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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Chemical-Biological Cyclic Process for Hexavalent Chromium Reduction to Trivalent Chromium in Aqueous Medium - 20224

Conventional treatment of chromium contamination focuses on immobilization of the highly toxic and water-soluble form Cr(VI), by reducing it to the relatively less toxic and less mobile trivalent form, Cr(III), using reducing compounds like ferrous sulfate or ferrous iron, Fe(II). The Cr(VI) also respond to biodegradation and subsequent reduction. During the reduction reaction, Fe(II) is oxidized to ferric, Fe(III), which, being at the highest oxidation state, has no ability to reduce Cr(VI), and therefore remediation process terminates. The good news is that metal-reducing bacteria, S. oneidensis MR-1, can regenerate Fe(II) from Fe(III) with the help of an organic electron donor in an appropriate bacterial media. Thus, in the Cr(VI) chemical remediation process, Fe(II) to Fe(III) conversion is reversed by the biological process, regenerating Fe(II) and the Cr(VI) chemical reduction process continues in a cyclic fashion. This study presents the results of regeneration of Fe(II) from fresh Fe(III) as well as from the reaction products of Cr(VI) and Fe(II). Both fresh Fe(III) and reaction product Fe(III) exhibited the same reduction behavior. Fe(II) production increased with the increase of initial concentration of Fe(III), resulting in 87.5% Fe(II) regeneration. The extent of Fe(III) reduction (Fe(II)t/Fe(III)0.hour) was 21 times higher than the extent of Cr(VI) reduction (Cr(VI)t/Cr(VI)0.hour) by S. oneidensis MR-1. In a cyclic process of sequential Cr(VI) addition, the amount of Fe(II) regeneration decreased with the increase in cycle number, a fixed quantity of starting S. oneidensis MR-1 could regenerate Fe(II) at least five times in a ten-hour period. More importantly, regenerated Fe(II) instantly reduced Cr(VI) to Cr(III). So, Fe(II) regeneration with metal-reducing bacteria has a good potential for application in groundwater and wastewater remediation in reducing Cr(VI) to Cr(III). As a comparison of chemical to biological transformation, chemical transformation of Cr(VI) by Fe(II) was almost 600 times greater than that of biological transformation. Therefore a chemical-biological cyclic process offers potential applications for remediation of groundwater and hexavalent chromium contaminated waste sites. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Recycling of Lead Pastes from Spent Lead–Acid Batteries: Thermodynamic Constraints for Desulphurization

Lead–acid batteries are important to modern society because of their wide usage and low cost. The primary source for production of new lead–acid batteries is from recycling spent lead–acid batteries. In spent lead–acid batteries, lead is primarily present as lead pastes. In lead pastes, the dominant component is lead sulfate (PbSO 4 , mineral name anglesite) and lead oxide sulfate (PbO•PbSO 4 , mineral name lanarkite), which accounts for more than 60% of lead pastes. In the recycling process for lead–acid batteries, the desulphurization of lead sulfate is the key part to the overall process. In this work, the thermodynamic constraints for desulphurization via the hydrometallurgical route for recycling lead pastes are presented. The thermodynamic constraints are established according to the thermodynamic model that is applicable and important to recycling of lead pastes via hydrometallurgical routes in high ionic strength solutions that are expected to be in industrial processes. The thermodynamic database is based on the Pitzer equations for calculations of activity coefficients of aqueous species. The desulphurization of lead sulfates represented by PbSO 4 can be achieved through the following routes. (1) conversion to lead oxalate in oxalate-bearing solutions; (2) conversion to lead monoxide in alkaline solutions; and (3) conversion to lead carbonate in carbonate solutions. Among the above three routes, the conversion to lead oxalate is environmentally friendly and has a strong thermodynamic driving force. Oxalate-bearing solutions such as oxalic acid and potassium oxalate solutions will provide high activities of oxalate that are many orders of magnitude higher than those required for conversion of anglesite or lanarkite to lead oxalate, in accordance with the thermodynamic model established for the oxalate system. An additional advantage of the oxalate conversion route is that no additional reductant is needed to reduce lead dioxide to lead oxide or lead sulfate, as there is a strong thermodynamic force to convert lead dioxide directly to lead oxalate. As lanarkite is an important sulfate-bearing phase in lead pastes, this study evaluates the solubility constant for lanarkite regarding the following reaction, based on the solubility data, PbO•PbSO 4 + 2H + ⇌ 2Pb 2+ + SO 4 2– + H 2 O(l).

25 ENERGY STORAGE↗
DOE OSTI2021

An exploration of benchtop X–ray emission spectroscopy for precise characterization of the sulfur redox state in cementitious materials

The evolution of sulfur chemistry in cements is best known in the bailiwick of failure mechanisms via sulfate attack but is equally important for its contributions to the reduction capacity of cementitious materials often used for immobilizing nuclear waste streams destined for long-term storage, e.g., cementitious waste forms (CWF). The total reduction capacity of CWFs, encompassing contributions from both S and Fe reductants, and its implications toward radionuclide immobilization is most often studied by destructive wet chemistry methods requiring acid digestion in the presence of Ce(IV) and subsequent titration and colorimetric interpretation. Here, we investigate a similarly analytical but nondestructive alternative, benchtop high resolution wavelength-dispersive x-ray fluorescence spectroscopy, most commonly known as x-ray emission spectroscopy (XES), for probing the bulk sulfur oxidation state distribution. We present here an initial investigation of S XES, including an improved experimental protocol for lab XES of inhomogeneous samples, both as a complement to the Ce(IV) test and for new scientific opportunities that it enables for observing changes in sulfur chemistry. We discuss future improvements and opportunities, including: (1) the practical challenges associated with coordinating XES and Ce(IV) liquid extraction for a more comprehensive perspective on reduction capacity and for a high-precision evaluation of uncertainties in the Ce(IV) test; and (2) new opportunities, due to the nondestructive nature of XES, for controlled evolution studies aimed at elucidating specific chemical responses of CWF’s exposed to invasive gas or liquid species or to accelerated aging by radiative dose or thermal treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Analysis of Microbial Communities as Indicators of Microbially Induced Corrosion Potential in Stainless Steel Piping

The 200 West Area Pump-and-Treat (200W P&T) facility is part of the final remedy decision for the 200 ZP-1 Operable Unit (OU) and is the interim remedial action for 200-UP-1 OU at the Hanford Site. The facility also treats water from other sources across the site, including 200-DV-1 OU perched water, groundwater from the 200-BP-5 OU, and leachate from the Environmental Restoration Disposal Facility. The facility originally operated a biological treatment process for nitrate that resulted in systemic biofouling and loss of injection well capacity, requiring frequent and costly well rehabilitation. Biofouling has also contributed to corrosion of welds and pitting of stainless-steel piping at the facility. The biological treatment for nitrate was suspended at the end of 2019 calendar year to eliminate negative impacts from biological treatments which improve facility operations and treatment of carbon tetrachloride. Evaluation of the 200W P&T facility’s response to operational improvements, specifically the suspension of the biological treatment, provides information on the potential for continued microbially induced corrosion (MIC). To this end, historical data sets (2015-2017) were compared with molecular biological analyses of 200W P&T water samples from 2018-2020 to quantify trends in total microbial biomass and specific microbial indicator species (iron, sulfate, nitrate, and manganese reducing bacteria) known to cause and enhance metal corrosion. Results showed unequivocal reductions (in excess of 90%) in all microbiological indicators measured following the suspension of the biological treatment. Although abundance measurements for all corrosive MIC populations initially declined after removal of the treatment system, nitrate-reducing bacteria (nirK) and sulfate-reducing bacteria remain highly abundant in the system, an order of magnitude higher than the number of cells present prior to the removal of the biological treatment system [5.14e (1.4) cells/L, vs. 1.14e (0.07) cells/L, reported as average (±SD) for n=3]. In addition, there was an unexpected inflection point in 2019 where all microbial indicators increased unexpectedly in abundance in 2020 by as much as two orders of magnitude compared to 2019 samples. Given the limited number of water samples available for this analysis, the cause of the increase in microbial indicators post-biological treatment has not yet been determined. Systematic sampling of the facility for continued monitoring is recommended so that the responses of MIC populations can be evaluated to ensure that further corrosion is avoided, allowing the 200W P&T facility to operate safely and efficiently at design capacity.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Shipping regulations lead to large reduction in cloud perturbations

Global shipping accounts for 13% of global emissions of SO2, which, once oxidized to sulfate aerosol, acts to cool the planet both directly by scattering sunlight and indirectly by increasing the albedo of clouds. This cooling due to sulfate aerosol offsets some of the warming effect of greenhouse gasses and is the largest uncertainty in determining the change in the Earth’s radiative balance by human activity. Ship tracks—the visible manifestation of the indirect of effect of ship emissions on clouds as quasi-linear features—have long provided an opportunity to quantify these effects. However, they have been arduous to catalog and typically studied only in particular regions for short periods of time. Using a machine-learning algorithm to automate their detection we catalog more than 1 million ship tracks to provide a global climatology. We use this to investigate the effect of stringent fuel regulations introduced by the International Maritime Organization in 2020 on their global prevalence since then, while accounting for the disruption in global commerce caused by COVID-19. We find a marked, but clearly nonlinear, decline in ship tracks globally: An 80% reduction in SO x emissions causes only a 25% reduction in the number of tracks detected.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Expanded Diversity of Microbial Groups Capable of Anaerobic Pyrite Reduction and Assimilation of Dissolution Products

Pyrite, the most abundant iron sulfide mineral in the Earth's crust, has traditionally been considered as a sink for iron and sulfur in the absence of oxygen. Recent research, however, has shown that anaerobic methanogenic archaea can reductively dissolve pyrite and assimilate its products as sources of iron and sulfur. This study explores whether other anaerobic bacteria, including fermentative, nitrate-, iron oxide-, fumarate-, and sulfate-respiring bacteria, can also reduce pyrite and use its dissolution products as sources of iron and sulfur. Results indicate that heterotrophic bacteria respiring fumarate or sulfate, or fermenting organic carbon, can reduce pyrite and assimilate released iron and sulfur. In contrast, nitrate- or iron oxide-respiring cells did not reduce pyrite, suggesting that microbial pyrite reduction is metabolism-specific. All strains capable of reducing pyrite could also use mackinawite as an iron and sulfur source. With the exception of fermentative Bacteroides, strains did not require direct contact with pyrite to reduce the mineral, indicating extracellular electron transfer via electron shuttles. These findings expand the known diversity of microbial groups capable of pyrite reduction and highlight the mineral's lability in various anaerobic environments, with potential implications for the biogeochemical cycles of iron, sulfur, carbon, and oxygen.

58 GEOSCIENCES↗
DOE OSTI2022

Effect of fluctuating redox conditions on trace metal release from wetland soils from South Carolina and stream sediments from Tennessee

Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating oxic and anoxic conditions, trace metals can be mobilized or sequestered in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. We conducted a systematic laboratory-based microcosm study to examine the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal (copper (Cu), nickel (Ni), zinc (Zn), cobalt (Co), iron (Fe), and manganese (Mn)) concentrations. The dataset includes the results of the variation in metal concentrations due to redox fluctuations in wetland soils and stream sediments. Additionally, the variation in the bioavailable concentration of metals obtained using passive samplers based on diffuse gradient in thin-films technique is included in the dataset. We have also reported the change in the pH values and dissolved oxygen concentrations in the microcosms during the entire study of 24 days. The dataset also contains the dissolved organic carbon and sulfate concentrations, and the data on fractions of metals bound to reducible and oxidizable phases. For materials from both the wetlands and the stream, anoxic conditions favored Co and Zn release, which corresponded with the reductive dissolution of iron oxides. In contrast, dissolved Cu concentrations increased under oxic conditions for both sites and correlated positively with the release of sulfate. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Upon redox fluctuations in wetland soils, the bioavailability of Zn and Cu increased, whereas bioavailable Ni and Co decreased. This study illustrates that different trace metals display distinct bioavailability patterns during oxic-anoxic fluctuations in natural environments. The biogeochemical cycling of carbon and nitrogen in systems with redox fluctuations may be influenced by these patterns in trace metal availability in addition to the availability of electron donors and acceptors.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Trends and source apportionment of aerosols in Europe during 1980-2018

Aerosols have significantly affected health, environment, and climate in Europe. Aerosol concentrations have been declining since the 1980s in Europe,mainly owing to a reduction of local aerosol and precursor emissions.Emissions from other source regions of the world, which have been changing rapidly as well, may also perturb the historical and future trends of aerosols and change their radiative impact in Europe. This study examines trends of aerosols in Europe during 1980–2018 and quantifies contributions from 16 source regions using the Community Atmosphere Model version 5 with Explicit Aerosol Source Tagging (CAM5-EAST). The simulated near-surface total mass concentration of sulfate, black carbon, and primary organic carbon had a 62 % decrease during 1980–2018. The majority of which was contributed to reductions of local emissions in Europe, and 8 %–9 % was induced by a decrease in emissions from Russia–Belarus–Ukraine. With the decreases in the fractional contribution of local emissions, aerosols transported from other source regions are increasingly important for air quality in Europe. During 1980–2018, the decrease in sulfate loading led to a warming effect of 2.0 W m –2 in Europe, with 12 % coming from changes in non-European sources, especially from North America and Russia–Belarus–Ukraine. According to the Shared Socioeconomic Pathways (SSP) scenarios, contributions to the sulfate radiative forcing over Europe from both local European emissions and non-European emissions should decrease at a comparable rate in the next 3 decades, suggesting that future changes in non-European emissions are as important as European emissions for causing possible regional climate change associated with aerosols in Europe.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Significance of lysogeny for the metabolism of Desulfovibrio spp. strains isolated from aquatic environments of Georgia

Sulphate-reducing bacteria (SRB) are ecologically important group of anaerobic micro-organisms that can reduce sulphate to form hydrogen sulphide-a toxic gas causing iron corrosion on metal surfaces. In this work, SRB strains were isolated from aquatic environments in the country of Georgia to determine their lysogenicity and the role of temperate phages in host metabolism. SRB strains were isolated in samples from the Black Sea coast of Georgia. Based on their genetic, cytological and physiological properties of bacteria, 10 Georgian isolates were assigned to the genus Desulfovibrio. Temperate bacteriophages were induced from three out of ten strains by UV-exposure. Comparison of metal (Fe and Cr) reduction and utilization of various carbon sources by the wild-type (lysogenic) bacterial strains and their UV-irradiated counterparts was done. Temperate phage in the cells of SRB could alter significant functions of bacteria and may have a contribution in the acquisition of different traits by SRB. This article pointed to a significant role for temperate bacteriophages in the metabolism and metabolic potential of host strains of SRB, which were first isolated from the aquatic environment of Georgia.

temperate phage↗
DOE OSTI2020

Hydration-Induced Disorder Lowers the Energy Barriers for Methyl Rotation in Drug Molecules

The thermally activated dynamics of methyl groups are important for biochemical activity as they allow for a more efficient sampling of the energy landscape. In this work, we compare methyl rotations in the dry and variously hydrated states of three primary drugs under consideration to treat the recent coronavirus disease (COVID-19), namely, hydroxychloroquine and its sulfate, dexamethasone and its sodium diphosphate, and remdesivir. We find that the main driving force behind the considerable reduction in the activation energy for methyl rotations in the hydrated state is the hydration-induced disorder in the methyl group local environments. Furthermore, the activation energy for methyl rotations in the hydration-induced disordered state is much lower than that in an isolated drug molecule, indicating that neither isolated molecules nor periodic crystalline structures can be used to analyze the potential landscape governing the side group dynamics in drug molecules. Instead, only the explicitly considered disordered structures can provide insight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Assessing the climate impact of an improved volcanic sulfate aerosol representation in E3SM

Accurately simulating historical surface temperature variations is essential for evaluating climate models, yet many struggle to reproduce the mid-20th-century temperature trends associated with significant volcanic eruptions. This study examines the impact of volcanic sulfate aerosol representation on these biases using the Energy Exascale Earth System Model (E3SM). The standard CMIP6 protocol prescribes volcanic forcing through radiative perturbations, omitting volcanic aerosol–cloud interactions (VACIs). Here, we implement an emission-based approach with an updated volcanic eruption inventory that directly incorporates volcanic sulfur dioxide (SO 2 ) emissions, enabling a more process-based representation of volcanic forcing. This approach leads to improved surface temperature variability and a modest reduction in cold biases between 1940 and 1980 compared to the CMIP6 setup. Additionally, we assess cloud property responses to a more realistic volcanic sulfate aerosol representation, which weakens cloud-induced cooling during periods of lower volcanic activity. However, despite these refinements, a significant temperature cold bias remains, indicating that further improvements in atmospheric chemistry, aerosol microphysics, cloud processes, and model parameterizations are needed to fully resolve this issue in E3SM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Concentration and Recovery of Rare Earth Elements from Eastern US Coal Refuse

Recent studies funded by the US Department of energy have shown that coal and coal byproducts contain elevated contents of Rare Earth Elements (REEs), making them a potential resource for these critical materials. The approach employed in this research focused on the concentration and extraction of REEs from fine coal refuse derived from various preparation plants in the Appalachian coal basin of the United States. Initial efforts in this research focused on the identification and characterization of REEs in various fine coal refuse streams from nine distinct industrial preparation plants in Appalachia. The average REE content in these materials was determined to be approximately 200 ppm, but the REE content showed a strong correlation to the aluminum content, suggesting that the REEs are closely associated with the clay minerals present in the refuse. Given the relatively low REE concentrations, initial efforts sought to concentrate the REEs through decarbonization and dispersive liberation steps. In these tests, high-shear agitation in the presence of a polyelectrolyte, followed by sedimentation was able to isolate the REE-enriched fine clay particles from siliceous gangue minerals. Following the dispersive liberation step, all samples were found to have an REE content greater than 300 ppm, a benchmark used for many initial exploratory studies. In one case, the REE content was increased by more than 125%. Subsequent extraction tests initially utilized a direct ion-exchange leaching approach with ammonium sulfate as lixiviant. In all cases, the simple ion-exchange leaching process failed to recover significant quantities of rare earth elements, ultimately suggesting that the REEs in fine coal waste may be passivated or bound in a colloidal phase. To access this colloidal phase, several alternative approaches were evaluated, including leaching with alternative ion-exchange lixiviants, reductive leaching, gas-purged leaching, and others. The approach that showed the most promise was strong alkaline pretreatment, followed by ion-exchange leaching with ammonium sulfate at pH 4. A combination of strong alkali and high-temperatures treatment successfully liberated the REEs, converting them to a form amenable to ion-exchange leaching. The highest REE recovery achieved with this method was determined to be 39%. Lastly, bench-scale solvent extraction tests were used to further concentrate REEs in the leach solution and demonstrate that mixed rare earth concentrates can be successfully produced from fine coal refuse.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Climate response to off-equatorial stratospheric sulfur injections in three Earth system models – Part 1: Experimental protocols and surface changes

There is now substantial literature on climate model studies of equatorial or tropical stratospheric SO 2 injections that aim to counteract the surface warming produced by rising concentrations of greenhouse gases. Here we present the results from the first systematic intercomparison of climate responses in three Earth system models wherein the injection of SO 2 occurs at different latitudes in the lower stratosphere: CESM2-WACCM6, UKESM1.0 and GISS-E2.1-G. The first two use a modal aerosol microphysics scheme, while two versions of GISS-E2.1-G use a bulk aerosol (One-Moment Aerosol, OMA) and a two-moment (Multiconfiguration Aerosol TRacker of mIXing state, MATRIX) microphysics approach, respectively. Our aim in this work is to determine commonalities and differences between the climate model responses in terms of the distribution of the optically reflective sulfate aerosols produced from the oxidation of SO 2 and in terms of the surface response to the resulting reduction in solar radiation. A focus on understanding the contribution of characteristics of models transport alongside their microphysical and chemical schemes, and on evaluating the resulting stratospheric responses in different models, is given in the companion paper (Bednarz et al., 2023). The goal of this exercise is not to evaluate these single-point injection simulations as stand-alone proposed strategies to counteract global warming; instead we determine sources and areas of agreement and uncertainty in the simulated responses and, ultimately, the possibility of designing a comprehensive intervention strategy capable of managing multiple simultaneous climate goals through the combination of different injection locations. We find large disagreements between GISS-E2.1-G and the CESM2-WACCM6 and UKESM1.0 models regarding the magnitude of cooling per unit of aerosol optical depth (AOD) produced, which varies from 4.7 K per unit of AOD in CESM2-WACCM6 to 16.7 K in the GISS-E2.1-G version with two-moment aerosol microphysics. By normalizing the results with the global mean response in each of the models and thus assuming that the amount of SO 2 injected is a free parameter that can be managed independently, we highlight some commonalities in the overall distributions of the aerosols, in the inter-hemispheric surface temperature response and in shifts to the Intertropical Convergence Zone, as well as some areas of disagreement, such as the extent of the aerosol confinement in the equatorial region and the efficiency of the transport to polar latitudes. In conclusion, we demonstrate that it is possible to use these simulations to produce more comprehensive injection strategies in multiple climate models. However, large differences in the injection magnitudes can be expected, potentially increasing inter-model spreads in some stratospheric quantities (such as aerosol distribution) while reducing the spread in the surface response in terms of temperature and precipitation; furthermore, the selection of the injection locations may be dependent on the models' specific stratospheric transport.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Controls on Iron Reduction and Biomineralization over Broad Environmental Conditions as Suggested by the Firmicutes Orenia metallireducens Strain Z6

Microbial iron reduction is a ubiquitous biogeochemical process driven by diverse microorganisms in a variety of environments. However, it is often difficult to separate the biological from the geochemical controls on bioreduction of Fe(III) oxides. In this study, we investigated the primary driving factor(s) that mediate secondary iron mineral formation over a broad range of environmental conditions using a single dissimilatory iron reducer, Orenia metallireducens strain Z6. A total of 17 distinct geochemical conditions were tested with differing pH (6.5–8.5), temperature (22–50 °C), salinity (2–20% NaCl), anions (phosphate and sulfate), electron shuttle (anthraquinone-2,6-disulfonate), and Fe(III) oxide mineralogy (ferrihydrite, lepidocrocite, goethite, hematite, and magnetite). The observed rates and extent of iron reduction differed significantly with k int between 0.186 and 1.702 mmol L –1 day –1 and Fe(II) production ranging from 6.3% to 83.7% of the initial Fe(III). Using X-ray absorption and scattering techniques (EXAFS and XRD), we identified and assessed the relationship between secondary minerals and the specific environmental conditions. It was inferred that the observed bifurcation of the mineralization pathways may be mediated by differing extents of Fe(II) sorption on the remaining Fe(III) minerals. These results expand our understanding of the controls on biomineralization during microbial iron reduction and aid the development of practical applications.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

North Atlantic Oscillation response in GeoMIP experiments G6solar and G6sulfur: why detailed modelling is needed for understanding regional implications of solar radiation management

The realization of the difficulty of limiting global-mean temperatures to within 1.5 or 2.0°C above pre-industrial levels stipulated by the 21st Conference of Parties in Paris has led to increased interest in solar radiation management (SRM) techniques. Proposed SRM schemes aim to increase planetary albedo to reflect more sunlight back to space and induce a cooling that acts to partially offset global warming. Under the auspices of the Geoengineering Model Intercomparison Project, we have performed model experiments whereby global temperature under the high-forcing SSP5-8.5 scenario is reduced to follow that of the medium-forcing SSP2-4.5 scenario. Two different mechanisms to achieve this are employed: the first via a reduction in the solar constant (experiment G6solar) and the second via modelling injections of sulfur dioxide (experiment G6sulfur) which forms sulfate aerosol in the stratosphere. Results from two state-of-the-art coupled Earth system models (UKESM1 and CESM2-WACCM6) both show an impact on the North Atlantic Oscillation (NAO) in G6sulfur but not in G6solar. Both models show a persistent positive anomaly in the NAO during the Northern Hemisphere winter season in G6sulfur, suggesting an increase in zonal flow and an increase in North Atlantic storm track activity impacting the Eurasian continent and leading to high-latitude warming over Europe and Asia. These results are broadly consistent with previous findings which show similar impacts from stratospheric volcanic aerosol on the NAO and emphasize that detailed modelling of geoengineering processes is required if accurate impacts of SRM effects are to be simulated. Differences remain between the two models in predicting regional changes over the continental USA and Africa, suggesting that more models need to perform such simulations before attempting to draw any conclusions regarding potential continental-scale climate change under SRM.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Constructing synthetic organosulfur additive for high voltage lithium-ion batteries

Despite its high anodic stability, common organosulfur solvents such as ethyl methyl sulfone and sulfolane typically exhibit poor solid-electrolyte interphase (SEI) formation capability. Here, to address this, the fluorinated organic sulfate 4-(trifluoromethyl)-1,3,2-dioxathiolane 2,2-dioxide (TFDTD) was developed as an effective additive for tailoring organosulfur-based electrolytes in lithium-ion batteries. This development was guided by the functionality selection principle and careful evaluation of feasibility in organic synthesis. TFDTD can be readily synthesized through the reaction between trifluoropropylene glycol and sulfuryl chloride. The ring structure of the organic sulfate enables the formation of a stable SEI on the anode, while the fluorination of the sulfate not only enhances its chemical stability and oxidation potential, but also its effectiveness to protect the anode by increasing its reduction potential, rendering it preferentially reduced on the anode surface before the decomposition of other electrolyte components. Introducing TFDTD facilitates the generation of a robust solidelectrolyte interphase on the graphite anode, significantly enhancing cell performance. Moreover, coupling the use of TFDTD with vinylene carbonate provides further protection on the cathode surface, enabling exceptionally stable, high-voltage, long-term cycling of Gr||NMC full cells.

Functionality selection principle↗
DOE OSTI2022

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗