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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Green hydrogen from microalgal liquefaction byproducts with ammonia recovery and effluent recycle for developing circular processes

Hydrothermal liquefaction is a promising technology for microalgae-based biofuel production. However, hydrothermal liquefaction’s aqueous wastes have little established reuse, and contain significant fractions of toxic ammoniacal nitrogen. Careful reuse of this waste can assure microalgae-based biofuels are produced with less environmental impact and larger energy efficiency. Microbial electrolysis cells were investigated to valorize this waste product by converting the leftover organics into hydrogen and remove ammonia. Waste hydrothermal liquefaction aqueous phase from two microalgal strains, Tetraselmis sp. and Chlorella sp. were used as feedstocks for hydrogen production in microbial electrolysis cells. Chlorella and Tetraselmis aqueous phase-fed microbial electrolysis cells reach an average current density of 5.1 ± 0.19 A/m 2 and 3.8 ± 0.08 A/m 2 . Compound removal rates and mass removal percentages were also investigated for each feedstock. Additionally, acetic acid, propionic acid, ethanol, and glycerol were effectively removed from the aqueous byproduct. Further, microbial electrolysis cells separated up to 34.3% of ammoniacal nitrogen present in the aqueous phase. Charge transfer analysis indicated that proton transfer, not ammonium transfer, contributed to the majority of the hydrogen production in the cathode. Finally, the microbial electrolysis cell effluent was reused to grow the same microalgal strains, leading to the development of a circular biofuel production system. Microalgae regrowth studies using microbial electrolysis cell effluent showed nearly complete removal of total organic carbon, but significantly less removal of total nitrogen. Tetraselmis sp. growth occurred with the Tetraselmis-derived MEC effluent, however, the control medium without effluent produced the most growth. These findings support the possibility of a circular biofuel framework using MECs, but additional constraints, including the removal of inorganic contaminants, are necessary to realize the circular processes.

09 BIOMASS FUELS↗
DOE OSTI2022

Sustainable Aviation Fuel from Hydrothermal Liquefaction of Wet Wastes

Hydrothermal liquefaction (HTL) uses heat and pressure to liquefy the organic matter in biomass/waste feedstocks to produce biocrude. When hydrotreated the biocrude is converted into transportation fuels including sustainable aviation fuel (SAF). Further, by liquifying the organic matter in wet wastes such as sewage sludge, manure, and food waste, HTL can prevent landfilling or other disposal methods such as anerobic digestion, or incineration. A significant roadblock to the development of a new route for SAF is the strict approval process, and the large volumes required (>400 L) for testing. Tier α and β testing can predict some of the properties required for ASTM testing with <400 mL samples. The current study is the first to investigate the potential for utilizing wet-waste HTL biocrude (WWHTLB) as an SAF feedstock. Herein, several WWHTLB samples were produced from food waste, sewage sludge, and fats, oils, and grease, and subsequently hydrotreated and distilled to produce SAF samples. The fuels (both undistilled and distilled samples) were analyzed via elemental and 2D-GC-MS. Herein, we report the Tier α and β analysis of an SAF sample derived originally from a WWHTLB. The results of this work indicate that the upgraded WWHTLB material exhibits key fuel properties, including carbon number distribution, distillation profile, surface tension, density, viscosity, heat of combustion, and flash point, which all fall within the required range for aviation fuel. WWHTLB has therefore been shown to be a promising candidate feedstock for the production of SAF.

09 BIOMASS FUELS↗
NASA NTRS1999

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Non-NASA Center↗
NASA NTRS2014

Alteration of Basaltic Glass to Mg/Fe-Smectite under Acidic Conditions: A Potential Smectite Formation Mechanism on Mars

Phyllosilicates of the smectite group including Mg- and Fe-saponite and Fe(III)-rich nontronite have been identified on Mars. Smectites are believed to be formed under neutral to alkaline conditions that prevailed on early Mars. This hypothesis is supported by the observation of smectite and carbonate deposits in Noachian terrain on Mars. However, smectite may have formed under mildly acidic conditions. Abundant smectite formations have been detected as layered deposits hundreds of meters thick in intracrater depositional fans and plains sediments, while no large deposits of carbonates are found. Development of mildly acidic conditions at early Mars might allow formation of smectite but inhibit widespread carbonate precipitation. Little is known regarding the mechanisms of smectite formation from basaltic glass under acidic conditions. The objective of this study was to test a hypothesis that Mars-analogue basaltic glass alters to smectite minerals under acidic conditions (pH 4). The effects of Mg and Fe concentrations and temperature on smectite formation from basaltic glass were evaluated. Phyllosilicate synthesis was performed in batch reactors (Parr acid digestion vessel) under reducing hydrothermal conditions at 200 C and 100 C. Synthetic basaltic glass with a composition similar to that of the Gusev crater rock Adirondack (Ground surface APXS measurement) was used in these experiments. Basaltic glass was prepared by melting and quenching procedures. X-ray diffraction (XRD) analysis indicated that the synthesized glass was composed of olivine, magnetite and X-ray amorphous phase. Samples were prepared by mixing 250 mg Adirondack with 0.1 M acetic acid (final pH 4). In order to study influence of Mg concentration on smectite formation, experiments were performed with addition of 0, 1 and 10 mM MgCl2. After 1, 7 and 14 day incubations the solution composition was analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the altered glass and formed phyllosilicates were examined by XRD analysis. Mineralogical changes were significant in Adirondack incubated with 10 mM MgCl2 at pH 4 and heated at 200 C. X-ray diffraction analysis revealed formation of phyllosilicate during 14 day incubation (Figure 1). Smectite was confirmed as the phyllosilicate after treatments with glycerol and KCl and heating to 550 C. The position of 02l (4.60 A) and 060 (1.54 A) diffraction bands were indicative of trioctahedral smectite such as saponite. Analysis of solution composition demonstrated that aqueous concentration of Mg decreased from 10 mM to approx.4 mM after 7 day incubation likely due to saponite formation. Smectite also formed in Adirondack incubated with 0 mM MgCl2 at pH 4 and heated at 200 C. However, diffraction peak positions of 02l (4.52 A) and 060 (1.51 A) suggested formation of dioctahedral nontronite. The 100degC Mg and Fe(II) treated basaltic glass experiments are ongoing and results will be presented.

Peretyazhko, Tanya↗
NASA NTRSDate not supplied

INCORPORATION OF NITROGEN INTO ORGANICS PRODUCED BY FISCHER-TROPSCH TYPE CHEMISTRY

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feedstock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydrocarbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N. Reaction mixtures contained CO (~60-80 mM), 150 mM ammonium chloride, and water with a native iron catalyst, which also served as a source of H2 through the reduction of water. Three initial experiments were conducted at 110, 154 and 185 °C and heated for several days. Following the reaction, samples were analyzed by gas chromatography-mass spectrometry, direct analysis in real time mass spectrometry and liquid chromatography-mass spectrometry.

A. S. Burton↗
DOE OSTI2023

Life-cycle analysis of sustainable aviation fuel production through catalytic hydrothermolysis

Catalytic hydrothermolysis (CH) is a sustainable aviation fuel (SAF) pathway that has been recently approved for use in aircraft fuel production. In alignment with broader sustainable aviation goals, SAF production through CH requires a quantitative assessment of carbon intensity (CI) impacts. In this study, a current-day life-cycle analysis (LCA) was performed on SAF produced via CH to determine the CI. Various oily feedstocks were considered, including vegetable oils (soybean, carinata, camelina and canola) and low-burden oils and greases (corn oil, yellow grease and brown grease). Life-cycle inventory data were collected on all processes within the CH LCA boundary: feedstock cultivation and/or collection, preprocessing, hydrothermal cleanup and CH, biocrude refining, fuel transportation and end use through combustion. Baseline results show that the CH-produced SAF can be generated with CI reductions ranging from 48 to 82% compared with conventional jet fuel. Modest improvements to CI can be achieved through incremental changes to the brown grease CH process, such as relaxing the dewatering specification and implementing renewable natural gas and electricity, which could decrease the CI from 22.9 to 7.9 g CO 2 e/MJ. Total CH fuel production potential was also assessed on the basis of current or near-future feedstock availability and CI. The total biofuel production potential of CH (SAF and renewable fuel co-products) in the US sums to approximately 3487 million gallons per year, with 97% of these volumes having a CI below 50% of that for petroleum jet fuel. The study shows that from an LCA perspective, CH offers a viable SAF pathway that is comparable with existing SAF pathways like hydroprocessed esters and fatty acids.

09 BIOMASS FUELS↗
DOE OSTI2026

Synergistic Interactions During Co-Hydrothermal Liquefaction of Food Waste and Biomass Model Compounds for Increased Sustainable Aviation Fuel Production

Hydrothermal liquefaction (HTL) of lignocellulosic biomass is plagued with low biocrude yields owing to the tendency of highly reactive oxygenated intermediates to condense to form biochars. By contrast, the high protein content in food waste is comprised of substantial nitrogen species, which are known to interact strongly with oxygenates through Maillard, amide, and peptide bond formation reactions. Co-feeding food waste and lignocellulose opens new reaction pathways for biocrude formation but is currently poorly understood. This work evaluated the molecular level interactions between food waste and lignocellulose model compounds and the corresponding effect on product yields and quality. Food waste–cellulose and food waste–xylan feedstock blends achieved maximum biocrude carbon yield improvements of 12.2% and 10.1%, respectively, relative to a simple linear model that interpolates between the yields of the pure feedstocks. Increases in biocrude yield were balanced by corresponding decreases in char yield, indicating synergistic interactions between the feeds during HTL. Biocrude volatility analysis revealed that increased biocrude yield preferentially benefitted the jet fuel fraction, which comprised up to 22.6% of the total carbon yield for food waste–cellulose blends. Biocrude and char were analyzed using GC–MS and FT-IR spectroscopy to investigate the source of synergistic trends and provide greater mechanistic understanding. Key cofeeding effects included the promotion of retro-aldol condensation reactions and trans-esterification of fatty acids, sequestering carbon in the biocrude phase via the inhibition of char formation while increasing biocrude volatility toward jet fuel-range compounds. These results indicate the potential for judicious selection of HTL cofeeds to increase both biocrude yield and selectivity to desired fuel precursors, including sustainable aviation fuel.

Maillard reaction↗
NASA NTRS1994

Carbonates in the Kaidun chondrite

Kaidun is a remarkable chondrite breccia fall containing lithic clasts that span a wide range of chondrite groups including C and E chondrites, as well as having clasts with characteristics not yet found in existing chondrite samples. The dominant lithology in Kaidun appears to be CR chondritic, consonant with recent O isotope data. The carbonates in Kaidun are presented as one mineralogical basis for comparing it to the other hydrated chondrites and to better understand its relative alteration history. The four polished thin sections of Kaidun studied contained a variety of lithologies that we classified into four groups -- CR, E, CM-like, and dark inclusions (DIs). DIs contain sulfide and magnetite morphologies that superficially resemble CI chondrites, and some of the previously reported CI lithologies in Kaidun may be what we term DIs. Carbonates were found in all lithologies studied. Carbonates in Kaidun are similar in composition to those in CR chondrites. Some of the DIs in Kaidun, previously characterized as CI, have carbonates similar to those in CR chondrites and are unlike those in CI or CM chondrites. Most carbonates in Kaidun and CR chondrites are calcites, some of which formed at temperatures above 250 C. Dolomite is less common and some may be metastable. Alteration temperatures in the Renazzo CR chondrite were estimated to be approximately 300 C, based on O isotope fractionation between phyllosilicates and magnetite. Temperatures of up to 450 C were proposed for the alteration of a CR-like dark inclusion in Kaidun, based on the presence of hydrothermal pentlandite veins. The alteration temperatures for Kaidun and the other CR chondrites are considerably higher than those suggested for CI or CM parent bodies.

Weisberg, M. K.↗
NASA NTRS2020

Incorporation of Nitrogen into Organics Produced by Fischer-Tropsch Type Chemistry

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feed-stock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydro-carbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases; and a separate suite of studies included sulfur as sulfide minerals or H2S, which yielded products such as thiols and amino acids. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. As a consequence, it is difficult to extrapolate these results to geologic systems or to evaluate how variations in reactant compositions would affect the distribution of products over time. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N.

Burton, A. S.↗
NASA NTRS1996

Surveying Dead Trees and CO2-Induced Stressed Trees Using AVIRIS in the Long Valley Caldera

Since 1980 the Long Valley Caldera in the eastern Sierra Nevada (California) has shown signs of renewed volcanic activity. Frequent earthquakes, a re-inflation of the caldera, hydrothermal activity and gas emissions are the outer symptoms of this renewed activity. In 1990 and 1991 several areas of dying trees were found around Mammoth Mountain. The cause of the die off of the trees was first sought in the persistent drought in the preceding years. However, the trees died regardless of age and species. Farrar et al. (1995) started a soil-gas survey in 1994 in the dead-tree areas and found carbon dioxide concentrations ranging from 30 to 96% at soil depths between 30 and 60 cm. CO2 concentrations in the atmosphere are usually around 0.03% and in the soil profile CO2 levels do commonly not exceed 4 to 5%. Although not much is known about the effect of high levels of carbon dioxide in the soil profile on roots, it is most likely that the trees are dying due to oxygen deprivation: the CO2 drives the oxygen out of the soil. So far, four sites of dead trees have been mapped around Mammoth Mountain. The two largest dying trees sites are located near Horseshoe Lake and near Mammoth Mountain Main Lodge covering approximately an area of 10 and 8 ha respectively. Analysis of the gas composition regarding the He-3/He-4 ratio and the percentage biogenic carbon reveals the source of the gas: the magma body beneath the Long Valley Caldera. Until recently it was not known that volcanoes release abundant carbon dioxide from their flanks as diffuse soil emanations. As a result of the magma gas emission around Mammoth Mountain there is an excellent sequence of dead trees, stressed trees, healthy trees and bare soil surfaces. This research site provides excellent opportunities to: (1) Study the capabilities of imaging spectrometry to map stressed (and dead) pine and fir species; (2) Study methods to separate the vivid vegetation, stressed vegetation and dead vegetation from the soil background of glacial deposits and crystalline rocks. The dead tree areas are located on the flanks of Mammoth Mountain (N:37 deg 37' 45" and W:119 deg 02' 05") at an elevation between 2600 and 3000 meters. The area is covered by an open type of Montane Forest. The dominant tree species are Lodgepole Pine (Pinus contorta), the Red Fir (Abies magnifica) and the Jeffrey Pine (Pinus jeffreyi). The soil surface near Horseshoe Lake is generally fairly bright. The surface is covered by glacial deposits (till) consisting mainly of weathered granitic rocks.

deJong, Steven M.↗
NASA NTRS1997

Early Evolution of Earth's Geochemical Cycle and Biosphere: Implications for Mars Exobiology

Carbon (C) has played multiple key roles for life and its environment. C has formed organics, greenhouse gases, aquatic pH buffers, redox buffers, and magmatic constituents affecting plutonism and volcanism. These roles interacted across a network of reservoirs and processes known as the biogeochemical C cycle. Changes in the cycle over geologic time were driven by increasing solar luminosity, declining planetary heat flow, and continental and biological evolution. The early Archean C cycle was dominated by hydrothermal alteration of crustal rocks and by thermal emanations of CO2 and reduced species (eg., H2, Fe(2+) and sulfides). Bioorganic synthesis was achieved by nonphotosynthetic CO2-fixing bacteria (chemoautotrophs) and, possibly, bacteria (organotrophs) utilizing any available nonbiological organic C. Responding both to abundant solar energy and to a longterm decline in thermal sources of chemical energy and reducing power, the blaspheme first developed anoxygenic photosynthesis, then, ultimately, oxygenic photosynthesis. O2-photosynthesis played a central role in transforming the ancient environment and blaspheme to the modem world. The geochemical C cycles of early Earth and Mars were quite similar. The principal differences between the modem C cycles of these planets arose during the later evolution of their heat flows, crusts, atmospheres and, perhaps, their blasphemes.

DesMarais, David J.↗
NASA NTRS1999

Post-Viking microbiology: new approaches, new data, new insights

In the 20 years since the Viking experiments, major advances have been made in the areas of microbial systematics, microbial metabolism, microbial survival capacity, and the definition of environments on earth, suggesting that life is more versatile and tenacious than was previously appreciated. Almost all niches on earth which have available energy, and which are compatible with the chemistry of carbon-carbon bonds, are known to be inhabited by bacteria. The oldest known bacteria on earth apparently evolved soon after the formation of the planet, and are heat loving, hydrogen and/or sulfur metabolizing forms. Among the two microbial domains (kingdoms) is a great deal of metabolic diversity, with members of these forms being able to grow on almost any known energy source, organic or inorganic, and to utilize an impressive array of electron acceptors for anaerobic respiration. Both hydrothermal environments and the deep subsurface environments have been shown to support large populations of bacteria, growing on energy supplied by geothermal energy, thus isolating these ecosystems from the rest of the global biogeochemical cycles. This knowledge, coupled with new insights into the history of the solar system, allow one to speculate on possible evolution and survival of life forms on Mars.

Review↗
DOE OSTI2026

PERFORMANCE ANALYSIS OF AN ENGINEERING SCALE HYDROTHERMAL LIQUEFACTION SYSTEM

This work evaluates the Modular Hydrothermal Liquefaction System (MHTLS), an engineering-scale, integrated continuous HTL plant operated at the Pacific Northwest National Laboratory (PNNL), for converting realistic wet wastes into energy-dense biocrudes. The production campaigns discussed here processed algae, sewage sludges, lignocellulosic blends, Industrial food waste, and engineered food-waste slurries at 350?°C and around 200?bar, with nominal feed rates of ~12?L?h?¹. We report biocrude yields and composition, establish mass and elemental (C, N) balances, and quantify energy performance via heater duties, heat-exchanger behavior, and system-level efficiencies. Biocrudes contained 76–80?wt?% C (dry, ash-free) with HHVs of 38-41?MJ?kg?¹, substantially higher than feed materials HHVs of 16.6–26.1?MJ?kg?¹ and approaching petroleum fuels. Dry, ash-free biocrude yields of 32–53?wt?% corresponded to 43–71?wt?% carbon yields, with 18–40?wt?% of feed carbon routed to the aqueous phase. Thermal efficiencies were 50-65%, and total energy efficiencies, including reactor heat input, were 35-55%. A counter-current tube-in-tube heat exchanger delivered U values of 200–450?W?m?²?K?¹, with fouling-induced declines impacting heat recovery and heater duty. The analysis highlights three priorities for the process intensification of HTL: robust, fouling-resistant heat recovery, hydrodynamically suitable reactor and heat-exchanger designs, simplified and predictable solids management, and biocrude-water separation.

Biocrude production↗
DOE OSTI2020

Hydrothermal liquefaction of Cyanidioschyzon merolae and Salicornia bigelovii Torr.: The interaction effect on product distribution and chemistry

Hydrothermal liquefaction (HTL) has proven to be a promising technology for processing wet biomass into valuable biofuel intermediates. We investigated the influence of HTL process parameters on the individual and co-liquefaction of Salicornia bigelovii Torr. (SL) and Cyanidioschyzon merolae (CM) biomass and their respective product properties and characteristics. SL and CM biomasses were subjected to HTL conditions of process temperatures (250–350 °C), 10 wt% solid loading, 30 min reaction time, and co-liquefaction ratios (80–20, 50–50, 20–80, CM-SL, respectively). The individual maximum HTL biocrude yields for CM (34.63 wt%) and SL (7.63 wt%) were obtained at 300 °C. In both cases, biocrude oils had a higher carbon and hydrogen content relative to those of the original biomass. The HHV (higher heating value) values for the biocrude samples ranged from 24.2 to 33.12 MJ/kg, which were significantly higher than those of the original biomasses. A positive synergistic effect was observed during the co-liquefaction of two biomasses, where the experimental yield of biocrude oil was higher than the theoretical value. During the co-liquefaction experiments, a maximum biocrude yield of 32.95 wt% was obtained at 300 °C and 80–20 CM-SL biomass mix ratio. Co-liquefaction led to an increase in the energy content of the co-liquefied biocrude oil and a higher energy recovery rate. Finally, the properties of HTL products and biomasses were determined with TGA, CHN elemental analyzer, GC/MS, bomb calorimeter, HACH Spectrophotometer, and ICP OES.

09 BIOMASS FUELS↗
NASA NTRS2000

Geology and geochemistry of paleosols developed on the Hekpoort Basalt, Pretoria Group, South Africa

The Hekpoort paleosols comprise a regional paleoweathering horizon developed on 2.224 +/- 0.021 Ga basaltic andesite lavas at the top of the Hekpoort Formation of the Pretoria Group, Transvaal Supergroup, South Africa. In five separate profiles, from outcrops along road cuts near Waterval Onder and the Daspoort Tunnel and in three drill cores from the Bank Break Area (BB3, BB8, and BB14), the top of the paleosol is a sericite-rich zone. The sericite zone grades downward into a chlorite-rich zone. In core BB8 and in the road cut at the Daspoort Tunnel, we sampled the underlying or parent basaltic andesite into which the chlorite zone grades. We did not obtain samples of the parent material at Waterval Onder and in cores BB3 and BB14, but chemical analyses indicate that the chlorite and sericite zones in these profiles derive from underlying lavas similar to the ones we sampled in core BB8 and at the Daspoort Tunnel. The presence of apparent rip-up clasts of the paleosol in the overlying ironstones of the Strubenkop Formation in the cores from Bank Break makes it very unlikely that most of the alteration was a result of interactions with hydrothermal fluids. Desiccation cracks at the top of the paleosol that were filled with sand during the deposition of the overlying sediments at Waterval Onder point to a subaerial weathering origin. Very little, if any, Al, Ti, Zr, V, or Cr moved a discernible distance during weathering of any of the five profiles. The vertical distribution of Fe, Mg, Mn, Ni, and Co indicates that these elements were largely removed from the top of the soil during weathering. The overall abundance of these elements in each of the profiles indicates that a significant fraction of the complement lost from the top subsequently reprecipitated in the lower portion of the soil as constituents of an Fe2(+) -rich smectite. The loss of Fe from the top of the soil during weathering of the Hekpoort paleosols indicates that atmospheric PO2 was less than 8 x 10(-4) atm about 2.22 Ga. Fe2(+) -rich smectite should only precipitate during soil formation if atmospheric PCO2 is less than or equal to 2 x 10(-2) atm (Rye, Kuo, and Holland, 1995). Ca and Na were largely lost during weathering. Some Na was apparently added to the sericite zone in cores BB3, BB8, and BB14 after weathering. All five profiles are enriched in K and Rb, and most are enriched in Ba. The distribution of these elements indicates that they all were added during post-weathering hydrothermal metasomatism. Rb-Sr analysis of the paleosol at the Daspoort Tunnel indicates that metasomatism last affected that profile 1.925 +/- 0.032 Ga (Macfarlane and Holland, 1991).

Non-NASA Center↗
NASA NTRS2023

Surface Volatile Composition as Evidence for Hydrothermal Processes Lasting Longer in Triton’s Interior than Pluto’s

Ocean worlds, or icy bodies in the outer solar system that have or once had subsurface liquid water oceans, are among the most compelling topics of astrobiology. Typically, confirming the existence of a subsurface ocean requires close spacecraft observations. However, combining our understanding of the chemistry that takes place in a subsurface ocean with our knowledge of the building blocks that formed potential ocean worlds provides an opportunity to identify tracers of endogenic activity in the surface volatiles of Pluto and Triton. We show here that the current composition of the volatiles on the surfaces and in the atmospheres of Pluto and Triton are deficient in carbon, which can only be explained by the loss of CH4 through a combination of aqueous chemistry and atmospheric processes. Furthermore, we find that the relative nitrogen and water abundances are within the range observed in building block analogs, comets, and chondrites. A lower limit for N/Ar in Pluto's atmosphere also suggests source building blocks that have a cometary or chondritic composition, all pointing to an origin for their nitrogen as NH3 or organics. Triton's lower abundance of CH4 compared to Pluto, and the detection of CO2 at Triton but not at Pluto points to aqueous chemistry in a subsurface ocean that was more efficient at Triton than Pluto. These results have applications to other large Kuiper Belt objects as well as the assessment of formation locations and times for the four giant planets given future probe measurements of noble gas abundances and isotope ratios.

Solar system formation↗
NASA NTRS1998

Earth's early biosphere

Understanding our own early biosphere is essential to our search for life elsewhere, because life arose on Earth very early and rocky planets shared similar early histories. The biosphere arose before 3.8 Ga ago, was exclusively unicellular and was dominated by hyperthermophiles that utilized chemical sources of energy and employed a range of metabolic pathways for CO2 assimilation. Photosynthesis also arose very early. Oxygenic photosynthesis arose later but still prior to 2.7 Ga. The transition toward the modern global environment was paced by a decline in volcanic and hydrothermal activity. These developments allowed atmospheric O2 levels to increase. The O2 increase created new niches for aerobic life, most notably the more advanced Eukarya that eventually spawned the megascopic fauna and flora of our modern biosphere.

Review↗