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Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗
DOE OSTI2023

A Coacervate-Based Mixed-Conducting Binder for High-Power, High-Energy Batteries

Polymer binders add crucial structural integrity to lithium ion battery composite cathodes, but industry standard binders, such as polyvinylidene fluoride (PVDF), are insulating to ions and electrons, detrimentally adding resistance to the overall system. In this work, we use electrostatics to stabilize a blend of a charged conjugated polymer with an oppositely charged polyelectrolyte, providing a processable, stable binder with high ionic and electronic conduction. Using LiFePO4 cathodes as a model system, we show significant improvement in rate capability and stability, with the conducting binder enabling a 39% utilization at 6C compared to 1.6% when PVDF is the binder. Additionally, the conducting binder affords a 63% capacity retention over 400 C/2 cycles, compared to only a 6% retention over 400 cycles when PVDF is the binder. These results show that electrostatically stabilized complexation is a promising strategy to integrate both electronic and ionic conductivity into a binder, while simultaneously maintaining stability and processability.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Batch Extraction Studies to Evaluate Trace Element Behavior in PUREX Conditions

The multilab Intentional Forensics Venture is working to identify which stable elements (i.e., taggants) at trace concentrations relative to U would persist throughout the nuclear fuel cycle in a voluntary fuel tagging scheme. A taggant would provide the nuclear forensics community with a “barcode” to help identify nuclear materials found outside of regulatory control. A portion of this project was focused on reprocessing effects and determining which, if any, elements would coextract with U(VI) in standard Pu–U reduction extraction (PUREX) conditions. Elements with a propensity to coextract could, in theory, be used as taggants from a PUREX perspective. Although retention is not a performance requirement, the taggant signature would need to partition predictably from the U stream after the PUREX process to maintain forensic utility. This report documents results from several batch extraction studies with numerous trace elements from HNO 3 (1.5–5 M), with and without U(VI), into 30% tri-n-butyl phosphate (TBP) in kerosene. Extraction and back-extraction tests were used to evaluate nearly 60 elements in surrogate conditions for PUREX, and distribution coefficients (i.e., D-values) for most species were <0.1, indicating few species are likely to co-extract with U through PUREX. Additional studies are needed to optimize sample volumes and dilutions to dial in these low D-values. The D-values (D) were determined for several of the more promising elements, including Re and Se. Ultimately, we conclude that only a limited number of the ~ 60 elements investigated are extractable in the U stream of PUREX, based on measured D values, meaning most candidate elemental taggants would likely be lost at this stage of the nuclear fuel cycle, even when considering a range of acid concentrations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Nanostructured ZnO-Based Electrochemical Sensor with Anionic Surfactant for the Electroanalysis of Trimethoprim

In this research, detection of trimethoprim (TMP) was carried out using a nanostructured zinc oxide nanoparticle-modified carbon paste electrode (ZnO/CPE) with an anionic surfactant and sodium dodecyl sulphate (SDS) with the help of voltametric techniques. The electrochemical nature of TMP was studied in 0.2 M pH 3.0 phosphate-buffer solution (PBS). The developed electrode displayed the highest peak current compared to nascent CPE. Effects of variation in different parameters, such as pH, immersion time, scan rate, and concentration, were investigated. The electrode process of TMP was irreversible and diffusion controlled with two electrons transferred. The effective concentration range (8.0 × 10 -7 M–1.0 × 10 -5 M) of TMP was obtained by varying the concentration with a lower limit of detection obtained to be 2.58 × 10 -8 M. In addition, this approach was effectively employed in the detection of TMP in pharmaceutical dosages and samples of urine with the excellent recovery data, suggesting the potency of the developed electrode in clinical and pharmaceutical sample analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Whole-Ecosystem Warming Increases Plant-Available Nitrogen and Phosphorus in an Ombrotrophic Bog

Warming is expected to increase the net release of carbon from peatland soils, contributing to future warming. This positive feedback may be moderated by the response of peatland vegetation to rising atmospheric [CO 2 ] or to increased soil nutrient availability. We asked whether a gradient of whole-ecosystem warming (from + 0 °C to + 9 °C) would increase plant-available nitrogen and phosphorus in an ombrotrophic bog in northern Minnesota, USA, and whether elevated [CO 2 ] would modify the nutrient response. We tracked changes in plant-available nutrients across space and through time and in comparison with other nutrient pools, and assessed whether nutrient warming responses were captured by a point version of the land-surface model, ELM-SPRUCE. We found that warming exponentially increased plant-available ammonium and phosphate, but that nutrient dynamics were unaffected by elevated [CO 2 ]. The warming response increased by an order of magnitude between the first and fourth year of the experimental manipulation, perhaps because of dramatic mortality of Sphagnum mosses in the surface peat of the warmest treatments. However, neither the magnitude nor the temporal dynamics of the responses were captured by ELM-SPRUCE. Here, relative increases in plant-available ammonium and phosphate with warming were similar, but the response varied across raised hummocks and depressed hollows and with peat depth. Plant-available nutrient dynamics were only loosely correlated with inorganic and organic porewater nutrients, likely representing different processes. Future predictions of peatland nutrient availability under climate change scenarios must account for dynamic changes in nutrient acquisition by plants and microbes, as well as microtopography and peat depth.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

A Rapid Microfluidic Neptunium Extraction Using a Supported Liquid Membrane Module

Extraction of neptunium from acidic matrices is important for its quantification, but its complex redox chemistry can cause variable yields. This study develops a microfluidic redox extraction for rapidly separating neptunium from submilliliter samples, achieving up to 90% process yield in less than 10 min for samples as small as 100 μL, with over 97% steady-state yield achieved after 20 min. It uses a supported liquid membrane module loaded with 30 vol % tributyl phosphate in n-dodecane, which performs forward- and back-extractions in a single, continuous step. Neptunium is first oxidized to +6 for extraction and then reduced during stripping. Bromate was selected as an oxidant over permanganate for its greater compatibility with the organic phase, achieving complete oxidation in under 30 s. Ascorbic acid and hydrogen peroxide were both effective reductants. Finally, the system’s high yield and rapid kinetics make it promising for future separations from complex mixtures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Novel Microbial Routes to Synthesize Industrially Significant Precursor Compounds

Ethylene is the most widely employed organic precursor compound in industry. The potential to impact ethylene formation via recently discovered microbial processes is tenable using plentiful CO2 feedstocks. The overall long-term objective of this project was to develop an industrially compatible microbial process to synthesize ethylene in high yields. The key objective of this project was to fully define and initially characterized a recently discovered and genetically regulated anaerobic pathway to produce high levels of ethylene called the Dihydroxyacetone Phosphate - Ethylene Pathway in phototrophic bacteria. This was addressed through the following specific aims: 1. Fully probe the catalytic potential of all enzymes of the DHAP ethylene pathway and determine the regulatory mechanism of DHAP-ethylene pathway gene expression. 2. Discover effective and active ethylene enzymes encoded in cultured and uncultured organisms from anoxic environments. 3.Model the thermodynamics and kinetics of ethylene synthetic pathways to guide engineering efforts in integrating best performing DHAP-ethylene pathway enzymes into model bacteria chassis for enhance ethylene yields. Through this project we discovered the initially missing genetic and enzyme component of the DHAP-ethylene pathway that directly synthesized ethylene and other important industrial compounds like methane and ethane from specific substrates. We uncovered and partially characterized a nitrogenase-like reductase that functions in DHAP-ethylene pathway specifically and in methionine synthesis in general. This nitrogenase-like system is called the Methylthio-Alkane Reductase (MAR) for its ability to cleave volatile organic sulfur compounds into methanethiol (CH3-SH) for methionine synthesis and a hydrocarbon byproduct. Key to the DHAP-ethylene pathway, MAR is the essential enzyme that cleaves 2-methylthioethanol (CH3-S-CH2-CH2-OH) into ethylene. Coordinately, we uncovered that the MAR genes and genes associated with conversion of methanethiol (CH3-SH) to methionine are under genetic control of a LysR Type Transcriptional Regulator called SalR, whose activity is dependent upon the amount of sulfate available to the cell. When sulfate as the preferred sulfur source for cell growth drops below 200 micromolar, SalR become active for expressing the MAR and methionine biosynthesis genes to enable the cell to grow from volatile organic sulfur compounds and make ethylene. Metabolic thermos-kinetic modeling revealed that these MAR reactions for ethylene and other hydrocarbon production are highly thermodynamically favorable and are one of the largest driving forces for ethylene production by the DHAP-ethylene pathway for high ethylene yields. Modeling also indicated that a key aldolase and to a lesser extent an isomerase of the DHAP-ethylene pathway for production of the ethylene precursor, 2-methylthioethanol, also would increase ethylene yields. Through metagenomic mining and gene synthesis by the JGI DNA synthesis program, over 500 aldolase and isomerase homologs were synthesized and screened. From this, variants were uncovered with substantially higher activity that increased ethylene yields 5-fold via the aldolase reaction and 1.5-fold via the isomerase reaction. Each of these elements that increase ethylene production were integrated together via plasmid under appropriate gene promoter elements in the phototrophic bacterium, Rhodospirillum rubrum, resulting in at least 3 orders of magnitude increase in ethylene yield from carbon dioxide feedstock.

10 SYNTHETIC FUELS↗
DOE OSTI2021

Phospholipase D and phosphatidylinositol-4-phosphate 5-kinase 1 are involved in the regulation of oligodendrocyte morphological differentiation

Highlights: • PLD and PIP5K1 are involved in the regulation of oligodendroglial cell morphological differentiation. • Inhibition of PLD or PIP5K1 decreases differentiation or myelin marker expression. • PLD and PIP5K1 regulate differentiation of oligodendrocyte precursor cells. • Inhibition of PLD or PIP5K1 decreases differentiation marker expression of oligodendrocyte precursor cells. Oligodendroglial cells (oligodendrocytes) differentiate to form the myelin that wraps neuronal axons in the central nervous system (CNS). This myelin sheath supports the propagation of saltatory conduction and protects axons from physical stresses. When oligodendrocytes do not normally differentiate to myelinate axons, their key functions as oligodendrocytes in the CNS are severely impaired. The molecular mechanics that control differentiation still remain to be clarified. Arf6 belongs to the small GTPase family and is known to be a positive regulator of oligodendrocyte differentiation. Here, we show that the phospholipase D (PLD) and phosphatidylinositol-4-phosphate 5-kinase 1 (PIP5K1) molecules, the major effectors of Arf6, are involved in the regulation of oligodendrocyte differentiation. Knockdown of PLD1 or PIP5K type 1γ (PIP5K1C) by their respective specific siRNAs in mouse oligodendroglial FBD-102b cells inhibited morphological differentiation into structures bearing myelin-like processes; this finding is consistent with the concurrent changes in expression of differentiation and myelin marker proteins. Treatment with VU0155069 or UNC3230, specific inhibitors of PLD and PIP5K1, respectively, blunted morphological differentiation and decreased expression of myelin and differentiation marker proteins. Similar results have been obtained in studies using primary oligodendrocytes. These results suggest that the major Arf6 effector molecules PLD and PIP5K1 are among the molecules involved in the regulation of morphological differentiation in oligodendrocytes prior to myelination.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

CMPO-Functionalized Silica Sorbents for pH-Tunable Separation and Enrichment of Rare-Earth Elements from Environmental Matrices

Rare-earth elements (REEs) are crucial in many applications, yet mutual separation is challenging due to their similar chemical behavior. Octylphenyl- N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) is an organophosphorus ligand originally developed for extracting actinides and lanthanides from spent nuclear fuel. Here, we report a pH-tunable CMPOfunctionalized silica sorbent for selective REE separation from complex aqueous matrices. A CMPO-associated silica gel sorbent was synthesized and characterized by Brunauer−Emmett−Teller (BET) surface area, scanning electron microscopy, and X-ray photoelectron spectroscopy to confirm the surface functionalization and binding behavior. Sorbent performance was evaluated by using a synthetic 46- element solution and a real phosphate rock fertilizer leachate. Notably, REEs were successfully eluted with ultrapure water, demonstrating reversible desorption controlled by pH adjustment. Packed-bed column studies increased the REE mass fraction from 3.6% to 64% (20-fold enrichment), with up to 30-fold enrichment of neodymium. The adsorption process follows the Langmuir isotherm behavior and follows pseudo-second-order kinetics. The uptake capacity of 1 μmol of REEs per 4.2 μmol of CMPO supports the formation of a predominantly 4:1 ligand:rare earth element(III) pseudocomplex. These results demonstrate CMPO-functionalized silica as a selective, water-elutable, and low-chemical-input platform for sustainable REE recovery from environmental and industrial sources.

chelating ligands↗
DOE OSTI2024

Kinetics and Mechanism of Ce(IV) Phase Transfer by the Neutral Extractants Tributyl Phosphate and N,N -Di(2-ethylhexyl)isobutyramide

Tributyl phosphate and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA) are uranium-selective extractants that could be used to recover low-enriched uranium from commercial used nuclear fuel. The economic viability of liquid-liquid extraction processes for chemical separations depends on both thermodynamic and kinetic considerations. Here we used microfluidic droplet extraction to measure interfacial phase transfer rate constants for the extraction and stripping of Ce(IV), a non-radioactive actinide surrogate. The Damkohler numbers for each system were calculated and the phase transfer processes were determined to be diffusion-limited under all conditions, contrary to prior studies using constant interface stirred cells and single drop methods. A well-extracted 2:1 DEHiBA/Ce(IV) complex in the organic phase was determined from batch distribution studies, suggesting a different extraction mechanism for Ce(IV) compared with poorly extracted Pu(IV). Finally, phase disengagement rates were found to be rapid in both systems, in agreement with other studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

The mevalonate pathway of isoprenoid biosynthesis supports metabolic flexibility in Mycobacterium marinum

ABSTRACT Isoprenoids are a diverse class of natural products that are essential in all domains of life. Most bacteria synthesize isoprenoids through either the methylerythritol phosphate (MEP) pathway or the mevalonate (MEV) pathway, while a small subset encodes both pathways, including the pathogen Mycobacterium marinum (Mm). It is unclear whether the MEV pathway is functional in Mm, or why Mm encodes seemingly redundant metabolic pathways. Here, we show that the MEP pathway is essential in Mm, while the MEV pathway is dispensable in culture, with the ΔMEV mutant having no growth defect in axenic culture but a competitive growth defect compared to WT Mm. We found that the MEV pathway does not play a role in ex vivo or in vivo acute infection but does play a role in survival of peroxide stress. Metabolite profiling revealed that modulation of the MEV pathway causes compensatory changes in the concentration of MEP intermediates DOXP and CDP-ME, suggesting that the MEV pathway is functional and that the pathways interact at the metabolic level. Finally, the MEV pathway is upregulated early in the shift down to hypoxia, suggesting that it may provide metabolic flexibility to this bacterium. Interestingly, we found that our complemented strains, which vary in copy number of the polyprenyl synthetase idsB2 , responded differently to peroxide and UV stresses, suggesting a role for this gene as a determinant of downstream prenyl phosphate metabolism. Together, these findings suggest that MEV may serve as an anaplerotic pathway to make isoprenoids under stress conditions. IMPORTANCE Organisms from all domains of life utilize isoprenoids to carry out thousands of critical and auxiliary cellular processes, including signaling, maintaining membrane integrity, stress response, and host-pathogen interactions. The common precursor of all isoprenoids is synthesized via one of two biosynthetic pathways. Importantly, some bacteria encode both pathways, including M. marinum . We found that only one pathway is essential in M. marinum , while the nonessential pathway may confer metabolic flexibility to help the bacterium better adapt to various environmental conditions. We also found that the polyprenyl synthetase IdsB2 plays an important role in driving such phenotypes. Further, we demonstrate metabolic interplay between both functional pathways. These insights represent the first characterization of isoprenoid biosynthesis in dual pathway-encoding mycobacteria.

Qabar, Christine M. [Department of Plant and Micro↗
DOE OSTI2022

Regulation of Translation by Lysine Acetylation in Escherichia coli

Numerous cellular processes are regulated in response to the metabolic state of the cell. One such regulatory mechanism involves lysine acetylation, a covalent modification involving the transfer of an acetyl group from central metabolite acetyl-coenzyme A or acetyl phosphate to a lysine residue in a protein.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Impact of longitudinal phase-matching variations on three-wave nonlinear interactions

A general study of three-wave nonlinear mixing in the presence of longitudinal variations in phase-matching conditions is presented. The efficiency of second-harmonic generation and optical parametric amplification is quantified using a normalized set of equations and a polynomial description of the wave-vector mismatch as a function of the longitudinal coordinate. These modeling results are used to estimate the impact of spatial variations in wave-vector mismatch experimentally obtained for five partially deuterated potassium dihydrogen phosphate crystals. The longitudinal inhomogeneities in the properties of crystals of similar quality are not expected to have a significant impact on their use for second-harmonic generation and optical parametric amplification, but the efficiency of nonlinear processes in crystals with larger variations could decrease.

36 MATERIALS SCIENCE↗
NASA NTRS1999

A Quantitative Study of Oxygen as a Metabolic Regulator

An acute reduction in oxygen (O2) delivery to a tissue is generally associated with a decrease in phosphocreatine, increases in ADP, NADH/NAD, and inorganic phosphate, increased rates of glycolysis and lactate production, and reduced rates of pyruvate and fatty acid oxidation. However, given the complexity of the human bioenergetic system and its components, it is difficult to determine quantitatively how cellular metabolic processes interact to maintain ATP homeostasis during stress (e.g., hypoxia, ischemia, and exercise). Of special interest is the determination of mechanisms relating tissue oxygenation to observed metabolic responses at the tissue, organ, and whole body levels and the quantification of how changes in tissue O2 availability affect the pathways of ATP synthesis and the metabolites that control these pathways. In this study, we extend a previously developed mathematical model of human bioenergetics to provide a physicochemical framework that permits quantitative understanding of O2 as a metabolic regulator. Specifically, the enhancement permits studying the effects of variations in tissue oxygenation and in parameters controlling the rate of cellular respiration on glycolysis, lactate production, and pyruvate oxidation. The whole body is described as a bioenergetic system consisting of metabolically distinct tissue/organ subsystems that exchange materials with the blood. In order to study the dynamic response of each subsystem to stimuli, we solve the ordinary differential equations describing the temporal evolution of metabolite levels, given the initial concentrations. The solver used in the present study is the packaged code LSODE, as implemented in the NASA Lewis kinetics and sensitivity analysis code, LSENS. A major advantage of LSENS is the efficient procedures supporting systematic sensitivity analysis, which provides the basic methods for studying parameter sensitivities (i.e., changes in model behavior due to parameter variation). Sensitivity analysis establishes relationships between model predictions and problem parameters (i.e., initial concentrations, rate coefficients, etc). It helps determine the effects of uncertainties or changes in these input parameters on the predictions, which ultimately are compared with experimental observations in order to validate the model. Sensitivity analysis can identify parameters that must be determined accurately because of their large effect on the model predictions and parameters that need not be known with great precision because they have little or no effect on the solution. This capability may prove to be important in optimizing the design of experiments, thereby reducing the use of animals. This approach can be applied to study the metabolic effects of reduced oxygen delivery to cardiac muscle due to local myocardial ischemia and the effects of acute hypoxia on brain metabolism. Other important applications of sensitivity analysis include identification of quantitatively relevant pathways and biochemical species within an overall mechanism, when examining the effects of a genetic anomaly or pathological state on energetic system components and whole system behavior.

Radhakrishnan, Krishnan↗
NASA NTRS1997

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

White, Gary L.↗
NASA NTRS2003

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗
DOE OSTI2022

Reimport of carbon from cytosolic and vacuolar sugar pools into the Calvin–Benson cycle explains photosynthesis labeling anomalies

Significance Photosynthesis metabolites are quickly labeled when 13 CO 2 is fed to leaves, but the time course of labeling reveals additional contributing processes involved in the metabolic dynamics of photosynthesis. The existence of three such processes is demonstrated, and a metabolic flux model is developed to explore and characterize them. The model is consistent with a slow return of carbon from cytosolic and vacuolar sugars into the Calvin–Benson cycle through the oxidative pentose phosphate pathway. Our results provide insight into how carbon assimilation is integrated into the metabolic network of photosynthetic cells with implications for global carbon fluxes.

59 BASIC BIOLOGICAL SCIENCES↗