Search NASA⌕ Search

SEARCH · Search NASA

Results for “nitrogen mineralization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 217 records · Page 12

Contrasting geochemical and fungal controls on decomposition of lignin and soil carbon at continental scale

Lignin is an abundant and complex plant polymer that may limit litter decomposition, yet lignin is sometimes a minor constituent of soil organic carbon (SOC). Accounting for diversity in soil characteristics might reconcile this apparent contradiction. Tracking decomposition of a lignin/litter mixture and SOC across different North American mineral soils using lab and field incubations, here we show that cumulative lignin decomposition varies 18-fold among soils and is strongly correlated with bulk litter decomposition, but not SOC decomposition. Climate legacy predicts decomposition in the lab, and impacts of nitrogen availability are minor compared with geochemical and microbial properties. Lignin decomposition increases with some metals and fungal taxa, whereas SOC decomposition decreases with metals and is weakly related with fungi. Decoupling of lignin and SOC decomposition and their contrasting biogeochemical drivers indicate that lignin is not necessarily a bottleneck for SOC decomposition and can explain variable contributions of lignin to SOC among ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Data for: Spatial access and resource limitations control carbon mineralization in soils

This dataset contains data and code used for the paper "Spatial access and resource limitations control carbon mineralization in soils", https://doi.org/10.1016/j.soilbio.2021.108427. Core-scale soil carbon fluxes are ultimately regulated by pore-scale dynamics of substrate availability and microbial access. These are constrained by physicochemical and biochemical phenomena (e.g. spatial access and hydrologic connectivity, physical occlusion, adsorption-desorption with mineral surfaces, nutrient and resource limitations). We conducted an experiment to determine how spatial access and resource limitations influence core-scale water-soluble soil organic matter (SOM) mineralization, and how these are regulated by antecedent moisture conditions. Intact soil cores were incubated at field-moist vs. drought conditions, after which they were saturated from above (to simulate precipitation) or below (to simulate groundwater recharge). Soluble carbon (acetate) and nitrogen (nitrate) forms were added to some cores during the rewetting process to alleviate potential nutrient limitations. Soil respiration was measured during the incubation, after which pore water was extracted from the saturated soils and analyzed for water soluble organic carbon concentrations and characterization. Our results showed that carbon (C) amendments increased the cumulative carbon dioxide (CO2) evolved from the soil cores, suggesting that the soils were C-limited. Drought and rewetting increased soil respiration, and there was a greater abundance of complex aromatic molecules in pore waters sampled from these soils. This newly available substrate appeared to alleviate nutrient limitations on respiration, because there were no further respiration increases with subsequent C and N amendments. We had hypothesized that respiration would be influenced by wetting direction, as simulated precipitation would mobilize C from the surface. However, as a main effect, this response was seen only in the C-amended soils, indicating that surface-C may not have been bioavailable. At the pore scale (pore water samples), drought and the C, N amendments caused a net loss of identified molecules when the soils were rewet from below, whereas wetting from above caused a net increase in identified molecules, suggesting that fresh inputs stimulated the C-and N-limited microbial populations present deeper in the soil profile. Our experiment highlights the complex and interactive role of antecedent moisture conditions, wetting direction, and resource limitations in driving core-scale C fluxes.This dataset contains a compressed (.zip) archive of the data and R scripts used for this manuscript. The dataset includes files in .csv format, which can be accessed and processed using MS Excel or R. This archive can also be accessed on GitHub at https://github.com/kaizadp/TES_spatial_access_2021 (DOI: 10.5281/zenodo.5522938).

54 ENVIRONMENTAL SCIENCES↗

“Tailing” Phenomenon During Polymer Propagation at The Milne Point Polymer Flood

Chemical flooding simulators traditionally assume that polymer retention follows the Langmuir isotherm, while fractional-flow calculations assume concentration-independent retention. Both models predict a delay in propagation of the polymer front (in proportion to the retention value), followed by a rapid rise in produced polymer concentration to the injected level. In contrast, laboratory retention studies for the Milne Point polymer flood (North Slope of Alaska) consistently show virtually no delay in polymer propagation, a rapid rise in produced polymer to 70-90% of the injected concentration, followed by produced concentration gradually approaching the injected value over many pore volumes. From a practical viewpoint, this behavior means that retention causes no significant delay in propagation of the polymer bank (and therefore the oil bank), but the effective viscosity and displacement efficiency are less than originally planned. This paper explores why this polymer “tailing” phenomenon occurs. During core floods, effluent was analyzed for brine-tracer concentration, viscosity, total organic carbon, and total nitrogen. The latter three items allowed three independent measures of polymer concentration and polymer retention. Experiments were performed with Milne Point core material, oil, brine, and conditions. Mechanistic experiments were also performed with packs of glass beads with controlled levels of various minerals. In Milne Point cores, the presence of the tailing phenomenon was not sensitive to flow rate, polymer concentration, core heterogeneity, or whether the core was preserved, cleaned of oil, or cleaned and resaturated with oil, or cleaned, re-saturated and aged with oil. The three independent measures of polymer concentration confirmed that the tailing phenomenon was not an artifact associated with polymer degradation or detection interferences. Tailing was also observed during mechanistic floods using glassbead packs when sufficient levels of illite or kaolinite were present. This observation was consistent with high levels of illite noted in Milne Point cores. The tailing was not noted during mechanistic floods that contained beads with montmorillonite, chlorite, calcium carbonate, dolomite, siderite, pyrite, or calcium sulfate. A model is proposed to account for the tailing phenomenon. This work suggests that mineralogy analysis (especially for illite and kaolinite) may reveal whether tailing should be accounted for during simulations of polymer propagation/retention in a given field application.

Seright, Randy↗

Soil Carbon Dynamics Following Land Use Changes and Conversion to Oil Palm Plantations in Tropical Lowlands Inferred From Radiocarbon

We measured the 14C and 13C isotopic values of soil organic carbon in mineral soil from lowland tropical forests to provide insight into how quickly carbon is turning over in the soil following conversion of primary forests to oil palm plantations. In addition to areas converted to oil palm plantations in Peru, Indonesia, and Cameroon, we examine pastures and secondary forests in Peru as a comparison to the carbon cycling processes operating in the oil palm plantations.This dataset includes radiocarbon (Δ14C) and stable carbon (δ13C) isotopes of soil organic carbon in mineral soils from natural lowland forests and oil palm plantations in Peru, Indonesia, and Cameroon. We additionally examine plots of secondary forests following agricultural use and pastures on cleared natural forest in Peru. In addition to isotopic data, this dataset includes soil carbon and nitrogen concentrations and stock, soil texture (percent sand, silt, and clay), pH, ECEC (effective cation exchange capacity), base saturation, and bulk density. Soils were sampled in 4 depth increments to 100 cm depth.This dataset supports the publication Finstad et al., 2020. Finstad, K., van Straaten, O., Veldkamp, E., & McFarlane, K. (2020). Soil carbon dynamics following land use changes and conversion to oil palm plantations in tropical lowlands inferred from radiocarbon. Global Biogeochemical Cycles, 34, e2019GB006461. https://doi.org/10.1029/2019GB006461

54 ENVIRONMENTAL SCIENCES↗

Enhanced H 2 production from subsurface through organic acids stimulation Report

Geologic hydrogen (H 2 ) generation through serpentinization of ultramafic rocks presents a promising alternative to conventional hydrogen production, utilizing Earth's abundant magnesium- and iron-rich minerals. This study explores the use of short-chain organic acids (specifically malic acid, MA; and citric acid, CA) to enhance hydrogen yields by stimulating mineral dissolution and iron oxidation from ultramafic rock samples. Batch experiments were conducted with crushed peridotite samples from the Tamarack Complex (Minnesota) and Del Puerto Ophiolite (California). Experiments employed 0.05 M and 0.1 M solutions of MA or CA, under 500 psi (35 bar) nitrogen pressure, at temperatures up to 150 °C. Real-time gas monitoring, aqueous chemistry and solid-phase analyses were performed to track reaction progress and hydrogen production.

08 HYDROGEN↗

Enhanced H 2 production from subsurface through organic acids stimulation

Geologic hydrogen (H₂) generation through serpentinization of ultramafic rocks presents a promising alternative to conventional hydrogen production, utilizing Earth's abundant magnesium- and iron-rich minerals. This study explores the use of short-chain organic acids (specifically malic acid, MA; and citric acid, CA) to enhance hydrogen yields by stimulating mineral dissolution and iron oxidation from ultramafic rock samples. Batch experiments were conducted with crushed peridotite samples from the Tamarack Complex (Minnesota) and Del Puerto Ophiolite (California). Experiments employed 0.05 M and 0.1 M solutions of MA or CA, under 500 psi (35 bar) nitrogen pressure, at temperatures up to 150 °C. Real-time gas monitoring, aqueous chemistry and solid-phase analyses were performed to track reaction progress and hydrogen production.

08 HYDROGEN↗

Combining organic amendments with enhanced rock weathering shifts soil carbon storage in croplands

Enhanced rock weathering (ERW) involves applying crushed silicate minerals to cropland soils to remove carbon dioxide and stabilize the global climate. If practiced widely, ERW has the potential to mitigate climate change and improve soil health and crop productivity. However, most ERW studies emphasize inorganic carbon (IC) chemistry, using model-based estimates and short-term mesocosms. Limited field data exist on how ERW interacts with organic amendments to affect organic carbon (C) cycling in soils. In a three-year field study in conventionally managed, irrigated maize fields, we monitored how key soil variables responded to crushed rock-alone, and in combination with compost and/or biochar. We measured weathering indicators (pH, major cations, and IC contents) and organic fractions, including particulate organic matter (POM), mineral-associated organic matter (MAOM), microbial biomass C, and water-extractable organic C. Rock-alone treatments increased weathering proxies (pH and IC) and showed an increasing trend in POM and MAOM, relative to control. In contrast, combining crushed rock with organic amendments resulted in lower soil organic C and nitrogen (N) concentrations (in both POM and MAOM) compared to organic amendments alone, though IC increased in the rock+compost treatment. Combining rock with both compost and biochar (compost/biochar) significantly lowered MAOM-N compared to compost/biochar alone. Overall, co-applying rock with organic inputs may promote weathering and C accrual but slow the accrual rate of organic C and N relative to organic amendments alone. Quantifying these trade-offs over multiple years and scales is critical to integrating ERW with existing soil health practices and climate mitigation strategies.

Biological and medical sciences↗

Combined Gamma Ray/neutron Spectroscopy for Mapping Lunar Resources

Some elements in the Moon can be resources, such as hydrogen and oxygen. Other elements, like Ti or the minerals in which they occur, such as ilmenite, could be used in processing lunar materials. Certain elements can also be used as tracers for other elements or lunar processes, such as hydrogen for mature regoliths with other solar-wind-implanted elements like helium, carbon, and nitrogen. A complete knowledge of the elemental composition of a lunar region is desirable both in identifying lunar resources and in lunar geochemical studies, which also helps in identifying and using lunar resources. The use of gamma ray and neutron spectroscopy together to determine abundances of many elements in the top few tens of centimeters of the lunar surface is discussed. To date, very few discussions of elemental mapping of planetary surfaces considered measurements of both gamma rays and the full range of neutron energies. The theories for gamma ray and neutron spectroscopy of the Moon and calculations of leakage fluxes are presented here with emphasis on why combined gamma ray/neutron spectroscopy is much more powerful than measuring either radiation alone.

Reedy, R. C.↗

Solar System Science With the Single Aperture Large Telescope for Universe Studies Space Observatory

Single Aperture Large Telescope for Universe Studies (SALTUS) is a NASA Astrophysics Probe Explorer (APEX)-class mission concept employing a robust far-infrared pointed space observatory. SALTUS comprises a 14-m inflatable reflector that provides 16× the sensitivity and 4× the angular resolution of Herschel, with a sunshield that radiatively cools the primary to 45 K, along with cryogenic detectors that collectively span the 34 to 660 μm far-infrared spectral range at high and moderate spectral resolutions. The high sensitivity and high spectral resolving power of the SALTUS heterodyne receivers enable both submillimeter and far-infrared observations of trace compounds comprising water and its isotopologues, hydrogen deuteride (HD), and a plethora of molecular species containing carbon, hydrogen, nitrogen, oxygen, phosphorus, or sulfur (CHNOPS), all of which are obscured by the Earth’s atmosphere. The high sensitivity and broadband spectral coverage of the SALTUS far-infrared grating spectrometer enables far-infrared observations of the lattice vibrational spectral signatures of ices and mineral grains contained within a wide variety of solar system targets, including comets, planetary atmospheres, near Enceladus’ plumes, and on the surfaces of icy moons, Jupiter trojans, centaurs, and Kuiper Belt objects. A key objective of SALTUS is to measure HDO∕H 2 O in both Jupiter family and Oort cloud comets. Additional observations will allow us to characterize the water torus around Saturn generated by its icy moon Enceladus, determine the source of stratospheric water in the giant planets, ascertain the time evolution of water on Venus, and search for H 2 O plumes on Europa, Ganymede, and Callisto. SALTUS will measure HD∕H 2 in all four giant planets to constrain models of their origin. SALTUS can also measure the abundance of CHNOPS-containing molecules and halides in the atmosphere of Venus and in the comae of comets. We review the extensive amount of solar system science achievable with SALTUS for both the Guaranteed Time Observation and the Guest Observer APEX mission observing programs.

Carrie M. Anderson↗

Murchison xenoliths

C3 xenoliths in a C2 host (Murchison) are unique among known meteoritic xenolith-host occurrences. They offer an opportunity to determine possible effects on the xenoliths by the hydrated host. Eleven xenoliths were found ranging from 2 to 13 mm. Four of these Murchison Xenoliths (MX1, MX2, MX3 and MX4) have been studied in detail. MX1 and MX2 were large enough for trace element, oxygen isotope, carbon isotope, bulk carbon and bulk nitrogen determinations. All four were studied petrographically and by analytical SEM. The xenoliths cannot be unequivocally identified as C3V or C3O subtypes. MX1 contains some matrix phyllosilicate, indicating reaction with water. MX1, MX2 and MX3 all show extensive alteration by an FeO-rich medium, and some minerals in them contain ferric iron. MX4, however, exhibits very minor alteration by FeO only. Oxygen isotopic and chemical data show that the alteration of these xenoliths did not take place in the Murchison host. The alterations occurred in one or more parent bodies, which were later disrupted to release these xenoliths that ultimately accreted onto the Murchison parent body.

Olsen, Edward J.↗

Understanding Soil Microbial Sources of Nitrous Acid and their Effect on Carbon-Nitrogen Cycle Interactions

Descriptions of soil emissions of reactive nitrogen (NO y ) in climate models are underdeveloped or non-existent, due to the fact that details of the mechanisms leading to nitrous acid (HONO) and nitrogen di-oxide (NO 2 ) formation in soil are lacking. This represents a major gap in our understanding of a significant land-atmosphere interaction that prevents us from scaling these processes from the laboratory scale to the ecosystem and global scales. There is a critical need to include these mechanisms into climate models since NO y controls the oxidative capacity of the atmosphere and the lifetime of greenhouse gases and the rate of secondary aerosol formation that directly and indirectly affect climate. The first objective of this proposal is to conduct laboratory and field measurements of NO y fluxes from diverse soil types and determine the mechanism of biogenic NO y formation. The working hypothesis based on preliminary data is that soil HONO and NO 2 is ultimately derived from ammonia-oxidizing archaea (AOA) and bacteria (AOB) that are widespread, but whose abundance varies across ecosystems. In the case of NO 2 , reactive oxygen species derived from iron-containing minerals and heterotrophic bacteria drive NO-to-NO 2 conversion. The approach is to link soil fluxes of HONO and NO 2 to AOA, AOB, and other heterotrophs using a combination of laboratory and field experiments, isotopic analysis, and molecular techniques to address how variability in land surfaces and edaphic properties impact emissions. In addition, we will determine the effect of HONO and NO 2 on nitrogen immobilization and the photo-oxidative capacity of soil. The working hypothesis is that HONO uptake in soil will be a source of nitrosonium and hydroxyl radical that will lead to thermal- and photodegradation of soil organic matter to CO 2 and CO, and the incorporation of N in soil organic matter. We will use surface-sensitive mass spectrometry techniques and gas phase detection to study N-immobilization in soil and subsequent enhancements in reactivity that lead to decomposition of organic matter. The results will be used to reduce the uncertainty in projections from the Community Earth System Model (CESM) stemming from inaccurate representations of soil NO y emissions. The proposed research is significant because, in addition to demonstrating new mechanisms of NO y formation and loss, it will be a crucial first step towards modeling the land-atmosphere exchange of HONO and NO 2 in the CESM. Improved model treatment of land-air exchange of NO y is key for understanding feedbacks between human activity and climate, and addressing societal concerns about the fate of N and C emitted to the atmosphere.

54 ENVIRONMENTAL SCIENCES↗

Effect of oxygen concentration in ZDP containing oils on surface composition and wear

A pin-on-disk wear study was performed with the lubricants dibutyl sebacate (DBS) and mineral oil (MO) with and without 1 weight percent zinc-dialkyl-dithiophospatee (ZDP) as an additive. The pin was annealed pure iron and the disk was M-2 tool steel. The selected load and speed guaranteed boundary lubrication. The ambient atmospheric oxygen concentration in an oxygen-nitrogen mixture was varied from 0 percent to 20 percent in order to examine its relationship to ZDP effectiveness. Auger electron spectroscopy combined with argon ion bombardment (depth profiling) was used to determine surface elemental composition on the pin when tested in DBS with and without ZDP. The ambient atmosphere was found to cause large variations in wear rate and surface composition. With MO, ZDP reduced wear under all conditions, but had little advantage over oxides formed at 20 percent oxygen atmosphere. With DBS, ZDP reduced wear at 0 percent oxygen, but gave varied results at other oxygen concentrations. Depth profiling revealed sulfuide formation at 0 percent oxygen and probably sulfates at 20 percent oxygen. The results are significant because varied oxygen concentrations can occur under actual lubricating conditions in practical machinery.

Brainard, W. A.↗

Changes in ratio of soluble sugars and free amino nitrogen in the apical meristem during floral transition of tobacco

Under a modification of the nutrient diversion hypothesis, we propose that an inequality in carbohydrate and nitrogen translocation to the apical meristem may be a controlling factor in floral transition. Experiments were conducted in controlled-environment chambers to determine the associations between microscopic characteristics of the transition from vegetative to floral stages of the apical meristem of flue-cured tobacco and to assimilate concentrations in the plant and apical meristem. Low temperature, nitrogen withdrawal, and restriction of nitrogen uptake were used as treatment variables. In all of these stress treatments, flowering occurred at a lesser number of leaves than in control treatments. Low temperature stress accelerated the time of transition to the floral stage as compared with a high temperature control; however, nitrogen stress did not accelerate the time of transition. All stress treatments affected the levels of nitrogen and carbohydrate in whole plants. Most notable was an increase in the percentage of starch and a decrease in the percentage of total soluble carbohydrate induced by the stress treatments. These data indicate that tobacco plants under stress accumulate excess carbohydrate in the form of starch. An apparent inequality in the relative concentrations of carbohydrate and nitrogen in the apical meristem was observed in all treatments at the time of floral transition and is in support of the nutrient diversion hypothesis.

NASA Discipline Number 61-10↗

Organic Matter in the Outer Solar System

Many solid bodies in the outer Solar System are covered with ices of various compositions, including water, carbon dioxide, methane, nitrogen, and other molecules that are solid at the low temperatures that prevail there. These ices have all been detected by remote sensing observations made with telescopes on Earth, or more recently, spacecraft in orbit (notably Galileo at Jupiter). The data also reveal other solid materials that could be minerals or complex carbon-bearing organic molecules. A study in progress using large ground-based telescopes to acquire infrared spectroscopic data, and laboratory results on the optical properties of complex organic matter, seeks to identify the non-icy materials on several satellites of Saturn, Uranus, and Neptune. The work on the satellites of Saturn is in part preparatory to the Cassini spacecraft investigation of the Saturn system, which will begin in 2004 and extend for four years.

Cruiskshank, Dale P.↗

Dimmable Electronic Ballast for a Gas Discharge Lamp

Titanium dioxide (TiO2) is the most efficient photocatalyst for organic oxidative degradation. TiO2 is effective not only in aqueous solution, but also in nonaqueous solvents and in the gas phase. It is photostable, biologically and chemically inert, and non-toxic. Low-energy UV light (approximately 375 nm, UV-A) can be used to photoactivate TiO2. TiO2 photocatalysis has been used to mineralize most types of organic compounds. Also, TiO2 photocatalysis has been effectively used in sterilization. This effectiveness has been demonstrated by its aggressive destruction of microorganisms, and aggressive oxidation effects of toxins. It also has been used for the oxidation of carbon monoxide to carbon dioxide, and ammonia to nitrogen. Despite having many attractive features, advanced photocatalytic oxidation processes have not been effectively used for air cleaning. One of the limitations of the traditional photocatalytic systems is the ballast that powers (lights) the bulbs. Almost all commercial off-the-shelf (COTS) ballasts are not dimmable and do not contain safety features. COTS ballasts light the UV lamp as bright as the bulb can be lit, and this results in shorter bulb lifetime and maximal power consumption. COTS magnetic ballasts are bulky, heavy, and inefficient. Several iterations of dimmable electronic ballasts have been developed. Some manifestations have safety features such as broken-bulb or over-temperature warnings, replace-bulb alert, logbulb operational hours, etc. Several electronic ballast boards capable of independently lighting and controlling (dimming) four fluorescent (UV light) bulbs were designed, fabricated, and tested. Because of the variation in the market bulb parameters, the ballast boards were designed with a very broad range output. The ballast boards can measure and control the current (power) for each channel.

Raducanu, Marius↗

Characterization of Nanoscale Pores in Tight Gas Sandstones Using Complex Techniques: A Case Study of a Linxing Tight Gas Sandstone Reservoir

Pore structures with rich nanopores and permeability in tight gas reservoirs are poorly understood up to date. Advanced techniques are needed to be employed to accurately characterize pore structures, especially tiny pores which include micron and nanopores. In this study, various experimental techniques such as scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) T 2 , nitrogen adsorption method, and NMR cryoporometry (NMRC) are combined to interrogate the complex pore systems of the tight gas reservoir in the Linxing formation, Ordos Basin, China. Results show that tight gas sandstones are primarily comprised of residual interparticle and clay-dominated pores. Clay and quartz are two dominate minerals while pyrite occupies a nontrivial amount as well. The permeability of tight gas sandstones is very low, exhibiting an extremely poor positive correlation with porosity. While pore types and relative pore contents are more influential factors on the permeability, accurate characterization of pore size distribution is critical for the permeability of tight gas sandstones. Therefore, complementary characterization methods are carried out, indicating that neither small pores with radii < 100 nm (around peak 1 in NMR T 2 distribution) nor large pores with radii > 5 μ m (around peak 3 in NMR T 2 distribution) control the permeability by analyzing the connectivity of the pores in various size ranges, but rather pores averaging approximately 350 ± X nm (around peak 2 in NMR T 2 distribution) have sufficient connectivity to host and transmit hydrocarbons. The pore size of tight gas sandstones is dominated by the clay-rich mineral assemblage. The study shows that the NMRC technique can be a very promising method, especially when referred to as a promising “roadmap” on how to interrogate tight formations such as the tight gas sands or even shale especially for the nanopore characterization.

15 GEOTHERMAL ENERGY↗

Thermal and Evolved Gas Analysis of Geologic Samples Containing Organic Materials: Implications for the 2007 Mars Phoenix Scout Mission

The Thermal and Evolved Gas Analyzer (TEGA) instrument scheduled to fly onboard the 2007 Mars Phoenix Scout Mission will perform differential scanning calorimetry (DSC) and evolved gas analysis (EGA) of soil samples and ice collected from the surface and subsurface at a northern landing site on Mars. We have been developing a sample characterization data library using a laboratory DSC integrated with a quadrupole mass spectrometer to support the interpretations of TEGA data returned during the mission. The laboratory TEGA test-bed instrument has been modified to operate under conditions similar to TEGA, i.e., reduced pressure (e.g., 100 torr) and reduced carrier gas flow rates. We have previously developed a TEGA data library for a variety of volatile-bearing mineral phases, including Fe-oxyhydroxides, phyllosilicates, carbonates, and sulfates. Here we examine the thermal and evolved gas properties of samples that contain organics. One of the primary objectives of the Phoenix Scout Mission is to search for habitable zones by assessing organic or biologically interesting materials in icy soil. Nitrogen is currently the carrier gas that will be used for TEGA. In this study, we examine two possible modes of detecting organics in geologic samples; i.e., pyrolysis using N2 as the carrier gas and combustion using O2 as the carrier gas.

Lauer, H. V., Jr.↗

Reduced diffusion and enhanced retention of multiple radionuclides from pore structure characterization of barrier materials for enhanced repository performance

Fluid flow and chemical transport in porous media are the macroscopic consequences of pore structure, which integrates geometry (e.g., pore size and surface area, pore-size distribution) and topology (e.g., pore connectivity). Low-permeability geological media whose pores are poorly interconnected will exhibit the characteristics of anomalous diffusion and sample size-dependent effective porosity, which will strongly impact long-term net diffusion and retention of radionuclides in geological repository settings involving different host rocks and barrier materials. A suite of innovative and complementary experimental approaches is utilized to study the microscopic pore structure and macroscopic fluid flow & chemical transport for a range of host rocks and barrier materials, in addition to standard clay minerals and reference rocks. With a particular focus on quantifying the presence and magnitude of “isolated” pores for a reduced effective porosity in low-permeability geomedia, the integrated methodologies for basic properties and pore structure characterization of these geomedia include X-ray diffraction, thin section petrography, grain size distribution, water immersion porosimetry after vacuum-pulling for full saturation, mercury intrusion porosimetry, nitrogen physisorption, scanning electron microscopy, X-ray computed tomography, and (ultra-)small angle neutron (X-ray) scattering. In addition, custom-designed gas diffusion, tracer recipe involving a range of anionic and cationic chemicals with subsequent analyses by laser ablation and inductively coupled plasma-mass spectrometry, along with batch sorption, column transport, and imbibition tests were conducted for coupled effects of pore structure and chemical retention/transport. From the perspectives of pore structure in conjunction with multiple and complementary approaches to examining a range of sample sizes under different observational scales, we find that the poor pore connectivity is prevalent in low-permeability media (mudstone and crystalline rock) that is related to geological processes (e.g., compaction, diagenesis and thermal maturation). For example, the deep and organic matter-rich mudstones have a much smaller effective porosity than the total porosity (as a result of poor pore connectivity) and associated diffusion coefficient, and the effective porosity & diffusion coefficients are also dependent upon the sample sizes used in the measurement. Similarly, most of the pore space in the shallow mudstone is also controlled by pore-throat diameters in the 5-50 nm range of intergranular pore types from its fine-grained nature, but with an overall good pore connectivity. However, the nm-sized pore space (physically pore-network architecture) and strong sorption capacities (chemical retention from clay minerals) of both shallow and deep mudstones lead to the synergistic retention of cationic radionuclides and their utilities as effective host rocks and barrier materials. Our unique approaches of studying how the micro-scale pore structure affect macro-scale fluid flow, diffusion & retention, and chemical transport produce improved mechanistic understanding, and realistic quantification, of diffusion and retention of typical radionuclides in a range of generic host rocks and barrier materials (clay/shale, salt, crystalline rock, and tuff), with the overall results leading to scientifically-based understanding of enhanced isolation (from both diffusion and retention) of radionuclides and improved confidence on the long-term performance of geological repository to store high-level radioactive wastes. In addition to the training of 25 undergraduates, graduates, and postdocs of UTA, the scientists (organizations) involved in performing this work (e.g., discussion, sample sharing, and operation of SANS and SAXS instruments) include Ed Matteo, Yifeng Wang, and Kristopher Kuhlman (Sandia National Laboratories), Jens Birkholzer, Liange Zheng, Tim Kneafsey, and Sharon Borglin (Lawrence Berkeley National Laboratory), Mavrik Zavarin (Lawrence Livermore National Laboratory), Yukio Tachi and Yuta Fukatsu (Japan Atomic Energy Agency), Mieke de Craen (Euridice, Belgium), Markus Bleuel (NIST), Wei-Ren Chen, Gergely Nagy, Changwoo Do, William Heller, Larry Anovitz, and Kenneth Littrell (ORNL), as well as Jan Illvsky, Ivan Kuzmenko, Ju-Sang Park and Jon Almers (ANL). Key deliverables include a total of 13 peer-reviewed journal articles (nine published and three under review), 23 presentations at scientific conferences (AAPG, AAPG Southwest Section, AGU, Asian Clay Conference, GSA, GSA South-Central Section, IHLRWM, InterPore, International Conference on Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, International Conference on Coupled Processes in Fractured Geological Media: Observation, Modeling and Application), and academic institutions (UTA, New Mexico State University; University of Poitiers, France; University of Helsinki, Finland; Uppsala University, Sweden; Istanbul Technical University, Turkey) and other organizations (Andra, France; Posiva Oy, Finland).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗