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NASA NTRSDate not supplied

Variability of Organic Matter Across Ci Chondrites and Ryugu

Petrologic and isotopic analysis of the mineral components of regolith samples from asteroid 162173 Ryugu collected by the JAXA Hayabusa2 spacecraft indicate a strong affinity with CI chondrite meteorites. Preliminary investigations of organic matter in Hayabusa2 samples also report similarities with insoluble organic matter in CI and CM chondrites. However, the Ryugu samples also contain a wide diversity of organic functional chemistry not previously observed in those aqueously altered chondrites. Due to their rarity, organic matter in CI chondrites is understudied relative to other chondrite classes. Here we investigate several CI samples with the same analytical approaches used for samples collected by Hayabusa2 for a more accurate comparison between CI and Ryugu organic matter.

Hayabusa2↗
NASA NTRS2023

Virus Infection of Phytoplankton Increases Average Molar Mass and Reduces Hygroscopicity of Aerosolized Organic Matter

Viral infection of phytoplankton is a pervasive mechanism of cell death and bloom termination, which leads to the production of dissolved and colloidal organic matter that can be aerosolized into the atmosphere. Earth-observing satellites can track the growth and death of phytoplankton blooms on weekly time scales but the impact of viral infection on the cloud forming potential of associated aerosols is largely unknown. Here, we determine the influence of viral-derived organic matter, purified viruses, and marine hydrogels on the cloud condensation nuclei activity of their aerosolized solutions, compared to organic exudates from healthy phytoplankton. Dissolved organic material derived from exponentially growing and infected cells of well-characterized eukaryotic phytoplankton host-virus systems, including viruses from diatoms, coccolithophores and chlorophytes, was concentrated, desalted, and nebulized to form aerosol particles composed of primarily of organic matter. Aerosols from infected phytoplankton cultures resulted in an increase in critical activation diameter and average molar mass in three out of five combinations evaluated, along with a decrease in organic kappa (hygroscopicity) compared to healthy cultures and seawater controls. The infected samples also displayed evidence of increased surface tension depression at realistic cloud water vapor supersaturations. Amending the samples with xanthan gum to simulate marine hydrogels increased variability in organic kappa and surface tension in aerosols with high organic to salt ratios. Our findings suggest that the pulses of increased dissolved organic matter associated with viral infection in surface waters may increase the molar mass of dissolved organic compounds relative to surface waters occupied by healthy phytoplankton or low phytoplankton biomass.

Atmospheric science↗
NASA NTRS2023

STXM-C-XANES, IR Microspectroscopy, and Raman Microspectroscopy Analysis of Organic Matter in the Chwichiya 002 C3.00-Ungrouped Chondrite

Chwichiya 002 is a C3.00-ungrouped carbonaceous chondrite discovered in Western Sahara in 2018. The presence of hydrated phases in Chwichiya 002 was not confirmed by XRD analysis, and only a faint water and Si-O band attributed to phyllosilicate were observed by infrared transmission spectroscopy, indicating a very low degree of aqueous alteration (Meteoritical Bulletin, 2020). The structural order of polycyclic aromatic hydrocarbons evaluated by Raman spectroscopy indicates that the effect of thermal metamorphism is less severe than in the Semarkona meteorite, an LL3.00 ordinary chondrite (Meteoritical Bulletin, 2020). Chiwichiya 002 is a very primitive carbonaceous chondrite and an important information source for the early stage of the evolution of organic matter in the solar system. In this study, we investigated the molecular structure and distribution of organic matter in Chiwichiya 002 by Carbon X-ray Absorption Near Edge Structure (C-XANES) analysis using a Scanning Transmission X-ray Microscope (STXM). The STXM-C-XANES analysis has a spatial resolution of 20~100 nm and can observe the spatial distribution of organic materials in microstructures. In addition, to investigate the degree of thermal metamorphism of the organic matter, micro-IR, and micro-Raman spectroscopic analyses were performed. In addition, the Murchison CM2 chondrite was also analyzed for comparison. To evaluate contamination during analytical procedures, antigorite, which was heated in air at 500°C for 5 hours to eliminate organic matter was also analyzed in the same manner. The samples were milled into 100 nm-thick, thin sections using a Focused Ion Beam (FIB), and C-XANES spectra were obtained using the STXM at the High Energy Accelerator Research Organization, Photon Factory (PF), BL-19B. The obtained C-XANES spectra were smoothed and then fitted with Gaussian functions using the method of Le Guillou et al. (2018). The C-XANES showed that the ratio of oxygenated functional group (ketone, phenolic) carbons in Chwichiya 002 was lower than in Murchison, whereas the ratio of aliphatic carbons was almost the same. This may reflect the low degree of aqueous alteration of Chwichiya 002. In addition, contamination peaks were detected at 287.3-287.7 eV and 288.3-288.7 eV in the C-XANES spectra of some of the antigorite samples. The source of these peaks is under investigation. Raman spectroscopic analysis showed that the intensity ratio of the D band to the G band of Chwichiya 002 was slightly higher than that of Murchison. IR absorption spectra showed aromatic absorption at 1630 cm -1 , but there was little absorption due to aliphatic C-H around 2900 cm -1 . These results suggest that the organic matter in Chwichiya 002 may be more heated than in Murchison.

Chwichiya 002↗
NASA NTRS1974

Spectral mapping of soil organic matter

Multispectral remote sensing data were examined for use in the mapping of soil organic matter content. Computer-implemented pattern recognition techniques were used to analyze data collected in May 1969 and May 1970 by an airborne multispectral scanner over a 40-km flightline. Two fields within the flightline were selected for intensive study. Approximately 400 surface soil samples from these fields were obtained for organic matter analysis. The analytical data were used as training sets for computer-implemented analysis of the spectral data. It was found that within the geographical limitations included in this study, multispectral data and automatic data processing techniques could be used very effectively to delineate and map surface soils areas containing different levels of soil organic matter.

Kristof, S. J.↗
NASA NTRS1988

Observed effects of soil organic matter content on the microwave intensity of soils

In order to determine the significance of organic matter content on the microwave emissivity of soils when estimating soil moisture, field experiments were conducted in which 1.4 GHz microwave emissivity data were collected over test plots of sandy loam soil with different organic matter levels (1.8, 4.0, and 6.1 percent) for a range of soil moisture values. Analyses of the observed data show only minor variation in microwave emissivity due to a change in organic matter content at a given moisture level for soils with similar texture and structure. Predictions of microwave emissivity made using a dielectric model for aggregated soils exhibit the same trends and type of response as the measured data when appropriate values for the input parameters were utilized.

Jackson, T. J.↗
NASA NTRS1990

Observed effects of soil organic matter content on the microwave emissivity of soils

In order to determine the significance of organic matter content on the microwave emissivity of soils when estimating soil moisture, field experiments were conducted in which 1.4 GHz microwave emissivity data were collected over test plots of sandy loam soil with different organic matter levels (1.8, 4.0, and 6.1 percent) for a range of soil moisture values. Analyses of the observed data show only minor variation in microwave emissivity due to a change in organic matter content at a given moisture level for soils with similar texture and structure. Predictions of microwave emissivity made using a dielectric model for aggregated soils exhibit the same trends and type of response as the measured data when appropriate values for the input parameters were utilized.

O'Neill, P. E.↗
NASA NTRS2012

In Situ Mapping of the Organic Matter in Carbonaceous Chondrites and Mineral Relationships

Carbonaceous chondrite organic matter represents a fossil record of reactions that occurred in a range of physically, spatially and temporally distinct environments, from the interstellar medium to asteroid parent bodies. While bulk chemical analysis has provided a detailed view of the nature and diversity of this organic matter, almost nothing is known about its spatial distribution and mineralogical relationships. Such information is nevertheless critical to deciphering its formation processes and evolutionary history.

Clemett, Simon J.↗
NASA NTRS2015

Interstellar and Solar System Organic Matter Preserved in Interplanetary Dust

Interplanetary dust particles (IDPs) collected in the Earth's stratosphere derive from collisions among asteroids and by the disruption and outgassing of short‐period comets. Chondritic porous (CP) IDPs are among the most primitive Solar System materials. CP‐IDPs have been linked to cometary parent bodies by their mineralogy, textures, C‐content, and dynamical histories. CP‐IDPs are fragile, fine‐grained (less than um) assemblages of anhydrous amorphous and crystalline silicates, oxides and sulfides bound together by abundant carbonaceous material. Ancient silicate, oxide, and SiC stardust grains exhibiting highly anomalous isotopic compositions are abundant in CP‐IDPs, constituting 0.01 - 1 % of the mass of the particles. The organic matter in CP‐IDPs is isotopically anomalous, with enrichments in D/H reaching 50x the terrestrial SMOW value and 15N/14N ratios up to 3x terrestrial standard compositions. These anomalies are indicative of low T (10‐100 K) mass fractionation in cold molecular cloud or the outermost reaches of the protosolar disk. The organic matter shows distinct morphologies, including sub‐um globules, bubbly textures, featureless, and with mineral inclusions. Infrared spectroscopy and mass spectrometry studies of organic matter in IDPs reveals diverse species including aliphatic and aromatic compounds. The organic matter with the highest isotopic anomalies appears to be richer in aliphatic compounds. These materials also bear similarities and differences with primitive, isotopically anomalous organic matter in carbonaceous chondrite meteorites. The diversity of the organic chemistry, morphology, and isotopic properties in IDPs and meteorites reflects variable preservation of interstellar/primordial components and Solar System processing. One unifying feature is the presence of sub‐um isotopically anomalous organic globules among all primitive materials, including IDPs, meteorites, and comet Wild‐2 samples returned by the Stardust mission.

Messenger, Scott↗
NASA NTRSDate not supplied

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗
NASA NTRS2005

HRTEM and EFTEM Studies of Phyllosilicate-Organic Matter Associations in Matrix and Dark Inclusions in the EET92042 CR2 Carbonaceous Chondrite

Based on petrologic and isotopic observations, the CR chondrites represent one of the most primitive carbonaceous chondrite groups. The organic matter in CR chondrite matrices is considered to be among the most ancient carbonaceous matter known, potentially providing a link between organic matter in the interstellar medium and our solar system [1]. However, the organic chemistry of CR chondrites may be complicated by the fact that these meteorites have undergone moderate secondary alteration, which potentially overprints primordial features [2]. Although the general effects of this alteration have been documented [2], the details of the fine-grained mineralogy and alteration styles of CR matrices are not fully understood. Here we present TEM observations of matrix in EET 92042, a CR chondrite that contains particularly primitive insoluble organic matter [1]. Preliminary studies [3] determined that EET 92042 matrix is heterogeneous in terms of mineralogy, texture, and petrographic fabric on the micron scale. EET 92042 contains magnetite-rich regions, foliated matrix and dark inclusions (DIs). Some chondrules show fine-grained rims, similar to those described by [4].

Abreu, Neyda M.↗
NASA NTRS2021

Photochemical and Microbial Degradation of Chromophoric Dissolved Organic Matter Exported from Tidal Marshes

Wetlands export chromophoric dissolved organic matter (CDOM) to estuaries, where CDOM is removed and transformed through biotic and abiotic process, subsequently impacting nutrient cycling, light availability, ecosystem metabolism, and phytoplankton activity. We examined the bioavailability and photoreactivity of CDOM exported from four Chesapeake Bay tidal marshes across three seasons and along an estuarine salinity gradient using three incubation treatments: 14-day microbial (MD), 7-day combined photochemical/microbial (PB+MD), and 7-day microbial incubation after photobleaching (MD after PB). CDOM absorption at 300 nm (aCDOM300) and dissolved organic carbon (DOC) concentrations showed strong seasonality, with minima in winter, but CDOM quality (absorption spectral slopes, fluorescence component ratios) was less variable seasonally. PB+MD over 7 days decreased aCDOM300 (–56.0%), humic-like fluorescence (–67.6%), and DOC (–17.8%), but increased the spectral slope ratio SR (=S275-295/S300-350) (+94.8%), suggesting a decrease in CDOM molecular weight. Photochemistry dominated the PB+MD treatment. Photoreactivity was greater during the winter and in marsh/watershed versus down-estuary sites, likely due to less previous light exposure. Prior photobleaching increased the bioavailability of marsh-exported CDOM, resulting in a greater loss of aCDOM300 and DOC, and a greater increase in humic-like fluorescence (–6.0%, –5.9%, and +18.4% change, respectively, over 7-day MD after PB incubations, versus –2.8%, –5.5%, and +2.6% change, respectively, over 14-day MD incubations). CDOM exported from a marsh downstream of a major wastewater treatment plant showed the greatest photoreactivity and bioavailability. This highlights the significance of human activity on estuarine CDOM quality and biogeochemical cycles.

Dissolved organic matter↗
NASA NTRS2012

In Situ Carbon and Sulfur Isotope Analysis of Archean Organic Matter and Pyrite

Stable isotopic compositions of biologically important elements (e.g., C and S) in sedimentary rocks are valuable biosignatures to the extent that they indicate the presence and variable expression of microbial metabolisms in space and time. Strong interactions between the carbon and sulfur cycles (e.g., via organic matter remineralization during microbial sulfate reduction) make coordinated, in situ C and S isotope analysis by secondary ion mass spectrometry (SIMS) a particularly powerful tool. In rocks ranging in age from 2.7-2.5 Ga, expansions in the ranges of delta C-13 of organic matter and delta S-34 of pyrite likely reflect the increasing influence of oxygenic photosynthesis in the surface ocean (as well as methane and sulfur metabolisms in deeper waters), whereas the large range of mass independent sulfur isotope fractionation (Delta S-33) suggests that the atmosphere remained anoxic until approx 2.4 Gyr ago. We report in situ delta C-13 measurements of organic matter in the approx 2.7-2.6 Ga Carawine Dolomite, Marra Mamba Iron Formation, and Jeerinah, Wittenoom, and Tumbiana Formations, as well as the approx 2.5 Ga Mount McRae Shale. We also report in situ delta S-24 and Delta S-33 measurements of pyrite associated with organic matter in a subset of these samples. In a single square cm sample of the Tumbiana Formation with bulk delta C-13(sub org) of -49.7% (VPDB), two distinct kerogen types have delta C-13 values, measured in situ, consistent with oxygenic photosynthesis (-33%) and methane metabolism (-52%). In a sample from the ABDP-9 core, radiobitumen associated with a uraniferous mineral grain is C-13-enriched by 8% (-26.8%0) relative to average in situ kerogen (-34.9%0) and similar in delta C-13 to solvent extractable hydrocarbons from the Mount McRae Shale (avg delta C-13 = -27.1 %). Average reproducibility for delta C-13 was 0.4% (2 SD) using a 6 micron spot and 0.8% using a 3 micron spot. In situ sulfur isotope analyses of 33 authigenic pyrite grains in 3 samples of the ABDP-9 core using a 10 micron spot (2 SD reproducibility = 0.4% for delta S-34 and -0.1% for Delta S-33) show a range of 28.1 % in delta S-34 (-10.3 to 17.8%) and 13.3%0 in Delta S-33 (-3.8 to 9.5%), whereas the range from 132 bulk analyses across 84 m of core is 19.4% for delta S-34 and 11.5% for Delta S-33. Coordinated, in situ carbon and sulfur isotope analyses in one ABDP-9 sample are shown. In situ values from this kerogen-pyrite association are within 0.1% of the bulk value in the case of delta C-13 and higher by several permil in the case of delta S-34 and Delta S-33. Coordinated in situ carbon and sulfur isotope analyses in rocks deposited during key intervals of environmental change (e.g., the Great Oxidation Event) can refine our understanding of the mode and tempo of change. In Earth's oldest sedimentary rocks, and in extraterrestrial samples, these coordinated in situ analyses may reveal biosignatures in the form of isotopic correlations at the scale of individual microorganisms and their microhabitats.

Williford, K. H.↗
NASA NTRS1992

High dimensional reflectance analysis of soil organic matter

Recent breakthroughs in remote-sensing technology have led to the development of high spectral resolution imaging sensors for observation of earth surface features. This research was conducted to evaluate the effects of organic matter content and composition on narrowband soil reflectance across the visible and reflective infrared spectral ranges. Organic matter from four Indiana agricultural soils, ranging in organic C content from 0.99 to 1.72 percent, was extracted, fractionated, and purified. Six components of each soil were isolated and prepared for spectral analysis. Reflectance was measured in 210 narrow bands in the 400- to 2500-nm wavelength range. Statistical analysis of reflectance values indicated the potential of high dimensional reflectance data in specific visible, near-infrared, and middle-infrared bands to provide information about soil organic C content, but not organic matter composition. These bands also responded significantly to Fe- and Mn-oxide content.

Henderson, T. L.↗
NASA NTRS1989

Spectral band selection for classification of soil organic matter content

This paper describes the spectral-band-selection (SBS) algorithm of Chen and Landgrebe (1987, 1988, and 1989) and uses the algorithm to classify the organic matter content in the earth's surface soil. The effectiveness of the algorithm was evaluated comparing the results of classification of the soil organic matter using SBS bands with those obtained using Landsat MSS bands and TM bands, showing that the algorithm was successful in finding important spectral bands for classification of organic matter content. Using the calculated bands, the probabilities of correct classification for climate-stratified data were found to range from 0.910 to 0.980.

Henderson, Tracey L.↗