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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Tuning crack-inclusion interaction with an applied T -stress

The interaction between cracks and inclusions plays an important role in the fracture behavior of particulate composites. It is commonly recognized that an inclusion stiffer than the matrix tends to deflect an approaching crack away while a softer inclusion attracts the crack. Here, we demonstrate by analytical modeling and numerical simulations that the crack-inclusion interaction can be tuned by an applied T-stress. Under a sufficiently large compressive applied T-stress, cracks can be attracted to stiffer inclusions while repelled by softer ones, therefore reversing the conventional trend. Potential applications of this work include composite electrodes in lithium-ion batteries and hydraulic fracturing.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Annual PM2.5 and cardiovascular mortality rate data: Trends modified by county socioeconomic status in 2,132 US counties

This article contains data on county-level socioeconomic status for 2132 US counties and each county's average annual cardiovascular mortality rate (CMR) and fine particulate matter (PM2.5) concentration for 21 years (1990e2010). County CMR, PM2.5, and socioeconomic data were obtained from the US National Center for Health Statistics, US Environmental Protection Agency's Community Multiscale Air Quality modeling system, and the US Census, respectively. Annual socioeconomic indices were created using seven county-level measures from the 1990, 2000, and 2010 US Census using factor analysis. Quintiles of this index were used to generate categories of county socioeconomic status. This national data set contains data for annual PM2.5 and CMR changes over a time-period when there was a significant reduction in US air pollutants (following the enactment of the 1970 Clean Air Act). These data are associated with the article “The contribution of improved air quality to reduced cardiovascular mortality: Declines in socioeconomic differences over time” [1]. Data are stored in a comma separated value format and can be downloaded from the USEPA ScienceHub data repository (https://doi.org/10.23719/ 1506014).

Socioeconomic status↗
DOE OSTI2026

Independent and interactive effects of wet bulb globe temperature and air pollution exposures on suicide mortality

Background: Individual components of the ambient environment, such as temperature and air pollution, exist as part of a complex mixture and have been associated with suicide; however, their interactive effects remain poorly understood. This study examined the independent and interactive effects of wet bulb globe temperature (WBGT), nitrogen dioxide (NO 2 ), and fine particulate matter (PM 2.5 ) on suicide mortality. Methods: We identified 7,551 suicide cases in Utah, USA, from 2000 to 2016 and assigned exposure to daily maximum WBGT (sourced from the European Center for Medium-Range Weather Forecasts) and PM 2.5 and NO 2 concentrations (sourced from a national spatiotemporal ensemble model) using decedent’s residential address at the time of death. A case-crossover design with conditional logistic regression was used to estimate the independent and interactive effects of WBGT max , PM 2.5 , and NO 2 on suicide. For exposure windows, we considered single days preceding suicide (lag 0 to 6) and their averages across preceding days (lag 0–1, 0–3, and 0–6). Analyses were stratified by season. Results: We identified a significant association between WBGT max and suicide across all seasons (odds ratio [OR] = 1.05, 95% confidence interval [CI]: 1.01, 1.10; per 5 °C increase on lag 0–3 days). The associations were stronger in the warm season (March 22 to September 21), with ORs and 95% CIs ranging from 1.08 (1.02, 1.15) to 1.20 (1.10, 1.30) per 5 °C increase depending on the lag periods. We observed synergistic interactions between WBGT max and PM 2.5 and NO 2 in the warm season, associated with higher odds of suicide. The associations of WBGT max with suicide were most pronounced at high NO 2 levels. Conclusions: We found evidence of synergistic interactions between WBGT max and PM 2.5 and NO 2 on suicide in the warm season, emphasizing the need for considering the combined effects of heat stress and air pollution in suicide prevention strategies.

Fine particulate matter↗
DOE OSTI2022

Solid-phase Mn speciation in suspended particles along meltwater-influenced fjords of West Greenland

Manganese (Mn) is an essential micro-nutrient that can limit or, along with iron (Fe), co-limit phytoplankton growth in the ocean. Glacier meltwater is thought to be a key source of trace metals to high latitude coastal systems, but little is known about the nature of Mn delivered to glacially-influenced fjords and adjacent coastal waters. In this work, we combine in-situ dissolved Mn (dMn) measurements of surface waters with Mn K-edge X-ray absorption spectroscopy (XAS) data of suspended particles in four fjords of West Greenland. Data were collected from transects of up to 100 km in fjords with different underlying bedrock geology from 64 to 70°N. We found that dMn concentrations generally decreased conservatively with increasing salinity (from 80 to 120 nM at salinity < 8 to < 40 nM at salinities > 25). Dissolved Fe (dFe) trends in these fjords similarly declined with increasing distance from glacier outflows (declining from > 20 nM to < 8 nM). However, the dMn/dFe ratio increased rapidly likely due to the greater stability of dMn at intermediate salinities (i.e. 10–20) compared to rapid precipitation of dFe across the salinity gradient. The XAS data indicated a widespread presence of Mn(II)-rich suspended particles near fjord surfaces, with structures akin to Mn(II)-bearing phyllosilicates. However, a distinct increase in Mn oxidation state with depth and the predominance of birnessite-like Mn(IV) oxides was observed for suspended particles in a fjord with tertiary basalt geology. The similar dMn behaviour in fjords with different suspended particle Mn speciation (i.e., Mn(II)-bearing phyllosilicates and Mn(IV)-rich birnessite) is consistent with the decoupling of dissolved and particulate Mn and suggests that dMn concentrations on the scale of these fjords are controlled primarily by dilution of a freshwater dMn source rather than exchange between dissolved and particle phases. This work provides new insights into the Mn cycle in high latitude coastal waters, where small changes in the relative availabilities of dMn, dFe and macronutrients may affect the identity of the nutrient(s) proximally limiting primary production.

58 GEOSCIENCES↗
DOE OSTI2020

What fuel properties enable higher thermal efficiency in spark-ignited engines?

The Co-Optimization of Fuels and Engines (Co-Optima) initiative from the US Department of Energy aims to co-develop fuels and engines in an effort to maximize energy efficiency and the utilization of renewable fuels. Many of these renewable fuel options have fuel chemistries that are different from those of petroleum-derived fuels. Because practical market fuels need to meet specific fuel-property requirements, a chemistry-agnostic approach to assessing the potential benefits of candidate fuels was developed using the Central Fuel Property Hypothesis (CFPH). The CFPH states that fuel properties are predictive of the performance of the fuel, regardless of the fuel's chemical composition. In order to use this hypothesis to assess the potential of fuel candidates to increase efficiency in spark-ignition (SI) engines, the individual contributions towards efficiency potential in an optimized engine must be quantified in a way that allows the individual fuel properties to be traded off for one another. This review article begins by providing an overview of the historical linkages between fuel properties and engine efficiency, including the two dominant pathways currently being used by vehicle manufacturers to reduce fuel consumption. Then, a thermodynamic-based assessment to quantify how six individual fuel properties can affect efficiency in SI engines is performed: research octane number, octane sensitivity, latent heat of vaporization, laminar flame speed, particulate matter index, and catalyst light-off temperature. The relative effects of each of these fuel properties is combined into a unified merit function that is capable of assessing the fuel property-based efficiency potential of fuels with conventional and unconventional compositions.

42 ENGINEERING↗
DOE OSTI2025

Pseudo-viscous modeling of transport in dense granular flows for thermal energy storage applications

Dense, granular flows were examined to effectively capture and model bulk viscous properties in thin packed beds. A modified Couette cell with particle image velocimetry was used to experimentally determine pseudo-viscosity properties of four particulate media with varying morphologies: (1) iron oxide-coated SiO 2 particles, (2) CARBOBEAD CP30-60 particles, (3) CARBOBEAD CP40-100 particles, and (4) Al 2 O 3 beads. The pseudo-viscosity functions were fitted using a power law to correlate the measured shear stress as a function of measured shear rate. The pseudo-viscous functions were used as inputs to computation fluid dynamics models for a single-phase viscous fluid to predict granular flow profiles. Steady-state free surface velocity profiles at angular velocities <7 rad/s predicted by the model were in good agreement with the experimental particle image velocimetry measurements, resulting in Pearson correlation coefficients of 0.97 for iron-oxide coated SiO 2 particles and 0.95 for CP30-60 particles. As a result, this alternative approach to measuring pseudo-viscous properties under shearing and modeling bulk transport behavior of granular flow using computation fluid dynamics model offered significant reduction in computational load compared to discrete element methods.

14 SOLAR ENERGY↗
DOE OSTI2023

Divergent accumulation of amino sugars and lignins mediated by soil functional carbon pools under tropical forest conversion

Tropical primary forests are being destroyed at an alarming rate and converted for other land uses which is expected to greatly influence soil carbon (C) cycling. However, our understanding of how tropical forest conversions affect the accumulation of compounds in soil functional C pools remains unclear. Here, we collected soils from primary forests (PF), secondary forests (SF), oil-palm (OP), and rubber plantations (RP), and assessed the accumulation of plant- and microbial-derived compounds within soil organic carbon (SOC), particulate (POC) and mineral-associated (MAOC) organic C. PF conversion to RP greatly decreased SOC, POC, and MAOC concentrations, whereas conversion to SF increased POC concentrations and decreased MAOC concentrations, and conversion to OP only increased POC concentrations. PF conversion to RP decreased lignin concentrations and increased amino sugar concentrations in SOC pools which increased the stability of SOC, whereas conversion to SF only increased the lignin concentrations in POC, and conversion to OP just increased lignin concentrations in POC and decreased it in MAOC. We observed divergent dynamics of amino sugars (decrease) and lignin (increase) in SOC with increasing SOC. Only lignin concentrations increased in POC with increasing POC and amino sugars concentrations decreased in MAOC with increasing MAOC. Conversion to RP significantly decreased soil enzyme activities and microbial biomasses. Lignin accumulation was associated with microbial properties, whereas amino sugar accumulation was mainly associated with soil nutrients and stoichiometries. These results suggest that the divergent accumulation of plant- and microbial-derived C in SOC was delivered by the distribution and original composition of functional C pools under forest conversions. Forest conversions changed the formation and stabilization processes of SOC in the long run which was associated with converted plantations and management. As a result, the important roles of soil nutrients and stoichiometry also provide a natural-based solution to enhance SOC sequestration via nutrient management in tropical forests.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Natural and Anthropogenically Influenced Isoprene Oxidation in Southeastern United States and Central Amazon

Anthropogenic emissions alter secondary organic aerosol (SOA) formation chemistry from naturally emitted isoprene. Here, we use correlations of tracers and tracer ratios to provide new perspectives on sulfate, NO x , and particle acidity influencing isoprene-derived SOA in two isoprene-rich forested environments representing clean to polluted conditions-wet and dry seasons in central Amazonia and Southeastern U.S. summer. We used a semivolatile thermal desorption aerosol gas chromatograph (SV-TAG) and filter samplers to measure SOA tracers indicative of isoprene/HO 2 (2-methyltetrols, C5-alkene triols, 2-methyltetrol organosulfates) and isoprene/NO x (2-methylglyceric acid, 2-methylglyceric acid organosulfate) pathways. Summed concentrations of these tracers correlated with particulate sulfate spanning three orders of magnitude, suggesting that 1 μg m -3 reduction in sulfate corresponds with at least ~0.5 μg m -3 reduction in isoprene-derived SOA. We also find that isoprene/NO x pathway SOA mass primarily comprises organosulfates, ~97% in the Amazon and ~55% in Southeastern United States. We infer under natural conditions in high isoprene emission regions that preindustrial aerosol sulfate was almost exclusively isoprene-derived organosulfates, which are traditionally thought of as representative of an anthropogenic influence. We further report the first field observations showing that particle acidity correlates positively with 2-methylglyceric acid partitioning to the gas phase and negatively with the ratio of 2-methyltetrols to C 5 -alkene triols.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Mobility of Radionuclides in Fractured Carbonate Rocks: Lessons from a Field-Scale Transport Experiment

Current research on radionuclide disposal is mostly conducted in granite, clay, saltstone, or volcanic tuff formations. These rock types are not always available to host a geological repository in every nuclear waste-generating country, but carbonate rocks may serve as a potential alternative. To assess their feasibility, a forced gradient cross-borehole tracer experiment was conducted in a saturated fractured chalk formation. The mobility of stable Sr and Cs (as analogs for their radioactive counterparts), Ce (an actinide analog), Re (a Tc analog), bentonite particles, and fluorescent dye tracers through the flow path was analyzed. The migration of each of these radionuclide analogs (RAs) was shown to be dependent upon their chemical speciation in solution, their interactions with bentonite, and their sorption potential to the chalk rock matrix. The brackish groundwater resulted in flocculation and immobilization of most particulate RAs. Nevertheless, the high permeability of the fracture system allowed for fast overall transport times of all aqueous RAs investigated. This study suggests that the geochemical properties of carbonate rocks may provide suitable conditions for certain types of radionuclide storage (in particular, brackish, high-porosity, and low-permeability chalks). Nevertheless, careful consideration should be given to high-permeability fracture networks that may result in high radionuclide mobility.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Midlatitude Ozone Depletion and Air Quality Impacts from Industrial Halogen Emissions in the Great Salt Lake Basin

We report aircraft observations of extreme levels of HCl and the dihalogens Cl 2 , Br 2 , and BrCl in an industrial plume near the Great Salt Lake, Utah. Complete depletion of O 3 was observed concurrently with halogen enhancements as a direct result of photochemically produced halogen radicals. Observed fluxes for Cl 2 , HCl, and NO x agreed with facility-reported emissions inventories. Bromine emissions are not required to be reported in the inventory, but are estimated as 173 Mg year –1 Br 2 and 949 Mg year –1 BrCl, representing a major uncounted oxidant source. A zero-dimensional photochemical box model reproduced the observed O 3 depletions and demonstrated that bromine radical cycling was principally responsible for the rapid O 3 depletion. Inclusion of observed halogen emissions in both the box model and a 3D chemical model showed significant increases in oxidants and particulate matter (PM 2.5 ) in the populated regions of the Great Salt Lake Basin, where winter PM 2.5 is among the most severe air quality issues in the U.S. The model shows regional PM 2.5 increases of 10%–25% attributable to this single industrial halogen source, demonstrating the impact of underreported industrial bromine emissions on oxidation sources and air quality within a major urban area of the western U.S.

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

Life Cycle Emissions and Health Cost Impacts of Producing Ethanol and Electricity from Willow and Switchgrass in the Riparian Buffers of Mid-Atlantic United States

The United States (US Mid-Atlantic Region (MAR) has the potential to grow a variety of perennial feedstocks such as switchgrass and shrub willow to increase domestic energy production. These cellulosic feedstocks have also shown improved ecosystem services, such as soil carbon sequestration, nitrate leaching reduction, and flood mitigation along rivers and streams as partially harvested riparian buffers. To examine the effects on greenhouse gases (GHGs) and criteria air pollutants (CAPs) from using these feedstocks to produce ethanol or electricity, we conducted a comprehensive life cycle assessment (LCA) and estimated the impact on human health costs when land use is changed from corn production for ethanol. Results indicate up to 54% reduced GHG per hectare from using willow and switchgrass feedstock sources to produce ethanol instead of corn. However, there was a trade-off in terms of CAP emission, as grass-based energy emitted more NO x and SO x compared to the corn ethanol pathway, except for SO X emissions from willow-based electricity. Electricity from cellulosic biomass had higher particulate matter (PM) emission compared to that from corn ethanol. Estimates for health cost to society ranged from $2498 ha –1 for electricity from switchgrass to a net benefit of $448 ha –1 for ethanol production from willow, depending on varying biomass yield under different market scenarios. Although using cellulosic feedstocks to produce bioenergy has great potential to reduce GHG emissions, CAP control measures are needed to manage CAP-induced health costs.

Bioenergy↗
DOE OSTI2026

Observations of Nocturnal Sulfuric Acid Formation in Pittsburgh, PA

Measurements of sulfuric acid (H 2 SO 4 ) and sulfur trioxide (SO 3 ) were conducted in Pittsburgh, Pennsylvania, during field campaigns in Fall 2023 and Fall 2024. These measurements identified nocturnal concentrations of H 2 SO 4 comparable to those of daytime values. Nocturnal H 2 SO 4 concentrations were observed to increase by 5 × 10 5 to 5 × 10 7 molecules cm –3 above background on 16 of the 31 measurement nights. The median peak concentration during events was 6.5 × 10 6 molecules cm –3 , with a maximum of 1.0 × 10 8 molecules cm –3 , exceeding previously reported nighttime concentrations. Increases in H 2 SO 4 concentrations were positively correlated with the anomalously high SO 3 concentrations and condensation sink rates, indicating that the formation of H 2 SO 4 increased to overcome the loss rates to particles. Increases in particulate mass and the mass fraction of metals commonly emitted from coal combustion and steel production were also observed. The air masses were traced back to the southeast of Pittsburgh, a region home to a steel mill, coke plant, and a steel processing plant. The observations indicate a previously unrecognized nighttime formation pathway for H 2 SO 4 , potentially from heterogeneous catalysis with metal or black carbon, originating from steel and coke plant emissions. Further measurements are needed to identify key compounds and chemical processes driving these increases in nocturnal H 2 SO 4 concentrations.

aerosols↗
DOE OSTI2023

Visualizing Overall Water Splitting on Single Microcrystals of Phosphorus-Doped BiVO 4 by Photo-SECM

Particulate bismuth vanadate (BiVO4) has attracted considerable interest as a promising photo(electro)catalyst for visible-light-driven water oxidation, however, overall water splitting (OWS) has been difficult to attain because its conduction band is too positive for efficient hydrogen evolution. Using photo-scanning electrochemical microscopy (photo-SECM) with a chemically modified nanotip, we visualized for the first time the OWS at a single truncated bipyramidal microcrystal of phosphorus-doped BiVO 4 . The tip simultaneously served as a light guide to illuminate the photocatalyst and as an electrochemical nanoprobe to observe and quantitatively measure local oxygen and hydrogen fluxes. The obtained current patterns for both O 2 and H 2 agree well with the accumulation of photogenerated holes and electrons on {010} basal and {110} lateral facets, respectively. Furthermore, the developed experimental approach is an important step towards nanoelectrochemical mapping of the activity of photocatalyst particles at the sub-facet level.

bismuth vanadate↗
DOE OSTI2024

Two decades of aerosol trends over India: seasonal characteristics and urban-rural dynamics

Abstract India faces significant air quality challenges, with one of the highest air pollution levels of any country in the world. Here, we examine two decades (2001–2019) of both particulate matter (PM 2.5 ) concentration and aerosol optical depth (AOD) over the country. Increases are seen between the two decadal averages, for 2001–2010 and 2011–2019, in western India, particularly in the Indo-Gangetic Plain (IGP). IGP region, including Bihar, West Bengal, Jharkhand, and Uttar Pradesh, shows the highest increases in AOD (+0.03, 13%) and PM 2.5, s (+8 µ g m −3 ). Seasonal AOD patterns fluctuate, with the IGP experiencing the highest wintertime increase, especially in Bihar (+0.07). In summer, there are increases in AOD along the southern and eastern coastal areas. Monsoons cause a slight rise in AOD, except in Rajasthan. In the post-monsoon season, the IGP experiences a notable increase in AOD (+0.057, 25%), potentially driven by biomass burning in Bihar (+0.11) and Uttar Pradesh (+0.075). Dividing our study area into urban and peri-urban clusters ( n = 2791), AOD is found to be similar, possibly due to advective mixing. However, the differences between urban and rural areas become more noticeable, especially in the second decade. Correlations between AOD and PM 2.5, g vary across locations, with the highest found in Kanpur ( R 2 = 0.61) and weaker in Delhi ( R 2 = 0.42), highlighting the need for more ground monitoring. However, it suggests that satellite-derived AOD can generally be used to examine trends in PM 2.5 over longer time frames.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Tracking Soiling Losses: Assessment, Uncertainty, and Challenges in Mapping

Several models have been presented in the recent years to estimate the magnitude of soiling from environmental parameters. However, these models are often based on data from a single site, or at most a few sites, and only limited data are, as of yet, available on their uncertainty. The present work aims to present a first comparative analysis of soiling estimation models, using measured soiling data from various locations in the USA. The study also investigates the impact that the source of the input data can have on the estimation. The results show that the model selection is only one of the factors that can affect the evaluation. Indeed, the use of satellite-derived or ground-mounted particulate matter data can lead to the generation of different soiling maps, with factors greater than 2x between the modeled losses. The current challenges and the unanswered questions that can bias soiling estimation are discussed. Additionally, potential research directions to improve the quality of soiling modeling are identified.

14 SOLAR ENERGY↗
DOE OSTI2022

Effects of experimental nitrogen deposition on soil organic carbon storage in Southern California drylands

Atmospheric nitrogen (N) deposition is enriching soils with N across biomes. Soil N enrichment can increase plant productivity and affect microbial activity, thereby increasing soil organic carbon (SOC), but such responses vary across biomes. Drylands cover ~45% of Earth's land area and store ~33% of global SOC contained in the top 1 m of soil. Nitrogen fertilization could, therefore, disproportionately impact carbon (C) cycling, yet whether dryland SOC storage increases with N remains unclear. To understand how N enrichment may change SOC storage, we separated SOC into plant–derived, particulate organic C (POC), and largely microbially derived, mineral–associated organic C (MAOC) at four N deposition experimental sites in Southern California. Theory suggests that N enrichment increases the efficiency by which microbes build MAOC (C stabilization efficiency) if soil pH stays constant. But if soils acidify, a common response to N enrichment, then microbial biomass and enzymatic organic matter decay may decrease, increasing POC but not MAOC. We found that N enrichment had no effect on C fractions except for a decrease in MAOC at one site. Specifically, despite reported increases in plant biomass in three sites and decreases in microbial biomass and extracellular enzyme activities in two sites that acidified, POC did not increase. Furthermore, microbial C use and stabilization efficiency increased in a non–acidified site, but without increasing MAOC. Instead, MAOC decreased by 16% at one of the sites that acidified, likely because it lost 47% of the exchangeable calcium (Ca) relative to controls. Indeed, MAOC was strongly and positively affected by Ca, which directly and, through its positive effect on microbial biomass, explained 58% of variation in MAOC. Finally, long–term effects of N fertilization on dryland SOC storage appear abiotic in nature, such that drylands where Ca–stabilization of SOC is prevalent and soils acidify, are most at risk for significant C loss.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Indoor air quality in California homes with code-required mechanical ventilation

Data were collected in 70 detached houses built in 2011-2017 in compliance with the mechanical ventilation requirements of California's building energy efficiency standards. Each home was monitored for a 1-week period with windows closed and the central mechanical ventilation system operating. Pollutant measurements included time-resolved fine particulate matter (PM 2.5 ) indoors and outdoors and formaldehyde and carbon dioxide (CO 2 ) indoors. Time-integrated measurements were made for formaldehyde, NO 2 , and nitrogen oxides (NO X ) indoors and outdoors. Operation of the cooktop, range hood, and other exhaust fans was continuously recorded during the monitoring period. Onetime diagnostic measurements included mechanical airflows and envelope and duct system air leakage. All homes met or were very close to meeting the ventilation requirements. On average, the dwelling unit ventilation fan moved 50% more airflow than the minimum requirement. Pollutant concentrations were similar to or lower than those reported in a 2006-2007 study of California new homes built in 2002-2005. Mean and median indoor concentrations were lower by 44% and 38% for formaldehyde and 44% and 54% for PM 2.5 . Ventilation fans were operating in only 26% of homes when first visited, and the control switches in many homes did not have informative labels as required by building standards.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗