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DOE OSTI2016

Alpha- and Gammaproteobacterial Methanotrophs Codominate the Active Methane-Oxidizing Communities in an Acidic Boreal Peat Bog

The objective of this study was to characterize metabolically active, aerobic methanotrophs in an ombrotrophic peatland in the Marcell Experimental Forest, in Minnesota. Methanotrophs were investigated in the field and in laboratory incubations using DNA-stable isotope probing (SIP), expression studies on particulate methane monooxygenase ( pmoA ) genes, and amplicon sequencing of 16S rRNA genes. Potential rates of oxidation ranged from 14 to 17 μmol of CH 4 g dry weight soil –1 day –1 . Within DNA-SIP incubations, the relative abundance of methanotrophs increased from 4% in situ to 25 to 36% after 8 to 14 days. Phylogenetic analysis of the 13 C-enriched DNA fractions revealed that the active methanotrophs were dominated by the genera Methylocystis (type II; Alphaproteobacteria ), Methylomonas , and Methylovulum (both, type I; Gammaproteobacteria). In field samples, a transcript-to-gene ratio of 1 to 2 was observed for pmoA in surface peat layers, which attenuated rapidly with depth, indicating that the highest methane consumption was associated with a depth of 0 to 10 cm. Metagenomes and sequencing of cDNA pmoA amplicons from field samples confirmed that the dominant active methanotrophs were Methylocystis and Methylomonas . Although type II methanotrophs have long been shown to mediate methane consumption in peatlands, our results indicate that members of the genera Methylomonas and Methylovulum (type I) can significantly contribute to aerobic methane oxidation in these ecosystems.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2011

Mass Spectrometry on Future Mars Landers

Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

Brinckerhoff, W. B.↗

NASA NTRS2021

Comparison of Monthly IMERG Precipitation Estimates with PACRAIN Atoll Observations

Satellite-based precipitation estimates provide valuable information where surface observations are not readily available, especially over the large expanses of the ocean where in situ precipitation observations are very sparse. This study compares monthly precipitation estimates from the Integrated Multisatellite Retrievals for GPM (IMERG) with gauge observations from 37 low-lying atolls from the Pacific Rainfall Database for the period June 2000–August 2020. Over the analysis period, IMERG estimates are slightly higher than the atoll observations by 0.67% with a monthly correlation of 0.68. Seasonally, DJF shows excellent agreement with a near-zero bias, while MAM shows IMERG is low by 4.6%, and JJA is high by 1.2%. SON exhibits the worst performance, with IMERG overestimating by 6.5% compared to the atolls. The seasonal correlations are well contained in the range 0.67–0.72, with the exception of SON at 0.62. Furthermore, SON has the highest RMSE at 4.70 mm day^(−1), making it the worst season for all metrics. Scatterplots of IMERG versus atolls show IMERG, on average, is generally low for light precipitation accumulations and high for intense precipitation accumulations, with best agreement at intermediate rates. Seasonal variations exist at light and intermediate rate accumulations, but IMERG consistently overestimates at intense precipitation rates. The differences between IMERG and atolls vary over time but do not exhibit any discernible trend or dependence on atoll population. The PACRAIN atoll gauges are not wind-loss corrected, so application of an appropriate adjustment would increase the precipitation amounts compared to IMERG. These results provide useful insight to users as well as valuable information for future improvements to IMERG.

David T. Bolvin↗

DOE OSTI2018

Quantifying dry supercritical CO 2 -induced changes of the Utica Shale

Traditionally, shale formations have been studied as sealing layers that prevent vertical migration of hydrocarbons and CO2 due to their low permeability and fracture porosity. Recent research has focused on storing CO2 in hydrocarbon-bearing shale formations that have already undergone depletion through primary production and using CO2 as a potential fracturing agent for unconventional reservoirs. The injected CO2 will interact with shale components (i.e. clays, organic matter) and affect rock properties through chemical alteration, matrix swelling/shrinkage, and related geomechanical effects. As changes in rock properties will impact both anthropogenic CO2 storage and hydraulic fracturing, it is imperative to increase our understanding of the CO2-shale interactions. In-situ Fourier Transform infrared (FT-IR) spectroscopy coupled with high temperature and pressure capability was used to examine the interaction of dry CO2 on Utica Shale, clay, and kerogen samples at the molecular scale and characterize vibrational changes of sorption bands sensitive to the gas-solid environment. The Utica Shale was also analyzed for micro and macro-scale chemical and physical changes before and after exposure to dry CO2 at subsurface storage conditions using surface relocation techniques via high-resolution field-emission scanning electron microscopy (FE-SEM). Brunauer-Emmett-Teller (BET) surface area/pore size analysis and quantitative adsorption isotherms were applied to understand changes in surface area, pore volumes, and understand the storage potential of CO2 in the Utica Shale sample. FT-IR and feature relocation via FE-SEM indicate carbonate formation and dissolution occurs in shale exposed to dry CO2. Results indicate that etching and pitting occur, with minor calcite precipitation along the surface of the shale sample. Quantitative isotherm results indicate that shales with a higher content of kerogen and illite-smectite clays would be expected to have the highest CO2 storage capacity provided these constituents were accessible for interaction.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2018

In Situ and Surface-Enhanced Raman Spectroscopy Study of Electrode Materials in Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) represent next-generation energy sources with high energy conversion efficiencies, low pollutant emissions, good flexibility with a wide variety of fuels, and excellent modularity suitable for distributed power generation. As an electrochemical energy conversion device, the SOFC’s performance and reliability depend sensitively on the catalytic activity and stability of electrode materials. To date, however, the development of electrode materials and microstructures is still based largely on trial-and-error methods because of the inadequate understanding of electrode process mechanisms. Therefore, the identification of key descriptors/properties for electrode materials or functional heterogeneous interfaces, especially under in situ/operando conditions, may provide guidance for the design of optimal electrode materials and microstructures. Here, Raman spectroscopy is ideally suited for the probing and mapping of chemical species present on electrode surfaces under operating conditions. And to boost the sensitivity toward electrode surface species, the surface-enhanced Raman spectroscopy (SERS) technique can be employed, in which thermally robust SERS probes (e.g., Ag@SiO 2 core–shell nanoparticles) are designed to make in situ/operando analysis possible. Furthermore, this review summarizes recent progresses in the investigation of SOFC electrode materials through Raman spectroscopic techniques, including topics of early stage carbon deposition (coking), coking-resistant anode modification, sulfur poisoning, and cathode degradation. In addition, future perspectives for utilizing the in situ/operando SERS for investigations of other electrochemical surfaces and interfaces are also discussed.

25 ENERGY STORAGE↗

DOE OSTI2013

Main Features for the Conceptualization of the Post-Closure Evolution Scenario of the Cigeo LIL-HL Waste Repository - 13105

In France, in order to commission the planned geological repository by 2025, a license application for the industrial project of this geological repository called Cigeo (Centre Industriel de Stockage Geologique) must be submitted and reviewed by the competent authorities by 2015. On the basis of its preliminary design set up in 2009 and on the associated requirements for long-term safety, an overall conceptual model has been developed in order to prepare the performance and safety analysis. The Cigeo repository makes use of the passive safety response characteristics of both the engineered and geological barriers that allow: - resisting water ingress, with repository designs favoring the limitation of the water flows; - limiting the release of radionuclides and chemical toxics; - delaying and mitigating the spread of radionuclides and chemical toxics. In order to evaluate the performance of the various elements, a conceptual model of the thermo-hydro-chemico-mechanical (THMC) evolution of the different components of the repository has been designed. It takes stock of a 20 years research effort which allowed data to be obtained from various surface geological campaigns, in-situ experiments in URLs and wastes characterization, and advances in numerical simulation to be utilised. Based on the best available knowledge to date, this conceptual model constitutes a robust basis for the definition and development of the long-term safety scenarios. It also helps identifying the residual uncertainties, and provides guidelines for additional research and system optimizations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2013

Boron neutron capture therapy (BNCT) for liver metastasis in an experimental model: dose–response at five-week follow-up based on retrospective dose assessment in individual rats

Boron neutron capture therapy (BNCT) was proposed for untreatable colorectal liver metastases. Employing an experimental model of liver metastases in rats, we recently demonstrated that BNCT mediated by boronophenylalanine (BPA-BNCT) at 13 Gy prescribed to tumor is therapeutically useful at 3-week follow-up. The aim of the present study was to evaluate dose–response at 5-week follow-up, based on retrospective dose assessment in individual rats. BDIX rats were inoculated with syngeneic colon cancer cells DHD/K12/TRb. Tumor-bearing animals were divided into three groups: BPA-BNCT (n = 19), Beam only (n = 8) and Sham (n = 7) (matched manipulation, no treatment). For each rat, neutron flux was measured in situ and boron content was measured in a pre-irradiation blood sample for retrospective individual dose assessment. For statistical analysis (ANOVA), individual data for the BPA-BNCT group were pooled according to absorbed tumor dose, BPA-BNCT I: 4.5–8.9 Gy and BPA-BNCT II: 9.2–16 Gy. At 5 weeks post-irradiation, the tumor surface area post-treatment/pre-treatment ratio was 12.2 +/- 6.6 for Sham, 7.8 +/- 4.1 for Beam only, 4.4 +/- 5.6 for BPA-BNCT I and 0.45 +/- 0.20 for BPA-BNCT II; tumor nodule weight was 750 +/- 480 mg for Sham, 960 +/- 620 mg for Beam only, 380 +/- 720 mg for BPA-BNCT I and 7.3 +/- 5.9 mg for BPA-BNCT II. The BPA-BNCT II group exhibited statistically significant tumor control with no contributory liver toxicity. Potential threshold doses for tumor response and significant tumor control were established at 6.1 and 9.2 Gy, respectively.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2013

Imaging Liquids Using Microfluidic Cells

Chemistry occurring in the liquid and liquid surface is important in many applications. Chemical imaging of liquids using vacuum based analytical techniques is challenging due to the difficulty in working with liquids with high volatility. Recent development in microfluidics enabled and increased our capabilities to study liquid in situ using surface sensitive techniques such as electron microscopy and spectroscopy. Due to its small size, low cost, and flexibility in design, liquid cells based on microfluidics have been increasingly used in studying and imaging complex phenomena involving liquids. This paper presents a review of microfluidic cells that were developed to adapt to electron microscopes and various spectrometers for in situ chemical analysis and imaging of liquids. The following topics will be covered including cell designs, fabrication techniques, unique technical features for vacuum compatible cells, and imaging with electron microscopy and spectroscopy. Challenges are summarized and recommendations for future development priority are proposed.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2016

Growth Mode Transition in Complex Oxide Heteroepitaxy: Atomically Resolved Studies

Here we performed investigations of the atomic-scale surface structure of epitaxial La 5/8 Ca 3/8 MnO 3 thin films as a model system dependent on growth conditions in pulsed laser deposition with emphasis on film growth kinetics. Postdeposition in situ scanning tunneling microscopy was combined with in operando reflective high-energy electron diffraction to monitor the film growth and ex situ X-ray diffraction for structural analysis. We find a correlation between the out-of-plane lattice parameter and both adspecies mobility and height of the Ehrlich–Schwoebel barrier, with mobility of adatoms greater over the cationically stoichiometric terminations. We find that the data suggest that the out-of-plane lattice parameter is dependent on the mechanism of epitaxial strain relaxation, which is controlled by the oxidative power of the deposition environment.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Kilometer-Scale Hydrologic Exchange Flows in a Gravel Bed River Corridor and Their Implications to Solute Migration

In this work, a well-characterized field site along a major river corridor was used to investigate the dynamic pathways and impacts of subsurface hydrogeologic structures on kilometer-scale hydrologic exchange flows between river water and groundwater. A aqueous uranium (U aq ) plume exists at the site that discharges to the Columbia River. We performed temporally intensive monitoring of specific conductance (SpC) and U aq concentrations within the plume at increasing distances from the river shoreline and at locations both within and outside a presumed subsurface pathway of lateral hydrologic exchange. Specific conductance and U aq were utilized as in-situ tracers of hydrologic exchange and associated groundwater-surface water mixing. Monitoring data was collected for an approximate two year period during which seasonal river elevations varied by more than 2 m causing distinct events of river water intrusion and retreat from the near-shore aquifer, and large temporal variations in well-water analyte concentrations. Statistical clustering analysis was applied to identify well groupings exhibiting common time series behaviors. PFLOTRAN was implemented within a modeling domain of 3.3 x 1.9 km with dynamic flow boundary conditions and accurate subsurface topography for the basal aquitard underlying the aquifer. In-silico calculations of river water tracer behavior were performed to assess predominant flow directions and velocities influenced by river stage variations and variable aquitard topography, and their collective influences on SpC and U aq concentrations. We demonstrate complicated multidirectional flow behaviors at the kilometer scale resulting from hydrologic exchange and subsurface structure that influence plume dynamics and determine the overall system behavior.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1991

Moderate Resolution Imaging Spectrometer (MODIS) design evolution and associated development and verification of data product efforts

The Moderate Resolution Imaging Spectrometer (MODIS) is a key observing facility to be flown on the Earth Observing System (EOS). The facility is composed of two instruments called MODIS-N (nadir) and MODIS-T (tilt). The MODIS-N is being built under contract to NASA by the Santa Barbara Research Center. The MODIS-T is being fabricated by the Engineering Directorate at the Goddard Space Flight Center. The MODIS Science Team has defined nearly 40 biogeophysical data products for studies of the ocean and land surface and properties of the atmosphere including clouds that can be expected to be produced from the MODIS instruments shortly after the launch of EOS. The ocean, land, atmosphere, and calibration groups of the MODIS Science Team are now proceeding to plan and implement the operations and facilities involving the analysis of data from existing spaceborne, airborne, and in-situ sensors required to develop and validate the algorithms that will produce the geophysical data products. These algorithm development and validation efforts will be accomplished wherever possible within the context of existing or planned national and international experiments or programs such as those in the World Climate Research Program.

Salomonson, Vincent V.↗

NASA NTRS1995

Comparison between global latent heat flux computed from multisensor (SSM/I and AVHRR) and from in situ data

Comprehensive Ocean-Atmosphere Data Set (COADS) and satellite-derived parameters are input to a similarity theory-based model and treated in completely equivalent ways to compute global latent heat flux (LHF). In order to compute LHF exclusively from satellite measurements, an empirical relationship (Q-W relationship) is used to compute the air mixing ratio from Special Sensor Microwave/Imager (SSM/I) precipitable water W and a new one is derived to compute the air temperature also from retrieved W(T-W relationship). First analyses indicate that in situ and satellite LHF computations compare within 40%, but systematic errors increase the differences up to 100% in some regions. By investigating more closely the origin of the discrepancies, the spatial sampling of ship reports has been found to be an important source of error in the observed differences. When the number of in situ data records increases (more than 20 per month), the agreement is about 50 W/sq m rms (40 W/sq m rms for multiyear averages). Limitations of both empirical relationships and W retrieval errors strongly affect the LHF computation. Systematic LHF overestimation occurs in strong subsidence regions and LHF underestimation occurs within surface convergence zones and over oceanic upwelling areas. The analysis of time series of the different parameters in these regions confirms that systematic LHF discrepancies are negatively correlated with the differences between COADS and satellite-derived values of the air mixing ratio and air temperature. To reduce the systematic differences in satellite-derived LHF, a preliminary ship-satellite blending procedure has been developed for the air mixing ratio and air temperature.

Jourdan, Didier↗

NASA NTRS2006

Drilling Automation Demonstrations in Subsurface Exploration for Astrobiology

This project proposes to study subsurface permafrost microbial habitats at a relevant Arctic Mars-analog site (Haughton Crater, Devon Island, Canada) while developing and maturing the subsurface drilling and drilling automation technologies that will be required by post-2010 missions. It builds on earlier drilling technology projects to add permafrost and ice-drilling capabilities to 5m with a lightweight drill that will be automatically monitored and controlled in-situ. Frozen cores obtained with this drill under sterilized protocols will be used in testing three hypotheses pertaining to near-surface physical geology and ground H2O ice distribution, viewed as a habitat for microbial life in subsurface ice and ice-consolidated sediments. Automation technologies employed will demonstrate hands-off diagnostics and drill control, using novel vibrational dynamical analysis methods and model-based reasoning to monitor and identify drilling fault states before and during faults. Three field deployments, to a Mars-analog site with frozen impact crater fallback breccia, will support science goals, provide a rigorous test of drilling automation and lightweight permafrost drilling, and leverage past experience with the field site s particular logistics.

Glass, Brian↗

NASA NTRS2008

The NASA NEESPI Data Portal: Products, Information, and Services

Studies have indicated that land cover and use changes in Northern Eurasia influence global climate system. However, the procedures are not fully understood and it is challenging to understand the interactions between the land changes in this region and the global climate. Having integrated data collections form multiple disciplines are important for studies of climate and environmental changes. Remote sensed and model data are particularly important die to sparse in situ measurements in many Eurasia regions especially in Siberia. The NASA GES DISC (Goddard Earth Sciences Data and Information Services Center) NEESPI data portal has generated infrastructure to provide satellite remote sensing and numerical model data for atmospheric, land surface, and cryosphere. Data searching, subsetting, and downloading functions are available. ONe useful tool is the Web-based online data analysis and visualization system, Giovanni (Goddard Interactive Online Visualization ANd aNalysis Infrastructure), which allows scientists to assess easily the state and dynamics of terrestrial ecosystems in Northern Eurasia and their interactions with global climate system. Recently, we have created a metadata database prototype to expand the NASA NEESPI data portal for providing a venue for NEESPI scientists fo find the desired data easily and leveraging data sharing within NEESPI projects. The database provides product level information. The desired data can be found through navigation and free text search and narrowed down by filtering with a number of constraints. In addition, we have developed a Web Map Service (WMS) prototype to allow access data and images from difference data resources.

Shen, Suhung↗

NASA NTRS2016

Productivity Challenges for Mars Rover Operations

Achieving consistently high levels of productivity for surface exploration missions has been a challenge for Mars missions. While the rovers have made major discoveries and accomplished a large number of objectives, they often require a great deal of effort from the operations teams and achievingobjectives can take longer than anticipated. This paper describes the early stages of a multi-year project to investigate solutions for enhancing surface mission productivity. A primary focus of this early stage is to conduct in-depth studies of Mars Science Laboratory science campaigns to gain a deeper understanding of the factors that impact productivity, and to use this understanding to identify potential changes to flight software and ground operations practices to increase productivity. We present the science campaigns we have selected along with a conceptual model of how surface missions achieve objectives that is used to guide the study. We also provide some early thoughts on the technologies, and their interactions, which we believe will play an important role in addressing surface mission productivity challenges.We are in the early stages of a multi-year project to studyand address productivity challenges of future surface missions. We have identified campaigns from the MSL missionfor study which we believe will yield valuable informationabout the nature of surface mission productivity challenges.Based on preliminary analysis from the data collected weanticipate that the lessons from these case studies will helpdevelop and mature our concepts for changes to flight andground systems to address these challenges.While the focus of our work is on Mars rover missions, webelieve the concepts in the work will be applicable to a variety of in-situ explorers, including Venus, and Titan, as wellas orbital missions, such as the Europa orbiter. These missions will also benefit from the ability to adapt and respondto the latest state of the spacecraft and its environment.

Gaines, Daniel↗

NASA NTRS2024

Design of a Family of Mars Chemical Transportation Elements

NASA’s Mars Architecture Team (MAT) has recently developed a collection of concepts to assess the capabilities and constraints presented by architectures incorporating large-scale Mars In-Situ Resource Utilization (ISRU) propellant production. The focus of this manuscript is on the concept design of chemical propellant-based transportation systems including a dual role lander/ascent vehicle and an in-space transporter. Mission performance analyses performed during a recent design analysis cycle derived the 300,000 kg propellant production capacity utilized for preliminary concept designs of enabling surface ISRU systems, power systems, fluid handling systems, and their concept of operation, detailed in companion papers.

Mars↗

NASA NTRS2024

Design of a Family of Mars Chemical Transportation Elements

Mars↗

DOE OSTI2019

Complex Sources and Impacts on Remediation and Monitoring Approaches

Remedy selection, implementation, and coordination with tank farm activities for adjacent waste sites need to be facilitated by a technically defensible description of sources and their relative strength and temporal contributions to groundwater contamination. Detailed data describing contaminant source releases are typically not available, so source locations are highly uncertain. Furthermore, data on sources and model parameters are not readily available through direct measurements. Instead, source data are often derived by extrapolation from a few direct and/or indirect measurements, while model parameters are commonly estimated using inverse modeling or calibration methods. Because the conceptual model of sources will influence the mass and timing of the flux of contaminants to groundwater, uncertainty in the source terms should be considered. Even though a best-fit model can often be identified, it may not be the best representation of the sources given the sparse, uncertain nature of the data used for estimating source terms. To support future feasibility studies, a systematic approach is needed for identifying remediation and monitoring activities appropriate under conditions of uncertainty. In this study, an integrated assessment of alternative conceptual model elements has been examined using the B-Complex site in the Hanford Central Plateau to demonstrate how multiple sources in a waste management complex can be described to identify their relative contributions to groundwater. The heterogeneous structure of the system is modeled based on available field information on the lithological data for both the vadose zone and aquifer. The approach includes a simulation assessment and linkages to site data, with an uncertainty analysis applied to evaluate the effects of source term uncertainty on contaminant mass flux to groundwater. An integrated assessment of alternative conceptual model elements was evaluated to identify how parameter uncertainty impacts both temporal and spatial uncertainties associated with vadose zone source terms. Modeling scenarios identify important characteristics of remediation target zones to provide context for how surface barriers, in situ remedies, and water-table treatment zones can be designed to account for source dynamics. Ramifications for remediation and monitoring are discussed within the context of the source term uncertainty. The described approach facilitates systematically addressing alternative conceptual model questions in relation to remediation and monitoring and supports the remedial investigation/ feasibility study process and the remediation strategy development for the Hanford Central Plateau.

Rockhold, Mark L.↗