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NASA NTRS2005

Dry Acid Deposition and Accumulation on the Surface of Mars and in the Atacama Desert, Chile

It has been discovered recently that soils from certain regions of the Chilean Atacama Desert have some characteristics that are similar to the surface materials tested by the Viking Landers. Navarro-Gonzalez et al. demonstrated that the quantity and diversity of heterotrophic bacteria increase as a function of local water availability in the Atacama, and that for some soil samples collected in the driest regions, no culturable bacteria could be isolated. Additionally, Navarro-Gonzalez et al. reported that pyrolysis-GCMS analysis of soils collected from these regions revealed extremely low levels of organic matter. Although the mechanism resulting in the low level of organics in these regions was not established by Navarro-Gonzalez, the condition of organic-depleted, near-sterile soil offers an interesting Earth analog of the martian surface material, as the Viking Gas Exchange (GEx) experiment and Labeled Release (LR) experiment were unable to demonstrate the presence of culturable bacteria, and the Viking pyrolysis- GCMS was unable to detect organic compounds.

Quinn, R. C.↗
NASA NTRS1981

Organic analysis of the Antarctic carbonaceous chondrites

Thus far, organic analysis of carbonaceous chondrites has proven the only fruitful means of examining complex organic matter of extraterrestrial origin. The present paper presents the results of organic analysis of two Antarctic meteorites, Allan Hills (77306) and Yamato (74662), which may be considered free from terrestrial contamination. Ion-exchange chromatography, gas chromatography and mass spectrometery of meteorite samples reveal the presence in Yamato of 15 and in Allan Hills of 20 protein and nonprotein amino acids, the most abundant of which are glycine and alanine. Abundances of the D and L enantiomers of each amino acid are also found to be nearly equal. Data thus indicate an abiotic extraterrestrial origin for the matter, and confirm a lack of terrestrial contamination.

Kotra, R. K.↗
NASA NTRS2014

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

humic acid↗
NASA NTRS2015

Indigenous Carbonaceous Matter and Boron Associated with Halite Crystals in Nakhla

We report here the observation of indigenous organic matter spatially associated with, and in several cases embedded within, halite crystals located in alteration veins inside the Martian meteorite Nakhla. Further-more, we have also detected enrichments of boron (B) in these halites far in excess of those previously reported in bulk Martian meteorites. Boron in Martian halites has not been detected previously.

Thomas-Keprta, K. L.↗
NASA NTRS2000

The AstroBiology Explorer (ABE) MIDEX Mission

The Astrobiology Explorer (ABE) is a Medium-Class Explorer (MIDEX) mission concept currently under study at NASA's Ames Research Center. ABE will conduct infrared (IR) spectroscopic observations with much better sensitivity than Infrared Space Observatory (ISO) or the Stratospheric Observatory for Infrared Astronomy program (SOFIA) in order to address outstanding astrobiologically important problems in astrochemistry as well as important astrophysical investigations. The core observational astrobiology program would make fundamental scientific progress in understanding the cosmic history of molecular carbon, the distribution of organic matter in the diffuse interstellar medium, tracing the chemical history of complex organic molecules in the interstellar medium, and the evolution of organic ices in young planetary systems. The ABE instrument concept includes a 0.5 m aperture Cassegrain telescope and a suite of three moderate resolution (R = 1000 - 4000) spectrographs which cover the entire lambda = 2.5-20 micron spectral region. Use of large format (1024 x 1024 pixel or larger) IR detector arrays will allow each spectrograph to cover an entire octave of spectral range per exposure without any moving parts. The telescope is passively cooled by a sun shade to below 65 K, and the detectors are cooled with solid H2 cryogen to approximately 8 K. ABE will be placed in an Earth-trailing one AU solar orbit by a Delta II launch vehicle. This energetically favorable orbit provides a low thermal background, affords good access to the entire sky over the one year mission lifetime, and allows adequate communications bandwidth. The spacecraft will be stabilized in three axes and will be pointed to an accuracy of approximately one arcsecond at ABE's several thousand individual scientific targets.

Greene, Thomas↗
NASA NTRS1996

Fossilization processes in siliceous thermal springs: trends in preservation along thermal gradients

To enhance our ability to extract palaeobiological and palaeoenvironmental information from ancient thermal spring deposits, we have studied the processes responsible for the development and preservation of stromatolites in modern subaerial thermal spring systems in Yellowstone National Park (USA). We investigated specimens collected from silica-depositing thermal springs along the thermal gradient using petrographic techniques and scanning electron microscopy. Although it is known that thermophilic cyanobacteria control the morphogenesis of thermal spring stromatolites below 73 degrees C, we have found that biofilms which contain filamentous thermophiles contribute to the microstructural development of subaerial geyserites that occur along the inner rims of thermal spring pools and geyser effluents. Biofilms intermittently colonize the surfaces of subaerial geyserites and provide a favoured substrate for opaline silica precipitation. We have also found that the preservation of biotically produced microfabrics of thermal spring sinters reflects dynamic balances between rates of population growth, decomposition of organic matter, silica deposition and early diagenesis. Major trends in preservation of thermophilic organisms along the thermal gradient are defined by differences in the mode of fossilization, including replacement, encrustation and permineralization.

NASA Discipline Exobiology↗
NASA NTRS2006

'Nano' Morphology and Element Signatures of Early Life on Earth: A New Tool for Assessing Biogenicity

The relatively young technology of NanoSIMS is unlocking an exciting new level of information from organic matter in ancient sediments. We are using this technique to characterize Proterozoic organic material that is clearly biogenic as a guide for interpreting controversial organic structures in either terrestrial or extraterrestrial samples. NanoSIMS is secondary ion mass spectrometry for trace element and isotope analysis at sub-micron resolution. In 2005, Robert et al. [1] combined NanoSIMS element maps with optical microscopic imagery in an effort to develop a new method for assessing biogenicity of Precambrian structures. The ability of NanoSIMS to map simultaneously the distribution of organic elements with a 50 nm spatial resolution provides new biologic markers that could help define the timing of life s development on Earth. The current study corroborates the work of Robert et al. and builds on their study by using NanoSIMS to map C, N (as CN), S, Si and O of both excellently preserved microfossils and less well preserved, non-descript organics in Proterozoic chert from the ca. 0.8 Ga Bitter Springs Formation of Australia.

Oehler, D. Z.↗
NASA NTRS2021

Challenges and opportunities for enhancing food security and greenhouse gas mitigation in smallholder farming in sub-Saharan Africa. A review

Smallholder farmers struggle to achieve food security in many countries of sub-Saharan Africa (SSA). It is urgently required to find appropriate practices for enhancing crop production while avoiding large increases in greenhouse gas (GHG) emissions in SSA. This review aims to identify common smallholder farming practices for enhancing crop production, to assess how these affect GHG emissions and to identify strategies that not only enhance crop production but also mitigate GHG emissions in SSA. To increase crop production and ensure food security, smallholder farmers usually expand agricultural land, develop water harvesting and irrigation techniques and increase cropping intensity and fertilizer use. These practices may result in changing carbon stocks and GHG emissions, potentially creating trade-offs between food security and GHG mitigation. Agricultural land expansion at the expense of forests is the most dominant source of GHG emissions in SSA. While water harvesting and irrigation can increase soil organic carbon, they can trigger GHG emissions. Increasing cropping intensity can enhance the decomposition of soil organic matter, thus releasing carbon dioxide. Increasing nitrogen fertilizer use can enhance soil organic carbon, but also leads to increasing nitrous oxide emissions. An integrated land, water and nutrient management strategy is necessary to enhance crop production and mitigate GHG emissions. Among the most relevant strategies found, agroforestry practices in degraded and marginal lands could replace expanding agricultural croplands. In addition, water management, via adequate rainwater harvesting and irrigation techniques, together with appropriate nutrient management should be considered. Therefore, a land-water-nutrient nexus (LWNN) approach will enable an integrated and sustainable solution to increasing crop production and mitigating GHG emissions. Various technical, economic and policy barriers hinder implementing the LWNN approach on the ground, but these may be overcome through developing appropriate technologies, disseminating them through farmer to farmer approaches and developing specific policies to address smallholder land tenure issues and motivate long-term investment.

Sub-Sahara Africa↗
NASA NTRS1979

The photolytic degradation and oxidation of organic compounds under simulated Martian conditions

Cosmochemical considerations suggest various potential sources for the accumulation of organic matter on Mars. However the Viking Molecular Analysis did not indicate any indigenous organic compounds on the surface of Mars. Their disappearance from the top layer is most likely caused by the combined action of the high solar radiation flux and various oxidizing species in the Martian atmosphere and regolith. In this study the stability of several organic substances and a sample of the Murchison meteorite was tested under simulated Martian conditions. After adsorption on powdered quartz, samples of adenine, glycine and naphthalene were irradiated with UV light at various oxygen concentrations and exposure times. In the absence of oxygen, adenine and glycine appeared stable over the given irradiation period, whereas a definite loss was observed in the case of naphthalene, as well as in the volatilizable and pyrolizable content of the Murchison meteorite. The presence of oxygen during UV exposure caused a significant increase in the degradation rate of all samples. It is likely that similar processes have led to the destruction of organic materials on the surface of Mars.

Oro, J.↗
NASA NTRS2019

Uncertainties in the Geostationary Ocean Color Imager (GOCI) Remote Sensing Reflectance for Assessing Diurnal Variability of Biogeochemical Processes

Short-term (sub-diurnal) biological and biogeochemical processes cannot be fully captured by the current suite of polar-orbiting satellite ocean color sensors, as their temporal resolution is limited to potentially one clear image per day. Geostationary sensors, such as the Geostationary Ocean Color Imager (GOCI) from the Republic of Korea, allow the study of these short-term processes because their orbit permit the collection of multiple images throughout each day for any area within the sensor’s field of regard. Assessing the capability to detect sub-diurnal changes in in-water properties caused by physical and biogeochemical processes characteristic of open ocean and coastal ocean ecosystems, however, requires an understanding of the uncertainties introduced by the instrument and/or geophysical retrieval algorithms. This work presents a study of the uncertainties during the daytime period for an ocean region with characteristically low-productivity with the assumption that only small and undetectable changes occur in the in-water properties due to biogeochemical processes during the daytime period. The complete GOCI mission data were processed using NASA’s SeaDAS/l2gen package. The assumption of homogeneity of the study region was tested using three-day sequences and diurnal statistics. This assumption was found to hold based on the minimal diurnal and day-to-day variability in GOCI data products. Relative differences with respect to the midday value were calculated for each hourly observation of the day in order to investigate what time of the day the variability is greater. Also, the influence of the solar zenith angle in the retrieval of remote sensing reflectances and derived products was examined. Finally, we determined that the uncertainties in water-leaving “remote-sensing” reflectance (Rrs) for the 412,443, 490, 555, 660 and 680 nm bands on GOCI are 8.05 x 10(exp -4), 5.49 x 10(exp -4), 4.48 x 10(exp -4), 2.51 x 10(exp -4), 8.83 x 10(exp -5), and 1.36 x 10(exp -4)/sr, respectively, and 1.09 x 10(exp -2)/cu.mgm for the chlorophyll-a concentration (Chl-a), 2.09 x 10(exp -3)/m for the absorption coefficient of chromophoric dissolved organic matter at 412 nm (a(sub g) (412)), and 3.7 mg/cu.m for particulate organic carbon (POC). These R(sub rs) values can be considered the threshold values for detectable changes of the in-water properties due to biological, physical or biogeochemical processes from GOCI.

Concha, Javier↗
NASA NTRS2019

Uncertainties in the Geostationary Ocean Color Imager (GOCI) Remote Sensing Reflectance for Assessing Diurnal Variability of Biogeochemical Processes

Short-term (sub-diurnal) biological and biogeochemical processes cannot be fully captured by the current suite of polar-orbiting satellite ocean color sensors, as their temporal resolution is limited to potentially one clear image per day. Geostationary sensors, such as the Geostationary Ocean Color Imager (GOCI) from the Republic of Korea, allow the study of these short-term processes because their orbit permit the collection of multiple images throughout each day for any area within the sensor’s field of regard. Assessing the capability to detect sub-diurnal changes in in-water properties caused by physical and biogeochemical processes characteristic of open ocean and coastal ocean ecosystems, however, requires an understanding of the uncertainties introduced by the instrument and/or geophysical retrieval algorithms. This work presents a study of the uncertainties during the daytime period for an ocean region with characteristically low-productivity with the assumption that only small and undetectable changes occur in the in-water properties due to biogeochemical processes during the daytime period. The complete GOCI mission data were processed using NASA’s SeaDAS/l2gen package. The assumption of homogeneity of the study region was tested using three-day sequences and diurnal statistics. This assumption was found to hold based on the minimal diurnal and day-to-day variability in GOCI data products. Relative differences with respect to the midday value were calculated for each hourly observation of the day in order to investigate what time of the day the variability is greater. Also, the influence of the solar zenith angle in the retrieval of remote sensing reflectances and derived products was examined. Finally, we determined that the uncertainties in water-leaving “remote-sensing” reflectance (Rrs) for the 412, 443, 490, 555, 660 and 680 nm bands on GOCI are 8.05 × 10−4, 5.49 × 10−4, 4.48 × 10−4, 2.51 × 10−4, 8.83 × 10−5, and 1.36 × 10−4 sr−1, respectively, and 1.09 × 10−2 mg m−3 for the chlorophyll-a concentration (Chl-a), 2.09 × 10−3 m−1 for the absorption coefficient of chromophoric dissolved organic matter at 412 nm (ag (412)), and 3.7 mg m−3 for particulate organic carbon (POC). These Rrs values can be considered the threshold values for detectable changes of the in-water properties due to biological, physical or biogeochemical processes from GOCI.

Geostationary Ocean Color Imager (GOCI)↗
NASA NTRS2000

Extraterrestrial Organic Chemistry: From the Interstellar Medium to the Origins of Life

Extraterrestrially delivered organics in the origin of cellular life. Various processes leading to the emergence of cellular life from organics delivered from space to earth or other planetary bodies in the solar system will be reviewed. The focus will be on: (1) self-assembly of amphiphilic material to vesicles and other structures, such as micelles and multilayers, and its role in creating environments suitable for chemical catalysis, (2) a possible role of extraterrestrial delivery of organics in the formation of the simplest bioenergetics (3) mechanisms leading from amino acids or their precursors to simple peptides and, subsequently, to the evolution of metabolism. These issues will be discussed from two opposite points of view: (1) Which molecules could have been particularly useful in the protobiological evolution; this may provide focus for searching for these molecules in interstellar media. (2) Assuming that a considerable part of the inventory of organic matter on the early earth was delivered extraterrestrially, what does relative abundance of different organics in space tell us about the scenario leading to the origin of life.

Pohorille, Andrew↗
NASA NTRS2002

Peptides at Membrane Surfaces and their Role in the Origin of Life

All ancestors of contemporary cells (protocells) had to transport ions and organic matter across membranous walls, capture and utilize energy and transduce environmental signals. In modern organisms, all these functions are preformed by membrane proteins. We make the parsimonious assumption that in the protobiological milieu the same functions were carried out by their simple analogs - peptides. This, however, required that simple peptides could self-organize into ordered, functional structures. In a series of detailed, molecular-level computer simulations we demonstrated how this is possible. One example is the peptide (LSLLLSL)3 which forms a trameric bundle capable of transporting protons across membranes. Another example is the transmembrane pore of the influenza M2 protein. This aggregate of four identical alpha-helices, each built of 25 amino acids, forms an efficient and selective voltage-gated proton channel. Our simulations explain the gating mechanism in this channel. The channel can be re-engineered into a simple proton pump.

Pohorille, Andrew↗
NASA NTRS2010

The Spatial Distribution and Mineralogical Association of Organics in the Tagish Lake and Bells Carbonaceous Chondrites

Chondritic meteorites represent some of the most primitive Solar System materials available for laboratory analysis. While the presence of simple organic molecules has been well documented in such materials [1], little is known about their spatial distribution and to what extent, if any, they exhibit specific mineralogical associations. This dichotomy arises since organic analysis typically involves solvent extraction as a preliminary step. To address these issues we have used two-step laser mass spectrometry (L 2MS) to map in situ the spatial distribution of aromatic and conjugated organics at the micron scale in freshly exposed surfaces of the Tagish Lake and Bells carbonaceous chondrites. Our specific goals are two-fold; firstly to investigate if and how abundance of organic species varies within the meteorite matrix both as an ensemble, and with respect to functional group (e.g., R-OH vs. RCH3) and between members of the same homologous series (e.g., R-H vs. R-(CH2)H). Secondly, to determine whether observed spatial variations can be related to specific mineralogical and/or physical characteristics of the host matrix. In regard to the latter we are particularly interested in the role that carbonaceous nanoglobules [2] play as reservoirs of organic matter. Such globules, which are believed to have formed by photochemical processing of organic-rich ices in the presolar cold molecular cloud or the outermost reaches of the early protosolar disk, are abundant in both the Bells and Tagish Lake chondrites and are noteworthy for having particularly high enrichments in 2H and 15N [3,4].

Clemett, S. J.↗
NASA NTRS2013

Coordinated in Situ Analyses of Organic Nanoglobules in the Sutter's Mill Meteorite

The Sutter's Mill meteorite is a newly fallen carbonaceous chondrite that was collected and curated quickly after its fall. Preliminary petrographic and isotopic investigations suggest affinities to the CM2 carbonaceous chondrites. The primitive nature of this meteorite and its rapid recovery provide an opportunity to investigate primordial solar system organic matter in a unique new sample. Here we report in-situ analyses of organic nanoglobules in the Sutter's Mill meteorite using UV fluorescence imaging, Fourier-transform infrared spectroscopy (FTIR), scanning transmission electron microscopy (STEM), NanoSIMS, and ultrafast two-step laser mass spectrometry (ultra-L2MS).

Nakamura-Messenger, K.↗
NASA NTRS2013

Global and Regional Temperature-change Potentials for Near-term Climate Forcers

We examine the climate effects of the emissions of near-term climate forcers (NTCFs) from 4 continental regions (East Asia, Europe, North America and South Asia) using results from the Task Force on Hemispheric Transport of Air Pollution Source-Receptor global chemical transport model simulations. We address 3 aerosol species (sulphate, particulate organic matter and black carbon) and 4 ozone precursors (methane, reactive nitrogen oxides (NOx), volatile organic compounds and carbon monoxide). We calculate the global climate metrics: global warming potentials (GWPs) and global temperature change potentials (GTPs). For the aerosols these metrics are simply time-dependent scalings of the equilibrium radiative forcings. The GTPs decrease more rapidly with time than the GWPs. The aerosol forcings and hence climate metrics have only a modest dependence on emission region. The metrics for ozone precursors include the effects on the methane lifetime. The impacts via methane are particularly important for the 20 yr GTPs. Emissions of NOx and VOCs from South Asia have GWPs and GTPs of higher magnitude than from the other Northern Hemisphere regions. The analysis is further extended by examining the temperature-change impacts in 4 latitude bands, and calculating absolute regional temperature-change potentials (ARTPs). The latitudinal pattern of the temperature response does not directly follow the pattern of the diagnosed radiative forcing. We find that temperatures in the Arctic latitudes appear to be particularly sensitive to BC emissions from South Asia. The northern mid-latitude temperature response to northern mid-latitude emissions is approximately twice as large as the global average response for aerosol emission, and about 20-30% larger than the global average for methane, VOC and CO emissions.

North America↗
NASA NTRS2014

Decarboxylation of Carbon Compounds as a Potential Source for CO2 and CO Observed by SAM at Yellowknife Bay, Gale Crater, Mars

Martian carbon was detected in the Sheepbed mudtsone at Yellowknife Bay, Gale Crater, Mars by the Sample Analysis at Mars (SAM) instrument onboard Curiosity, the rover of the Mars Science Laboratory missio]. The carbon was detected as CO2 thermally evolved from drilled and sieved rock powder that was delivered to SAM as a <150-micron-particle- size fraction. Most of the CO2 observed in the Cumberland (CB) drill hole evolved between 150deg and 350deg C. In the John Klein (JK) drill hole, the CO2 evolved up to 500deg C. Hypotheses for the source of the the CO2 include the breakdown of carbonate minerals reacting with HCl released from oxychlorine compounds, combustion of organic matter by O2 thermally evolved from the same oxychlorine minerals, and the decarboxylation of organic molecules indigenous to the martian rock sample. Here we explore the potential for the decarboxylation hypothesis.

Eigenbrode, J. L.↗
NASA NTRS2020

Preservation of Organic Carbon in Dolomitized Cambrian Stromatolites and Implications for Microbial Biosignatures in Diagenetically Replaced Carbonate Rock

Stromatolites have been a major focus in the search for ancient microbial life, however, the organic carbon biosignatures of dolomitized stromatolites have not yet been fully characterized or correlated with their dolomitizing conditions. Although dolomitization rarely preserves microbial morphology, the presence of organic carbon can provide valuable information for characterization of fossils’ biogenicity, syngenicity, and indigeneity to their host rock. The Cambrian Allentown Formation in New Jersey, USA, is an excellent example of dolomitized stromatolites and thrombolites containing diagenetically modified microbial biosignatures. Based on XRD and EPMA data, the dolomite composition is typically stoichiometric, with varying degrees of cationic ordering. The outcrop underwent early dolomitization in a marginal-marine setting and later burial diagenesis resulting in multi-generational dolomite formation: (1) 2 microspar dolomite formed by early diagenetic replacement at or near the surface, (2) zoned dolomite formed penecontemporaneously with the microspar phase as rhombohedral crystals by infilling primary pore spaces within the microspar matrix. The rhombic crystals continued to grow outward in alternating stages of Fe-enriched and -depleted fluids, which were preserved in zoned rims and revealed by cathodoluminescence, and (3) saddle dolomite formed during late stage deep burial with Fe- and Mn-rich fluids, and occurs as a void-filling, high-temperature phase. Organic carbon, characterized using confocal Raman microscopy, has an exclusive distribution within the microspar dolomite, and the D and G bands’ characteristics reveal similar thermal alteration to the host rock, indicating that the mapped organic carbon is indigenous and syngenetic with the Cambrian carbonates. The findings presented in this study reveal organic matter found within microspar of various dolomitized facies deriving from different source pools of organic carbon. This study sheds light on biosignatures in secondary dolostones and may aid biosignature detection in older carbonate rocks on Earth and Mars.

Dolomitization↗