Hydrogen Isotope Labeling of Pharmaceuticals Via Dual Hydrogen Isotope Exchange Pathways Using CdS Quantum Dot Photocatalyst
Explore the source record for details and available documents.
Maity, Rajendra↗
SEARCH · Search NASA
Results for “Isotopic”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Titanium and chromium isotopic compositions of calcium-aluminum-rich inclusions: Implications for the sources of isotopic anomalies and the formation of distinct isotopic reservoirs in the early Solar System
As the earliest-dated solids in our Solar System, calcium-aluminum-rich inclusions (CAIs) provide a record of their formation environment near the young Sun and hold clues to the formation of planetary-scale isotopic reservoirs in the solar protoplanetary disk. Although CAIs from several CV, CK, CM, CO, and ordinary chondrites have been analyzed previously for their Ti isotopic compositions, CAIs from just three CV chondrites have been analyzed for their Cr isotopic compositions, and only a handful of CAIs have been measured for both their Ti and Cr isotopic compositions. We report mass-independent Ti and Cr isotopic anomalies in several CAIs from CV and CK chondrites; this is the first report of the Cr isotopic composition of a CAI from a CK chondrite. With this data, we aim to better constrain the compositional range of CAIs in ε 50 Ti versus ε 54 Cr space, thereby facilitating the isotopic characterization of the material inherited by the solar protoplanetary disk and the role of CAIs in the formation of distinct planetary-scale isotopic reservoirs in our early Solar System. The narrow range in isotopic anomalies in CAIs when compared to other early-formed refractory inclusions such as platy hibonite crystals (PLACs) and spinel-hibonite inclusions (SHIBs) suggests that CAIs record the mixing of these precursor materials and the averaging of their larger isotopic anomalies. The isotopic composition of CAIs is therefore likely the result of a combination of factors, including mixing of material inherited from their formation region, heterogeneous carrier phase distribution, and thermal processing in the disk. The ε 50 Ti and ε 54 Cr isotopic compositions of CAIs are not correlated, further demonstrating that these isotopic anomalies have different carrier phases. The Ti and Cr isotopic compositions of CAIs additionally show that CAIs alone cannot be responsible for the compositional difference between the non-carbonaceous chondritic (NC) and carbonaceous chondritic (CC) isotopic reservoirs but nevertheless do play a role in the formation of these large-scale isotopic reservoirs in the early Solar System.
58 GEOSCIENCES↗
Experimental determinations of carbon and hydrogen isotope fractionations and methane clumped isotope compositions associated with ethane pyrolysis from 550 to 600°C
Methane clumped isotope compositions signify the relative natural abundances of rare, doubly substituted isotopic species of methane ( 13 CH 3 D and 12 CH 2 D 2 ) and have emerged as a new isotopic tool to trace the sources, sinks, and lifecycles of methane in the environment. Such measurements can identify equilibration (or reequilibration) temperatures if found to be in isotopic equilibrium or non-equilibrium processes (e.g., kinetically controlled reactions or mixing) if not in isotopic equilibrium. Naturally occurring thermogenic methane—formed by the thermally activated breakdown of larger organic molecules—has been found to have clumped isotope compositions consistent with equilibrium at reasonable gas formation temperatures in some settings and non-equilibrium processes occurring during either formation, migration, storage, or extraction in others. To explore the potential controls on the isotopic composition of thermogenic methane, we conducted isothermal time-series ethane pyrolysis experiments at 550 and 600 °C to measure methane and ethane 13 C/ 12 C and D/H fractionations and methane clumped isotope compositions (resolved 13 CH 3 D and 12 CH 2 D 2 ). We explore the effects of modifying the initial clumped isotope composition of ethane and the addition of water vapor to pyrolysis experiments. We observe that ethane and methane 13 C/ 12 C are controlled by kinetic isotope effects and Rayleigh distillation processes. In contrast, ethane and methane D/H and methane clumped isotope compositions appear to be controlled by a combination of these processes and hydrogen isotope exchange. The hydrogen isotope exchange processes lead to isotopic equilibrium as reaction completion is approached for both D/H (ethane/methane) and methane clumped isotope compositions. Here, we develop a chemical model based on a mass balance approach that accounts for inheritance vs. hydrogen-abstraction formation pathways for singly and doubly substituted isotopologues of ethane and methane that is compared to the experimental data. The model allows the determination of carbon and hydrogen kinetic isotope effects associated with ethane cracking and hydrogen abstraction reactions that, where applicable, we compare to prior theoretical constraints. From the comparison of the model to the experimental data, we infer that the kinetically controlled ethane and methane bulk isotope compositions and methane clumped isotope compositions are controlled by kinetic isotope effects (both primary and secondary) associated with both C–C bond and C–H bond cleavage reactions. Specifically, the methane clumped isotope compositions likely result from a combination of clumped isotope effects associated with ethane breakdown and/or assembly of methane isotopologues (expressed in terms of γ-factor parameters ≠ 1) and combinatorial effects that arise probabilistically. We discuss our experimental results in the context of recent pyrolysis experiments and observations of naturally occurring thermogenic methane. We consider a proposal consistent with observations from nature that the hydrogen isotope exchange reactions that promote equilibration of methane isotopic molecules at or near formation temperature may be facilitated by free radicals generated by pyrolysis reactions. In this framework, isotope exchange effectively ceases when pyrolysis effectively ceases locking in compositions that can be consistent with peak formation temperatures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Investigating Stable Oxygen and Carbon Isotopic Variability in Speleothem Records Over the Last Millennium Using Multiple Isotope-Enabled Climate Models
The incorporation of water isotopologues into the hydrology of general circulation models (GCMs) facilitates the comparison between modeled and measured proxy data in paleoclimate archives. However, the variability and drivers of measured and modeled water isotopologues, as well as the diversity of their representation in different models, are not well constrained. Improving our understanding of this variability in past and present climates will help to better constrain future climate change projections and decrease their range of uncertainty. Speleothems are a precisely datable terrestrial paleoclimate archives and provide well-preserved (semi-)continuous multivariate isotope time series in the lower latitudes and mid-latitudes and are therefore well suited to assess climate and isotope variability on decadal and longer timescales. However, the relationships of speleothem oxygen and carbon isotopes to climate variables are influenced by site-specific parameters, and their comparison to GCMs is not always straightforward. Here we compare speleothem oxygen and carbon isotopic signatures from the Speleothem Isotopes Synthesis and Analysis database version 2 (SISALv2) to the output of five different water-isotope-enabled GCMs (ECHAM5-wiso, GISS-E2-R, iCESM, iHadCM3, and isoGSM) over the last millennium (850–1850 CE). We systematically evaluate differences and commonalities between the standardized model simulation outputs. The goal is to distinguish climatic drivers of variability for modeled isotopes and compare them to those of measured isotopes. We find strong regional differences in the oxygen isotope signatures between models that can partly be attributed to differences in modeled surface temperature. At low latitudes, precipitation amount is the dominant driver for stable water isotope variability; however, at cave locations the agreement between modeled temperature variability is higher than for precipitation variability. While modeled isotopic signatures at cave locations exhibited extreme events coinciding with changes in volcanic and solar forcing, such fingerprints are not apparent in the speleothem isotopes. This may be attributed to the lower temporal resolution of speleothem records compared to the events that are to be detected. Using spectral analysis, we can show that all models underestimate decadal and longer variability compared to speleothems (albeit to varying extents). We found that no model excels in all analyzed comparisons, although some perform better than the others in either mean or variability. Therefore, we advise a multi-model approach whenever comparing proxy data to modeled data. Considering karst and cave internal processes, e.g., through isotope-enabled karst models, may alter the variability in speleothem isotopes and play an important role in determining the most appropriate model. By exploring new ways of analyzing the relationship between the oxygen and carbon isotopes, their variability, and co-variability across timescales, we provide methods that may serve as a baseline for future studies with different models using, e.g., different isotopes, different climate archives, or different time periods.
isotope-enabled simulations↗
Conclusions • Multimaterial and isotopically-labeled specimens were successfully fabricated via FFF-AM • Raman spectroscopy, atomic force microscopy, and neutron scattering show promise for direct measurements of interlayer diffusion in the multimaterial and isotopically-labeled specimens • Although isotopically-labeled specimens offer the greatest potential for experimentally verifying FFF-AM process models, substituting hydrogen with deuterium alters the thermal and rheological properties of the HDPE polymer
Multimaterial and Isotopically Labeled Specimen Fabrication via Material Extrusion Additive Manufacturing for Interlayer Diffusion Analysis
Jones, Haley W. [Savannah River National Laborator↗
Natural isotopic compositions of titanium, iron, and nickel observed in commercial fuel pellets – Promising candidate elements for stable isotope tagging
Stable isotope taggants would constitute unique identifiers for nuclear fuel cycle materials, resulting in expedited timelines and high confidence provenance assessments for nuclear forensics investigations. However, reliably identifying and interpreting stable isotope taggants in nuclear materials recovered from outside of regulatory control will largely be predicated on the assumption that the taggant element intrinsic to the untagged nuclear material exhibits natural isotopic ratios. Here, we present high-precision Ti, Fe, and Ni isotope compositions in 13 commercial low-enriched uranium (LEU) fuel pellets to assess the suitability of these transition metals as stable isotope taggants. Our investigations reveal limited isotope variations among the fuel pellets in all three elements, which are consistent with small mass-dependent isotope fractionations, comparable to variations previously reported for natural samples. In practice, isotopically tagged nuclear materials are expected to fall along isotopic mixing lines, since intrinsic background levels of taggant elements dilute the taggant towards natural isotope compositions. Furthermore, the observation that Ti, Fe, and Ni isotope compositions in a suite of LEU fuel pellets are close to or indistinguishable from estimates for the Bulk Silicate Earth demonstrates that a two end-member mixing assumption would be valid for these transition metals, indicating that all three are promising candidate elements for stable isotope tagging. Finally, we present mass balance calculations to quantify isotopic perturbations expected from admixing isotopically anomalous Ti, Fe, and Ni taggants to assess the interplay between elemental and taggant concentrations and find favorable compromises for facilitating successful taggant identification with current analytical methods.
Intentional forensics↗
Fractionation of Iron and Titanium Isotopes By Ilmenite and the Isotopic Compositions of Lunar Magma Ocean Cumulates
Basaltic volcanism on the Moon produced low- and high-Ti mare basalt suites that are also distinct with respect to their iron, titanium, and magnesium iso- topic compositions. Here, the equilibrium fractionation of Fe and Ti isotopes between ilmenite and melt was experimentally investigated in order to evaluate the role of ilmenite in generating the isotopic compositional variability among the lunar mare basalts. Ilmenite crystallization experiments were conducted using two bulk compositions: an ilmenite-saturated basaltic andesite and an ilmenite-saturated Apollo 14 black glass, and the Fe and Ti isotopic compo- sitions of the experimental ilmenites and glass (quenched melt) were analyzed using solution MC-ICPMS after hand-picking. Additionally, Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements on synthetic ilmenite were conducted and compared to previous NRIXS measurements on synthetic lunar glasses in order to derive temperature-dependent equilibrium ilmenite-melt Fe isotopic fractionations. Experimentally determined ilmenite-melt fractionations were then incorporated into a lunar magma ocean crystallization model that tracks the major element and isotopic compositional evolution of lunar magma ocean cumulates and residual liquid. There is good agreement between the Fe equilibrium isotopic fractionation measured by NRIXS and the laboratory equili- bration experiments, and we find that the isotopic fractionation is sensitive to il- menite compositional differences (0 vs. 10% Fe3+). Further, the light Ti isotopic composition of ilmenite relative to the melt (∆49Ti ilmenite-melt = −0.09 ± 0.03h at 1100°C) is consistent with the higher coordination of Ti in ilmenite relative to melts and results of previous studies. The modeled Ti isotopic compositions for lunar magma ocean cumulates display Ti isotopic variability sufficient to explain the low- and high-Ti mare basalt sources. However, the difference in Fe isotopic composition between the low- and high-Ti mare basalts cannot be attributed solely to ilmenite fractionation. Instead, Fe isotopic fractionation by additional products of lunar magma ocean crystallization, such as clinopy- roxene, is required to generate the inferred Fe and Mg isotopic variability in the lunar mantle. Alternatively, the Fe and Mg isotopic compositions of the lunar mare basalts may indicate Fe-Mg interdiffusion has occurred in the Ti- rich component of the mare basalt source regions via reaction between ilmenite cumulates and the olivine- and pyroxene-rich lunar mantle.
Kelsey Prissel↗
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↗
Chromium isotopes in an acidic fluvial system: Implications for modern and ancient Cr isotope records
Chromium is an important redox-active element, with significant Cr isotope fractionations driven by redox transformations in the natural environment and quantified through laboratory experiments. Recent work has demonstrated that non-redox-driven transformations can also produce small variations in Cr isotopes, but the role of these processes in controlling environmental Cr isotope variations remains unclear. The highly acidic but biologically diverse acid rock drainage system in Río Tinto, Spain (and affiliated rivers) provides a unique opportunity to examine how non-redox-related processes can substantially affect the isotopic composition of Cr in a natural system. Our results suggest that under conditions where Cr redox transformations are obviated, Cr cycling is largely controlled by formation of Fe-oxyhydroxides and Fe-hydroxysulfates, Cr adsorption, and Cr speciation, with little apparent Cr isotope fractionation between source materials, waters, and sediments. Moderate Cr isotope shifts, however, may be the result of non-redox processes, including adsorption to organic ligands and potentially biological uptake. These results add to a growing body of evidence for the importance of non-redox transformations in contributing to environmental Cr isotope variations, with implications for the use of chromium isotopes in studies of sedimentary Cr isotope records. In particular, this study is a validation of the potential for sulfide weathering in the Proterozoic to deliver relatively unfractionated Cr isotopes to the ocean, despite rising and sustained high oxygen levels.
54 ENVIRONMENTAL SCIENCES↗
The Zn, S, and Cl Isotope Compositions of Mare Basalts: Implications for the Effects of Eruption Style and Pressure on Volatile Element Stable Isotope Fractionation on the Moon
We compare the stable isotope compositions of Zn, S, and Cl for Apollo mare basalts to better constrain the sources and timescales of lunar volatile loss. Mare basalts have broadly elevated yet limited ranges in δ(66)Zn, δ(34)S, and δ(37)Cl_(SBC+WSC) values of 1.27 ± 0.71, 0.55 ± 0.18, and 4.1 ± 4.0‰, respectively, compared to the silicate Earth at 0.15, –1.28, and 0‰, respectively. We find that the Zn, S, and Cl isotope compositions are similar between the low- and high-Ti mare basalts, providing evidence of a geochemical signature in the mare basalt source region that is inherited from lunar formation and magma ocean crystallization. The uniformity of these compositions implies mixing following mantle overturn, as well as minimal changes associated with subsequent mare magmatism. Degassing of mare magmas and lavas did not contribute to the large variations in Zn, S, and Cl isotope compositions found in some lunar materials (i.e., 15‰ in δ(66)Zn, 60‰ in δ(34)S, and 30‰ in δ(37)Cl). This reflects magma sources that experienced minimal volatile loss due to high confining pressures that generally exceeded their equilibrium saturation pressures. Alternatively, these data indicate effective isotopic fractionation factors were near unity. Our observations of S isotope compositions in mare basalts contrast to those for picritic glasses (Saal and Hauri 2021), which vary widely in S isotope compositions from –14.0 to 1.3‰, explained by extensive degassing of picritic magmas under high-P/P_(Sat) values (>0.9) during pyroclastic eruptions. The difference in the isotope compositions of picritic glass beads and mare basalts may result from differences in effusive (mare) and explosive (picritic) eruption styles, wherein the high-gas contents necessary for magma fragmentation would result in large effective isotopic fractionation factors during degassing of picritic magmas. Additionally, in highly vesiculated basalts, the δ(34)S and δ(37)Cl values of apatite grains are higher and more variable than the corresponding bulk-rock values. The large isotopic range in the vesiculated samples is explained by late-stage low-pressure “vacuum” degassing (P/P-(Sat) ~ 0) of mare lavas wherein vesicle formation and apatite crystallization took place post-eruption. Bulk-rock mare basalts were seemingly unaffected by vacuum degassing. Degassing of mare lavas only became important in the final stages of crystallization recorded in apatite—potentially facilitated by cracks/fractures in the crystallizing flow. We conclude that samples with wide-ranging volatile element isotope compositions are likely explained by localized processes, which do not represent the bulk Moon.
Halogens↗
A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis
A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.
Boehme, Susan E.↗
Behaviour of cadmium isotopes in sulfidic waters and sediments of the Black Sea: Implications for global cadmium cycling and the application of cadmium isotopes as a paleo-oceanographic proxy
The cadmium isotope system has found use as a tracer for biological productivity, redox and organic carbon burial in the oceans. There are, however, very few observational constraints on Cd isotopic behaviour in modern sulfidic marine conditions, limiting our understanding of the modern Cd cycle, and our ability to use Cd isotope measurements of ancient sedimentary deposits as a paleoceanographic proxy. Here we study the behaviour of dissolved Cd in the water column of the Black Sea and its incorporation into sediments on the basin floor. The isotopic composition of dissolved Cd in the upper ∼50 m of the Black Sea water column is controlled by a combination of biological uptake and regeneration along with mixing of river water and Mediterranean seawater. Cadmium declines to <2 % of its peak subsurface concentration within the zone of nitrate-reduction but above the sulfide chemocline. The isotopic composition of dissolved Cd below the sulfide chemocline evolves in a manner that is consistent with experimental Cd sulfide fractionation factors, providing field-based support for these earlier studies. In contrast, the stability of the dissolved Cd isotopic signature above the chemocline, despite a large reduction in dissolved Cd concentrations, is explained by diffusion towards the Cd-sulfide sink below the chemocline. Sediments accumulating in the deep Black Sea below the sulfide chemocline have isotopic compositions that are similar to dissolved Cd in its near-surface aqueous concentration maximum. Sediments accumulating at shallower depths have lighter isotopic compositions that are likely affected by non-sulfidic burial pathways mediated by macrofaunal mixing and diagenesis of shallow burial phases. Our study shows that the isotopic composition of bulk sediments accumulating under sulfidic conditions is similar to dissolved Cd in the upper water column, supporting its use as a paleo-chemical proxy for ancient seawater as long as basin-scale controls on open ocean seawater sources are considered. We show that Cd burial in the deep Black Sea, predominantly as CdS, accounts for ∼0.5–15 % of total annual Cd burial in the global ocean.
Biogeochemical cycles↗
A Chlorine Isotope Transect Across the Sudbury Impact Deposits Reveals Enigmatic Isotopic Fractionation
Volatile elements play an important role in a variety of cosmochemical and geochemical processes. As such, there has been significant interest in their abundance and isotopic composition. Chlorine is an important element for tracing these processes because it is incompatible in nearly all minerals, extremely volatile, and strongly hydrophilic [1]. The Cl isotope composition ( 37 Cl/ 35 Cl) of meteoritic components, therefore, can provide useful information regarding the isotopic reservoirs that were present in the early Solar System and any secondary processes that may have occurred on different parent bodies (e.g., [2-4]). There is a relatively narrow range in the Cl isotope compositions of terrestrial, Martian, and chondritic meteorites (δ 37 Cl ~ −6 to +4‰) (e.g., [2,3,5,6]), with exceptions to this being the Moon and Vesta (up to ~ +81‰ and ~ +40‰, respectively) [4, 5, 7-10]. One hypothesis for the extreme Cl isotope fractionation observed on the Moon is degassing following large-scale (possibly even crust-breaching) impact events [7-9]. The role of hypervelocity impacts and impact-generated magmatism in the isotopic evolution of planetary materials, however, has been until recently an area of limited published research with the majority of works focusing on the effects of impact shock (e.g., [10-13]). The ~ 1.85 Ga Sudbury impact crater [14] located in Ontario, Canada, is one of the three largest impact craters on Earth with good exposures of its impact melt sheet and overlying breccias [15,16]. The impact melt sheet, called the Sudbury Igneous Complex (SIC), is up to 5 km thick [17], with an estimated original volume of >10 4 km 3 [18], and differentiated. Recent work demonstrated evaporative loss and isotope fractionation of the moderately volatile element zinc and suggest melt sheets produced by impacts could have a significant effect on the Earth’s volatile inventory [19]. In this study we investigate the abundance and isotopic composition of Cl as well the water abundance of apatite from the SIC and the overlying crater-fill to test the hypothesis that large-scale impacts may have generated the extensive Cl isotopic fractionation observed on the Moon.
Sudbury↗
Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets
We investigated the isotopic fractionation of CH4 and hydrogen (H2) in the stratosphere by incorporating isotope-specific rate coefficients into the Lawrence Livermore National Laboratory (LLNL) 2D model and comparing the model results with new observations from the NASA ER-2 aircraft (funded through a separate task under the Upper Atmosphere Research Program). The model results reveal that fractionation which occurs in the stratosphere has a significant influence on isotope compositions in the free troposphere, an important point which had previously been ignored, unrecognized or unquantified for many long-lived trace gases, including CH4 and H2 which we have focused our efforts on to date. Our analyses of the model results and new isotope observations have also been used to test how well the kinetic isotope effects are known, at least to within the uncertainties in model chemistry and transport. Overall, these results represent an important step forward in our understanding of isotope fractionation in the atmosphere and demonstrate that stratospheric isotope fractionation cannot be ignored in modeling studies which use isotope observations in the troposphere to infer the global budgets of CH4 (an important greenhouse gas) and of H2 (a gas whose atmospheric budget must be better quantified, particularly before a large human perturbation from fuel cell use is realized). Our analyses of model results and observations from the NASA ER-2 aircraft are briefly summarized separately below for CH4, H2, and H2O and for the contribution of these modeling studies to date to our understanding of isotope fractionation for N2O, CO2, and O3 as well.
Boering, Kristie A.↗
Cadmium isotope systematics in sedimentary carbonate: Extending the utility of the cadmium isotope palaeo-productivity proxy
The cadmium (Cd) isotope compositions of seven Holocene (<11.7 ka) carbonate sediments, including the bulk carbonate, as well as the > 140 μm (zooplankton), <63 μm and < 20 μm (phytoplankton) fractions, and individual species of foraminifera isolated from the bulk carbonate were obtained for sub-samples processed using the Cd-cleaning and Mg/Ca cleaning methods. The respective Cd isotope systematics of each carbonate archive were then compared with the Cd isotope signature within the ocean using modern seawater data. We show that a constant Cd isotope fractionation factor of -0.25 ± 0.03 ‰ (2SE, n = 4) describes the partitioning of Cd from seawater into the carbonate phase ($Δ^{114}Cd_{CdC O_3 - seawater}$), allowing for accurate reconstructions of the past seawater nutrient regime. The Cd isotope signature of the < 63 µm and < 20 µm (phytoplankton) fractions can display comparable values to those recorded in the modern surface ocean, and can be used to model the magnitude of Cd uptake and utilisation in the past ocean. Individual species of planktic and benthic foraminifera, which inhabit different depths of the water column, can provide a full surface to deep water column reconstruction of the Cd nutrient regime, while infaunal benthic foraminifera can be used to interrogate the Cd isotope systematics of sediment porewaters. Bulk sediment and the > 140 µm (zooplankton) fraction also retain important information relating to the overlying water column Cd isotope systematics and can serve as essential archives for palaeo-productivity reconstructions where the separation of individual components from the bulk sediment is not possible. This new Cd isotope palaeo-productivity toolkit can considerably aid reconstruction efforts and vastly improves the ability to quantify the role of phytoplankton in modulating carbon sequestration through transitions in Earth’s climate evolution.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Stable isotope equilibria in the dihydrogen-water-methane-ethane-propane system. Part 2: Experimental determination of hydrogen isotopic equilibrium for ethane-H2 from 30 to 200 °C and propane-H2 from 75 to 200 °C
The stable isotopic compositions of light n-alkanes, including methane, ethane, and propane, are often used to identify the sources and thermal maturity of natural gas samples. Though stable isotopic compositions of these molecules are commonly assumed to be controlled by kinetic isotope effects, recent studies have proposed both carbon and hydrogen isotopic equilibrium may also occur in some samples. Assessing whether samples are in isotopic equilibrium requires knowledge of light alkane equilibrium fractionation factors over geologically relevant temperatures for formation and storage (up to ∼300 °C). In this study, we report experimental results of hydrogen isotopic equilibrium between ethane and H2 from 30 to 200 °C and propane and H2 from 75 to 200 °C. We compare these results with high-level theoretical calculations and provide a preferred polynomial fit to describe equilibrium fractionation factors. Comparison of these fractionation factors with a compilation of ∼500 compiled environmental gas samples supports the proposal that many (∼50%) of these natural gas samples exhibit hydrogen isotopic compositions consistent with having formed in or attained methane-ethane-propane hydrogen isotopic equilibrium over geologically relevant temperatures for formation and storage (50–300 °C).
Turner, Andrew C↗
Radon Isotopes and Stable Water Isotopes from Coal Creek Watershed, Colorado (2021)
The radon isotope and stable water isotope data for Coal Creek Watershed, Colorado, consists of d2H, d18O, and 222Rn values from samples collected at 8 stream location along Coal Creek, samples from 7 groundwater springs within the watershed, and precipitation isotope samples collected by Next Generation Water Observing System (NGWOS) from a collector within the watershed. All stream and spring samples were collected between June and October, 2021, and precipitation isotope samples were collected between November 2020 and September 2021. These data were collected to evaluate how groundwater contributions to Coal Creek originating from a fractured hillslope and alluvial fan respond to summer monsoon rains and seasonal drying. Understanding of groundwater-surface water interactions in montane systems in critical for the future of water availability in the Western US as groundwater contributions are expected to become more important for sustaining summer stream flows. This data package contains: (1) a csv of all radon samples; (2) a csv of all stream and spring isotope samples; (3) a csv of precipitation isotope samples; and (4) a csv of locations for each sampling site. The dataset additionally includes a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata; and a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type.
54 ENVIRONMENTAL SCIENCES↗