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At least 379 records · Page 21

Investigation of fuel film formation and soot emissions in a GDI engine during cold-start with Split-injection strategies

This study investigates the impact of fuel-film formation on engine-out soot emissions in a gasoline direct injection (GDI) engine under cold-start conditions. Split-injection strategies were applied by varying the number of injections, injection duration, and total fuel quantity to affect wall wetting and control the average in-cylinder equivalence ratio. A combined experimental and numerical approach was employed to analyze fuel-film deposition, combustion efficiency, and engine-out soot and unburnt hydrocarbons (UHC) emissions. In particular, fuel film distribution estimated by means of non-reacting, 3-D, computational fluid dynamics (CFD) simulations, together with experimentally measured soot data, were used to investigate fuel film formation and its role in soot generation. In the experiments, a skip-fired engine control strategy was applied to mimic the transient nature of engine cold-start operation. The results indicate that, under the same total number of injections, increasing the average in-cylinder equivalence ratio through longer injection durations improves combustion stability, as indicated by the decrease of the coefficient of variation of IMEP n (Net Indicated Mean Effective Pressure) from 6.0 % to 0.6 %. However, this strategy leads to higher soot emissions, which increased by nearly an order of magnitude, primarily due to enhanced wall-film formation. In contrast, increasing the number of injections while maintaining a constant equivalence ratio significantly impacts fuel-film deposition and, consequently, soot emissions, with a fivefold reduction of the measured engine-out soot, decreasing from 3.5 mg to 0.7 mg. A soot-film correlation was developed and achieved a high coefficient of determination (r 2 = 0.95) and was further extended to account for spark timing effects. These findings confirm the effectiveness of split-injection for avoiding wall film formation and soot emissions, and the critical role of fuel film in soot generation, supporting the hypothesis that pool fires play a crucial role in contributing to soot formation under these cold-start conditions. In conclusion, the study also indicates the value of a predictive soot-film correlation for developing cold-start emission control strategies.

Engine Cold-start↗

Mechanical ventilation and indoor air quality in recently constructed U.S. homes in marine and cold-dry climates

Data were collected to characterize whole-house mechanical ventilation (WHMV) and indoor air quality (IAQ) in 55 homes in the Marine climate of Oregon and the Cold-Dry climate of Colorado in the U.S. Sixteen homes were monitored for two weeks, with and without WHMV operating. Ventilation airflows; airtightness; time-resolved CO 2 , PM2.5 and radon; and time-integrated NO 2 , NO X and formaldehyde were measured. Participants provided information about IAQ-impacting activities, perceptions and ventilation use. All homes had operational cooktop ventilation and bathroom exhaust. Thirty homes had equipment that could meet the ASHRAE 62.2–2010 standard with continuous or controlled runtime and 34 had some WHMV operating as found. Thirty-five of 46 participants with WHMV reported they did not know how to operate it, and only half of the systems were properly labeled. Two-week homes had lower formaldehyde, radon, CO 2 and NO (NO X -NO 2 ) when operated with WHMV, and had faster PM 2.5 decays following indoor emission events. Overall IAQ satisfaction was similar in Oregon and Colorado, but more Colorado participants (19% vs 3%) felt their IAQ could be improved and more reported dryness as a problem (58% vs. 14%). The collected data indicate that there are benefits of operating WHMV, even when continuous use may not be needed because outdoor pollutant concentrations are low and indoor sources do not present substantial challenges.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Interactions among soil texture, pore structure, and labile carbon influence soil carbon gains

Perennial vegetation with high plant diversity, e.g., restored prairie, is known for stimulation of soil carbon (C) gains, due in part to enhanced formation of pore structure beneficial for long-term C storage. However, the prevalence of this phenomenon across soils of different types remains poorly understood. The aim of the study was to assess the associations between pore structure, soil C, and their differences in monoculture switchgrass and polyculture restored prairie vegetation across a wide range of soils dominating the Upper Midwest of the USA. Six experimental sites were sampled, representing three soil types with texture ranging from sandy to silt loams. The two vegetation systems studied at each site were (i) monoculture switchgrass (Panicum virgatum L.), and (ii) polyculture restored prairie, also containing switchgrass as one of its species. X-ray computed micro-tomography (µCT) was employed to analyze soil pore structure. Structural equation modeling and multiple path analyses were used to assess direct and indirect effects of soil texture and pore characteristics on microbial biomass C (MBC), particulate organic matter (POM), dissolved organic C (DOC), short-term respiration (CO 2 ), and, ultimately, soil organic C (SOC). Across studied sites, prairie increased fractions of medium (50–150 µm Ø) pores by 11–45 %, SOC by 3–69 %, and MBC by 18–59 % (except for one site). The greater were the prairie-induced increases in the medium pore volumes, the greater were the prairie-induced SOC gains. Greater C losses via CO 2 and DOC contributed to slower C accumulation in the prairie soil. We surmise that the interactive feedback loop relating medium pores and soil C acts across a wide range of soil textures and is an important mechanism through which perennial vegetation with high plant diversity, such as restored prairie, promotes rapid SOC gains.

54 ENVIRONMENTAL SCIENCES↗

Satellite-based aerosol optical depth estimates over the continental U.S. during the 2020 wildfire season: Roles of smoke and land cover

Wildfires produce smoke that can affect an area >1000 times the burn extent, with far-reaching human health, ecologic, and economic impacts. Accurately estimating aerosol load within smoke plumes is therefore crucial for understanding and mitigating these impacts. We evaluated the effectiveness of the latest Collection 6.1 MODIS Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm in estimating aerosol optical depth (AOD) across the U.S. during the historic 2020 wildfire season. We compared satellite-based MAIAC AOD to ground-based AERONET AOD measurements during no-, light-, medium-, and heavy-smoke conditions identified using the Hazard Mapping System Fire and Smoke Product. This smoke product consists of maximum extent smoke polygons digitized by analysts using visible band imagery and classified according to smoke density. We also examined the strength of the correlations between satellite- and ground-based AOD for major land cover types under various smoke density levels. MAIAC performed well in estimating AOD during smoke-affected conditions. Correlations between MAIAC and AERONET AOD were strong for medium- (r = 0.91) and heavy-smoke (r = 0.90) density, and MAIAC estimates of AOD showed little bias relative to ground-based AERONET measurements (normalized mean bias = 3 % for medium, 5 % for heavy smoke). During two high AOD, heavy smoke episodes, MAIAC underestimated ground-based AERONET AOD under mixed aerosol (i.e., smoke and dust; median bias = −0.08) and overestimated AOD under smoke-dominated (median bias = 0.02) aerosol. MAIAC most overestimated ground-based AERONET AOD over barren land (mean NMB = 48 %). Our findings indicate that MODIS MAIAC can provide robust estimates of AOD as smoke density increases in coming years. Increased frequency of mixed aerosol and expansion of developed land could affect the performance of the MAIAC algorithm in the future, however, with implications for evaluating wildfire-associated health and welfare effects and air quality standards.

54 ENVIRONMENTAL SCIENCES↗

Combining organic amendments with enhanced rock weathering shifts soil carbon storage in croplands

Enhanced rock weathering (ERW) involves applying crushed silicate minerals to cropland soils to remove carbon dioxide and stabilize the global climate. If practiced widely, ERW has the potential to mitigate climate change and improve soil health and crop productivity. However, most ERW studies emphasize inorganic carbon (IC) chemistry, using model-based estimates and short-term mesocosms. Limited field data exist on how ERW interacts with organic amendments to affect organic carbon (C) cycling in soils. In a three-year field study in conventionally managed, irrigated maize fields, we monitored how key soil variables responded to crushed rock-alone, and in combination with compost and/or biochar. We measured weathering indicators (pH, major cations, and IC contents) and organic fractions, including particulate organic matter (POM), mineral-associated organic matter (MAOM), microbial biomass C, and water-extractable organic C. Rock-alone treatments increased weathering proxies (pH and IC) and showed an increasing trend in POM and MAOM, relative to control. In contrast, combining crushed rock with organic amendments resulted in lower soil organic C and nitrogen (N) concentrations (in both POM and MAOM) compared to organic amendments alone, though IC increased in the rock+compost treatment. Combining rock with both compost and biochar (compost/biochar) significantly lowered MAOM-N compared to compost/biochar alone. Overall, co-applying rock with organic inputs may promote weathering and C accrual but slow the accrual rate of organic C and N relative to organic amendments alone. Quantifying these trade-offs over multiple years and scales is critical to integrating ERW with existing soil health practices and climate mitigation strategies.

Biological and medical sciences↗

Getting to the root of the problem: Soil carbon and microbial responses to root inputs within a buried paleosol along an eroding hillslope in southwestern Nebraska, USA

Large quantities of soil carbon (C) can persist within paleosols for millennia due to burial and subsequent isolation from plant-derived inputs, atmospheric conditions, and microbial activity at the modern surface. Erosion exposes buried soils to modern root-derived C influx via root exudation and root turnover, thus stimulating microbial activity leading to SOC decomposition and accumulation through organo-mineral stabilization of modern C. With this study we aim to quantify how modern root-derived C inputs impact paleosol C decomposition and stabilization across varying degrees of isolation from modern surface conditions in southwestern Nebraska, USA, where hillslope erosion is bringing a buried Late-Pleistocene-early Holocene paleosol (the “Brady Soil”) closer to the modern surface. We collected Brady Soil samples from 0.2m, 0.4m, and 1.2m below the modern surface and conducted two lab-based incubations. Soils were amended with either (1) a lab-synthesized mixture of low molecular weight compounds (12 atom% 13 C), or (2) 13 C enriched root residues (92 atom% 13 C), in 30-day and 240-day incubation experiments, respectively. Here we determined microbial responses to synthetic root exudates and residues by partitioning the 13 C label from Brady Soil C, including measurements of total, root, and primed C respiration, microbial biomass C (MBC), microbial C use efficiency (CUE). To assess the capacity of isolated paleosols to accrue modern plant C, we used Nano-scale Secondary Ion Mass Spectrometry imaging. We found that: (1) adding root-derived C inputs primed Brady Soil C across all depths, and was mediated by depth and composition of root additions; (2) root-derived C inputs stimulated microbial biomass C (MBC) growth similarly across depths, but the magnitude of CUE and MBC varied by chemistry of root-derived additions; (3) new particulate organic matter was incorporated into mineral-associated pools over time; (4) material from the added root residues was found in association with bacterial cells and fungal hyphae as well as with soil aggregate and mineral surfaces. Our study shows that paleosols defy expectations of C content and reactivity with depth, and changes in land cover and climate will expose buried paleosols to modern surface conditions, increasing respired C. This work highlights the importance of evaluating the role resurfacing buried soils through landscape change plays in C cycle feedbacks to the climate system.

54 ENVIRONMENTAL SCIENCES↗

Use of Transmission Electron Microscopy for Analysis of Aerosol Particles and Strategies for Imaging Fragile Particles

For over 25 years, transmission electron microscopy (TEM) has provided a method for the study of aerosol particles with sizes from below the optical diffraction limit to several microns, resolving the particles as well as smaller features. The wide use of this technique to study aerosol particles has contributed important insights about environmental aerosol particle samples and model atmospheric systems. TEM produces an image that is a 2D projection of aerosol particles that have been impacted onto grids and, through associated techniques and spectroscopies, can contribute additional information such as the determination of elemental composition, crystal structure, and 3D particle structures. Soot, mineral dust, and organic/inorganic particles have all been analyzed using TEM and spectroscopic techniques. TEM, however, has limitations that are important to understand when interpreting data including the ability of the electron beam to damage and thereby change the structure and shape of particles, especially in the case of particles composed of organic compounds and salts. In this paper, we concentrate on the breadth of studies that have used TEM as the primary analysis technique. Another focus is on common issues with TEM and cryogenic-TEM. Insights for new users on best practices for fragile particles, that is, particles that are easily susceptible to damage from the electron beam, with this technique are discussed. Tips for readers on interpreting and evaluating the quality and accuracy of TEM data in the literature are also provided and explained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two-Dimensional Copper Iodide-Based Inorganic–Organic Hybrid Semiconductors: Synthesis, Structures, and Optical and Transport Properties

A group of copper iodide-based hybrid semiconductors with the general formula of 2D-CuI(L) 0.5 (L = organic ligands) are synthesized and structurally characterized. All compounds are two-dimensional (2D) networks made of one-dimensional (1D) copper iodide staircase chains that are interconnected by bidentate nitrogen-containing ligands. Results from optical absorption and emission experiments and density functional theory (DFT) calculations reveal that their photoluminescence (PL) can be systematically tuned by adjusting the lowest unoccupied molecular orbital (LUMO) energies of the organic ligands. Charge carrier transport measurements were carried out for the first time on single crystals of selected 2D-CuI(L) 0.5 structures, and the results show that they possess p-type conductivity with a Hall mobility of ~1 cm 2 V -1 s -1 for 2D-CuI(pm) 0.5 and 0.13 cm 2 V -1 s -1 for 2D-CuI(pz) 0.5 , respectively. These values are comparable to or higher than the mobilities of typical highly luminescent organic semiconductors. Finally, this work suggests that robust, high-dimensional copper iodide hybrid semiconductors are promising candidates to be considered as a new type of emissive layer for light-emitting diode (LED) devices.

36 MATERIALS SCIENCE↗

Fuel Properties of Oxymethylene Ethers with Terminating Groups from Methyl to Butyl

Oxymethylene ethers (OMEs) have been studied as possible additives or replacements for diesel fuels. Typically, studies have considered only methyl-terminated OMEs. Recent structure-property relationship models suggest that extended-alkyl OMEs may provide improvements to many of the properties of methyl-terminated OMEs that make them less suitable as diesel fuel blendstocks. In this work, we describe the synthesis and characterization of 16 different OMEs with methyl, ethyl, propyl, butyl, isopropyl, and isobutyl terminating alkyl groups with varying oxymethylene chain length. Indicated Cetane Number, Lower Heating Value, Flash Point, Density, Viscosity, Vapor Pressure, and Oxidative Stability are tested via ASTM standard methods. Additionally, Water Solubility, Boiling Point, seal material compatibility, and sooting propensity (via the Yield Sooting Index) are measured for these fuels. For diesel compatibility, all tested OMEs except smaller methyl and ethyl OMEs, and the branched isopropyl OME, meet cetane number requirements. Further, extending the alkyl end group increases the heating value, but all OMEs, due to their oxygen content, have heating values less than diesel; despite this, all OMEs show significant reductions in soot production per unit heating value. Only the heaviest OMEs meet diesel viscosity requirements, and most are higher density than diesel. OMEs with larger alkyl groups show the highest stability under accelerated auto-oxidation conditions. Increases in alkyl group length cause order of magnitude reduction in water solubility, from hundreds of g/L for methyl terminated OMEs to hundreds of mg/L for butyl terminated OMEs. Limited seal material testing indicates that PEEK polymers are unaffected by OMEs; while extended alkyl groups may improve compatibility with FKM (Viton), other common elastomers (NBR, silicone) remain incompatible with all tested OMEs. Overall, it is found that methyl-terminated OMEs exhibit the most potential for soot reduction, but OMEs with larger propyl and butyl terminating alkyl groups show improved compatibility with existing diesel systems.

09 BIOMASS FUELS↗

Flow Reactor Study of the Soot Precursors of Novel Cycloalkanes as Synthetic Jet Fuel Compounds: Octahydroindene, p -Menthane, and 1,4-Dimethylcyclooctane

Sustainable aviation fuels (SAFs) or Synthetic aviation turbine fuels (SATFs) derived from nonpetroleum sources are essential for energy security and a strong rural and agricultural economy. Airplanes operating on SAF can have lower particle emissions compared to those of conventional jet fuel, reducing air quality impacts near airports. Processing biobased isoprene or wood and agricultural waste can produce cycloalkane-rich fuels with properties meeting ASTM International’s SATF requirements. The unique structures of these cycloalkanes yield lower soot emissions because of their lack of aromatic rings. We measured the soot formation tendency as yield sooting index (YSI) and used laminar flow reactor experiments to evaluate soot precursors formed for isoprene-derived compounds p-menthane and 1,4-dimethylcyclooctane (DMCO), and octahydroindene (OHI)─ produced from woody biomass via catalytic fast pyrolysis. The combustion chemistry of the OHI and DMCO has not been previously studied. Experiments were conducted at 10 bar from 800 to 1200 K, equivalence ratios of 1.0 and 3.0, and residence times of 1.0 and 0.6 s, respectively. Experimentally detected species were used to elucidate the mechanisms of soot precursor formation. OHI exhibited the highest YSI (94.5) and formed a high concentration of benzene primarily by direct dehydrogenation of the six-membered ring. p-Menthane (YSI 92.0) and DMCO (YSI 85.0) oxidation products included fewer aromatic components but higher benzene precursors, including 1,3-butadiene, propyne, and allene. This suggests that the ring-opening pathway is dominant over the dehydrogenation pathway in the benzene formation for these compounds. This experimental speciation provides insight into the influence of the cycloalkane structure on the sooting tendencies of potential SAF blend components, thereby aiding in fuel design processes.

09 BIOMASS FUELS↗

Life-Cycle Greenhouse Gas Emissions and Human Health Trade-Offs of Organic Waste Management Strategies

Waste-to-energy systems can play an important role in diverting organic waste from landfills. However, real-world waste management can differ from idealized practices, and emissions driven by microbial communities and complex chemical processes are poorly understood. This study presents a comprehensive life-cycle assessment, using reported and measured data, of competing management alternatives for organic municipal solid waste including landfilling, composting, dry anaerobic digestion (AD) for the production of renewable natural gas (RNG), and dry AD with electricity generation. Landfilling is the most greenhouse gas (GHG)-intensive option, emitting nearly 400 kg CO 2e per tonne of organic waste. Composting raw organics resulted in the lowest GHG emissions, at -41 kg CO 2e per tonne of waste, while upgrading biogas to RNG after dry AD resulted in -36 to -2 kg CO 2e per tonne. Monetizing the results based on social costs of carbon and other air pollutant emissions highlights the importance of ground-level NH3 emissions from composting nitrogen-rich organic waste or post-AD solids. However, better characterization of material-specific NH 3 emissions from landfills and land-application of digestate is essential to fully understand the trade-offs between alternatives.

54 ENVIRONMENTAL SCIENCES↗

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↗

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↗