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NASA NTRS2023

Phytoplankton Diversity and Chemotaxonomy in Contrasting North Pacific Ecosystems

Background. Phytoplankton is the base of majority of ocean ecosystems. It is responsible for half of the global primary production, and different phytoplankton taxa have a unique role in global biogeochemical cycles. In addition, phytoplankton abundance and diversity are highly susceptible to climate induced changes, hence monitoring of phytoplankton and its diversity is important and necessary. Methods. Water samples for phytoplankton and photosynthetic pigment analyses were collected in boreal winter 2017, along transect in the North Pacific Subtropical Gyre (NPSG) and the California Current System (CCS). Phytoplankton community was analyzed using light and scanning electron microscopy and photosynthetic pigments by high-performance liquid chromatography. To describe distinct ecosystems, monthly average satellite data of MODIS Aqua Sea Surface temperature and Chlorophyll a concentration, as well as Apparent Visible Wavelength were used. Results. A total of 207 taxa have been determined, mostly comprised of coccolithophores (35.5%), diatoms (25.2%) and dinoflagellates (19.5%) while cryptophytes, phytoflagellates and silicoflagellates were included in the group ``others" (19.8%). Phytoplankton spatial distribution was distinct, indicating variable planktonic dispersal rates and specific adaptation to ecosystems. Dinoflagellates, and nano-scale coccolithophores dominated NPSG, while micro-scale diatoms, and cryptophytes prevailed in CCS. A clear split between CCS and NPSG is evident in dendogram visualising LINKTREE constrained binary divisive clustering analysis done on phytoplankton counts and pigment oncentrations. Of all pigments determined, alloxanthin, zeaxanthin, divinyl chlorophyll b and lutein have highest correlation to phytoplankton counts. Conclusion. Combining chemotaxonomy and microscopy is an optimal method to determine phytoplankton diversity on a large-scale transect. Distinct communities between the two contrasting ecosystems of North Pacific reveal phytoplankton groups specific adaptations to trophic state, and support the hypothesis of shift from microto nano-scale taxa due to sea surface temperatures rising, favoring stratification and oligotrophic conditions.

oceanography↗

NASA NTRS2013

Spring-Summer Temperatures Since AD 1780 Reconstructed from Stable Oxygen Isotope Ratios in White Spruce Tree-Rings from the Mackenzie Delta, Northwestern Canada

High-latitude delta(exp 18)O archives deriving from meteoric water (e.g., tree-rings and ice-cores) can provide valuable information on past temperature variability, but stationarity of temperature signals in these archives depends on the stability of moisture source/trajectory and precipitation seasonality, both of which can be affected by atmospheric circulation changes. A tree-ring delta(exp 18)O record (AD 1780-2003) from the Mackenzie Delta is evaluated as a temperature proxy based on linear regression diagnostics. The primary source of moisture for this region is the North Pacific and, thus, North Pacific atmospheric circulation variability could potentially affect the tree-ring delta(exp 18)O-temperature signal. Over the instrumental period (AD 1892-2003), tree-ring delta(exp 18)O explained 29% of interannual variability in April-July minimum temperatures, and the explained variability increases substantially at lower-frequencies. A split-period calibration/verification analysis found the delta(exp 18)O-temperature relation was time-stable, which supported a temperature reconstruction back to AD 1780. The stability of the delta(exp 18)O-temperature signal indirectly implies the study region is insensitive to North Pacific circulation effects, since North Pacific circulation was not constant over the calibration period. Simulations from the NASA-GISS ModelE isotope-enabled general circulation model confirm that meteoric delta(exp 18)O and precipitation seasonality in the study region are likely insensitive to North Pacific circulation effects, highlighting the paleoclimatic value of tree-ring and possibly other delta(exp 18)O records from this region. Our delta(exp 18)O-based temperature reconstruction is the first of its kind in northwestern North America, and one of few worldwide, and provides a long-term context for evaluating recent climate warming in the Mackenzie Delta region.

Canada↗

NASA NTRS2010

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗

NASA NTRS2007

NASA Tech Briefs, February 2007

Topics covered include: Calibration Test Set for a Phase-Comparison Digital Tracker; Wireless Acoustic Measurement System; Spiral Orbit Tribometer; Arrays of Miniature Microphones for Aeroacoustic Testing; Predicting Rocket or Jet Noise in Real Time; Computational Workbench for Multibody Dynamics; High-Power, High-Efficiency Ka-Band Space Traveling-Wave Tube; Gratings and Random Reflectors for Near-Infrared PIN Diodes; Optically Transparent Split-Ring Antennas for 1 to 10 GHz; Ice-Penetrating Robot for Scientific Exploration; Power-Amplifier Module for 145 to 165 GHz; Aerial Videography From Locally Launched Rockets; SiC Multi-Chip Power Modules as Power-System Building Blocks; Automated Design of Restraint Layer of an Inflatable Vessel; TMS for Instantiating a Knowledge Base With Incomplete Data; Simulating Flights of Future Launch Vehicles and Spacecraft; Control Code for Bearingless Switched- Reluctance Motor; Machine Aided Indexing and the NASA Thesaurus; Arbitrating Control of Control and Display Units; Web-Based Software for Managing Research; Driver Code for Adaptive Optics; Ceramic Paste for Patching High-Temperature Insulation; Fabrication of Polyimide-Matrix/Carbon and Boron-Fiber Tape; Protective Skins for Aerogel Monoliths; Code Assesses Risks Posed by Meteoroids and Orbital Debris; Asymmetric Bulkheads for Cylindrical Pressure Vessels; Self-Regulating Water-Separator System for Fuel Cells; Self-Advancing Step-Tap Drills; Array of Bolometers for Submillimeter- Wavelength Operation; Delta-Doped CCDs as Detector Arrays in Mass Spectrometers; Arrays of Bundles of Carbon Nanotubes as Field Emitters; Staggering Inflation To Stabilize Attitude of a Solar Sail; and Bare Conductive Tether for Decelerating a Spacecraft.

Source record↗

NASA NTRSDate not supplied

NASA’s Student Airborne Science Activation for Minority Serving Institutions: Inaugural Program, Educational Outcomes, and Lessons Learned

The NASA Student Airborne Science Activation (SaSa) for Minority Serving Institutions (MSIs) held its inaugural summer research program for early career undergraduates interested in the Geosciences. SaSa is a NASA Science Activation funded 8-week summer internship program. Twenty-four first- and second-year undergraduates from MSIs across the U.S. participated in the summer program - June 6 to July 29, 2022. Students had the opportunity to gain hands-on research experience in all components of an airborne science campaign including flying on-board a NASA research aircraft to collect atmospheric measurements. Students conducted independent research projects related to the atmosphere, ocean, and geosciences that feed into NASA’s broader Earth Science Division’s and Decadal Survey goals using air quality, meteorological, and oceanic measurements from surface, airborne, and satellite-based observations. The program split its time between partner institution, University of Maryland Baltimore County and NASA’s Wallops Flight Facility in Wallops Island, Virginia. Students also made site visits at partner institutions, including: Hampton University, University of Maryland Eastern Shore, Morgan State University, Howard University, and Coppin State University and attended lectures from visiting faculty and NASA Subject Matter Experts. Students were guided on their research projects by near-peer graduate mentors, SaSa program leadership, co-Is at partner institutions, and NASA scientists to address two major research themes: 1) how human-caused air pollution has human and environmental implications, and 2) how large-scale meteorological factors influence local weather conditions. Students sorted into research groups, based on sub-discipline areas in the Geosciences, including: “Clouds, Aerosols and Radiation”, “Meteorology and Planetary Boundary Layer”, “Air Quality: Particle Pollution and Trace Gases”, and “Air-Water-Land Interface”. Their research was presented as 3-minute lightning talks and in-person poster presentations at a close-out event at NASA Goddard Space Flight Center in Greenbelt, Maryland. The students’ inter- and trans-disciplinary research experiences centered in the use of multiple ground, airborne, and satellite remote sensing NASA Earth Science Division assets. Providing a unique experience aligned to recognize the societal benefits that NASA contributes in the areas of resource management, air quality monitoring and policy decisions, energy and weather predictions, and research on the Earth’s climate. The SaSa program aims to increase the number of students from MSIs that identify as underrepresented or underserved individuals in the Geosciences discipline, Earth System Science graduate programs, and the NASA workforce. A summary of the summer research program, educational, scientific, and programmatic outcomes, as well as lessons learned will be presented.

NASA↗

NASA NTRS2019

TPSAS-NF1676L-32493-DND

The Committee on Earth Observation Satellites (CEOS) System Engineering Office (SEO) has supported the Open Data Cube (ODC) initiative to provide a data architecture solution that has value to its global users and increases the impact of EO satellite data. ODC is an open-source platform for processing satellite data. We have developed software products and tools around the core ODC that would help users perform machine learning on EO satellite data. The recent United Nations (UN) Sustainable Development Agenda provides a shared blueprint for peace and prosperity for people and for the planet, considering our current situation and helping to create a plan. The core of this agenda is a set of seventeen Sustainable Development Goals (SDGs), which represent an urgent call for action by all countries - both developed and developing - in a global partnership. The CEOS SEO team has recently developed and released a set of innovative Jupyter notebooks addressing UN SDGs 6.6.1 (spatial extents of water-related ecosystems), 11.3.1 (ratio of land consumption rate to population growth rate), and 15.3.1 (proportion of land that is degraded over total land area). These notebooks empower users by providing features that will assist with streamlining analysis ready data retrieval, processing, and visualization. We have recently incorporated several machine learning techniques in these notebooks. In this paper, we present the lessons learned from our experience on classifying land using supervised and unsupervised machine learning techniques using ODC framework for UN SDGs. We identify the current limitations of ODC to seamlessly support machine learning techniques. We propose features that would help machine learning, specifically within the ODC framework. We propose a thematic indexing/loading of data for both unsupervised learning as well as data annotation/labeling pipeline. Currently, ODC supports machine learning by separating data-management from the analysis process. It works as a mechanism to load cubes of data. ODC does not natively support features that are vital in machine learning such as validation splits, fair/balanced sampling, establishing load size constraints, etc. We believe that our proposed features will empower users by providing features that bring machine learning techniques closed to ODC. Enhancements to ODC to better accommodate machine learning techniques can assist in fulfilling UN SDGs such as 6.3.2, 6.4.2, 6.6.1, 11.3.1, 14.1.1, 15.1.1, 15.3.1, and 15.4.2.

Syed R Rizvi↗

NASA NTRS2019

Versatile Nuclear Thermal Propulsion (NTP)

A study was initiated to investigate propulsion stage and mission architecture options potentially enabled by fission energy. One initial concept is a versatile Nuclear Thermal Propulsion (NTP) system with a maximum specific impulse of 900 s and a maximum thrust (per engine) of 15 klbf. The system assumes a monopropellant stage (hydrogen), and is designed to also provide 300 lbf of thrust (potentially split between multiple thrusters) at an Isp > 500 s for orbital maneuvering and station keeping. Boost pumps are used to assist with engine decay heat removal and low thrust engine burns, and to compensate for partial tank depressurization during full thrust engine burns. Potential stage assembly orbits that take full advantage of launch vehicle payload mass and volume capabilities are being assessed. The potential for using NTP engines to also generate a small to moderate amount of electrical power is also being evaluated. A first generation versatile NTP stage could enable 8 of 9 upcoming opportunities for short (less than 24 month) round trip human missions to Mars. A second generation versatile NTP is under consideration that could potentially provide a maximum specific impulse of 1800 s at 15 klbf, and enable ambitious missions throughout the solar system. The second generation NTP system under consideration would also allow a choice of volatiles to be used as propellant. This would potentially allow in-situ resources such as water, ammonia, methane, or other compounds to be used directly as propellant by the second generation engine.

Houts, Michael G.↗

NASA NTRS2019

Versatile Nuclear Thermal Propulsion (NTP)

Houts, Mike↗

NASA NTRS2001

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗

NASA NTRSDate not supplied

Progress of 2.05 uM Fiber Laser Development for A Martian Co2 Dial

We have proposed a new concept for differential absorption lidar (DIAL) operating in the 2050 nm CO 2 absorption band for atmospheric CO 2 and pressure observations on Mars. This concept has earned us funding from NASA's PICASSO Program to advance 2050 nm fiber laser technology for future space applications. The laser design is an all-fiber master oscillator and power amplifier (MOPA) system. The master oscillator with pulse shaping and several stages of fiber preamplifiers has been built. Preliminary tests show the output pulse energy can reach 1 mJ, meeting our baseline goal. However, the current power amplifier design has an issue with undesired parasitic lasing at a different frequency, which exhausts pump energy and limits the laser energy. We have modified the power amplifier design to suppress parasitic lasing, and higher laser power energy is expected. To achieve high measurement accuracy, the laser frequency must be stabilized. A fraction of the master oscillator is split to lock the laser frequency to the center of the selected absorption line. The laser can then be shifted to a frequency far from the absorption line center, where extinction due to CO 2 and other trace gases is minimal, serving as the offline reference. The online wavelength is optimized at 2050.44156 nm, ensuring a CO 2 absorption optical depth (AOD) of approximately 1.1 at 3 km, which maximizes the signal-to-noise ratio (SNR) for measurements in the lower Martian atmosphere. At the conference, we will provide more details about this project and report on the progress of instrument development.

DIAL↗

NASA NTRS1992

Application of computational fluid dynamics to the design of the film cooled STME subscale nozzle for the National Launch System

The status of computational fluid dynamics (CFD) calculations for the Space Transportation Main Engine (STME) film/dump cooled nozzle design is presented, with an emphasis on the timely impact of CFD on the design of the sub-scale nozzle coolant system. The following aspects of the sub-scale coolant delivery system were analyzed with CFD: 1) a design trade study of a mechanical flow splitting device for uniform distribution of the subsonic cavity flow, 2) a design trade study of the subsonic cavity lip to achieve film integrity, and 3) an analysis of the primary flow interaction with the core/secondary coolant streams. All design calculations were performed with the Generalized Aerodynamic Simulation Program (GASP), a 3-D, multi-block, generalized Navier-Stokes code capable of solving with frozen, finite-rate or equilibrium chemical kinetics. The initial design of the subsonic cavity flow used square posts to distribute the sonic orifice jets into a uniform flow. Calculations for this design indicated that an unacceptable mal-distribution of film occurred. Design modifications involving curved and slotted posts were computed in an effort to uniformly distribute the secondary coolant flow. Analysis of these configurations showed that although the flowfield improved in uniformity, it was still unacceptable, especially at higher feed pressures. Results from these studies were then incorporated into a design that resulted in the insertion of a porous metal ring into the subsonic cavity. Subsequent water flow model studies showed that this concept was successful in uniformly distributing flow exiting the cavity. In addition to the design of the subsonic cavity, CFD was also used to analyze the secondary coolant lip and the primary flow interaction with the core/secondary coolant streams. A series of calculations were first performed to modify the subsonic cavity lip contour. The flow over the modified lip was then computed simultaneously with the primary injectors to determine the impact of the subsonic coolant stream on the primary slot jets. Pressure, temperature, velocity, and coolant mass fraction contours are presented for these configurations. Information is given in viewgraph form.

Garrett, Joseph L.↗

NASA NTRS2012

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Socki, Richard A.↗

NASA NTRS2018

ICESat-2 Photon Classification: Finding Signal Photons in the ATL03 Geolocated Photon Data Product

ICESat-2 carries NASA's next-generation laser altimeter, ATLAS, (Advanced Topographic Laser Altimeter System), designed to measure changes in ice sheet height, sea ice freeboard, and vegetation canopy height. ATLAS contains a photon-counting lidar which transmits green (532-nm) pulses at 10kHz. Each pulse is split into 3 pairs of beams (one strong and one weak). Approximately 1014 photons per pulse travel from ATLAS through the atmosphere to reflect off the Earth's surface. Some return back into the ATLAS telescope where they are recorded. Photons from sunlight and instrument noise at the same wavelength are also recorded. The flight software time tags all photons within a 500m to 6 km range window and generates histograms. Using the histograms, it selects a telemetry window which varies from 20m over flat surfaces to hundreds of meters over rougher terrain. ATL03 contains the time, height (relative to the WGS-84 ellipsoid), latitude and longitude of every photon within the telemetry window. The basic challenge is to determine which of these photons were reflected off the surface. We have developed an algorithm that identifies these signal photons and assigns a confidence level (low, medium, or high) to each signal photon based on the signal to noise ratio. We present an overview of the signal identification algorithm and show the results on actual ICESat-2 data over ice sheet, sea ice, vegetated, and water surfaces. Higher level ATLAS products work with aggregations of the photons in order to determine the ellipsoidal height of the Earth, canopy height and structure, and other quantities of geophysical interest.

Remote Sensing↗

NASA NTRS2009

Use of NASA Satellite Data in Aiding Mississippi Barrier Island Restoration Projects

This presentation discusses a NASA Stennis Space Center project in which NASA-supported satellite and aerial data is being used to aid state and federal agencies in restoring the Mississippi barrier islands. Led by the Applied Science and Technology Project Office (ASTPO), this project will produce geospatial information products from multiple NASA-supported data sources, including Landsat, ASTER, and MODIS satellite data as well as ATLAS multispectral, CAMS multispectral, AVIRIS hyperspectral, EAARL, and other aerial data. Project objectives include the development and testing of a regional sediment transport model and the monitoring of barrier island restoration efforts through remote sensing. Barrier islands provide invaluable benefits to the State of Mississippi, including buffering the mainland from storm surge impacts, providing habitats for valuable wildlife and fisheries habitat, offering accessible recreational opportunities, and preserving natural environments for educating the public about coastal ecosystems and cultural resources. Unfortunately, these highly valued natural areas are prone to damage from hurricanes. For example, Hurricane Camille in 1969 split Ship Island into East and West Ship Island. Hurricane Georges in 1998 caused additional land loss for the two Ship Islands. More recently, Hurricanes Ivan, Katrina, Rita, Gustav, and Ike impacted the Mississippi barrier islands. In particular, Hurricane Katrina caused major damage to island vegetation and landforms, killing island forest overstories, overwashing entire islands, and causing widespread erosion. In response, multiple state and federal agencies are working to restore damaged components of these barrier islands. Much of this work is being implemented through federally funded Coastal Impact Assessment and Mississippi Coastal Improvement programs. One restoration component involves the reestablishment of the island footprints to that in 1969. Our project will employ NASA remote sensing data and products to support these federally funded efforts on multiple fronts. Landsat and ASTER data is being analyzed to assess changes in barrier island land cover over the last 35 years. ASTER, SRTM, and EAARL terrain products and other NASA airborne imagery are being applied in assessing changes in barrier island geomorphology and geospatial extent. MODIS data is being examined as a tool for sediment transport modeling by supplying geospatial data that quantifies in-water sediment concentrations. MODIS satellite data is being assessed for monitoring changes in the spatial extent of individual barrier islands. Results thus far indicate that NASA data products are useful in assessing barrier island conditions and changes. This value is enhanced with additional historical geospatial data, commercial high resolution satellite data, other non-NASA aerial imagery, and field survey data. The project s products are relevant to the Gulf of Mexico Alliance priority issues, including coastal habitat conservation, restoration and coastal community resilience. Such products will be available to state and federal agencies involved with coastal restoration. Potential end-users of these products include the National Park Service, U.S. Geological Survey, U.S. Army Corps of Engineers, Environmental Protection Agency, Mississippi Department of Environmental Quality, and Mississippi Department of Marine Resources.

Giardino, Marco↗

NASA NTRS2014

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

NASA NTRS2000

Early Spring in Europe: A Result of More Dominant North-Atlantic Southwesterlies?

Abstract A 1999 study reports an advancement of spring in Europe by 0.2 days per year in the 30 years since 1960. Our analysis indicates that this trend results directly from a change in the late-winter surface winds over the eastern North Atlantic: the southwesterly direction became more dominant, and the speed of these southwesterlies increased slightly. Splitting the 52-year NCEP reanalysis dataset into the First Half, FH (1948-1973)), and the Second Half, SH (1974-1999), we analyze the wind direction for the February mean at three sites at 45N: site A at 30W, site B at 20W, and site C at 10W. The incidence (number of years) of the southwesterlies in SH Vs. (FH) at these sites respectively increased in SH as follows: 24(18), 19(12), 14(l 1); whereas the incidence of northeasterlies decreased: 0(2), 1(2), and 1(6). When the February mean wind is southwesterly, the monthly mean sensible heat flux from the ocean at these sites takes zero or slightly negative values, that is, the surface air is warmer than the ocean. Analyzing the scenario in the warm late winter 1990, we observe that the sensible heat flux from the ocean surface in February 1990 shows a "tongue" of negative values extending southwest from southern England to 7N. This indicates that the source of the maritime air advected into Europe lies to the south of the "tongue." Streamline analysis suggests that the Southwestern or southcentral North Atlantic is the source. For February 1990, we find strong, ascending motions over Europe at 700 mb, up to -0.4 Pa/s as monthly averages. Associated with the unstable low-levels of the troposphere are positive rain and cloud anomalies. Thus, positive in situ feedback over land in late winter (when shortwave absorption is not significant) apparently further enhances the surface temperature through an increase in the greenhouse effect due to increased water vapor and cloudiness.

Otterman, J.↗

NASA NTRS2021

Synthesis and Characterization of Fe(III)-Fe(II)- Mg- Al Smectite Solid Solutions and Implications for Planetary Science

This study demonstrates the synergies and limits of multiple measurement types for the detection of smectite chemistry and oxidation state on planetary surfaces to infer past geochemical conditions. Smectite clay minerals are common products of water-rock interactions throughout the solar system, and their detection and characterization provides important clues about geochemical conditions and past environments if sufficient information about their composition can be discerned. Here, we synthesize and report on the spectroscopic properties of a suite of smectite samples that span the intermediate compositional range between Fe(II), Fe(III), Mg, and Al end-member species using bulk chemical analyses, X-ray diffraction, Vis/IR reflectance spectroscopy, UV and green-laser Raman spectroscopy, and Mössbauer spectroscopy. Our data show that smectite composition and the oxidation state of octahedral Fe can be reliably identified in the near infrared on the basis of combination and fundamental metal-OH stretching modes between 2.1–2.9 μm, which vary systematically with chemistry. Smectites dominated by Mg or Fe(III) have spectrally distinct fundamental and combination stretches, whereas Al-rich and Fe(II)-rich smectites have similar fundamental minima near 2.76 μm, but have distinct combination M-OH features between 2.24 and 2.36 μm. We show that with expanded spectral libraries that include intermediate composition smectites and both Fe(III) and Fe(II) oxidation states, more refined characterization of smectites from MIR data is now possible, as the position of the 450 cm–1 absorption shifts systematically with octahedral Fe content, although detailed analysis is best accomplished in concert with other characterization methods. Our data also provide the first Raman spectral libraries of smectite clays as a function of chemistry, and we demonstrate that Raman spectroscopy at multiple excitation wavelengths can qualitatively distinguish smectite clays of different structures and can enhance interpretation by other types of analyses. Our sample set demonstrates how X-ray diffraction can distinguish between dioctahedral and trioctahedral smectites using either the (02,11) or (06,33) peaks, but auxiliary information about chemistry and oxidation state aids in specific identifications. Finally, the temperature-dependent isomer shift and quadrupole splitting in Mössbauer data are insensitive to changes in Fe content but reliability differentiates Fe within the smectite mineral structure.

Valerie K Fox↗

NASA NTRS1994

Global ozone observations from the UARS MLS: An overview of zonal-mean results

Global ozone observations from the Microwave Limb Sounder (MLS) aboard the Upper Atmosphere Research Satellite (UARS) are presented, in both vertically resolved and column abundance formats. The authors review the zonal-mean ozone variations measured over the two and a half years since launch in September 1991. Well-known features such as the annual and semiannual variations are ubiquitous. In the equatorial regions, longer-term changes are believed to be related to the quasi-biennial oscillation (QBO), with a strong semiannual signal above 20 hPa. Ozone values near 50 hPa exhibit an equatorial low from October 1991 to June 1992, after which the low ozone pattern splits into two subtropical lows (possibly in connection with residual circulation changes tied to the QBO) and returns to an equatorial low in September 1993. The ozone hole development at high southern latitudes is apparent in MLS column data integrated down to 100 hPa, the MLS data reinforce current knowledge of this lower-stratospheric phenomenon by providing a height-dependent view of the variations. The region from 30 deg S to 30 deg N (an area equal to half the global area) shows very little change in the ozone column from year to year and within each year. The most striking ozone changes have occurred at northern midlatitudes, with the October 1992 to July 1993 column values significantly lower than during the prior year. The zonal-mean changes manifest themselves as a slower rate of increase during the 1992/93 winter, and there is some evidence for a lower fall minimum. A recovery occurs during late summer of 1993; early 1994 values are significantly larger than during the two previous winters. The timing and latitudinal extent of the northern midlatitude decreases appear to rule out observed ClO enhancements in the Arctic vortex, with related chemical processing and ozone dilution effects, as a unique cause. Local depletion from ClO-related chemical mechanisms alone is also not sufficient, based on MLS ClO data. The puzzling asymmetric nature of the changes probably requires a dynamical component as an explanation. A combination of effects (including chemical destruction via heterogeneous processes and QBO phasing) apparently needs to be invoked. This dataset will place constraints on future modeling studies, which are required to better understand the source of the observed changes.

Froidevaux, Lucien↗