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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Broadband differential absorption sensor for detecting gaseous species

A remote sensor system comprising a laser transmitter that emits a pulse of broadband laser illumination comprising a plurality of wavelengths and a receiver configured to detect laser illumination backscatter. The sensor system further includes a computing system configured to determine a plurality of species number densities along a travel path of the laser illumination. Determining the plurality of species number densities includes determining a first number density of a first species based on a first set of optical transmission values from the backscatter data for a first subset of wavelengths of the plurality of wavelengths and a first attenuation cross-section of the first species. Additional species are determined based on additional sets of optical transmission values from the backscatter data for additional subsets of wavelengths of the plurality of wavelengths and additional cross-sections of additional species.

Smith, Mark W.↗
DOE OSTI2021

Effectiveness and outcomes of invasive species removal in Hawaiian streams

Despite aquatic invasive species (AIS) being a widely recognized threat to native biodiversity in streams on subtropical and tropical oceanic islands across the Pacific, AIS management has been constrained by concerns that methods of removal could result in more harm than good. In this study, we assessed the effectiveness and outcomes of combining hand-netting and streamside sequestration of native species with AIS removal via three-pass electrofishing tailored for Hawaiian Island watersheds. Removals were conducted in 13 watersheds on the island of O‘ahu following a before-after, control-impact design to assess how AIS removal and post-removal community reassembly varied by surface flow and target species of interest. We found that removals resulted in a sharp reduction in AIS densities without altering native species densities. Removal efficacy was greatest in streams with intermediate mean discharge irrespective of target group or pre-removal AIS densities. Long-term monitoring demonstrated that removals led to persistent shifts in community composition reflecting sustained reductions in AIS densities. These findings indicate that electrofishing can be a valuable tool for AIS management in Hawaiian and other subtropical Pacific island streams, so long as steps are taken to minimize potential harm to at-risk and culturally important native species.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Interactions between U.S. biofuels policy and the Endangered Species Act

The Renewable Fuel Standard (RFS) is the primary policy governing the use of biofuels in the United States. Following the 2007 enactment of the RFS, there has been substantial expansion in the use of cropland to produce biofuel feedstocks, including corn and soybeans. Both the conversion of land and the ongoing cultivation of these crops can, depending on management practices, lead to negative environmental outcomes including degraded water quality, increased water use, increased greenhouse gas emissions, and loss or degradation of wildlife habitat. These outcomes have the potential to affect threatened and endangered species protected under the U.S. Endangered Species Act (ESA). The ESA requires federal agencies to consult with the U.S. Fish and Wildlife Service or the National Marine Fisheries Service to ensure that an agency's actions are not likely to jeopardize the existence of imperiled species, nor result in the destruction or adverse modification of their habitat. However, formal consultation has not yet been completed between the U.S. Environmental Protection Agency—the agency charged with implementing the RFS—and the wildlife services, thereby hindering mitigation or remediation of potential impacts. This analysis explores the likely effects of the RFS on land use changes and critical habitat, illustrates example pathways by which threatened and endangered species may be affected, and proposes solutions to help redress this harm. The findings suggest a need for further consultation and assessment of the interactions between the RFS and ESA as well as additional research to support the species-conservation and policymaking processes.

09 BIOMASS FUELS↗
DOE OSTI2023

Determination of aquatic hazard concentrations for the oil spill response product class of surface washing agents using species sensitivity distributions

Surface washing agents (SWAs) are a diverse class of oil spill response products intended to facilitate removal of stranded oil from shorelines. This class of agents has high application rates relative to other categories of spill response products, but global toxicity data is generally limited to two standard test species: inland silverside and mysid shrimp. Here, in this study, we provide a framework to maximize the utility of limited toxicity data across a product class. To characterize species sensitivity to SWAs, the toxicity of three agents spanning a range of chemical and physical properties were tested in eight species. The relative sensitivity of mysids shrimp and inland silversides as surrogate test organisms was determined. Toxicity normalized species sensitivity distributions (SSDn) were used to estimate fifth centile hazard concentration (HC5) values for SWAs with limited toxicity data. Chemical toxicity distributions (CTD) of SWA HC5 values were used to compute a fifth centile chemical hazard distribution (HD5) to provide a more comprehensive assessment of hazard across a spill response product class with limited toxicity data than traditional single species or single agent approaches can give.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2023

An investigation on the structural stability of $\mathrm{ZIF}$-8 in water versus water-derived oxidative species in aqueous environment

We report the zeolitic-imidazolate-framework-8 (ZIF-8) is one of the extensively studied metal-organic frameworks (MOF) materials because of its unique structure. For its potential applicability in numerous fields, it becomes crucial to have detailed studies on the structural stability of ZIF-8, especially in aqueous environments. A number of studies have been conducted to investigate the breakdown process of the ZIF-8 structure in water; which is known as the hydrolysis of ZIF-8. However, those studies reported different opposing experimental observations on the role of water on the structural stability of ZIF-8, which created obscurity in understanding this phenomenon. This study explored the effects of different water-derived species on the structural stability of ZIF-8; specifically, examined the effects of only water and water with different oxidative species that may be generated by water molecules' dissociation under external energy or catalyst presence. To this effort, we experimentally probed the physical and chemical structural changes of ZIF-8 in DI water and three different solutions of hydrogen peroxides (H 2 O 2 ); taking H 2 O 2 as the source of oxidative species. To assess the changes in elemental compositions, chemical bonds, functional groups, crystal structure, and morphology, all the samples were analyzed by X-ray photoelectron spectroscopy (XPS), energy-dispersive x-ray (EDX) spectroscopy, Fourier Transform Infrared (FTIR) spectroscope, X-ray diffractometer (XRD), and scanning electron microscope (SEM). Significant structural changes in ZIF-8 occurred mainly in the presence of oxidative species in water. Notably, oxidative species' concentration exceeding 1 M heightened the deformation of the ZIF-8 structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Plutonium reactive transport in fractured granite: Multi-species experiments and simulations

Plutonium (Pu) in the subsurface environment can transport in different oxidation states as an aqueous solute or as colloidal particles. The transport behavior of Pu is affected by the relative abundances of these species and can be difficult to predict when they simultaneously exist. This study investigates the concurrent transport of Pu intrinsic colloids, Pu(IV) (aq) and Pu(V-VI) (aq) through a combination of controlled experiments and semi-analytical dual-porosity transport modeling. Pu transport experiments were conducted in a fractured granite at high and low flow rates to elucidate sorption processes and their scaling behavior. In the experiments, Pu(IV) (aq) was the least mobile of the Pu species, Pu(V-VI) (aq) had intermediate mobility, and the colloidal Pu, which consisted mainly of precipitated and/or hydrolyzed Pu(IV), was the most mobile. The semi-analytical modeling revealed that the sorption of each Pu species was rate-limited, as the sorption could not be described by assuming local equilibrium in the experiments. The model was able to describe the sorption of the different Pu species that occurring either on fracture surfaces, in the pores of the rock matrix, or simultaneously in both locations. While equally good fits to the data could be achieved using any of these assumptions, a fracture-dominated process was considered to be the most plausible because it provided the most reasonable estimates of sorption rate constants. Importantly, a key result of this work is that the sorption rate constant of all Pu species tends to decrease with increasing time scales, which implies that Pu will tend to be more mobile at longer time scales than observations at shorter time scales suggest. This result has important implications for predicting the environmental impacts of Pu in the safety assessments of geologic repositories for radioactive waste disposal, and we explore potential mechanistic bases for upscaling the sorption rate constants to time and distance scales that cannot be practically evaluated in experiments.

58 GEOSCIENCES↗
DOE OSTI2021

Hanseniaspora smithiae sp. nov., a Novel Apiculate Yeast Species From Patagonian Forests That Lacks the Typical Genomic Domestication Signatures for Fermentative Environments

During a survey of Nothofagus trees and their parasitic fungi in Andean Patagonia (Argentina), genetically distinct strains of Hanseniaspora were obtained from the sugar-containing stromata of parasitic Cyttaria spp. Phylogenetic analyses based on the single-gene sequences (encoding rRNA and actin) or on conserved, single-copy, orthologous genes from genome sequence assemblies revealed that these strains represent a new species closely related to Hanseniaspora valbyensis. Additionally, delimitation of this novel species was supported by genetic distance calculations using overall genome relatedness indices (OGRI) between the novel taxon and its closest relatives. To better understand the mode of speciation in Hanseniaspora , we examined genes that were retained or lost in the novel species in comparison to its closest relatives. These analyses show that, during diversification, this novel species and its closest relatives, H. valbyensis and Hanseniaspora jakobsenii , lost mitochondrial and other genes involved in the generation of precursor metabolites and energy, which could explain their slower growth and higher ethanol yields under aerobic conditions. Similarly, Hanseniaspora mollemarum lost the ability to sporulate, along with genes that are involved in meiosis and mating. Based on these findings, a formal description of the novel yeast species Hanseniaspora smithiae sp. nov. is proposed, with CRUB 1602 H as the holotype.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Diversity of Sordariales Fungi: Identification of Seven New Species of Naviculisporaceae Through Morphological Analyses and Genome Sequencing

Thanks to next-generation sequencing (NGS) technologies, the diversity of fungi can now be investigated through the analysis of their genome sequences. Naviculisporaceae is a family within the Sordariales, whose diversity is not well-known, with only one genome sequence published for this family. Here, we report on the isolation and cultivation of 20 new strains of Naviculisporaceae. Their genome sequences, as well as those of the five commercially available strains, were determined, thus providing complete genome sequences for 25 new Naviculisporaceae strains. Species delimitation was conducted using a combination of (1) ITS + LSU phylogenetic analysis of the new isolates along with other known species of the family, (2) comparisons between DNA barcode sequences of the new strains with those of the known species, and (3) average genome-wide nucleotide identity calculation. We built a phylogenomic tree and studied the organization of the mating-type locus. In vitro fruiting was obtained for 16 strains, enabling the definition of seven new species, namely Pseudorhypophila gallica, Pseudorhypophila guyanensis Rhypophila alpibus, Rhypophila brasiliensis, Rhypophila camarguensis, Rhypophila reunionensis and Rhypophila thailandica, as well as two new combinations, namely Pseudorhypophila latipes and Pseudorhypophila oryzae. Eight strains for which in vitro fruiting was not obtained may belong to additional new species. These results expand the known diversity of the Naviculisporaceae and greatly enlarge the genomic data available for the family.

Naviculisporaceae↗
NASA NTRS2012

Metallic Species, Oxygen and Silicon in the Lunar Exosphere: Upper Limits and Prospects for LADEE Measurements

The only species that have been so far detected in the lunar exosphere are Na, K, Ar,and He. However, models for the production and loss of species derived from the lunarregolith through micrometeoroid impact vaporization, sputtering, and photon-stimulateddesorption, predict that a host of other species should exist in the lunar exosphere.Assuming that loss processes are limited to ballistic escape, photoionization, and recyclingto the surface, we have computed column abundances and compared them to publishedupper limits for the Moon. Only for Ca do modeled abundances clearly exceed theavailable measurements. This result suggests the relevance of some loss processes thatwere not included in the model, such as the possibility of gas-to-solid phasecondensation during micrometeoroid impacts or the formation of stable metallic oxides.Our simulations and the recalculation of efficiencies for resonant light scattering showthat models for other species studied are not well constrained by existingmeasurements. This fact underlines the need for improved remote and in situmeasurements of the lunar exosphere such as those planned by the Lunar Atmosphereand Dust Environment Explorer (LADEE) spacecraft. Our simulations of the LADEEneutral mass spectrometer and visibleultraviolet spectrometer indicate that LADEE measurements promise to provide definitive observations or set stringent upper limitsfor all regolith-driven exospheric species. We predict that observations by LADEE willconstrain assumed model parameters for the exosphere of the Moon.

lunar exosphere↗
DOE OSTI2023

Little vertical and circumferential variations in stem xylem water Δ 2 H and Δ 18 O in three tree species

Vertical and circumferential patterns of xylem water isotope signatures in large trees are rarely characterized but may influence interpretation of water source investigations and soil/xylem water isotope offsets. Furthermore, to examine vertical and circumferential variation in xylem water δ 2 H and δ 18 O, we collected xylem tissue at 5 heights (0, 1, 4, 7 and 10 m) from three replicate trees of three species with contrasting xylem anatomy, two angiosperms (Liquidambar styraciflua and Quercus nigra) and one gymnosperm (Pinus taeda). Concurrently, we also determined δ 2 H and δ 18 O of groundwater, soil water, and recent precipitation. On a different day, we collected circumferential samples at 1 m from the same trees to test for sectorality effects. Water from stem and soil samples were cryogenically extracted and analyzed for δ 2 H and δ 18 O. Mean xylem water δ 2 H and δ 18 O were significantly different between species, both vertically and circumferentially. We did not find significant (p = 0.05) systematic variation in δ 2 H or δ 18 O with height. We found no significant evidence for sectorality effects on δ 2 H, δ 18 O. Variances of vertical synoptic xylem water δ 2 H or δ 18 O were similar between species, 7.2–10.4‰ for δ 2 H and 0.58–0.81‰ for δ 18 O. Circumferential variances were also similar between species, 4.0–6.0 for δ 2 H and 0.37–0.44 for δ 18 O. A mixing model showed that sweetgum, water oak and loblolly pine, were drawing most of their water from deep soil from 45 to 190 cm (84.7, 68.4 and 53.2%, respectively) however, soil water-excess values indicate δ 2 H fractionation effects on these estimates. Dual isotope mixing model evaluation with single and multiple sample configurations showed that source water estimates were not affected by within tree variability of xylem water signatures. Xylem water δ 2 H and δ 18 O variability with height or circumference, was 3.2 and 2.7 times less than between tree variation because of transient temporal and spatial processes and is, therefore, not likely to affect interpretations of water sourcing in these three species.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Quantitative Measurement of Positive and Negative Ion Species Ejected from a Li–O–H Surface by Hydrogen and Noble Gas Ion Irradiation

We report sputtering yields of Li + , H - , O - , and OH x - ion species from an Li–O–H surface for H, D, He, Ne, and Ar ion irradiation at 45° incidence in the energy range of 30–2000 eV. A Li film was deposited on a stainless steel target using Li evaporators in the LTX-β vessel, using the LTX-β Sample Exposure Probe (SEP), which includes an ultrahigh vacuum suitcase for transferring targets without significant contamination from air exposure. The SEP was used to transfer the Li-coated target from LTX-β to a separate Sample Exposure Station (SES) to perform ion exposure measurements. The SEP was also used for characterization of the Li-coated target utilizing X-ray photoelectron spectroscopy in a different chamber, showing that the lithium film surface was oxidized. Ion exposures were performed using an electron cyclotron resonance plasma source in the SES. Sputtered/ejected species were sampled by a quadrupole mass spectrometer with capabilities for detecting positive and negative ions, and an energy filter for determining the mean kinetic energy of the ejected ion species. All ion irradiations caused Li + ions to be ejected, while causing impurity ions such as H + , H - , O - and OH - to be ejected. Measured ion energies of Li + ions from a Li–O–H surface suggested that the typical sheath potential on the divertor surface can trap sputtered Li + ions, which were previously reported as ~ 60% of total sputtered Li species from Li targets (Allain and Ruzic in Nucl Fusion 42:202, 2002). Hence, our results for the sputtering yields of ejected ion species and their associated ion energies from a Li–O–H surface indicates that lithium sputtering is suppressed and impurity removal is enhanced due to the sheath potential at the divertor surface for fusion reactor applications.

Plasma-material interaction↗
DOE OSTI2023

Reproductive Responses to Increased Shoot Density and Global Change Drivers in a Widespread Clonal Wetland Species, Schoenoplectus americanus

The expansion of many wetland species is a function of both clonal propagation and sexual reproduction. The production of ramets through clonal propagation enables plants to move and occupy space near parent ramets, while seeds produced by sexual reproduction enable species to disperse and colonize open or disturbed sites both near and far from parents. The balance between clonal propagation and sexual reproduction is known to vary with plant density but few studies have focused on reproductive allocation with density changes in response to global climate change. Schoenoplectus americanus is a widespread clonal wetland species in North America and a dominant species in Chesapeake Bay brackish tidal wetlands. Long-term experiments on responses of S. americanus to global change provided the opportunity to compare the two modes of propagation under different treatments. Seed production increased with increasing shoot density, supporting the hypothesis that factors causing increased clonal reproduction (e.g., higher shoot density) stimulate sexual reproduction and dispersal of genets. The increase in allocation to sexual reproduction was mainly the result of an increase in the number of ramets that flowered and not an increase in the number of seeds per reproductive shoot, or the ratio between the number of flowers produced per inflorescence and the number of flowers that developed into seeds. Seed production increased in response to increasing temperatures and decreased or did not change in response to increased CO2 or nitrogen. Results from this comparative study demonstrate that plant responses to global change treatments affect resource allocation and can alter the ability of species to produce seeds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Species- and element-specific patterns of metal flux from contaminated wetlands versus metals shed with exuviae in emerging dragonflies

Dragonfly adults and their aquatic immature stages are important parts of food webs and provide a link between aquatic and terrestrial components. During emergence, contaminants can be exported into terrestrial food webs as immature adults fly away or be shed with their exuviae and remain in the wetland. Our previous work established metals accumulating in dragonfly nymphs throughout a contaminated constructed wetland designed to regulate pH and sequester trace metals from an industrial effluent line. In this paper we evaluated the concentration and mass of metals leaving the wetland in flying emergents versus remaining in the wetland with the shed exuviae in 10 species of dragonflies belonging to 8 genera. Nine elements (Cu, Zn, Cd, Mn, V, Mg, Fe, Al, Pb) were evaluated that include essential and nonessential elements as well as trace and major metals. Metal concentrations in the emergent body and exuviae can differ by orders of magnitude. Aluminum, Fe, Mn, and Pb were largely shed in the exuviae. Vanadium and Cd were more variable among species but also tended to be shed with the exuviae. In contrast, Cu, Zn, and Mg showed a higher tendency to leave the wetland with an emerging dragonfly. Metals shed in dragonfly exuviae can moderate the transport of metals from contaminated wetlands. Taxonomic- and metal-specific variability in daily metal flux from the wetland depended upon concentration accumulated, individual body mass, and number of individuals emerging, with each factor's relative importance often differing among species. This illustrates the importance of evaluating the mass of metals in an individual and not only concentrations. Furthermore, differences in numbers of each species emerging will magnify differences in individual metal flux when calculating community metal flux. A better understanding of the variability of metal accumulation in nymphs/larvae and metal shedding during metamorphosis among both metals and species is needed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Root exudate composition from different plant species influences the growth of rhizosphere bacteria

Plant roots release exudates that fuel microbial activities and can structure rhizosphere microbial communities, but how different plant species use their root exudate to potentially select for different soil microbes in the rhizosphere is not well understood. Here, we investigated how root exudate from plants of three diverging lineages, Lactuca sativa (lettuce), Brassica juncea (mustard cabbage), and Zea mays (maize) influence the growth of their own rhizosphere bacteria (host) and those from other plant species (non-host) in growth bioassays. We found that on the community level, lettuce rhizosphere bacteria grew better in non-host exudate, but mustard cabbage and maize rhizosphere bacteria grew similarly well in both host and non-host exudate. However, individual bacteria taxa showed strong preferences for exudate from different plant species. The bacterial growth patterns were independent of C and N quantity, suggesting that certain exometabolic compounds may drive the growth patterns. Our results demonstrate that root exudate from a given plant species have the potential to stimulate or suppress soil bacteria and hint at a mechanism that different plant species use to select for their specific suite of rhizosphere bacteria. Furthermore, these findings contribute to our broader understanding of how root exudate quality could be a mechanism that plants use to select for distinct microbial communities in the rhizosphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

The effects of mixed-species root zones on the resistance of soil bacteria and fungi to long-term experimental and natural reductions in soil moisture

Mixed forest stands tend to be more resistant to drought than species-specific stands partially due to complementarity in root ecology and physiology. For this work, we asked whether complementary differences in the drought resistance of soil microbiomes might contribute to this phenomenon. We experimented on the effects of reduced soil moisture on bacterial and fungal community composition in species-specific (single species) and mixed-species root zones of Norway spruce and European beech forests in a 5-year-old throughfall-exclusion experiment and across seasonal (spring-summer-fall) and latitudinal moisture gradients. Bacteria were most responsive to changes in soil moisture, especially members of Rhizobiales, while fungi were largely unaffected, including ectomycorrhizal fungi (EMF). Community resistance was higher in spruce relative to beech root zones, corresponding with the proportions of drought-favored (more in spruce) and drought-sensitive bacterial taxa (more in beech). The spruce soil microbiome also exhibited greater resistance to seasonal changes between spring (wettest) and fall (driest). Mixed-species root zones contained a hybrid of beech- and spruce-associated microbiomes. Several bacterial populations exhibited either enhanced resistance or greater susceptibility to drought in mixed root zones. Overall, patterns in the relative abundances of soil bacteria closely tracked moisture in seasonal and latitudinal precipitation gradients and were more predictive of soil water content than other environmental variables. We conclude that complementary differences in the drought resistance of soil microbiomes can occur and the likeliest form of complementarity in mixed-root zones coincides with the enrichment of drought-tolerant bacteria associated with spruce and the sustenance of EMF by beech.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Mercury Reduction, Uptake, and Species Transformation by Freshwater Alga Chlorella vulgaris under Sunlit and Dark Conditions

As a major entry point of mercury (Hg) to aquatic food webs, algae play an important role in taking up and transforming Hg species in aquatic ecosystems. However, little is known how and to what extent Hg reduction, uptake, and species transformations are mediated by algal cells and their exudates, algal organic matter (AOM), under either sunlit or dark conditions. In this study, using Chlorella vulgaris (CV) as one of the most prevalent freshwater model algal species, we show that solar irradiation could enhance the reduction of mercuric Hg(II) to elemental Hg(0) by both CV cells and AOM. AOM reduced more Hg(II) than algal cells themselves due to cell surface adsorption and uptake of Hg(II) inside the cells under solar irradiation. Synchrotron radiation X-ray absorption near-edge spectroscopy (SR-XANES) analyses indicate that sunlight facilitated the transformation of Hg to less bioavailable species, such as β-HgS and Hg-phytochelatins, compared to Hg(Cysteine) 2 -like species formed in algal cells in the dark. These findings highlight important functional roles and potential mechanisms of algae in Hg reduction and immobilization under varying lighting conditions and how these processes may modulate Hg cycling and bioavailability in the aquatic environment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

The speciation of Tc after the extraction of Tc(IV) from H 2 O and 1 M HNO 3 by dibutylphosphoric acid (HDBP) in dodecane has been studied by X-ray absorption fine structure (XAFS) spectroscopy. Results show the formation of dimeric species with Tc 2 O 2 and Tc 2 O units, and the formulas [Tc 2 O 2 (DBP·HDBP) 4 ] (1) and [Tc 2 O(NO 3 ) 2 (DBP) 2 (DBP·HDBP) 2 ] (2) were, respectively, proposed for the species extracted from H 2 O and 1 M HNO 3 . The interatomic Tc–Tc distances found in the Tc 2 O 2 and Tc 2 O units [2.55(3) and 3.57(4) Å, respectively] are similar to the ones found in Tc(IV) dinuclear species. It is likely that the speciation of Tc(IV) in dodecane is due to the extraction of a species with a Tc 2 O unit for (2) and to the redissolution of a Tc(IV)-DBP solid for (1). The XAFS results for (1) and (2) were compared to that obtained for the extraction of Tc(IV) with TBP/HDBP/dodecane from 0.5 M HNO 3 , (3) which highlight the formation of Tc mononuclear nitrate species {i.e. [Tc(NO 3 ) 3 (DBP)] or [Tc(NO 3 ) 2 (DBP·HDBP)]}. These results confirm the importance of the preparation and speciation of the Tc(IV) aqueous solutions prior to extraction and how much this influences and drives the final Tc speciation in organic extraction. Here, these studies outline the complexity of Tc separation chemistry and provide insights into the behavior of Tc during the reprocessing of used nuclear fuel.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Inorganic Sulfur Species Formed upon Heterogeneous OH Oxidation of Organosulfates: A Case Study of Methyl Sulfate

In this report recent studies reveal that organosulfates at the particle surface can be oxidized by gas-phase OH radicals with significant rates. Inorganic sulfur species, such as the bisulfate ion (HSO 4 - ) and sulfate ion (SO 4 2- ), can be formed upon these heterogeneous oxidation processes through the formation and subsequent reactions of sulfate radical anions (SO 4 •- ) in the particle phase. However, the amount of inorganic sulfur species produced in these heterogeneous oxidation reactions is not known. We investigate the heterogeneous OH oxidation of sodium methyl sulfate (CH 3 SO 4 Na), the smallest organosulfate detected in atmospheric particles, using an oxidation flow reactor at a relative humidity of 75%. We quantify the kinetics by measuring the decay of CH 3 SO 4 Na and the amount of HSO 4 - and SO 4 2- formed upon oxidation using ion chromatography. Kinetic measurements determine the heterogeneous OH reaction rate to be (5.72 ± 0.14) x 10 -13 cm 3 molecule -1 s -1 , with an effective OH uptake coefficient, γ eff , of 0.31 ± 0.06. The molar yield of inorganic sulfur species, defined as the total number of moles of HSO 4 - and SO 4 2- formed per mole of CH 3 SO 4 Na consumed upon oxidation, is found to be significant and has an average value of 0.62 ± 0.18 upon oxidation. A kinetic model is developed to describe the kinetics and inorganic sulfur species formation upon oxidation. Model simulations suggest that CH 3 SO 4 Na tends to decompose rapidly into formaldehyde and SO 4 •- , and the reaction of SO 4 •- with CH 3 SO 4 Na plays a significant role in both governing the kinetics and the formation of inorganic sulfur species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗