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At least 37 records · Page 2

Soil Water Percolation Chemistry, April 2017 to March 2019, BR-Ma2, Manaus

Soil water percolation chemistry including major cations, anions and isotope geochemistry. Samples were collected from six passive wick flux meters across three topographic positions (valley, slope and plateau). Data has been processed to compute the monthly mean for each topographic position where two flux meters were installed at each topographic position. All samples were processed at the Geology, Geochemistry and Geomaterials Research Laboratory (GGRL) in Los Alamos, NM USA. The metadata tab included in the .csv has additional information on locations where the sensors were installed, and other installation/maintenance details. Contact ksolander@lanl.gov if you need to use this dataset for additional information.

54 ENVIRONMENTAL SCIENCES↗

Ca-isotopes as a robust tracer of magmatic differentiation

The large mass difference (~10%) between the two most abundant isotopes of calcium, 40 Ca and 44 Ca, gives Ca great potential in tracking mass-dependent fractionation during magmatic processes. Resolvable Ca-isotope fractionation during fractional crystallization of magma, particularly by feldspar in evolved melts, has been theoretically inferred but not robustly tested in nature. To further explore the effects of magmatic differentiation on Ca-isotope systematics, we studied the late-Permian alkaline igneous suite of the Øyangen Caldera, Oslo Rift, Norway, consisting of volcanic and intrusive units ranging from basanitic to rhyolitic compositions. Major and trace element variations and modeling demonstrate that the main series of samples (N = 21), including basanites, ring-dyke syenites, and central-dome syenites, likely documents a co-genetic and closed-system fractional crystallization sequence. Our data show minimal δ 44/40 Ca variation (< 0.05 ‰) in the intermediate magma and a marked increase in δ 44/40 Ca in the felsic magma of the Øyangen Caldera (from 0.62 ± 0.02 ‰ to 1.15 ± 0.03 ‰ relative to Ca standard, SRM915a). The systematic increase is best explained by equilibrium isotopic fractionation dominated by alkali feldspar in the fractionating mineral assemblage. This is further supported by strong correlations between δ 44/40 Ca, CaO, and Eu/Eu* in the main-series samples. Implementing a Monte Carlo approach, isotopic modeling of the liquid line of descent using Rayleigh fractionation is highly consistent with the observed Ca-isotope evolution. For the first time, we confirm prominent Ca stable isotope fractionation in felsic-stage differentiation of alkaline magma and constrain the isotope fractionation factors of plagioclase and K-feldspar. Integrated with extant estimations on mineral fractionation factors from the literature, our results suggest increasing fractionation effects of rock-forming minerals with decreasing Ca content. Finally, the affirmation of significant Ca-isotope fractionation in alkaline magma by feldspar empowers the application of Ca as a versatile tracer of crustal evolution, allowing further tests in other magmatic conditions across various planetary objects.

58 GEOSCIENCES↗

The oxygen stable isotope composition of CRM 125-A UO 2 standard reference material

While there is a clear need for standardized reference materials for analytical calibrations and for inter-laboratory comparisons, there are not currently any for the oxygen stable isotopic composition of uranium oxides. In this paper we summarize the results from four laboratories by seven different methods of oxygen stable isotope analyses using fluorination techniques of CRM 125-A UO 2 Standard Reference Material. We synthesize these data and methods to arrive at a consensus oxygen stable isotope composition for CRM 125-A $δ$ 18 O = -9.63‰ (±0.29‰) VSMOW. We discuss methodological differences between analytical approaches, including furnace vs laser heating, fluorination using BrF 5 or ClF 3 , as well as calibration strategies. We highlight the potential effects of calibration scale compression from single-point calibrations using reference material with $δ$ 18 O values having a large relative difference from the sample being analyzed. We demonstrate how calibration scale compression can yield differences in calibrated $δ$ 18 O values up to ~2‰ for samples with ~20‰ difference from a single reference material, if the calibration slope of different analytical systems differs by 0.1. In conclusion, we suggest the use of liquid water calibration standards sealed in silver capillary tubes for multi-point calibrations of fluorination analysis systems.

07 ISOTOPE AND RADIATION SOURCES↗

Utah FORGE: Geochemical Data for Cold Groundwaters and Produced Geothermal Fluids

Geochemical data for cold groundwaters and produced geothermal fluids around the Utah FORGE site. The data is compiled into four tables in the attached Excel File. Table 1 is a compilation of compositions (anions, cations, weak acids, oxygen, hydrogen, and carbon isotopes) for cold groundwaters and produced geothermal waters in the Milford valley, Utah. Table 2 is a compilation of noble gas (He, Ne, Ar) and He and Ne isotopic compositions for cold groundwaters and produced geothermal waters in the Milford valley, Utah. Table 3 provides values for calculated advective and diffusive fluxes of helium. Table 4 provides values of calculated subsurface stored heat between the Opal Mound fault and the Utah FORGE site, which are related to volumes of recently solidified magmatic heat sources.

15 GEOTHERMAL ENERGY↗

Using groundwater noble gas measurements to confirm paleorecharge hypotheses at Pahute Mesa, Nevada National Security Site, Nevada, USA

Pahute Mesa (Nevada, USA) was the site of 85 underground nuclear tests between 1965 and 1992 whose residual radio-chemical inventory poses a contaminant threat to local groundwater resources. To assess the fate and transport of these radionuclides in groundwater, several geochemical studies, including this one, have been conducted to understand long-term groundwater flow patterns at, and downgradient of, Pahute Mesa. Groundwater samples from the Pahute Mesa area at the Nevada National Security Site were analyzed for noble gases ( 3 He/ 4 He isotopic ratio and He, Ne, Kr, Ar and Xe concentrations) to infer groundwater recharge temperatures and provide additional evidence in support of groundwater flow patterns and the presence of late-pluvial Pleistocene groundwater. These data confirm recent findings (based on groundwater geochemistry and isotope compositions) that most recharge in the area occurred under temperature conditions much cooler than are found today, except near major drainages where ephemeral run of continues to recharge shallow groundwater. These noble gas data indicate that noble gas recharge temperatures and terrigenic He components have been reset where groundwater has flowed upward over barriers formed by caldera margins, or near the regional discharge area (Oasis Valley) where shallow groundwater has interacted with shallow soil gas. This evidence from groundwater noble gas measurements, in combination with other isotopic and geochemical studies, supports the current understanding of the unusual hydrogeology and recharge history of Pahute Mesa.

54 ENVIRONMENTAL SCIENCES↗

Accuracy and precision of ESI-Orbitrap-IRMS observations of hours to tens of hours via reservoir injection

Here, orbitrap isotope ratio mass spectrometry (Orbitrap-IRMS) has recently been applied to high-precision, natural-abundance isotope ratio measurements of a diverse range of compounds, including amino acids, oxyanions, fatty acids, and metals. These measurements can characterize many isotope ratios simultaneously at high (≈1.0‰) precision. In a successful experiment, observed precision will track the shot-noise limit and be limited by experimental time. Some isotope ratios, for example those involving 17 O in organic compounds or multiply-substituted (‘clumped’) isotopologues, require experimental times of hours to tens of hours to achieve desired precision, while current sample introduction techniques focus on observations on the order of seconds to tens of minutes. In this study, we characterize Orbitrap-IRMS performance for three long duration measurements (individual acquisitions ≥1 h and as long as 24 h) using an automated reservoir injection system coupled to a Q Exactive HF Orbitrap with an electrospray ionization (ESI) source. First, we characterize long-term intra-measurement stability through a 24-h long measurement of acetone. We report the following isotope ratios and precisions (as acquisition errors, errors on the observed ratio within this measurement (σ AE )): 13 C/ 12 C (σ AE = 0.07‰), 17 O/ 16 O (σ AE = 1.1‰), 18 O/ 16 O (σ AE = 0.3‰), and 13 C 13 C/ 12 C (σ AE = 0.65‰). The σ AE of each tracks the shot noise limit throughout and is limited by the challenging conditions (high resolution and low numbers of ions per scan) required for 17 O/ 16 O measurement in the presence of 13 C via Orbitrap. Second, we characterize inter-measurement stability via a sequence of seven 75-min analyses of perchlorate. We observe the following ratios and acquisition errors: 37 Cl/ 35 Cl (σ AE = 0.09‰); 17 O/ 16 O (σ AE = 1.6‰); 18 O/ 16 O (σ AE = 0.7‰), 37 Cl 17 O/ 35 Cl 16 O (σ AE = 2.7‰), and 37 Cl 18 O/ 35 Cl 16 O (σ AE = 1.2‰). However, we find that inter-measurement drift between acquisitions limits our accuracy and precision for standardized measurements (i.e., error on reported δ values) to ≈1‰ for the 37 Cl/ 35 Cl measurement. Hence, the benefits of low σ AE may not be fully realized. Third, we demonstrate accuracy via sample/standard comparisons of a methionine sample with 13 C enrichment of ≈20‰ relative to a known standard. Using a sequence of seven 60-min analyses, we recover the following isotope ratios and standardized precisions (i.e., error on reported δ values, denoted propagated acquisition errors, σ PAE ): 33 S/ 32 S (σ PAE = 1.0‰), 34 S/ 32 S (σ PAE = 0.7‰), 15 N/ 14 N (σ PAE = 2.1‰), 2 H/ 1 H (σ PAE = 3.2‰), 13 C/ 12 C (σ PAE = 0.4‰), 18 O/ 16 O (σ PAE = 1.6‰), & 13 C 13 C/ 12 C (σ PAE = 2.8‰) with confirmation of accurate results for the known 13 C/ 12 C and 13 C 13 C/ 12 C enrichments. Together, our results demonstrate the viability of Orbitrap-IRMS for long duration measurements of diverse sample types via an automated reservoir injection system. Inter-measurement stability remains a challenge; we expect our methods to be most applicable to extended measurements of hard-to-observe properties, such as 17 O in organics and clumped isotopologues.

58 GEOSCIENCES↗

Partitioning maternal and exogenous diet contributions to otolith 87 Sr/ 86 Sr in kokanee salmon ( Oncorhynchus nerka )

Strontium isotopes ( 87 Sr/ 86 Sr) recorded in the otoliths of Pacific salmon (Oncorhynchus spp.) are commonly used to identify natal origin. For species that migrate at or soon after emergence, the embryonic region of the otolith provides the only record of provenance. However, maternal contribution of Sr from the yolk can confound the isotopic signature of the natal site. We experimentally quantified maternal and exogenous diet contributions to otolith 87 Sr/ 86 Sr over embryonic development in kokanee salmon (Oncorhynchus nerka). Eggs from two populations in isotopically distinct lakes were incubated and reared in a common water source. Timing of developmental events and proportional contribution from yolk to otolith 87 Sr/ 86 Sr differed significantly between the two populations. We suggest that the magnitude of difference in 87 Sr/ 86 Sr between yolk and water, the relative concentrations of Sr and Ca in these isotopic sources, and population-specific effects on otolith growth and composition contribute to this variation. Furthermore, understanding how these factors affect otolith 87 Sr/ 86 Sr could extend the use of otolith geochemistry for determining provenance to species and populations in which natal site rearing is limited.

59 BASIC BIOLOGICAL SCIENCES↗

New loading method for high precision Sm isotope analysis of nuclear materials using thermal ionization mass spectrometry

This work demonstrates an analytical protocol for high precision Sm isotope analysis by thermal ionization mass spectrometry (TIMS) using a Pt activator. Here, the method permits precise measurements of small aliquots (1–20 ng) of Sm on single Re filament using a modified static-total evaporation technique. This study represents the first attempt to use such protocols for Sm isotope analyses while reducing the loading size of Sm for TIMS. The method could potentially be deployed to study geological, meteorites and lunar samples containing low Sm concentrations, to monitor neutron irradiation exposure based on 149,150 Sm, or to measure Sm isotopic composition in other types of nuclear samples.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Measuring multiple cosmogenic nuclides in glacial cobbles sheds light on Greenland Ice Sheet processes

The behavior of the Greenland Ice Sheet during the Pleistocene remains uncertain due to the paucity of evidence predating the Last Glacial Maximum. In this study, we employ a novel approach, cosmogenic nuclide analysis of individual subglacially-derived cobbles, which allows us to make inferences about ice sheet processes and subglacial erosion. From three locations in western Greenland, we collected 86 cobbles from the current ice sheet margin and nine cobbles exposed on the modern proglacial land surface. We measured the concentration of in situ 10 Be in all cobbles (n = 95) and 26 Al and 14 C in a subset (n = 14). Cobbles deposited during Holocene retreat have 10 Be exposure ages generally consistent with the timing of ice retreat determined by other methods. Conversely, most of the 86 subglacial cobbles contain very low concentrations of 10 Be (median 1.0×10 3 atoms g –1 ), although several have ~10 4 and one has ~10 5 atoms g –1 . The low concentrations of 10 Be in most subglacial cobbles imply that their source areas under the Greenland Ice Sheet are deeply eroded, preserving minimal evidence of surface or near-surface exposure. The presence of measurable 14 C in ten of the cobbles requires that they experienced cosmogenic nuclide production within the past ~30 ka; however, 14 C/ 10 Be ratios of ~6 suggest that nuclide production occurred during shielding by overlying material. Only two of the 86 subglacial cobbles definitively have cosmogenic nuclide concentrations consistent with prior surface exposure. Overall, isotopic analysis of subglacial cobbles indicates that much of western Greenland's subglacial landscape is characterized by deep erosion and minimal subaerial exposure.

58 GEOSCIENCES↗

New K-feldspar Pb isotope results for Mesozoic arc crust in the Pacific Northwest, U.S.A. and Canada: comparison with the Mojave-Salinia province of southern California and Implications for Baja-BC

Measurements of lead isotopic compositions in detrital K-feldspar have been increasingly used as a tool to assess sediment provenance. We compiled a database of previously published Pb isotope data from 700 bedrock K-feldspar samples and 1,423 age-corrected bedrock whole rock samples from western North American igneous and metamorphic bodies. Additionally, we report 66 new K-feldspar Pb isotope data for plutons throughout the Pacific Northwest region of the United States and British Columbia. Results show that the Pb isotope values of plutonic K-feldspar depend on the isotopically juvenile or evolved nature of underlying crust. Samples obtained from the mid Cretaceous – mid Eocene Coast Plutonic Complex, North Cascades, and Intermontane superterrane that occur west of the initial 87 Sr/ 86 Sr (Sri) = 0.706 isopleth exhibit a highly restricted 207 Pb/ 206 Pb and 208 Pb/ 206 Pb values centred upon 0.83 and 2.03, respectively. Conversely, rocks overlying older continental crust further east such as the Middle Jurassic – Late Cretaceous Omineca crystalline belt, Idaho batholith, and Boulder Batholith exhibit far greater variation of Pb isotope values that parallel the 100 Ma isochron calculated from a two-stage Pb evolution model. We demonstrate that Pb isotopic results from the Idaho and Boulder Batholith region can be used to define distinctive subregions for Pb isotopic provenance analysis, and compare these signatures to the Mojave-Salinian batholith of southern California and western Arizona, as these two areas have previously been proposed as source regions for extraregional sediment that was deposited within the Nanaimo Basin during the Campanian – Maastrichtian. Future Pb isotopic analysis of detrital K-feldspar from the Nanaimo Basin of southwestern British Columbia may effectively distinguish between potential extraregional sources separated by thousands of kilometres.

Coast Plutonic Complex↗

Soil Water Chemistry and Water and Nitrogen Isotopes, Teller Road Site and Kougarok Hillslope, Seward Peninsula, Alaska, 2016 - 2019

Data includes results from soil pore-water ions and isotopes sampled from July 2016 through August 2019 at Kougarok Hillslope at mile marker 64 (KG_MM64), Kougarok Road at mile marker 51 (KG_MM51), and the Teller site at mile marker 27 (TL_MM27) in the Seward Peninsula, Alaska. Water was collected using rhizons, wicks, and a sipper. This dataset is used in the Conroy et al., in prep.NGEE Arctic Project SummaryThe Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Surface Water Chemistry and Water and Nitrogen Isotopes, Teller Road Site, Seward Peninsula, Alaska, 2016 and 2017

Data include results from water chemistry and water isotope analyses for surface water samples collected at the NGEE Arctic Teller Road site at mile marker 27 (TL_MM27) on the Seward Peninsula, Alaska, July through September of 2016 and May through September of 2017. The samples were collected using automated samplers (ISCO Model 6712; Teledyne, USA), with regular collection (every 24 hrs in 2016 and every 48 hrs in 2017). Surface water samples were collected from three locations along the main drainage: ISCO 1 from the tributary (64.729060°, -165.946210°), ISCO 3 which was located upstream (64.733640°, -165.955410°) and ISCO 2 which was located downstream (64.726410°, -165.946820°). Dataset includes a *.pdf user guide and one *.csv data file.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Neutron capture signatures determined from gadolinium isotope compositions of uranium ore concentrates using MC-ICPMS

We present Gd isotope compositions on 25 well-characterized uranium ore concentrates (UOCs). About half the UOCs have isotope depletions in 157 Gd coupled with anticorrelated excesses in 158 Gd due to neutron capture effects. UOCs from older ore bodies and with higher U contents show larger neutron capture effects than UOCs from younger ore bodies with lower U contents. These Gd data are correlated with their previously measured Sm isotope compositions, and we use the Sm data to estimate the neutron fluence of these samples. In conclusion, this work demonstrates how Gd isotope signatures can be employed as a new tool for nuclear forensics.

Earth Sciences↗

High-dimensional isotomics, part 2: Observations of over 100 constraints on methionine's isotome

The abundances of different isotopic forms of a compound, or isotopologues, will vary based on its physical and chemical history. The number of isotopologues increases combinatorically with the size of a molecule, and even small molecules such as amino acids have thousands of potentially observable isotopic variants. However, due to the analytical challenges of separating and observing isotopologues, only a few dimensions of isotopic diversity are routinely measured. Overcoming these challenges requires both an experimental method to observe many isotopic properties and a theoretical framework for interpreting these experiments. In Part 1, we presented such a theoretical framework; here, we demonstrate an experimental method, which we apply to methionine. Our approach uses a Q Exactive HF Orbitrap to perform several “M + N experiments”, where a sample is ionized, a subset of its isotopologues with cardinal mass N daltons greater than the unsubstituted isotopologue is selected and fragmented, and the proportions of all detectable isotopic forms of those fragment ions are quantified. We perform M + 1, M + 2, M + 3, and M + 4 experiments of a methionine sample and standard where the sample has a 100 ‰ enrichment of 13C at the methyl carbon relative to the natural 13C abundance at that position in the standard, and is otherwise identical to the standard. We observe isotopic forms of 8 fragment ion species for each version of the M + N experiment. With the assistance of a forward model of expected mass spectra, we identify isotopic peaks for each fragment ion based on observed mass and abundance, screen these for data quality, and quantify abundances for 146 unique isotopic peaks at precisions of ≈ 0.3–3 ‰. We present our direct observations and use them to reconstruct the concentrations of 19 individual singly, doubly, and triply-substituted isotopologues; doing so gives fewer constraints and broader error bars than working with the direct observations, but may be more interpretable for some applications. We also examine possibilities for measuring additional peaks, which are primarily limited by the detection limit of the Orbitrap-IRMS method. We then suggest some possible uses of our direct measurements for chemical forensics and hypothesis testing. Furthermore, our results demonstrate the diversity of isotopic constraints currently observable and interpretable for organic molecules.

58 GEOSCIENCES↗

Brachiopod δ 34 S CAS microanalyses indicate a dynamic, climate-influenced Permo-Carboniferous sulfur cycle

Early isotopic studies of sulfate in carbonate minerals (carbonate associated sulfate; CAS) suggested that carbonates can provide a reliable, well-dated archive of the marine sulfur cycle through time. However, subsequent research has shown that diagenetic alteration can impose highly heterogeneous CAS sulfur isotopic compositions (δ 34 S CAS ) among different carbonate phases within sediments. Such alteration necessitates targeted sampling of well-preserved, primary carbonate phases. Here, we present a new record of Carboniferous and Early Permian brachiopod δ 34 S CAS generated from over 130 measurements of microsampled brachiopod shells. Our record refines existing brachiopod δ 34 S CAS records and confirms a large, ~6.5‰ δ 34 S CAS decrease in the Early Carboniferous. Importantly, the record also features a novel 3–5‰ increase in δ 34 S CAS near the Serpukhovian-Bashkirian boundary (323.4 Ma) that coincides with carbonate δ 13 C and δ 18 O increases. Variability in δ 34 S CAS is minor both within (≤0.3‰) and among (≤2‰) individual co-depositional brachiopod specimens. A taxon-specific δ 34 S CAS offset is present one species (Composita subtilita) that also exhibits a δ 13 C offset, supporting the existence of biological “vital effects” on δ 34 S CAS . Geologic evidence and mathematical modeling of the Permo-Carboniferous carbon and sulfur cycles suggest that changes in the burial ratio of organic carbon to pyrite sulfur (R C:S ) are insufficient to explain the observed mid-Carboniferous δ 34 S CAS record. We find that changes in the 34 S depletion of pyrite relative to seawater sulfate ( 34 ε) or in the δ 34 S of the input to the ocean (δ 34 S in ) are also needed. Large additions of O 2 from organic carbon burial during the Permo-Carboniferous cannot be entirely compensated for with sulfur cycle changes; lower than modern late Visean pO 2 and/or additional O 2 sinks are needed to keep pO 2 at plausible levels. Based on the geologic context surrounding our record's mid-Carboniferous δ 34 S CAS increase, we advocate for simultaneous changes in pyrite burial, 34 ε, and δ 34 S in , driven by sea level or tectonically induced changes in environments of sulfur burial, as a viable mechanism to produce rapid seawater δ 34 S changes.

54 ENVIRONMENTAL SCIENCES↗

Position-specific carbon isotopes of Murchison amino acids elucidate extraterrestrial abiotic organic synthesis networks

The Murchison meteorite is a well-studied carbonaceous chondrite with relatively high concentrations of amino acids thought to be endogenous to the meteorite, in part because they are characterized by carbon isotope (δ 13 C) values higher than those typical of terrestrial amino acids. Past studies have proposed that extraterrestrial amino acids in the Murchison meteorite could have formed by Strecker synthesis (for α-amino acids), Michael addition (for β-amino acids), or reductive amination, but a lack of constraints have prevented confident discrimination among these possibilities, or assignment of specific formation pathways to each of several specific amino acids. Position-specific carbon isotope analysis differentiates amongst these mechanisms by relating molecular sites to isotopically distinct carbon sources and by constraining isotope effects associated with elementary chemical reactions. Prior measurements of the position-specific carbon isotopic composition of α-alanine from the Murchison CM chondrite demonstrated that alanine’s high δ 13 C VPDB value is attributable to the amine carbon (δ 13 C VPDB = +142 ± 20‰), consistent with Strecker synthesis drawing on 13 C-rich carbonyl groups in precursors (Chimiak et al., 2021). Here, we measured the δ 13 C composition of fragment ions generated by electron impact ionization of derivatized α-alanine, β-alanine, and aspartic acid from Murchison via gas chromatography-Fourier transform mass spectrometry. α-Alanine’s amine carbon yielded δ 13 C VPDB = +109 ± 21‰, which is consistent with the previously measured value and with formation from 13 C-rich precursors. β-Alanine’s amine carbon presents a lower δ 13 C VPDB = +33 ± 24‰, which supports formation from 13 C-rich precursors but potentially via a Michael addition mechanism rather than Strecker synthesis. Aspartic acid’s amine carbon has δ 13 C VPDB = -14 ± 5‰, suggesting synthesis from precursors distinct from those that generated the alanine isomers. Further, these measurements indicate that Murchison amino acids are a mixture of compounds made from different synthesis mechanisms, though some subsets likely drew on the same substrates; this conclusion highlights the complexity of extraterrestrial organic synthesis networks and the potential of emerging methods of isotope ratio analysis to elucidate the details of those networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗