B-type) is stronger than Cd interactions(2.4 eV for B-type and 0.39 eV for A-type). Cd interaction with the A-type surface is very weak. The distinct behavior of the A-type and B-type surfaces perceived in our study explain the need of maintaining the A-type surface during growth for smooth and stoichiometric growth.

Tile drainage as karst: Conduit flow and diffuse flow in a tile-drained watershed

USGS Publications Warehouse

Schilling, K.E.; Helmers, M.

2008-01-01

The similarity of tiled-drained watersheds to karst drainage basins can be used to improve understanding of watershed-scale nutrient losses from subsurface tile drainage networks. In this study, short-term variations in discharge and chemistry were examined from a tile outlet collecting subsurface tile flow from a 963 ha agricultural watershed. Study objectives were to apply analytical techniques from karst springs to tile discharge to evaluate water sources and estimate the loads of agricultural pollutants discharged from the tile with conduit, intermediate and diffuse flow regimes. A two-member mixing model using nitrate, chloride and specific conductance was used to distinguish rainwater versus groundwater inputs. Results indicated that groundwater comprised 75% of the discharge for a three-day storm period and rainwater was primarily concentrated during the hydrograph peak. A contrasting pattern of solute concentrations and export loads was observed in tile flow. During base flow periods, tile flow consisted of diffuse flow from groundwater sources and contained elevated levels of nitrate, chloride and specific conductance. During storm events, suspended solids and pollutants adhered to soil surfaces (phosphorus, ammonium and organic nitrogen) were concentrated and discharged during the rapid, conduit flow portion of the hydrograph. During a three-day period, conduit flow occurred for 5.6% of the time but accounted for 16.5% of the total flow. Nitrate and chloride were delivered primarily with diffuse flow (more than 70%), whereas 80-94% of total suspended sediment, phosphorus and ammonium were exported with conduit and intermediate flow regimes. Understanding the water sources contributing to tile drainage and the manner by which pollutant discharge occurs from these systems (conduit, intermediate or diffuse flow) may be useful for designing, implementing and evaluating non-point source reduction strategies in tile-drained landscapes. ?? 2007 Elsevier B.V. All rights reserved.

The story of Amazonian climate change on Mars as told by carbonates in Miller Range Nakhlites

NASA Astrophysics Data System (ADS)

Evans, M. E.; Niles, P. B.; Locke, D.; Chapman, P.

2017-12-01

This is a story about rocks from Mars, and how they reveal environmental changes on Mars. A specific region of volcanic rocks formed on Mars about 1.3 billion years ago (bya). This region is now known as the Nakhla lava pile. The rocks were likely formed near the surface. Chemical analysis of these rocks confirms that they formed on Mars, because rocks on Earth have different oxygen isotope values. Sometime later, perhaps 0.7 bya, very small amounts of subsurface water on Mars percolated through the lava pile. The water contained dissolved carbon dioxide (CO2) from contact with the atmosphere of Mars. Ions in the water bonded with rock ions to create tiny, white, carbonate minerals along the cracks within the lava pile. The Nakhla subsurface water temperature was likely cool ( 15°C), which is different from the hot water that possibly created minerals on older Mars rocks. About 11 million years ago, an asteroid impacted Mars over the Nakhla lava pile. The impact rebound ejected mass from the surface and subsurface, and some rocks escaped the gravity of Mars. These rocks floated in space for over 10.9 million years before they fell to Earth as meteorites. The most famous of these meteorites, named Nakhla, fell over Egypt in 1911 and fragmented into 40 pieces. A total of 11 similar meteorites, known as Nakhlites, have been collected across the Earth. Four of these meteorites fell into a remote region of Antarctica called the Miller Range (MIL). They were collected by the National Science Foundation (NSF) "Antarctica Search for Meteorite" (ANSMET) program. This study analyzed the stable isotope geochemistry of the carbonates on the four MIL Nakhlites. Antarctica is an analog for carbonate formation on recent Mars because it forms the minerals in a cold environment with a thin film of water. Carbonates from oceans are dominated by the oxygen isotopic values of the water, but in Mars and Antarctica the carbonates are also influenced by the oxygen in the atmospheric CO2. This study reveals that terrestrial carbonates have different carbon isotope values from martian carbonates. The carbon isotope values of the Mars atmospheric CO2 that formed the MIL Nakhlite carbonates was different from the modern atmosphere (as measured by the MSL Curiosity rover). This difference may be due somewhat to loss of atmospheric gas to space over the past billion years.

Exploration of a Subsurface Biosphere in a Volcanic Massive Sulfide: Results of the Mars Analog Rio Tinto Drilling Experiment

NASA Astrophysics Data System (ADS)

Stoker, C. R.; Stevens, T.; Amils, R.; Fernandez, D.

2005-12-01

Biological systems on Earth require three key ingredients-- liquid water, an energy source, and a carbon source, that are found in very few extraterrestrial environments. Previous examples of independent subsurface ecosystems have been found only in basalt aquifers. Such lithotrophic microbial ecosystems (LME) have been proposed as models for steps in the early evolution of Earth's biosphere and for potential biospheres on other planets where the surface is uninhabitable, such as Mars and Europa.. The Mars Analog Rio Tinto Experiment (MARTE) has searched in a volcanic massive sulfide deposit in Rio Tinto Spain for a subsurface biosphere capable of living without sunlight or oxygen and found a subsurface ecosystem driven by the weathering of the massive sulfide deposit (VMS) in which the rock matrix provides sufficient resources to support microbial metabolism, including the vigorous production of H2 by water-rock interactions. Microbial production of methane and sulfate occurred in the sulfide orebody and microbial production of methane and hydrogen sulfide continued in an anoxic plume downgradient from the sulfide ore. Organic carbon concentrations in the parent rock were too low to support microbes. The Rio Tinto system thus represents a new type of subsurface ecosystem with strong relevance for exobiological studies. Commercial drilling was used to reach the aquifer system at 100 m depth and conventional laboratory techniques were used to identify and characterize the biosphere. Then, the life search strategy that led to successful identification of this biosphere was applied to the development of a robotic drilling, core handling, inspection, subsampling, and life detection system built on a prototype planetary lander that was deployed in Rio Tinto Spain in September 2005 to test the capability of a robotic drilling system to search for subsurface life. A remote science team directed the simulation and analyzed the data from the MARTE robotic drill. The results of this experiment have important implications for the strategy for searching for life on Mars.

Comparative Single-Cell Genomics of Chloroflexi from the Okinawa Trough Deep-Subsurface Biosphere.

PubMed

Fullerton, Heather; Moyer, Craig L

2016-05-15

Chloroflexi small-subunit (SSU) rRNA gene sequences are frequently recovered from subseafloor environments, but the metabolic potential of the phylum is poorly understood. The phylum Chloroflexi is represented by isolates with diverse metabolic strategies, including anoxic phototrophy, fermentation, and reductive dehalogenation; therefore, function cannot be attributed to these organisms based solely on phylogeny. Single-cell genomics can provide metabolic insights into uncultured organisms, like the deep-subsurface Chloroflexi Nine SSU rRNA gene sequences were identified from single-cell sorts of whole-round core material collected from the Okinawa Trough at Iheya North hydrothermal field as part of Integrated Ocean Drilling Program (IODP) expedition 331 (Deep Hot Biosphere). Previous studies of subsurface Chloroflexi single amplified genomes (SAGs) suggested heterotrophic or lithotrophic metabolisms and provided no evidence for growth by reductive dehalogenation. Our nine Chloroflexi SAGs (seven of which are from the order Anaerolineales) indicate that, in addition to genes for the Wood-Ljungdahl pathway, exogenous carbon sources can be actively transported into cells. At least one subunit for pyruvate ferredoxin oxidoreductase was found in four of the Chloroflexi SAGs. This protein can provide a link between the Wood-Ljungdahl pathway and other carbon anabolic pathways. Finally, one of the seven Anaerolineales SAGs contains a distinct reductive dehalogenase homologous (rdhA) gene. Through the use of single amplified genomes (SAGs), we have extended the metabolic potential of an understudied group of subsurface microbes, the Chloroflexi These microbes are frequently detected in the subsurface biosphere, though their metabolic capabilities have remained elusive. In contrast to previously examined Chloroflexi SAGs, our genomes (several are from the order Anaerolineales) were recovered from a hydrothermally driven system and therefore provide a unique window into the metabolic potential of this type of habitat. In addition, a reductive dehalogenase gene (rdhA) has been directly linked to marine subsurface Chloroflexi, suggesting that reductive dehalogenation is not limited to the class Dehalococcoidia This discovery expands the nutrient-cycling and metabolic potential present within the deep subsurface and provides functional gene information relating to this enigmatic group. Copyright © 2016 Fullerton and Moyer.

Depositionally controlled recycling of iron and sulfur in marine sediments and its isotopic consequences

NASA Astrophysics Data System (ADS)

Riedinger, N.; Formolo, M.; Arnold, G. L.; Vossmeyer, A.; Henkel, S.; Sawicka, J.; Kasten, S.; Lyons, T. W.

2011-12-01

The continental margin off Uruguay and Argentina is characterized by highly dynamic depositional conditions. This variable depositional regime significantly impacts the biogeochemical cycles of iron and sulfur. Mass deposit related redeposition of reduced minerals can lead to the reoxidation of these phases and thus to an overprint of their geochemical primary signatures. Due to rapid burial these oxidized phases are still present in deeper subsurface sediments. To study the effects of sediment relocation on the sulfur and iron inventory we collected shallow and deep subsurface sediment samples via multicorer and gravity cores, respectively, in the western Argentine Basin during the RV Meteor Expedition M78/3 in May-July 2009. The samples were retrieved from shelf, slope and deep basin sites. The concentration and sulfur isotope composition of acid volatile sulfur (AVS), chromium reducible sulfur (CRS), elemental sulfur and total organic sulfur were determined. Furthermore, sequential iron extraction techniques were applied assess the distribution of iron oxide phases within the sediment. The investigated sediments are dominated by terrigenous inputs, with high amounts of reactive ferric iron minerals and only low concentrations of calcium carbonate. Total organic carbon concentrations show strong variation in the shallow subsurface sediments ranging between approximately 0.7 and 6.4 wt% for different sites. These concentrations do not correlate with water depths. Pore water accumulations of hydrogen sulfide are restricted to an interval at the sulfate-methane transition (SMT) zone a few meters below the sediment surface. In these deeper subsurface sediments pyrite is precipitated in this zone of hydrogen sulfide excess, whereas the accumulation of authigenic AVS and elemental sulfur (up to 2000 ppm) occurs at the upper and lower boundary of the sulfidic zone due the reaction of iron oxides with limited amounts of sulfide. Furthermore, our preliminary results indicate that there is a link between modern deposition in the shallow subsurface sediments and the long-term signals being buried and preserved in the deep subsurface layers. The data show that the burial of elemental sulfur into deep subsurface sediments can fuel the deep biosphere and has consequences for isotopic overprints tied, for example, to oxidation and disproportionation processes in the deeper sediments.

Diffusion of cis-5,8,11,14,17-eicosapentaenoic acid (1); carbon dioxide (2)

NASA Astrophysics Data System (ADS)

Winkelmann, J.

This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) cis-5,8,11,14,17-eicosapentaenoic acid; (2) carbon dioxide

Fungal Survival in a Chemosynthetic Ecosystem

NASA Astrophysics Data System (ADS)

Kiel Reese, B.; Sobol, M. S.; Hoshino, T.; Inagaki, F.; Eder, E.; Nicora, C. D.; Heyman, H. M.; Kyle, J. E.; Hoyt, D. W.; Tfaily, M. M.; Metz, T. O.

2018-05-01

Fungi possess metabolic pathways capable of utilizing previously considered non-bioavailable energy reserves. Metabolically active fungi occupy a unique niche within the subsurface, providing an organic carbon source for heterotrophic prokaryotes.

Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material.

PubMed

Bai, Jing; Liu, Chongxuan; Ball, William P

2009-10-15

A diffusion cell method was applied to measure the effective pore diffusion coefficient (Dp) for U(VI) under strictly controlled chemical conditions in a silt/clay sediment from the U.S. Department of Energy Hanford site, WA. "Inward-flux" diffusion studies were conducted in which [U(VI)] in both aqueous and solid phases was measured as a function of distance in the diffusion cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed contaminant U(VI) in the solid phase containing extractable background U(VI). The effect of sorption kinetics on U(VI) interparticle diffusion was evaluated by comparing sorption-retarded diffusion models with sorption described either as equilibrium or intraparticle diffusion-limited processes. Both experimental and modeling results indicated that (1) a single pore diffusion coefficient can simulate the diffusion of total aqueous U(VI), and (2) the local equilibrium assumption (LEA) is appropriate for modeling sorption-retarded diffusion under the given experimental conditions. Dp of 1.6-1.7 x 10(-6) cm2/s was estimated in aqueous solution at pH 8.0 and saturated with respect to calcite, as relevant to some subsurface regions of the Hanford site.

In-Situ Groundwater Treatment Technology Using Biodegradation

DTIC Science & Technology

1987-05-01

ice,� Park Drive, P.O. Box 12297, Research Trianglc Pgrk: NC 1 ?770Q 17. . COSAI COOES IL. SUBJEC TERMS (Coas on MuWMz d1 naicnay &W MO uf by I I, a...OF TABLES v 1 . ABSTRACT 1 2. INTRODUCTION 2 3. SUBSURFACE MICROBIOLOGY 5 3.1 Subsurface Biological Activity 5 3.2 Environmental Factors 5 3.2.1...Sulfate during the First Five Months 30 5.2 Column 1 Effluent Versus Time Data for Carbon Tetrachloride, Bromodichloromethane, and Bromoform during the

Workshop to develop deep-life continental scientific drilling projects

DOE PAGES

Kieft, T. L.; Onstott, T. C.; Ahonen, L.; ...

2015-05-29

The International Continental Scientific Drilling Program (ICDP) has long espoused studies of deep subsurface life, and has targeted fundamental questions regarding subsurface life, including the following: "(1) What is the extent and diversity of deep microbial life and what are the factors limiting it? (2) What are the types of metabolism/carbon/energy sources and the rates of subsurface activity? (3) How is deep microbial life adapted to subsurface conditions? (4) How do subsurface microbial communities affect energy resources? And (5) how does the deep biosphere interact with the geosphere and atmosphere?" (Horsfield et al., 2014) Many ICDP-sponsored drilling projects have includedmore » a deep-life component; however, to date, not one project has been driven by deep-life goals, in part because geomicrobiologists have been slow to initiate deep biosphere-driven ICDP projects. Therefore, the Deep Carbon Observatory (DCO) recently partnered with the ICDP to sponsor a workshop with the specific aim of gathering potential proponents for deep-life-driven ICDP projects and ideas for candidate drilling sites. Twenty-two participants from nine countries proposed projects and sites that included compressional and extensional tectonic environments, evaporites, hydrocarbon-rich shales, flood basalts, Precambrian shield rocks, subglacial and subpermafrost environments, active volcano–tectonic systems, megafan deltas, and serpentinizing ultramafic environments. The criteria and requirements for successful ICDP applications were presented. Deep-life-specific technical requirements were discussed and it was concluded that, while these procedures require adequate planning, they are entirely compatible with the sampling needs of other disciplines. As a result of this workshop, one drilling workshop proposal on the Basin and Range Physiographic Province (BRPP) has been submitted to the ICDP, and several other drilling project proponents plan to submit proposals for ICDP-sponsored drilling workshops in 2016.« less

Enhanced open ocean storage of CO2 from shelf sea pumping.

PubMed

Thomas, Helmuth; Bozec, Yann; Elkalay, Khalid; de Baar, Hein J W

2004-05-14

Seasonal field observations show that the North Sea, a Northern European shelf sea, is highly efficient in pumping carbon dioxide from the atmosphere to the North Atlantic Ocean. The bottom topography-controlled stratification separates production and respiration processes in the North Sea, causing a carbon dioxide increase in the subsurface layer that is ultimately exported to the North Atlantic Ocean. Globally extrapolated, the net uptake of carbon dioxide by coastal and marginal seas is about 20% of the world ocean's uptake of anthropogenic carbon dioxide, thus enhancing substantially the open ocean carbon dioxide storage.

Experimental Evidence that Hemlock Mortality Enhances Carbon Stabilization in Southern Appalachian Forest Soils

NASA Astrophysics Data System (ADS)

Fraterrigo, J.; Ream, K.; Knoepp, J.

2017-12-01

Forest insects and pathogens (FIPs) can cause uncertain changes in forest carbon balance, potentially influencing global atmospheric carbon dioxide (CO2) concentrations. We quantified the effects of hemlock (Tsuga canadensis L. Carr.) mortality on soil carbon fluxes and pools for a decade following either girdling or natural infestation by hemlock woolly adelgid (HWA; Adelges tsugae) to improve mechanistic understanding of soil carbon cycling response to FIPs. Although soil respiration (Rsoil) was similar among reference plots and plots with hemlock mortality, both girdled and HWA-infested plots had greater activities of β-glucosidase, a cellulose-hydrolyzing extracellular enzyme, and decreased O-horizon mass and fine root biomass from 2005 to 2013. During this period, total mineral soil carbon accumulated at a higher rate in disturbed plots than in reference plots in both the surface (0-10 cm) and subsurface (10-30 cm); increases were predominantly in the mineral-associated fraction of the soil organic matter. In contrast, particulate organic matter carbon accrued slowly in surface soils and declined in the subsurface of girdled plots. δ13C values of this fraction demonstrate that particulate organic matter carbon in the surface soil has become more microbially processed over time, suggesting enhanced decomposition of organic matter in this pool. Together, these findings indicate that hemlock mortality and subsequent forest regrowth has led to enhanced soil carbon stabilization in southern Appalachian forests through the translocation of carbon from detritus and particulate soil organic matter pools to the mineral-associated organic matter pool. These findings have implications for ecosystem management and modeling, demonstrating that forests may tolerate moderate disturbance without diminishing soil carbon storage when there is a compensatory growth response by non-host trees.

Sediment carbon fate in phreatic karst (Part 1): Conceptual model development

NASA Astrophysics Data System (ADS)

Husic, A.; Fox, J.; Agouridis, C.; Currens, J.; Ford, W.; Taylor, C.

2017-06-01

Recent research has paid increased attention to quantifying the fate of carbon pools within fluvial networks, but few, if any, studies consider the fate of sediment organic carbon in fluviokarst systems despite that karst landscapes cover 12% of the earth's land surface. The authors develop a conceptual model of sediment carbon fate in karst terrain with specific emphasis upon phreatic karst conduits, i.e., those located below the groundwater table that have the potential to trap surface-derived sediment and turnover carbon. To assist with their conceptual model development, the authors study a phreatic system and apply a mixture of methods traditional and novel to karst studies, including electrical resistivity imaging, well drilling, instantaneous velocimetry, dye tracing, stage recording, discrete and continuous sediment and water quality sampling, and elemental and stable carbon isotope fingerprinting. Results show that the sediment transport carrying capacity of the phreatic karst water is orders of magnitude less than surface streams during storm-activated periods promoting deposition of fine sediments in the phreatic karst. However, the sediment transport carrying capacity is sustained long after the hydrologic event has ended leading to sediment resuspension and prolonged transport. The surficial fine grained laminae occurs in the subsurface karst system; but unlike surface streams, the light-limited conditions of the subsurface karst promotes constant heterotrophy leading to carbon turnover. The coupling of the hydrological processes leads to a conceptual model that frames phreatic karst as a biologically active conveyor of sediment carbon that recharges degraded organic carbon back to surface streams. For example, fluvial sediment is estimated to lose 30% of its organic carbon by mass during a one year temporary residence within the phreatic karst. It is recommended that scientists consider karst pathways when attempting to estimate organic matter stocks and carbon transformation in fluvial networks.

Know your audience: public perception of geology from anecdote to evidence

NASA Astrophysics Data System (ADS)

Gibson, Hazel

2015-04-01

One of the basic strategies of science communication is to 'know your audience' (Nerlich et al, 2010), yet often scientists are communicating to a distant and diffuse audience that cannot be seen or directly engaged with. Both traditional written reports and emerging online media provide limited or no opportunity to engage audiences in dialogues with the communicator that can convey the public's own levels of knowledge. In those circumstances it becomes almost impossible to know your audience. For geoscientists, this decoupling from the intended audience is made more problematic when conveying new technical issues such as carbon capture and storage or deep geological disposal of radioactive waste, which are rooted in the unfamiliar subsurface (Sharma et al, 2007; Ashworth et al, 2009). Those geologists who have engaged with the public in these novel realms often have fashioned informal ways to overcome their audience's geological unfamiliarity based on the trial-and-error of personal experience, but such anecdotal lessons are rarely applicable to wider communities of practice. In recent years, however, our ad hoc intuitive ideas about how to comprehend public perceptions of geology have gained rigour from evidence-based theory (Singleton et al, 2009). This presentation highlights one example of this, using an ongoing study into the public understanding of the geological subsurface in south west England. Results from a combination of interviews and questionnaires were assessed using the established psychological technique: 'mental models' (Morgan et al, 2002). The work demonstrates how a mixed method approach can move geoscience communication beyond casual assumptions and individual rules of thumb to a more robust scientific way of thinking.

Improved Ionic Diffusion through the Mesoporous Carbon Skin on Silicon Nanoparticles Embedded in Carbon for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Kim, Hyeonjin; Ahn, Hyo-Jin

2018-02-21

Because of their combined effects of outstanding mechanical stability, high electrical conductivity, and high theoretical capacity, silicon (Si) nanoparticles embedded in carbon are a promising candidate as electrode material for practical utilization in Li-ion batteries (LIBs) to replace the conventional graphite. However, because of the poor ionic diffusion of electrode materials, the low-grade ultrafast cycling performance at high current densities remains a considerable challenge. In the present study, seeking to improve the ionic diffusion, we propose a novel design of mesoporous carbon skin on the Si nanoparticles embedded in carbon by hydrothermal reaction, poly(methyl methacrylate) coating process, and carbonization. The resultant electrode offers a high specific discharge capacity with excellent cycling stability (1140 mA h g -1 at 100 mA g -1 after 100 cycles), superb high-rate performance (969 mA h g -1 at 2000 mA g -1 ), and outstanding ultrafast cycling stability (532 mA h g -1 at 2000 mA g -1 after 500 cycles). The battery performances are surpassing the previously reported results for carbon and Si composite-based electrodes on LIBs. Therefore, this novel approach provides multiple benefits in terms of the effective accommodation of large volume expansions of the Si nanoparticles, a shorter Li-ion diffusion pathway, and stable electrochemical conditions from a faster ionic diffusion during cycling.

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas. The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.

Terrestrial Subsurface Ecosystem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkins, Michael J.; Fredrickson, Jim K.

2015-10-15

The Earth’s crust is a solid cool layer that overlays the mantle, with a varying thickness of between 30-50 km on continental plates, and 5-10 km on oceanic plates. Continental crust is composed of a variety of igneous, metamorphic, and sedimentary rocks that weather and re-form over geologic cycles lasting millions to billions of years. At the crust surface, these weathered minerals and organic material combine to produce a variety of soils types that provide suitable habitats and niches for abundant microbial diversity (see Chapter 4). Beneath this soil zone is the subsurface. Once thought to be relatively free ofmore » microorganisms, recent estimates have calculated that between 1016-1017 g C biomass (2-19% of Earth’s total biomass) may be present in this environment (Whitman et al., 1998;McMahon and Parnell, 2014). Microbial life in the subsurface exists across a wide range of habitats: in pores associated with relatively shallow unconsolidated aquifer sediments to fractures in bedrock formations that are more than a kilometer deep, where extreme lithostatic pressures and temperatures are encountered. While these different environments contain varying physical and chemical conditions, the absence of light is a constant. Despite this, diverse physiologies and metabolisms enable microorganisms to harness energy and carbon for growth in water-filled pore spaces and fractures. Carbon and other element cycles are driven by microbial activity, which has implications for both natural processes and human activities in the subsurface, e.g., bacteria play key roles in both hydrocarbon formation and degradation. Hydrocarbons are a major focus for human utilization of the subsurface, via oil and gas extraction and potential geologic CO2 sequestration. The subsurface is also utilized or being considered for sequestered storage of high-level radioactive waste from nuclear power generation and residual waste from past production of weapons grade nuclear materials. While our understanding of the subsurface is continually improving, it is clear that only a small fraction of microbial habitats have been sampled and studied. In this chapter, we will discuss these studies in the context of the distribution of microbial life in the subsurface, the stresses that microorganisms must overcome to survive in these environments, and the metabolic strategies that are employed to harness energy in a region of the planet far-removed from sunlight. Finally, we will consider both beneficial and deleterious effects of microbial activity in the subsurface on human activities in this environment.« less

Study on the formation of graphene by ion implantation on Cu, Ni and CuNi alloy

NASA Astrophysics Data System (ADS)

Kim, Janghyuk; Kim, Hong-Yeol; Jeon, Jeong Heum; An, Sungjoo; Hong, Jongwon; Kim, Jihyun

2018-09-01

This study identifies the details for direct synthesis of graphene by carbon ion implantation on Cu, Ni and CuNi alloy. Firstly, diffusion and concentration of carbon atoms in Cu and Ni are estimated separately. The concentrations of carbon atoms near the surfaces of Cu and Ni after carbon ion implantation and subsequent thermal annealing were correlated with the number of atoms and with the coverage or thickness of graphene. Systematic experiments showed that the Cu has higher carbon diffusivity and graphene coverage than Ni but higher temperatures and longer annealing times are required to synthesize graphene, similar to those in chemical vapor deposition method. The CuNi system shows better graphene coverage and quality than that on a single metal catalyst even after a short annealing time, as it has larger carbon diffusivity and lower carbon solubility than Ni and shows lower activation energy than Cu.

Diffusion of cis-3-methyl-2-pent-2-enyl-cyclopent-2-enone (1); carbon dioxide (2)

NASA Astrophysics Data System (ADS)

Winkelmann, J.

This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) cis-3-methyl-2-pent-2-enyl-cyclopent-2-enone; (2) carbon dioxide

Robust Representation of Integrated Surface-subsurface Hydrology at Watershed Scales

NASA Astrophysics Data System (ADS)

Painter, S. L.; Tang, G.; Collier, N.; Jan, A.; Karra, S.

2015-12-01

A representation of integrated surface-subsurface hydrology is the central component to process-rich watershed models that are emerging as alternatives to traditional reduced complexity models. These physically based systems are important for assessing potential impacts of climate change and human activities on groundwater-dependent ecosystems and water supply and quality. Integrated surface-subsurface models typically couple three-dimensional solutions for variably saturated flow in the subsurface with the kinematic- or diffusion-wave equation for surface flows. The computational scheme for coupling the surface and subsurface systems is key to the robustness, computational performance, and ease-of-implementation of the integrated system. A new, robust approach for coupling the subsurface and surface systems is developed from the assumption that the vertical gradient in head is negligible at the surface. This tight-coupling assumption allows the surface flow system to be incorporated directly into the subsurface system; effects of surface flow and surface water accumulation are represented as modifications to the subsurface flow and accumulation terms but are not triggered until the subsurface pressure reaches a threshold value corresponding to the appearance of water on the surface. The new approach has been implemented in the highly parallel PFLOTRAN (www.pflotran.org) code. Several synthetic examples and three-dimensional examples from the Walker Branch Watershed in Oak Ridge TN demonstrate the utility and robustness of the new approach using unstructured computational meshes. Representation of solute transport in the new approach is also discussed. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC0500OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for the United States Government purposes.

Stochastic Spectral Analysis for Characterizing Hydraulic Diffusivity in an Alluvial Fan Aquifer with River Stimulus

NASA Astrophysics Data System (ADS)

Wang, Y. L.; Zha, Y.; Yeh, T. C. J.; Wen, J. C.

2015-12-01

Estimation of subsurface hydraulic diffusivity was carried out to understand the characteristics of Zhuoshui River alluvial fan, Taiwan. The fan, an important agricultural and industrial region with high water demand, is located at middle Taiwan with an area of 1800 km2. The prior geo-investigations suggest that the main recharge region of the fan is at an apex along the river. The distribution of soil hydraulic diffusivity was estimated by fusing naturally recurring stimulus provided by river and groundwater head. Specifically, the variance and power spectrum provided by temporal and spatial change of groundwater head in response to river stage variations are analyzed to estimate hydraulic diffusivity distribution. It is found that the hydraulic diffusivity of the fan is at the range from 0.08 to 16 m2/s. The average hydraulic diffusivity at the apex, middle, and tail of the fan along the river is about 0.4, 0.6, and 1.0 m2/s, respectively.

An adsorption diffusion model for removal of para-chlorophenol by activated carbon derived from bituminous coal.

PubMed

Sze, M F F; McKay, G

2010-05-01

Batch adsorption experiments were carried out to study the adsorptive removal and diffusion mechanism of para-chlorophenol (p-CP) onto Calgon Filtrasorb 400 (F400) activated carbon. The external mass transfer resistance is negligible in the adsorption process carried out under different conditions in batch operation. Intraparticle diffusion model plots were used to correlate the batch p-CP adsorption data; three distinct linear sections were obtained for every batch operation. The textural properties of F400 activated carbon showed that it has a large portion of supermicropores, which is comparable to the size of the p-CP molecules. Due to the stronger interactions between p-CP molecules and F400 micropores, p-CP molecules predominantly diffused and occupied active sites in micropore region by hopping mechanism, and eventually followed by a slow filling of mesopores and micropores. This hypothesis is proven by the excellent agreement of the intraparticle diffusion model plots and the textural properties of F400 activated carbon. Copyright 2009 Elsevier Ltd. All rights reserved.

Interstitial and Interlayer Ion Diffusion Geometry Extraction in Graphitic Nanosphere Battery Materials.

PubMed

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun; Wang, Bei; Bremer, Peer-Timo; Papka, Michael E; Curtiss, Larry A; Pascucci, Valerio

2016-01-01

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermally annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.

Surface diffusion of a carbon-adatom on Au(110) surfaces

NASA Astrophysics Data System (ADS)

Kim, E.; Safavi-Naini, A.; Hite, D. A.; McKay, K. S.; Pappas, D. P.; Weck, P. F.; Sadeghpour, H. R.

We have investigated the surface diffusion of carbon-adatom on gold surfaces using density functional theory and detailed scanning probe microscopy. The decoherence of trapped-ion quantum gates due to heating of their motional modes is a fundamental science and engineering problem. In an effort to understand heating at the trap-electrode surfaces, we investigate the possible source of noise by focusing on the diffusion of carbon-containing adsorbates onto the Au(110) surface. In this study, we show how the diffusive motion of carbon adatom on gold surface significantly affects the energy landscape and adatom dipole moment variation. A simple model for the diffusion noise, which varies quadratically with the variation of the dipole moment, qualitatively reproduces the measured noise spectrum, and the estimate of the noise spectral density is in accord with measured values. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the United States Department of Energy's NNSA under Contract DE-AC04-94AL85000.

Interstitial and Interlayer Ion Diffusion Geometry Extraction in Graphitic Nanosphere Battery Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun

2016-01-01

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermallymore » annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.« less

Interstitial and interlayer ion diffusion geometry extraction in graphitic nanosphere battery materials

DOE PAGES

Gyulassy, Attila; Knoll, Aaron; Lau, Kah Chun; ...

2016-01-31

Large-scale molecular dynamics (MD) simulations are commonly used for simulating the synthesis and ion diffusion of battery materials. A good battery anode material is determined by its capacity to store ion or other diffusers. However, modeling of ion diffusion dynamics and transport properties at large length and long time scales would be impossible with current MD codes. To analyze the fundamental properties of these materials, therefore, we turn to geometric and topological analysis of their structure. In this paper, we apply a novel technique inspired by discrete Morse theory to the Delaunay triangulation of the simulated geometry of a thermallymore » annealed carbon nanosphere. We utilize our computed structures to drive further geometric analysis to extract the interstitial diffusion structure as a single mesh. Lastly, our results provide a new approach to analyze the geometry of the simulated carbon nanosphere, and new insights into the role of carbon defect size and distribution in determining the charge capacity and charge dynamics of these carbon based battery materials.« less

“Conjugate Channeling” Effect in Dislocation Core Diffusion: Carbon Transport in Dislocated BCC Iron

PubMed Central

Ishii, Akio; Li, Ju; Ogata, Shigenobu

2013-01-01

Dislocation pipe diffusion seems to be a well-established phenomenon. Here we demonstrate an unexpected effect, that the migration of interstitials such as carbon in iron may be accelerated not in the dislocation line direction , but in a conjugate diffusion direction. This accelerated random walk arises from a simple crystallographic channeling effect. is a function of the Burgers vector b, but not , thus a dislocation loop possesses the same everywhere. Using molecular dynamics and accelerated dynamics simulations, we further show that such dislocation-core-coupled carbon diffusion in iron has temperature-dependent activation enthalpy like a fragile glass. The 71° mixed dislocation is the only case in which we see straightforward pipe diffusion that does not depend on dislocation mobility. PMID:23593255

"Conjugate channeling" effect in dislocation core diffusion: carbon transport in dislocated BCC iron.

PubMed

Ishii, Akio; Li, Ju; Ogata, Shigenobu

2013-01-01

Dislocation pipe diffusion seems to be a well-established phenomenon. Here we demonstrate an unexpected effect, that the migration of interstitials such as carbon in iron may be accelerated not in the dislocation line direction ξ, but in a conjugate diffusion direction. This accelerated random walk arises from a simple crystallographic channeling effect. c is a function of the Burgers vector b, but not ξ, thus a dislocation loop possesses the same everywhere. Using molecular dynamics and accelerated dynamics simulations, we further show that such dislocation-core-coupled carbon diffusion in iron has temperature-dependent activation enthalpy like a fragile glass. The 71° mixed dislocation is the only case in which we see straightforward pipe diffusion that does not depend on dislocation mobility.

Electric-field noise from carbon-adatom diffusion on a Au(110) surface: First-principles calculations and experiments

NASA Astrophysics Data System (ADS)

Kim, E.; Safavi-Naini, A.; Hite, D. A.; McKay, K. S.; Pappas, D. P.; Weck, P. F.; Sadeghpour, H. R.

2017-03-01

The decoherence of trapped-ion quantum gates due to heating of their motional modes is a fundamental science and engineering problem. This heating is attributed to electric-field noise arising from the trap-electrode surfaces. In this work, we investigate the source of this noise by focusing on the diffusion of carbon-containing adsorbates on the surface of Au(110). We show by density functional theory, based on detailed scanning probe microscopy, how the carbon adatom diffusion on the gold surface changes the energy landscape and how the adatom dipole moment varies with the diffusive motion. A simple model for the diffusion noise, which varies quadratically with the variation of the dipole moment, predicts a noise spectrum, in accordance with the measured values.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balashov, Victor N.; Brantley, Susan L.; Guthrie, George D.

One idea for mitigating the increase in fossil- fuel generated carbon dioxide (CO 2) in the atmosphere is to inject CO 2 into subsurface saline sandstone reservoirs, thereby storing it in those geologic formations and out of the atmosphere.

The Relationship between Litho-Sequential Stratigraphy, Chemostratigraphy of Khuff Carbonates: Implication for Facies and Paleoenvironmental Recognition and Correlation, Central Saudi Arabia

NASA Astrophysics Data System (ADS)

Abdullatif, Osman; Abdlmutalib, Ammar; Ahmed, Jarrah; Abdelgadir, Mohamed; Adam, Ammar

2017-04-01

The Permian-Triassic Khuff Formation carbonate reservoirs (and equivalents) in the Middle East are estimated to contain about 15-20 % of the world's gas reserves. Excellently exposed outcropping Khuff strata in central Saudi Arabia provide good outcrop equivalents to the Khuff Formation in the subsurface. The Khuff Formation is composed of five members and from bottom to top are Ash Shiqqah, Huqayl, Duhaysan, Midnab and Khartam members. The Carbonates lithofacies dominate with minor terrestrial clastics, and the paleoenvironments vary from terrestrial, sabkha, tidal-intertidal and open marine environments. This study investigates the relationship between lithostratigraphy, sequence stratigraphy and chemostratigraphy by integration of both field and laboratory sedimentological and chemical elements data. The vertical chemical elements profiles along the Khuff members show variations in their chemical elements content with the variation in lithofacies types, staking pattern, depositional and stratigraphic pattern. The chemostratigraphic distribution of the chemical elements also showed variation within and between the Khuff members. There is a general agreement between chemostratigraphic analyses based on vertical profiles and binary cross plots. The Khuff members and their stratigraphic boundaries can be differentiated based on their chemostratigraphic signatures. Moreover, the lithofacies and depositional paleoenvironmental of different Khuff members can be identified based on their chemical element contents. Chemostratigraphic zones or clusters are markedly established indicating different lithofacies and depositional paleoenvironments. Terrestrial, channel, lacustrine, shoreline to open marine carbonate lithofacies, as building blocks of sequence stratigraphy, all may be distinguished based on their chemical signatures. These outcrop analog results might be of significance to lithofacies, paleoenvironmental, stratigraphic identification, classification and correlation of Khuff Formation in the subsurface. The results might also provide guides and application to reservoir Khuff Formation identification, layering and zonation in the subsurface.

MX Siting Investigation Water Resources Program.

DTIC Science & Technology

1980-10-31

bedrock units are highly dependent upon the degree of secondary permeability ( fractures and solution open- ings). Although the first unit is believed to...the Fortification Range. Carbonate rocks, largely limestone and dolomite , are exposed in the Bristol and Highland I ranges. Deposits composing the...infiltration of precipitation, surface runoff, and subsurface underflow from fractured or solutioned volcanic and/or carbonate bedrock. Recharge by di- Irect

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

Computing eddy-driven effective diffusivity using Lagrangian particles

DOE PAGES

Wolfram, Phillip J.; Ringler, Todd D.

2017-08-14

A novel method to derive effective diffusivity from Lagrangian particle trajectory data sets is developed and then analyzed relative to particle-derived meridional diffusivity for eddy-driven mixing in an idealized circumpolar current. Quantitative standard dispersion- and transport-based mixing diagnostics are defined, compared and contrasted to motivate the computation and use of effective diffusivity derived from Lagrangian particles. We compute the effective diffusivity by first performing scalar transport on Lagrangian control areas using stored trajectories computed from online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) using the Model for Prediction Across Scales Ocean (MPAS-O). Furthermore, the Lagrangian scalar transport scheme is comparedmore » against an Eulerian scalar transport scheme. Spatially-variable effective diffusivities are computed from resulting time-varying cumulative concentrations that vary as a function of cumulative area. The transport-based Eulerian and Lagrangian effective diffusivity diagnostics are found to be qualitatively consistent with the dispersion-based diffusivity. All diffusivity estimates show a region of increased subsurface diffusivity within the core of an idealized circumpolar current and results are within a factor of two of each other. The Eulerian and Lagrangian effective diffusivities are most similar; smaller and more spatially diffused values are obtained with the dispersion-based diffusivity computed with particle clusters.« less

Computing eddy-driven effective diffusivity using Lagrangian particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolfram, Phillip J.; Ringler, Todd D.

A novel method to derive effective diffusivity from Lagrangian particle trajectory data sets is developed and then analyzed relative to particle-derived meridional diffusivity for eddy-driven mixing in an idealized circumpolar current. Quantitative standard dispersion- and transport-based mixing diagnostics are defined, compared and contrasted to motivate the computation and use of effective diffusivity derived from Lagrangian particles. We compute the effective diffusivity by first performing scalar transport on Lagrangian control areas using stored trajectories computed from online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) using the Model for Prediction Across Scales Ocean (MPAS-O). Furthermore, the Lagrangian scalar transport scheme is comparedmore » against an Eulerian scalar transport scheme. Spatially-variable effective diffusivities are computed from resulting time-varying cumulative concentrations that vary as a function of cumulative area. The transport-based Eulerian and Lagrangian effective diffusivity diagnostics are found to be qualitatively consistent with the dispersion-based diffusivity. All diffusivity estimates show a region of increased subsurface diffusivity within the core of an idealized circumpolar current and results are within a factor of two of each other. The Eulerian and Lagrangian effective diffusivities are most similar; smaller and more spatially diffused values are obtained with the dispersion-based diffusivity computed with particle clusters.« less

Authigenic carbon entombed in methane-soaked sediments from the northeastern transform margin of the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Paull, Charles K.; Ussler, William; Peltzer, Edward T.; Brewer, Peter G.; Keaten, Rendy; Mitts, Patrick J.; Nealon, Jeffrey W.; Greinert, Jens; Herguera, Juan-Carlos; Elena Perez, M.

2007-06-01

Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ˜10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (-53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (-51.9±8.1‰ PDB). However, the δ13C value of the CO 2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (-35.8‰ to -2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (-40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO 2 in the vent gas. There appears to be two carbon sources for the authigenic carbonates: (1) deeply-sourced, isotopically heavy CO 2 (˜+12‰); and (2) isotopically light DIC derived from local anaerobic oxidation of methane at the sulfate-methane interface in the shallow subsurface. Addition of isotopically light methane-derived carbon at the seafloor may completely mask the isotopically heavy CO 2 signature (+12.4‰) in the underlying sediments. Thus, the authigenic carbonates may have formed from the same methane- and carbon dioxide-bearing fluid, but under different migration and alteration conditions, depending on how it migrated through the sediment column.

Using satellite-derived optical thickness to assess the influence of clouds on terrestrial carbon uptake

Treesearch

S.J. Cheng; A.L. Steiner; D.Y. Hollinger; G. Bohrer; K.J. Nadelhoffer

2016-01-01

Clouds scatter direct solar radiation, generating diffuse radiation and altering the ratio of direct to diffuse light. If diffuse light increases plant canopy CO2 uptake, clouds may indirectly influence climate by altering the terrestrial carbon cycle. However, past research primarily uses proxies or qualitative categories of clouds to connect...

Anaerobic decomposition of humic substances by Clostridium from the deep subsurface

PubMed Central

Ueno, Akio; Shimizu, Satoru; Tamamura, Shuji; Okuyama, Hidetoshi; Naganuma, Takeshi; Kaneko, Katsuhiko

2016-01-01

Decomposition of humic substances (HSs) is a slow and cryptic but non-negligible component of carbon cycling in sediments. Aerobic decomposition of HSs by microorganisms in the surface environment has been well documented; however, the mechanism of anaerobic microbial decomposition of HSs is not completely understood. Moreover, no microorganisms capable of anaerobic decomposition of HSs have been isolated. Here, we report the anaerobic decomposition of humic acids (HAs) by the anaerobic bacterium Clostridium sp. HSAI-1 isolated from the deep terrestrial subsurface. The use of 14C-labelled polycatechol as an HA analogue demonstrated that the bacterium decomposed this substance up to 7.4% over 14 days. The decomposition of commercial and natural HAs by the bacterium yielded lower molecular mass fractions, as determined using high-performance size-exclusion chromatography. Fourier transform infrared spectroscopy revealed the removal of carboxyl groups and polysaccharide-related substances, as well as the generation of aliphatic components, amide and aromatic groups. Therefore, our results suggest that Clostridium sp. HSAI-1 anaerobically decomposes and transforms HSs. This study improves our understanding of the anaerobic decomposition of HSs in the hidden carbon cycling in the Earth’s subsurface. PMID:26743007

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE PAGES

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

2016-08-09

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

Comparative Study of Effects of CO 2 Concentration and pH on Microbial Communities from a Saline Aquifer, a Depleted Oil Reservoir, and a Freshwater Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulliver, Djuna M.; Lowry, Gregory V.; Gregory, Kelvin B.

Injected CO 2 from geologic carbon storage is expected to impact the microbial communities of proposed storage sites, such as depleted oil reservoirs and deep saline aquifers, as well as overlying freshwater aquifers at risk of receiving leaking CO 2. Microbial community change in these subsurface sites may affect injectivity of CO 2, permanence of stored CO 2, and shallow subsurface water quality. The effect of CO 2 concentration on the microbial communities in fluid collected from a depleted oil reservoir and a freshwater aquifer was examined at subsurface pressures and temperatures. The community was exposed to 0%, 1%, 10%,more » and 100% pCO 2 for 56 days. Bacterial community structure was analyzed through 16S rRNA gene clone libraries, and total bacterial abundance was estimated through quantitative polymerase chain reaction. Changes in the microbial community observed in the depleted oil reservoir samples and freshwater samples were compared to previous results from CO 2-exposed deep saline aquifer fluids. Overall, results suggest that CO 2 exposure to microbial communities will result in pH-dependent population change, and the CO 2-selected microbial communities will vary among sites. In conclusion, this is the first study to compare the response of multiple subsurface microbial communities at conditions expected during geologic carbon storage, increasing the understanding of environmental drivers for microbial community changes in CO 2-exposed environments.« less

Non-viable Microbial Community Structure and Geochemistry of Deep Subsurface Shales at Marcellus Shale Energy and Environment Laboratory

NASA Astrophysics Data System (ADS)

Akondi, R.; Trexler, R.; Sharma, S.; Mouser, P. J.; Pfiffner, S. M.

2016-12-01

The deep subsurface is known to harbor diverse communities of living microbes, and can therefore be expected to also harbor an equally diverse and likely different set of non-viable microbial populations. In this study, diglyceride fatty acids, (DGFA, biomarkers for non-viable microbes) as well as their compound specific isotopes (CSIA) were used to study the yield and variety of DGFAs in deep subsurface mid-Devonian sediments of different lithologies. Pristine sidewall cores were obtained from intervals in the Marcellus, Mahantango, and the Marcellus/Mahantango formation interface. The biomarkers were extracted and DGFAs were methylated to fatty acid methyl esters (FAMEs) and analyzed using GC-MS, while the CSIAs were performed using GC-irMS. Sediments were also analyzed for total organic carbon (TOC), stable carbon isotopic composition of organic carbon (δ13Corg), inorganic carbon (δ13Ccarb), and nitrogen (δ15Norg). TOC concentration was highest in the Marcellus and there was a general trend of increasing TOC from Mahantango to the Marcellus. The δ13Corg and δ13Ccarb increased and decreased respectively from Mahantango to the Marcellus while δ15Norg did not show any trend. The FAME profiles consisted of normal saturated, monounsaturated, polyunsaturated, branched, epoxy, terminally branched, hydroxyl, and dimethyl esters. The total biomass yield and variety of DGFA-FAME profiles were higher in the Mahantango compared to the samples from the Marcellus formation and Marcellus/Mahantango interface, suggesting the presence of more paleo-microbial activity in the less consolidated Mahantango formation. We attribute this to the smaller pore throat sizes within the Marcellus formation compared to the Mahantango formation. Since organic matter in the sediments is also one of the key sources of energy for microbial metabolism, bulk 13C and CSIA of the lipids will be used to understand the source(s) and pathways of the carbon cycling within the microbial communities.

Two-Relaxation-Time Lattice Boltzmann Method and its Application to Advective-Diffusive-Reactive Transport

DOE PAGES

Yan, Zhifeng; Yang, Xiaofan; Li, Siliang; ...

2017-09-05

The lattice Boltzmann method (LBM) based on single-relaxation-time (SRT) or multiple-relaxation-time (MRT) collision operators is widely used in simulating flow and transport phenomena. The LBM based on two-relaxation-time (TRT) collision operators possesses strengths from the SRT and MRT LBMs, such as its simple implementation and good numerical stability, although tedious mathematical derivations and presentations of the TRT LBM hinder its application to a broad range of flow and transport phenomena. This paper describes the TRT LBM clearly and provides a pseudocode for easy implementation. Various transport phenomena were simulated using the TRT LBM to illustrate its applications in subsurface environments.more » These phenomena include advection-diffusion in uniform flow, Taylor dispersion in a pipe, solute transport in a packed column, reactive transport in uniform flow, and bacterial chemotaxis in porous media. Finally, the TRT LBM demonstrated good numerical performance in terms of accuracy and stability in predicting these transport phenomena. Therefore, the TRT LBM is a powerful tool to simulate various geophysical and biogeochemical processes in subsurface environments.« less

Two-relaxation-time lattice Boltzmann method and its application to advective-diffusive-reactive transport

NASA Astrophysics Data System (ADS)

Yan, Zhifeng; Yang, Xiaofan; Li, Siliang; Hilpert, Markus

2017-11-01

The lattice Boltzmann method (LBM) based on single-relaxation-time (SRT) or multiple-relaxation-time (MRT) collision operators is widely used in simulating flow and transport phenomena. The LBM based on two-relaxation-time (TRT) collision operators possesses strengths from the SRT and MRT LBMs, such as its simple implementation and good numerical stability, although tedious mathematical derivations and presentations of the TRT LBM hinder its application to a broad range of flow and transport phenomena. This paper describes the TRT LBM clearly and provides a pseudocode for easy implementation. Various transport phenomena were simulated using the TRT LBM to illustrate its applications in subsurface environments. These phenomena include advection-diffusion in uniform flow, Taylor dispersion in a pipe, solute transport in a packed column, reactive transport in uniform flow, and bacterial chemotaxis in porous media. The TRT LBM demonstrated good numerical performance in terms of accuracy and stability in predicting these transport phenomena. Therefore, the TRT LBM is a powerful tool to simulate various geophysical and biogeochemical processes in subsurface environments.

Two-Relaxation-Time Lattice Boltzmann Method and its Application to Advective-Diffusive-Reactive Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Zhifeng; Yang, Xiaofan; Li, Siliang

The lattice Boltzmann method (LBM) based on single-relaxation-time (SRT) or multiple-relaxation-time (MRT) collision operators is widely used in simulating flow and transport phenomena. The LBM based on two-relaxation-time (TRT) collision operators possesses strengths from the SRT and MRT LBMs, such as its simple implementation and good numerical stability, although tedious mathematical derivations and presentations of the TRT LBM hinder its application to a broad range of flow and transport phenomena. This paper describes the TRT LBM clearly and provides a pseudocode for easy implementation. Various transport phenomena were simulated using the TRT LBM to illustrate its applications in subsurface environments.more » These phenomena include advection-diffusion in uniform flow, Taylor dispersion in a pipe, solute transport in a packed column, reactive transport in uniform flow, and bacterial chemotaxis in porous media. Finally, the TRT LBM demonstrated good numerical performance in terms of accuracy and stability in predicting these transport phenomena. Therefore, the TRT LBM is a powerful tool to simulate various geophysical and biogeochemical processes in subsurface environments.« less

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

Growth of methanogens on a Mars soil simulant.

PubMed

Kral, Timothy A; Bekkum, Curtis R; McKay, Christopher P

2004-12-01

Currently, the surface of Mars is probably too cold, too dry, and too oxidizing for life, as we know it, to exist. But the subsurface is another matter. Life forms that might exist below the surface could not obtain their energy from photosynthesis, but rather they would have to utilize chemical energy. Methanogens are one type of microorganism that might be able to survive below the surface of Mars. A potential habitat for existence of methanogens on Mars might be a geothermal source of hydrogen, possibly due to volcanic or hydrothermal activity, or the reaction of basalt and anaerobic water, carbon dioxide, which is abundant in the martian atmosphere, and of course, subsurface liquid water. We report here that certain methanogens can grow on a Mars soil simulant when supplied with carbon dioxide, molecular hydrogen, and varying amounts of water.

Fractional Diffusion Analysis of the Electromagnetic Field In Fractured Media Part II: 2.5-D Approach

NASA Astrophysics Data System (ADS)

Ge, J.; Everett, M. E.; Weiss, C. J.

2012-12-01

A 2.5D finite difference (FD) frequency-domain modeling algorithm based on the theory of fractional diffusion of electromagnetic (EM) fields generated by a loop source lying above a fractured geological medium is addressed in this paper. The presence of fractures in the subsurface, usually containing highly conductive pore fluids, gives rise to spatially hierarchical flow paths of induced EM eddy currents. The diffusion of EM eddy currents in such formations is anomalous, generalizing the classical Gaussian process described by the conventional Maxwell equations. Based on the continuous time random walk (CTRW) theory, the diffusion of EM eddy currents in a rough medium is governed by the fractional Maxwell equations. Here, we model the EM response of a 2D subsurface containing fractured zones, with a 3D loop source, which results the so-called 2.5D model geometry. The governing equation in the frequency domain is converted using Fourier transform into k domain along the strike direction (along which the model conductivity doesn't vary). The resulting equation system is solved by the multifrontal massively parallel solver (MUMPS). The data obtained is then converted back to spatial domain and the time domain. We find excellent agreement between the FD and analytic solutions for a rough halfspace model. Then FD solutions are calculated for a 2D fault zone model with variable conductivity and roughness. We compare the results with responses from several classical models and explore the relationship between the roughness and the spatial density of the fracture distribution.

Effects of anisotropies in turbulent magnetic diffusion in mean-field solar dynamo models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pipin, V. V.; Kosovichev, A. G.

2014-04-10

We study how anisotropies of turbulent diffusion affect the evolution of large-scale magnetic fields and the dynamo process on the Sun. The effect of anisotropy is calculated in a mean-field magnetohydrodynamics framework assuming that triple correlations provide relaxation to the turbulent electromotive force (so-called the 'minimal τ-approximation'). We examine two types of mean-field dynamo models: the well-known benchmark flux-transport model and a distributed-dynamo model with a subsurface rotational shear layer. For both models, we investigate effects of the double- and triple-cell meridional circulation, recently suggested by helioseismology and numerical simulations. To characterize the anisotropy effects, we introduce a parameter ofmore » anisotropy as a ratio of the radial and horizontal intensities of turbulent mixing. It is found that the anisotropy affects the distribution of magnetic fields inside the convection zone. The concentration of the magnetic flux near the bottom and top boundaries of the convection zone is greater when the anisotropy is stronger. It is shown that the critical dynamo number and the dynamo period approach to constant values for large values of the anisotropy parameter. The anisotropy reduces the overlap of toroidal magnetic fields generated in subsequent dynamo cycles, in the time-latitude 'butterfly' diagram. If we assume that sunspots are formed in the vicinity of the subsurface shear layer, then the distributed dynamo model with the anisotropic diffusivity satisfies the observational constraints from helioseismology and is consistent with the value of effective turbulent diffusion estimated from the dynamics of surface magnetic fields.« less

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

PubMed

Ong, Mitchell T; Verners, Osvalds; Draeger, Erik W; van Duin, Adri C T; Lordi, Vincenzo; Pask, John E

2015-01-29

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.

Zones of life in the subsurface of hydrothermal vents: A synthesis

NASA Astrophysics Data System (ADS)

Larson, B. I.; Houghton, J.; Meile, C. D.

2011-12-01

Subsurface microbial communities in Mid-ocean Ridge (MOR) hydrothermal systems host a wide array of unique metabolic strategies, but the spatial distribution of biogeochemical transformations is poorly constrained. Here we present an approach that reexamines chemical measurements from diffuse fluids with models of convective transport to delineate likely reaction zones. Chemical data have been compiled from bare basalt surfaces at a wide array of mid-ocean ridge systems, including 9°N, East Pacific Rise, Axial Seamount, Juan de Fuca, and Lucky Strike, Mid-Atlantic Ridge. Co-sampled end-member fluid from Ty (EPR) was used to constrain reaction path models that define diffuse fluid compositions as a function of temperature. The degree of mixing between hot vent fluid (350 deg. C) and seawater (2 deg. C) governs fluid temperature, Fe-oxide mineral precipitation is suppressed, and aqueous redox reactions are prevented from equilibrating, consistent with sluggish kinetics. Quartz and pyrite are predicted to precipitate, consistent with field observations. Most reported samples of diffuse fluids from EPR and Axial Seamount fall along the same predicted mixing line only when pyrite precipitation is suppressed, but Lucky Strike fluids do not follow the same trend. The predicted fluid composition as a function of temperature is then used to calculate the free energy available to autotrophic microorganisms for a variety of catabolic strategies in the subsurface. Finally, the relationships between temperature and free energy is combined with modeled temperature fields (Lowell et al., 2007 Geochem. Geophys., Geosys.) over a 500 m x 500 m region extending downward from the seafloor and outward from the high temperature focused hydrothermal flow to define areas that are energetically most favorable for a given metabolic process as well as below the upper temperature limit for life (~120 deg. C). In this way, we can expand the relevance of geochemical model predictions of bioenergetics by predicting functionally-defined 'Zones of Life' and placing them spatially within the boundary of the 120 deg. C isotherm, estimating the extent of subsurface biosphere beneath mid-ocean ridge hydrothermal systems. Preliminary results indicate that methanogenesis yields the most energy per kg of vent fluid, consistent with the elevated CH4(aq) seen at all three sites, but may be constrained by temperatures too hot for microbial life while available energy from the oxidation of Fe(II) peaks near regions of the crust that are more hospitable.

Importance of solar subsurface heating in ocean general circulation models

NASA Astrophysics Data System (ADS)

Rochford, Peter A.; Kara, A. Birol; Wallcraft, Alan J.; Arnone, Robert A.

2001-12-01

The importance of subsurface heating on surface mixed layer properties in an ocean general circulation model (OGCM) is examined using attenuation of solar irradiance with depth below the ocean surface. The depth-dependent attenuation of subsurface heating is given by global monthly mean fields for the attenuation of photosynthetically available radiation (PAR), kPAR. These global fields of kPAR are derived from Sea-viewing Wide Field-of-view Sensor (SeaWiFS) data on the spectral diffuse attenuation coefficient at 490 nm (k490), and have been processed to have the smoothly varying and continuous coverage necessary for use in OGCM applications. These monthly fields provide the first complete global data sets of subsurface optical fields that can be used for OGCM applications of subsurface heating and bio-optical processes. The effect on global OGCM prediction of sea surface temperature (SST) and surface mixed layer depth (MLD) is examined when solar heating, as given by monthly mean kPAR and PAR fields, is included in the model. It is found that subsurface heating yields a marked increase in the SST predictive skill of the OGCM at low latitudes. No significant improvement in MLD predictive skill is obtained when including subsurface heating. Use of the monthly mean kPAR produces an SST decrease of up to 0.8°C and a MLD increase of up to only 4-5 m for climatological surface forcing, with this primarily confined to the equatorial regions. Remarkably, a constant kPAR value of 0.06 m-1, which is indicative of optically clear open ocean conditions, is found to serve very well for OGCM prediction of SST and MLD over most of the global ocean.

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

NASA Astrophysics Data System (ADS)

Nimmo, John R.; Creasey, Kaitlyn M.; Perkins, Kim S.; Mirus, Benjamin B.

2017-03-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

Preferential flow, diffuse flow, and perching in an interbedded fractured-rock unsaturated zone

USGS Publications Warehouse

Nimmo, John R.; Creasey, Kaitlyn M; Perkins, Kimberlie; Mirus, Benjamin B.

2017-01-01

Layers of strong geologic contrast within the unsaturated zone can control recharge and contaminant transport to underlying aquifers. Slow diffuse flow in certain geologic layers, and rapid preferential flow in others, complicates the prediction of vertical and lateral fluxes. A simple model is presented, designed to use limited geological site information to predict these critical subsurface processes in response to a sustained infiltration source. The model is developed and tested using site-specific information from the Idaho National Laboratory in the Eastern Snake River Plain (ESRP), USA, where there are natural and anthropogenic sources of high-volume infiltration from floods, spills, leaks, wastewater disposal, retention ponds, and hydrologic field experiments. The thick unsaturated zone overlying the ESRP aquifer is a good example of a sharply stratified unsaturated zone. Sedimentary interbeds are interspersed between massive and fractured basalt units. The combination of surficial sediments, basalts, and interbeds determines the water fluxes through the variably saturated subsurface. Interbeds are generally less conductive, sometimes causing perched water to collect above them. The model successfully predicts the volume and extent of perching and approximates vertical travel times during events that generate high fluxes from the land surface. These developments are applicable to sites having a thick, geologically complex unsaturated zone of substantial thickness in which preferential and diffuse flow, and perching of percolated water, are important to contaminant transport or aquifer recharge.

Molecular simulation of gas adsorption and diffusion in a breathing MOF using a rigid force field.

PubMed

García-Pérez, E; Serra-Crespo, P; Hamad, S; Kapteijn, F; Gascon, J

2014-08-14

Simulation of gas adsorption in flexible porous materials is still limited by the slow progress in the development of flexible force fields. Moreover, the high computational cost of such flexible force fields may be a drawback even when they are fully developed. In this work, molecular simulations of gas adsorption and diffusion of carbon dioxide and methane in NH2-MIL-53(Al) are carried out using a linear combination of two crystallographic structures with rigid force fields. Once the interactions of carbon dioxide molecules and the bridging hydroxyls groups of the framework are optimized, an excellent match is found for simulations and experimental data for the adsorption of methane and carbon dioxide, including the stepwise uptake due to the breathing effect. In addition, diffusivities of pure components are calculated. The pore expansion by the breathing effect influences the self-diffusion mechanism and much higher diffusivities are observed at relatively high adsorbate loadings. This work demonstrates that using a rigid force field combined with a minimum number of experiments, reproduces adsorption and simulates diffusion of carbon dioxide and methane in the flexible metal-organic framework NH2-MIL-53(Al).

Using dynamic flux chambers to estimate the natural attenuation rates in the subsurface at petroleum contaminated sites.

PubMed

Verginelli, Iason; Pecoraro, Roberto; Baciocchi, Renato

2018-04-01

In this work, we introduce a screening method for the evaluation of the natural attenuation rates in the subsurface at sites contaminated by petroleum hydrocarbons. The method is based on the combination of the data obtained from standard source characterization with dynamic flux chambers measurements. The natural attenuation rates are calculated as difference between the flux of contaminants estimated with a non-reactive diffusive model starting from the concentrations of the contaminants detected in the source (soil and/or groundwater) and the effective emission rate of the contaminants measured using dynamic flux chambers installed at ground level. The reliability of this approach was tested in a contaminated site characterized by the presence of BTEX in soil and groundwater. Namely, the BTEX emission rates from the subsurface were measured in 4 seasonal campaigns using dynamic flux chambers installed in 14 sampling points. The comparison of measured fluxes with those predicted using a non-reactive diffusive model, starting from the source concentrations, showed that, in line with other recent studies, the modelling approach can overestimate the expected outdoor concentration of petroleum hydrocarbons even up to 4 orders of magnitude. On the other hand, by coupling the measured data with the fluxes estimated with the diffusive non-reactive model, it was possible to perform a mass balance to evaluate the natural attenuation loss rates of petroleum hydrocarbons during the migration from the source to ground level. Based on this comparison, the estimated BTEX loss rates in the test site were up to almost 0.5kg/year/m 2 . These rates are in line with the values reported in the recent literature for natural source zone depletion. In short, the method presented in this work can represent an easy-to-use and cost-effective option that can provide a further line of evidence of natural attenuation rates expected at contaminated sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Pathways and transformations of dissolved methane and dissolved inorganic carbon in Arctic tundra watersheds: Evidence from analysis of stable isotopes

DOE PAGES

Throckmorton, Heather M.; Heikoop, Jeffrey M.; Newman, Brent D.; ...

2015-11-08

Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO 2) and methane (CH 4) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH 4 and CO 2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO 2) and CH 4 in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DICmore » and CH 4 cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH 4 and DIC balance by estimating mechanisms of CH 4 and DIC production and transport pathways and oxidation of subsurface CH 4. We observed a shift from acetoclastic (July) toward hydrogenotropic (September) methanogenesis at sites located toward the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH 4 production mechanism. The majority of subsurface CH 4 was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH 4 oxidation. Thus, surprisingly, CH 4 oxidation only consumed approximately 2.51± 0.82% (July) and 0.79 ± 0.79% (September) of CH 4 produced at the frost table, contributing to <0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. Furthermore, this work highlights the importance of spatial and temporal variability of CH 4 production at the watershed scale and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH 4 and CO 2 production.« less

Methane clathrate stability zone variations and gas transport in the Martian subsurface

NASA Astrophysics Data System (ADS)

Karatekin, O.; Gloesener, E.; Dehant, V. M. A.; Temel, O.

2016-12-01

During the last years, several detections of methane in the atmosphere of Mars were reported from Earth-based and Mars orbit instruments with abundances ranging to tens of parts-per-billion by volume (ppbv). Recently, the Curiosity rover detected methane with background levels of 0.7 ppbv and episodic releases of 7 ppbv. Although the methane sources are still unknown, this gas may have been stored in reservoirs of clathrate hydrate in the Martian subsurface where thermodynamics conditions are favourable to their presence. Clathrate hydrates are crystalline compounds constituted by cages formed by hydrogen-bonded water molecules inside of which guest gas molecules are trapped. In this study, methane clathrate stability in the Martian subsurface are investigated and their temporal and spatial variations are studied. Present-day maps of methane clathrate stability zone are produced by coupling the stability conditions of methane clathrate with a subsurface model using the available observations such as the the thermal inertia derived from TES MGS data. Then, a gas transport model has been used to study the methane flux at the surface due to the diffusion of different plausible methane volumes released by clathrate hydrates at variable depths under the Martian surface.

Diffusive Transfer of Oxygen From Seamount Basaltic Crust Into Overlying Sediments: an Example From the Clarion-Clipperton Fracture Zone, Equatorial Pacific Ocean

NASA Astrophysics Data System (ADS)

Kasten, S.; Mewes, K.; Mogollón, J.; Picard, A.; Rühlemann, C.; Eisenhauer, A.; Kuhn, T.; Ziebis, W.

2015-12-01

Within the Clarion-Clipperton Fracture Zone (CCFZ) located in the equatorial Pacific Ocean numerous seamounts, with diameters ranging from 3 to 30 km and varying heights above the surrounding seafloor of up to 2500 m, occur throughout the deep-sea plain. There is evidence that these may serve as conduits for low-temperature hydrothermal circulation of seawater through the oceanic crust. During RV SONNE cruise SO205 in April/May 2010 and BIONOD cruise with RV ĹATALANTE in spring 2012 we took piston and gravity cores for geochemical analyses, as well as for high-resolution pore-water oxygen and nutrient measurements. Specifically, we took cores along a transect at three sites, located 400, 700 and 1000 m away from the foot of a 240 m high seamount, called 'Teddy Bare'. At all 3 sites oxygen penetrates the entire sediment column of the organic carbon-poor sediment. More importantly, oxygen concentrations initially decrease with sediment depth but increase again at depths of 3 m and 7 m above the basaltic basement, suggesting an upward diffusion of oxygen from seawater circulating within the seamount crust into the overlying basal sediments. This is the first time this has been shown for the deep subsurface in the Pacific Ocean. Mirroring the oxygen concentrations nitrate concentrations accumulate with sediment depth but decrease towards the basement. Transport-reaction modeling revealed that (1) the diffusive flux of oxygen from the basaltic basement exceeds the oxygen consumption through organic matter oxidation and nitrification in the basal sediments and (2) the nutrient exchange between the sediment and the underlying basaltic crust occurs at orders-of-magnitude lower rates than between the sediment surface and the overlying bottom water. We furthermore show that the upward diffusion of oxygen from the basaltic basement affects the preservation of organic compounds within the oxic sediment column at all 3 sites. Our investigations indicate that an upward diffusion of oxygen from the basalt into the overlying sediment may be a widespread phenomenon in this area of the Pacific Ocean that is characterized by numerous seamounts.

Working Smarter Not Harder - Developing a Virtual Subsurface Data Framework for U.S. Energy R&D

NASA Astrophysics Data System (ADS)

Rose, K.; Baker, D.; Bauer, J.; Dehlin, M.; Jones, T. J.; Rowan, C.

2017-12-01

The data revolution has resulted in a proliferation of resources that span beyond commercial and social networking domains. Research, scientific, and engineering data resources, including subsurface characterization, modeling, and analytical datasets, are increasingly available through online portals, warehouses, and systems. Data for subsurface systems is still challenging to access, discontinuous, and varies in resolution. However, with the proliferation of online data there are significant opportunities to advance access and knowledge of subsurface systems. The Energy Data eXchange (EDX) is an online platform designed to address research data needs by improving access to energy R&D products through advanced search capabilities. In addition, EDX hosts private, virtualized computational workspaces in support of multi-organizational R&D. These collaborative workspaces allow teams to share working data resources and connect to a growing number of analytical tools to support research efforts. One recent application, a team digital data notebook tool, called DataBook, was introduced within EDX workspaces to allow teams to capture contextual and structured data resources. Starting with DOE's subsurface R&D community, the EDX team has been developing DataBook to support scientists and engineers working on subsurface energy research, allowing them to contribute and curate both structured and unstructured data and knowledge about subsurface systems. These resources span petrophysical, geologic, engineering, geophysical, interpretations, models, and analyses associated with carbon storage, water, oil, gas, geothermal, induced seismicity and other subsurface systems to support the development of a virtual subsurface data framework. The integration of EDX and DataBook allows for these systems to leverage each other's best features, such as the ability to interact with other systems (Earthcube, OpenEI.net, NGDS, etc.) and leverage custom machine learning algorithms and capabilities to enhance user experience, make access and connection to relevant subsurface data resources more efficient for research teams to use, analyze and draw insights. Ultimately, the public and private resources in EDX seek to make subsurface energy research more efficient, reduce redundancy, and drive innovation.

Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

NASA Astrophysics Data System (ADS)

Annewandter, R.

2013-12-01

The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced soil gas sampling during On-Site inspections. Gas transport has been widely studied with different numerical codes. However, gas transport of all radioxenons in the post-detonation regime and their possible fractionation is still neglected in the open literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radioxenons, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different diffusivities due to mass differences between the radioxenons. A previous study showed surface arrival time of a chemically inert gaseous tracer is affected by its diffusivity. They observed detectable amount for SF6 50 days after detonation and 375 days for He-3. They predict 50 and 80 days for Xe-133 and Ar-37 respectively. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations , fracture propagation in fractured, porous media, Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic differential equations by a complementary finite volume method. The parabolic and hyperbolic problem can be solved separately using the operator-splitting method (Implicit Pressure Explicit Saturation, IMPES). The resulting system of linear equations is solved by the algebraic multigrid library SAMG, developed at the Fraunhofer Institute for Algorithms and Scientific Computing. CSMP++ is developed at Montan University of Leoben, ETH Zuerich, Imperial College London and Heriot-Watt University in Edinburgh. To date, there has been no research investigating how subsurface transport impacts isotope activity ratios. The isotopic activity ratio method can be used to discriminate between civil release or nuclear explosion sources. This study examines possible fractionation of Xe-135, Xe-133m, Xe-133, Xe-131m during barometric pumping-driven subsurface migration, which can affect surface arrival times and isotopic activity ratios. Surface arrival times for the Noble gases Kr-81, Kr-85 and Ar-39 are also calculated.

Utilization of subsurface microbial electrochemical systems to elucidate the mechanisms of competition between methanogenesis and microbial iron(III)/humic acid reduction in Arctic peat soils

NASA Astrophysics Data System (ADS)

Friedman, E. S.; Miller, K.; Lipson, D.; Angenent, L. T.

2012-12-01

High-latitude peat soils are a major carbon reservoir, and there is growing concern that previously dormant carbon from this reservoir could be released to the atmosphere as a result of continued climate change. Microbial processes, such as methanogenesis and carbon dioxide production via iron(III) or humic acid reduction, are at the heart of the carbon cycle in Arctic peat soils [1]. A deeper understanding of the factors governing microbial dominance in these soils is crucial for predicting the effects of continued climate change. In previous years, we have demonstrated the viability of a potentiostatically-controlled subsurface microbial electrochemical system-based biosensor that measures microbial respiration via exocellular electron transfer [2]. This system utilizes a graphite working electrode poised at 0.1 V NHE to mimic ferric iron and humic acid compounds. Microbes that would normally utilize these compounds as electron acceptors donate electrons to the electrode instead. The resulting current is a measure of microbial respiration with the electrode and is recorded with respect to time. Here, we examine the mechanistic relationship between methanogenesis and iron(III)- or humic acid-reduction by using these same microbial-three electrode systems to provide an inexhaustible source of alternate electron acceptor to microbes in these soils. Chamber-based carbon dioxide and methane fluxes were measured from soil collars with and without microbial three-electrode systems over a period of four weeks. In addition, in some collars we simulated increased fermentation by applying acetate treatments to understand possible effects of continued climate change on microbial processes in these carbon-rich soils. The results from this work aim to increase our fundamental understanding of competition between electron acceptors, and will provide valuable data for climate modeling scenarios. 1. Lipson, D.A., et al., Reduction of iron (III) and humic substances plays a major role in anaerobic respiration in an Arctic peat soil. Journal of Geophysical Research-Biogeosciences, 2010. 115. 2. Friedman, E.S., et al., A cost-effective and field-ready potentiostat that poises subsurface electrodes to monitor bacterial respiration. Biosensors and Bioelectronics, 2012. 32(1): p. 309-313.

Deep subsurface microbial processes

USGS Publications Warehouse

Lovley, D.R.; Chapelle, F.H.

1995-01-01

Information on the microbiology of the deep subsurface is necessary in order to understand the factors controlling the rate and extent of the microbially catalyzed redox reactions that influence the geophysical properties of these environments. Furthermore, there is an increasing threat that deep aquifers, an important drinking water resource, may be contaminated by man's activities, and there is a need to predict the extent to which microbial activity may remediate such contamination. Metabolically active microorganisms can be recovered from a diversity of deep subsurface environments. The available evidence suggests that these microorganisms are responsible for catalyzing the oxidation of organic matter coupled to a variety of electron acceptors just as microorganisms do in surface sediments, but at much slower rates. The technical difficulties in aseptically sampling deep subsurface sediments and the fact that microbial processes in laboratory incubations of deep subsurface material often do not mimic in situ processes frequently necessitate that microbial activity in the deep subsurface be inferred through nonmicrobiological analyses of ground water. These approaches include measurements of dissolved H2, which can predict the predominant microbially catalyzed redox reactions in aquifers, as well as geochemical and groundwater flow modeling, which can be used to estimate the rates of microbial processes. Microorganisms recovered from the deep subsurface have the potential to affect the fate of toxic organics and inorganic contaminants in groundwater. Microbial activity also greatly influences 1 the chemistry of many pristine groundwaters and contributes to such phenomena as porosity development in carbonate aquifers, accumulation of undesirably high concentrations of dissolved iron, and production of methane and hydrogen sulfide. Although the last decade has seen a dramatic increase in interest in deep subsurface microbiology, in comparison with the study of other habitats, the study of deep subsurface microbiology is still in its infancy.

Biogeochemistry and geomicrobiology of cold-water coral carbonate mounds - lessons learned from IODP Expedition 307

NASA Astrophysics Data System (ADS)

Ferdelman, Timothy; Wehrmann, Laura; Mangelsdorf, Kai; Kano, Akihiro; Williams, Trevor; Jean-Pierre, Henriet

2010-05-01

Large mound structures associated with cold-water coral ecosystems commonly occur on the slopes of continental margins, for instance, west of Ireland in the Porcupine Seabight, the Gulf of Cadiz or the Straits of Florida. In the Porcupine Seabight over 1500 mounds of up to 5 km in diameter and 250 m height lie at water depths of 600 to 900 m. The cold-water coral reef ecosystems associated with these structures are considered to be "hotspots" of organic carbon mineralization and microbial systems. To establish a depositional and biogeochemical/diagenetic model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled in May 2005 during IODP Expedition 307. One major objective was to test whether deep sub-surface hydrocarbon flow and enhanced microbial activity within the mound structure was important in producing and stabilizing these sedimentary structures. Drilling results showed that the Challenger mound succession (IODP Site U1317) is 130 to 150 meters thick, and mainly consists of floatstone and rudstone facies formed of fine sediments and cold-water branching corals. Pronounced recurring cycles on the scales of several meters are recognized in carbonate content (up to 70% carbonate) and color reflectance, and are probably associated with Pleistocene glacial-interglacial cycles. A role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession. A broad sulfate-methane transition (approximately 50 m thick)within the Miocene sediments suggested that the zone of anaerobic oxidation of methane principally occurs below the moundbase. In the mound sediments, interstitial water profiles of sulfate, alkalinity, Mg, and Sr suggested a tight coupling between carbonate diagenesis and low rates of microbial sulfate reduction. Overall organic carbon mineralization within cold-water coral mound appeared to be dominated by low rates of iron- and sulfate-reduction that occur in discrete layers within the mound. This was consistent with distributions of total cell-counts, acetate turnover (Webster et al. 2009) and hydrogenase activity (Soffiento et al. 2009). However, biomarker lipid distributions suggested that the Miocene sediments underlying the mound, into which sulfate is diffusing, as well as the sediments from the non-cold water coral reference site (U1318) contain higher abundances of living microbes. The results obtained from Expedition 307 are consistent with a picture emerging from other biogeochemical studies of cold-water coral mound and reef sites. Unless impacted by some external forcing (e.g. fluid flow or erosion event), the microbial activity in the underlying cold-water coral mound sediments is largely decoupled from the highly diverse, active surface ecosystem. References: Soffiento B, Spivack AJ, Smith DC, and D'Hondt S (2009) Hydrogenase activity in deeply buried sediments of the Arctic and North Atlantic Oceans. Geomicro. J. 26: 537-545. Webster, G, Blazejak A, Cragg BA, Schippers A, Sass H, Rinna J, Tang X, Mathes F, Ferdelman TG., Fry JC, Weightman AJ, and Parkes RJ. 2009. Subsurface microbiology and biogeochemistry of a deep, cold-water carbonate mound from the Porcupine Seabight (IODP Expediton 307). Env. Microbiol., 11, 239-257, doi:10.1111/j.1462-2920.01759.x.

Spatial variability of upper ocean POC export in the Bay of Bengal and the Indian Ocean determined using particle-reactive 234Th

NASA Astrophysics Data System (ADS)

Subha Anand, S.; Rengarajan, R.; Sarma, V. V. S. S.; Sudheer, A. K.; Bhushan, R.; Singh, S. K.

2017-05-01

The northern Indian Ocean is globally significant for its seasonally reversing winds, upwelled nutrients, high biological production, and expanding oxygen minimum zones. The region acts as sink and source for atmospheric CO2. However, the efficiency of the biological carbon pump to sequester atmospheric CO2 and export particulate organic carbon from the surface is not well known. To quantify the upper ocean carbon export flux and to estimate the efficiency of biological carbon pump in the Bay of Bengal and the Indian Ocean, seawater profiles of total 234Th were measured from surface to 300 m depth at 13 stations from 19.9°N to 25.3°S in a transect along 87°E, during spring intermonsoon period (March-April 2014). Results showed enhanced in situ primary production in the equatorial Indian Ocean and the central Bay of Bengal and varied from 13.2 to 173.8 mmol C m-2 d-1. POC export flux in this region varied from 0 to 7.7 mmol C m-2 d-1. Though high carbon export flux was found in the equatorial region, remineralization of organic carbon in the surface and subsurface waters considerably reduced organic carbon export in the Bay of Bengal. Annually recurring anticyclonic eddies enhanced organic carbon utilization and heterotrophy. Oxygen minimum zone developed due to stratification and poor ventilation was intensified by subsurface remineralization. 234Th-based carbon export fluxes were not comparable with empirical statistical model estimates based on primary production and temperature. Region-specific refinement of model parameters is required to accurately predict POC export fluxes.

Detection of microbes in the subsurface

NASA Technical Reports Server (NTRS)

White, David C.; Tunlid, Anders

1989-01-01

The search for evidence of microbial life in the deep subsurface of Earth has implications for the Mars Rover Sampling Return Missions program. If suitably protected environments can be found on Mars then the instrumentation to detect biomarkers could be used to examine the molecular details. Finding a lipid in Martian soil would represent possibly the simplest test for extant or extinct life. A device that could do a rapid extraction possibly using the supercritical fluid technology under development now with a detection of the carbon content would clearly indicate a sample to be returned.

Formation of recent Pb-Ag-Au mineralization by potential sub-surface microbial activity

NASA Astrophysics Data System (ADS)

Tornos, Fernando; Velasco, Francisco; Menor-Salván, César; Delgado, Antonio; Slack, John F.; Escobar, Juan Manuel

2014-08-01

Las Cruces is a base-metal deposit in the Iberian Pyrite Belt, one of the world’s best-known ore provinces. Here we report the occurrence of major Pb-Ag-Au mineralization resulting from recent sub-surface replacement of supergene oxyhydroxides by carbonate and sulphide minerals. This is probably the largest documented occurrence of recent microbial activity producing an ore assemblage previously unknown in supergene mineralizing environments. The presence of microbial features in the sulphides suggests that these may be the first-described natural bacteriomorphs of galena. The low δ13C values of the carbonate minerals indicate formation by deep anaerobic microbial processes. Sulphur isotope values of sulphides are interpreted here as reflecting microbial reduction in a system impoverished in sulphate. We suggest that biogenic activity has produced around 3.1 × 109 moles of reduced sulphur and 1010 moles of CO2, promoting the formation of ca. 1.19 Mt of carbonates, 114,000 t of galena, 638 t of silver sulphides and 6.5 t of gold.

A large column analog experiment of stable isotope variations during reactive transport: II. Carbon mass balance, microbial community structure and predation

NASA Astrophysics Data System (ADS)

Druhan, Jennifer L.; Bill, Markus; Lim, HsiaoChien; Wu, Cindy; Conrad, Mark E.; Williams, Kenneth H.; DePaolo, Donald J.; Brodie, Eoin L.

2014-01-01

Here we report a combined analysis of carbon mass balance based on isotopic labeling and microbiological characterization during organic carbon stimulated bioreduction of a subsurface sediment in a large laboratory column experimental system. This combination of approaches allows quantification of both the cycling of carbon through multiple redox pathways and the associated spatial and temporal evolution of bacterial communities in response to this nutrient source. Carbon isotope mass balance facilitated by the use of 13C-labeled acetate as the electron donor showed evidence for a net loss of sediment organic carbon over the course of the amendment experiment. Furthermore, these data clearly demonstrated a source of isotopically labeled inorganic carbon that was not attributable to primary metabolism by acetate-oxidizing microorganisms. Fluid samples collected weekly over the duration of the 43-day amendment at <20 cm intervals along the flow path were analyzed for microbial composition by pyrosequencing of ribosomal RNA genes. The microbial community composition was transient, with distinct occurrences of Azoarcus, Geobacter and multiple sulfate reducing species over the course of the experiment. In combination with DNA sequencing data, the anomalous carbon cycling process is shown to occur exclusively during the period of predominant Geobacter species growth. Pyrosequencing indicated, and targeted cloning and sequencing confirmed the presence of several bacteriovorous protozoa, including species of the Breviata, Planococcus and Euplotes genera. Cloning and qPCR analysis demonstrated that Euplotes species were most abundant and displayed a growth trajectory that closely followed that of the Geobacter population. These results suggest a previously undocumented secondary turnover of biomass carbon related to protozoan grazing that was not sufficiently prevalent to be observed in bulk concentrations of carbon species in the system, but was clearly identified in the partitioning of carbon isotopes. This study demonstrates evidence for predator-prey relationships that impact subsurface microbial community dynamics and provides a novel indication of the impact of this relationship on the flux of carbon through a system via the microbial biomass pool. Overall, our approach provides high temporal and spatial sampling resolution at field relevant flow rates, while minimizing effects of mixing and transverse dispersion. The result is a quantitative carbon budget accounting for a diversity of processes that should be considered for inclusion in reactive transport models that aim to predict carbon turnover, nutrient flux, and redox reactions in natural and stimulated subsurface systems. the mobilization of previously stabilized, sediment-bound carbon; a carbon mass balance for a through-flowing sediment column over the course of a 43-day amendment using 13C-labeled acetate; a phylogenetic microbial community structure at <20 cm sampling resolution with distance away from the organic carbon source weekly over the 43-day amendment; protozoan grazing on the active Geobacteraceae population and the rapid turnover of microbial biomass carbon as a secondary cycling pathway. Such a high resolution, combined analysis of microbial populations and the associated carbon mass balance in a through-flowing system at field relevant flow rates provides novel, quantitative insights into the interface between biogeochemical cycling and bulk carbon fluxes in the near-surface environment.

Helium diffusion in carbonates

NASA Astrophysics Data System (ADS)

Amidon, W. H.; Cherniak, D. J.; Watson, E. B.; Hobbs, D.

2013-12-01

The abundance and large grain size of carbonate minerals make them a potentially attractive target for 4He thermochronology and 3He cosmogenic dating, although the diffusive properties of helium in carbonates remain poorly understood. This work characterizes helium diffusion in calcite and dolomite to better understand the crystal-chemical factors controlling He transport and retentivity. Slabs of cleaved natural calcite and dolomite, and polished sections of calcite cut parallel or normal to c, were implanted with 3He at 3 MeV with a dose of 5x1015/cm2. Implanted carbonates were heated in 1-atm furnaces, and 3He distributions following diffusion anneals were profiled with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For 3He transport normal to cleavage surfaces in calcite, we obtain the following Arrhenius relation over the temperature range 78-300°C: Dcalcite = 9.0x10-9exp(-55 × 6 kJ mol-1/RT) m2sec-1. Diffusion in calcite exhibits marked anisotropy, with diffusion parallel to c about two orders of magnitude slower than diffusion normal to cleavage faces. He diffusivities for transport normal to the c-axis are similar in value to those normal to cleavage surfaces. Our findings are broadly consistent with helium diffusivities from step-heating measurements of calcite by Copeland et al. (2007); these bulk degassing data may reflect varying effects of diffusional anisotropy. Helium diffusion normal to cleavage surfaces in dolomite is significantly slower than diffusion in calcite, and has a much higher activation energy for diffusion. For dolomite, we obtain the following Arrhenius relation for He diffusion over the temperature range 150-400°C: Ddolomite = 9.0x10-8exp(-92 × 9 kJ mol-1/RT) m2sec-1. The role of crystallographic structure in influencing these differences among diffusivities was evaluated using the maximum aperture approach of Cherniak and Watson (2011), in which crystallographic structures are sectioned along possible diffusion directions and the maximum interstitial apertures in each 'slice' in the structure are identified. Preliminary results show that observed differences in diffusivities are consistent with the size of the smallest maximum aperture along each diffusion direction. In calcite, the smallest maximum apertures are ~0.92 and ~0.66 angstroms for cleavage-normal and c-axis parallel directions respectively. In dolomite, the smallest maximum aperture is ~0.78 angstroms for the cleavage normal direction. Work is in progress on characterizing helium diffusion for other orientations in dolomite, and in other carbonates, including aragonite and magnesite, and in implementing these diffusion findings in the interpretation and modeling of bulk volume diffusion in heterogeneous calcite crystals common in many geologic applications. Copeland et al. (2007) GCA 71, 4488-4511 Cherniak and Watson, (2011) Chem. Geo. 288, 149-161

Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

PubMed

Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

2016-06-22

Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C).

Insight into the role of the promoters Pt, Ru and B in inhibiting the deactivation of Co catalysts in Fischer-Tropsch synthesis

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Liu, Hongxia; Li, Qiaohong; Wang, Baojun; Ling, Lixia; Li, Debao

2018-09-01

In order to probe into the roles of the promoters Pt, Ru and B in inhibiting the deactivation of Co catalysts in FTS reactions, the adsorption ability of neighboring surface C and subsurface C atom around the promoters (Pt, Ru and B), and the mechanisms of surface C diffusion, accumulation, hydrogenation and penetration are examined by density functional theory calculations over the promoters Pt, Ru and B-modified Co catalysts, as well as the pure Co catalysts. Our results clearly show that compared to Co catalysts, both PtCo and RuCo bimetallic catalysts promote surface C hydrogenation, and inhibit surface C diffusion, accumulation and penetration, and therefore the ability of resistance toward deactivation and the stability of Co-based catalysts are enhanced; the promoter B cannot effectively improve the ability of resistance toward deactivation. Thus, the sequence for resistance toward deactivation of Co-based catalyst is BCo < Co < PtCo < RuCo. Moreover, the activation free energy of surface C accumulation to C2 species increases with the increasing of surface C adsorption free energy, namely, the adsorption characteristic of surface C species well represent the surface carbon deposition. Our results not only give an explanation for reported experiment that the Pt, Ru and B-modified Co catalysts exhibit ability of resistance toward deactivation in FTS at a molecular level, but also provide a clue for the design of efficient Co-based catalysts in FTS reactions.

Subsurface Growth of CoSi2 by Deposition of Co on Si-Capped CoSi2 Seed Regions

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; George, T.; Pike, W. T.

1991-01-01

At a growth temperature of 800 C, Co deposited on Si(111) diffuses through a Si cap and exhibits oriented growth on buried CoSi2 grains, a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2 provided the thickness of the Si cap is less than a critical value between 100 and 200 nm for a deposition rate of 0.01 nm/s. Steady-state endotaxy is modeled under the assumption that the process is controlled by Co diffusion.

M4SF-17LL010302072: The Roles of Diffusion and Corrosion in Radionuclide Retardation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zavarin, Mavrik; Balboni, E.; Atkins-Duffin, Cindy

This progress report (Level 4 Milestone Number M4SF-17LL010302072) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Disposal R&D Activity Number M4SF-17LL01030207 and Crystalline International Collaborations Activity Number M4SF-17LL01030208. The focus of this research is the interaction of radionuclides with Engineered Barrier System (EBS) and host rock materials at various physicochemical conditions relevant to subsurface repository environments. They include both chemical and physical processes such as solubility, sorption, and diffusion.

Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peters, Catherine A

2013-02-28

Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevantmore » in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of mineral accessible surface area, and should not be used in reactive transport modeling. Our work showed that reaction rates would be overestimated by three to five times.« less

Fluorescence tomography characterization for sub-surface imaging with protoporphyrin IX

PubMed Central

Kepshire, Dax; Davis, Scott C.; Dehghani, Hamid; Paulsen, Keith D.; Pogue, Brian W.

2009-01-01

Optical imaging of fluorescent objects embedded in a tissue simulating medium was characterized using non-contact based approaches to fluorescence remittance imaging (FRI) and sub-surface fluorescence diffuse optical tomography (FDOT). Using Protoporphyrin IX as a fluorescent agent, experiments were performed on tissue phantoms comprised of typical in-vivo tumor to normal tissue contrast ratios, ranging from 3.5:1 up to 10:1. It was found that tomographic imaging was able to recover interior inclusions with high contrast relative to the background; however, simple planar fluorescence imaging provided a superior contrast to noise ratio. Overall, FRI performed optimally when the object was located on or close to the surface and, perhaps most importantly, FDOT was able to recover specific depth information about the location of embedded regions. The results indicate that an optimal system for localizing embedded fluorescent regions should combine fluorescence reflectance imaging for high sensitivity and sub-surface tomography for depth detection, thereby allowing more accurate localization in all three directions within the tissue. PMID:18545571

A metagenomic window into carbon metabolism at 3 km depth in Precambrian continental crust

PubMed Central

Magnabosco, Cara; Ryan, Kathleen; Lau, Maggie C Y; Kuloyo, Olukayode; Sherwood Lollar, Barbara; Kieft, Thomas L; van Heerden, Esta; Onstott, Tullis C

2016-01-01

Subsurface microbial communities comprise a significant fraction of the global prokaryotic biomass; however, the carbon metabolisms that support the deep biosphere have been relatively unexplored. In order to determine the predominant carbon metabolisms within a 3-km deep fracture fluid system accessed via the Tau Tona gold mine (Witwatersrand Basin, South Africa), metagenomic and thermodynamic analyses were combined. Within our system of study, the energy-conserving reductive acetyl-CoA (Wood-Ljungdahl) pathway was found to be the most abundant carbon fixation pathway identified in the metagenome. Carbon monoxide dehydrogenase genes that have the potential to participate in (1) both autotrophic and heterotrophic metabolisms through the reversible oxidization of CO and subsequent transfer of electrons for sulfate reduction, (2) direct utilization of H2 and (3) methanogenesis were identified. The most abundant members of the metagenome belonged to Euryarchaeota (22%) and Firmicutes (57%)—by far, the highest relative abundance of Euryarchaeota yet reported from deep fracture fluids in South Africa and one of only five Firmicutes-dominated deep fracture fluids identified in the region. Importantly, by combining the metagenomics data and thermodynamic modeling of this study with previously published isotopic and community composition data from the South African subsurface, we are able to demonstrate that Firmicutes-dominated communities are associated with a particular hydrogeologic environment, specifically the older, more saline and more reducing waters. PMID:26325359

Electric-field noise from carbon-adatom diffusion on a Au(110) surface: First-principles calculations and experiments

DOE PAGES

Kim, E.; Safavi-Naini, A.; Hite, D. A.; ...

2017-03-01

The decoherence of trapped-ion quantum bits due to heating of their motional modes is a fundamental science and engineering problem. This heating is attributed to electric-field noise arising from processes on the trap-electrode surfaces. In this work, we address the source of this noise by focusing on the diffusion of carbon-containing adsorbates on the surface of Au(110). We show by detailed scanned probe microscopy and density functional theory how the carbon adatom diffusion on the gold surface changes the energy landscape, and how the adatom dipole moment varies with the diffusive motion. Lastly, a simple model for the diffusion noise,more » which varies quadratically with the variation of the dipole moment, qualitatively reproduces the measured noise spectrum, and the estimate of the noise spectral density is in accord with measured values.« less

Electric-field noise from carbon-adatom diffusion on a Au(110) surface: First-principles calculations and experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, E.; Safavi-Naini, A.; Hite, D. A.

The decoherence of trapped-ion quantum bits due to heating of their motional modes is a fundamental science and engineering problem. This heating is attributed to electric-field noise arising from processes on the trap-electrode surfaces. In this work, we address the source of this noise by focusing on the diffusion of carbon-containing adsorbates on the surface of Au(110). We show by detailed scanned probe microscopy and density functional theory how the carbon adatom diffusion on the gold surface changes the energy landscape, and how the adatom dipole moment varies with the diffusive motion. Lastly, a simple model for the diffusion noise,more » which varies quadratically with the variation of the dipole moment, qualitatively reproduces the measured noise spectrum, and the estimate of the noise spectral density is in accord with measured values.« less

Adapting HYDRUS-1D to simulate overland flow and reactive transport during sheet flow deviations

USDA-ARS?s Scientific Manuscript database

The HYDRUS-1D code is a popular numerical model for solving the Richards equation for variably-saturated water flow and solute transport in porous media. This code was adapted to solve rather than the Richards equation for subsurface flow the diffusion wave equation for overland flow at the soil sur...

Effect of deep injection on field-scale emissions of 1,3-dichloropropene and chloropicrin from bare soil

USDA-ARS?s Scientific Manuscript database

Fumigating soil is important for the production of many high-value vegetable, fruit, and tree crops, but fumigants are toxic and highly volatile which can lead to significant atmospheric emissions. A field experiment was conducted to measure emissions and subsurface diffusion of a mixture of 1,3-di...

A multi-scale experimental and simulation approach for fractured subsurface systems

NASA Astrophysics Data System (ADS)

Viswanathan, H. S.; Carey, J. W.; Frash, L.; Karra, S.; Hyman, J.; Kang, Q.; Rougier, E.; Srinivasan, G.

2017-12-01

Fractured systems play an important role in numerous subsurface applications including hydraulic fracturing, carbon sequestration, geothermal energy and underground nuclear test detection. Fractures that range in scale from microns to meters and their structure control the behavior of these systems which provide over 85% of our energy and 50% of US drinking water. Determining the key mechanisms in subsurface fractured systems has been impeded due to the lack of sophisticated experimental methods to measure fracture aperture and connectivity, multiphase permeability, and chemical exchange capacities at the high temperature, pressure, and stresses present in the subsurface. In this study, we developed and use microfluidic and triaxial core flood experiments required to reveal the fundamental dynamics of fracture-fluid interactions. In addition we have developed high fidelity fracture propagation and discrete fracture network flow models to simulate these fractured systems. We also have developed reduced order models of these fracture simulators in order to conduct uncertainty quantification for these systems. We demonstrate an integrated experimental/modeling approach that allows for a comprehensive characterization of fractured systems and develop models that can be used to optimize the reservoir operating conditions over a range of subsurface conditions.

Thermal Expansion and Diffusion Coefficients of Carbon Nanotube-Polymer Composites

NASA Technical Reports Server (NTRS)

Wei, Chengyu; Srivastava, Deepak; Cho, Kyeongjae; Biegel, Bryan (Technical Monitor)

2001-01-01

Classical molecular dynamics (MD) simulations employing Brenner potential for intra-nanotube interactions and van der Waals forces for polymer-nanotube interface have been used to investigate thermal expansion and diffusion characteristics of carbon nanotube-polyethylene composites. Addition of carbon nanotubes to polymer matrix is found to significantly increase the glass transition temperature Tg, and thermal expansion and diffusion coefficients in the composite above Tg. The increase has been attributed to the temperature dependent increase of the excluded volume for the polymer chains, and the findings could have implications in the composite processing, coating and painting applications.

Methods for characterizing subsurface volatile contaminants using in-situ sensors

DOEpatents

Ho, Clifford K [Albuquerque, NM

2006-02-21

An inverse analysis method for characterizing diffusion of vapor from an underground source of volatile contaminant using data taken by an in-situ sensor. The method uses one-dimensional solutions to the diffusion equation in Cartesian, cylindrical, or spherical coordinates for isotropic and homogenous media. If the effective vapor diffusion coefficient is known, then the distance from the source to the in-situ sensor can be estimated by comparing the shape of the predicted time-dependent vapor concentration response curve to the measured response curve. Alternatively, if the source distance is known, then the effective vapor diffusion coefficient can be estimated using the same inverse analysis method. A triangulation technique can be used with multiple sensors to locate the source in two or three dimensions. The in-situ sensor can contain one or more chemiresistor elements housed in a waterproof enclosure with a gas permeable membrane.

Nitrogen removal in wood chip combined substrate baffled subsurface-flow constructed wetlands: impact of matrix arrangement and intermittent aeration.

PubMed

Li, Huai; Chi, Zifang; Yan, Baixing; Cheng, Long; Li, Jianzheng

2017-02-01

In this study, two lab-scale baffled subsurface-flow constructed wetlands (BSFCWs), including gravel-wood chips-slag and gravel-slag-wood chips, were operated at different intermittent aeration to evaluate the effect of artificial aeration and slow-released carbon source on the treatment efficiency of high-strength nitrogen wastewater. Results indicated that gravel-slag-wood chips extended aerobic/anaerobic alternating environment to gravel and slag zones and maintained anaerobic condition in the subsequent wood chip section. The order of gravel-slag-wood chip was more beneficial to pollutant removal. Sufficient carbon source supply resulted from wood-chip-framework substrate simultaneously obtained high removals of COD (97%), NH 4 + -N (95%), and TN (94%) in BSFCWs at 2 h aeration per day. The results suggest that intermittent aeration combined with wood chips could achieve high nitrogen removal in BSFCWs.

Kinetic Effect on the Freezing of Ammonium-Sodium-Carbonate-Chloride Brines and Implications for Origin of Ceres' Bright Spots

NASA Astrophysics Data System (ADS)

Hodyss, R. P.; Thomas, E. C.; Vu, T. H.; Johnson, P. V.; Choukroun, M.

2017-12-01

Subsurface brines on Ceres containing natrite (Na2CO3) and smaller amounts of NH4Cl or NH4HCO3 have been proposed to reach the dwarf planet's surface from an internal reservoir, where the brines freeze and result in bright spots across Ceres. Kinetically frozen solutions containing the likely constituents of Ceres' subsurface brines (ammonium, sodium, carbonate, and chloride ions) were studied via infrared and micro-Raman spectroscopy, where the flash-frozen mixtures were found to preferentially form ammonium chloride and ammonium bicarbonate, even in sodium-dominated solutions. Additionally, sodium chloride only formed when sodium or chloride (or both) were present in excess in the brine solutions. Raman spectroscopy was further employed to analyze the effect of vacuum exposure on these frozen brines over longer periods of time to simulate the surface conditions of Ceres.

Influences and interactions of inundation, peat, and snow on active layer thickness

DOE PAGES

Atchley, Adam L.; Coon, Ethan T.; Painter, Scott L.; ...

2016-05-18

Active layer thickness (ALT), the uppermost layer of soil that thaws on an annual basis, is a direct control on the amount of organic carbon potentially available for decomposition and release to the atmosphere as carbon-rich Arctic permafrost soils thaw in a warming climate. Here, we investigate how key site characteristics affect ALT using an integrated surface/subsurface permafrost thermal hydrology model. ALT is most sensitive to organic layer thickness followed by snow depth but is relatively insensitive to the amount of water on the landscape with other conditions held fixed. Furthermore, the weak ALT sensitivity to subsurface saturation suggests thatmore » changes in Arctic landscape hydrology may only have a minor effect on future ALT. But, surface inundation amplifies the sensitivities to the other parameters and under large snowpacks can trigger the formation of near-surface taliks.« less

Evidence for methane in Martian meteorites

PubMed Central

Blamey, Nigel J. F.; Parnell, John; McMahon, Sean; Mark, Darren F.; Tomkinson, Tim; Lee, Martin; Shivak, Jared; Izawa, Matthew R. M.; Banerjee, Neil R.; Flemming, Roberta L.

2015-01-01

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity. PMID:26079798

Evidence for methane in Martian meteorites.

PubMed

Blamey, Nigel J F; Parnell, John; McMahon, Sean; Mark, Darren F; Tomkinson, Tim; Lee, Martin; Shivak, Jared; Izawa, Matthew R M; Banerjee, Neil R; Flemming, Roberta L

2015-06-16

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity.

Metagenomic identification of active methanogens and methanotrophs in serpentinite springs of the Voltri Massif, Italy.

PubMed

Brazelton, William J; Thornton, Christopher N; Hyer, Alex; Twing, Katrina I; Longino, August A; Lang, Susan Q; Lilley, Marvin D; Früh-Green, Gretchen L; Schrenk, Matthew O

2017-01-01

The production of hydrogen and methane by geochemical reactions associated with the serpentinization of ultramafic rocks can potentially support subsurface microbial ecosystems independent of the photosynthetic biosphere. Methanogenic and methanotrophic microorganisms are abundant in marine hydrothermal systems heavily influenced by serpentinization, but evidence for methane-cycling archaea and bacteria in continental serpentinite springs has been limited. This report provides metagenomic and experimental evidence for active methanogenesis and methanotrophy by microbial communities in serpentinite springs of the Voltri Massif, Italy. Methanogens belonging to family Methanobacteriaceae and methanotrophic bacteria belonging to family Methylococcaceae were heavily enriched in three ultrabasic springs (pH 12). Metagenomic data also suggest the potential for hydrogen oxidation, hydrogen production, carbon fixation, fermentation, and organic acid metabolism in the ultrabasic springs. The predicted metabolic capabilities are consistent with an active subsurface ecosystem supported by energy and carbon liberated by geochemical reactions within the serpentinite rocks of the Voltri Massif.

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

DOE PAGES

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; ...

2014-12-19

We report that lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF more » $$\\bar{6}$$ anion. Li + prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li + solvation. Corresponding analysis for the PF $$\\bar{6}$$ anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. In conclusion, these results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.« less

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pezeshki, Alan M.; Sacci, Robert L.; Delnick, Frank M.

Here, an improved method for quantitative measurement of the charge transfer, finite diffusion, and ohmic overpotentials in redox flow batteries using electrochemical impedance spectroscopy is presented. The use of a pulse dampener in the hydraulic circuit enables the collection of impedance spectra at low frequencies with a peristaltic pump, allowing the measurement of finite diffusion resistances at operationally relevant flow rates. This method is used to resolve the rate-limiting processes for the V 2+/V 3+ redox couple on carbon felt and carbon paper electrodes in the vanadium redox flow battery. Carbon felt was limited by both charge transfer and ohmicmore » resistance, while carbon paper was limited by charge transfer, finite diffusion, and ohmic resistances. The influences of vanadium concentration and flow field design also are quantified.« less

The Influence of Hydrophilic Interactions on the Sorption and Mobility of Naproxen at Environmentally-Relevant Concentrations

NASA Astrophysics Data System (ADS)

Muller, K.; Ramsburg, C. A.

2011-12-01

Managed underground storage of reclaimed wastewater is currently one viable option for meeting increasing demands on water resources, yet the attenuation of many emerging contaminants within the subsurface environment is not well understood. Pharmaceuticals are of particular concern due to the rapid increase in development and use of these compounds, observations of incomplete removal during wastewater treatment, and emerging concerns over ecosystem effects. Assessment of the subsurface attenuation of pharmaceuticals is difficult because the compounds are polar, pH-active, and present at low-concentration (ng/L). Predictions of sorption that only consider hydrophobic interactions with soil organic matter may not fully describe the extent to which reversible sequestration influences pharmaceutical attenuation. In fact, hydrophilic interactions (i.e. ion exchange, cation-induced sorption, hydrogen bonding, etc) may represent important contributions to total sorption, especially when aqueous solutes are present at low concentration. Here we assess the sorption of naproxen - an acidic pharmaceutical - to three subsurface materials using equilibrium batch experiments and 1-d column experiments. Subsurface materials evaluated include Ottawa sand (quartz with negligible organic carbon and negligible iron oxide), Aplite sand (quartz and feldspar with negligible organic carbon, 0.2% wt iron oxide), and a Hinckley series silty-sand (quartz and feldspar with 0.95% wt organic carbon, and 0.4% wt iron oxides). Sorption of naproxen to the Ottawa sand was negligible and did not result in measurable retardation when naproxen was introduced to the porous medium at a concentration of 275 ng/L. Batch experiments suggest that Aplite sand offers quantifiable interaction (52% of the mass introduced is associated with the solid phase when the aqueous concentration is 1000 ng/L and the solid to liquid ratio is 1.4:1 v/v); however, column data are indicative of markedly less interaction and retardation. Naproxen sorption to the Hinckley series material was considerable (99% of the mass introduced is associated with the solid phase when the aqueous concentration is 1000 ng/L and the solid to liquid ratio is 1:1 v/v). Predictions of naproxen sorption based upon the fraction of organic carbon and the organic-carbon partitioning coefficient (Koc) greatly underestimated the sorption observed in all experiments conducted with the Hinckley series material. Assessment of sorption under 1 mM NaH2PO4 (a sorbant with a strong affinity for hydrophilic sites) suggests that hydrophobic interactions account for approximately 45% of the total interaction. Breakthrough of naproxen (C0 ~ 20 ug/L) was substantially retarded in experiments conducted with the Hinckley material and a thermally-treated Hinckley material (negligible organic carbon). These results highlight the potential role of hydrophilic interactions during the transport and attenuation of acidic pharmaceuticals at solute concentrations typical of water reuse applications.

Negative Ion Drift Velocity and Longitudinal Diffusion in Mixtures of Carbon Disulfide and Methane

NASA Technical Reports Server (NTRS)

Dion, Michael P.; Son, S.; Hunter, S. D.; deNolfo, G. A.

2011-01-01

Negative ion drift velocity and longitudinal diffusion has been measured for gas mixtures of carbon disulfide (CS2) and methane (CH4)' Measurements were made as a function of total pressure, CS2 partial pressure and electric field. Constant mobility and thermal-limit longitudinal diffusion is observed for all gas mixtures tested. Gas gain for some of the mixtures is also included.

Carbon Characteristics and Biogeochemical Processes of Uranium Accumulating Organic Matter Rich Sediments in the Upper Colorado River Basin

NASA Astrophysics Data System (ADS)

Boye, K.; Noel, V.; Tfaily, M. M.; Dam, W. L.; Bargar, J.; Fendorf, S. E.

2015-12-01

Uranium plume persistence in groundwater aquifers is a problem on several former ore processing sites on floodplains in the upper Colorado River Basin. Earlier observations by our group and others at the Old Rifle Site, CO, have noted that U concentrations are highest in organic rich, fine-grained, and, therefore, diffusion limited sediment material. Due to the constantly evolving depositional environments of floodplains, surficial organic matter may become buried at various stages of decomposition, through sudden events such as overbank flooding and through the slower progression of river meandering. This creates a discontinuous subsurface distribution of organic-rich sediments, which are hotspots for microbial activity and thereby central to the subsurface cycling of contaminants (e.g. U) and biologically relevant elements (e.g. C, N, P, Fe). However, the organic matter itself is poorly characterized. Consequently, little is known about its relevance in driving biogeochemical processes that control U fate and transport in the subsurface. In an investigation of soil/sediment cores from five former uranium ore processing sites on floodplains distributed across the Upper Colorado River Basin we confirmed consistent co-enrichment of U with organic-rich layers in all profiles. However, using C K-edge X-ray Absorption Spectroscopy (XAS) coupled with Fourier-Transformed Ion-Cyclotron-Resonance Mass-Spectroscopy (FT-ICR-MS) on bulk sediments and density-separated organic matter fractions, we did not detect any chemical difference in the organic rich sediments compared to the surrounding coarser-grained aquifer material within the same profile, even though there were differences in organic matter composition between the 5 sites. This suggests that U retention and reduction to U(IV) is independent of C chemical composition on the bulk scale. Instead it appears to be the abundance of organic matter in combination with a limited O2 supply in the fine-grained material that stimulate anaerobic microbial processes responsible for U enrichment. Thus, the chemical composition of organic matter is subordinate to the physical environment and total organic matter content in controlling U reduction and retention processes.

Fluctuations in Species-Level Protein Expression Occur during Element and Nutrient Cycling in the Subsurface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilkins, Michael J.; Wrighton, Kelly C.; Nicora, Carrie D.

2013-03-05

While microbial activities in environmental systems play a key role in the utilization and cycling of essential elements and compounds, microbial activity and growth frequently fluctuates in response to environmental stimuli and perturbations. To investigate these fluctuations within a saturated aquifer system, we monitored a carbon-stimulated in situ Geobacter population while iron reduction was occurring, using 16S rRNA abundances and high-resolution tandem mass spectrometry proteome measurements. Following carbon amendment, 16S rRNA analysis of temporally separated samples revealed the rapid enrichment of Geobacter-like environmental strains with strong similarity to G. bemidjiensis. Tandem mass spectrometry proteomics measurements suggest high carbon flux throughmore » Geobacter respiratory pathways, and the synthesis of anapleurotic four carbon compounds from acetyl-CoA via pyruvate ferredoxin oxidoreductase activity. Across a 40-day period where Fe(III) reduction was occurring, fluctuations in protein expression reflected changes in anabolic versus catabolic reactions, with increased levels of biosynthesis occurring soon after acetate arrival in the aquifer. In addition, localized shifts in nutrient limitation were inferred based on expression of nitrogenase enzymes and phosphate uptake proteins. These temporal data offer the first example of differing microbial protein expression associated with changing geochemical conditions in a subsurface environment.« less

Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; Bernoulli, Daniel

2005-02-01

The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

Simple dielectric mixing model in the monitoring of CO2 leakage from geological storage aquifer

NASA Astrophysics Data System (ADS)

Abidoye, L. K.; Bello, A. A.

2017-03-01

The principle of the dielectric mixing for multiphase systems in porous media has been employed to investigate CO2-water-porous media system and monitor the leakage of CO2, in analogy to scenarios that can be encountered in geological carbon sequestration. A dielectric mixing model was used to relate the relative permittivity for different subsurface materials connected with the geological carbon sequestration. The model was used to assess CO2 leakage and its upward migration, under the influences of the depth-dependent characteristics of the subsurface media as well as the fault-connected aquifers. The results showed that for the upward migration of CO2 in the subsurface, the change in the bulk relative permittivity (εb) of the CO2-water-porous media system clearly depicts the leakage and movement of CO2, especially at depth shallower than 800 m. At higher depth, with higher pressure and temperature, the relative permittivity of CO2 increases with pressure, while that of water decreases with temperature. These characteristics of water and supercritical CO2, combine to limit the change in the εb, at higher depth. Furthermore, it was noted that if the pore water was not displaced by the migrating CO2, the presence of CO2 in the system increases the εb. But, with the displacement of pore water by the migrating CO2, it was shown how the εb profile decreases with time. Owing to its relative simplicity, composite dielectric behaviour of multiphase materials can be effectively deployed for monitoring and enhancement of control of CO2 movement in the geological carbon sequestration.

Spatially explicit simulation of peatland hydrology and carbon dioxide exchange: Influence of mesoscale topography

NASA Astrophysics Data System (ADS)

Sonnentag, O.; Chen, J. M.; Roulet, N. T.; Ju, W.; Govind, A.

2008-06-01

Carbon dynamics in peatlands are controlled, in large part, by their wetness as defined by water table depth and volumetric liquid soil moisture content. A common type of peatland is raised bogs that typically have a multiple-layer canopy of vascular plants over a Sphagnum moss ground cover. Their convex form restricts water supply to precipitation and water is shed toward the margins, usually by lateral subsurface flow. The hydraulic gradient for lateral subsurface flow is governed by the peat surface topography at the mesoscale (˜200 m to 5 km). To investigate the influence of mesoscale topography on wetness, evapotranspiration (ET), and gross primary productivity (GPP) in a bog during the snow-free period, we compare the outputs of a further developed version of the daily Boreal Ecosystem Productivity Simulator (BEPS) with observations made at the Mer Bleue peatland, located near Ottawa, Canada. Explicitly considering mesoscale topography, simulated total ET and GPP correlate well with measured ET (r = 0.91) and derived gross ecosystem productivity (GEP; r = 0.92). Both measured ET and derived GEP are simulated similarly well when mesoscale topography is neglected, but daily simulated values are systematically underestimated by about 10% and 12% on average, respectively, due to greater wetness resulting from the lack of lateral subsurface flow. Owing to the differences in moss surface conductances of water vapor and carbon dioxide with increasing moss water content, the differences in the spatial patterns of simulated total ET and GPP are controlled by the mesotopographic position of the moss ground cover.

Molecular simulation study of dynamical properties of room temperature ionic liquids with carbon pieces

DOE PAGES

Feng, Guang; Zhao, Wei; Cummings, Peter T.; ...

2016-03-29

Room temperature ionic liquids (RTILs) with dispersed carbon pieces exhibit distinctive physiochemical properties. In order to explore the molecular mechanism, RTILs/carbon pieces mixture we investigated it by molecular dynamics (MD) simulation in this work. Rigid and flexible carbon pieces in the form of graphene with different thicknesses and carbon nanotubes in different sizes were dispersed in a representative RTIL 1-butyl-3-methyl-imidazolium dicyanamide ([Bmim][DCA]). Our study demonstrated that the diffusion coefficients of RTILs in the presence of flexible carbons are similar to those of bulk RTILs at varying temperatures, which is in contrast to the decreased diffusion of RTILs in the presencemore » of rigid carbons. In addition, interfacial ion number density at rigid carbon surfaces was higher than that at flexible ones, which is correlated with the accessible external surface area of carbon pieces. The life time of cation-anion pair in the presence of carbon pieces also exhibited a dependence on carbon flexibility. RTILs with dispersed rigid carbon pieces showed longer ion pair life time than those with flexible ones, in consistence with the observation in diffusion coefficients. Furthermore, this work highlights the necessity of including the carbon flexibility when performing MD simulation of RTILs in the presence of dispersed carbon pieces in order to obtain the reliable dynamical and interfacial structural properties.« less

Modified free volume theory of self-diffusion and molecular theory of shear viscosity of liquid carbon dioxide.

PubMed

Nasrabad, Afshin Eskandari; Laghaei, Rozita; Eu, Byung Chan

2005-04-28

In previous work on the density fluctuation theory of transport coefficients of liquids, it was necessary to use empirical self-diffusion coefficients to calculate the transport coefficients (e.g., shear viscosity of carbon dioxide). In this work, the necessity of empirical input of the self-diffusion coefficients in the calculation of shear viscosity is removed, and the theory is thus made a self-contained molecular theory of transport coefficients of liquids, albeit it contains an empirical parameter in the subcritical regime. The required self-diffusion coefficients of liquid carbon dioxide are calculated by using the modified free volume theory for which the generic van der Waals equation of state and Monte Carlo simulations are combined to accurately compute the mean free volume by means of statistical mechanics. They have been computed as a function of density along four different isotherms and isobars. A Lennard-Jones site-site interaction potential was used to model the molecular carbon dioxide interaction. The density and temperature dependence of the theoretical self-diffusion coefficients are shown to be in excellent agreement with experimental data when the minimum critical free volume is identified with the molecular volume. The self-diffusion coefficients thus computed are then used to compute the density and temperature dependence of the shear viscosity of liquid carbon dioxide by employing the density fluctuation theory formula for shear viscosity as reported in an earlier paper (J. Chem. Phys. 2000, 112, 7118). The theoretical shear viscosity is shown to be robust and yields excellent density and temperature dependence for carbon dioxide. The pair correlation function appearing in the theory has been computed by Monte Carlo simulations.

Advanced CO 2 Leakage Mitigation using Engineered Biomineralization Sealing Technologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spangler, Lee; Cunningham, Alfred; Phillips, Adrienne

2015-03-31

This research project addresses one of the goals of the DOE Carbon Sequestration Program (CSP). The CSP core R&D effort is driven by technology and is accomplished through laboratory and pilot scale research aimed at new technologies for greenhouse gas mitigation. Accordingly, this project was directed at developing novel technologies for mitigating unwanted upward leakage of carbon dioxide (CO 2) injected into the subsurface as part of carbon capture and storage (CCS) activities. The technology developed by way of this research project is referred to as microbially induced calcite precipitation (MICP).

Applications of geohydrologic concepts in geology

USGS Publications Warehouse

Maxey, G.B.; Hackett, J.E.

1963-01-01

Subsurface water, an active agent in many geologic proceses, must be considered in interpreting geologic phenomena. Principles of the occurrence, distribution, and movement of subsurface waters are well established and readily applicable. In many interpretations in geologic literature, geohydrologic principles have been employed realistically, but in many others these principles have been either ignored or violated. Explanations of genesis of underclays and associated deposits afford some examples wherein principles of movement and activity of vadose and ground water have been ignored and others in which they have been used advantageously. Postulates stating that waters percolate downward from swamp areas do not allow for the usual movement of subsurface water in such environments. The idea that sediments were leached by vadose water after uplift satisfies the geohydrologic requirements. Weathering and solution form porous and permeable zones subjacent to unconformities in dense rocks such as carbonates and granites; this illustrates the geohydrologic and economic significance of unconformities. Examples are Mohawkian carbonate aquifers of northern Illinois and oil-bearing limestones of Mississippian age of eastern Montana. The flushing effects of meteoric water and other hydrodynamic factors active during erosion periods are important elements in the genesis and concentration of brines. Explanation of the origin and occurrence of brines must include consideration of the geohydrologic environments throughout their geologic history. ?? 1963.

Adsorption-desorption and hysteresis phenomenon of tebuconazole in Colombian agricultural soils: Experimental assays and mathematical approaches.

PubMed

Mosquera-Vivas, Carmen S; Martinez, María J; García-Santos, Glenda; Guerrero-Dallos, Jairo A

2018-01-01

The adsorption-desorption, hysteresis phenomenon, and leachability of tebuconazole were studied for Inceptisol and Histosol soils at the surface (0-10 cm) and in the subsurface (40-50 cm) of an agricultural region from Colombia by the batch-equilibrium method and mathematical approaches. The experimental K fa and K d (L kg -1 ) values (7.9-289.2) decreased with depth for the two Inceptisols and increased with depth for the Histosol due to the organic carbon content, aryl and carbonyl carbon types. Single-point and desorption isotherms depended on adsorption reversibility and suggested that tebuconazole showed hysteresis; which can be adequately evaluated with the single-point desorption isotherm and the linear model using the hysteresis index HI. The most suitable mathematical approach to estimate the adsorption isotherms of tebuconazole at the surface and in the subsurface was that considering the combination of the n-octanol-water partition coefficient, pesticide solubility, and the mass-balance concept. Tebuconazole had similar moderate mobility potential as compared with the values of other studies conducted in temperate amended and unamended soils, but the risk of the fungicide to pollute groundwater sources increased when the pesticide reached subsurface soil layers, particularly in the Inceptisols. Copyright © 2017 Elsevier Ltd. All rights reserved.

Briefing on geological sequestration

EPA Science Inventory

Geological sequestration (GS) is generally recognized as the injection and long-term (e.g., hundreds to thousands of years) trapping of gaseous, liquid or supercritical carbon dioxide (CO2) in subsurface media – primarily saline formations, depleted or nearly depleted oil and gas...

Nematoda from the terrestrial deep subsurface of South Africa.

PubMed

Borgonie, G; García-Moyano, A; Litthauer, D; Bert, W; Bester, A; van Heerden, E; Möller, C; Erasmus, M; Onstott, T C

2011-06-02

Since its discovery over two decades ago, the deep subsurface biosphere has been considered to be the realm of single-cell organisms, extending over three kilometres into the Earth's crust and comprising a significant fraction of the global biosphere. The constraints of temperature, energy, dioxygen and space seemed to preclude the possibility of more-complex, multicellular organisms from surviving at these depths. Here we report species of the phylum Nematoda that have been detected in or recovered from 0.9-3.6-kilometre-deep fracture water in the deep mines of South Africa but have not been detected in the mining water. These subsurface nematodes, including a new species, Halicephalobus mephisto, tolerate high temperature, reproduce asexually and preferentially feed upon subsurface bacteria. Carbon-14 data indicate that the fracture water in which the nematodes reside is 3,000-12,000-year-old palaeometeoric water. Our data suggest that nematodes should be found in other deep hypoxic settings where temperature permits, and that they may control the microbial population density by grazing on fracture surface biofilm patches. Our results expand the known metazoan biosphere and demonstrate that deep ecosystems are more complex than previously accepted. The discovery of multicellular life in the deep subsurface of the Earth also has important implications for the search for subsurface life on other planets in our Solar System.

Microbiological and Geochemical Survey of CO2-Dominated Mofette and Mineral Waters of the Cheb Basin, Czech Republic.

PubMed

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO 2 at the surface that occurs in the form of CO 2 -rich mineral springs and wet and dry mofettes. So far, the influence of CO 2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO 2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas ) and iron (e.g., Gallionella, Sideroxydans ) cycling shaped the core community. Additionally, CO 2 -influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe 2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments.

Microbiological and Geochemical Survey of CO2-Dominated Mofette and Mineral Waters of the Cheb Basin, Czech Republic

PubMed Central

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO2 at the surface that occurs in the form of CO2-rich mineral springs and wet and dry mofettes. So far, the influence of CO2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas) and iron (e.g., Gallionella, Sideroxydans) cycling shaped the core community. Additionally, CO2-influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments. PMID:29321765

BLT-EC (Breach, Leach and Transport-Equilibrium Chemistry) data input guide. A computer model for simulating release and coupled geochemical transport of contaminants from a subsurface disposal facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacKinnon, R.J.; Sullivan, T.M.; Kinsey, R.R.

1997-05-01

The BLT-EC computer code has been developed, implemented, and tested. BLT-EC is a two-dimensional finite element computer code capable of simulating the time-dependent release and reactive transport of aqueous phase species in a subsurface soil system. BLT-EC contains models to simulate the processes (container degradation, waste-form performance, transport, chemical reactions, and radioactive production and decay) most relevant to estimating the release and transport of contaminants from a subsurface disposal system. Water flow is provided through tabular input or auxiliary files. Container degradation considers localized failure due to pitting corrosion and general failure due to uniform surface degradation processes. Waste-form performancemore » considers release to be limited by one of four mechanisms: rinse with partitioning, diffusion, uniform surface degradation, and solubility. Transport considers the processes of advection, dispersion, diffusion, chemical reaction, radioactive production and decay, and sources (waste form releases). Chemical reactions accounted for include complexation, sorption, dissolution-precipitation, oxidation-reduction, and ion exchange. Radioactive production and decay in the waste form is simulated. To improve the usefulness of BLT-EC, a pre-processor, ECIN, which assists in the creation of chemistry input files, and a post-processor, BLTPLOT, which provides a visual display of the data have been developed. BLT-EC also includes an extensive database of thermodynamic data that is also accessible to ECIN. This document reviews the models implemented in BLT-EC and serves as a guide to creating input files and applying BLT-EC.« less

Estimation of Mars radar backscatter from measured surface rock populations

USGS Publications Warehouse

Baron, J.E.; Simpson, R.A.; Tyler, G.L.; Moore, H.J.; Harmon, J.K.

1998-01-01

Reanalysis of rock population data at the Mars Viking Lander sites has yielded updated values of rock fractional surface coverage (about 0.16 at both sites, including outcrops) and new estimates of rock burial depths and axial ratios. These data are combined with a finite difference time domain (FDTD) numerical scattering model to estimate diffuse backscatter due to rocks at both the Lander l (VL1) and Lander 2 (VL2) sites. We consider single scattering from both surface and subsurface objects of various shapes, ranging from an ideal sphere to an accurate digitized model of a terrestrial rock. The FDTD cross-section calculations explicitly account for the size, shape, composition, orientation, and burial state of the scattering object, the incident wave angle and polarization, and the composition of the surface. We calculate depolarized specific cross sections at 12.6 cm wavelength due to lossless rock-like scatterers of about 0.014 at VL1 and 0.023 at VL2, which are comparable to the measured ranges of 0.019-0.032 and 0.012-0.018, respectively. We also discuss the variation of the diffuse cross section as the local angle of incidence, ??i, changes. Numerical calculations for a limited set of rock shapes indicate a marked difference between the angular backscattering behavior of wavelength-scale surface and subsurface rocks: while subsurface rocks scatter approximately as a cosine power law, surface rocks display a complex variation, often with peak backscattering at high incidence angles (??i = 70??-75??). Copyright 1998 by the American Geophysical Union.

Physics-based subsurface visualization of human tissue.

PubMed

Sharp, Richard; Adams, Jacob; Machiraju, Raghu; Lee, Robert; Crane, Robert

2007-01-01

In this paper, we present a framework for simulating light transport in three-dimensional tissue with inhomogeneous scattering properties. Our approach employs a computational model to simulate light scattering in tissue through the finite element solution of the diffusion equation. Although our model handles both visible and nonvisible wavelengths, we especially focus on the interaction of near infrared (NIR) light with tissue. Since most human tissue is permeable to NIR light, tools to noninvasively image tumors, blood vasculature, and monitor blood oxygenation levels are being constructed. We apply this model to a numerical phantom to visually reproduce the images generated by these real-world tools. Therefore, in addition to enabling inverse design of detector instruments, our computational tools produce physically-accurate visualizations of subsurface structures.

Vadose Zone Flow and Transport of Dissolved Organic Carbon at Multiple Scales in Humid Regimes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jardine, Philip M; Mayes, Melanie; Mulholland, Patrick J

2006-06-01

Scientists must embrace the necessity to offset global CO{sub 2} emissions regardless of politics. Efforts to enhance terrestrial organic carbon sequestration have traditionally focused on aboveground biomass and surface soils. An unexplored potential exists in thick lower horizons of widespread, mature soils such as Alfisols, Ultisols, and Oxisols. We present a case study of fate and transport of dissolved organic carbon (DOC) in a highly weathered Ultisol, involving spatial scales from the laboratory to the landscape. Our objectives were to interpret processes observed at various scales and provide an improved understanding of coupled hydrogeochemical mechanisms that control DOC mobility andmore » sequestration in deep subsoils within humid climatic regimes. Our approach is multiscale, using laboratory-scale batch and soil columns (0.2 by 1.0 m), an in situ pedon (2 by 2 by 3 m), a well-instrumented subsurface facility on a subwatershed (0.47 ha), and ephemeral and perennial stream discharge at the landscape scale (38.4 ha). Laboratory-scale experiments confirmed that lower horizons have the propensity to accumulate DOC, but that preferential fracture flow tends to limit sequestration. Intermediate-scale experiments demonstrated the beneficial effects of C diffusion into soil micropores. Field- and landscape-scale studies demonstrated coupled hydrological, geochemical, and microbiological mechanisms that limit DOC sequestration, and their sensitivity to local environmental conditions. Our results suggest a multi-scale approach is necessary to assess the propensity of deep subsoils to sequester organic C in situ. By unraveling fundamental organic C sequestration mechanisms, we improve the conceptual and quantitative understanding needed to predict and alter organic C budgets in soil systems.« less

Multiscale approach to (micro)porosity quantification in continental spring carbonate facies: Case study from the Cakmak quarry (Denizli, Turkey)

NASA Astrophysics Data System (ADS)

De Boever, Eva; Foubert, Anneleen; Oligschlaeger, Dirk; Claes, Steven; Soete, Jeroen; Bertier, Pieter; Özkul, Mehmet; Virgone, Aurélien; Swennen, Rudy

2016-07-01

Carbonate spring deposits gained renewed interest as potential contributors to subsurface reservoirs and as continental archives of environmental changes. In contrast to their fabrics, petrophysical characteristics - and especially the importance of microporosity (< 1µm) - are less understood. This study presents the combination of advanced petrophysical and imaging techniques to investigate the pore network characteristics of three, common and widespread spring carbonate facies, as exposed in the Pleistocene Cakmak quarry (Denizli, Turkey): the extended Pond, the dipping crystalline Proximal Slope Facies and the draping Apron and Channel Facies deposits formed by encrustation of biological substrate. Integrating mercury injection capillary pressure, bulk and diffusion Nuclear Magnetic Resonance (NMR), NMR profiling and Brunauer-Emmett-Teller (BET) measurements with microscopy and micro-computer tomography (µ-CT), shows that NMR T2 distributions systematically display a single group of micro-sized pore bodies, making up between 6 and 33% of the pore space (average NMR T2 cut-off value: 62 ms). Micropore bodies are systematically located within cloudy crystal cores of granular and dendritic crystal textures in all facies. The investigated properties therefore do not reveal differences in micropore size or shape with respect to more or less biology-associated facies. The pore network of the travertine facies is distinctive in terms of (i) the percentage of microporosity, (ii) the connectivity of micropores with meso- to macropores, and (ii) the degree of heterogeneity at micro- and macroscale. Results show that an approach involving different NMR experiments provided the most complete view on the 3-D pore network especially when microporosity and connectivity are of interest.

Diffusional Transport of Organic Solutes in Subsurface Clay Lenses and Layers

NASA Astrophysics Data System (ADS)

Demond, A. H.; Ayral, D.; Goltz, M. N.

2009-12-01

The storage of organic solvents in clay lenses and layers in the subsurface creates long-term contaminant sources. Because of the low hydraulic conductivities of clay, it is thought that organic movement into clay lenses occurs through the process of diffusion. The ratio of the effective diffusion coefficient in the porous medium and the diffusion coefficient in bulk water is usually given by the tortuosity factor which accounts for the reduced area and the increased path length in the porous medium. However, there is field evidence which suggests that the concentrations in these lenses exceed that which can be accounted for by simple diffusion. There are reports, for example, of tortuosity factors greater than 1.0, which theoretically is not possible. Clays such as montmorillonite or bentonite shrink and swell depending on water content, and similar behavior can occur in the presence of organic solvents. In fact, research has shown that the basal spacing of bentonite can decrease by 50% when permeated with heptane. Such contraction of the clay structure can lead to the formation of cracks and macropores, with a concomitant alteration of the diffusional pathways that solutes follow. Models formulated for diffusional transport in soil are available to calculate the tortuosity factor as a function of water content. In addition, models are available to simulate phenomena in which the diffusion coefficient is concentration dependent. However, calculations of diffusional transport using such models show that they may not adequately reflect the impact of the alteration of the clay structure. However, modeling the transport of organic solutes in clay as a dual-domain system with some minimal advective transport in macropores can yield tortuosity factors greater than 1.0. Thus, it appears the cracking of clay in contact with organic solvents and a resultant advective component to transport of the solute may be an explanation of field observations.

Subsurface injection of liquid waste in Florida, United States of America

USGS Publications Warehouse

Vecchioli, John

1981-01-01

In 1979, liquid waste was injected into the subsurface of Florida by 10 injection systems at an aggregate average rate of 165,000 m3/d. All the systems inject into carbonate rocks that contain salty water. Extensive precautions are taken in the construction of the injection wells and in the monitoring of their operation to provide assurance that overlying and laterally contiguous freshwater resources do not become contaminated with either the injected waste or the saltwater displaced by the waste. Several concerns relating to the effectiveness of the confining bed above the injection zone for containing the injected wastes have arisen over the years. These concerns accentuate the value of a well-planned and implemented monitoring program from which one can evaluate the potential impact of waste injection on the subsurface environment.

Diffusion and Leaching Behavior of Radionuclides in Category 3 Waste Encasement Concrete and Soil Fill Material – Summary Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mattigod, Shas V.; Wellman, Dawn M.; Bovaird, Chase C.

2011-08-31

One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Such concrete encasement would contain and isolate the waste packages from the hydrologic environment and would act as an intrusion barrier. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages in concrete. These concrete-encased waste stacks are expected to vary in size with maximum dimensions of 6.4 m long, 2.7 m wide, and 4 m high. The waste stacks are expectedmore » to have a surrounding minimum thickness of 15 cm of concrete encasement. These concrete-encased waste packages are expected to withstand environmental exposure (solar radiation, temperature variations, and precipitation) until an interim soil cover or permanent closure cover is installed, and to remain largely intact thereafter. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion and move into the surrounding subsurface environment. Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability of the surrounding soil to retard radionuclide migration. The retardation factors for radionuclides contained in the waste packages can be determined from measurements of diffusion coefficients for these contaminants through concrete and fill material. Some of the mobilization scenarios include (1) potential leaching of waste form before permanent closure cover is installed; (2) after the cover installation, long-term diffusion of radionuclides from concrete waste form into surrounding fill material; (3) diffusion of radionuclides from contaminated soils into adjoining concrete encasement and clean fill material. Additionally, the rate of diffusion of radionuclides may be affected by the formation of structural cracks in concrete, the carbonation of the buried waste form, and any potential effect of metallic iron (in the form of rebars) on the mobility of radionuclides. The radionuclides iodine-129 ({sup 129}I), technetium-99 ({sup 99}Tc), and uranium-238 ({sup 238}U) are identified as long-term dose contributors in Category 3 waste (Mann et al. 2001; Wood et al. 1995). Because of their anionic nature in aqueous solutions, {sup 129}I, {sup 99}Tc, and carbonate-complexed {sup 238}U may readily leach into the subsurface environment (Serne et al. 1989, 1992a, b, 1993, and 1995). The leachability and/or diffusion of radionuclide species must be measured to assess the long-term performance of waste grouts when contacted with vadose-zone pore water or groundwater. Although significant research has been conducted on the design and performance of cementitious waste forms, the current protocol conducted to assess radionuclide stability within these waste forms has been limited to the Toxicity Characteristic Leaching Procedure, Method 1311 Federal Registry (EPA 1992) and ANSI/ANS-16.1 leach test (ANSI 1986). These tests evaluate the performance under water-saturated conditions and do not evaluate the performance of cementitious waste forms within the context of waste repositories which are located within water-deficient vadose zones. Moreover, these tests assess only the diffusion of radionuclides from concrete waste forms and neglect evaluating the mechanisms of retention, stability of the waste form, and formation of secondary phases during weathering, which may serve as long-term secondary hosts for immobilization of radionuclides. The results of recent investigations conducted under arid and semi-arid conditions (Al-Khayat et al. 2002; Garrabrants et al. 2002; Garrabrants and Kosson 2003; Garrabrants et al. 2004; Gervais et al. 2004; Sanchez et al. 2002; Sanchez et al. 2003) provide valuable information suggesting structural and chemical changes to concrete waste forms which may affect contaminant containment and waste form performance. However, continued research is necessitated by the need to understand: the mechanism of contaminant release; the significance of contaminant release pathways; how waste form performance is affected by the full range of environmental conditions within the disposal facility; the process of waste form aging under conditions that are representative of processes occurring in response to changing environmental conditions within the disposal facility; the effect of waste form aging on chemical, physical, and radiological properties, and the associated impact on contaminant release. Recent reviews conducted by the National Academies of Science recognized the efficacy of cementitious materials for waste isolation, but further noted the significant shortcomings in our current understanding and testing protocol for evaluating the performance of various formulations.« less

Review and developments of dissemination models for airborne carbon fibers

NASA Technical Reports Server (NTRS)

Elber, W.

1980-01-01

Dissemination prediction models were reviewed to determine their applicability to a risk assessment for airborne carbon fibers. The review showed that the Gaussian prediction models using partial reflection at the ground agreed very closely with a more elaborate diffusion analysis developed for the study. For distances beyond 10,000 m the Gaussian models predicted a slower fall-off in exposure levels than the diffusion models. This resulting level of conservatism was preferred for the carbon fiber risk assessment. The results also showed that the perfect vertical-mixing models developed herein agreed very closely with the diffusion analysis for all except the most stable atmospheric conditions.

Transport of carbon ion test particles and hydrogen recycling in the plasma of the Columbia tokamak HBT'' (High Beta Tokamak)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jian-Hua.

Carbon impurity ion transport is studied in the Columbia High Beta Tokamak (HBT), using a carbon tipped probe which is inserted into the plasma (n{sub e} {approx} 1 {minus} 5 {times} 10{sup 14} (cm{sup {minus}3}), T{sub e} {approx} 4 {minus} 10 (eV), B{sub t} {approx} 0.2 {minus} 0.4(T)). Carbon impurity light, mainly the strong lines of C{sub II}(4267A, emitted by the C{sup +} ions) and C{sub III} (4647A, emitted by the C{sup ++} ions), is formed by the ablation or sputtering of plasma ions and by the discharge of the carbon probe itself. The diffusion transport of the carbon ionsmore » is modeled by measuring the space-and-time dependent spectral light emission of the carbon ions with a collimated optical beam and photomultiplier. The point of emission can be observed in such a way as to sample regions along and transverse to the toroidal magnetic field. The carbon ion diffusion coefficients are obtained by fitting the data to a diffusion transport model. It is found that the diffusion of the carbon ions is classical'' and is controlled by the high collisionality of the HBT plasma; the diffusion is a two-dimensional problem and the expected dependence on the charge of the impurity ion is observed. The measurement of the spatial distribution of the H{sub {alpha}} emissivity was obtained by inverting the light signals from a 4-channel polychromator, the data were used to calculate the minor-radial influx, the density, and the recycling time of neutral hydrogen atoms or molecules. The calculation shows that the particle recycling time {tau}{sub p} is comparable with the plasma energy confinement time {tau}{sub E}; therefore, the recycling of the hot plasma ions with the cold neutrals from the walls is one of the main mechanisms for loss of plasma energy.« less

Measurement of Three-Dimensional Anisotropic Thermal Diffusivities for Carbon Fiber-Reinforced Plastics Using Lock-In Thermography

NASA Astrophysics Data System (ADS)

Ishizaki, Takuya; Nagano, Hosei

2015-11-01

A new measurement technique to measure the in-plane thermal diffusivity, the distribution of in-plane anisotropy, and the out-of-plane thermal diffusivity has been developed to evaluate the thermal conductivity of anisotropic materials such as carbon fiber-reinforced plastics (CFRPs). The measurements were conducted by using a laser-spot-periodic-heating method. The temperature of the sample is detected by using lock-in thermography. Thermography can analyze the phase difference between the periodic heat input and the temperature response of the sample. Two kinds of samples, unidirectional (UD) and cross-ply (CP) pitch-based CFRPs, were fabricated and tested in an atmospheric condition. All carbon fibers of the UD sample run in one direction [90°]. The carbon fibers of the CP sample run in two directions [0°/90°]. It is found that, by using lock-in thermography, it is able to visualize the thermal anisotropy and calculate the angular dependence of the in-plane thermal diffusivity of the CFRPs. The out-of-plane thermal diffusivity of CFRPs was also measured by analyzing the frequency dependence of the phase difference.

CO2 diffusion into pore spaces limits weathering rate of an experimental basalt landscape

USGS Publications Warehouse

van Haren, Joost; Dontsova, Katerina; Barron-Gafford, Greg A.; Troch, Peter A.; Chorover, Jon; DeLong, Stephen B.; Breshears, David D.; Huxman, Travis E.; Pelletier, Jon D.; Saleska, Scott; Zeng, Xubin; Ruiz, Joaquin

2017-01-01

Basalt weathering is a key control over the global carbon cycle, though in situ measurements of carbon cycling are lacking. In an experimental, vegetation-free hillslope containing 330 m3 of ground basalt scoria, we measured real-time inorganic carbon dynamics within the porous media and seepage flow. The hillslope carbon flux (0.6–5.1 mg C m–2 h–1) matched weathering rates of natural basalt landscapes (0.4–8.8 mg C m–2 h–1) despite lacking the expected field-based impediments to weathering. After rainfall, a decrease in CO2 concentration ([CO2]) in pore spaces into solution suggested rapid carbon sequestration but slow reactant supply. Persistent low soil [CO2] implied that diffusion limited CO2 supply, while when sufficiently dry, reaction product concentrations limited further weathering. Strong influence of diffusion could cause spatial heterogeneity of weathering even in natural settings, implying that modeling studies need to include variable soil [CO2] to improve carbon cycling estimates associated with potential carbon sequestration methods.

Sorption and modeling of mass transfer of toxic chemical vapors in activated-carbon fiber-cloth adsorbers

USGS Publications Warehouse

Lordgooei, M.; Sagen, J.; Rood, M.J.; Rostam-Abadi, M.

1998-01-01

A new activated-carbon fiber-cloth (ACFC) adsorber coupled with an electrothermal regenerator and a cryogenic condenser was designed and developed to efficiently capture and recover toxic chemical vapors (TCVs) from simulated industrial gas streams. The system was characterized for adsorption by ACFC, electrothermal desorption, and cryogenic condensation to separate acetone and methyl ethyl ketone from gas streams. Adsorption dynamics are numerically modeled to predict system characteristics during scale-up and optimization of the process in the future. The model requires diffusivities of TCVs into an activated-carbon fiber (ACF) as an input. Effective diffusivities of TCVs into ACFs were modeled as a function of temperature, concentration, and pore size distribution. Effective diffusivities for acetone at 65 ??C and 30-60 ppmv were measured using a chromatography method. The energy factor for surface diffusion was determined from comparison between the experimental and modeled effective diffusivities. The modeled effective diffusivities were used in a dispersive computational model to predict mass transfer zones of TCVs in fixed beds of ACFC under realistic conditions for industrial applications.

Measurement of CO2 diffusivity for carbon sequestration: a microfluidic approach for reservoir-specific analysis.

PubMed

Sell, Andrew; Fadaei, Hossein; Kim, Myeongsub; Sinton, David

2013-01-02

Predicting carbon dioxide (CO(2)) security and capacity in sequestration requires knowledge of CO(2) diffusion into reservoir fluids. In this paper we demonstrate a microfluidic based approach to measuring the mutual diffusion coefficient of carbon dioxide in water and brine. The approach enables formation of fresh CO(2)-liquid interfaces; the resulting diffusion is quantified by imaging fluorescence quenching of a pH-dependent dye, and subsequent analyses. This method was applied to study the effects of site-specific variables--CO(2) pressure and salinity levels--on the diffusion coefficient. In contrast to established, macro-scale pressure-volume-temperature cell methods that require large sample volumes and testing periods of hours/days, this approach requires only microliters of sample, provides results within minutes, and isolates diffusive mass transport from convective effects. The measured diffusion coefficient of CO(2) in water was constant (1.86 [± 0.26] × 10(-9) m(2)/s) over the range of pressures (5-50 bar) tested at 26 °C, in agreement with existing models. The effects of salinity were measured with solutions of 0-5 M NaCl, where the diffusion coefficient varied up to 3 times. These experimental data support existing theory and demonstrate the applicability of this method for reservoir-specific testing.

An Urban Diffusion Simulation Model for Carbon Monoxide

ERIC Educational Resources Information Center

Johnson, W. B.; And Others

1973-01-01

A relatively simple Gaussian-type diffusion simulation model for calculating urban carbon (CO) concentrations as a function of local meteorology and the distribution of traffic is described. The model can be used in two ways: in the synoptic mode and in the climatological mode. (Author/BL)

Active Serpentinization and the Potential for a Diverse Subsurface Biosphere

NASA Astrophysics Data System (ADS)

Canovas, P. A.; Shock, E.

2013-12-01

The ubiquitous nature of serpentinization and the unique fluids it generates have major consequences for habitat generation, abiotic organic synthesis, and biosynthesis. The production of hydrogen from the anaerobic hydrolysis of ultramafic minerals sets the redox state of serpentinizing fluids to be thermodynamically favorable for these processes. Consequently, a host of specialized microbial populations and metabolisms can be sustained. Active low-temperature serpentinizing systems, such as the Samail ophiolite in Oman, offer an ideal opportunity to investigate biogeochemical processes during the alteration of ultramafic minerals. At the Samail ophiolite in particular, serpentinization may provide the potential for an active subsurface microbial community shielded from potentially unfavorable surface conditions. Support for this assertion comes from geochemical data including Mg, Ca, CH4 (aq), and H2 (aq) abundances indicating that methane is a product of serpentinization. To further investigate viable metabolic strategies, affinity calculations were performed on both the surface waters and the hyperalkaline springs, which may be considered as messengers of processes occurring in the subsurface. Almost all sites yield positive affinities (i.e., are thermodynamically favorable) for a diverse suite of serpentinization metabolisms including methanogenesis, anammox, and carbon monoxide, nitrate, and sulfate reduction with hydrogen, as well as anaerobic methanotrophy coupled to nitrate, nitrite, and sulfate reduction. Reaction path modeling was performed to ascertain the extent to which serpentinization and mixing of surface waters with hyperalkaline spring waters in the subsurface can generate suitable habitats. The serpentinization model simulates the reaction of pristine Oman harzburgite with surface water to quantify the redox state and generation of hyperalkaline spring water. Preliminary results show that water-rock ratios as high as 100 could effectively reduce the system and create a thermodynamic drive sufficient to convert all of the dissolved inorganic carbon into methane. This indicates that the system is poised to create the reducing conditions necessary to support a subsurface biosphere very early in the serpentinizing process, and that the subsurface biosphere could extend upwards to very near the surface. The mixing model simulates the percolation of surface water into the active serpentinization zone. During the mixing process, methane is calculated to be more stable than carbonate species until approximately 100g of surface water have been added to 1 kg of the serpentinizing fluid. These results suggest that unreacted surface water flowing directly into the serpentinizing zone can create the disequilibria necessary for methanogenesis, and possibly other metabolisms, to proceed while still maintaining the low redox state of the system. As long as the recharge to the hyperalkaline reservoir does not exceed ten percent of the reservoir, methanogenesis and other serpentinization metabolisms can thrive off the disequilibria generated through mixing.

Microbial carbon cycling in Lost City hydrothermal chimneys and other serpentinite-hosted ecosystems (Invited)

NASA Astrophysics Data System (ADS)

Brazelton, W. J.; Lang, S. Q.; Morrill, P. L.; Twing, K. I.; Crespo-Medina, M.; Morgan-Smith, D.; Früh-Green, G. L.; Schrenk, M. O.

2013-12-01

Ultramafic rocks formed in the Earth's mantle and uplifted into the crust represent an immense but poorly described reservoir of carbon. The biological availability of this rock-hosted carbon reservoir is unknown, but the set of geochemical reactions known as serpentinization can mobilize carbon from the subsurface and trigger the growth of dense microbial communities. Serpentinite-hosted ecosystems such as the chimney biofilms of the Lost City hydrothermal field can support dense populations of bacteria and archaea fueled by the copious quantities of H2 and methane (CH4) released by serpentinization (1-5). The metabolic pathways involved, however, remain unknown, and conventional interpretations of genomic and experimental data are complicated by the unusual carbon speciation in these environments. Carbon dioxide is scarce due to the highly reducing, high pH conditions. Instead, the predominant forms of carbon are CH4 and formate (5). Despite its natural abundance, however, direct evidence for CH4-derived biomass is lacking (1,4,5), and the role of formate is potentially significant but largely unexplored (1,5). To gain a more generalized perspective of carbon cycling in serpentinite-hosted ecosystems, we have recently investigated fluids and rocks collected from serpentinizing ophiolites in California, Canada, and Italy. Our results point to potentially H2-utilizing, autotrophic Betaproteobacteria thriving in shallow, oxic-anoxic transition zones and anaerobic Clostridia inhabiting anoxic, subsurface zones (1,6). The carbon sources utilized by the Clostridia are unknown, but preliminary metagenomic evidence is consistent with a fermentation-style metabolic strategy that may be conducive to an oxidant-limited, subsurface environment. Curiously, despite the abundance of H2 and CH4 in these continental springs, none of the geochemical, genomic, or experimental results obtained thus far contain any evidence for biological methanogenesis (1,6). This is in stark contrast to the dense populations of methanogen-like archaea in Lost City chimneys. Clearly, the role of methanogens must be constrained in order to gain a firm understanding of the carbon flux from serpentinite ecosystems, and future potential investigations of these systems will be discussed. References 1. Schrenk MO, Brazelton WJ, Lang SQ. 2013. Rev. Mineral. Geochem. 75:575-606. 2. Schrenk MO, Kelley DS, Bolton SA, Baross JA. 2004. Environ. Microbiol. 6:1086-1095. 3. Brazelton WJ, Schrenk MO, Kelley DS, Baross JA. 2006. Appl. Environ. Microbiol. 72:6257-6270. 4. Brazelton WJ, Mehta MP, Kelley DS, Baross JA. 2011. mBio2:4. doi:10.1128/mBio.00127-11. 5. Lang SQ, Früh-Green GL, Bernasconi SM, Lilley MD, Proskurowski G, Méhay S, Butterfield D a. 2012. Geochim. Cosmochim. Acta. 92:82-99. 6. Brazelton WJ, Morrill PL, Szponar N, Schrenk MO. 2013. Appl. Environ. Microbiol. 79:3906.

Beneath the surface: Characteristics of oceanic ecosystems under weak mixing conditions A theoretical investigation

NASA Astrophysics Data System (ADS)

Beckmann, Aike; Hense, Inga

2007-12-01

This study considers an important biome in aquatic environments, the subsurface ecosystem that evolves under low mixing conditions, from a theoretical point of view. Employing a conceptual model that involves phytoplankton, a limiting nutrient and sinking detritus, we use a set of key characteristics (thickness, depth, biomass amplitude/productivity) to qualitatively and quantitatively describe subsurface biomass maximum layers (SBMLs) of phytoplankton. These SBMLs are defined by the existence of two community compensation depths in the water column, which confine the layer of net community production; their depth coincides with the upper nutricline. Analysing the results of a large ensemble of simulations with a one-dimensional numerical model, we explore the parameter dependencies to obtain fundamental steady-state relationships that connect primary production, mortality and grazing, remineralization, vertical diffusion and detrital sinking. As a main result, we find that we can distinguish between factors that determine the vertically integrated primary production and others that affect only depth and shape (thickness and biomass amplitude) of this subsurface production layer. A simple relationship is derived analytically, which can be used to estimate the steady-state primary productivity in the subsurface oligotrophic ocean. The fundamental nature of the results provides further insight into the dynamics of these “hidden” ecosystems and their role in marine nutrient cycling.

Briefing on geological sequestration (Tulsa)

EPA Science Inventory

Geological sequestration (GS) is generally recognized as the injection and long-term (e.g., hundreds to thousands of years) trapping of gaseous, liquid or supercritical carbon dioxide (CO2) in subsurface media – primarily saline formations, depleted or nearly depleted oil and gas...

CO2 Sparging Phase 3 Full Scale Implementation and Monitoring Report

EPA Pesticide Factsheets

In-situ carbon dioxide (CO2) sparging was designed and implemented to treat a subsurface causticbrine pool (CBP) formed as a result of releases from historical production of industrial chemicals at theLCP Chemicals Site, Brunswick, GA (Site).

BIOVENTING OF CHLORINATED SOLVENTS FOR GROUND-WATER CLEANUP THROUGH BIOREMEDIATION

EPA Science Inventory

Chlorinated solvents such as tetrachloroethylene, trichloroethylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, and dichloromethane (methylene chloride) can exist in contaminated subsurface material as (1) the neat oil, (2) a component of a mixed oily waste, (3) a solu...

Stream-subsurface nutrient dynamics in a groundwater-fed stream

NASA Astrophysics Data System (ADS)

Rezanezhad, F.; Niederkorn, A.; Parsons, C. T.; Van Cappellen, P.

2015-12-01

The stream-riparian-aquifer interface plays a major role in the regional flow of nutrients and contaminants due to a strong physical-chemical gradient that promotes the transformation, retention, elimination or release of biogenic elements. To better understand the effect of the near-stream zones on stream biogeochemistry, we conducted a field study on a groundwater-fed stream located in the rare Charitable Research Reserve, Cambridge, Ontario, Canada. This study focused on monitoring the spatial and temporal distributions of nutrient elements within the riparian and hyporheic zones of the stream. Several piezometer nests and a series of passive (diffusion) water samplers, known as peepers, were installed along longitudinal and lateral transects centered on the stream to obtain data on the groundwater chemistry. Groundwater upwelling along the stream resulted in distinctly different groundwater types and associated nitrate concentrations between small distances in the riparian zone (<4m). After the upstream source of the stream surface water, concentrations of nutrients (NO3-, NH4+, SO42- and carbon) did not significantly change before the downstream outlet. Although reduction of nitrate and sulphate were found in the riparian zone of the stream, this did not significantly influence the chemistry of the adjacent stream water. Also, minimal retention in the hyporheic zones limited reduction of reactive compounds (NO3- and SO42-) within the stream channel. The results showed that the dissolved organic carbon (DOC) and residence time of water in the hyporheic zone and in surface water limited denitrification.

Evidence of a dynamic microbial community structure and predation through combined microbiological and stable isotope characterization

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Bill, M.; Lim, H. C.; Wu, C.; Conrad, M. E.; Williams, K. H.; DePaolo, D. J.; Brodie, E.

2014-12-01

The speciation, reactivity and mobility of carbon in the near surface environment is intimately linked to the prevalence, diversity and dynamics of native microbial populations. We utilize this relationship by introducing 13C-labeled acetate to sediments recovered from a shallow aquifer system to track both the cycling of carbon through multiple redox pathways and the associated spatial and temporal evolution of bacterial communities in response to this nutrient source. Results demonstrate a net loss of sediment organic carbon over the course of the amendment experiment. Furthermore, these data demonstrated a source of isotopically labeled inorganic carbon that was not attributable to primary metabolism by acetate-oxidizing microorganisms. Fluid samples analyzed weekly for microbial composition by pyrosequencing of ribosomal RNA genes showed a transient microbial community structure, with distinct occurrences of Azoarcus, Geobacter and multiple sulfate reducing species over the course of the experiment. In combination with DNA sequencing data, the anomalous carbon cycling process is shown to occur exclusively during the period of predominant Geobacter species growth. Pyrosequencing indicated, and targeted cloning and sequencing confirmed the presence of several bacteriovorous protozoa, including species of the Breviata, Planococcus and Euplotes genera. Cloning and qPCR analysis demonstrated that Euplotes species were most abundant and displayed a growth trajectory that closely followed that of the Geobacter population. These results suggest a previously undocumented secondary turnover of biomass carbon related to protozoan grazing that was not sufficiently prevalent to be observed in bulk concentrations of carbon species in the system, but was clearly identifiable in the partitioning of carbon isotopes. The impact of predator-prey relationships on subsurface microbial community dynamics and therefore the flux of carbon through a system via the microbial biomass pool suggests a diversity of processes that should be considered for inclusion in reactive transport models that aim to predict carbon turnover, nutrient flux, and redox reactions in natural and stimulated subsurface systems.

The Serpentinite Subsurface Microbiome

NASA Astrophysics Data System (ADS)

Schrenk, M. O.; Nelson, B. Y.; Brazelton, W. J.

2011-12-01

Microbial habitats hosted in ultramafic rocks constitute substantial, globally-distributed portions of the subsurface biosphere, occurring both on the continents and beneath the seafloor. The aqueous alteration of ultramafics, in a process known as serpentinization, creates energy rich, high pH conditions, with low concentrations of inorganic carbon which place fundamental constraints upon microbial metabolism and physiology. Despite their importance, very few studies have attempted to directly access and quantify microbial activities and distributions in the serpentinite subsurface microbiome. We have initiated microbiological studies of subsurface seeps and rocks at three separate continental sites of serpentinization in Newfoundland, Italy, and California and compared these results to previous analyses of the Lost City field, near the Mid-Atlantic Ridge. In all cases, microbial cell densities in seep fluids are extremely low, ranging from approximately 100,000 to less than 1,000 cells per milliliter. Culture-independent analyses of 16S rRNA genes revealed low-diversity microbial communities related to Gram-positive Firmicutes and hydrogen-oxidizing bacteria. Interestingly, unlike Lost City, there has been little evidence for significant archaeal populations in the continental subsurface to date. Culturing studies at the sites yielded numerous alkaliphilic isolates on nutrient-rich agar and putative iron-reducing bacteria in anaerobic incubations, many of which are related to known alkaliphilic and subsurface isolates. Finally, metagenomic data reinforce the culturing results, indicating the presence of genes associated with organotrophy, hydrogen oxidation, and iron reduction in seep fluid samples. Our data provide insight into the lifestyles of serpentinite subsurface microbial populations and targets for future quantitative exploration using both biochemical and geochemical approaches.

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes

PubMed Central

2015-01-01

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption. PMID:26369420

The Role of Alpine Wetlands as Hot Spots of Dissolved Organic Carbon Fluxes in the East River, Colorado

NASA Astrophysics Data System (ADS)

Winnick, M.; Rainaldi, G. R.; Lawrence, C. R.; McCormick, M. E.; Hsu, H. T.; Druhan, J. L.; Williams, K. H.; Maher, K.

2016-12-01

Dissolved organic carbon (DOC) is a critical chemical attribute of freshwater systems, affecting nutrient availability, toxicity and solubility of metals, and biological activity via the absorption of light and microbial consumption of O2 during DOC mineralization. Although DOC contributions to streams are distributed across the landscape in the shallow subsurface, many studies have demonstrated area-outsized contributions from riparian zones with high biological productivity and low subsurface O2 concentrations. In the East River, CO, a high-elevation watershed located in the central Rocky Mountains, initial observations show that DOC concentrations of two tributaries, Rock Creek and Gothic Creek, are elevated by 3-10 times compared to concentrations in the main East River and its other tributaries. These elevated concentrations are qualitatively linked to the unique presence of large wetlands in the headwaters of Rock and Gothic creeks, which due to potential anoxic conditions, experience reduced rates of organic matter decomposition and serve as an elevated source of DOC. In this study we quantify the cycling of organic matter in these alpine wetlands and their area-outsized contributions to East River DOC fluxes. We present concentration profiles of DOC along stream reaches and along subsurface flowpaths that span the transition from hillslope to wetland coupled with high-resolution mapping of chronically-saturated zones and calculate area-weighted fluxes of DOC from wetlands to Rock and Gothic creeks at multiple times through the 2016 growing season. Additionally, soil and groundwater DOC fluxes are compared with depth-resolved organic carbon content from soil cores, substrate quality (C:N), and soil surface CO2 fluxes to evaluate organic carbon budgets in the hillslope and wetland areas feeding Rock Creek. The characterization of these hotspots of DOC generation and transport in the East River is vital to the ability to predict nutrient cycling changes into the future.

Electrochemical Impedance Imaging via the Distribution of Diffusion Times

NASA Astrophysics Data System (ADS)

Song, Juhyun; Bazant, Martin Z.

2018-03-01

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

Solid-state selective (13)C excitation and spin diffusion NMR to resolve spatial dimensions in plant cell walls.

PubMed

Foston, Marcus; Katahira, Rui; Gjersing, Erica; Davis, Mark F; Ragauskas, Arthur J

2012-02-15

The average spatial dimensions between major biopolymers within the plant cell wall can be resolved using a solid-state NMR technique referred to as a (13)C cross-polarization (CP) SELDOM (selectively by destruction of magnetization) with a mixing time delay for spin diffusion. Selective excitation of specific aromatic lignin carbons indicates that lignin is in close proximity to hemicellulose followed by amorphous and finally crystalline cellulose. (13)C spin diffusion time constants (T(SD)) were extracted using a two-site spin diffusion theory developed for (13)C nuclei under magic angle spinning (MAS) conditions. These time constants were then used to calculate an average lower-limit spin diffusion length between chemical groups within the plant cell wall. The results on untreated (13)C enriched corn stover stem reveal that the lignin carbons are, on average, located at distances ∼0.7-2.0 nm from the carbons in hemicellulose and cellulose, whereas the pretreated material had larger separations.

The Study of Microbial Environmental Processes Related to the Natural Attenuation of Uranium at the Rifle Site using Systems-level Biology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Methe, Barbara; Lipton, Mary; Mahadevan, Krishna

Microbes exist in communities in the environment where they are fundamental drivers of global carbon, nutrient and metal cycles. In subsurface environments, they possess significant metabolic potential to affect these global cycles including the transformation of radionuclides. This study examined the influence of microbial communities in sediment zones undergoing biogeochemical cycling of carbon, nutrients and metals including natural attenuation of uranium. This study examined the relationship of both the microbiota (taxonomy) and their metabolic capacity (function) in driving carbon, nutrient and metal cycles including uranium reduction at the Department of Energy (DOE) Rifle Integrated Field Research Challenge (RIFRC). Objectives ofmore » this project were: 1) to apply systems-level biology through application of ‘metaomics’ approaches (collective analyses of whole microbial community DNA, RNA and protein) to the study of microbial environmental processes and their relationship to C, N and metals including the influence of microbial communities on uranium contaminant mobility in subsurface settings undergoing natural attenuation, 2) improve methodologies for data generation using metaomics (collectively metagenomics, metatranscriptomics and proteomics) technologies and analysis and interpretation of that data and 3) use the data generated from these studies towards microbial community-scale metabolic modeling. The strategy for examining these subsurface microbial communities was to generate sequence reads from microbial community DNA (metagenomics or whole genome shotgun sequencing (WGS)) and RNA (metatranscriptomcs or RNAseq) and protein information using proteomics. Results were analyzed independently and through computational modeling. Overall, the community model generated information on the microbial community structure that was observed using metaomic approaches at RIFRC sites and thus provides an important framework for continued community modeling development. The model as created is capable of predicting the response of the community structure in changing environments such as anoxic/oxic conditions or limitations by carbon or nutrients. The ability to more accurately model these responses is critical to understanding carbon and energy flows in an ecosystem is critical towards improving our ability to make predictions that can be used to design more efficient remediation and management strategies, and better understand the implications of environmental perturbations on these ecosystems.« less

Framework for the assessment of interaction between CO2 geological storage and other sedimentary basin resources.

PubMed

Michael, K; Whittaker, S; Varma, S; Bekele, E; Langhi, L; Hodgkinson, J; Harris, B

2016-02-01

Sedimentary basins around the world considered suitable for carbon storage usually contain other natural resources such as petroleum, coal, geothermal energy and groundwater. Storing carbon dioxide in geological formations in the basins adds to the competition for access to the subsurface and the use of pore space where other resource-based industries also operate. Managing potential impacts that industrial-scale injection of carbon dioxide may have on other resource development must be focused to prevent potential conflicts and enhance synergies where possible. Such a sustainable coexistence of various resource developments can be accomplished by implementing a Framework for Basin Resource Management strategy (FBRM). The FBRM strategy utilizes the concept of an Area of Review (AOR) for guiding development and regulation of CO2 geological storage projects and for assessing their potential impact on other resources. The AOR is determined by the expected physical distribution of the CO2 plume in the subsurface and the modelled extent of reservoir pressure increase resulting from the injection of the CO2. This information is used to define the region to be characterised and monitored for a CO2 injection project. The geological characterisation and risk- and performance-based monitoring will be most comprehensive within the region of the reservoir containing the carbon dioxide plume and should consider geological features and wells continuously above the plume through to its surface projection; this region defines where increases in reservoir pressure will be greatest and where potential for unplanned migration of carbon dioxide is highest. Beyond the expanse of the carbon dioxide plume, geological characterisation and monitoring should focus only on identified features that could be a potential migration conduit for either formation water or carbon dioxide.

Elemental sulfur in Eddy County, New Mexico

USGS Publications Warehouse

Hinds, Jim S.; Cunningham, Richard R.

1970-01-01

Sulfur has been reported in Eddy County, N. Mex., in rocks ranging from Silurian to Holocene in age at depths of 0-15,020 feet. Targets of present exploration are Permian formations in the Delaware Basin and northwest shelf areas at depths of less than 4,000 feet. Most of the reported sulfur occurrences in the shelf area are in the 'Abo' (as used by some subsurface geologists), Yeso, and San Andres Formations and the Artesia Group. Sulfur deposition in the dense dolomites of the 'Abo,' Yeso, and San Andres Formations is attributed to the reduction of ionic sulfate by hydrogen sulfide in formation waters in zones of preexisting porosity and permeability. A similar origin accounts for most of the sulfur deposits in the formations of the Artesia Group, but some of the sulfur in these formations may have originated in place through the alteration of anhydrite to carbonate and sulfur by the metabolic processes of bacteria in the presence of hydrocarbons. Exploration in the Delaware Basin area is directed primarily toward the Castile Formation. Sulfur deposits in the Castile Formation are found in irregular masses of cavernous brecciated secondary carbonate rock enveloped by impermeable anhydrite. The carbonate masses, or 'castiles,' probably originated as collapse features resulting from subsurface solution and upward stopping. Formation of carbonate rock and sulfur in the castiles is attributed to the reduction of brecciated anhydrite by bacteria and hydrocarbons in the same process ascribed to the formation of carbonate and sulfur in the caprocks of salt domes.

High virus-to-cell ratios indicate ongoing production of viruses in deep subsurface sediments.

PubMed

Engelhardt, Tim; Kallmeyer, Jens; Cypionka, Heribert; Engelen, Bert

2014-07-01

Marine sediments cover two-thirds of our planet and harbor huge numbers of living prokaryotes. Long-term survival of indigenous microorganisms within the deep subsurface is still enigmatic, as sources of organic carbon are vanishingly small. To better understand controlling factors of microbial life, we have analyzed viral abundance within a comprehensive set of globally distributed subsurface sediments. Phages were detected by electron microscopy in deep (320 m below seafloor), ancient (∼14 Ma old) and the most oligotrophic subsurface sediments of the world's oceans (South Pacific Gyre (SPG)). The numbers of viruses (10(4)-10(9) cm(-3), counted by epifluorescence microscopy) generally decreased with sediment depth, but always exceeded the total cell counts. The enormous numbers of viruses indicate their impact as a controlling factor for prokaryotic mortality in the marine deep biosphere. The virus-to-cell ratios increased in deeper and more oligotrophic layers, exhibiting values of up to 225 in the deep subsurface of the SPG. High numbers of phages might be due to absorption onto the sediment matrix and a diminished degradation by exoenzymes. However, even in the oldest sediments, microbial communities are capable of maintaining viral populations, indicating an ongoing viral production and thus, viruses provide an independent indicator for microbial life in the marine deep biosphere.

Contaminated environments in the subsurface and bioremediation: organic contaminants.

PubMed

Holliger, C; Gaspard, S; Glod, G; Heijman, C; Schumacher, W; Schwarzenbach, R P; Vazquez, F

1997-07-01

Due to leakages, spills, improper disposal and accidents during transport, organic compounds have become subsurface contaminants that threaten important drinking water resources. One strategy to remediate such polluted subsurface environments is to make use of the degradative capacity of bacteria. It is often sufficient to supply the subsurface with nutrients such as nitrogen and phosphorus, and aerobic treatments are still dominating. However, anaerobic processes have advantages such as low biomass production and good electron acceptor availability, and they are sometimes the only possible solution. This review will focus on three important groups of environmental organic contaminants: hydrocarbons, chlorinated and nitroaromatic compounds. Whereas hydrocarbons are oxidized and completely mineralized under anaerobic conditions in the presence of electron acceptors such as nitrate, iron, sulfate and carbon dioxide, chlorinated and nitroaromatic compounds are reductively transformed. For the aerobic often persistent polychlorinated compounds, reductive dechlorination leads to harmless products or to compounds that are aerobically degradable. The nitroaromatic compounds are first reductively transformed to the corresponding amines and can subsequently be bound to the humic fraction in an aerobic process. Such new findings and developments give hope that in the near future contaminated aquifers can efficiently be remediated, a prerequisite for a sustainable use of the precious-subsurface drinking water resources.

Treatment of boundary conditions in through-diffusion: A case study of (85)Sr(2+) diffusion in compacted illite.

PubMed

Glaus, M A; Aertsens, M; Maes, N; Van Laer, L; Van Loon, L R

2015-01-01

Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of (85)Sr(2+) tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment. Copyright © 2015 Elsevier B.V. All rights reserved.

Denitrifying bioreactors for nitrate removal from tile drained cropland

USDA-ARS?s Scientific Manuscript database

Denitrification bioreactors are a promising technology for mitigation of nitrate-nitrogen (NO3-N) losses in subsurface drainage water. Bioreactors are constructed with carbon substrates, typically wood chips, to provide a substrate for denitrifying microorganisms. Researchers in Iowa found that for ...

Low Elevation Old Channel Features of the Willamette River Floodplain Support High Subsurface Denitrification Rates

EPA Science Inventory

Background/Question/Methods: Large river floodplains are poor nitrate pollution buffers when polluted groundwater moves beneath biogeochemically retentive zones prior to entering the main channel. However, in floodplain regions with extensive backwaters and organic carbon acc...

Asymmetric Signature of Glacial Antarctic Intermediate Water in the Central South Pacific

NASA Astrophysics Data System (ADS)

Tapia, R.; Nuernberg, D.; Ho, S. L.; Lamy, F.; Ullermann, J.; Gersonde, R.; Tiedemann, R.

2017-12-01

Southern Ocean Intermediate Waters (SOIWs) play a key role in modulating the global climate on glacial-interglacial time scales as they connect the Southern Ocean and the tropics. Despite their importance, the past evolution of the SOIWs in the central South Pacific is largely unknown due to a dearth of sedimentary archives. Here we compare Mg/Ca-temperature, stable carbon and oxygen isotope records from surface-dwelling (G. bulloides) and deep-dwelling (G. inflata) planktic foraminifera at site PS75/059-2 (54°12.9' S, 125°25.53' W; recovery 13.98 m; 3.613 m water depth), located north of the modern Subantarctic Front. Our study focuses on the temperature and salinity variability controlled by SOIWs, which were subducted at the Subantarctic Front during the Last Glacial Maximum (LGM; 29-17ka BP) and the Penultimate Glacial Maximum (PGM; 180-150ka BP). During both glacial periods conditions at the subsurface ocean were colder and fresher relative to the Holocene (<10ka) suggesting an enhanced presence of SOIWs. In spite of the comparable subsurface cooling during both glacial, the subsurface ocean during the PGM was saltier and 0.35‰ more depleted in δ13C in comparison to the LGM. Interestingly, the mean δ13C value of the PGM is comparable to the Carbon Isotope Minimum Events, which might suggests a larger contribution of "old" low δ13C deep waters to the study site during the PGM. A Latitudinal comparison of subsurface proxies suggests glacial asymmetries in the advection of SOIWs into the central Pacific, plausibly related to glacial changes in the convection depth of SOIWs at the South Antarctic Front area rather than changes in production of the SOIWs.

Microbial Community Shifts due to Hydrofracking: Observations from Field-Scale Observations and Laboratory-Scale Incubations

NASA Astrophysics Data System (ADS)

Mouser, P. J.; Ansari, M.; Hartsock, A.; Lui, S.; Lenhart, J.

2012-12-01

The use of fluids containing chemicals and variable water sources during the hydrofracking of unconventional shale is the source of considerable controversy due to perceived risks from altered subsurface biogeochemistry and the potential for contaminating potable water supplies. Rapid shifts in subsurface biogeochemistry are often driven by available macronutrients combined with the abundance and metabolic condition of the subsurface microbiota. While the depth that fracturing occurs in the Marcellus formation is reasonably deep to pose little risk to groundwater supplies, no published studies have systematically characterized the indigenous microbial population and how this community is altered through variable fluid management practices (e.g., chemical composition, source water makeup). In addition, limited information is available on how shallower microbial communities and geochemical conditions might be affected through the accidental release of these fluids to groundwater aquifers. Our measurements indicate field-applied and laboratory-generated fracking fluids contain levels of organic carbon greater than 300 mg/l and nitrogen concentrations greater than 80 mg/l that may differentially stimulate microbial growth in subsurface formations. In contrast to certain inorganic constituents (e.g., chloride) which increase in concentration through the flowback period; dissolved organic carbon levels decrease with time after the fracturing process through multiple attenuation processes (dilution, sorption, microbial utilization). Pyrosequencing data of the 16S rRNA gene indicate a shift from a more diverse source water microbial community to a less diverse community typical of a brine formation as time after fracturing increases. The introduction of varying percentages of a laboratory-generated fracking fluid to microcosm bottles containing groundwater and aquifer media stimulated biogeochemical changes similar to the introduction of landfill leachate, another wastewater containing elevated carbon, nitrogen, and complex organic constituents (e.g., decreased redox conditions, stepwise utilization of available terminal electron acceptors, enriched Fe(II) and sulfide concentrations). These research findings are important for understanding how fluids used during shale energy development may alter in situ microbial communities and provide insight into processes that attenuate the migration of these fluids in shallow aquifers and deep shale formations.

Microbiome composition and geochemical characteristics of deep subsurface high-pressure environment, Pyhäsalmi mine Finland

PubMed Central

Miettinen, Hanna; Kietäväinen, Riikka; Sohlberg, Elina; Numminen, Mikko; Ahonen, Lasse; Itävaara, Merja

2015-01-01

Pyhäsalmi mine in central Finland provides an excellent opportunity to study microbial and geochemical processes in a deep subsurface crystalline rock environment through near-vertical drill holes that reach to a depth of more than two kilometers below the surface. However, microbial sampling was challenging in this high-pressure environment. Nucleic acid yields obtained were extremely low when compared to the cell counts detected (1.4 × 104 cells mL−1) in water. The water for nucleic acid analysis went through high decompression (60–130 bar) during sampling, whereas water samples for detection of cell counts by microscopy could be collected with slow decompression. No clear cells could be identified in water that went through high decompression. The high-pressure decompression may have damaged part of the cells and the nucleic acids escaped through the filter. The microbial diversity was analyzed from two drill holes by pyrosequencing amplicons of the bacterial and archaeal 16S rRNA genes and from the fungal ITS regions from both DNA and RNA fractions. The identified prokaryotic diversity was low, dominated by Firmicute, Beta- and Gammaproteobacteria species that are common in deep subsurface environments. The archaeal diversity consisted mainly of Methanobacteriales. Ascomycota dominated the fungal diversity and fungi were discovered to be active and to produce ribosomes in the deep oligotrophic biosphere. The deep fluids from the Pyhäsalmi mine shared several features with other deep Precambrian continental subsurface environments including saline, Ca-dominated water and stable isotope compositions positioning left from the meteoric water line. The dissolved gas phase was dominated by nitrogen but the gas composition clearly differed from that of atmospheric air. Despite carbon-poor conditions indicated by the lack of carbon-rich fracture fillings and only minor amounts of dissolved carbon detected in formation waters, some methane was found in the drill holes. No dramatic differences in gas compositions were observed between different gas sampling methods tested. For simple characterization of gas composition the most convenient way to collect samples is from free flowing fluid. However, compared to a pressurized method a relative decrease in the least soluble gases may appear. PMID:26579109

Sequential geophysical and flow inversion to characterize fracture networks in subsurface systems

DOE PAGES

Mudunuru, Maruti Kumar; Karra, Satish; Makedonska, Nataliia; ...

2017-09-05

Subsurface applications, including geothermal, geological carbon sequestration, and oil and gas, typically involve maximizing either the extraction of energy or the storage of fluids. Fractures form the main pathways for flow in these systems, and locating these fractures is critical for predicting flow. However, fracture characterization is a highly uncertain process, and data from multiple sources, such as flow and geophysical are needed to reduce this uncertainty. We present a nonintrusive, sequential inversion framework for integrating data from geophysical and flow sources to constrain fracture networks in the subsurface. In this framework, we first estimate bounds on the statistics formore » the fracture orientations using microseismic data. These bounds are estimated through a combination of a focal mechanism (physics-based approach) and clustering analysis (statistical approach) of seismic data. Then, the fracture lengths are constrained using flow data. In conclusion, the efficacy of this inversion is demonstrated through a representative example.« less

Sequential geophysical and flow inversion to characterize fracture networks in subsurface systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mudunuru, Maruti Kumar; Karra, Satish; Makedonska, Nataliia

Subsurface applications, including geothermal, geological carbon sequestration, and oil and gas, typically involve maximizing either the extraction of energy or the storage of fluids. Fractures form the main pathways for flow in these systems, and locating these fractures is critical for predicting flow. However, fracture characterization is a highly uncertain process, and data from multiple sources, such as flow and geophysical are needed to reduce this uncertainty. We present a nonintrusive, sequential inversion framework for integrating data from geophysical and flow sources to constrain fracture networks in the subsurface. In this framework, we first estimate bounds on the statistics formore » the fracture orientations using microseismic data. These bounds are estimated through a combination of a focal mechanism (physics-based approach) and clustering analysis (statistical approach) of seismic data. Then, the fracture lengths are constrained using flow data. In conclusion, the efficacy of this inversion is demonstrated through a representative example.« less

Trends and future challenges in sampling the deep terrestrial biosphere.

PubMed

Wilkins, Michael J; Daly, Rebecca A; Mouser, Paula J; Trexler, Ryan; Sharma, Shihka; Cole, David R; Wrighton, Kelly C; Biddle, Jennifer F; Denis, Elizabeth H; Fredrickson, Jim K; Kieft, Thomas L; Onstott, Tullis C; Peterson, Lee; Pfiffner, Susan M; Phelps, Tommy J; Schrenk, Matthew O

2014-01-01

Research in the deep terrestrial biosphere is driven by interest in novel biodiversity and metabolisms, biogeochemical cycling, and the impact of human activities on this ecosystem. As this interest continues to grow, it is important to ensure that when subsurface investigations are proposed, materials recovered from the subsurface are sampled and preserved in an appropriate manner to limit contamination and ensure preservation of accurate microbial, geochemical, and mineralogical signatures. On February 20th, 2014, a workshop on "Trends and Future Challenges in Sampling The Deep Subsurface" was coordinated in Columbus, Ohio by The Ohio State University and West Virginia University faculty, and sponsored by The Ohio State University and the Sloan Foundation's Deep Carbon Observatory. The workshop aims were to identify and develop best practices for the collection, preservation, and analysis of terrestrial deep rock samples. This document summarizes the information shared during this workshop.

Stable, geochemically mediated biospheres in the Deep Mine Microbial Observatory, SD, USA

NASA Astrophysics Data System (ADS)

Osburn, M. R.; Casar, C. P.; Kruger, B.; Flynn, T. M.

2017-12-01

The terrestrial subsurface is a vast reservoir of life, hosting diverse microbial ecosystems with varying levels of connectivity to surface inputs. Understanding long term ecosystem dynamics within the subsurface biosphere is very challenging due to limitations in accessibility, sample availability, and slow microbial growth rates. The establishment of the Deep Mine Microbial Observatory (DeMMO) at the Sanford Underground Research Facility, SD, USA has allowed for bimonthly sampling for nearly two years at six sites spanning 250 to 1500 m below the surface. Here we present a time-resolved analysis of the geomicrobiology of the six DeMMO sites, which have been created from legacy mine boreholes modified to allow for controlled sampling. Our interdisciplinary approach includes analysis of passively draining fracture fluid for aqueous and gas geochemistry, DNA sequencing, microscopy, and isotopic measurements of organic and inorganic substrates. Fluid geochemistry varies significantly between sites, but is relatively stable over time for a given site, even through significant external perturbations such as drilling and installation of permanent sampling devices into the boreholes. The fluid-hosted microbial diversity follows these trends, with consistent populations present at each site through time, even through drilling events. For instance, the shallowest site (DeMMO 1) consistently hosts >30% uncharacterized phyla and >25% Omnitrophica whereas the deepest site (DeMMO 6) is dominated by Firmicutes and Bacterioidetes. Microbial diversity appears to respond to the availability of energy sources such as organic carbon, sulfate, sulfide, hydrogen, and iron. Carbon isotopic measurements reveal closed system behavior with significant recycling of organic carbon into the DIC pool. Together these observations suggest DeMMO hosts isolated subsurface microbial populations adapted to local geochemistry that are stable on yearlong timescales.

Spectral distribution of UV range diffuse reflectivity for Si+ ion implanted polymers

NASA Astrophysics Data System (ADS)

Balabanov, S.; Tsvetkova, T.; Borisova, E.; Avramov, L.; Bischoff, L.

2008-05-01

The analysis of the UV range spectral characteristics can supply additional information on the formed sub-surface buried layer with implanted dopants. The near-surface layer (50÷150 nm) of bulk polymer samples have been implanted with silicon (Si+) ions at low energies (E = 30 keV) and a wide range of ion doses (D = 1.1013 ÷ 1, 2.1017 cm-2). The studied polymer materials were: ultra-high-molecular-weight polyethylene (UHMWPE), poly-methyl-metacrylate (PMMA) and poly-tetra-fluor-ethylene (PTFE). The diffuse optical reflectivity spectra Rd = f(λ) of the ion implanted samples have been measured in the UV range (λ = 220÷350 nm). In this paper the dose dependences of the size and sign of the diffuse optical reflectivity changes λRd = f(D) have been analysed.

Vapor-phase exchange of perchloroethene between soil and plants

USGS Publications Warehouse

Struckhoff, G.C.; Burken, J.G.; Schumacher, J.G.

2005-01-01

Tree core concentrations of tetrachloroethylene (perchloroethene, PCE) at the Riverfront Superfund Site in New Haven, MO, were found to mimic the profile of soil phase concentrations. The observed soil-tree core relationship was stronger than that of groundwater PCE to tree core concentrations at the same site. Earlier research has shown a direct, linear relationship between tree core and groundwater concentrations of chlorinated solvents and other organics. Laboratory-scale experiments were performed to elucidate this phenomenon, including determining partitioning coefficients of PCE between plant tissues and air and between plant tissues and water, measured to be 8.1 and 49 L/kg, respectively. The direct relationship of soil to tree core PCE concentrations was hypothesized to be caused by diffusion between tree roots and the soil vapor phase in the subsurface. The central findings of this research are discovering the importance of subsurface vapor-phase transfer for VOCs and uncovering a direct relationship between soil vapor-phase chlorinated solvents and uptake rates that impact contaminant translocation from the subsurface and transfer into the atmosphere. ?? 2005 American Chemical Society.

Assessment of Mitigation Systems on Vapor Intrusion ...

EPA Pesticide Factsheets

Vapor intrusion is the migration of subsurface vapors, including radon and volatile organic compounds (VOCs), in soil gas from the subsurface to indoor air. Vapor intrusion happens because there are pressure and concentration differentials between indoor air and soil gas. Indoor environments are often negatively pressurized with respect to outdoor air and soil gas (for example, from exhaust fans or the stack effect), and this pressure difference allows soil gas containing subsurface vapors to flow into indoor air through advection. In addition, concentration differentials cause VOCs and radon to migrate from areas of higher to lower concentrations through diffusion, which is another cause of vapor intrusion. Current practice for evaluating the vapor intrusion pathway involves a multiple line of evidence approach based on direct measurements in groundwater, external soil gas, subslab soil gas, and/or indoor air. No single line of evidence is considered definitive, and direct measurements of vapor intrusion can be costly, especially where significant spatial and temporal variability require repeated measurements at multiple locations to accurately assess the chronic risks of long-term exposure to volatile organic compounds (VOCs) like chloroform, perchloroethylene (PCE), and trichloroethylene (TCE).

Wells for In Situ Extraction of Volatiles from Regolith (WIEVR)

NASA Technical Reports Server (NTRS)

Walton, Otis R.

2013-01-01

A document discusses WIEVRs, a means to extract water ice more efficiently than previous approaches. This water may exist in subsurface deposits on the Moon, in many NEOs (Near- Earth Objects), and on Mars. The WIEVR approach utilizes heat from the Sun to vaporize subsurface ice; the water (or other volatile) vapor is transported to a surface collection vessel where it is condensed (and collected). The method does not involve mining and extracting regolith before removing the frozen volatiles, so it uses less energy and is less costly than approaches that require mining of regolith. The only drilling required for establishing the WIEVR collection/recovery system is a well-bore drill hole. In its simplest form, the WIEVRs will function without pumps, compressors, or other gas-moving equipment, relying instead on diffusive transport and thermally induced convection of the vaporized volatiles for transport to the collection location(s). These volatile extraction wells could represent a significant advance in extraction efficiency for recovery of frozen volatiles in subsurface deposits on the Moon, Mars, or other extraterrestrial bodies.

Liquid Water in the Extremely Shallow Martian Subsurface

NASA Technical Reports Server (NTRS)

Pavlov, A.; Shivak, J. N.

2012-01-01

Availability of liquid water is one of the major constraints for the potential Martian biosphere. Although liquid water is unstable on the surface of Mars due to low atmospheric pressures, it has been suggested that liquid films of water could be present in the Martian soil. Here we explored a possibility of the liquid water formation in the extremely shallow (1-3 cm) subsurface layer under low atmospheric pressures (0.1-10 mbar) and low ("Martian") surface temperatures (approx.-50 C-0 C). We used a new Goddard Martian simulation chamber to demonstrate that even in the clean frozen soil with temperatures as low as -25C the amount of mobile water can reach several percents. We also showed that during brief periods of simulated daylight warming the shallow subsurface ice sublimates, the water vapor diffuses through porous surface layer of soil temporarily producing supersaturated conditions in the soil, which leads to the formation of additional liquid water. Our results suggest that despite cold temperatures and low atmospheric pressures, Martian soil just several cm below the surface can be habitable.

Optimal doping control of magnetic semiconductors via subsurfactant epitaxy.

PubMed

Zeng, Changgan; Zhang, Zhenyu; van Benthem, Klaus; Chisholm, Matthew F; Weitering, Hanno H

2008-02-15

"Subsurfactant epitaxy" is established as a conceptually new approach for introducing manganese as a magnetic dopant into germanium. A kinetic pathway is devised in which the subsurface interstitial sites on Ge(100) are first selectively populated with Mn, while lateral diffusion and clustering on or underneath the surface are effectively suppressed. Subsequent Ge deposition as a capping layer produces a novel surfactantlike phenomenon as the interstitial Mn atoms float towards newly defined subsurface sites at the growth front. Furthermore, the Mn atoms that failed to float upwards are uniformly distributed within the Ge capping layer. The resulting doping levels of order 0.25 at. % would normally be considered too low for ferromagnetic ordering, but the Curie temperature exceeds room temperature by a comfortable margin. Subsurfactant epitaxy thus enables superior dopant control in magnetic semiconductors.

Large depth high-precision FMCW tomography using a distributed feedback laser array

NASA Astrophysics Data System (ADS)

DiLazaro, Thomas; Nehmetallah, George

2018-02-01

Swept-source optical coherence tomography (SS-OCT) has been widely employed in the medical industry for the high resolution imaging of subsurface biological structures. SS-OCT typically exhibits axial resolutions on the order of tens of microns at speeds of hundreds of kilohertz. Using the same coherent heterodyne detection technique, frequency modulated continuous wave (FMCW) ladar has been used for highly precise ranging for distances up to kilometers. Distributed feedback lasers (DFBs) have been used as a simple and inexpensive source for FMCW ranging. Here, we use a bandwidth-combined DFB array for sub-surface volume imaging at a 27 μm axial resolution over meters of distance. 2D and 3D tomographic images of several semi-transparent and diffuse objects at distances up to 10 m will be presented.

Sulfur/Carbonate Springs and Life in Glacial Ice

NASA Technical Reports Server (NTRS)

Allen, Carlton; Grasby, Stephen; Longazo, Teresa

2001-01-01

Ice in the near subsurface of Mars apparently discharges liquid water on occasion. Cold-tolerant microorganisms are known to exist within terrestrial glacial ice, and may be brought to the surface as a result of melting events. We are investigating a set of springs that deposit sulfur and carbonate minerals, as well as evidence of microbial life, on the surface of a glacier in the Canadian arctic. Additional information is contained in the original extended abstract.

Entrainment and mixing of shelf/slope waters in the near-surface Gulf Stream

NASA Astrophysics Data System (ADS)

Lillibridge, J. L., III; Hitchcock, G.; Rossby, T.; Lessard, E.; Mork, M.; Golmen, L.

1990-08-01

An interdisciplinary study of the entrainment of shelf and slope waters in the Gulf Stream front was undertaken in October 1985 northeast of Cape Hatteras. Fifteen hydrographic transects of the Gulf Stream front and of the shelf water intrusion known as Ford water were completed in 2 1/2 days with a towed undulating profiler, the SeaSoar, equipped with a conductivity-temperature-depth probe and a fluorometer. Upstream sections within 50 km of the shelf break show entrainment of surface and subsurface waters along the northern edge of the high-velocity Gulf Stream. The low-salinity core, first observed at 70 m, is subducted to >100 m. The subsurface Ford water is also at a maximum in chlorophyll, fluorescence, and dissolved oxygen and contains a distinct diatom assemblage of nearshore species. Productivity rates in the Ford water may be equivalent to those in slope waters. Expendable current profilers yield an estimated transport for subsurface shelf waters of 1 to 5×105 m3 s-1 and indicate that vertical shear at the depth of maximum static stability is typically 2×10-2 s-1. A bulk Richardson number is estimated over vertical scales of several meters by combining SeaSoar density profiles with velocity shear from concurrent expendable current profiler deployments. The minimum values are generally >1, and only infrequently are they at or below the 0.25 threshold for shear instability. The presence of double-diffusive processes around the low-salinity core of Ford water is indicated by elevated conductivity Cox numbers. The stability parameter "Turner angle" shows that low-salinity Ford water and its associated T-S property front are sites of double-diffusive mixing, given general agreement between the distributions of Turner angle and Cox number. We conclude that double-diffusive processes are more important than shear flow instability in governing cross-isopycnal mixing. However, downstream transit times are so swift that no measurable change or decay occurs in the Ford water. This explains the occurrence of distinct shelf water phytoplankton species within the low-salinity waters downstream of Cape Hatteras.

Multi-Sensor Mapping of Diffuse Degassing of C-O-H Compounds in Terrestrial Hydrothermal Systems

NASA Astrophysics Data System (ADS)

Schwandner, F. M.; Shock, E. L.

2004-12-01

In-situ single-sensor detection and mapping of diffuse degassing phenomena in hydrothermal and volcanic areas can be used to elucidate subsurface tectonic structures, assess emission rates, and to monitor emission variability (Williams 1985; Chiodini et al. 1996, Werner et al., 2003). More than one technique has been deployed to measure several gas species simultaneously (e.g., Crenshaw et al. 1982), and correlations of one gas species (usually CO2) with physical parameters like heat flux (Brombach et al., 2001), or with one other gas species (Rn, He) have been demonstrated (Barberi & Carapezza 1994; Williams-Jones et al., 2000). Recently, correlations of multiple gas species with one another were reported (Schwandner et al., 2004), leading to the possibility of quantitative mapping of subsurface hydrothermal chemical processes by simultaneous measurement of reaction partners and products that continuously and diffusely degas. In the present study, we joined a fully-quantitative multi-sensor instrument (Draeger Multiwarn II) to a modified accumulation-chamber sensing method (Chiodini et al., 1996) and measured diffuse degassing of CH4, H2, CO2, CO, and H2S. In this approach, each batch of gas that is recirculated through the detector is simultaneously analyzed by all sensors. To test this approach we chose two magmatically influenced, hydrothermally active areas at Yellowstone National Park (USA): Sylvan Springs and the Greater Obsidian Pool Area. The area near Obsidian Pool was previously studied during a diffuse CO2 degassing campaign (Werner & Brantley, 2004). Preliminary results show that elevated reduced gas emissions appear to be most prominent near hydrothermal pools, whereas CO2-dominated degassing anomalies highlight subsurface tectonic structures. This multimodal distribution allows us to distinguish deep degassing sources (CO2 anomalies) from shallow localized hydrothermal processes (reduced gas anomalies). The results permit us to positively identify and partially map a previously-inferred active lineament in the Obsidian Pool area. In addition, reduced gas data are yielding areal ratio distributions of CO/CO2, H2/CH4, and CO/CH4, that may be indicative of reactions such as the catalytic hydrogenation of CO2 (Sabatier-Process) and of CO (Fischer-Tropsch-Process) within the shallow hydrothermal system. Barberi & Carapezza (1994). Bull. Volcanol. 56(5): 335-342. Brombach, et al. (2001). Geophys. Res. Lett. 28(1): 69-72. Crenshaw et al. (1982). Nature 300: 345-346. Chiodini et al. (1996). Bull. Volcanol. 58(1): 41-50. Schwandner et al. (2004). JGR D 109: D04301, doi:10.1029/2003JD003890. Werner & Brantley (2004) JGR B 105: 10,831-10,846. Werner et al. (2003). Earth Planet. Sci. Lett. 210: 561-577. Williams (1985). Science 229(4713): 551-553. Williams-Jones et al. (2000). Bull. Volcanol. 62: 130-142.

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1993-01-01

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Electrochemical Impedance Imaging via the Distribution of Diffusion Times.

PubMed

Song, Juhyun; Bazant, Martin Z

2018-03-16

We develop a mathematical framework to analyze electrochemical impedance spectra in terms of a distribution of diffusion times (DDT) for a parallel array of random finite-length Warburg (diffusion) or Gerischer (reaction-diffusion) circuit elements. A robust DDT inversion method is presented based on complex nonlinear least squares regression with Tikhonov regularization and illustrated for three cases of nanostructured electrodes for energy conversion: (i) a carbon nanotube supercapacitor, (ii) a silicon nanowire Li-ion battery, and (iii) a porous-carbon vanadium flow battery. The results demonstrate the feasibility of nondestructive "impedance imaging" to infer microstructural statistics of random, heterogeneous materials.

Effect of porous structure of catalyst layer on effective oxygen diffusion coefficient in polymer electrolyte fuel cell

NASA Astrophysics Data System (ADS)

Inoue, Gen; Kawase, Motoaki

2016-09-01

It is important to reduce the oxygen diffusion resistance through PEFC porous electrode, because it is the key to reduce the PEFC cost. However, the gas diffusion coefficient of CL is lower than MPL in spite of framework consisted of same carbon blacks. In this study, in order to understand the reasons of the lower gas diffusion performance of CL, the relationship between a carbon black agglomerate structure and ionomer adhesion condition is evaluated by a numerical analysis with an actual reconstructed structure and a simulated structure. As a result, the gas diffusion property of CL strongly depends on the ionomer adhesion shape. In the case of adhesion shape with the same curvature of ionomer interface, each pore can not be connected enough. So the pore tortuosity increases. Moreover, in the case of existence of inefficient large pores formed by carbon black agglomerate and ununiformly coated ionomer, the gas diffusion performance decrease rapidly. As the measurement values in actual CL are almost equal to that with model structure with inefficient large pores. These characteristics can be confirmed by actual cross-section image obtained by FIB-SEM.

New approaches in the indirect quantification of thermal rock properties in sedimentary basins: the well-log perspective

NASA Astrophysics Data System (ADS)

Fuchs, Sven; Balling, Niels; Förster, Andrea

2016-04-01

Numerical temperature models generated for geodynamic studies as well as for geothermal energy solutions heavily depend on rock thermal properties. Best practice for the determination of those parameters is the measurement of rock samples in the laboratory. Given the necessity to enlarge databases of subsurface rock parameters beyond drill core measurements an approach for the indirect determination of these parameters is developed, for rocks as well a for geological formations. We present new and universally applicable prediction equations for thermal conductivity, thermal diffusivity and specific heat capacity in sedimentary rocks derived from data provided by standard geophysical well logs. The approach is based on a data set of synthetic sedimentary rocks (clastic rocks, carbonates and evaporates) composed of mineral assemblages with variable contents of 15 major rock-forming minerals and porosities varying between 0 and 30%. Petrophysical properties are assigned to both the rock-forming minerals and the pore-filling fluids. Using multivariate statistics, relationships then were explored between each thermal property and well-logged petrophysical parameters (density, sonic interval transit time, hydrogen index, volume fraction of shale and photoelectric absorption index) on a regression sub set of data (70% of data) (Fuchs et al., 2015). Prediction quality was quantified on the remaining test sub set (30% of data). The combination of three to five well-log parameters results in predictions on the order of <15% for thermal conductivity and thermal diffusivity, and of <10% for specific heat capacity. Comparison of predicted and benchmark laboratory thermal conductivity from deep boreholes of the Norwegian-Danish Basin, the North German Basin, and the Molasse Basin results in 3 to 5% larger uncertainties with regard to the test data set. With regard to temperature models, the use of calculated TC borehole profiles approximate measured temperature logs with an error of <3°C along a 4 km deep profile. A benchmark comparison for thermal diffusivity and specific heat capacity is pending. Fuchs, Sven; Balling, Niels; Förster, Andrea (2015): Calculation of thermal conductivity, thermal diffusivity and specific heat capacity of sedimentary rocks using petrophysical well logs, Geophysical Journal International 203, 1977-2000, doi: 10.1093/gji/ggv403

CARBON AND SULFUR ACCUMULATION AND IRON MINERAL TRANSFORMATION IN PERMEABLE REACTIVE BARRIERS CONTAINING ZERO-VALENT IRON

EPA Science Inventory

Permeable reactive barrier technology is an in-situ approach for remediating groundwater contamination that combines subsurface fluid flow management with passive chemical treatment. Factors such as the buildup of mineral precipitates, buildup of microbial biomass (bio-fouling...

Optimization of denitrifying bioreactor performance with agricultural residue-based filter media

USDA-ARS?s Scientific Manuscript database

Denitrification bioreactors are a promising technology for mitigation of nitrate-nitrogen (NO3-N) losses in subsurface drainage water. Bioreactors are constructed with carbon substrates, typically wood chips, to provide a substrate for denitrifying microorganisms. Columns were packed with wood chips...

Using N-Limiting Growth Conditions to Remove Atrazine from Groundwater: Laboratory Studies.

USDA-ARS?s Scientific Manuscript database

Typically, respiratory redox reactions are the driving mechanism behind in situ bioremediations that use a carbon substrate. This is because electron (e-) donor availability generally restricts subsurface microbial activity. Thus, microbial growth and respiration can be greatly stimulated by the a...

Overall adsorption rate of metronidazole, dimetridazole and diatrizoate on activated carbons prepared from coffee residues and almond shells.

PubMed

Flores-Cano, J V; Sánchez-Polo, M; Messoud, J; Velo-Gala, I; Ocampo-Pérez, R; Rivera-Utrilla, J

2016-03-15

This study analyzed the overall adsorption rate of metronidazole, dimetridazole, and diatrizoate on activated carbons prepared from coffee residues and almond shells. It was also elucidated whether the overall adsorption rate was controlled by reaction on the adsorbent surface or by intraparticle diffusion. Experimental data of the pollutant concentration decay curves as a function of contact time were interpreted by kinetics (first- and second-order) and diffusion models, considering external mass transfer, surface and/or pore volume diffusion, and adsorption on an active site. The experimental data were better interpreted by a first-order than second-order kinetic model, and the first-order adsorption rate constant varied linearly with respect to the surface area and total pore volume of the adsorbents. According to the diffusion model, the overall adsorption rate is governed by intraparticle diffusion, and surface diffusion is the main mechanism controlling the intraparticle diffusion, representing >90% of total intraparticle diffusion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Reconstruction of the thermal environment evolution in urban areas from underground temperature distribution.

PubMed

Yamano, Makoto; Goto, Shusaku; Miyakoshi, Akinobu; Hamamoto, Hideki; Lubis, Rachmat Fajar; Monyrath, Vuthy; Taniguchi, Makoto

2009-04-15

It is possible to estimate the ground surface temperature (GST) history of the past several hundred years from temperature profiles measured in boreholes because the temporal variation in GST propagates into the subsurface by thermal diffusion. This "geothermal method" of reconstructing GST histories can be applied to studies of thermal environment evolution in urban areas, including the development of "heat islands." Temperatures in boreholes were logged at 102 sites in Bangkok, Jakarta, Taipei, Seoul and their surrounding areas in 2004 to 2007. The effects of recent surface warming can be recognized in the shapes of most of the obtained temperature profiles. The preliminary results of reconstruction of GST histories through inversion analysis show that GST increased significantly in the last century. Existing temperature profile data for the areas in and around Tokyo and Osaka can also be used to reconstruct GST histories. Because most of these cities are located on alluvial plains in relatively humid areas, it is necessary to use a model with groundwater flow and a layered subsurface structure for reconstruction analysis. Long-term records of subsurface temperatures at multiple depths may demonstrate how the GST variation propagates downward through formations. Time series data provide information on the mechanism of heat transfer (conduction or advection) and the thermal diffusivity. Long-term temperature monitoring has been carried out in a borehole located on the coast of Lake Biwa, Japan. Temperatures at 30 and 40 m below the ground surface were measured for 4 years and 2 years, respectively, with a resolution of 1 mK. The obtained records indicate steady increases at both depths with different rates, which is probably the result of some recent thermal event(s) near the surface. Borehole temperatures have also been monitored at selected sites in Bangkok, Jakarta, and Taiwan.

The distribution of ground ice on Mars

NASA Technical Reports Server (NTRS)

Mellon, M. T.; Jakosky, B. M.

1993-01-01

A wealth of geologic evidence indicates that subsurface water ice has played an important role in the evolution of Martian landforms. Theoretical models of the stability of ground ice show that in the near-surface regolith ice is currently stable at latitudes poleward of about +/- 40 deg and below a depth of a few centimeters to a meter, with some variations with longitude. If ice is not previously present at a particular location where it is stable, atmospheric water will diffuse into the regolith and condense as ice, driven by the annual subsurface thermal oscillations. The lower boundary of this ice deposit is found to occur at a depth (typically a few meters) where the annual thermal oscillations give way to the geothermal gradient. In the equatorial regions near-surface ice is currently not stable, resulting in the sublimation of any existing ice and subsequent loss to the atmosphere. However, subliming ice might be maintained at a steady-state depth, where diffusion and loss to the atmosphere are balanced by resupply from a possible deeper source of water (either deeper, not yet depleted, ice deposits or ground water). This depth is typically a few tens to hundreds of meters and depends primarily on the surface temperature and the nature of the geothermal gradient, being deeper for a higher surface temperature and a lower geothermal gradient. Such an equatorial deposit is characterized by the regolith ice content being low nearer the surface and increasing with depth in the deposit. Oscillations in the orbit will affect this picture of ground ice in two ways: by causing periodic changes in the pattern of near-surface stability and by producing subsurface thermal waves that may be capable of driving water ice deeper into the regolith.

Biological, Physical and Chemical Data From Gulf of Mexico Gravity and Box Core MRD05-04

USGS Publications Warehouse

Osterman, Lisa E.; Campbell, Pamela L.; Swarzenski, Peter W.; Ricardo, John P.

2010-01-01

This paper presents the benthic foraminiferal census data, magnetic susceptibility measurements, vanadium and organic geochemistry (carbon isotope, sterols, and total organic carbon) data from the MRD05-04 gravity and box cores. The MRD05-04 cores were obtained from the Louisiana continental shelf in an on-going initiative to examine the geographic and temporal extent of hypoxia, low-oxygen bottom-water content, and geochemical transport. The development of low-oxygen bottom water conditions in coastal waters is dependent upon a new source of bio-available nutrients introduced into a well-stratified water column. A number of studies have concluded that the development of the current seasonal hypoxia (dissolved oxygen < 2 mg L-1) in subsurface waters of the northern Gulf of Mexico is related to increased transport of nutrients (primarily nitrogen, but possibly also phosphorous) by the Mississippi River. However, the development of earlier episodes of seasonal low-oxygen subsurface water on the Louisiana shelf may be related to Mississippi River discharge.

Metagenomic identification of active methanogens and methanotrophs in serpentinite springs of the Voltri Massif, Italy

PubMed Central

Thornton, Christopher N.; Hyer, Alex; Twing, Katrina I.; Longino, August A.; Lang, Susan Q.; Lilley, Marvin D.; Früh-Green, Gretchen L.; Schrenk, Matthew O.

2017-01-01

The production of hydrogen and methane by geochemical reactions associated with the serpentinization of ultramafic rocks can potentially support subsurface microbial ecosystems independent of the photosynthetic biosphere. Methanogenic and methanotrophic microorganisms are abundant in marine hydrothermal systems heavily influenced by serpentinization, but evidence for methane-cycling archaea and bacteria in continental serpentinite springs has been limited. This report provides metagenomic and experimental evidence for active methanogenesis and methanotrophy by microbial communities in serpentinite springs of the Voltri Massif, Italy. Methanogens belonging to family Methanobacteriaceae and methanotrophic bacteria belonging to family Methylococcaceae were heavily enriched in three ultrabasic springs (pH 12). Metagenomic data also suggest the potential for hydrogen oxidation, hydrogen production, carbon fixation, fermentation, and organic acid metabolism in the ultrabasic springs. The predicted metabolic capabilities are consistent with an active subsurface ecosystem supported by energy and carbon liberated by geochemical reactions within the serpentinite rocks of the Voltri Massif. PMID:28149702

Oxidation of Carbon/Carbon through Coating Cracks

NASA Technical Reports Server (NTRS)

Jacobson, N. S.; Roth, d. J.; Rauser, R. W.; Cawley, J. D.; Curry, D. M.

2008-01-01

Reinforced carbon/carbon (RCC) is used to protect the wing leading edge and nose cap of the Space Shuttle Orbiter on re-entry. It is composed of a lay-up of carbon/carbon fabric protected by a SiC conversion coating. Due to the thermal expansion mismatch of the carbon/carbon and the SiC, the SiC cracks on cool-down from the processing temperature. The cracks act as pathways for oxidation of the carbon/carbon. A model for the diffusion controlled oxidation of carbon/carbon through machined slots and cracks is developed and compared to laboratory experiments. A symmetric cylindrical oxidation cavity develops under the slots, confirming diffusion control. Comparison of cross sectional dimensions as a function of oxidation time shows good agreement with the model. A second set of oxidation experiments was done with samples with only the natural craze cracks, using weight loss as an index of oxidation. The agreement of these rates with the model is quite reasonab

Identification and Removal of Contaminant Sequences From Ribosomal Gene Databases: Lessons From the Census of Deep Life

PubMed Central

Sheik, Cody S.; Reese, Brandi Kiel; Twing, Katrina I.; Sylvan, Jason B.; Grim, Sharon L.; Schrenk, Matthew O.; Sogin, Mitchell L.; Colwell, Frederick S.

2018-01-01

Earth’s subsurface environment is one of the largest, yet least studied, biomes on Earth, and many questions remain regarding what microorganisms are indigenous to the subsurface. Through the activity of the Census of Deep Life (CoDL) and the Deep Carbon Observatory, an open access 16S ribosomal RNA gene sequence database from diverse subsurface environments has been compiled. However, due to low quantities of biomass in the deep subsurface, the potential for incorporation of contaminants from reagents used during sample collection, processing, and/or sequencing is high. Thus, to understand the ecology of subsurface microorganisms (i.e., the distribution, richness, or survival), it is necessary to minimize, identify, and remove contaminant sequences that will skew the relative abundances of all taxa in the sample. In this meta-analysis, we identify putative contaminants associated with the CoDL dataset, recommend best practices for removing contaminants from samples, and propose a series of best practices for subsurface microbiology sampling. The most abundant putative contaminant genera observed, independent of evenness across samples, were Propionibacterium, Aquabacterium, Ralstonia, and Acinetobacter. While the top five most frequently observed genera were Pseudomonas, Propionibacterium, Acinetobacter, Ralstonia, and Sphingomonas. The majority of the most frequently observed genera (high evenness) were associated with reagent or potential human contamination. Additionally, in DNA extraction blanks, we observed potential archaeal contaminants, including methanogens, which have not been discussed in previous contamination studies. Such contaminants would directly affect the interpretation of subsurface molecular studies, as methanogenesis is an important subsurface biogeochemical process. Utilizing previously identified contaminant genera, we found that ∼27% of the total dataset were identified as contaminant sequences that likely originate from DNA extraction and DNA cleanup methods. Thus, controls must be taken at every step of the collection and processing procedure when working with low biomass environments such as, but not limited to, portions of Earth’s deep subsurface. Taken together, we stress that the CoDL dataset is an incredible resource for the broader research community interested in subsurface life, and steps to remove contamination derived sequences must be taken prior to using this dataset. PMID:29780369

Identification and Removal of Contaminant Sequences From Ribosomal Gene Databases: Lessons From the Census of Deep Life.

PubMed

Sheik, Cody S; Reese, Brandi Kiel; Twing, Katrina I; Sylvan, Jason B; Grim, Sharon L; Schrenk, Matthew O; Sogin, Mitchell L; Colwell, Frederick S

2018-01-01

Earth's subsurface environment is one of the largest, yet least studied, biomes on Earth, and many questions remain regarding what microorganisms are indigenous to the subsurface. Through the activity of the Census of Deep Life (CoDL) and the Deep Carbon Observatory, an open access 16S ribosomal RNA gene sequence database from diverse subsurface environments has been compiled. However, due to low quantities of biomass in the deep subsurface, the potential for incorporation of contaminants from reagents used during sample collection, processing, and/or sequencing is high. Thus, to understand the ecology of subsurface microorganisms (i.e., the distribution, richness, or survival), it is necessary to minimize, identify, and remove contaminant sequences that will skew the relative abundances of all taxa in the sample. In this meta-analysis, we identify putative contaminants associated with the CoDL dataset, recommend best practices for removing contaminants from samples, and propose a series of best practices for subsurface microbiology sampling. The most abundant putative contaminant genera observed, independent of evenness across samples, were Propionibacterium , Aquabacterium , Ralstonia , and Acinetobacter . While the top five most frequently observed genera were Pseudomonas , Propionibacterium , Acinetobacter , Ralstonia , and Sphingomonas . The majority of the most frequently observed genera (high evenness) were associated with reagent or potential human contamination. Additionally, in DNA extraction blanks, we observed potential archaeal contaminants, including methanogens, which have not been discussed in previous contamination studies. Such contaminants would directly affect the interpretation of subsurface molecular studies, as methanogenesis is an important subsurface biogeochemical process. Utilizing previously identified contaminant genera, we found that ∼27% of the total dataset were identified as contaminant sequences that likely originate from DNA extraction and DNA cleanup methods. Thus, controls must be taken at every step of the collection and processing procedure when working with low biomass environments such as, but not limited to, portions of Earth's deep subsurface. Taken together, we stress that the CoDL dataset is an incredible resource for the broader research community interested in subsurface life, and steps to remove contamination derived sequences must be taken prior to using this dataset.

Effects of Mars Regolith Analogs, UVC radiation, Temperature, Pressure, and pH on the Growth and Survivability of Methanogenic Archaea and Stable Carbon Isotope Fractionation: Implications for Surface and Subsurface Life on Mars

NASA Astrophysics Data System (ADS)

Sinha, Navita

Mars is one of the suitable bodies in our solar system that can accommodate extraterrestrial life. The detection of plumes of methane in the Martian atmosphere, geochemical evidence, indication of flow of intermittent liquid water on the Martian surface, and geomorphologies of Mars have bolstered the plausibility of finding extant or evidence of extinct life on its surface and/or subsurface. However, contemporary Mars has been considered as an inhospitable planet for several reasons, such as low atmospheric surface pressure, low surface temperature, and intense DNA damaging radiation. Despite the hostile conditions of Mars, a few strains of methanogenic archaea have shown survivability in limited surface and subsurface conditions of Mars. Methanogens, which are chemolithoautotrophic non-photosynthetic anaerobic archaea, have been considered ideal models for possible Martian life forms for a long time. The search for biosignatures in the Martian atmosphere and possibility of life on the Martian surface under UVC radiation and deep subsurface under high pressure, temperature, and various pHs are the motivations of this research. Analogous to Earth, Martian atmospheric methane could be biological in origin. Chapter 1 provides relevant information about Mars' habitability, methane on Mars, and different strains of methanogens used in this study. Chapter 2 describes the interpretation of the carbon isotopic data of biogenic methane produced by methanogens grown on various Mars analogs and the results provide clues to determine ambiguous sources of methane on Mars. Chapter 3 illustrates the sensitivity of hydrated and desiccated cultures of halophilic and non-halophilic methanogens to DNA-damaging ultraviolet radiations, and the results imply that UVC radiation may not be an enormous constraint for methanogenic life forms on the surface of Mars. Chapters 4, 5, and 6 discuss the data for the survivability, growth, and morphology of methanogens in presumed deep subsurface physicochemical conditions such as temperature, pressure, hydrogen concentration, and pH of Mars. Finally, chapter 7 provides conclusions, limitations of the experiments, and future perspective of the work. Overall, the quantitative measurements obtained in the various sections of this novel work provide insights to atmospheric biosignatures and survivability of methanogenic organisms on the surface and subsurface of Mars.

A trench study to assess transfer of pesticides in subsurface lateral flow for a soil with contrasting texture on a sloping vineyard in Beaujolais.

PubMed

Peyrard, X; Liger, L; Guillemain, C; Gouy, V

2016-01-01

Subsurface lateral flow in both texture-contrast soils and catchments with shallow bedrock is suspected to be a non-point source of contamination of watercourses by pesticides used in agriculture. As a case study, the north of the Beaujolais region (eastern France) provides a favorable environment for such contamination due to its agro-pedo-climatic conditions. Environments seen in the Beaujolais region include intense viticulture, permeable and shallow soils, steep hillslopes, and storms that occur during the periods of pesticide application. Watercourse contamination by pesticides has been widely observed in this region, and offsite pesticide transport by subsurface lateral flow is suspected to be involved in diffuse and chronic presence of pesticides in surface water. In order to confirm and quantify the potential role of such processes in pesticide transfer, an automated trench system has been designed. The trench was set up on a steep farmed hillslope in a texture-contrast soil. It was equipped with a tipping bucket flow meter and an automatic sampler to monitor pesticide concentrations in lateral flow at fine resolution, by means of a flow-dependent sampling strategy. Four pesticides currently used in vine growing were studied to provide a range of mobility properties: one insecticide (chlorpyrifos-methyl) and three fungicides (spiroxamine, tebuconazole, and dimethomorph). With this system, it was possible to study pesticide concentration dynamics in the subsurface lateral flow, generated by substantial rainfall events following pesticide applications. The experimental design ascertained to be a suitable method in which to monitor subsurface lateral flow and related transfer of pesticides.

Plant-based plume-scale mapping of tritium contamination in desert soils

USGS Publications Warehouse

Andraski, Brian J.; Stonestrom, David A.; Michel, R.L.; Halford, K.J.; Radyk, J.C.

2005-01-01

Plant-based techniques were tested for field-scale evaluation of tritium contamination adjacent to a low-level radioactive waste (LLRW) facility in the Amargosa Desert, Nevada. Objectives were to (i) characterize and map the spatial variability of tritium in plant water, (ii) develop empirical relations to predict and map subsurface contamination from plant-water concentrations, and (iii) gain insight into tritium migration pathways and processes. Plant sampling [creosote bush, Larrea tridentata (Sessé & Moc. ex DC.) Coville] required one-fifth the time of soil water vapor sampling. Plant concentrations were spatially correlated to a separation distance of 380 m; measurement uncertainty accounted for <0.1% of the total variability in the data. Regression equations based on plant tritium explained 96 and 90% of the variation in root-zone and sub-root-zone soil water vapor concentrations, respectively. The equations were combined with kriged plant-water concentrations to map subsurface contamination. Mapping showed preferential lateral movement of tritium through a dry, coarse-textured layer beneath the root zone, with concurrent upward movement through the root zone. Analysis of subsurface fluxes along a transect perpendicular to the LLRW facility showed that upward diffusive-vapor transport dominates other transport modes beneath native vegetation. Downward advective-liquid transport dominates at one endpoint of the transect, beneath a devegetated road immediately adjacent to the facility. To our knowledge, this study is the first to document large-scale subsurface vapor-phase tritium migration from a LLRW facility. Plant-based methods provide a noninvasive, cost-effective approach to mapping subsurface tritium migration in desert areas.

Carbon Cycling and pH regulation on the Scotian Shelf, NW Atlantic

NASA Astrophysics Data System (ADS)

Thomas, Helmuth

2015-04-01

This presentation intends to describe the biogeochemical context for ocean acidification studies on the Scotian Shelf. The seasonality of the dominant processes, regulating surface ocean CO2 conditions, including pH, will be assessed as well as cross-shelf transports of CO2, acidity and nutrient, the latter ones exerting the "subsurface control" of CO2 air-sea fluxes and surface pH. Methods summary: The seasonal variability of inorganic carbon in the surface waters of the Scotian Shelf region of the Canadian northwestern Atlantic Ocean was assessed using hourly measurements of the partial pressure of CO2 (pCO2), and hydrographic variables obtained by an autonomous moored instrument (44.3°N and 63.3°W). These measurements were complemented by seasonal shipboard sampling of dissolved inorganic carbon (DIC), total alkalinity (TA), and pCO2, at the mooring site, and over the larger spatial scale. The Scotian Shelf is a 700 km long section of the continental shelf off Nova Scotia. Bounded by the Laurentian Channel to the northeast, and by the Northeast Channel and the Gulf of Maine to the southwest, it varies in width from 120 to 240 km covering roughly 120,000 km2 with an average depth of 90 m . Convective mixin in winter time and coastal upwelling and the associated favorable wind conditions on the Scotian Shelf have long been recognized. Strong winds of speeds greater than 10 m s-1, blowing to the northeast, and persisting for several days force relatively cold, saline, water toward the surface, displacing the warmer, fresher water offshore. Upwelling events have frequently been observed in the region in winter, and modeling studies have reproduced these observed events. Furthermore, these events may play a role in initiating and sustaining the spring phytoplankton bloom by displacing nutrient-depleted surface water and bring nutrient-rich waters up to the surface. Biological processes were found to be the dominant control on mixed-layer DIC, with the delivery of carbon-rich subsurface waters also playing an important role. The region acts as a net source of CO2 to the atmosphere at the annual scale, with a reversal of this trend occurring only during the diatom dominated spring phytoplankton bloom, when a pronounced undersaturation of the surface waters is reached for a short period. During that time, the pH is at its annual maximum (pH≈8.15), while the Aragonite saturation state reaches its minimum just before the onset of the spring bloom in late March. After of the spring bloom period, the competing effects of temperature and biology influence surface pCO2 in roughly equal magnitude. During that time carbon fixation is driven by the smaller phytoplankton size classes, which can grow in warmer, nutrient poor conditions. In the Scotian Shelf region the summertime population these numerically abundant small cells accounts for approximately 10-20% of annual carbon uptake. The regional mean surface water pH is roughly 7.8 in April and increases to greater than 8.0 in September; subsurface pH is approximately 7.6 throughout the region and indicates a seasonal decrease due to the respiration of organic matter at depth. The surface aragonite saturation state increases from less than 2.0 to values as high as 3.2 between April and September; the region as a whole exhibits relatively low saturation states, however values approaching 1.0 were only observed in the Cabot Strait at depths below roughly 100m. Subsurface onshore gradients of CO2 and nutrient species yield onshore carbon, nutrient and hydrogen ion (H+) fluxes in subsurface waters, which in turn regulate surface pH and fuel the CO2 outgassing from the Scotian Shelf.

Evaluating the diffusion coefficient of dopamine at the cell surface during amperometric detection: disk vs ring microelectrodes.

PubMed

Trouillon, Raphaël; Lin, Yuqing; Mellander, Lisa J; Keighron, Jacqueline D; Ewing, Andrew G

2013-07-02

During exocytosis, small quantities of neurotransmitters are released by the cell. These neurotransmitters can be detected quantitatively using electrochemical methods, principally with disk carbon fiber microelectrode amperometry. An exocytotic event then results in the recording of a current peak whose characteristic features are directly related to the mechanisms of exocytosis. We have compared two exocytotic peak populations obtained from PC12 cells with a disk carbon fiber microelectrode and with a pyrolyzed carbon ring microelectrode array, with a 500 nm ring thickness. The specific shape of the ring electrode allows for precise analysis of diffusion processes at the vicinity of the cell membrane. Peaks obtained with a ring microelectrode array show a distorted average shape, owing to increased diffusion pathways. This result has been used to evaluate the diffusion coefficient of dopamine at the surface of a cell, which is up to an order of magnitude smaller than that measured in free buffer. The lower rate of diffusion is discussed as resulting from interactions with the glycocalyx.

Compatibility of buffered uranium carbides with tungsten.

NASA Technical Reports Server (NTRS)

Phillips, W. M.

1971-01-01

Results of compatibility tests between tungsten and hyperstoichiometric uranium carbide alloys run at 1800 C for 1000 and 2500 hours. These tests compared tungsten-buffered uranium carbide with tungsten-buffered uranium-zirconium carbide. The zirconium carbide addition appeared to widen the homogeneity range of the uranium carbide, making additional carbon available for reaction. Reaction layers could be formed by either of two diffusion paths, one producing UWC2, while the second resulted in the formation of W2C. UWC2 acts as a diffusion barrier for carbon and slows the growth of the reaction layer with time, while carbon diffusion is relatively rapid in W2C, allowing equilibrium to be reached in less than 2500 hours at a temperature of 1800 C.

Climatic Controls on the Porewater Chemistry of Mid-Continental Wetlands

NASA Astrophysics Data System (ADS)

Levy, Zeno Francis

Wetlands develop where climate and physiography conspire to maintain saturated soils at the land surface, support diverse plant and animal communities, and serve as globally important sinks for atmospheric carbon. The chemistry of wetland porewaters impacts near-surface biological communities and subsurface biogeochemical processes that influence carbon cycling in the environment. Wetland porewater chemistry is a dynamic byproduct of complex hydrogeological processes that cause meteoric waters to enter groundwater systems (recharge) or groundwater to flow to the land surface (discharge). Changes in climate can alter subsurface hydraulic gradients that determine the recharge and discharge functions of wetlands, which in turn control the hydrogeochemical evolution of wetland porewaters. The climate of mid-continental North America is influenced by competing air masses with vastly different temperature and moisture contents originating from the Pacific Coast, the Gulf of Mexico, and the Arctic. The interactions of these air masses result in large dynamic shifts of climate regimes characterized by decadal-scale oscillations between periods of drought and heavy rain. Over the course of the 20th century, a shift occurred towards wetter climate in the mid-continental region. This dissertation examines the impact of this climate shift on the porewater chemistry of two very different wetland systems, located only 350 km apart: the Glacial Lake Agassiz Peatlands (GLAP) of northern Minnesota and the Cottonwood Lake Study Area (CLSA) of North Dakota. The former study site consists of a large (7,600 km2), circumboreal peatland that developed an extensive blanket of peat over the last 5000 years on a relatively flat glacial lake bed within a sub-humid to semi-arid climate gradient characterized by small annual atmospheric moisture surpluses and frequent droughts. The latter study site consists of a 0.92 km2 complex of small (meter-scale) "prairie pothole" wetlands located on a hummocky glacial stagnation moraine under semi-arid climate where wetlands frequently fill and dry with surface ponds over low-permeability glacial till in response to snowmelt runoff and evapotranspiration. Both sites have been the subject of long-term hydrological study since c. 1980 and are well-established examples of the sensitivity of wetland functions to changes in climate. The first chapter of this dissertation utilizes a semi-conservative tracer suite (pH, Ca, Mg, Sr, 87Sr/86Sr) to fingerprint discharge of calcareous groundwater to GLAP peat along a 6 km transect from a bog crest downslope to an internal fen water track and bog islands. However, stable isotopes of the peat porewaters (delta18O and delta 2H) show that the subsurface throughout the entire study area is currently flushed with recharge from the near surface peat. I hypothesize that back-diffusion of groundwater-derived solutes from the peat matrix to active pore-spaces has allowed the geochemical signal from paleo-hydrogeologic discharge to persist into the current regime of dilute recharge. This effect promotes methane generation in the peatland subsurface by allowing transport of labile carbon compounds from the land surface to depth while maintaining geochemical conditions (i.e. pH) in the deep peat favorable to biogenic methane production. The results of this study show that autogenic hydrogeochemical feedback mechanisms contribute to the resilience of peatlands systems and associated ecological functions against climate change. The second chapter of this dissertation consists of a detailed geoelectrical survey of a well-studied, closed-basin prairie wetland (P1) in the CLSA that has experienced record drought and heavy rains (i.e. deluge) during the late 20th century. Subsurface storage of sulfate (SO4) salts allows many such closed-basin prairie wetlands to maintain moderate surface water salinities (TDS from 1 to 10 g L-1) that influence communities of aquatic biota. I imaged saline lenses of sulfate-rich porewater (TDS > 10 g L-1) in wetland sediments beneath the bathymetric low of the wetland and within the currently ponded area along the shoreline of a prior pond stand. Analyses of long-term (1979-2014) groundwater and surface water levels in the wetland suggest that the saline lenses formed during paleo-droughts when the groundwater levels dropped below the wetland bed and are stable in the subsurface on at least centennial timescales. I hypothesize a "drought-induced recharge" mechanism by which wetlands maintain moderate surface water salinity by subsurface storage during droughts when the wetlands dry and intermittent runoff events flush surface salts down secondary porosity created by desiccation fractures and terrestrial plant roots. Drought-derived saline groundwater has the potential to increase wetland salinity during record wet climate conditions currently prevalent in the Prairie Pothole Region. The third chapter of this dissertation extends the findings of the second chapter by a detailed geochemical survey of wetland porewater, pond water, and upland groundwater in the P1 basin. (Abstract shortened by ProQuest.).

Geochemistry of halogens in the Milk River aquifer, Alberta, Canada

USGS Publications Warehouse

Fabryka-Martin, J.; Whittemore, Donald O.; Davis, S.N.; Kubik, P.W.; Sharma, Prakash

1991-01-01

Analytical data are presented for Cl, Br and I on a regional scale for the Milk River aquifer. The three halides show strikingly similar spatial distributions and are highly correlated. Concentrations are low in the freshwater portions of the aquifer but increase by as much as two orders of magnitude along the margins. However, halide ratios reach nearly constant values moving down-gradient, suggesting the dominance of a common subsurface source for these ions. Ratios of Cl/I and Cl/Br are less than those of seawater and fit an origin derived from the diagenesis of organic matter in the sediments. Halide ratios rule out leakage and/or diffusion from the underlying Colorado Group as a major influence on the chemistry; the favored hypothesis is altered connate seawater diffusing from low-permeability units within the Milk River Formation as the primary source of salts. This hypothesis of an internal source has important implications for solute sources in other aquifers affected by saline waters because it does not require the importation of a distant fluid. The 129I/I ratio has a meteoric value in groundwater collected near the recharge area, but ratios for downflow waters are only 8-70% of this value. Due to the 16 Ma half-life of 129I, these data indicate that most of the increase in dissolved I cannot derive from concentration of a meteoric source by ion filtration, but must have a subsurface origin. Concentrations of 129I produced in situ by spontaneous fission of 238U attain measurable levels only in the oldest waters sampled (ages ??? 105 a), in which it may account for nearly 90% of the total dissolved 129I concentration. Water ages based upon 36Cl/Cl data range up to 2 Ma if uncorrected for any dilution by subsurface sources of dead Cl. If one assumes that the subsurface contributions of Cl contribute at least 90% of total Cl in the distal portion, then the 36Cl-based ages are reduced to ??? 1 Ma, somewhat greater than those estimated by hydrodynamic modeling. ?? 1991.

An investigation of the sensitivity of low-field nuclear magnetic resonance to microbial growth and activity

NASA Astrophysics Data System (ADS)

Zhang, C.; Keating, K.

2014-12-01

Microbes and microbial processes play a significant role in shaping subsurface environments and are involved in applications ranging from microbially enhanced oil recovery to soil and groundwater contaminant remediation. Stimulated microbial growth in such applications could cause wide variety of changes of physical/chemical properties in the subsurface; however, due to the complexity of subsurface systems,it is difficult to monitor the growth of microbes and microbial activity in porous media. The focus of this research is to determine if low-field nuclear magnetic resonance (NMR), a method used in well logging to characterize fluids in hydrocarbon reservoirs or water in aquifers, can be used to directly detect the presence and the growth of microbes in geologic media. In this laboratory study, low-field NMR (2 MHz) relaxation measurements were collected on microbial suspensions with measured densities (i.e. biomasses), microbial pellets (live and dead), and inoculated silica. We focus on the direct contribution of microbes to the NMR signals in the absence of biomineralization. Shewanella oneidensis (MR-1), a facultative metal reducer known to play an important role in subsurface environments, were used as a model organism and were inoculated under aerobic condition. Data were collected using a CPMG pulse sequence, which was to determine the T2-distribution, and using a gradient spin-echo (PGSE) plus CPMG pulse sequence, which was used to encode diffusion properties and determine the effective diffusion-spin-spin relaxation correlation (D-T2) plot. Our data show no obvious change in the T2-distribution as S. oneidensis density varied in suspension, but show a clear distinction in the T2-distribution and D-T2 plots between live and dead cell pellets. A decrease in the T2-distribution is observed in the inoculated sand column. These results will provide a basis for understanding the effect of microbes within geologic media on low-field NMR measurements. This research is necessary to determine if NMR measurements can ultimately to be used to monitor microbial growth and activity in oil reservoirs or contaminated aquifers.

Out of the dark: transitional subsurface-to-surface microbial diversity in a terrestrial serpentinizing seep (Manleluag, Pangasinan, the Philippines)

PubMed Central

Woycheese, Kristin M.; Meyer-Dombard, D'Arcy R.; Cardace, Dawn; Argayosa, Anacleto M.; Arcilla, Carlo A.

2015-01-01

In the Zambales ophiolite range, terrestrial serpentinizing fluid seeps host diverse microbial assemblages. The fluids fall within the profile of Ca2+-OH−-type waters, indicative of active serpentinization, and are low in dissolved inorganic carbon (DIC) (<0.5 ppm). Influx of atmospheric carbon dioxide (CO2) affects the solubility of calcium carbonate as distance from the source increases, triggering the formation of meter-scale travertine terraces. Samples were collected at the source and along the outflow channel to determine subsurface microbial community response to surface exposure. DNA was extracted and submitted for high-throughput 16S rRNA gene sequencing on the Illumina MiSeq platform. Taxonomic assignment of the sequence data indicates that 8.1% of the total sequence reads at the source of the seep affiliate with the genus Methanobacterium. Other major classes detected at the source include anaerobic taxa such as Bacteroidetes (40.7% of total sequence reads) and Firmicutes (19.1% of total reads). Hydrogenophaga spp. increase in relative abundance as redox potential increases. At the carbonate terrace, 45% of sequence reads affiliate with Meiothermus spp. Taxonomic observations and geochemical data suggest that several putative metabolisms may be favorable, including hydrogen oxidation, H2-associated sulfur cycling, methanogenesis, methanotrophy, nitrogen fixation, ammonia oxidation, denitrification, nitrate respiration, methylotrophy, carbon monoxide respiration, and ferrous iron oxidation, based on capabilities of nearest known neighbors. Scanning electron microscopy and energy dispersive X-ray spectroscopy suggest that microbial activity produces chemical and physical traces in the precipitated carbonates forming downstream of the seep's source. These data provide context for future serpentinizing seep ecosystem studies, particularly with regards to tropical biomes. PMID:25745416

Out of the dark: transitional subsurface-to-surface microbial diversity in a terrestrial serpentinizing seep (Manleluag, Pangasinan, the Philippines).

PubMed

Woycheese, Kristin M; Meyer-Dombard, D'Arcy R; Cardace, Dawn; Argayosa, Anacleto M; Arcilla, Carlo A

2015-01-01

In the Zambales ophiolite range, terrestrial serpentinizing fluid seeps host diverse microbial assemblages. The fluids fall within the profile of Ca(2+)-OH(-)-type waters, indicative of active serpentinization, and are low in dissolved inorganic carbon (DIC) (<0.5 ppm). Influx of atmospheric carbon dioxide (CO2) affects the solubility of calcium carbonate as distance from the source increases, triggering the formation of meter-scale travertine terraces. Samples were collected at the source and along the outflow channel to determine subsurface microbial community response to surface exposure. DNA was extracted and submitted for high-throughput 16S rRNA gene sequencing on the Illumina MiSeq platform. Taxonomic assignment of the sequence data indicates that 8.1% of the total sequence reads at the source of the seep affiliate with the genus Methanobacterium. Other major classes detected at the source include anaerobic taxa such as Bacteroidetes (40.7% of total sequence reads) and Firmicutes (19.1% of total reads). Hydrogenophaga spp. increase in relative abundance as redox potential increases. At the carbonate terrace, 45% of sequence reads affiliate with Meiothermus spp. Taxonomic observations and geochemical data suggest that several putative metabolisms may be favorable, including hydrogen oxidation, H2-associated sulfur cycling, methanogenesis, methanotrophy, nitrogen fixation, ammonia oxidation, denitrification, nitrate respiration, methylotrophy, carbon monoxide respiration, and ferrous iron oxidation, based on capabilities of nearest known neighbors. Scanning electron microscopy and energy dispersive X-ray spectroscopy suggest that microbial activity produces chemical and physical traces in the precipitated carbonates forming downstream of the seep's source. These data provide context for future serpentinizing seep ecosystem studies, particularly with regards to tropical biomes.

Effect of carbon ion irradiation on Ag diffusion in SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Effect of carbon ion irradiation on Ag diffusion in SiC

DOE PAGES

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.; ...

2015-11-14

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Evaluation of diffuse and preferential flow pathways of infiltrated precipitation and irrigation using oxygen and hydrogen isotopes

NASA Astrophysics Data System (ADS)

Ma, Bin; Liang, Xing; Liu, Shaohua; Jin, Menggui; Nimmo, John R.; Li, Jing

2017-05-01

Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (18O) and hydrogen (2H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10-40 cm depth in the grassland and arable land, and 10-60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ18O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ18O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ18O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ18O spikes at 20-50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

Computational Modeling of the Geologic Sequestration of Carbon Dioxide

EPA Science Inventory

Geologic sequestration of CO2 is a component of C capture and storage (CCS), an emerging technology for reducing CO2 emissions to the atmosphere, and involves injection of captured CO2 into deep subsurface formations. Similar to the injection of hazardous wastes, before injection...

Organic Carbon as Inhibitor to SVOC and Metal Migration in Stormwater Drywells Discharging to the Subsurface-SLIDES

EPA Science Inventory

The Safe Drinking Water Act (SDWA) authorizes the Underground Injection Control (UIC) program to protect underground drinking water (USDW) sources from contamination caused by underground injection wells, including regulation of stormwater drainage drywells for parking lot and ro...

COMPARISON OF METHODS TO DETERMINE OXYGEN DEMAND FOR BIOREMEDIATION OF A FUEL CONTAMINATED AQUIFER

EPA Science Inventory

Four analytical methods were compared for estimating concentrations of fuel contaminants in subsurface core samples. The methods were total organic carbon, chemical oxygen demand, oil and grease, and a solvent extraction of fuel hydrocarbons combined with a gas chromatographic te...

Using Nitrogen Limiting Growth Conditions to Remove Atrazine from Groundwater: Laboratory Studies

USDA-ARS?s Scientific Manuscript database

In the past microbial redox reactions have been the driving mechanism behind in situ bioremediations that use a carbon substrate. This is because subsurface microbial activity is generally restricted by electron (e-) donor availability and microbial activity, growth and respiration, can be stimulat...

An Inverse Analysis Approach to the Characterization of Chemical Transport in Paints

PubMed Central

Willis, Matthew P.; Stevenson, Shawn M.; Pearl, Thomas P.; Mantooth, Brent A.

2014-01-01

The ability to directly characterize chemical transport and interactions that occur within a material (i.e., subsurface dynamics) is a vital component in understanding contaminant mass transport and the ability to decontaminate materials. If a material is contaminated, over time, the transport of highly toxic chemicals (such as chemical warfare agent species) out of the material can result in vapor exposure or transfer to the skin, which can result in percutaneous exposure to personnel who interact with the material. Due to the high toxicity of chemical warfare agents, the release of trace chemical quantities is of significant concern. Mapping subsurface concentration distribution and transport characteristics of absorbed agents enables exposure hazards to be assessed in untested conditions. Furthermore, these tools can be used to characterize subsurface reaction dynamics to ultimately design improved decontaminants or decontamination procedures. To achieve this goal, an inverse analysis mass transport modeling approach was developed that utilizes time-resolved mass spectroscopy measurements of vapor emission from contaminated paint coatings as the input parameter for calculation of subsurface concentration profiles. Details are provided on sample preparation, including contaminant and material handling, the application of mass spectrometry for the measurement of emitted contaminant vapor, and the implementation of inverse analysis using a physics-based diffusion model to determine transport properties of live chemical warfare agents including distilled mustard (HD) and the nerve agent VX. PMID:25226346

Reactor Meltdown: Critical Zone Processes In Siliciclastics Unlikely To Be Directly Transferable To Carbonates

NASA Astrophysics Data System (ADS)

Gulley, J. D.; Cohen, M. J.; Kramer, M. G.; Martin, J. B.; Graham, W. D.

2013-12-01

Carbonate terrains cover 20% of Earth's ice-free land and are modified through interactions between rocks, water and biota that couple ecosystems processes to weathering reactions within the critical zone. Weathering in carbonate systems differs from the Critical Zone Reactor model developed for siliciclastic systems because reactions in siliciclastic critical zones largely consist of incongruent weathering (e.g., feldspar to secondary clay minerals) that typically occur in the soil zone within a few meters of the land surface. These incongruent reactions create regolith, which is removed by physical transport mechanisms that drive landscape denudation. In contrast, carbonate critical zones are mostly composed of homogeneous and soluble minerals, which dissolve congruently with the weathering products exported in solution, limiting regolith in the soil mantle to small amounts of insoluble residues. These reactions can extend to depths greater than 2 km below the surface. As water at the land surface drains preferentially through vertical joints and horizontal bedding planes of the carbonate critical zones, it is 'charged' with biologically-derived carbon dioxide, which decreases pH, dissolves carbonate rock, and enlarges subsurface flowpaths through feedbacks between flow and dissolution. Caves are extreme end products of this process and are key morphological features of carbonate critical zones. Caves link surface processes to the deep subsurface and serve as efficient delivery agents for oxygen, carbon and nutrients to zones within the critical zone that are deficient in all three, interrupting vertical and horizontal chemical gradients that would exist if caves were not present. We present select data from air and water-filled caves in the upper Floridan aquifer, Florida, USA, that demonstrate how caves, acting as very large preferential flow paths, alter processes in carbonate relative to siliciclastic critical zones. While caves represent an extreme end member of hydraulic and chemical heterogeneity that has no direct counterpart siliciclastic systems, these large voids provide easily accessible laboratories to investigate processes in carbonate critical zones, and how they differ from standard siliciclastic models of critical zones.

Pseudowollastonite Carbonation Could Enable New Frontiers in Carbon Storage

NASA Astrophysics Data System (ADS)

Plattenberger, D.; Tao, Z.; Ling, F. T.; Peters, C. A.; Clarens, A. F.

2017-12-01

One of the primary challenges of CO2 mineral trapping is that precipitation reactions are reversible. A wide range of solid magnesium, iron, or calcium carbonates (such as magnesite, MgCO3) can be synthesized by reacting mineral silicates (such as olivine, Mg2SiO4) with CO2 to produce mineral carbonates. However, if CO2 remains present at high concentrations, as would be the case in many subsurface environments, the carbonate minerals could re-dissolve, making the precipitated carbonates impermanent forms of storage. In this work, we study pseudowollastonite (CaSiO3), a crystalline form of calcium silicate that is common in slags, cement, and calcium-rich volcanic formations, for its potential to produce other secondary mineral phases that may be resistant to dissolution under low pH conditions. These secondary mineral precipitation phases have morphologies and X-ray diffraction patterns that resemble both calcium silicate hydrate gels as well as crystalline calcium silicate carbonate hydrates. The combination of these phases forms a complex system that may resist acid attack while providing strength and limiting flow in the subsurface environment. High pressure and temperature column experiments carried out in our lab show that pseudowollastonite carbonation effectively lowers permeability in columns of sintered glass beads. Many of the pore throats are clogged by precipitates, as seen using micro X-ray tomography of intact columns and electron microscopy of thin sections. The spatial distribution of the products suggests that calcite forms toward the inlet of the columns where the pCO2 is highest. This forms a barrier that reduces, but does not eliminate, the availability of CO2 deeper in the porous media where the secondary phases precipitate. The existence of the calcite zone drives the reduction in permeability and the depth of this zone is self-limiting, which could have important implications for limiting leakage and unwanted migration of CO2 in some instances.

Carbon Cycling and Storage in Mangrove Forests

NASA Astrophysics Data System (ADS)

Alongi, Daniel M.

2014-01-01

Mangroves are ecologically and economically important forests of the tropics. They are highly productive ecosystems with rates of primary production equal to those of tropical humid evergreen forests and coral reefs. Although mangroves occupy only 0.5% of the global coastal area, they contribute 10-15% (24 Tg C y-1) to coastal sediment carbon storage and export 10-11% of the particulate terrestrial carbon to the ocean. Their disproportionate contribution to carbon sequestration is now perceived as a means for conservation and restoration and a way to help ameliorate greenhouse gas emissions. Of immediate concern are potential carbon losses to deforestation (90-970 Tg C y-1) that are greater than these ecosystems' rates of carbon storage. Large reservoirs of dissolved inorganic carbon in deep soils, pumped via subsurface pathways to adjacent waterways, are a large loss of carbon, at a potential rate up to 40% of annual primary production. Patterns of carbon allocation and rates of carbon flux in mangrove forests are nearly identical to those of other tropical forests.

Carbon cycling and storage in mangrove forests.

PubMed

Alongi, Daniel M

2014-01-01

Mangroves are ecologically and economically important forests of the tropics. They are highly productive ecosystems with rates of primary production equal to those of tropical humid evergreen forests and coral reefs. Although mangroves occupy only 0.5% of the global coastal area, they contribute 10-15% (24 Tg C y(-1)) to coastal sediment carbon storage and export 10-11% of the particulate terrestrial carbon to the ocean. Their disproportionate contribution to carbon sequestration is now perceived as a means for conservation and restoration and a way to help ameliorate greenhouse gas emissions. Of immediate concern are potential carbon losses to deforestation (90-970 Tg C y(-1)) that are greater than these ecosystems' rates of carbon storage. Large reservoirs of dissolved inorganic carbon in deep soils, pumped via subsurface pathways to adjacent waterways, are a large loss of carbon, at a potential rate up to 40% of annual primary production. Patterns of carbon allocation and rates of carbon flux in mangrove forests are nearly identical to those of other tropical forests.

Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

NASA Astrophysics Data System (ADS)

Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

2014-05-01

Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared to the non reactive one. On the basis of a reaction-diffusion-convection model, we classify the various possible cases and show that the difference between the solutal expansion coefficients of the reactant and of the product governs the type of density profile building up in the aqueous solution and thus the stability of the system. By contrast to non reactive density profiles, reactive density profiles can feature a minimum that induces a delay of the buoyancy-driven convection. This work identifies the parameters that could influence the dissolution-driven convection in the aquifers, and thus impact the safety of the sequestration. In other words, this theoretical study shows that it is crucial to analyse the composition and reactivity of potential storage sites to choose those that will be most efficient for long-term CO2 sequestration.

Adsorption of basic dyes on granular activated carbon and natural zeolite.

PubMed

Meshko, V; Markovska, L; Mincheva, M; Rodrigues, A E

2001-10-01

The adsorption of basic dyes from aqueous solution onto granular activated carbon and natural zeolite has been studied using an agitated batch adsorber. The influence of agitation, initial dye concentration and adsorbent mass has been studied. The parameters of Langmuir and Freundlich adsorption isotherms have been determined using the adsorption data. Homogeneous diffusion model (solid diffusion) combined with external mass transfer resistance is proposed for the kinetic investigation. The dependence of solid diffusion coefficient on initial concentration and mass adsorbent is represented by the simple empirical equations.

Influence of oxygen concentration, fuel composition, and strain rate on synthesis of carbon nanomaterials

NASA Astrophysics Data System (ADS)

Hou, Shuhn-Shyurng; Huang, Wei-Cheng

2015-02-01

This paper investigates the influence of flame parameters including oxygen concentration, fuel composition, and strain rate on the synthesis of carbon nanomaterials in opposed-jet ethylene diffusion flames with or without rigid-body rotation. In the experiments, a mixture of ethylene and nitrogen was introduced from the upper burner; meanwhile, a mixture of oxygen and nitrogen was supplied from the lower burner. A nascent nickel mesh was used as the catalytic metal substrate to collect deposited materials. With non-rotating opposed-jet diffusion flames, carbon nanotubes (CNTs) were successfully produced for oxygen concentrations in the range of 21-50 % at a fixed ethylene concentration of 20 %, and for ethylene concentrations ranging from 14 to 24 % at a constant oxygen concentration of 40 %. With rotating opposed-jet diffusion flames, the strain rate was varied by adjusting the angular velocities of the upper and lower burners. The strain rate governed by flow rotation greatly affects the synthesis of carbon nanomaterials [i.e., CNTs and carbon nano-onions (CNOs)] either through the residence time or carbon sources available. An increase in the angular velocity lengthened the residence time of the flow and thus caused the diffusion flame to experience a decreased strain rate, which in turn produced more carbon sources. The growth of multi-walled CNTs was achieved for the stretched flames experiencing a higher strain rate [i.e., angular velocity was equal to 0 or 1 rotations per second (rps)]. CNOs were synthesized at a lower strain rate (i.e., angular velocity was in the range of 2-5 rps). It is noteworthy that the strain rate controlled by flow rotation greatly influences the fabrication of carbon nanostructures owing to the residence time as well as carbon source. Additionally, more carbon sources and higher temperature are required for the synthesis of CNOs compared with those required for CNTs (i.e., about 605-625 °C for CNTs and 700-800 °C for CNOs).

Low-Angle Radar Tracking

DTIC Science & Technology

1976-02-01

Transition from Specular Reflection to Diffuse Scattering. . . 10 Composition of the Electric-Field Vector as Seen at the Radar...r t (16) R • FIGURE P COMPOSITION OF THE ELECTRIC-FIELD VECTOR AS SEEN AT THE RADAR, R, IN FIG. 2. The electric field at the radar, E, is the sum...wavelengths in the VHP and UHF ranges even subsurface characteristics can be important. So in a field experiment one must be careful to measure

Reactive Membrane Barriers for Containment of Subsurface Contamination

DOE Office of Scientific and Technical Information (OSTI.GOV)

William A. Arnold; Edward L. Cussler

2007-02-26

The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe{sup 0}) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents andmore » cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe{sup 0} and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu{sup 2+}) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe{sup 0} barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a factor of three when groundwater was used in place of deionized water. The performance of high density polyethylene (HDPE) membranes containing Fe{sup 0} was then evaluating using carbon tetrachloride as the target contaminant. Only with a hydrophilic additive (glycerol), was the iron able to extend lag times. Lag times were increased by a factor of 15, but only 2-3% of the iron was used, likely due to formation of oxide precipitates on the iron surface, which slowed the reaction. With thicker membranes and lower carbon tetrachloride concentrations, it is expected that performance will improve. Previous models for reactive membranes were also extended. The lag time is a measurement of when the barrier is breached, but contaminants do slowly leak through prior to the lag time. Thus, two parameters, the leakage and the kill time, were developed to determine when a certain amount of pollutant has escaped (the kill time) or when a given exposure (concentration x time) occurs (the leakage). Finally, a model was developed to explain the behavior of mobile reaction products in reactive barrier membranes. Although the goal of the technology is to avoid such products, it is important to be able to predict how these products will behave. Interestingly, calculations show that for any mobile reaction products, one half of the mass will diffuse into the containment area and one half will escape, assuming that the volumes of the containment area and the surrounding environment are much larger than the barrier membrane. These parameters/models will aid in the effective design of barrier membranes.« less

Grazing-incidence X-ray diffraction from a crystal with subsurface defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gaevskii, A. Yu., E-mail: transilv@mail.ru; Golentus, I. E.

2015-03-15

The diffraction of X rays incident on a crystal surface under grazing angles under conditions of total external reflection has been investigated. An approach is proposed in which exact solutions to the dynamic problem of grazing-incidence diffraction in an ideal crystal are used as initial functions to calculate the diffuse component of diffraction in a crystal with defects. The diffuse component of diffraction is calculated for a crystal with surface defects of a dilatation-center type. Exact formulas of the continuum theory which take into account the mirror-image forces are used for defect-induced atomic displacements. Scattering intensity maps near Bragg peaksmore » are constructed for different scan modes, and the conditions for detecting primarily the diffuse component are determined. The results of dynamic calculations of grazing-incidence diffraction in defect-containing crystals are compared with calculations in the kinematic approximation.« less

New vistas in the determination of hydrogen in aerospace engine metal alloys

NASA Technical Reports Server (NTRS)

Danford, M. D.

1986-01-01

The application of diffusion theory to the analysis of hydrogen desorption data has been studied. From these analyses, important information concerning hydrogen solubilities and the nature of the hydrogen distributions in the metal has been obtained. Two nickel base alloys, Rene' 41 and Waspaloy, and one ferrous alloy, 4340 steel, were studied in this work. For the nickel base alloys, it was found that the hydrogen distributions after electrolytic charging conformed closely to those which would be predicted by diffusion theory. The hydrogen distributions in electrolytically charged 4340 steel, on the other hand, were essentially uniform in nature, which would not be predicted by diffusion theory. Finally, it has been found that the hydrogen desorption is completely explained by the nature of the hydrogen distribution in the metal, and that the 'fast' hydrogen is not due to surface and subsurface hydride formation, as was originally proposed.

Dispersive—diffusive transport of non-sorbed solute in multicomponent solutions

NASA Astrophysics Data System (ADS)

Hu, Qinhong; Brusseau, Mark L.

1995-10-01

The composition of fuels, mixed-solvent wastes and other contaminants that find their way into the subsurface are frequently chemically complex. The dispersion and diffusion characteristics of multicomponent solutions in soil have rarely been compared to equivalent single-solute systems. The purpose of this work was to examine the diffusive and dispersive transport of single- and multi-component solutions in homogeneous porous media. The miscible displacement technique was used to investigate the transport behavior of 14C-labelled 2,4-dichlorophenoxyacetic acid ( 2,4-D) in two materials for which sorption of 2,4-D was minimal. Comparison of breakthrough curves collected for 2,4-D in single- and multi-component solutions shows that there is little, if any, difference in transport behavior over a wide range of pore-water velocities (70, 7, 0.66 and 0.06 cm h -1). Thus, dispersivities measured with a non-sorbing single-solute solution should be applicable to multicomponent systems.

Dynamics of Phenanthrenequinone on Carbon Nano-Onion Surfaces Probed by Quasielastic Neutron Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anjos, Daniela M; Mamontov, Eugene; Brown, Gilbert M

We used quasielastic neutron scattering (QENS) to study the dynamics of phenanthrenequinone (PQ) on the surface of onion-like carbon (OLC), or so called carbon onions, as a function of surface coverage and temperature. For both the high- and low-coverage samples, we observed two diffusion processes; a faster process and nearly an order of magnitude slower process. On the high-coverage surface, the slow diffusion process is of long-range translational character, whereas the fast diffusion process is spatially localized on the length scale of ~ 4.7 . On the low-coverage surface, both diffusion processes are spatially localized; on the same length scalemore » of ~ 4.7 for the fast diffusion and a somewhat larger length scale for the slow diffusion. Arrhenius temperature dependence is observed except for the long-range diffusion on the high-coverage surface. We attribute the fast diffusion process to the generic localized in-cage dynamics of PQ molecules, and the slow diffusion process to the long-range translational dynamics of PQ molecules, which, depending on the coverage, may be either spatially restricted, or long-range. On the low-coverage surface, uniform surface coverage is not attained, and the PQ molecules experience the effect of spatial constraints on their long-range translational dynamics. Unexpectedly, the dynamics of PQ molecules on OLC as a function of temperature and surface coverage bears qualitative resemblance to the dynamics of water molecules on oxide surfaces, including practically temperature-independent residence times for the low-coverage surface. The dynamics features that we observed may be universal across different classes of surface adsorbates.« less

Sustainable intensive thermal use of the shallow subsurface-a critical view on the status quo.

PubMed

Vienken, T; Schelenz, S; Rink, K; Dietrich, P

2015-01-01

Thermal use of the shallow subsurface for heat generation, cooling, and thermal energy storage is increasingly gaining importance in reconsideration of future energy supplies. Shallow geothermal energy use is often promoted as being of little or no costs during operation, while simultaneously being environmentally friendly. Hence, the number of installed systems has rapidly risen over the last few decades, especially among newly built houses. While the carbon dioxide reduction potential of this method remains undoubted, concerns about sustainability and potential negative effects on the soil and groundwater due to an intensified use have been raised-even as far back as 25 years ago. Nevertheless, consistent regulation and management schemes for the intensified thermal use of the shallow subsurface are still missing-mainly due to a lack of system understanding and process knowledge. In the meantime, large geothermal applications, for example, residential neighborhoods that are entirely dependent up on shallow geothermal energy use or low enthalpy aquifer heat storage, have been developed throughout Europe. Potential negative effects on the soil and groundwater due to an intensive thermal use of the shallow subsurface as well as the extent of potential system interaction still remain unknown. © 2014, National Ground Water Association.

Effects of basin size on low-flow stream chemistry and subsurface contact time in the neversink river watershed, New York

USGS Publications Warehouse

Wolock, D.M.; Fan, J.; Lawrence, G.B.

1997-01-01

The effects of basin size on low-flow stream chemistry and subsurface contact time were examined for a part of the Neversink River watershed in southern New York State. Acid neutralizing capacity (ANC), the sum of base cation concentrations (SBC), pH and concentrations of total aluminum (Al), dissolved organic carbon (DOC) and silicon (Si) were measured during low stream flow at the outlets of nested basins ranging in size from 0.2 to 166.3 km2. ANC, SBC, pH, Al and DOC showed pronounced changes as basin size increased from 0.2 to 3 km2, but relatively small variations were observed as basin size increased beyond 3 km2. An index of subsurface contact time computed from basin topography and soil hydraulic conductivity also showed pronounced changes as basin size increased from 0.2 to 3 km2 and smaller changes as basin size increased beyond 3 km2. These results suggest that basin size affects low-flow stream chemistry because of the effects of basin size on subsurface contact time. ?? 1997 by John Wiley & Sons, Ltd.

Ab initio study of novel carbon nanofoam structure as an anode material for Li secondary battery

NASA Astrophysics Data System (ADS)

Park, Hanjin; Park, Sora; Kang, Seoung-Hun; Kwon, Young-Kyun

2014-03-01

Using ab inito density functional theory, we investigate the adsorption and diffusion properties of Li atoms on a new carbon nanostructure, which may be used as an anode of Li secondary battery. We focus on a special carbon nanofoam structure consisting of Schwarzite structures with negative Gaussian curvature as core parts, which are interconnected through (4,4) CNT segments. Considering the symmetry of the nanofoam structure, we find various Li adsorption sites exhibiting relatively large binding energies (>= 2 . 00 eV). Based on these adsorption sites, we identify several diffusion paths on the outside or inside surface of the nanofoam structure and examine the diffusion barriers along the paths. Our results show that Li atom can diffuse almost freely due to its low energy barriers on both outside and inside surfaces. Finally, we also evaluate the energy gain tendency and the volume expansion as well as the average binding energy while adding Li atoms to estimate the Li-capacity and recyclability of the system, which are important characterisitics for anode materials. We conclude that the carbon nanofoam structure would be better as an anode material than graphite in Li capacity and volume expansion.

ABIOTIC DEGRADATION OF TRICHLOROETHYLENE UNDER THERMAL REMEDIATION CONDITIONS

EPA Science Inventory

The degradation of TCE (C₂HCl₃) to carbon dioxide (CO₂) and chloride (Cl^-) has been reported to occur during thermal remediation of subsurface environments. The overall goal of this study was to evaluate abiotic degradation of TCE at el...

Analytic solutions for colloid transport with time- or depth-dependent retention in porous media

USDA-ARS?s Scientific Manuscript database

Elucidating and quantifying the transport of industrial nanoparticles (e.g. silver, carbon nanotubes, and graphene oxide) and other colloid-size particles such as viruses and bacteria is important to safeguard and manage the quality of the subsurface environment. Analytic solutions were derived for...

40 CFR 98.441 - Reporting threshold.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Reporting threshold. 98.441 Section 98...) MANDATORY GREENHOUSE GAS REPORTING Geologic Sequestration of Carbon Dioxide § 98.441 Reporting threshold. (a... amount of CO2 for long-term containment in subsurface geologic formations. There is no threshold. (b...

Infrared emission contrast for the visualization of subsurface graphical features in artworks

NASA Astrophysics Data System (ADS)

Mercuri, Fulvio; Paoloni, Stefano; Cicero, Cristina; Zammit, Ugo; Orazi, Noemi

2018-03-01

In this paper a method is presented based on the use of active infrared thermography for the detection of subsurface graphical features in artworks. A theoretical model for the thermographic signal describing the physical mechanisms which allow the identification of the buried features has been proposed and thereafter it has been applied to the analysis of the results obtained on specifically made test samples. It is shown that the proposed model predictions adequately describe the experimental results obtained on the test samples. A comparative analysis between the proposed technique and infrared reflectography is also presented. The comparison shows that active thermography can be more effective in the detection of features buried below infrared translucent layers and, in addition, that it can provide information about the depth of the detected features, particularly in highly IR diffusing materials.

Phytoplankton division rates in light-limited environments: two adaptations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivkin, R.B.; Voytek, M.A.; Seliger, H.H.

1982-02-26

Red tide-forming dinoflagellates maximize cell numbers during periods of low light intensities in two ways. For short-term exposures to suboptimal light intensities such as might occur during recirculation in frontal convergences, cell division rates can be maintained at the expense of stored carbon for up to two generation times. During longer periods, corresponding to subsurface transport below a pycnocline, cell division rates eventually decrease as a portion of the fixed carbon is diverted to replenishing stored carbon. As a result, maximum rates of cell division can be resumed rapidly upon advection into surface waters where light intensities are optimal formore » growth.« less

Dynamic and structural properties of room-temperature ionic liquids near silica and carbon surfaces.

PubMed

Li, Song; Han, Kee Sung; Feng, Guang; Hagaman, Edward W; Vlcek, Lukas; Cummings, Peter T

2013-08-06

The dynamic and structural properties of a room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium(trifluoromethanesulfonimide) ([C4mim][Tf2N]) confined in silica and carbon mesopores were investigated by molecular dynamics (MD) simulations and nuclear magnetic resonance (NMR) experiments. The complex interfacial microstructures of confined [C4mim][Tf2N] are attributed to the distinctive surface features of the silica mesopore. The temperature-dependent diffusion coefficients of [C4mim][Tf2N] confined in the silica or carbon mesopore exhibit divergent behavior. The loading fraction (f = 1.0, 0.5, and 0.25) has a large effect on the magnitude of the diffusion coefficient in the silica pore and displays weaker temperature dependence as the loading fraction decreases. The diffusion coefficients of mesoporous carbon-confined [C4mim][Tf2N] are relatively insensitive to the loading faction and exhibit a temperature dependence that is similar to the bulk dependence at all loading levels. Such phenomena can be attributed to the unique surface heterogeneity, dissimilar interfacial microstructures, and interaction potential profile of RTILs near silica and carbon walls.

Predictive modeling of CO2 sequestration in deep saline sandstone reservoirs: Impacts of geochemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balashov, Victor N.; Guthrie, George D.; Hakala, J. Alexandra

2013-03-01

One idea for mitigating the increase in fossil-fuel generated CO{sub 2} in the atmosphere is to inject CO{sub 2} into subsurface saline sandstone reservoirs. To decide whether to try such sequestration at a globally significant scale will require the ability to predict the fate of injected CO{sub 2}. Thus, models are needed to predict the rates and extents of subsurface rock-water-gas interactions. Several reactive transport models for CO{sub 2} sequestration created in the last decade predicted sequestration in sandstone reservoirs of ~17 to ~90 kg CO{sub 2} m{sup -3|. To build confidence in such models, a baseline problem including rockmore » + water chemistry is proposed as the basis for future modeling so that both the models and the parameterizations can be compared systematically. In addition, a reactive diffusion model is used to investigate the fate of injected supercritical CO{sub 2} fluid in the proposed baseline reservoir + brine system. In the baseline problem, injected CO{sub 2} is redistributed from the supercritical (SC) free phase by dissolution into pore brine and by formation of carbonates in the sandstone. The numerical transport model incorporates a full kinetic description of mineral-water reactions under the assumption that transport is by diffusion only. Sensitivity tests were also run to understand which mineral kinetics reactions are important for CO{sub 2} trapping. The diffusion transport model shows that for the first ~20 years after CO{sub 2} diffusion initiates, CO{sub 2} is mostly consumed by dissolution into the brine to form CO{sub 2,aq} (solubility trapping). From 20-200 years, both solubility and mineral trapping are important as calcite precipitation is driven by dissolution of oligoclase. From 200 to 1000 years, mineral trapping is the most important sequestration mechanism, as smectite dissolves and calcite precipitates. Beyond 2000 years, most trapping is due to formation of aqueous HCO{sub 3}{sup -}. Ninety-seven percent of the maximum CO{sub 2} sequestration, 34.5 kg CO{sub 2} per m{sup 3} of sandstone, is attained by 4000 years even though the system does not achieve chemical equilibrium until ~25,000 years. This maximum represents about 20% CO{sub 2} dissolved as CO{sub 2},aq, 50% dissolved as HCO{sub 3}{sup -}{sub ,aq}, and 30% precipitated as calcite. The extent of sequestration as HCO{sub 3}{sup -} at equilibrium can be calculated from equilibrium thermodynamics and is roughly equivalent to the amount of Na+ in the initial sandstone in a soluble mineral (here, oligoclase). Similarly, the extent of trapping in calcite is determined by the amount of Ca2+ in the initial oligoclase and smectite. Sensitivity analyses show that the rate of CO{sub 2} sequestration is sensitive to the mineral-water reaction kinetic constants between approximately 10 and 4000 years. The sensitivity of CO{sub 2} sequestration to the rate constants decreases in magnitude respectively from oligoclase to albite to smectite.« less

Simulation studies of chemical erosion on carbon based materials at elevated temperatures

NASA Astrophysics Data System (ADS)

Kenmotsu, T.; Kawamura, T.; Li, Zhijie; Ono, T.; Yamamura, Y.

1999-06-01

We simulated the fluence dependence of methane reaction yield in carbon with hydrogen bombardment using the ACAT-DIFFUSE code. The ACAT-DIFFUSE code is a simulation code based on a Monte Carlo method with a binary collision approximation and on solving diffusion equations. The chemical reaction model in carbon was studied by Roth or other researchers. Roth's model is suitable for the steady state methane reaction. But this model cannot estimate the fluence dependence of the methane reaction. Then, we derived an empirical formula based on Roth's model for methane reaction. In this empirical formula, we assumed the reaction region where chemical sputtering due to methane formation takes place. The reaction region corresponds to the peak range of incident hydrogen distribution in the target material. We adopted this empirical formula to the ACAT-DIFFUSE code. The simulation results indicate the similar fluence dependence compared with the experiment result. But, the fluence to achieve the steady state are different between experiment and simulation results.

Control of the Structure of Diffusion Layer in Carbon Steels Under Nitriding with Preliminary Deposition of Copper Oxide Catalytic Films

NASA Astrophysics Data System (ADS)

Petrova, L. G.; Aleksandrov, V. A.; Malakhov, A. Yu.

2017-07-01

The effect of thin films of copper oxide deposited before nitriding on the phase composition and the kinetics of growth of diffusion layers in carbon steels is considered. The process of formation of an oxide film involves chemical reduction of pure copper on the surface of steel specimens from a salt solution and subsequent oxidation under air heating. The oxide film exerts a catalytic action in nitriding of low- and medium-carbon steels, which consists in accelerated growth of the diffusion layer, the nitride zone in the first turn. The kinetics of the nitriding process and the phase composition of the layer are controlled by the thickness of the copper oxide precursor, i.e., the deposited copper film.

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

DOE PAGES

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk; ...

2017-04-05

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of Fe, Mn, and As to the surface waters, whereas the sediments act as a sink for V. Iron and Mn fluxes are substantial, ranging from 50 to 30,000 and 770 to 4,300 nmol cm -2 day -1, respectively, whereas As fluxes are much less, ranging from 2.1 to 17 nmol cm -2 day -1. Vanadium fluxes range from 3.0 nmol cm -2 day -1 directed into the sediment to 1.7 nmol cm -2 day -1 directed out of the sediment« less

Arsenic, vanadium, iron, and manganese biogeochemistry in a deltaic wetland, southern Louisiana, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Telfeyan, Katherine; Breaux, Alexander; Kim, Jihyuk

Geochemical cycling of the redox-sensitive trace elements arsenic (As) and vanadium (V) was examined in shallow pore waters from a marsh in an interdistributary embayment of the lower Mississippi River Delta. In particular, we explore how redox changes with depth and distance from the Mississippi River affect As and V cycling in the marsh pore waters. Previous geophysical surveys and radon mass balance calculations suggested that Myrtle Grove Canal and bordering marsh receive fresh groundwater, derived in large part from seepage of the Mississippi River, which subsequently mixes with brackish waters of Barataria Bay. In addition, the redox geochemistry ofmore » pore waters in the wetlands is affected by Fe and S cycling in the shallow subsurface (0-20 cm). Sediments with high organic matter content undergo SO 4 2- reduction, a process ubiquitous in the shallow subsurface but largely absent at greater depths (~3 m). Instead, at depth, in the absence of organic-rich sediments, Fe concentrations are elevated, suggesting that reduction of Fe(III) oxides/oxyhydroxides buffers redox conditions. Arsenic and V cycling in the shallow subsurface are decoupled from their behavior at depth, where both V and As appear to be removed from solution by either diffusion or adsorption onto, or co-precipitation with, authigenic minerals within the deeper aquifer sediments. Pore water As concentrations are greatest in the shallow subsurface (e.g., up to 315 nmol kg -1 in the top ~20 cm of the sediment) but decrease with depth, reaching values <30 nmol kg -1 at depths between 3 and 4 m. Vanadium concentrations appear to be tightly coupled to Fe cycling in the shallow subsurface, but at depth, V may be adsorbed to clay or sedimentary organic matter (SOM). Diffusive fluxes are calculated to examine the export of trace elements from the shallow marsh pore waters to the overlying canal water that floods the marsh. The computed fluxes suggest that the shallow sediment serves as a source of Fe, Mn, and As to the surface waters, whereas the sediments act as a sink for V. Iron and Mn fluxes are substantial, ranging from 50 to 30,000 and 770 to 4,300 nmol cm -2 day -1, respectively, whereas As fluxes are much less, ranging from 2.1 to 17 nmol cm -2 day -1. Vanadium fluxes range from 3.0 nmol cm -2 day -1 directed into the sediment to 1.7 nmol cm -2 day -1 directed out of the sediment« less

Evaluation of equivalent defect heat generation in carbon epoxy composite under powerful ultrasonic stimulation by using infrared thermography

NASA Astrophysics Data System (ADS)

Derusova, D. A.; Vavilov, V. P.; Pawar, S. S.

2015-04-01

Low velocity impact is a frequently observed event during the operation of an aircraft composite structure. This type of damage is aptly called as “blind-side impact damage” as it is barely visible as a dent on the impacted surface, but may produce extended delaminations closer to the rear surface. One-sided thermal nondestructive testing is considered as a promising technique for detecting impact damage but because of diffusive nature of optical thermal signals there is drop in detectability of deeper subsurface defects. Ultrasonic Infrared thermography is a potentially attractive nondestructive evaluation technique used to detect the defects through observation of vibration-induced heat generation. Evaluation of the energy released by such defects is a challenging task. In this study, the thin delaminations caused by impact damage in composites and which are subjected to ultrasonic excitation are considered as local heat sources. The actual impact damage in a carbon epoxy composite which was detected by applying a magnetostrictive ultrasonic device is then modeled as a pyramid-like defect with a set of delaminations acting as an air-filled heat sources. The temperature rise expected on the surface of the specimen was achieved by varying energy contribution from each delamination through trial and error. Finally, by comparing the experimental temperature elevations in defective area with the results of temperature simulations, we estimated the energy generated by each defect and defect power of impact damage as a whole. The results show good correlation between simulations and measurements, thus validating the simulation approach.

The influence of the ocean circulation state on ocean carbon storage and CO2 drawdown potential in an Earth system model

NASA Astrophysics Data System (ADS)

Ödalen, Malin; Nycander, Jonas; Oliver, Kevin I. C.; Brodeau, Laurent; Ridgwell, Andy

2018-03-01

During the four most recent glacial cycles, atmospheric CO2 during glacial maxima has been lowered by about 90-100 ppm with respect to interglacials. There is widespread consensus that most of this carbon was partitioned in the ocean. It is, however, still debated which processes were dominant in achieving this increased carbon storage. In this paper, we use an Earth system model of intermediate complexity to explore the sensitivity of ocean carbon storage to ocean circulation state. We carry out a set of simulations in which we run the model to pre-industrial equilibrium, but in which we achieve different states of ocean circulation by changing forcing parameters such as wind stress, ocean diffusivity and atmospheric heat diffusivity. As a consequence, the ensemble members also have different ocean carbon reservoirs, global ocean average temperatures, biological pump efficiencies and conditions for air-sea CO2 disequilibrium. We analyse changes in total ocean carbon storage and separate it into contributions by the solubility pump, the biological pump and the CO2 disequilibrium component. We also relate these contributions to differences in the strength of the ocean overturning circulation. Depending on which ocean forcing parameter is tuned, the origin of the change in carbon storage is different. When wind stress or ocean diapycnal diffusivity is changed, the response of the biological pump gives the most important effect on ocean carbon storage, whereas when atmospheric heat diffusivity or ocean isopycnal diffusivity is changed, the solubility pump and the disequilibrium component are also important and sometimes dominant. Despite this complexity, we obtain a negative linear relationship between total ocean carbon and the combined strength of the northern and southern overturning cells. This relationship is robust to different reservoirs dominating the response to different forcing mechanisms. Finally, we conduct a drawdown experiment in which we investigate the capacity for increased carbon storage by artificially maximising the efficiency of the biological pump in our ensemble members. We conclude that different initial states for an ocean model result in different capacities for ocean carbon storage due to differences in the ocean circulation state and the origin of the carbon in the initial ocean carbon reservoir. This could explain why it is difficult to achieve comparable responses of the ocean carbon pumps in model inter-comparison studies in which the initial states vary between models. We show that this effect of the initial state is quantifiable. The drawdown experiment highlights the importance of the strength of the biological pump in the control state for model studies of increased biological efficiency.

The effect of carbon surface chemical composition on the adsorption of acetanilide.

PubMed

Terzyk, Artur P

2004-04-01

The study of acetanilide adsorption-desorption performed at three temperatures (300, 310, and 320 K) and at two pH levels (7.0 and 1.5) on the series of D43/1 carbons (initial and modified with HNO3, fuming H2SO4, and gaseous NH3) is reported. Sorption data are additionally supplemented with the results of thermal analysis and calorimetric and kinetic measurements. It is shown that, generally, acetanilide adsorption at the neutral pH level is reversible (only on the more acidic carbons and at the lowest temperature does hysteresis occur due to the formation of hydrogen bonds with surface OH groups), and it decreases for the chemically modified carbons. In contrast, at the acidic pH level acetanilide adsorption is irreversible. A mechanism of irreversibility is proposed and it is shown that hysteresis is caused by the chemical reaction between the nucleophile (carbon) and the protonized acetanilide molecules. For all studied carbons, at the acidic pH level, adsorption increases and this is caused by the weakly basic character of acetanilide molecule. Adsorption results are described applying adsorbability and Dubinin-Astakhov, quasi-Freundlich and solution analogue of the Toth adsorption isotherm equations. Using the kinetic data, the effective diffusion coefficients and the energy of diffusion are calculated. It is shown that the diffusion is mainly a surface process, and the contribution of the pore diffusion increases with the rise in temperature. By applying different correlations between the parameters obtained from the theoretical description of experimental data and those characterizing the chemical composition of the studied carbons, the role of the latter in the adsorption and kinetics of acetanilide adsorption is determined.

Final Report: Molecular Mechanisms of Interfacial Reactivity in Near Surface and Extreme Geochemical Environments (DE-SC0009362)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dixon, David A

2016-03-27

The prediction of the long-term stability and safety of geologic sequestration of greenhouse gases requires a detailed understanding of subsurface transport and chemical interactions between the disposed greenhouse gases and the geologic media. In this regard, mineral-fluid interactions are of prime importance since reactions that occur on or near the interface can assist in the long term sequestration of CO2 by trapping in mineral phases such as carbonates, as well as influencing the subsurface migration of the disposed fluids via creation or plugging of pores or fractures in the host rock strata. Previous research on mineral-fluid interaction for subsurface CO2more » storage has focused almost entirely on the aqueous phase, i.e., reactivity with aqueous solutions or brines containing dissolved CO2. However, interactions with neat to water-saturated non-aqueous fluids are of equal if not greater importance since supercritical CO2 (scCO2) is less dense than the aqueous phase or oil which will create a buoyant scCO2 plume that ultimately will dominate the pore volume within the caprock, and the injected scCO2 will contain water soon after injection and this water can be highly reactive. Collectively, therefore, mineral interactions with water-saturated scCO2-dominated fluids are pivotal and could result in the stable sequestration of CO2 by trapping in mineral phases such as metal carbonates within otherwise permeable zones in the caprock. The primary objective is to unravel the molecular mechanisms governing the reactivity of mineral phases important in the geologic sequestration of CO2 with variably wet supercritical carbon dioxide as a function of T, P, and mineral structure using computational chemistry. This work is in close collaboration with the PNNL Geosciences effort. The focus of the work at The University of Alabama is computational studies of the formation of magnesium and calcium carbonates and oxides and their reactivity and providing computational support of the experimental efforts at PNNL, especially for energetics, structural properties, and interpretation of spectra.« less

Mineralizing Filamentous Bacteria from the Prony Bay Hydrothermal Field Give New Insights into the Functioning of Serpentinization-Based Subseafloor Ecosystems

PubMed Central

Pisapia, Céline; Gérard, Emmanuelle; Gérard, Martine; Lecourt, Léna; Lang, Susan Q.; Pelletier, Bernard; Payri, Claude E.; Monnin, Christophe; Guentas, Linda; Postec, Anne; Quéméneur, Marianne; Erauso, Gaël; Ménez, Bénédicte

2017-01-01

Despite their potential importance as analogs of primitive microbial metabolisms, the knowledge of the structure and functioning of the deep ecosystems associated with serpentinizing environments is hampered by the lack of accessibility to relevant systems. These hyperalkaline environments are depleted in dissolved inorganic carbon (DIC), making the carbon sources and assimilation pathways in the associated ecosystems highly enigmatic. The Prony Bay Hydrothermal Field (PHF) is an active serpentinization site where, similar to Lost City (Mid-Atlantic Ridge), high-pH fluids rich in H2 and CH4 are discharged from carbonate chimneys at the seafloor, but in a shallower lagoonal environment. This study aimed to characterize the subsurface microbial ecology of this environment by focusing on the earliest stages of chimney construction, dominated by the discharge of hydrothermal fluids of subseafloor origin. By jointly examining the mineralogy and the microbial diversity of the conduits of juvenile edifices at the micrometric scale, we find a central role of uncultivated bacteria belonging to the Firmicutes in the ecology of the PHF. These bacteria, along with members of the phyla Acetothermia and Omnitrophica, are identified as the first chimneys inhabitants before archaeal Methanosarcinales. They are involved in the construction and early consolidation of the carbonate structures via organomineralization processes. Their predominance in the most juvenile and nascent hydrothermal chimneys, and their affiliation with environmental subsurface microorganisms, indicate that they are likely discharged with hydrothermal fluids from the subseafloor. They may thus be representative of endolithic serpentinization-based ecosystems, in an environment where DIC is limited. In contrast, heterotrophic and fermentative microorganisms may consume organic compounds from the abiotic by-products of serpentinization processes and/or from life in the deeper subsurface. We thus propose that the Firmicutes identified at PHF may have a versatile metabolism with the capability to use diverse organic compounds from biological or abiotic origin. From that perspective, this study sheds new light on the structure of deep microbial communities living at the energetic edge in serpentinites and may provide an alternative model of the earliest metabolisms. PMID:28197130

Mineralizing Filamentous Bacteria from the Prony Bay Hydrothermal Field Give New Insights into the Functioning of Serpentinization-Based Subseafloor Ecosystems.

PubMed

Pisapia, Céline; Gérard, Emmanuelle; Gérard, Martine; Lecourt, Léna; Lang, Susan Q; Pelletier, Bernard; Payri, Claude E; Monnin, Christophe; Guentas, Linda; Postec, Anne; Quéméneur, Marianne; Erauso, Gaël; Ménez, Bénédicte

2017-01-01

Despite their potential importance as analogs of primitive microbial metabolisms, the knowledge of the structure and functioning of the deep ecosystems associated with serpentinizing environments is hampered by the lack of accessibility to relevant systems. These hyperalkaline environments are depleted in dissolved inorganic carbon (DIC), making the carbon sources and assimilation pathways in the associated ecosystems highly enigmatic. The Prony Bay Hydrothermal Field (PHF) is an active serpentinization site where, similar to Lost City (Mid-Atlantic Ridge), high-pH fluids rich in H 2 and CH 4 are discharged from carbonate chimneys at the seafloor, but in a shallower lagoonal environment. This study aimed to characterize the subsurface microbial ecology of this environment by focusing on the earliest stages of chimney construction, dominated by the discharge of hydrothermal fluids of subseafloor origin. By jointly examining the mineralogy and the microbial diversity of the conduits of juvenile edifices at the micrometric scale, we find a central role of uncultivated bacteria belonging to the Firmicutes in the ecology of the PHF. These bacteria, along with members of the phyla Acetothermia and Omnitrophica , are identified as the first chimneys inhabitants before archaeal Methanosarcinales . They are involved in the construction and early consolidation of the carbonate structures via organomineralization processes. Their predominance in the most juvenile and nascent hydrothermal chimneys, and their affiliation with environmental subsurface microorganisms, indicate that they are likely discharged with hydrothermal fluids from the subseafloor. They may thus be representative of endolithic serpentinization-based ecosystems, in an environment where DIC is limited. In contrast, heterotrophic and fermentative microorganisms may consume organic compounds from the abiotic by-products of serpentinization processes and/or from life in the deeper subsurface. We thus propose that the Firmicutes identified at PHF may have a versatile metabolism with the capability to use diverse organic compounds from biological or abiotic origin. From that perspective, this study sheds new light on the structure of deep microbial communities living at the energetic edge in serpentinites and may provide an alternative model of the earliest metabolisms.

Induced seismicity constraints on subsurface geological structure, Paradox Valley, Colorado

NASA Astrophysics Data System (ADS)

Block, Lisa V.; Wood, Christopher K.; Yeck, William L.; King, Vanessa M.

2015-02-01

Precise relative hypocentres of seismic events induced by long-term fluid injection at the Paradox Valley Unit (PVU) brine disposal well provide constraints on the subsurface geological structure and compliment information available from deep seismic reflection and well data. We use the 3-D spatial distribution of the hypocentres to refine the locations, strikes, and throws of subsurface faults interpre­ted previously from geophysical surveys and to infer the existence of previously unidentified subsurface faults. From distinct epicentre lineations and focal mechanism trends, we identify a set of conjugate fracture orientations consistent with shear-slip reactivation of late-Palaeozoic fractures over a widespread area, as well as an additional fracture orientation present only near the injection well. We propose simple Mohr-Coulomb fracture models to explain these observations. The observation that induced seismicity preferentially occurs along one of the identified conjugate fracture orientations can be explained by a rotation in the direction of the regional maximum compressive stress from the time when the fractures were formed to the present. Shear slip along the third fracture orientation observed near the injection well is inconsistent with the current regional stress field and suggests a local rotation of the horizontal stresses. The detailed subsurface model produced by this analysis provides important insights for anticipating spatial patterns of future induced seismicity and for evaluation of possible additional injection well sites that are likely to be seismically and hydrologically isolated from the current well. In addition, the interpreted fault patterns provide constraints for estimating the maximum magnitude earthquake that may be induced, and for building geomechanical models to simulate pore pressure diffusion, stress changes and earthquake triggering.

Genetic legacy of the deep subsurface recorded in the outflow channel of a terrestrial serpentinizing seep (Luzon, the Philippines)

NASA Astrophysics Data System (ADS)

Woycheese, K. M.; Meyer-Dombard, D. R.; Cardace, D.; Arcilla, C. A.

2014-12-01

The deep subsurface microbial community represents the largest biome on Earth, yet accessing this deep biosphere is challenging. Fluids seep along fractures from aquifers that may support diverse microbial communities, living off hydrogen gas generated by radiolysis, serpentinization, or thermogenic reactions. A serpentinizing seep, emanating fluids as high as pH 11.27, was found to accrete meters-long carbonate terraces in the Zambales ophiolite range (Luzon, the Philippines). Samples were collected at several locations along the Poon Bato (PB) River, focusing primarily on the pools and terraces formed by carbonate rimstone (Figure 1). As serpentinizing fluids are exposed to the atmosphere, dynamic niches are established in surface sediments. We propose that the high pH, reducing, high Ca+2 fluid pool terraces reflect remnants of deep subsurface microbial communities, based on high-throughput 16S rRNA sequencing data. In total, eight samples were collected for environmental DNA analysis. Post-sequence analysis revealed a total of 927126 counts, with an average of 115890.75 counts per sample. Many taxa aligned with cultured representatives of serpentinizing seep-associated taxa, including Bacteroidetes, Clostrida, Chloroflexi, Methylococcales, and Xanthomonadales. Geochemical data indicates an average fluid temperature of 28.9°C, and pH that varies from 9.22-11.27. Total carbon wt.% of solids was highest in a shallow pool shaped by boulders, where calcite precipitation occurred over nearly every surface. Dissolved oxygen (DO%) was highest at PB1 main pool (60%), although a calcite skin had formed along the air-water interface. Dissolved inorganic carbon (DIC) at PB1 main pool was 1.3 ppm, while at PB2 main pool, the DIC was higher (6.0 ppm). The lack of calcite skin may allow more direct access to atmospheric carbon dioxide at PB2. The isotopic value of carbon-13 was depleted at PB1 relative to PB2 (δ13C VPDB -25.4 ‰ versus δ13C VPDB ‰ -17.5, respectively). The DOC concentration at PB1 main pool was 0.3 ppm and 1.15 ppm at PB2. Given the low DIC concentrations at PB1, it is suggested that heterotrophy may dominate over autotrophy in the system. This suggests that the highly reducing, high pH fluids emanating from fluid seeps at Poon Bato influence surface communities via inundation with serpentinizing fluid.

U-tube based near-surface environmental monitoring in the Shenhua carbon dioxide capture and storage (CCS) project.

PubMed

Li, Qi; Song, Ranran; Shi, Hui; Ma, Jianli; Liu, Xuehao; Li, Xiaochun

2018-04-01

The CO 2 injected into deep formations during implementation of carbon dioxide (CO 2 ) capture and storage (CCS) technology may leak and migrate into shallow aquifers or ground surfaces through a variety of pathways over a long period. The leaked CO 2 can threaten shallow environments as well as human health. Therefore, almost all monitoring programs for CCS projects around the world contain near-surface monitoring. This paper presents a U-tube based near-surface monitoring technology focusing on its first application in the Shenhua CCS demonstration project, located in the Ordos Basin, Inner Mongolia, China. First, background information on the site monitoring program of the Shenhua CCS demonstration project was provided. Then, the principle of fluid sampling and the monitoring methods were summarized for the U-tube sampler system, and the monitoring data were analyzed in detail. The U-tube based monitoring results showed that the U-tube sampler system is accurate, flexible, and representative of the subsurface fluid sampling process. The monitoring indicators for the subsurface water and soil gas at the Shenhua CCS site indicate good stratification characteristics. The concentration level of each monitoring indicator decreases with increasing depth. Finally, the significance of this near-surface environmental monitoring technology for CO 2 leakage assessments was preliminarily confirmed at the Shenhua CCS site. The application potential of the U-tube based monitoring technology was also demonstrated during the subsurface environmental monitoring of other CCS projects.