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Bioenergy landscapes drive trophic shifts in generalist ants

Changes in trophic niche—the pathways through which an organism obtains energy and nutrients—are a fundamental way in which organisms respond to environmental conditions. But the capacity for species to alter their trophic niches in response to global change, and the ways they do so when able, remain largely unknown. Here we examine food webs in three long–term and large–scale experiments to test how resource availability and nutritional requirements interact to determine an organism's trophic niche in the context of one of the largest global trends in land use—the rise in bioenergy production. Here, we use carbon and nitrogen stable isotope analyses to characterize arthropod food webs across three biofuel crops representing a gradient in plant resource richness (corn monocultures, fields dominated by native switchgrass and restored prairie), and to quantify changes in the trophic niche of a widespread generalist ant species across habitats. In doing so, we measure the effects of basal resource richness on food chain length, niche breadth and trophic position. We frame our results in the context of two hypotheses that explain variation in trophic niche—the niche variation hypothesis which emphasizes the importance of resource diversity and ecological opportunity, and the optimal diet hypothesis which emphasizes dietary constraints and the availability of optimal resources. Increasing plant richness lengthened food chains by 10%–20% compared to monocultures. Niche breadths of generalist ants did not vary with resource richness, suggesting they were limited by optimal diet requirements and constraints rather than by ecological opportunity. The ants instead responded to changes in plant richness by shifting their estimated trophic position. In resource–poor monocultures, the ants were top predators, sharing a trophic position with predatory spiders. In resource–rich environments, in contrast, the ants were omnivores, relying on a mix of animal prey and plant–based resources. In addition to highlighting novel ecosystem impacts of alternate bioenergy landscapes, our results suggest that niche breadth and trophic diversification depend more on the presence of optimal resources than on ecological opportunity alone.

59 BASIC BIOLOGICAL SCIENCES↗

Spatial Study 2021: Sample-Based Surface Water Chemistry and Organic Matter Characterization across Watersheds in the Yakima River Basin, Washington, USA (v3)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin. The dataset provides geochemistry and organic matter characterization data generated from samples collected during the same two-week period at 47 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Related sensor data are published at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1892054. This data package was originally published September 2022. It was updated May 2023 (modified files) and November 2024 (new and modified files). See the change history section in the readme for more details. This dataset is comprised of one main data folder containing (1) file-level metadata; (2) data dictionary; (3) field metadata; (4) dissolved inorganic carbon (DIC), dissolved organic carbon (DOC; reported as non-purgeable organic carbon; NPOC), total nitrogen (TN), total suspended solids (TSS), ions, and benzene polycarboxylic acid (BPCA) concentration and stable isotope data; (5) averaged values from water chemistry data; (6) surface water sampling protocol; (7) sensor protocol (8) readme; (9) methods codes; (10) international generic-sample number (IGSN) mapping file; and (11) folder of high resolution characterization of organic matter via 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory). This folder contains two subfolders, one containing the .xml data files and the other containing instructions for using Formultitude (https://github.com/PNNL-Comp-Mass-Spec/Formultitude) and an R script to process the data based on the user's specific needs. All files are .csv, .pdf, .R, .ref, or .xml. We thank the United States Forest Service, Washington Department of Natural Resources, Washington Department of Fish and Wildlife, Washington State Parks, Confederated Tribes and Bands of the Yakama Nation, and Cowiche Canyon Conservancy for access to field locations where these samples were collected. We also thank the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗

Evaluating bloom potential of the green-tide forming alga Ulva ohnoi under ocean acidification and warming

Herein we discuss the occurrence of green-tides, whose bloom potential may be increased by various human activities and biogeochemical process, results in enormous economic losses and ecosystem collapse. In this study, we investigated the ecophysiology of the subtropical green-tide forming alga, Ulva ohnoi complex (hereafter: U. ohnoi), under simulated future ocean conditions in order to predict its bloom potential using photosynthesis and growth measurements, and stable isotope analyses. Our mesocosm system included four experimental conditions that simulated the individual and combined effects of elevated CO 2 and temperature, namely control (450 μatm CO 2 & 20 °C), acidification (900 μatm CO 2 & 20 °C), warming (450 μatm CO 2 & 25 °C), and greenhouse (900 μatm CO 2 & 25 °C). Photosynthetic electron transport rates (rETR) increased significantly under acidification conditions, but net photosynthesis and growth were not affected. In contrast, rETR, net photosynthesis, and growth all decreased significantly under elevated temperature conditions (i.e. both warming and greenhouse). These results represent the imbalance of energy metabolism between electron transport and O 2 production that may be expected under ocean acidification conditions. This imbalance appears to be related to carbon and nitrogen assimilation by U. ohnoi. In particular, 13 C and 15 N discrimination data suggest U. ohnoi prefers CO 2 and NH 4 + over HCO 3 - and NO 3 - as sources of carbon and nitrogen, respectively, and this results in increased N content in the thallus under ocean acidification conditions. Together, our results suggest a trade-off in which the bloom potential of U. ohnoi could increase under ocean acidification due to greater N accumulation and through the saving of energy during carbon and nitrogen metabolism, but that elevated temperatures could decrease U. ohnoi's bloom potential through a decrease in photosynthesis and growth.

54 ENVIRONMENTAL SCIENCES↗

Lipids represent a dynamic, yet stable pool of microbially-derived soil carbon

There is an emerging consensus that microorganisms are a primary source of persistent, slow-cycling soil organic matter (SOM), however which microbial residues contribute to SOM and what controls their accumulation remains unresolved. Lipids are a commonly overlooked biomolecular pool that could contribute significantly to stable SOM. While current estimates for phospholipid degradation in soils are rapid, lipids are structurally heterogeneous molecules that could turnover at different rates. Through a year-long soil incubation and compound-specific, stable isotope probing (SIP)-lipidomics, we were able to rigorously track the persistence of lipid compounds in silty and sandy switchgrass bioenergy crop soils. Here, we assessed the influence of lipid structure on soil lipid accrual and degradation as moderated by soil texture, since mineral association is presumed to be the primary mechanism for lipid persistence. After rapid incorporation of 13 C glucose into microbial biomass, we found 13 C label was retained broadly across chemically diverse lipid classes, even after one year. 13 C-labeled lipid profiles varied significantly with soil texture; however, we found no difference between sandy and silty soils in lipid retention, suggesting soil texture may only play a minor role in modulating lipid persistence. Only two lipid subclasses were found to be persistent (i.e., retention of 13 C label without significant degradation or production): phosphatidylinositol lipids and hydroxyceramide lipids, both of which are negatively charged, possibly facilitating stabilization by mineral complexation. However, several other subclasses displayed substantial ongoing production. In particular, the accumulation of triacylglycerol lipids across soil textures suggests that storage lipids may be an important component of SOC, highlighting a potential target for management strategies to promote C retention by lipid accrual. Overall, the retention for over a year of 13 C label in microbial intact lipid biomarkers reveals the importance of efficient biomass production and turnover when considering microbial C contributions to SOM.

compound-specific↗

Active virus-host interactions at sub-freezing temperatures in Arctic peat soil

Abstract Background Winter carbon loss in northern ecosystems is estimated to be greater than the average growing season carbon uptake and is primarily driven by microbial decomposers. Viruses modulate microbial carbon cycling via induced mortality and metabolic controls, but it is unknown whether viruses are active under winter conditions (anoxic and sub-freezing temperatures). Results We used stable isotope probing (SIP) targeted metagenomics to reveal the genomic potential of active soil microbial populations under simulated winter conditions, with an emphasis on viruses and virus-host dynamics. Arctic peat soils from the Bonanza Creek Long-Term Ecological Research site in Alaska were incubated under sub-freezing anoxic conditions with H 2 18 O or natural abundance water for 184 and 370 days. We sequenced 23 SIP-metagenomes and measured carbon dioxide (CO 2 ) efflux throughout the experiment. We identified 46 bacterial populations (spanning 9 phyla) and 243 viral populations that actively took up 18 O in soil and respired CO 2 throughout the incubation. Active bacterial populations represented only a small portion of the detected microbial community and were capable of fermentation and organic matter degradation. In contrast, active viral populations represented a large portion of the detected viral community and one third were linked to active bacterial populations. We identified 86 auxiliary metabolic genes and other environmentally relevant genes. The majority of these genes were carried by active viral populations and had diverse functions such as carbon utilization and scavenging that could provide their host with a fitness advantage for utilizing much-needed carbon sources or acquiring essential nutrients. Conclusions Overall, there was a stark difference in the identity and function of the active bacterial and viral community compared to the unlabeled community that would have been overlooked with a non-targeted standard metagenomic analysis. Our results illustrate that substantial active virus-host interactions occur in sub-freezing anoxic conditions and highlight viruses as a major community-structuring agent that likely modulates carbon loss in peat soils during winter, which may be pivotal for understanding the future fate of arctic soils' vast carbon stocks.

59 BASIC BIOLOGICAL SCIENCES↗

Organic matter concentration and composition of experimentally burned open air and muffle furnace vegetation chars across differing burn severity and feedstock types from Pacific Northwest, USA (v4).

This dataset represents results from an experimental study designed to compare how the chemical composition of organic matter changes across different burn conditions and feedstock materials. The dataset provides both solid and dissolved phase bulk concentration and organic matter characterization data from experimentally generated chars. Chars were created in a closed muffle furnace or on an open burn table from four different feedstock species representing vegetation commonly impacted by fire regimes across the Pacific Northwest, USA. This data can be used to compare how different burn conditions may influence resultant organic matter chemistry and help further our understanding of potential biogeochemical impacts on river corridors post-fire. This dataset is comprised of one data package readme, one data dictionary (dd), one file level metadata (flmd), fourteen burn table videos, burn table video metadata and three folders containing (A) data; (B) metadata and protocols; and (C) photos. The folder names and the file name of the data package readme include a version number which will be updated with future iterations of this data package. The data folder includes (1) solid carbon and solid nitrogen; (2) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) and total dissolved nitrogen (TN); (3) pH; (4) thermocouple time series temperature; (5) methods codes; (6) installation methods; (7) excitation emissions matrix (EEM) methods information; (8) a folder of excitation emissions matrix (EEM) fluorescence and absorbance spectra in dissolved organic matter and EEMs processing instructions; (9) solid state carbon-13 and solution state phosphorus nuclear magnetic resonance (13-C NMR and 31-P NMR) data and methods; (10) benzene polycarboxylic acid (BPCA) concentration and stable isotope data; (11) FTICR-MS methods; (12) Inductively coupled plasma (ICP) data for total calcium, magnesium, iron, aluminum, potassium, phosphorus, sodium, and sulfur along with sodium hydroxide-ethylenediaminetetraacetic acid (sodium hydroxide-EDTA) extractable calcium, magnesium, iron, aluminum, potassium, phosphorus, and sulfur; (13) a folder of phosphorus, carbon, and nitrogen X-ray absorption near edge structure (P-XANES, N-XANES, C-XANES) data for samples and standards; (14) P-XANES, N-XANES, C-XANES methods; (15) molybdate reactive phosphorus; and (16) folder of high resolution characterization of organic matter via 21 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) generated through the Environmental Molecular Sciences Laboratory (EMSL; https://www.pnnl.gov/environmental-molecular-sciences-laboratory). The FTICR folder contains .txt data files and a subfolder containing instruments for using Formularity (https://omics.pnl.gov/software/formularity) and an R script to process the data based on the user's specific needs. The metadata and protocols folder includes (1) international geo-sample number (IGSN) mapping file (2) burn and laboratory metadata; (3) burn protocol; (4) laboratory protocol; (5) vegetation collection metadata; and (6) vegetation collection protocol. The folder contains photos of the solid chars. All files are .csv, .txt, .pdf, .jpg, .jpeg, .R, .ref, or .mp4. The data package was originally published October 2022 (v1). It was updated April 2023 (v2; new data files), September 2023 (v3; new and corrected data files), and September 2024 (v4; new and added/updated files). Metadata files were also updated to reflect these changes. See the change history section in the readme for more details.

54 ENVIRONMENTAL SCIENCES↗

Alpha Decay Chains as Thermal Power Sources: Analysis and Applications for RTGs

Radioactive sources can provide power in remote and environmentally harsh locations such as the arctic or space. The generators powered by such sources are rugged and can withstand extreme temperatures, lack of sunlight, and require no human intervention for multiple years. Radioisotopes are used in thermoelectric generators to provide power at remote sites and deep in space. Isotopes like Pu-238, Cm-244, and Am-241 are used in these generators by NASA for power in space probes and spacecrafts. These power sources deliver a steady supply of energy over extended periods of time. Alpha particles created during decay do not travel far in a material. Their kinetic energy is transferred to heat that we can then convert into energy. Unlike beta and gamma decay, the slower-moving alpha particles stop in the material, making their energy available for use. Energy from these natural decay processes provides a reliable source of power. Spontaneous fission is rare and unreliable, and unlike induced fission processes, alpha decay occurs naturally and does not require external management or ignition. The ideal properties of an isotope for use as a power source depend upon the intended use. For use in an Arctic research base over a period of several years, but less than a decade, an isotope that provides high power output over a shorter lifespan may be the most suitable option. Whereas, for deep space missions where a consistent power source for decades or perhaps more than 100 years is needed that would require a very different isotope. One with a much longer half-life that would provide consistent power throughout that time and survive in that state in for these extended periods of time. These examples represent two extreme sides in terms of time frames. By analyzing the power produced by different radioactive decay processes over time, we can evaluate the suitability of various isotope decay chains for specific uses. Some unstable isotopes undergo a series of radioactive decays, transforming into different isotopes at each step and resulting in a stable isotope. The lists of isotopes in these decay processes are known as decay chains. Some of these chains, illustrated in the figures below, are currently being investigated for use in radioisotope thermoelectric generators (RTGs) designed for a range of operational durations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Modeling Isotope Separation in Electrochemical Lithium Deposition

Naturally occurring Li consists of two stable isotopes, 6 Li with an abundance of about 7.5%, and 7 Li making up the remainder with 92.5%. The development of a 6 Li enrichment technique, in terms of technical reliability and environmental safety to reach 6 Li future requirements, represents a key step in the roadmap for nuclear fusion energy supply worldwide. This paper uses finite element analysis-based models to simulate electrochemical Li isotope separation, which is an attractive method in terms of simplicity, safety, and scalability. In the model, we quantitatively analyze how different electrochemical factors including thermodynamics, charge-transfer kinetics, and diffusivities affect the separation process (separation factor), together with cell parameters, such as cell length and current density. The maximum separation factor of 1.128 could be obtained with the cell under the optimal thermodynamic, kinetic, and diffusive conditions, which is among the highest separation factors ever reported. Furthermore, these results will assist in designing the actual isotope separation setup with large separation factor and appropriate timing for sample collection.

07 ISOTOPE AND RADIATION SOURCES↗

High-resolution laser system for the S 3 -Low Energy Branch

Here, in this paper we present the first high-resolution laser spectroscopy results obtained at the GISELE laser laboratory of the GANIL-SPIRAL2 facility, in preparation for the first experiments with the S 3 -Low Energy Branch. Studies of neutron-deficient radioactive isotopes of erbium and tin represent the first physics cases to be studied at S 3 . The measured isotope-shift and hyperfine structure data are presented for stable isotopes of these elements. The erbium isotopes were studied using the 4f 12 6s 2 3 H 6 → 4f 12 ( 3 H)6s6p J = 5 atomic transition (415 nm) and the tin isotopes were studied by the 5s 2 5p 2 ( 3 P 0 ) → 5s 2 5p6s( 3 P 1 ) atomic transition (286.4 nm), and are used as a benchmark of the laser setup. Additionally, the tin isotopes were studied by the 5s 2 5p6s( 3 P 1 ) → 5s 2 5p6p( 3 P 2 ) atomic transition (811.6 nm), for which new isotope-shift data was obtained and the corresponding field-shift F 812 and mass-shift M 812 factors are presented.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The s process in massive stars, a benchmark for neutron capture reaction rates

A clear definition of the contribution from the slow neutron-capture process (s process) to the solar abundances between Fe and the Sr-Zr region is a crucial challenge for nuclear astrophysics. Robust s-process predictions are necessary to disentangle the contribution from other stellar processes producing elements in the same mass region. Nuclear uncertainties are affecting s-process calculations, but most of the needed nuclear input are accessible to present nuclear experiments or they will be in the near future. Neutron-capture rates have a great impact on the s process in massive stars, which is a fundamental source for the solar abundances of the lighter s-process elements heavier than Fe (weak s-process component). In this work we present a new nuclear sensitivity study to explore the impact on the s process in massive stars of 86 neutron-capture rates, including all the reactions between C and Si and between Fe and Zr. We derive the impact of the rates at the end of the He-burning core and at the end of the C-burning shell, where the 22 Ne(α,n) 25 Mg reaction is is the main neutron source. We confirm the relevance of the light isotopes capturing neutrons in competition with the Fe seeds as a crucial feature of the s process in massive stars. For heavy isotopes we study the propagation of the neutron-capture uncertainties, finding a clear difference of the impact of Fe and Co isotope rates with respect to the rates of heavier stable isotopes. The local uncertainty propagation due to the neutron-capture rates at the s-process branching points is also considered, discussing the example of 85 Kr. The complete results of our study for all the 86 neutron-capture rates are available online. Finally, we present the impact on the weak s process of the neutron-capture rates included in the new ASTRAL library (v0.2).

79 ASTRONOMY AND ASTROPHYSICS↗

Deuterated water as a substrate-agnostic isotope tracer for investigating reversibility and thermodynamics of reactions in central carbon metabolism

Stable isotope tracers are a powerful tool for the quantitative analysis of microbial metabolism, enabling pathway elucidation, metabolic flux quantification, and assessment of reaction and pathway thermodynamics. 13 C and 2 H metabolic flux analysis commonly relies on isotopically labeled carbon substrates, such as glucose. However, the use of 2 H-labeled nutrient substrates faces limitations due to their high cost and limited availability in comparison to 13 C-tracers. Furthermore, isotope tracer studies in industrially relevant bacteria that metabolize complex substrates such as cellulose, hemicellulose, or lignocellulosic biomass, are challenging given the difficulty in obtaining these as isotopically labeled substrates. In this study, we examine the potential of deuterated water ( 2 H 2 O) as an affordable, substrate-neutral isotope tracer for studying central carbon metabolism. We apply 2 H 2 O labeling to investigate the reversibility of glycolytic reactions across three industrially relevant bacterial species -C. thermocellum, Z. mobilis, and E. coli-harboring distinct glycolytic pathways with unique thermodynamics. We demonstrate that 2 H 2 O labeling recapitulates previous reversibility and thermodynamic findings obtained with established 13 C and 2 H labeled nutrient substrates. Furthermore, we exemplify the utility of this 2 H 2 O labeling approach by applying it to high-substrate C. thermocellum fermentations -a setting in which the use of conventional tracers is impractical-thereby identifying the glycolytic enzyme phosphofructokinase as a major bottleneck during high-substrate fermentations and unveiling critical insights that will steer future engineering efforts to enhance ethanol production in this cellulolytic organism. This study demonstrates the utility of deuterated water as a substrate-agnostic isotope tracer for examining flux and reversibility of central carbon metabolic reactions, which yields biological insights comparable to those obtained using costly 2 H-labeled nutrient substrates.

09 BIOMASS FUELS↗

Triple oxygen isotope compositions of globally distributed soil carbonates record widespread evaporation of soil waters

The stable isotopic composition of pedogenic carbonates is central to many studies of past climate and topography, providing a basis for our understanding of Earth's terrestrial history. A core assumption of many applications of oxygen isotope values (δ 18 O) of pedogenic carbonate is that they reflect the δ 18 O value of precipitation (rain/snow). Here, this assumption is violated if soil carbonates form in evaporated soil waters. In this work, we develop a means to identify evaporation in ancient soils using the triple oxygen isotope composition ( 16 O- 17 O- 18 O) of pedogenic carbonates.

58 GEOSCIENCES↗

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↗

Quantification of microcystin production and biodegradation rates in the western basin of Lake Erie

Abstract Cyanobacterial biomass forecasts currently cannot predict the concentrations of microcystin, one of the most ubiquitous cyanotoxins that threaten human and wildlife health globally. Mechanistic insights into how microcystin production and biodegradation by heterotrophic bacteria change spatially and throughout the bloom season can aid in toxin concentration forecasts. We quantified microcystin production and biodegradation during two growth seasons in two western Lake Erie sites with different physicochemical properties commonly plagued by summer Microcystis blooms. Microcystin production rates were greater with elevated nutrients than under ambient conditions and were highest nearshore during the initial phases of the bloom, and production rates were lower in later bloom phases. We examined biodegradation rates of the most common and toxic microcystin by adding extracellular stable isotope‐labeled microcystin‐LR (1 μ g L −1 ), which remained stable in the abiotic treatment (without bacteria) with minimal adsorption onto sediment, but strongly decreased in all unaltered biotic treatments, suggesting biodegradation. Greatest biodegradation rates (highest of −8.76 d −1 , equivalent to the removal of 99.98% in 18 h) were observed during peak bloom conditions, while lower rates were observed with lower cyanobacteria biomass. Cell‐specific nitrogen incorporation from microcystin‐LR by nanoscale imaging mass spectrometry showed that a small percentage of the heterotrophic bacterial community actively degraded microcystin‐LR. Microcystin production and biodegradation rates, combined with the microcystin incorporation by single cells, suggest that microcystin predictive models could be improved by incorporating toxin production and biodegradation rates, which are influenced by cyanobacterial bloom stage (early vs. late bloom), nutrient availability, and bacterial community composition.

59 BASIC BIOLOGICAL SCIENCES↗

δ 2 H isotopic offsets in xylem water measurements under cryogenic vacuum distillation: Quantifying and correcting wood‐water hydrogen exchange influences

Stable isotopes δ 18 O and δ 2 H are used to infer vegetation water sources. In some studies, significant xylem water δ 2 H offsets from potential source waters have been observed. The offsets appear to be more prevalent with cryogenic vacuum distillation (CVD) of plant water. Hypothesized mechanisms for these offsets include changes during plant water uptake and transport, and methodological problems. We propose that a large portion of the offsets are due to hydrogen isotope exchange between xylem water and non-crystalline hydroxyl groups of wood cellulose and hemicellulose during CVD. We present a method for estimating the hypothesized isotopic exchange between wood tissues and water, which is the result of Rayleigh and equilibrium fractionation. To estimate the exchange, we use published wood properties for North American tree species and isotope chemical relationships as a function of moisture content, CVD temperature and water extraction efficiency. A simple model of exchange between xylem water and hydroxyl groups captures the range of observations in studies in which CVD and non-CVD methods were compared. To evaluate the model, we compared observed δ 2 H offsets (sw-excess) values from two field datasets (90°C, n = 364, and 170°C, n = 43) to δ 2 H offsets estimated with our chemical model. We found good agreement between observed and estimated δ 2 H offsets for samples extracted at 90°C (r 2 = 0.69) but not for samples extracted at 170°C (r 2 = 0.20). The offset may be eliminated by increasing the extraction temperature to 229°C or by adding a standard sufficient to raise the moisture content to >150%. A correction can also be approximated by applying a theoretical calculation based on the extraction temperature, moisture content and water extraction efficiency.

54 ENVIRONMENTAL SCIENCES↗

Experimental and theoretical determinations of hydrogen isotopic equilibrium in the system CH 4 —H 2 —H 2 O from 3 to 200°C

The stable isotopic composition of methane (CH 4 ) is commonly used to fingerprint natural gas origins. Over the past 50 years, there have been numerous proposals that both microbial and thermogenic CH 4 can form in or later attain hydrogen isotopic equilibrium with water (H 2 O) and carbon isotopic equilibrium with carbon dioxide (CO 2 ). Evaluation of such proposals requires knowledge of the equilibrium fractionation factors between CH 4 and H 2 O or CO 2 at the temperatures where microbial and thermogenic CH 4 form in or are found in the environment, which is generally less than 200°C. Experimental determinations of these fractionation factors are only available above 200°C, requiring extrapolation of these results beyond the calibrated range or the use of theoretical calculations at lower temperatures. Here, we provide a calibration of the equilibrium hydrogen isotopic fractionation factor for CH 4 and hydrogen gas (H 2 ) ( D α CH4(g)–H2(g) ) based on experiments using γ-Al 2 O 3 and Ni catalysts from 3 to 200°C. Results were regressed as a 2 nd order polynomial of 1000 × ln D α CH4(g)–H2(g) vs. 1/T (K -1 ) yielding: 1000 × l n D α C H 4 ( g ) - H 2 ( g ) = 3.5317 × 10 7 T 2 + 2.7749 × 10 5 T - 179.48 We combine this calibration with previous experimental determinations of hydrogen isotope equilibrium between H 2 , H 2 O(g), and H 2 O(l) and we provide an interpolatable experimental calibration of 1000 × ln D α CH4(g)–H2O(l) from 3 to 200°C. Our resulting 4th order polynomial is the following equation: 1000 × l n D α C H 4 ( g ) - H 2 O l = - 7.9443 × 10 12 T 4 + 8.7772 × 10 10 T 3 - 3.4973 × 10 8 T 2 + 5.4398 × 10 5 T - 382.05 At 3°C, the value from our calibration differs by 93‰ relative to what would be calculated based on the extrapolation of the only experimental calibration currently available to temperatures below its calibrated range (lowest temperature of 200°C; Horibe and Craig, 1995). We additionally provide new theoretical estimates of hydrogen isotopic equilibrium between CH 4 (g), H 2 (g), and H 2 O(g) and carbon isotopic equilibrium between CH 4 (g) and CO 2 (g) using Path Integral Monte Carlo (PIMC) calculations. Our PIMC calculations for hydrogen isotopic equilibrium between CH 4 and H 2 agree 1:1 with our experiments. Finally, we compile carbon and hydrogen isotopic measurements of CH 4 , CO 2 , and H 2 O from various environmental systems and compare observed differences between carbon and hydrogen isotopes to those expected based on isotopic equilibrium. We find that isotopic compositions of some microbial gases from marine sedimentary, coalbed, and shale environments are consistent with those expected for CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. In contrast, microbial terrestrial and pure culture gases are not consistent with both CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. Overall, these results are explained qualitatively using previously developed conceptual models that link free energy gradients available to microorganisms to the degree that their enzymes can promote isotope-exchange reactions between CH 4 , CO 2 , and H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Precision Zinc Isotopic Measurement of Certified Reference Materials Relevant to the Environmental, Earth, Planetary and Biomedical Sciences

The zinc (Zn) stable isotope system has emerged as a powerful tool for investigating natural and anthropogenic processes of interest to disciplines extending from the Earth and planetary sciences to biomedical research. In nature, Zn isotopes typically fractionate ( 66 Zn/ 64 Zn) within the range of –1 and +1 permil (‰), and however, analytical limitations restrict the application of the Zn isotope system. Specifically, there is a lack of well-characterised matrix-matched reference materials covering most Zn isotope applications that are essential for validating laboratory performance, particularly given the contamination prone nature of Zn. Furthermore, the increasing demand for analysis of size-limited materials and sample types displaying small, sub-permil level Zn isotope variations requires improvements in measurement procedures. To address these limitations, the δ 66 Zn values of two pure Zn solutions and eighteen reference materials including the previously uncharacterised RGM-2, BCR-279, DOLT-4, DOLT-5, NASS-7, SBC-1, SGR-1b, MESS-3 and HISS-1, and the understudied QLO-1, SDC-1, BCR-414, NASS-6 and COQ-1 materials are reported. Furthermore, a 70 Zn- 67 Zn double-spike design has been implemented that routinely achieves intermediate measurement precision better than ± 0.02‰. This represents at least a two-fold improvement when compared with other double-spike designs, providing a robust platform of δ 66 Zn values required for quality control procedures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

COMBLE-Isotopic Links to Atmospheric Water’s Sources (ISLAS) Snow Sampling 2020 Field Campaign Report

Within the European Research Council (ERC)-funded project entitled Isotopic Links to Atmospheric Water’s Sources (ISLAS), researchers from the University of Bergen, Norway, used the stable isotope composition of atmospheric water vapor and precipitation to obtain information about the sources and transport processes of water vapor within arctic weather systems. In particular, during cold-air outbreak conditions, evaporation and precipitation occur in close proximity within the study area. With evaporation studied at a single location (Ny-Ålesund), ISLAS researchers wanted to be able to sample the resulting precipitation at several downstream locations. The U.S. Department of Energy Atmospheric Radiation Measurement (ARM) Cold-Air Outbreaks in the Marine Boundary Layer Experiment (COMBLE) site was one of those locations, included in an entire network of precipitation sampling stations reaching from Ny-Ålesund, where water vapor isotope measurements are conducted near the surface, to Longyearbyen, Tromsø, Andenes, Ålesund, and Bergen. Daily precipitation samples, enhanced by more frequent sampling during intense operational periods (IOPs), were conducted during four weeks from 20 February to 20 March 2020. The contribution from the ARM mobile facility (AMF) observatory, deployed at ANX (Andenes, Norway) during COMBLE, was valuable to understand the spatial coherence of water isotope signals from arctic and extratropical weather systems.

54 ENVIRONMENTAL SCIENCES↗