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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

SPRUCE Anaerobic oxidation of methane mitigates net methane production and responds to long-term experimental warming in a northern bog: Supporting data

This data set contains measurements of anaerobic oxidation of methane (AOM), net methane (CH4) production, carbon dioxide (CO2) production, and gross CH4 production measurements from the SPRUCE experiment (Hanson et al. 2017). CH4 is greenhouse gas with 45 times the sustained global warming potential of CO2 over 100 years, which may have significant implications on global climate change. The process of AOM plays a large role in the extent of CH4 emissions from wetland environments like those at the SPRUCE experiment site. This study conducted two on different dates. In experiment 1, net CH4 and CO2 production were measured with a gas chromatograph through the peat profile at in situ temperatures of the SPRUCE plots four times from May to October, 2016 (2016-05 to 2016-10). Two treatments were examined, a Porewater Treatment that was a 1:1 volumetric peat:porewater slurry and a No Porewater Treatment that was field-moist peat with no porewater added. Additionally, net CH4 production were measured at frequent intervals (from 4 hr to 9 d) in peat from selected SPRUCE plots from soil collected on October 16, 2016 (2016-10-16). Samples were collected from the SPRUCE plots, immediately made anaerobic, and transported to the University of Oregon for rate measurements within several days of collection. In experiment 2, AOM, net CH4 production, CO2 production, and gross CH4 production were measured through the peat profile at in situ field temperatures once from samples collected in July, 2021 (2021-07). The same two porewater treatments were examined. AOM was measured with a 13CH4 tracer method using a Picarro G2201-i analyzer for isotopic CO2/CH4 quantification with a small stable isotope module attached. This data set contains three data files in comma separate (*.csv) format. This data set is associated with the following publication: Barney, M, AM Hopple, LL Gregory, JK Keller, and SD Bridgham. 2024. Anaerobic oxidation of methane mitigates net methane production and responds to long-term experimental warming in a northern bog. Soil Biology and Biochemistry, 190, 109316. https://doi.org/10.1016/j.soilbio.2024.109316.

SPRUCE Experiment, Marcell Experimental Forest, Me↗
DOE OSTI2021

Organic contamination detection for isotopic analysis of water by laser spectroscopy

Hydrogen and oxygen stable isotope ratios (δ 2 H, δ 17 O, and δ 18 O values) are commonly used tracers of water. These ratios can be measured by isotope ratio infrared spectroscopy (IRIS). However, IRIS approaches are prone to errors induced by organic compounds present in plant, soil, and natural water samples. A novel approach using 17 O-excess values has shown promise for flagging spectrally contaminated plant samples during IRIS analysis. A systematic assessment of this flagging system is needed to prove it useful. Errors induced by methanol and ethanol water mixtures on measured IRIS and isotope ratio mass spectrometry (IRMS) results were evaluated. For IRIS analyses both liquid- and vapour-mode (via direct vapour equilibration) methods are used. The δ 2 H, δ 17 O, and δ 18 O values were measured and compared with known reference values to determine the errors induced by methanol and ethanol contamination. In addition, the 17 O-excess contamination detection approach was tested. This is a post-processing detection tool for both liquid and vapour IRIS triple-isotope analyses, utilizing calculated 17 O-excess values to flag contaminated samples. Organic contamination induced significant errors in IRIS results, not seen in IRMS results. Methanol caused larger errors than ethanol. Results from vapour-IRIS analyses had larger errors than those from liquid-IRIS analyses. The 17 O-excess approach identified methanol driven error in liquid- and vapour-mode IRIS samples at levels where isotope results became unacceptably erroneous. For ethanol contaminated samples, a mix of erroneous and correct flagging occurred with the 17 O-excess method. Here our results indicate that methanol is the more problematic contaminant for data corruption. The 17 O-excess method was therefore useful for data quality control. Organic contamination caused significant errors in IRIS stable isotope results. These errors were larger during vapour analyses than during liquid IRIS analyses, and larger for methanol than ethanol contamination. The 17 O-excess method is highly sensitive for detecting narrowband (methanol) contamination error in vapour and liquid analysis modes in IRIS.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Stable water isotopes and tritium data from porewater at Elkhorn Slough

Salt marshes are dynamic hydrologic systems where terrestrial groundwater, terrestrial surface water, and seawater mix due to bi-directional flows and pressure gradients. Due to the counteracting terrestrial and marine forcings that control these environments, we do not comprehensively understand water fluxes in these complex coastal systems. To understand the water sources, flow directions, and velocities in salt marsh porewater, we collected geochemical tracers across a hillslope-to-salt marsh continuum in a salt marsh experiencing daily inundation of estuarine surface water (SW) from tides and mixing of fresh seasonal groundwater. The experimental transect is located at the Elkhorn Slough National Estuarine Research Reserve.Here we present a data table (.csv) with the results of electrical conductivity, stable water isotopes, and tritium in porewater across several elevations in the hillslope-to-salt marsh continuum (information in the data set). We analyzed the stable water isotope samples by cavity ring-down spectroscopy in a Picarro L2130-i at the University of California Santa Cruz (accuracy of 0.025‰ and 0.1‰ for δ18O and δ2H, respectively). We measured the electric conductivity of the samples with an Orion Star™ A329 multiparameter meter (0.5% accuracy, Thermo Fisher Scientific, Massachusetts, USA). We analyzed 3H samples at Lawrence Livermore National Laboratory by helium-3 accumulation (Clarke et al., 1976; Surano et al., 1992).

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2010

Stable Chlorine Isotope Study: Application to Early Solar System Materials

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Mala,ira. M/↗
DOE OSTI2025

Using stable isotopes in water vapor to study the interdependence of clouds, atmospheric aerosols, and precipitation processes

This project deployed water vapor isotope measurements at the La Porte, Texas TRACER site during June-September 2022 to quantify mixing processes in sea breeze circulations. Using a Picarro L2130 analyzer, we collected high-frequency measurements of δD and δ¹⁸O that revealed how marine and terrestrial air masses mix during 46 identified sea breeze events. The isotopic tracers showed systematic changes during frontal passages, with composite analyses demonstrating vertical mixing between cool marine air and warmer air aloft. We developed a transilient matrix model that explicitly treats non-local mixing and isotopic fractionation to interpret the observations. The work directly supports TRACER's core objective of understanding convective initiation by constraining the vertical transport of water vapor and its interaction with Houston's aerosol-laden urban plume during sea breeze-convection coupling.

58 GEOSCIENCES↗
DOE OSTI2025

TRACER-iso Field Campaign Report

The TRACER-iso project took place from June 1 to September 30, 2022, as part of the intensive operational period (IOP) of the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility’s TRacking Aerosol Convection interactions ExpeRiment (TRACER) at the main project site at the La Porte, Texas, municipal airport. The project sought to use measurements of the stable isotopic composition of water vapor to better understand cloud-aerosol interactions in deep convection in a polluted urban setting.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Single-cell stable isotope probing in microbial ecology

Abstract Environmental and host-associated microbiomes are typically diverse assemblages of organisms performing myriad activities and engaging in a network of interactions that play out in spatially structured contexts. As the sum of these activities and interactions give rise to overall microbiome function, with important consequences for environmental processes and human health, elucidating specific microbial activities within complex communities is a pressing challenge. Single-cell stable isotope probing (SC-SIP) encompasses multiple techniques that typically utilize Raman microspectroscopy or nanoscale secondary ion mass spectrometry (NanoSIMS) to enable spatially resolved tracking of isotope tracers in cells, cellular components, and metabolites. SC-SIP techniques are uniquely suited for illuminating single-cell activities in microbial communities and for testing hypotheses about cellular functions generated for example from meta-omics datasets. Here, we illustrate the insights enabled by SC-SIP techniques by reviewing selected applications in microbiology and offer a perspective on their potential for future research.

Alcolombri, Uria (ORCID:0000000335615091)↗
DOE OSTI2021

Origin of water masses in Floridan Aquifer System revealed by 81 Kr

Groundwater in coastal aquifers serves as an essential resource in densely populated areas throughout the world. However, hydrological connection to the ocean leaves it at risk of salinization via changes in climate and hydrological cycles. Therefore, an accurate hydrological characterization of coastal aquifers is of the utmost importance. Although localized salinization of shallow aquifers has commonly been studied, geochemical constraints on the time scale of regional freshwater and seawater in coastal aquifers are limited especially in carbonate aquifers. Such information is not only crucial for water resource management, but also for understanding solute flux over the land-ocean boundary and for interpreting the geochemical signatures that each water mass carries. Toward this goal, we report tracer-based, subsurface residence times of groundwater in the Floridan Aquifer System in southern Florida, which is one of the most productive aquifers on Earth. The first application of Kr 81-an emerging tracer of old groundwater-to this aquifer has identified freshwater recharge during the last glacial period as anticipated from previous studies using other geochemical tools including radiocarbon, stable isotopes and noble gas concentrations. Moreover, freshwater of Holocene age was also detected at 100 km-distance from the recharge area, suggesting the possibility of an active flow system in the upgradient region. A contribution of fossil seawater that predates the last glacial maximum was locally identified, suggesting slow seawater circulation and limited but significant solute flux from the ocean into the aquifer for dolomitization. This also implies that the deep saline coastal groundwater can potentially serve as a paleo-seawater archive.

58 GEOSCIENCES↗
DOE OSTI2024

Deep desert aquifers as an archive for Mid- to Late Pleistocene hydroclimate: An example from the southeastern Mediterranean

Many efforts have been made to illuminate the nature of past hydroclimates in semi-arid and arid regions, where current and future shifts in water availability have enormous consequences on human subsistence. Deep desert aquifers, where groundwater is stored for prolonged periods, might serve as a direct record of major paleo-recharge events. To date, groundwater-based paleoclimate reconstructions have mainly focused on a relatively narrow timescale (up to ∼40 kyr), limited by the relatively short half-life of the widely used radiocarbon (5.73 kyr). Here we demonstrate the usage of deep regional aquifers in the arid southeastern Mediterranean as a hydroclimate archive for earlier Mid-to-Late Pleistocene epochs. State-of-the-art dating tools, primarily the 81 Kr radioisotope (t 1/2 = 229 kyr), were combined with other atmosphere-derived tracers to illuminate the impact of four distinguishable wetter episodes over the past 400 kyr, with differences in climatic conditions and paleo-recharge locations. Variations in stable water isotope composition suggest moisture transport from more proximal (Mediterranean) and distal (Atlantic) sources to different parts of the region at distinct times. Large variability in the computed noble gas-based recharge temperature (NGT), ranging ~15–30 °C, cannot be explained by climate variations solely, and points to different recharge pathways, including geothermal heating in the deep unsaturated zone and recharge from high-elevation (colder) regions. The obtained groundwater record complements and enhances the interpretation of other terrestrial archives in the arid region, including a contribution of valuable information regarding the moisture source origin as reflected in the deuterium-excess values, which is unattainable from the common practice analysis of calcitic cave deposits. We conclude that similar applications in other deep (hundred-m-order) regional groundwater systems (e.g., the Sahara desert aquifers) can significantly advance our understanding of long-term (up to 1 Myr) paleo-hydroclimate in arid regions, including places where no terrestrial remnants, such as cave, lake, and spring sediments, are available.

Atom Trap Trace Analysis↗
DOE OSTI2024

New insights into the flow dynamics of a deep freshwater aquifer in the semi-arid and saline Cuvelai-Etosha Basin, Northern Namibia: Results of a multi-environmental tracer study

Study region A paleo-megafan system of the Cubango River in the northern parts of the semi-arid Cuvelai-Etosha Basin, shared by Angola and Namibia. It hosts a deep freshwater aquifer, the so-called Kalahari-Ohangwena 2 (KOH-2), with the potential to resolve the imminent regional water supply shortages. Study focus Hydrogeochemical and multi-environmental tracer studies incorporating the use of age tracers 14 C, 36 Cl, 81 Kr and 4 He to determine the age of groundwater and provide insights into the flow dynamics of the KOH-2. New hydrological insights for the region Stable water isotopes and noble gas thermometry show that in a period with higher rainfall and recharge, temperatures were at least 3 – 4 °C lower than today. Several arguments led to the conclusion that younger groundwater, possibly of an age of 35,000 years, is mixed with ancient saline pore water. These include: 1) the correlation of measured 36 Cl and 81 Kr ratios, as well as 4 He concentrations, using a binary mixing model, and 2) the substantial variation in 81 Kr ages, ranging from 40,000 to 170,000 years, over relatively short distances—a phenomenon challenging to explain by advective groundwater flow equations. Consequently, the ages derived from 81 Kr measurements serve as indicators of the extent of freshening and therefore describe mixing ages rather than absolute travel times.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Capillary absorption spectroscopy for high temporal resolution measurements of stable carbon isotopes in soil and plant-based systems

Capillary Absorption Spectroscopy (CAS) is a relatively new analytical technique for performing stable isotope analysis. Here, we demonstrate the utility of CAS by recording and quantifying variation in 13C in controlled and biologically relevant applications. We calibrated CAS system response to increased 13CO2, with an observed ~4‰ increase in measured Δ13C for each 0.03 ppm shift in 13CO2 concentration. We leveraged this calibration to quantify rates of biogeochemical processes using a 13C tracer. For example, we monitored microbial respiration of 13C-glucose within an agricultural soil at 10 s quantification intervals and results demonstrated 8.6% ± 0.4 of added glucose was converted to 13CO2 within 1.5 h of incubation. We expanded the demonstration by adapting a rhizobox to permit continuous monitoring of 13CO2 in a soil (as distinct from plant) headspace to track the timing and quantify respiration rates of fresh plant photosynthate and observed a 3.5 h delay between plant exposure to a13CO2 tracer and the first signs of respiration by soil biota. These experiments highlight CAS is effective in producing high temporal resolution quantification of 13CO2 and demonstrate potential applications.

13CO2↗
DOE OSTI2020

Catchment storage and residence time in a periodically irrigated watershed

Understanding anthropogenic impacts on water storage and water flow pathways in catchments is an ongoing challenge in hydrology. Here, we study the dynamics of subsurface storage and residence time of water in a catchment in Berkeley, California, that is within a regional park but contains diverse land use within its perimeter, including a periodically irrigated golf course. Our study combines several isotopic tracers with water budget data to examine sources of water in a stream draining the site. Irrigation water, applied to a small area of the watershed, is a minor component of the water budget. However, geochemical tracers reveal that irrigation water is a significant fraction of stream flow downstream of the golf course during baseflow and during precipitation events. Isotopic tracers indicate that the watershed has a preference to release young water for stream flow generation, resulting in contrasting tritium ages for stream water and groundwater of 1.3 ± 0.5 year and 8.2 ± 1.7 year, respectively. We determined that the older water is a very small component (0.7%) of the stream water in the tail of an assumed exponential distribution. We used the seasonal variation of stable water isotopes in precipitation and stream water over two water years to explain the damping of the isotopic signature of stream water, which yields information about the catchment's response to the input signal. In conclusion, the methods described here may be applicable to other urban or suburban headwater catchments in areas with a component of non-natural recharge from, for example, leaky infrastructure, storm water routing or dry season irrigation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Understanding long-term groundwater flow at Pahute Mesa and vicinity, Nevada National Security Site, USA, from naturally occurring geochemical and isotopic tracers

Abstract Recently collected naturally occurring geochemical and isotopic groundwater tracers were combined with historic data from the Pahute Mesa area of the Nevada National Security Site (NNSS), Nevada, USA, to provide insights into long-term regional groundwater flow patterns, mixing and recharge. Pahute Mesa was the site of 85 nuclear detonations between 1965 and 1992, many of them deeply buried devices that introduced radionuclides directly into groundwater. The dataset examined included major ions and field measurements, stable isotopes of hydrogen (δ 2 H), oxygen (δ 18 O), carbon (δ 13 C) and sulfur (δ 34 S), and radioisotopes of carbon ( 14 C) and chloride ( 36 Cl). Analysis of the patterns of groundwater 14 C data and the δ 2 H and δ 18 O signatures indicates that groundwater recharge is predominantly of Pleistocene age, except for a few localized areas near major ephemeral drainages. Steep gradients in sulfate (SO 4 ) and chloride (Cl) define a region near the western edge of the NNSS where high-concentration groundwater flowing south from north of the NNSS merges with dilute groundwater flowing west from eastern Pahute Mesa in a mixing zone that coincides with a groundwater trough associated with major faults. The 36 Cl/Cl and δ 34 S data suggest that the source of the high Cl and SO 4 in the groundwater was a now-dry, pluvial-age playa lake north of the NNSS. Patterns of groundwater flow indicated by the combined data sets show that groundwater is flowing around the northwest margin of the now extinct Timber Mountain Caldera Complex toward regional discharge areas in Oasis Valley.

58 GEOSCIENCES↗
DOE OSTI2020

A Comparison of Groundwater Sampling Technologies, Including Passive Diffusion Sampling, for Radionuclide Contamination - 20205

Using traditional high-flow purge methods for long-term water quality monitoring of deep groundwater wells can be expensive, affect contaminant migration, and produce excessive volumes of discharge water that can be difficult to manage. The use of low-flow pumping methods and depth discrete bailers (DDBs) can reduce the cost of sampling deep groundwater wells. In general, using different pumping methods to obtain reproducible and representative groundwater can be challenging. Passive diffusion samplers (PDSs) have successfully been used in long-term monitoring for volatile organic compounds, major ions, and trace-elements, but application has been limited for stable and radioactive isotopes. Beginning in 2018, the United States Geological Survey (USGS) conducted three sampling events to test the ability of PDSs and DDBs to obtain reproducible and representative groundwater samples. The sampled well is completed in a regional, permeable carbonate aquifer and is one in a set of wells that have historically been used for tritium tracer testing. All samples were obtained at 180 m (590 ft) below land surface (bls) in a 13.97 cm (5.5 inch) uncased well that has a total depth of 202 m (662 ft) bls. The first sampling event deployed a regenerated cellulose dialysis membrane (RCDM) PDS for 14 days with deionized water as the blank. The second sampling event deployed a RCDM for 27 days also with deionized water as the blank. The third sampling event deployed a Dual Membrane (DM) PDS for 65 days using a blank of tritium-dead carbonate water. The DM PDS was used to assess the effect of longer term deployment on tritium concentrations and address whether or not the PDSs reached equilibrium with ambient groundwater. The day after each of the three passive samplers were retrieved a DDB was used to obtain discrete non-integrated groundwater samples. For each DDB sampling day, the bailer was lowered into the well 10 consecutive times to determine if the water chemistry changed from the first to the last bailed sample. Quality assurance samples including blanks and duplicates were obtained during all three sampling events. All blank waters had tritium concentrations less than 21±33 pCi/L. Major ion (e.g. calcium, chloride, sodium, and sulfate) results were compared between all samples obtained with RCDM and DDB. Major ion concentrations showed a coefficient of variation of less than 6% between all RCDM and DDB samples; however, the coefficient of variation between the different deployment times and the two different methods for trace-element concentrations was much larger, particularly for manganese (82%), lead (41%), and zinc (33%). Stable isotope values were compared between the RCDM and DDB samples. The DDB sample results all fell within analytical uncertainty and were considered representative of the formation groundwater. The stable isotope values from the RCDM samples indicated that a longer deployment time was necessary to gain equilibrium and to obtain representative groundwater samples. Tritium results from groundwater samples obtained from the RCDM, DM, and DDB indicate that groundwaters obtained with PDSs produced tritium concentrations 2 to 3 times higher (between 1,426 and 3,060±87 pCi/L) than groundwaters obtained with a DDB (479 to 1,219±51 pCi/L). The longer the passive diffusion samplers were deployed, the higher the tritium concentration, suggesting that equilibrium with tritium was not reached within a 27-day deployment. DDB samples showed tritium results declining from the first to the last bailed sample for all three sampling events. This research suggests that tritium results from groundwater samples obtained from PDSs are more reproducible than samples obtained from DDBs. Also, PDSs likely do not accumulate isotopes of water but rather equilibrate with the ambient groundwater. On the other hand, both PDSs and DDBs were able to provide representative groundwater samples for major ions and have the potential to produce representative groundwater samples for stable isotopes of water (δD and δ{sup 18}O). Utilizing the most effective method for sampling groundwater is important for long-term groundwater monitoring. Quantifying the ability of passive diffusion groundwater samplers to obtain representative radioactive chemistry samples will help determine if these methods can be a useful alternative to pumping and purging wells for long-term monitoring. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1997

Validity of the Temperature Reconstruction from Water Isotopes in Ice Cores

Well-documented present-day distributions of stable water isotopes (HDO and others) show the existence, in middle and high latitudes, of a linear relationship between the mean annual isotope content of precipitation (SD and 51"0) and the mean annual temperature at the precipitation site. Paleoclimatologists have used this relationship, which is particularly well obeyed over Greenland and Antarctica, to infer paleotemperatures from ice core data. There is, however, growing evidence that spatial and temporal isotope/ surface temperature slopes differ, thus complicating the use of stable water isotopes as paleothermometers. In this paper we review empirical estimates of temporal slopes in polar regions and relevant information that can be inferred from isotope models: simple, Rayleigh-type distillation models and (particularly over Greenland) general circulation models (GCMS) fitted with isotope tracer diagnostics. Empirical estimates of temporal slopes appear consistently lower than present-day spatial slopes and are dependent on the timescale considered. This difference is most probably due to changes in the evaporative origins of moisture, changes in the seasonality of the precipitation, changes in the strength of the inversion layer, or some combination of these changes. Isotope models have not yet been used to evaluate the relative influences of these different factors. The apparent disagreement in the temporal and spatial slopes clearly makes calibrating the isotope paleothermometer difficult. Nevertheless, the use of a (calibrated) isotope paleothermometer appears justified; empirical estimates and most (though not all) GCM results support the practice of interpreting ice core isotope records in terms of local temperature changes.

Jouzel, J.↗
DOE OSTI2024

Separation of Lipoproteins for Quantitative Analysis of 14 C-Labeled Lipid-Soluble Compounds by Accelerator Mass Spectrometry

To date, 14 C tracer studies using accelerator mass spectrometry (AMS) have not yet resolved lipid-soluble analytes into individual lipoprotein density subclasses. The objective of this work was to develop a reliable method for lipoprotein separation and quantitative recovery for biokinetic modeling purposes. The novel method developed provides the means for use of small volumes (10–200 µL) of frozen plasma as a starting material for continuous isopycnic lipoprotein separation within a carbon- and pH-stable analyte matrix, which, following post-separation fraction clean up, created samples suitable for highly accurate 14 C/ 12 C isotope ratio determinations by AMS. Manual aspiration achieved 99.2 ± 0.41% recovery of [5- 14 CH 3 ]-(2R, 4'R, 8'R)-α-tocopherol contained within 25 µL plasma recovered in triacylglycerol rich lipoproteins (TRL = Chylomicrons + VLDL), LDL, HDL, and infranatant (INF) from each of 10 different sampling times for one male and one female subject, n = 20 total samples. Small sample volumes of previously frozen plasma and high analyte recoveries make this an attractive method for AMS studies using newer, smaller footprint AMS equipment to develop genuine tracer analyses of lipophilic nutrients or compounds in all human age ranges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

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↗
DOE OSTI2024

Biomolecular budget of persistent, microbial-derived soil organic carbon: The importance of underexplored pools

The details of how soil microorganisms contribute to stable soil organic carbon pools are a pressing knowledge gap with direct implications for soil health and climate mitigation. It is now recognized that microbial necromass contributes substantially to the formation of stable soil carbon. However, the quantification of necromass in soils has largely been limited to model molecules such as aminosugar biomarkers. The abundance and chemical composition of other persistent microbial residues remain unresolved, particularly concerning how these pools may vary with microbial community structure, soil texture, and management practices. We use yearlong soil incubation experiments with an isotopic tracer to quantify the composition of persistent residues derived from microbial communities inhabiting sand or silt dominated soil with annual (corn) or perennial (switchgrass) monocultures. Persistent microbial residues were recovered in diverse soil biomolecular pools including metabolites, proteins, lipids, and mineral-associated organic matter (MAOM). The relative abundances of microbial contributions to necromass pools were consistent across cropping systems and soil textures. The greatest residue accumulation was not recovered in MAOM but in the light density fraction of soil debris that persisted after extraction by chemical fractionation using organic solvents. Necromass abundance was positively correlated with microbial biomass abundance and revealed a possible role of cell wall morphology in enhancing microbial carbon persistence; while gram-negative bacteria accounted for the greatest contribution to microbial-derived carbon by mass at one year, residues from gram-positive Actinobacteria and Firmicutes showed greater durability. Together these results offer a quantitative assessment of the relative importance of diverse molecular classes for generating durable soil carbon.

54 ENVIRONMENTAL SCIENCES↗