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DOE OSTI2021

Stability of tropical forest tree carbon-water relations in a rainfall exclusion treatment through shifts in effective water uptake depth

Increasing severity and frequency of drought is predicted for large portions of the terrestrial biosphere, with major impacts already documented in wet tropical forests. Using a 4-year rainfall exclusion experiment in the Daintree Rainforest in northeast Australia, we examined canopy tree responses to reduced precipitation and soil water availability by quantifying seasonal changes in plant hydraulic and carbon traits for 11 tree species between control and drought treatments. Even with reduced soil volumetric water content in the upper 1 m of soil in the drought treatment, we found no significant difference between treatments for predawn and midday leaf water potential, photosynthesis, stomatal conductance, foliar stable carbon isotope composition, leaf mass per area, turgor loss point, xylem vessel anatomy, or leaf and stem nonstructural carbohydrates. While empirical measurements of aboveground traits revealed homeostatic maintenance of plant water status and traits in response to reduced soil moisture, modeled belowground dynamics revealed that trees in the drought treatment shifted the depth from which water was acquired to deeper soil layers. Finally, these findings reveal that belowground acclimation of tree water uptake depth may buffer tropical rainforests from more severe droughts that may arise in future with climate change.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRSDate not supplied

CO2-Based Manufacturing System for Recombinant Protein Production

Space biomanufacturing is a potential In Situ Resource Utilization (ISRU) strategy to provide critical consumables and products while minimizing the launched mass for long-duration, deep space missions. On Earth, the primary biological conversion of CO 2 to biomass is through photosynthesis, and sugars from photosynthetic organisms are used as feedstocks for microbial biomanufacturing. The efficiency of non-biological reduction of CO 2 to organic molecules, such as acetate or ethanol, has greatly increased in recent years. We are designing a biomanufacturing system to rely on electrochemical CO 2 conversion products for carbon substrates to support microbial growth and production of recombinant proteins. The preliminary design includes a gas-permeable membrane bioreactor with dry salts that are rehydrated and mixed with the carbon source to support growth of bacteria or yeast. The system architecture has a partially automated bioprocessing system to concentrate biomass and purify recombinant protein. This system is designed to operate semi-autonomously with minimal crew intervention. The specific use-case scenario is to produce a thermal stable carbonic anhydrase to increase the efficiency of a proposed liquid amine CO 2 removal subsystem of an environmental control and life-support system (ECLSS) on Mars.

Biomanufacturing↗

NASA NTRSDate not supplied

Development of a Space Compatible Biomanufacturing System

Recombinant↗

NASA NTRS1992

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.

Non-NASA Center↗

NASA NTRSDate not supplied

Bioreactor Development for CO2-Based In Situ Resource Utilization Manufacturing

Sustainable long-duration manned missions on both the Moon and Mars will require in situ resource utilization (ISRU). Carbon dioxide (CO2) has great potential as a harvestable resource, making up 95% of the atmosphere on Mars and being produced as respiratory waste in spacecraft and future planetary habitats. Through ISRU, biomanufacturing has the capability to produce a near limitless array of products from local space resources. Here, a CO2-based ISRU recombinant protein producing bioreactor and associated biomanufacturing organisms were designed to produce a highly stable carbonic anhydrase (CA). Candidate organisms were selected by growth characterization on acetate and formic acid, carbon substrates that are synthesized via electrochemical conversion of CO2. To improve growth on the CO2 producing substrate formic acid and for direct integration of ISRU CO2, a synthetic Calvin-Benson-Bassam cycle was designed for use in Escherichia coli. Multiplex genetic modification in E. coli was facilitated by a tailored CRISPR/Cas9 and λ red recombineering two-vector system. For expression of CA, a blue light regulated T7 promoter was employed for dynamic and small molecule free induction. Efficient bioproduction through a fed-batch exponential feeding strategy was determined via mass balance analysis from ISRU substrates to biomass and CA yield. Flux balance analysis was used to model ISRU substrate metabolism and metabolic pathway engineering in candidate organisms under cultivation strategy conditions for both metabolism reconstruction and pathway design optimization. Finally, a small-scale, disposable bag bioreactor for use in the NASA Bioculture System infrastructure was designed to enable CO2-based CA biomanufacturing in reduced-gravity environments.

biomanufacturing↗

DOE OSTI2022

Dimethyl Carbonate: Review of Synthesis Routes and Catalysts Used

This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed. The major challenges associated with the conversion of CO2 to DMC are the low yields, low DMC selectivity, and thermodynamic limitations (alcohol carbonylation) of reversible reactions with low equilibrium constants. This occurs mainly due to the highly stable carbon dioxide molecules. The development of novel catalysts with high yields and high selectivity needs to be studied to overcome these technical challenges. In addition, to enhance the DMC yield, the use of dehydrating agents for water removal from the reaction mixture is recommended and discussed in detail in this article. This review critically examines the different catalysts used by investigators, along with their respective operating conditions and suitability in applications for the commercial synthesis of CO2-based DMC.

10 SYNTHETIC FUELS↗

NASA NTRSDate not supplied

Bioreactor Development for CO2-Based In Situ Resource Utilization Manufacturing

Sustainable long-duration manned missions on both the Moon and Mars will require in situ resource utilization (ISRU). Carbon dioxide (CO2) has great potential as a harvestable resource, making up 95% of the atmosphere on Mars and being produced as respiratory waste in spacecraft and future planetary habitats. Through ISRU, biomanufacturing has the capability to produce a near limitless array of products from local space resources, which include pharmaceuticals, bioplastics, chemical feedstocks, and industrial enzymes. Here, a CO2-based ISRU recombinant protein bioreactor and associated biomanufacturing organisms were designed to produce a highly stable carbonic anhydrase (CA). Initial work characterized candidate organisms for growth on acetate and formic acid, carbon substrates that can be synthesized via electrochemical conversion of CO2. To improve growth on the CO2 producing substrate formic acid and for direct integration of ISRU CO2, a synthetic Calvin-Benson-Bassam cycle was designed for use in Cyberlindnera jadinii and Escherichia coli. Genetic modifications in E. coli will be facilitated by a tailored CRISPR/Cas9 and λ red recombineering two-vector system. For expression of CA, a blue light regulated T7 promoter was employed for dynamic and small molecule free induction. Efficient bioproduction through a fed-batch exponential feeding strategy was determined via mass balance calculations from ISRU substrates to biomass and CA yield. Flux balance analysis was used to model ISRU substrate metabolism and metabolic pathway engineering in candidate organisms under cultivation strategy conditions for both metabolism reconstruction and pathway design optimization. Finally, a small-scale, disposable bag bioreactor concept for use in the NASA Bioculture System infrastructure was designed to enable CO2-based CA production in reduced-gravity environments.

Biomanufacturing, Pathway Engineering, Flux Balanc↗

DOE OSTI2025

Quantifying soil organic matter stock distribution and origin following over a century of maize-based cropping in the former tallgrass prairie region of central USA

Tallgrass prairie conversion to maize-based agriculture in central North America has resulted in substantial loss of soil organic carbon (SOC) in less than two centuries. However, evaluations of how management practices may mitigate SOC losses are generally limited in soil depth and/or duration, missing long-term SOC stock outcomes that manifest over timescales of decades or longer. To address this, we sampled soils in year 145 of the Morrow Plots experiment to (i) evaluate effects of crop rotation and fertility management on SOC stocks and (ii) distinguish prairie- versus maize-derived SOC after continuous maize cropping since 1876 using stable carbon isotope ( 13 C) natural abundance. Soil organic carbon stock by equivalent soil mass (ESM) was + 30.7 Mg C ha −1 (+31.7 %) higher under maize-oat-alfalfa than continuous maize, but similar between maize-soybean and continuous maize. NPK fertilization and manuring did not influence SOC stocks by ESM. Response of SOC stocks at 15 cm depth intervals to NPK fertilization varied by depth and crop rotation, with lower SOC stocks at 30–45 cm under continuous maize and maize-soybean. Maize-derived C ranged 19.5–59.6 % of SOC stock across depths, indicating the majority of SOC was still derived from tallgrass prairie even after 145 years of continuous maize cropping. Our results confirm the potential of diversified crop rotation for minimizing SOC losses relative to tallgrass prairie at the supracentennial scale, and highlight the importance of relic prairie soil organic matter for future crop production in central North America.

crop rotation↗

DOE OSTI2024

Controls on Stable Methane Isotope Values in Northern Peatlands and Potential Shifts in Values Under Permafrost Thaw Scenarios

Abstract Northern peatlands are a globally significant source of methane (CH 4 ), and emissions are projected to increase due to warming and permafrost loss. Understanding the microbial mechanisms behind patterns in CH 4 production in peatlands will be key to predicting annual emissions changes, with stable carbon isotopes (δ 13 C‐CH 4 ) being a powerful tool for characterizing these drivers. Given that δ 13 C‐CH 4 is used in top‐down atmospheric inversion models to partition sources, our ability to model CH 4 production pathways and associated δ 13 C‐CH 4 values is critical. We sought to characterize the role of environmental conditions, including hydrologic and vegetation patterns associated with permafrost thaw, on δ 13 C‐CH 4 values from high‐latitude peatlands. We measured porewater and emitted CH 4 stable isotopes, pH, and vegetation composition from five boreal‐Arctic peatlands. Porewater δ 13 C‐CH 4 was strongly associated with peatland type, with δ 13 C enriched values obtained from more minerotrophic fens (−61.2 ± 9.1‰) compared to permafrost‐free bogs (−74.1 ± 9.4‰) and raised permafrost bogs (−81.6 ± 11.5‰). Variation in porewater δ 13 C‐CH 4 was best explained by sedge cover, CH 4 concentration, and the interactive effect of peatland type and pH (r 2 = 0.50,p < 0.001). Emitted δ 13 C‐CH 4 varied greatly but was positively correlated with porewater δ 13 C‐CH 4 . We calculated a mixed atmospheric δ 13 C‐CH 4 value for northern peatlands of −65.3 ± 7‰ and show that this value is more sensitive to landscape drying than wetting under permafrost thaw scenarios. Our results suggest northern peatland δ 13 C‐CH 4 values are likely to shift in the future which has important implications for source partitioning in atmospheric inversion models.

Environmental Sciences & Ecology↗

DOE OSTI2024

Gigaton commercial-scale carbon storage and mineralization potential in stacked Columbia River basalt reservoirs

This work presents a detailed supercritical CO 2 storage resource estimation for the stacked basalt reservoirs in the Grande Ronde Basalt of the Columbia River Basalt Group in eastern Washington and Oregon. The assessment aims to derisk the commercialization potential of geologic carbon storage in basalt by leveraging both structural and mineralization trapping of CO 2 in basalt. The structural closures formed by anticlinal ridges and synclinal valleys in Yakima Fold Belt are excellent physical traps to accommodate injected supercritical CO 2 . Rigorous hydraulic testing, well logs and simulation results from the Wallula Basalt Pilot #1 well showed the occurrence of 17 suitable permeable injection zones (up to 2,496 mD) intercalated with dense seals (~2.6E-10 mD) in the Grand Ronde Basalt. In addition, geochemical studies showed fast reactions between supercritical CO 2 and dissolved basalt minerals to form stable carbonates. In conclusion, our calculation indicates up to 40 gigatons (P90) of mineralization storage resources exist in the Grande Ronde Basalt reservoirs.

58 GEOSCIENCES↗

DOE OSTI2021

Waterlevel, geochemical, and borehole data from Rifle, Colorado from 2006-2016

The files included in this data package provide site wide water level data, geochemical data, and borehole information associated with the Rifle site in Colorado during the Lawrence Berkeley National Lab (LBNL) led Integrated Field Research Challenge (IFRC) and Scientific Focus Area (SFA) research projects. The data informs hydrogeochemical interactions occurring in the watershed. The readme file contains detailed metadata for the files, including naming conventions, column headers, and data validation.The borehole information is provided in the file called rifle_boreholes.csv. It provides names and location for boreholes/wells at the Rifle. The waterlevel data is provided in the folder rifle_waterlevels. The geochemical data is provided in two folders: the rifle_floodplain_geochemistry folder has data which was collected from wells across the floodplain and a variety of offsite locations that contribute solutes to the floodplain given their upgradient locations. The rifle_plotC_geochemistry folder has data which was collected primarily in plot C, which was a focused study area in which a large number of groundwater manipulation / biostimulation experiments were conducted. While not all geochemical constituents are included for each well location and sampling date, they include anions, cations, trace metals, dissolved organic and inorganic carbon, stable isotopes of water and sulfur (as sulfate), and water quality parameters including pH, groundwater electrical conductivity (EC) and dissolved oxygen (DO). All files are in csv or txt format.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Contrasting growth responses of Qilian juniper ( Sabina przewalskii ) and Qinghai spruce ( Picea crassifolia ) to CO2 fertilization despite common water-use efficiency increases at the northeastern Qinghai–Tibetan plateau

Abstract Rising atmospheric carbon dioxide (CO2) may enhance tree growth and mitigate drought impacts through CO2 fertilization. However, multiple studies globally have found that rising CO2 has not translated into greater tree growth despite increases in intrinsic water-use efficiency (iWUE). The underlying mechanism discriminating between these two general responses to CO2 fertilization remains unclear. We used two species with contrasting stomatal regulation, the relatively anisohydric Qilian juniper (Sabina przewalskii) and the relatively isohydric Qinghai spruce (Picea crassifolia), to investigate the long-term tree growth and iWUE responses to climate change and elevated CO2 using tree ring widths and the associated cellulose stable carbon isotope ratios (δ13C). We observed a contrasting growth trend of juniper and spruce with juniper growth increasing while the spruce growth declined. The iWUE of both species increased significantly and with similar amplitude throughout the trees’ lifespan, though the relatively anisohydric juniper had higher iWUE than the relatively isohydric spruce throughout the period. Additionally, with rising CO2, the anisohydric juniper became less sensitive to drought, while the relatively isohydric spruce became more sensitive to drought. We hypothesized that rising CO2 benefits relatively anisohydric species more than relatively isohydric species due to greater opportunity to acquire carbon through photosynthesis despite warming and droughts. Our findings suggest the CO2 fertilization effect depends on the isohydric degree, which could be considered in future terrestrial ecosystem models.

Wang, Wenzhi↗

NASA NTRS2015

Indigenous Aliphatic Amines in the Aqueously Altered Orgueil Meteorite

The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. Ithas been extensively studied, and despite its extensive degree of aqueous alteration andsome documented instances of contamination, several indigenous organic compoundsincluding amino acids, carboxylic acids, and nucleobases have been detected in its carbon-rich matrix. We recently developed a novel gas chromatographic method for theenantiomeric and compound-specific isotopic analyses of meteoritic aliphatic monoamines inextracts and have now applied this method to investigate the monoamine content inOrgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to332 nmol g1of meteorite and compared this amine content in Orgueil with that of theCM2 Murchison meteorite, which experienced less parent-body aqueous alteration.Methylamine is four times more abundant in Orgueil than in Murchison. As with otherspecies, the amine content in Orgueil extracts shows less structural diversity than that inMurchison extracts. We measured the compound-specific stable carbon isotopic ratios(d13C) for 5 of the 12 monoamines detected in Orgueil and found a range ofd13C valuesfrom–20 to+59&. Thesed13C values fall into the range of other meteoritic organiccompounds, although they are13C-depleted relative to their counterparts extracted from theMurchison meteorite. In addition, we measured the enantiomeric composition for the chiralmonoamines (R)- and (S)-sec-butylamine in Orgueil, and found it was racemic withinexperimental error, in contrast with theL-enantiomeric excess found for its amino acidstructural analog isovaline. The racemic nature ofsec-butylamine in Orgueil wascomparable to that previously observed in Murchison, and to other CM2 and CR2carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2],LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us toplace some constraints on the effects of aqueous alteration observed over the monoamineconcentrations in Orgueil and Murchison, and to evaluate the primordial syntheticrelationships between meteoritic monoamines and amino acids.

Jose C Aponte↗

DOE OSTI2020

The Role of Synthetic Biology in Atmospheric Greenhouse Gas Reduction: Prospects and Challenges

The long atmospheric residence time of CO 2 creates an urgent need to add atmospheric carbon drawdown to CO 2 regulatory strategies. Synthetic and systems biology (SSB), which enables manipulation of cellular phenotypes, offers a powerful approach to amplifying and adding new possibilities to current land management practices aimed at reducing atmospheric carbon. The participants (in attendance: Christina Agapakis, George Annas, Adam Arkin, George Church, Robert Cook-Deegan, Charles DeLisi, Dan Drell, Sheldon Glashow, Steve Hamburg, Henry Jacoby, Henry Kelly, Mark Kon, Todd Kuiken, Mary Lidstrom, Mike MacCracken, June Medford, Jerry Melillo, Ron Milo, Pilar Ossorio, Ari Patrinos, Keith Paustian, Kristala Jones Prather, Kent Redford, David Resnik, John Reilly, Richard J. Roberts, Daniel Segre, Susan Solomon, Elizabeth Strychalski, Chris Voigt, Dominic Woolf, Stan Wullschleger, and Xiaohan Yang) identified a range of possibilities by which SSB might help reduce greenhouse gas concentrations and which might also contribute to environmental sustainability and adaptation. These include, among other possibilities, engineering plants to convert CO 2 produced by respiration into a stable carbonate, designing plants with an increased root-to-shoot ratio, and creating plants with the ability to self-fertilize. A number of serious ecological and societal challenges must, however, be confronted and resolved before any such application can be fully assessed, realized, and deployed.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2011

Distinct Purine Distribution in Carbonaceous Chondrites

Carbonaceous chondrite meteorites are known to contain a diverse suite of organic compounds, many of which are essential components of biochemistry. Amino acids, which are the monomers of proteins, have been extensively studied in such meteorites (e.g. Botta and Bada 2002; Pizzarello et aI., 2006). The origin of amino acids in meteorites has been firmly established as extraterrestrial based on their detection typically as racemic mixtures of amino acids, the presence of many non-protein amino acids, and non-terrestrial values for compound-specific deuterium, carbon, and nitrogen isotopic measurements. In contrast to amino acids, nucleobases in meteorites have been far less studied. Nucleobases are substituted one-ring (pyrimidine) or two-ring (purine) nitrogen heterocyclic compounds and serve as the information carriers of nucleic acids and in numerous coenzymes. All of the purines (adenine, guanine, hypoxanthine, and xanthine) and pyrimidines (uracil) previously reported in meteorites are biologically common and could be interpreted as the result of terrestrial contamination (e.g. van del' Velden and Schwartz, 1974.) Unlike other meteoritic organics, there have been no observations of stochastic molecular diversity of purines and pyrimidines in meteorites, which has been a criterion for establishing extraterrestrial origin. Maltins et al. (2008) performed compound-specific stable carbon isotope measurements for uracil and xanthine in the Murchison meteorite. They assigned a non-terrestrial origin for these nucleobases; however, the possibility that interfering indigenous molecules (e.g. carboxylic acids) contributed to the 13C-enriched isotope values for these nucleobases cannot be completely ruled out. Thus, the origin of these meteoritic nucleobases has never been established unequivocally. Here we report on our investigation of extracts of II different carbonaceous chondrites covering various petrographic types (Cl, CM, and CR) and degrees of aqueous alteration (l, 2, and 3) and one ureilite. Analysis via liquid chromatography coupled with electrospray triple-stage mass spectrometry or orbitrap mass spectrometry employed a targeted approach for analysis focused on the five canonical RNA/DNA nucleobases as well as 14 non-canonical pyrimidines and purines, which have bcen observed under plausible prebiotic reactions.

Callahan, Michael P.↗

DOE OSTI2020

Hollow fiber mid-ID spectrometer with UV laser ablation sampling for fine spatial reoslution of isotope ratios in solids

We describe a system that combines isotope ratio analysis via mid-infrared (Mid-IR) laser absorption spectroscopy with fine spatial resolution sampling using a UV pulsed laser. The UV laser ablates a pit in a solid on the order of 10 microns in diameter. The sample-derived particulates resulting from laser ablation pass through a micro-combustor, and the resulting gas is analyzed using Mid-IR laser absorption spectroscopy in a capillary absorption spectrometer (CAS). The CAS uses a hollow fiber optic waveguide with a reflective inner coating and a small internal volume on the order of 1ml. The hollow fiber both guides the laser light from source to detector and contains the gas sample at reduced pressure. Near unity overlap between the laser beam and sample enables sensitive analysis with ultra-small sample size. A prototype system has been demonstrated to enable stable carbon isotopic analysis (d13C) with 1 per mil precision using <1 picomole of carbon and is currently being used to study nutrient exchange in soil/root/microbial rhizosphere studies. The smaller sample size of this system is enabling fine spatial resolution analysis (on the order of 10 microns), which is roughly an order of magnitude smaller than was possible with an isotope ratio mass spectrometer (IRMS). In addition to rhizosphere studies, the system can provide a useful tool for fine scale isotope analysis with applications in biological, forensic, and environmental science.

capillary absorption spectroscopy, laser ablation,↗

DOE OSTI2024

Land cover and space use influence coyote carnivory: evidence from stable-isotope analysis

For many species, the relationship between space use and diet composition is complex, with individuals adopting varying space use strategies such as territoriality to facilitate resource acquisition. Coyotes ( Canis latrans ) exhibit two disparate types of space use; defending mutually exclusive territories (residents) or moving nomadically across landscapes (transients). Resident coyotes have increased access to familiar food resources, thus improved foraging opportunities to compensate for the energetic costs of defending territories. Conversely, transients do not defend territories and are able to redirect energetic costs of territorial defense towards extensive movements in search of mates and breeding opportunities. These differences in space use attributed to different behavioral strategies likely influence foraging and ultimately diet composition, but these relationships have not been well studied. We investigated diet composition of resident and transient coyotes in the southeastern United States by pairing individual space use patterns with analysis of stable carbon (δ 13 C) and nitrogen (δ 15 N) isotope values to assess diet. During 2016–2017, we monitored 41 coyotes (26 residents, 15 transients) with GPS radio-collars along the Savannah River area in the southeastern United States. We observed a canopy effect on δ 13 C values and little anthropogenic food in coyote diets, suggesting 13 C enrichment is likely more influenced by reduced canopy cover than consumption of human foods. We also observed other land cover effects, such as agricultural cover and road density, on δ 15 N values as well as reduced space used by coyotes, suggesting that cover types and localized, resident-like space use can influence the degree of carnivory in coyotes. Finally, diets and niche space did not differ between resident and transient coyotes despite differences observed in the proportional contribution of potential food sources to their diets. Although our stable isotope mixing models detected differences between the diets of resident and transient coyotes, both relied mostly on mammalian prey (52.8%, SD = 15.9 for residents, 42.0%, SD = 15.6 for transients). Resident coyotes consumed more game birds (21.3%, SD = 11.6 vs 13.7%, SD = 8.8) and less fruit (10.5%, SD = 6.9 vs 21.3%, SD = 10.7) and insects (7.2%, SD = 4.7 vs 14.3%, SD = 8.5) than did transients. Our findings indicate that coyote populations fall on a feeding continuum of omnivory to carnivory in which variability in feeding strategies is influenced by land cover characteristics and space use behaviors.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2012

The Role of (Delta)C-13 in the Search for Reduced Organics on the Surface of Mars

The capabilities of the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to detect trace amounts of organic carbon compounds are unprecedented, and MSL may be the first mission to reveal the presence of organic carbon on Mars. The search for reduced organic carbon on Mars is inextricably tied to: a) the preservation potential of the environment from which we take a solid sample, and b) the evolved gas analysis (EGA) techniques used by SAM to release volatiles from this solid sample. Several prospective targets have been identified for sample analysis at Gale Crater. Stratigraphic sequences of phyllosilicates and sulfates at Gale are thought to represent a period of global climate transition from a moderate pH lacustrine environment to an evaporitic environment, both of which could sequester organic carbon (Thomson et al. 2011). The sediment mound in Gale Crater contains a range of lithologies suggesting changes in redox conditions, and evidence of both lacustrine and fluvial depositional processes, which may have transported organic carbon from the layer in which it formed and resulted in its preservation elsewhere within the crater (Anderson and Bell, 2010). Inverted channel fills suggest erosion resistant material that could serve to preserve organics originally deposited in a low energy aqueous environment. The lithology sampled will affect not only the preservation of organics, but also our ability to detect organics during our evolved gas analysis, based on the sample matrix. For example, reduced organics may be trapped in the mineral structure, and thermal evolution of these organics will occur during thermal decomposition of the host mineral. If organics are occluded in minerals that have very high thermal decomposition temperatures, they may be, in effect, "too well preserved," and difficult to detect during EGA. Alternatively, the possible presence of perchlorate, or other strong oxidants in surface regolith, may result in destruction of structural information identifying organic molecules before reaching the QMS on SAM via oxidation to C02 during heating. If this is the case, the stable carbon isotopic composition (delta 13C) of the C02 evolved and measured by the Tunable Laser Spectrometer (TLS) on SAM may help identify the presence of organics. On Earth, biological activity can cause large fractionations of 13C/12C, which can preserved in sedimentary deposits and distinguish the organic products of biotic processes from inorganic atmospheric and geological reservoirs. It is plausible that similar fractionations could occur on Mars and be preserved in reduced organic matter in sediments. Bulk delta 13C measurements alone may not reveal a signature of trace organic carbon that may be present along with inorganic carbon. If both organic and inorganic carbon compounds are present, it may be possible to detect the organic carbon by comparing the 013C of pyrolysis and combustion experiments. The TLS on SAM is capable of obtaining high precision measurements of delta13C from C02 evolved during pyrolysis and combustion of solid regolith samples. Because carbonates are expected to be present at abundances of 0.1-1 % in Martian soil, and organics in the ppb range (Webster and Mahaffy, 2011), analog samples must represent this mix of reduced organic carbon and carbonate. The work presented here will examine the use of delta13C of C02 produced during combustion of bulk Mars analog samples as a proxy for detection of reduced organic carbon.

Stern, J. C.↗