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At least 55 records · Page 3

Stable isotopes contain substantial additive information about terrestrial carbon and water cycling

Abstract Stable isotope ratios of H ( δ 2 H ), O ( δ 18 O), and C ( δ 13 C) are linked to key biogeochemical processes of the water and carbon cycles; however, the degree to which isotope-associated processes are reflected in macroscale ecosystem flux observations remains unquantified. Here through formal information assessment, new measurements of δ 13 C of net ecosystem exchange ( NEE ) as well as δ 2 H and δ 18 O of latent heat ( LH ) fluxes across the United States National Ecological Observation Network (NEON) are used to determine conditions under which isotope measurements are informative of environmental exchanges. We find all three isotopic datasets individually contain comparable amounts of information about NEE and LH fluxes as wind speed observations. Such information from isotope measurements, however, is largely unique. Generally, δ 13 C provides more information about LH as aridity increases or mean annual precipitation decreases. δ 2 H provides more information about LH as temperatures or mean annual precipitation decreases, and also provides more information about NEE as temperatures decrease. Overall, we show that the stable isotope datasets collected by NEON contribute non-trivial amounts of new information about bulk environmental fluxes useful for interpreting biogeochemical and ecohydrological processes at landscape scales. However, the utility of this new information varies with environmental conditions at continental scales. This study provides an approach for quantifying the value adding non-traditional sensing approaches to environmental monitoring sites and the patterns identified here are expected to aid in modeling and data interpretation efforts focused on constraining carbon and water cycles’ mechanisms.

54 ENVIRONMENTAL SCIENCES↗

Triple oxygen and hydrogen stable isotope composition of water in Murchison carbonaceous chondrite accessed by thermogravimetry-enabled laser spectroscopy

For this work, we have developed the capability to measure 17 O/ 16 O in H 2 O and OH - of hydrous minerals by a technique using thermogravimetric analysis coupled with isotope ratio infrared spectroscopy (TGA-IRIS) on a suite of liquid water standards, terrestrial mineral standards, multi-mineral synthetic mixtures of terrestrial samples, and Murchison carbonaceous chondrite. This 17 O/ 16 O analytical capability is combined with the previously developed TGA-IRIS capability of 18 O/ 16 O, which enables us to calculate Δ `17 O values. Additionally, we have made 2 H/ 1 H measurements by TGA-IRIS on the suite of materials. Analyses of 328 standard water samples sealed into silver tubes (0.25 μL, 174 VSMOW and 154 GISP) analyzed over the course of three years yielded δ 18 O values by TGA-IRIS with precision of ±0.30 ‰, δ 17 O of ±0.24 ‰, Δ `17 O of ±0.126 ‰, and δ 2 H ± 7.5 ‰ (± 1 Std. Dev.). TGA-IRIS analyses of a suite of hydrous minerals (oxy-hydroxide, mica, serpentines, sulfide, phyllosillicates) yields similar precision. TGA-IRIS analyses of the CM2 carbonaceous chondrite Murchison resulted in δ 18 O, δ 17 O, Δ `17 O, and δ 2 H values of the H 2 O and/or OH - from its hydrous minerals. Δ `17 O values of Murchison H 2 O range from 1.034 ‰ at 350 °C, to -0.368 ‰ at 650 °C, to -1.75 ‰ at 850 °C. TGA-IRIS can generate Δ `17 O values of H 2 O and/or OH - in hydrous materials that are well within the precision needed for the analysis of meteoritic samples, as well as samples returned from asteroids, such as Ryugu and Bennu.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Marine Boundary Layer Decoupling and the Stable Isotopic Composition of Water Vapor

Decoupling of the subcloud layer in stratocumulus-topped marine boundary layers (STMBL) influences low-cloud cover by limiting the supply of water vapor from the surface. However, the relative importance of mixing between surface fluxes and other reservoirs of water vapor as a function of the degree of decoupling is poorly understood. Water vapor transport within the STMBL and its response to decoupling is explored using surface measurements of water vapor isotopic composition that were obtained from Graciosa Island, Azores, during the summer and fall of 2018. The data show an inverse relationship between the decoupling metric, Δq, and the degree of drying from an isotopically depleted water vapor source. The isotopic data require some degree of drying with an isotopically depleted source for coupled conditions, and likely require a small amount of mixing even for strongly decoupled conditions. The data are consistent with mixing between purely local reservoirs of water vapor, subjected to a small amount of condensation and fractionation, and do not require the invocation of large-scale transport of water vapor aloft or additional cloud-formation effects aloft.

54 ENVIRONMENTAL SCIENCES↗

Temporal Study 2022-2024: Sample-Based Surface Water Dissolved Inorganic Carbon, Dissolved Organic Carbon, Total Nitrogen, Stable Isotopes, and Total Suspended Solids from across Multiple Watersheds in the Yakima River Basin, Washington, USA

This dataset supports a broader study examining the drivers of temporal variability in sediment respiration rates in the Yakima River Basin. The dataset provides geochemistry data generated from samples collected at bi-weekly or monthly intervals at six sites across the Yakima River Basin in Washington, USA. Sample and sensor data from previous years (2021-2022) can be found at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1898912 and https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1892054, respectively. Related sensor data from 2022-2024 will be published separately. This dataset is comprised of one main data folder containing (1) file-level metadata; (2) data dictionary; (3) readme; (4) field metadata; (5) dissolved inorganic carbon (DIC) and averages; (6) dissolved organic carbon (DOC; reported as non-purgeable organic carbon; NPOC) and averages; (7) total dissolved nitrogen (TN) and averages; (8) total suspended solids (TSS); (9) stable isotopes; (10) surface water sampling protocol; (11) sensor protocol; (12) methods codes; and (13) international generic sample number (IGSN) mapping file. All files are .csv or .pdf. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. For data and scripts associated with "Shifts in rain-snow partitioning drive faster water transit times in the US Pacific Northwest" (Butler et al., 2026), go to https://data.ess-dive.lbl.gov/datasets/doi:10.15485/3025481

18-O↗

Surface Methane Concentrations Along the Mid-Atlantic Bight Driven by Aerobic Subsurface Production Rather Than Seafloor Gas Seeps

Relatively minor amounts of methane, a potent greenhouse gas, are currently emitted from the oceans to the atmosphere, but such methane emissions have been hypothesized to increase as oceans warm. Here, we investigate the source, distribution, and fate of methane released from the upper continental slope of the U.S. Mid-Atlantic Bight, where hundreds of gas seeps have been discovered between the shelf break and ~1,600 m water depth. Using physical, chemical, and isotopic analyses, we identify two main sources of methane in the water column: seafloor gas seeps and in situ aerobic methanogenesis which primarily occurs at 100–200 m depth in the water column. Stable isotopic analyses reveal that water samples collected at all depths were significantly impacted by aerobic methane oxidation, the dominant methane sink in this region, with the average fraction of methane oxidized being 50%. Due to methane oxidation in the deeper water column, below 200 m depth, surface concentrations of methane are influenced more by methane sources found near the surface (0–10 m depth) and in the subsurface (10–200 m depth), rather than seafloor emissions at greater depths.

54 ENVIRONMENTAL SCIENCES↗

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

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

58 GEOSCIENCES↗

Challenges in correlating oxygen stable isotope ratios of hydrates on uranium ore concentrates to process waters

Exchange of oxygen stable isotopes (δ 18 O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcination and reduced uranium oxide products. With this assumption, the δ 18 O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ 18 O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ 18 O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU 2 O 7 ·3H 2 O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO 2 ) 4 O 2 (OH) 5 ·5H 2 O and Na 2 (UO2) 6 O 4 (OH) 6 ·8H 2 O with a Na 2 U 2 O 7 minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ 18 O values of the water vapor yielded for two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ 18 O values. In conclusion, neither system revealed any correlation between the δ 18 O values of precipitation water, and the waters released during dehydration of the UOCs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Triple oxygen and hydrogen stable isotope composition of hydroxyl water in Orgueil (CI-type) and Tagish Lake (C2-type) carbonaceous chondrites

The primitive carbonaceous chondrites are of interest to cosmochemical science because they contain relatively large amounts of ‘water’ (H 2 O and/or OH – ) within phyllosilicate minerals. This water is evidence for the accretion of ices by their parent planetesimals, and thus represents an archive of the isotopic compositions of H 2 O in the protoplanetary environments. Here, in this study, we used thermogravimetry-enabled laser spectroscopy (TGA-IRIS) analyses of the Orgueil and Tagish Lake meteorites to make δ 2 H, δ 18 O, and Δ′ 17 O measurements of the H 2 O and OH – contained in the different hydrous minerals that comprise each meteorite. In Orgueil, we measured mass-weighted averages of OH – in the saponite and serpentine phyllosilicate matrix to be δ 2 H = 192 ‰, δ 18 O = 1.5 ‰, which are unquestionably of extraterrestrial origin with Δ′ 17 O = 1.0 ‰. For Tagish Lake, analogous values of OH– in the saponite and serpentine phyllosilicate matrix are δ 2 H = 704 ‰, δ 18 O = 11.3 ‰, and are similarly unambiguously extraterrestrial with Δ′ 17 O = 0.82 ‰. We estimate that the parent H 2 O involved in aqueous alteration of Orgueil had δ 18 O value ≥ +23 ‰. In Orgueil, we interpret the phyllosilicate petrographic relationships, and the δ 18 O values of OH – in saponite and serpentine to indicate that saponite formed first, at a lower temperature by 35 to 53 °C than serpentine. This suggests that the Orgueil parent body experienced increasing temperature during the phase of active aqueous alteration (prograde) which set the δ 18 O OH values of the serpentine and saponite. In the case of Tagish Lake, serpentine formed at a lower temperature by 32 to 60 °C than saponite, for the simplest case with constant δ 18 O H2O values. If serpentine formed first, followed by saponite formation at 32 to 60 °C °C higher temperature, this suggests that Tagish Lake sample TL1 underwent prograde aqueous alteration as the parent body heated up. We find evidence that the parent H 2 O for Orgueil, Tagish Lake sample TL1, and Murchison (based on data from a previous study) may have had Δ′ 17 O values of >0.64 ‰.

Aqueous alteration↗

Water Vapor Isotopic Composition During SAIL

Measurements of the stable isotopic composition of water vapor were collected between 21 November 2022 and 1 June 2023 at the SAIL campaign main site in Gothic Colorado. The data were obtained using a Los Gatos Research Triple Water Vapor Isotopic Analyzer from a heated and insulated inlet mounted on the roof of the guest instrument van. Standards were run periodically during the campaign and the data were corrected for humidity-dependent biases and were normalized to the VSMOW/SLAP scale. Uncertainties in dD and d18O are estimated to be 2.28 permil and 0.38 permil, respectively.

54 ENVIRONMENTAL SCIENCES↗

Effect of Groundwater Age and Recharge Source on Nitrate Concentrations in Domestic Wells in the San Joaquin Valley

Nitrate is one of the most abundant contaminants in groundwater globally, in the United States, and in California (CA). We studied well construction information, water chemistry, stable isotopes, and noble gases to understand how groundwater travel time and recharge source and mechanism control nitrate concentrations in domestic wells in the San Joaquin Valley (SJV), CA, a large semiarid, irrigated agricultural region. Using nonparametric statistics, we find a decreasing trend in nitrates with groundwater travel time and well depth. Samples collected from wells that are closer to rivers and that show indications of river water recharge, either low recharge temperature or low δ 18 O signature, have lower concentrations of nitrates than samples with isotopic signatures indicating mixed source or local precipitation recharge. The curbing effect of river water recharge on nitrate concentrations in domestic wells is similar for direct river recharge and water applied as irrigation. This suggests that irrigation with river water also has a diluting effect that reduces the concentration of nitrate found in groundwater. This conclusion supports the idea that flood-managed aquifer recharge may be considered for remediation of groundwater nitrate when designing replenishment of aquifers.

54 ENVIRONMENTAL SCIENCES↗

Environmental Controls on Water Vapor Deuterium Excess in the Coastal Boundary Layer: An Information Theory Perspective

We use information theory to quantify the environmental controls on water vapor deuterium excess (D-excess) in coastal Southern California from June 2023 through February 2024. Using Shannon entropy, mutual information (MI), and joint mutual information, metrics that capture both linear and nonlinear relationships, we identify the most informative variables and variable combinations governing D-excess across contrasting marine and continental regimes. Relative humidity with respect to sea surface temperature (RHS) is consistently the strongest individual predictor, explaining up to 27% of D-excess variability during marine conditions but only 10% in continental air masses. The Relative humidity(RHS) + sea surface temperature (SST) combination demonstrates synergistic effects, where their joint influence (explaining up to 36% of D-excess variability) exceeds what either variable achieves individually, confirming their coupled influence on deuterium excess. Wind direction complements RHS most effectively during continental conditions. The best three-variable combination (RHS + SST + Planetary Boundary Layer height) explains 38% of D-excess variability in marine air, while no combination exceeds 20% explanatory power during continental periods. Information theory shows that heteroscedasticity in D-excess relationships indicates regime shifts in controlling processes and quantifies fundamental constraints on predictor variables: some environmental factors like surface pressure or water vapor flux contain insufficient information content to explain D-excess variability regardless of their physical relevance. These results highlight the different predictability limits between marine and continental regimes, challenging the adequacy of linear models and providing a rigorous framework for quantifying the information content of isotope-climate relationships with implications for both modern and paleoclimate applications.

information theory↗

Data and script associated with “Shifts in Rain-Snow Partitioning Drive Faster Water Transit Times in the US Pacific Northwest”

This data package contains the data and code to use and run the Water Tracer enabled version of the Weather Research and Forecasting Hydrologic model (WT-WRF-Hydro) with the Sequential Precipitation Input Tagging (SPIT) framework. It is associated with the publication “Shifts in Rain-Snow Partitioning Drive Faster Water Transit Times in the US Pacific Northwest” published in Scientific Reports (Butler et al., 2026; https://doi.org/10.1038/s41598-026-46539-1). We use the Continental U.S. (CONUSII; Rasmussen et al., 2021) dataset to force the model with an historical climate (2006–2013) and a future climate (2086–2093) with a representative carbon pathway (RCP) 8.5 scenario. We use the model to calculate water transit times in five headwater catchments within the U.S. Pacific Northwest. We also show key hydrologic and environmental variables that affect water transit times and changes in the future. Finally, we use observed data to validate the model such as stream water isotopes, snowpack characteristics, and stream discharge. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. The data package consists of 11 folders: (1) "Figures" contains the exported figures used in the manuscript; (2) "Model_Isotope_Date" contains the WT-WRF-Hydro isotope date used in model validation; (3) “Model_Outputs_Future” contains the WT-WRF-Hydro future climate outputs; (4) “Model_Outputs_Historical” contains the WT-WRF-Hydro historical climate outputs; (5) “Model_Outputs_Weights_Areas” contains the WT-WRF-Hydro weights per catchment used to calculate water transit times and isotopes in stream water; (6) “MODIS_data_scripts” contains data used to validate snow conditions in the study area; (7) “Observed_Flow_Data” contains the observed streamflow data used in model validation; (8) “Observed_Isotope_Data” contains the observed stream water isotope data used in model validation; (9) “Scripts” contains the Python scripts used to general results and the figures; (10) “Statistic_Outputs” contains the water transit time statistical outputs reported in this manuscript; (11) “Validation_SNOTEL” contains the SNOTEL data used in model validation. The files in this data package have the following file extensions: .tif, .txt, .csv, .pdf, .py, .jpg, and .png.

American River↗

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

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

54 ENVIRONMENTAL SCIENCES↗

Vegetation water sources in California's Sierra Nevada (USA) are young and change over time, a multi-isotope ( δ 18 O, δ 2 H, 3 H) tracer approach.

Sierra Nevada forests transpire a significant amount of California's water resources, sparking interest in applying forest management to improve California's water supply. Determining the source water of evapotranspiration enables forest managers to make informed decisions. To this end, a significant interest in critical zone science is to develop new methods to work across time scales to predict subsurface water storage and use. Here, forest vegetation accessed young water and switched sources depending on availability, suggesting that forest drought vulnerability may depend on the range of water sources available (rain, snowmelt and deeply stored water). This finding also suggests that changes in transpiration rates may have immediate effects on water sources in close proximity to vegetation, and delayed effects on storage and runoff. New δ 18 O, δ 2 H and 3 H data were used to track precipitation, runoff, evapotranspiration and storage through the critical zone seasonally, including seasons where evapotranspiration and snowmelt were in phase (winter snowmelt) and out of phase (seasonally dry summer). The main source of this headwater catchment's runoff is derived from its meadow saturated zone water, which was dominated by snowmelt. Water that originated as snowmelt contributed to transpiration, unless other sources, such as recent rain, became available. In cases where xylem δ 18 O and δ 2 H signatures matched those of deeper saturated zone water, 3 H data showed that xylem water was distinctly younger than the deep saturated zone water. During 2016, which experienced relatively normal snowpack in winter and seasonally dry summer conditions, mean summer saturated zone water and vegetation water were similar in δ 18 O, –12.4 ± 0.04 ‰ and – 12.5 ± 0.3 ‰, respectively, but were distinctly different in 3 H, 5.5 ± 0.2 pCi/L and 13.7 ± 1.1 pCi/L, respectively. While δ 18 O shows that vegetation and meadow saturated zone water have similar origins, 3 H shows they have dissimilar ages.

58 GEOSCIENCES↗

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↗