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At least 19 records

Rn-222 tracing and stable isotope measurements of biogenic gas fluxes from methane saturated sediments

Transport of reduced biogenic gases from anoxic sediments and soils to the atmosphere can be quantitatively studied through measurement of radon-222/radium-226 disequilibrium. In previous work, seasonal variations in biogenic gas transport mechanisms, net fluxes and overall composition were documented. Now presented are direct field measurements of radon-222 activity in gases exiting organic rich sediments which show their usefulness for tracing of the stripping of dissolved biogenic gases from within the sediment column and transport via bubble ebullition. Methane is depleted in deuterium during the summer as compared with winter months and is in general lighter than in most marine sediments signaling the probable importance of acetate as an important precursor molecule. The significant seasonal isotopic variations observed illustrate the importance of understanding mechanisms and rates of biogenic gas production in order to interpret observed tropospheric isotopic data.

Martens, Christopher S.↗

Ammonia-oxidizing bacteria and archaea exhibit differential nitrogen source preferences

Ammonia-oxidizing microorganisms (AOM) contribute to one of the largest nitrogen fluxes in the global nitrogen budget. Four distinct lineages of AOM: ammonia-oxidizing archaea (AOA), beta- and gamma-proteobacterial ammonia-oxidizing bacteria (β-AOB and γ-AOB) and complete ammonia oxidizers (comammox), are thought to compete for ammonia as their primary nitrogen substrate. In addition, many AOM species can utilize urea as an alternative energy and nitrogen source through hydrolysis to ammonia. How the coordination of ammonia and urea metabolism in AOM influences their ecology remains poorly understood. Here we use stable isotope tracing, kinetics and transcriptomics experiments to show that representatives of the AOM lineages employ distinct regulatory strategies for ammonia or urea utilization, thereby minimizing direct substrate competition. The tested AOA and comammox species preferentially used ammonia over urea, while β-AOB favoured urea utilization, repressed ammonia transport in the presence of urea and showed higher affinity for urea than for ammonia. Characterized γ-AOB co-utilized both substrates. Furthermore, these results reveal contrasting niche adaptation and coexistence patterns among the major AOM lineages.

54 ENVIRONMENTAL SCIENCES↗

Acquisition of host-derived carbon in biomass of the ectomycorrhizal fungus Pisolithus microcarpus is correlated to fungal carbon demand and plant defences

Abstract Ectomycorrhizal (ECM) fungi are key players in forest carbon (C) sequestration, receiving a substantial proportion of photosynthetic C from their forest tree hosts in exchange for plant growth-limiting soil nutrients. However, it remains unknown whether the fungus or plant controls the quantum of C in this exchange, nor what mechanisms are involved. Here, we aimed to identify physiological and genetic properties of both partners that influence ECM C transfer. Using a microcosm system, stable isotope tracing, and transcriptomics, we quantified plant-to-fungus C transfer between the host plant Eucalyptus grandis and nine isolates of the ECM fungus Pisolithus microcarpus that range in their mycorrhization potential and investigated fungal growth characteristics and plant and fungal genes that correlated with C acquisition. We found that C acquisition by P. microcarpus correlated positively with both fungal biomass production and the expression of a subset of fungal C metabolism genes. In the plant, C transfer was not positively correlated to the number of colonized root tips, but rather to the expression of defence- and stress-related genes. These findings suggest that C acquisition by ECM fungi involves individual fungal demand for C and defence responses of the host against C drain.

59 BASIC BIOLOGICAL SCIENCES↗

Alkaloids are associated with increased microbial diversity and metabolic function in poison frogs

Shifts in host-associated microbiomes can impact both host and microbes. It is of interest to understand how perturbations, like the introduction of exogenous chemicals, impact microbiomes. In poison frogs (family Dendrobatidae), the skin microbiome is exposed to alkaloids that the frogs sequester for defense. These alkaloids are antimicrobial; however, their effect on the frogs’ skin microbiome is unknown. To test this, we characterized microbial communities from field-collected dendrobatid frogs. Then, we conducted a laboratory experiment to monitor the effect of the alkaloid decahydroquinoline (DHQ) on the microbiome of two frog species with contrasting alkaloid loads in nature. In both datasets, we found that alkaloid-exposed microbiomes were more phylogenetically diverse, with an increase in diversity among rare taxa. Further, to better understand the isolate-specific response to alkaloids, we cultured microbial isolates from poison frog skin and found that many isolates exhibited enhanced growth or were not impacted by the addition of DHQ. To further explore the microbial response to alkaloids, we sequenced the metagenomes from high- and low-alkaloid frogs and observed a greater diversity of genes associated with nitrogen and carbon metabolism in high-alkaloid frogs. From these data, we hypothesized that some strains may metabolize the alkaloids. We used stable isotope tracing coupled to nanoSIMS (nanoscale secondary ion mass spectrometry), which supported the idea that some of these isolates are able to metabolize DHQ. Together, these data suggest that poison frog alkaloids open new niches for skin-associated microbes with specific adaptations, such as alkaloid metabolism, that enable survival in this environment.

59 BASIC BIOLOGICAL SCIENCES↗

Prevalent root-derived phenolics drive shifts in microbial community composition and prime decomposition in forest soil

Phenolic compounds perform various functions in soil ranging from microbial substrate to toxin and form the basis of several plant-mediated processes. The aim of this study was to investigate how phenolics commonly exuded by tree roots influence soil organic matter (SOM) decomposition and interact with other labile forms of carbon (C) abundant in root exudates. Therefore, we performed a 38-day incubation experiment and assessed whether phenolic compounds (benzoic acid, caffeic acid and catechin) facilitated or inhibited SOM decomposition in a glucose-amended forest soil. Changes in decomposition, substrate use, fungal and bacterial community composition, and microbial abundance and activity were measured over time using 13 C-stable-isotope tracing, DNA-based molecular methods and enzyme assays. Our findings showed that phenolics inhibited microbial activity and abundance to varying degrees. Yet, benzoic acid was the only compound producing a substantial priming effect leading to a 21% increase in SOM decomposition, which was amplified in glucose-amended soils. This stimulation in microbial activity was associated with an increase in β-1,4-glucosidase activity and the bacterial genera Paraburkholderia and Caballeronia of the Burkholderiaceae family. Phenolics drove microbial community shifts in glucose-amended soils with negligible interactive effects. In conclusion, phenolic priming of SOM decomposition is associated with microbial community shifts and amplified in the presence of glucose. This evidence emphasizes the need for considering phenolics and interactions among root exudates as priming mechanisms in the rhizosphere and other soil environments where aromatics and phenolic compounds are abundant.

59 BASIC BIOLOGICAL SCIENCES↗

Tracing Carbon Metabolism with Stable Isotope Metabolomics Reveals the Legacy of Diverse Carbon Sources in Soil

Tracking the metabolic activity of whole soil communities can improve our understanding of the transformation and fate of carbon in soils. For this work, we used stable isotope metabolomics to trace 13 C from nine labeled carbon sources into the water-soluble metabolite pool of an agricultural soil over time. Soil was amended with a mixture of all nine sources, with one source isotopically labeled in each treatment. We compared changes in the 13 C enrichment of metabolites with respect to carbon source and time over a 48-day incubation and contrasted differences between soluble sources (glucose, xylose, amino acids, etc.) and insoluble sources (cellulose and palmitic acid). Whole soil metabolite profiles varied singularly by time, while the composition of 13 C-labeled metabolites differed primarily by carbon source (R 2 = 0.68) rather than time (R 2 = 0.07), with source-specific differences persisting throughout incubations. The 13 C labeling of metabolites from insoluble carbon sources occurred slower than that from soluble sources but yielded a higher average atom percent (atom%) 13 C in metabolite markers of biomass (amino acids and nucleic acids). The 13 C enrichment of metabolite markers of biomass stabilized between 5 and 15 atom% 13 C by the end of incubations. Temporal patterns in the 13 C enrichment of tricarboxylic acid cycle intermediates, nucleobases (uracil and thymine), and by-products of DNA salvage (allantoin) closely tracked microbial activity. Our results demonstrate that metabolite production in soils is driven by the carbon source supplied to the community and that the fate of carbon in metabolites do not generally converge over time as a result of ongoing microbial processing and recycling.

59 BASIC BIOLOGICAL SCIENCES↗

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Blake, Geoffrey A.↗

Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components

Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

Margolis, S. V.↗

The Effects of Experimentally Induced Zircon Annealing on Melt Inclusion-Zircon Geochemistry: A Case Study of Archean Zircon From the Barberton Complex

Crystalline melt inclusions (MIs) in Archean zircons can potentially constrain the evolution of magmatic processes. However, to obtain a homogeneous glassy MI representative of the parent melt, devitrified MIs must be heated at temperatures above the liquidus. Although, it is well known that radiation damaged domains in MI-host zircon undergo temperature-time dependent annealing, the effects of annealing on zircon stable isotope and trace element compositions has received less attention. In this study, we heated multiple aliquots of low-magnetism zircons with relatively low levels of radiation damage (Deff<9.6x1014 α-events/mg) from a 3.304 Ga tonalite gneiss xenolith from the Barberton greenstone belt (sample B87-18; Kamo and Davis, 1994) in an internally-heated pressure vessel at 0.4GPa and 1000–1200°C. Zircons were imaged by SEM (CL, BSE) to determine the zoning patterns around the MIs. The radiation damage preserved in the heated and unheated zircons was determined by measuring broadening of the 3(SiO4) Raman stretching band of zircon (FWHM). Oxygen isotope ratios (δ18O), OH/O ratios, and trace and rare earth element (TREE) concentrations were measured in the zircons and MIs using SIMS. The FWHM and Raman shift of the zircon 3(SiO4) band show a systematic increase of zircon crystallinity with increasing experimental temperature. Despite increasing crystallinity, the 3(SiO4) FWHM is not correlated with δ18O(Zrn) values in the heated or unheated zircons, suggesting that δ18O was not altered by laboratory heating in these low initial radiation damage zircons. FWHM and OH/O are positively correlated in both heated and unheated zircons. The unheated zircons have the largest FWHM and OH/O (OH/OMAX=3.5×10-4) suggesting that H2O was lost during experimental heating due to the progressive annealing of radiation-damaged domains in the zircons. Zircon TREE concentrations and FWHM values are not correlated despite the presence of TREE altered domains in both the heated and unheated zircons. Our results demonstrate that pre-experimental zircon TREE concentrations and δ18O(Zrn) remain intact during laboratory heating of crystalline MIs in zircon, while secondary H2O hosted in radiation damaged domains is partially lost. Thus, MIs in low initial radiation damage Archean zircon are a potentially viable tool for constraining melt compositions.

Joseph P. Gonzalez↗

Macrofossil records of West Antarctic Ice Sheet retreat during the Holocene

Marine macrofossils in emerged beaches around Antarctica represent a geochemical framework for interpreting meltwater signatures associated with variations in the adjacent ice sheet margins during the last 10,000 years. In particular, mollusc species provide ideal experimental templates for assessing hydrochemical variations in Antarctic coastal marine environments because of their excellent preservation, high abundances, circumpolar distributions, and carbonate shells, which incorporate trace elements and stable isotopes. Modern samples of the bivalve Adamussium colbecki, which were collected across a depth gradient in the vicinity of a glacial meltwater stream in West McMurdo Sound, revealed shell trace element concentrations that were significantly higher above 10 meters because of their exposure to meltwater runoff. This meltwater signature also was reflected by the shell oxygen isotopic composition, which was in equilibrium with the ambient seawater, as demonstrated by the overlap between the predicted and actual O-(delta-18)sub w values. These modern samples provide analogs for interpreting the geochemical records in their fossils, which were based solely on molluscan fossils, complement the above geochemical data by suggesting that the rate of beach emergence fluctuated around Antarctica during the mid-Holocene. Paleoenvironmental analysis of macrofossils from emerged beaches represents a new direction in Antarctic research that can be used to assess changes in the margins of the ice sheets since the Last Glacial Maximum. The resolution of these analyses will be enhanced by collaborations that are developing with scientists who are conducting comparable studies in other coastal regions around the continent.

Berkman, Paul Arthur↗

Ecosystem consequences of a nitrogen-fixing proto-organelle

Microscale symbioses can be critical to ecosystem functions, but the mechanisms of these interactions in nature are often cryptic. Here, we use a combination of stable isotope imaging and tracing to reveal carbon (C) and nitrogen (N) exchanges among three symbiotic primary producers that fuel a salmon-bearing river food web. Bulk isotope analysis, nanoSIMS (secondary ion mass spectrometry) isotope imaging, and density centrifugation for quantitative stable isotope probing enabled quantification of organism-specific C- and N-fixation rates from the subcellular scale to the ecosystem. After winters with riverbed-scouring floods, the macroalga Cladophora glomerata uses nutrients in spring runoff to grow streamers up to 10 m long. During summer flow recession, riverine N concentrations wane and Cladophora becomes densely epiphytized by three species of Epithemia, diatoms with N-fixing endosymbionts (proto-organelles) descended from a free-living Crocosphaera cyanobacterium. Over summertime epiphyte succession on Cladophora, N-fixation rates increased as Epithemia spp. became dominant, Cladophora C-fixation declined to near zero, and Epithemia C-fixation increased. Carbon transfer to caddisflies grazing on Cladophora with high densities of Epithemia was 10-fold higher than C transfer to caddisflies grazing Cladophora with low Epithemia loads. In response to demand for N, Epithemia allocates high levels of newly fixed C to its endosymbiont. Consequently, these endosymbionts have the highest rates of C and N accumulation of any taxon in this tripartite symbiosis during the biologically productive season and can produce one of the highest areal rates of N-fixation reported in any river ecosystem.

Marks, Jane C. [Northern Arizona Univ., Flagstaff,↗

Revealing the Mysteries of Venus: The DAVINCI Mission

The Deep Atmosphere Venus Investigation of Noble gases, Chemistry, and Imaging (DAVINCI) mission described herein has been selected for flight to Venus as part of the NASA Discovery Program. DAVINCI will be the first mission to Venus to incorporate science driven flybys and an instrumented descent sphere into a unified architecture. The anticipated scientific outcome will be a new understanding of the atmosphere, surface, and evolutionary path of Venus as a possibly once-habitable planet and analog to hot terrestrial exoplanets. The primary mission design for DAVINCI as selected features a preferred launch in summer/fall 2029, two flybys in 2030, and descent sphere atmospheric entry by the end of 2031. The in situ atmospheric descent phase subsequently delivers definitive chemical and isotopic composition of the Venus atmosphere during an atmospheric transect above Alpha Regio. These in situ investigations of the atmosphere and near infrared descent imaging of the surface will complement remote flyby observations of the dynamic atmosphere, cloud deck, and surface near infrared emissivity. The overall mission yield will be at least 60 Gbits (compressed) new data about the atmosphere and near surface, as well as the first unique characterization of the deep atmosphere environment and chemistry, including trace gases, key stable isotopes, oxygen fugacity, constraints on local rock compositions, and topography of a tessera.

James B Garvin↗

Molybdenum and Tungsten isotope compositions of UO 2 fuel pellets: Implications for isotopically enriched taggants

The addition of isotopically enriched taggants to material at the front end of the nuclear fuel cycle could be a powerful tool used to assist law enforcement authorities should material outside of regulatory control be found. Two potential candidates for this purpose are molybdenum (Mo) and tungsten (W) as both elements have five or more stable isotopes and are trace elements contained within nuclear fuel. So there is a concern that Mo and W could undergo isotope fractionation during processes like uranium enrichment and to date, it is unknown if nuclear fuels have natural Mo and W isotope compositions. If Mo and W isotopic variability is present in nuclear fuels, this would hinder the use of these elements as isotopic taggants because it would be difficult to discern the original taggant isotope composition with high confidence. Therefore, a set of 16 low enriched uranium (LEU) fuel pellets from US commercial producers was analyzed using multi collector-inductively coupled plasma mass spectrometry (MC-ICPMS) to determine Mo and W isotope compositions (i.e., 94 Mo/ 92 Mo, 95 Mo/ 92 Mo, 96 Mo/ 92 Mo, 97 Mo/ 92 Mo, 98 Mo/ 92 Mo, 183 W/ 182 W, 184 W/ 182 W, and 186 W/ 182 W). Relative to terrestrial standards, LEU fuel pellets have variable Mo and W isotope compositions, thereby complicating the use of these elements as isotopically enriched taggants. As such, this work demonstrates that the isotope composition of any potential taggant must be well characterized in the base nuclear fuel prior to any taggant addition. Furthermore, these results suggest that Mo and W are not ideal candidates for isotopically enriched taggants.

58 GEOSCIENCES↗

The Frasnian-Famennian mass killing event(s), methods of identification and evaluation

The absence of an abnormally high number of earlier Devonian taxa from Famennian sediments was repeatedly documented and can hardly be questioned. Primary recognition of the event(s) was based on paleontological data, especially common macrofossils. Most paleontologists place the disappearance of these common forms at the gigas/triangularis contact and this boundary was recently proposed as the Frasnian-Famennian (F-F) boundary. Not unexpectedly, alternate F-F positions were suggested caused by temporary Frasnian survivors or sudden post-event radiations of new forms. Secondary supporting evidence for mass killing event(s) is supplied by trace element and stable isotope geochemistry but not with the same success as for the K/T boundary, probably due to additional 300 ma of tectonic and diagenetic overprinting. Another tool is microfacies analysis which is surprisingly rarely used even though it can explain geochemical anomalies or paleontological overlap not detectable by conventional macrofacies analysis. The combination of microfacies analysis and geochemistry was applied at two F-F sections in western Canada and showed how interdependent the two methods are. Additional F-F sections from western Canada, western United States, France, Germany and Australia were sampled or re-sampled and await geochemical/microfacies evaluation.

Geldsetzer, H. H. J.↗

The Chemical and Isotopic Signatures of the Hibonite-rich FUN Inclusion "HIDALGO" in Dar al Gani 027 (CO3)

Refractory Ca-Al-rich Inclusions (CAIs) with FUN (Fractionation with Unidentified Nuclear effects) characteristics are peculiar samples among all high-temperature components in chondritic meteorites. They are generally characterized by strong mass-dependent isotopic fractionations in several elements (e.g., O, Mg, Ca, Ti), large (~5-20‰) enrichments or depletions in neutron-rich isotopes (e.g., 48 Ca, 50 Ti, 54 Cr), and low inferred abundances of 26 Al ( 26 Al/ 27 Al < 1×10 −5 ). Understanding the origins of these features in FUN CAIs can shed light on the astrophysical environment and chemical processes that took place in the early Solar System. A large fraction (slightly less than 50%) of the ~20 FUN CAIs discovered so far are hibonite-rich (such as HAL, SHAL and DH-H1, collectively called HAL-type inclusions hereafter). According to their elemental and isotopic signatures and the results of evaporation experiments, HAL-type inclusions are thought to have formed as a distillation residue. However, questions regarding the timing of the formation of HAL-type inclusions (or FUN inclusions in general) relative to those of regular CAIs and the decoupling between the 26 Al abundances and nucleosynthetic anomalies remain poorly understood. In 2021, we reported the discovery of a new HAL-type inclusion, HIDALGO (Hibonite in Dar al Gani CO3) in the CO3 chondrite Dar al Gani 027 (DaG027), based on its (fractionated) oxygen isotopic compositions and low inferred 26 Al/ 27 Al ratio of (1.50±0.02)×10 −5 . Since then, more work on other short-lived and stable isotope systems and trace element abundances has been conducted. Here we report these new results and discuss the implications for the possible formation history of HIDALGO and origins of shortlived radionuclides (SLRs).

Meteorite↗

Tracing priming effects in palsa peat carbon dynamics using a stable isotope-assisted metabolomics approach

Introduction: Peatlands store up to a third of global soil carbon, and in high latitudes their litter inputs are increasing and changing in composition under climate change. Although litter significantly influences peatland carbon and nutrient dynamics by changing the overall lability of peatland organic matter, the physicochemical mechanisms of this impact—and thus its full scope—remain poorly understood. Methods: We applied multimodal metabolomics (UPLC-HRMS, 1 H NMR) paired with 13 C Stable Isotope-Assisted Metabolomics (SIAM) to track litter carbon and its potential priming effects on both existing soil organic matter and carbon gas emissions. Through this approach, we achieved molecule-specific tracking of carbon transformations at unprecedented detail. Results: Our analysis revealed several key findings about carbon dynamics in palsa peat. Microbes responded rapidly to litter addition, producing a short-term increase in CO 2 emissions, fueled nearly exclusively by transformations of litter carbon. Litter inputs significantly contributed to the organic nitrogen pool through amino acids and peptide derivatives, which served as readily accessible nutrient sources for microbial communities. We traced the fate of plant-derived polyphenols including flavonoids like rutin, finding evidence of their degradation through heterocyclic C-ring fission, while accumulation of some polyphenols suggested their role in limiting overall decomposition. The SIAM approach detected subtle molecular changes indicating minimal and transient priming activity that was undetectable through conventional gas measurements alone. This transient response was characterized by brief microbial stimulation followed by rapid return to baseline metabolism. Pre-existing peat organic matter remained relatively stable; significant priming of its consumption was not observed, nor was its structural alteration. Discussion: This suggests that while litter inputs temporarily increase CO 2 emissions, they don’t sustain long-term acceleration of stored carbon decomposition or substantially decrease peat’s carbon store capacity. Our findings demonstrate how technological advancements in analytical tools can provide a more detailed view of carbon cycling processes in complex soil systems.

54 ENVIRONMENTAL SCIENCES↗