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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO 4 - ) has synthetic and natural sources. Synthetic ClO 4 - is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO 4 - in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO 4 - that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine ( 37 Cl/ 35 Cl) and oxygen ( 18 O/ 16 O, 17 O/ 16 O) and the isotopic abundance of radioactive 36 Cl in ClO 4 - can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO 4 - collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. We report isotopic data indicate that indigenous natural ClO 4 - was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO 4 - was present in the three remaining wells with natural ClO 4 - , and a minor fraction of Atacama-fertilizer-derived ClO4- was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO 4 - has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO 4 - in groundwater by flushing accumulated salts from the unsaturated zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Arctic Permafrost Thawing Enhances Sulfide Oxidation

Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw-induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO 2 ) is relatively unconstrained. Resolving this uncertainty is important as thaw-driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean-atmosphere system and increase pCO 2 , producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate (SO 4 2- ) sulfur ( 34 S/ 32 S) and oxygen ( 18 O/ 16 O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact on pCO 2 . Calculations found that approximately 80% of SO 4 2- in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover, 34 S/ 32 S ratios, 13 C/ 12 C ratios of dissolved IC, and sulfur X-ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values of pCO 2 over timescales shorter than carbonate compensation (~10 4 yr) and, for mainstem samples, higher values of pCO 2 over timescales longer than carbonate compensation but shorter than the residence time of marine (~10 7 yr). Furthermore, the absolute concentrations of and Mg 2+ in the Koyukuk River, as well as the ratios of SO 4 2- and Mg 2+ to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale-dependent feedback on warming.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Adsorption separation of heavier isotope gases in subnanometer carbon pores

Isotopes of heavier gases including carbon ( 13 C/ 14 C), nitrogen ( 13 N), and oxygen ( 18 O) are highly important because they can be substituted for naturally occurring atoms without significantly perturbing the biochemical properties of the radiolabelled parent molecules. These labelled molecules are employed in clinical radiopharmaceuticals, in studies of brain disease and as imaging probes for advanced medical imaging techniques such as positron-emission tomography (PET). Established distillation-based isotope gas separation methods have a separation factor ( S ) below 1.05 and incur very high operating costs due to high energy consumption and long processing times, highlighting the need for new separation technologies. Here, we show a rapid and highly selective adsorption-based separation of 18 O 2 from 16 O 2 with S above 60 using nanoporous adsorbents operating near the boiling point of methane (112 K), which is accessible through cryogenic liquefied-natural-gas technology. A collective-nuclear-quantum effect difference between the ordered 18 O 2 and 16 O 2 molecular assemblies confined in subnanometer pores can explain the observed equilibrium separation and is applicable to other isotopic gases.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass

Grindelia squarrosa (curlycup gumweed) biomass possesses unique biochemistry, cell wall composition, and leaf architecture tailored for prolific growth in arid and semiarid climates. Most notably, this plant has developed high levels of extractable resins that have high effective H/C eff ratios ((mol H - 2 x mol O)/mol C), which is hypothesized to lead to low coke formation during catalytic fast pyrolysis (CFP) over the ZSM-5 catalyst. In microscale experiments with high ZSM-5 loadings (biomass-to-catalyst mass ratio (B/C) ~ 0.1), in situ CFP generated high yields of aromatic hydrocarbons (30% carbon yield) while ex situ CFP favored aliphatic hydrocarbons (25% carbon yield). The difference between the two configurations was attributed to the constant catalyst temperature during ex situ CFP. Deactivation leading to partially deoxygenated vapor products occurred rapidly until B/C ≤ 0.5 by the adsorption of organic species blocking access to acid sites inside the micropores of the catalyst. This was followed by more gradual deactivation leading to primary vapor breakthrough, which we attribute to coke formation on acid sites on the external surface of ZSM-5 crystallites. Noncatalytic fast pyrolysis of Grindelia in a bench scale reactor produced oils with oxygen content (18 wt % on dry basis) and carbon yield (33%) comparable to those of CFP of woody biomass. The CFP of Grindelia further reduced the oxygen content to 7 wt % for in situ CFP and 4 wt % for ex situ CFP at B/C of 2-3. The good deoxygenation was attributed to a combination of a high H/C eff ratio and overall better quality of the pyrolysis vapors that were passed over the ZSM-5 catalyst. The high inorganic content of the Grindelia likely catalyzed pyrolysis to remove oxygenated coke precursors. This integrated CFP study demonstrated that Grindelia could be an important feedstock for generating stabilized noncatalytic and CFP oils for downstream processing into fuels and/or extraction of high-value chemicals. The preprocessing of this feedstock will be required to remove inorganics, which cause an irreversible deactivation of ZSM-5.

BIOMASS FUELS↗
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↗
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 OSTI2022

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

For this work, hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ~50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ~100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca 2+ , Mg 2+ , Na + , Sr2 + , Fe, Mn, Cl – , Br – ) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time. Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87 Sr/ 86 Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO 4 2– fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site. Water oxygen (δ 18 O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ 18 O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ 37 Cl in the FP fluids varied from ~ –0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ 37 Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition. Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO 4 2– in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Terrestrial photosynthesis inferred from plant carbonyl sulfide uptake

Terrestrial photosynthesis, or gross primary production (GPP), is the largest carbon flux in the biosphere, but its global magnitude and spatiotemporal dynamics remain uncertain. The global annual mean GPP is historically thought to be around 120 PgC yr −1 , which is about 30–50 PgC yr −1 lower than GPP inferred from the oxygen-18 ( 18 O) isotope and soil respiration. This disparity is a source of uncertainty in predicting climate–carbon cycle feedbacks. Here, in this study, we infer GPP from carbonyl sulfide, an innovative tracer for CO 2 diffusion from ambient air to leaf chloroplasts through stomata and mesophyll layers. We demonstrate that explicitly representing mesophyll diffusion is important for accurately quantifying the spatiotemporal dynamics of carbonyl sulfide uptake by plants. From the estimate of carbonyl sulfide uptake by plants, we infer a global contemporary GPP of 157 (±8.5) PgC yr −1 , which is consistent with estimates from 18 O (150–175 PgC yr −1 ) and soil respiration ($149^{+29}_{-23}$) PgC yr −1 ), but with an improved confidence level. Our global GPP is higher than satellite optical observation-driven estimates (120–140 PgC yr –1 ) that are used for Earth system model benchmarking. This difference predominantly occurs in the pan-tropical rainforests and is corroborated by ground measurements, suggesting a more productive tropics than satellite-based GPP products indicated. As GPP is a primary determinant of terrestrial carbon sinks and may shape climate trajectories, our findings lay a physiological foundation on which the understanding and prediction of carbon–climate feedbacks can be advanced.

Lai, Jiameng↗
DOE OSTI2022

Galápagos tortoise stable isotope ecology and the 1850s Floreana Island Chelonoidis niger niger extinction

A consequence of over 400 years of human exploitation of Galápagos tortoises (Chelonoidis niger ssp.) is the extinction of several subspecies and the decimation of others. As humans captured, killed, and/or removed tortoises for food, oil, museums, and zoos, they also colonized the archipelago resulting in the introduction of invasive plants, animals, and manipulated landscapes for farming, ranching, and infrastructure. Given current conservation and revitalization efforts for tortoises and their habitats, here we investigate nineteenth and twentieth century Galápagos tortoise dietary ecology using museum and archaeological specimens coupled with analysis of carbon (δ 13 C collagen and δ 13 Capatite), nitrogen (δ 15 N), hydrogen (δD) and oxygen (δ 18 O apatite ) stable isotopes and radiocarbon dating. We identify that Galápagos tortoise diets vary between and within islands over time, and that long-term anthropogenic impacts influenced change in tortoise stable isotope ecology by using 57 individual tortoises from 10 different subspecies collected between 1833 and 1967—a 134-year period. On lower elevation islands, which are often hotter and drier, tortoises tend to consume more C 4 vegetation (cacti and grasses). Our research suggests human exploitation of tortoises and anthropogenic impacts on vegetation contributed to the extinction of the Floreana Island tortoise (C. n. niger) in the 1850s.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

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↗
DOE OSTI2023

Temperature-dependent oxygen isotope fractionation in otoliths of juvenile Chinook salmon ( Oncorhynchus tshawytscha )

Oxygen thermometry has become a widely used technique for reconstructing thermal history in calcifying organisms but interpretation can be subject to predictive error from vital effects. To better understand these processes in Chinook salmon (Oncorhynchus tshawytscha) we experimentally constructed a temperature-dependent, otolith–water fractionation relationship for oxygen isotopes (δ 18 O) by rearing post-yolk absorptive juvenile fish at nominal temperatures from 6 to 21 °C. Temperature and otolith precipitation rate had significant effects on the otolith–water δ 18 O fractionation, but somatic growth rate did not. The slope of the δ 18 O fractionation equation also differed significantly from that of synthetic aragonite. Furthermore, our results suggest the expression of kinetic effects on δ 18 O fractionation in otoliths of Chinook salmon that are increasingly constrained at higher temperatures by other physical and physiological processes involved in mineral formation. Species-specific δ 18 O fractionation equations have considerable utility to reconstruct temperature history in Pacific salmon, but applications should recognize the potential for inferential uncertainty arising from interacting vital effects.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Influence of Tabula Rasa on Process- and Light-Induced Degradation of Solar Cells Fabricated From Czochralski Silicon

Monocrystalline Si solar cells are fabricated from Czochralski (Cz) Si, which contains 10 17 –10 18 cm -3 oxygen atoms. Cz Si undergoes degradation during high-temperature thermal processing steps, such as dopant diffusion to form the p - n junction. This degradation in the bulk minority carrier lifetime can be related to the formation of oxygen precipitates. We found that a high-temperature annealing process known as tabula rasa (TR) not only mitigates process-induced degradation via oxygen precipitate nuclei dissolution, but also modifies subsequent light-induced degradation. We report on the bulk carrier lifetime of n - and p -type Cz Si after TR, which homogenizes the interstitial oxygen in the bulk Si to its monoatomic form in either an N 2 or O 2 environment. A control sample, which was not subjected to a TR processing step, experienced severe process-induced degradation during a boron emitter thermal budget as oxygen precipitates were formed in the Si bulk. These precipitates could be imaged using photoluminescence. Additionally, samples that underwent a TR processing step prior to the boron emitter thermal budget show efficient gettering of metallic impurities compared to the control sample, which showed a decline in the implied open-circuit voltage after the gettering step. Furthermore, modification of the interstitial oxygen bonding by TR had a strong effect on the light-induced degradation kinetics. Instead of a typically observed monotonic decrease, minority carrier lifetime increases first, followed by a nonmonotonic decrease over a ~20 h period. Finally, we conclude that by modifying the interstitial oxygen bonding via TR pretreatment, p -type Cz Si wafers become substantially resistant to harsh solar cell processes and strongly modified light-induced degradation, which would open alternative ways to mitigate this degradation mechanism.

14 SOLAR ENERGY↗
DOE OSTI2023

Sustainable and Green Production of Nanostructured Cellulose by a 2-Step Mechano-Enzymatic Process

Nanostructured cellulose (NC) represents an emerging sustainable biomaterial for diverse biotechnological applications; however, its production requires hazardous chemicals that render the process ecologically unfriendly. Using commercial plant-derived cellulose, an innovative strategy for NC production based on the combination of mechanical and enzymatic approaches was proposed as a sustainable alternative to conventional chemical procedures. After ball milling, the average length of the fibers was reduced by one order of magnitude (down to 10–20 μm) and the crystallinity index decreased from 0.54 to 0.07–0.18. Moreover, a 60 min ball milling pre-treatment followed by 3 h Cellic Ctec2 enzymatic hydrolysis led to NC production (15% yield). Analysis of the structural features of NC obtained by the mechano-enzymatic process revealed that the diameters of the obtained cellulose fibrils and particles were in the range of 200–500 nm and approximately 50 nm, respectively. Interestingly, the film-forming property on polyethylene (coating ≅ 2 μm thickness) was successfully demonstrated and a significant reduction (18%) of the oxygen transmission rate was obtained. Altogether, these findings demonstrated that nanostructured cellulose could be successfully produced using a novel, cheap, and rapid 2-step physico-enzymatic process that provides a potential green and sustainable route that could be exploitable in future biorefineries.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Factors controlling the oxygen isotopic composition of lacustrine authigenic carbonates in Western China: implications for paleoclimate reconstructions

Abstract In the carbonate-water system, at equilibrium, the oxygen isotopic composition of carbonate is dependent not only on the temperature but also on the isotopic composition of host water in which the carbonate is formed. In this study, lake surface sediment and water samples were collected from 33 terminal lakes in Western China to evaluate controls on the oxygen isotopic composition of lacustrine authigenic carbonates (δ 18 O carb ) and its spatial distribution. Our results show that water oxygen isotopic composition (δ 18 O water ) rather than lake summer water temperature (T water ), is the main determinant of δ 18 O carb , irrespective of whether oxygen isotope equilibrium is achieved. There are significant linear correlations between δ 18 O carb and elevation, as well as that between δ 18 O carb and latitude for lakes located on the Tibetan Plateau. In Western China, the spatial distribution of δ 18 O carb is consistent with that of δ 18 O water , and is ultimately controlled by the isotopic composition of local precipitation (δ 18 O precipitation ) that depends on the source of water vapor. Therefore, changes in δ 18 O carb can be predominantly interpreted as variations of δ 18 O water , which in turn represent changes in δ 18 O precipitation for paleoclimate reconstructions in this region, and may be relevant to studies of other areas.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

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↗
DOE OSTI2022

The effect of oxygen concentration on the speciation of laser ablated uranium

Abstract In order to model the fate and transport of particles following a nuclear explosion, there must first be an understanding of individual physical and chemical processes that affect particle formation. One interaction pertinent to fireball chemistry and resultant debris formation is that between uranium and oxygen. In this study, we use laser ablation of uranium metal in different concentrations of oxygen gas, either 16 O 2 or 18 O 2 , to determine the influence of oxygen on rapidly cooling uranium. Analysis of recovered particulates using infrared absorption and Raman spectroscopies indicate that the micrometer-sized particulates are predominantly amorphous UO x (am-UO x , where 3 ≤ x ≤ 4) and UO 2 after ablation in 1 atm of pure O 2 and a 1% O 2 /Ar mixture, respectively. Energy dispersive X-ray spectroscopy (EDS) of particulates formed in pure O 2 suggest an O/U ratio of ~ 3.7, consistent with the vibrational spectroscopy analysis. Both am-UO x and UO 2 particulates convert to α-U 3 O 8 when heated. Lastly, experiments performed in 18 O 2 environments show the formation of 18 O-substituted uranium oxides; vibrational frequencies for am-U 18 O x are reported for the first time. When compared to literature, this work shows that cooling timescales can affect the structural composition of uranium oxides (i.e., crystalline vs. amorphous). This indicator can be used in current models of nuclear explosions to improve our predicative capabilities of chemical speciation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Zonal Patterns in Late Quaternary Tropical South American Precipitation

Speleothem oxygen isotope records (δ 18 O) of tropical South American rainfall in the late Quaternary show a zonal “South American Precipitation Dipole” (SAPD). The dipole is characterized by opposing east-west precipitation anomalies compared to the present—wetter in the east and drier in the west at the mid-Holocene (~7 ka), and drier in the east and wetter in the west at the Last Glacial Maximum (~21 ka). However, the SAPD remains enigmatic because it is expressed differently in western versus eastern δ18O records and isotope-enabled climate model simulations usually misrepresent the magnitude and/or spatial pattern of δ 18 O change. Here, we address the SAPD enigma in two parts. First, we re-interpret the δ 18 O data to account for upwind rainout effects that are known to be pervasive in tropical South America, but are not always considered in Quaternary paleoclimate studies. Our revised interpretation reconciles the δ 18 O data with cave infiltration and other proxy records, and indicates that the centroid of tropical South American rainfall has migrated zonally over time. Second, using an energy balance model of tropical atmospheric circulation, we hypothesize that zonal migration of the precipitation centroid can be explained by regional energy budget shifts, such as changing Saharan albedo associated with the African Humid Period, that have not been modeled in previous SAPD studies. This hypothesis of a migrating precipitation centroid presents a new framework for interpreting δ18O records from tropical South America and may help explain the zonal rainfall anomalies that predate the late Quaternary.

54 ENVIRONMENTAL SCIENCES↗