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Octane Requirements of Lean Mixed-Mode Combustion in a Direct-Injection Spark-Ignition Engine

Here, this study investigates the octane requirements of a hybrid flame propagation and controlled autoignition mode referred to as mixed-mode combustion (MMC), which allows for strong control over combustion parameters via a spark-initiated deflagration phase. Due to the throughput limitations associated with both experiments and 3-D computational fluid dynamics calculations, a hybrid 0-D and 1-D modeling methodology was developed, supported by experimental validation data. This modeling approach relied on 1-D, two-zone engine simulations to predict bulk in-cylinder thermodynamic conditions over a range of engine speeds, compression ratios, intake pressures, trapped residual levels, fueling rates, and spark timings. Those predictions were then transferred to a 0-D chemical kinetic model, which was used to evaluate the autoignition behavior of fuels when subjected to temperature–pressure trajectories of interest. Finally, the predicted autoignition phasings were screened relative to the progress of the modeled deflagration-based combustion in order to determine if an operating condition was feasible or infeasible due to knock or stability limits. The combined modeling and experimental results reveal that MMC has an octane requirement similar to modern stoichiometric spark-ignition engines in that fuels with high research octane number (RON) and high octane sensitivity (S) enable higher loads. Experimental trends with varying RON and S were well predicted by the model for 1000 and 1400 rpm, confirming its utility in identifying the compatibility of a fuel’s autoignition behavior with an engine configuration and operating strategy. However, the model was not effective in predicting (nor designed to predict) operability limits due to cycle-to-cycle variations, which experimentally inhibited operation of some fuels at 2000 rpm. Putting the operable limits and efficiency from MMC in the context of a state-of-the-art engine, the MMC showed superior efficiencies over the range investigated, demonstrating the potential to further improve fuel economy.

33 ADVANCED PROPULSION SYSTEMS↗

Persistent Polar Ocean Warming in a Strategically Geoengineered Climate

A novel geoengineering approach designed to moderate the effects of continued greenhouse gas emissions is examined in a large ensemble of 21st century climate simulations. Stratospheric sulfur injections are imposed at discrete latitudes of 15° and 30° in both hemispheres with the aim of minimizing changes in surface temperature, both in the global mean and in its gradients between hemispheres and from equator to pole. The approach successfully accomplishes these goals and reduces several major adverse impacts found in earlier geoengineering applications, such as overcooling the tropics and weakening rainfall over land. Nonetheless, responses over ocean are identified that drive shifts in the global ocean circulation and structure. The responses result in an acceleration of the meridional overturning circulation in the Atlantic Ocean and continued warming of the deep and polar oceans, particularly in the vicinity of southern Greenland, with the potential to drive continued cryospheric melt and global sea level rise. Related changes in tropical rainfall are also identified. Despite a successful moderation of surface warming and reduction of the planetary energy imbalance, these simulations demonstrate the potential complexity of the coupled climate response to geoengineering implementations, highlighting the need for significant advances in our understanding of the coupled climate system and the continued refinement of such strategies as a prerequisite to their successful implementation.

Fasullo, John↗

Reactive transport modeling of the Aquifer Thermal Energy Storage (ATES) system at Stockton University, New Jersey during seasonal operations

Hydrogeochemical processes associated with Aquifer Thermal Energy Storage (ATES) operations can often impact the system performance owing to mineral precipitation either at the wellbore or in the aquifer owing to changes in temperature and fluid disequilibria. Although failure of ATES systems due to mineral precipitation ("fouling") is common, predictive reactive-transport models have rarely been applied to plan their design and operation. Here, the objective of this study is to develop a reactive-transport model by coupling thermal, hydrological, and chemical (THC) processes to evaluate effects of introduced atmospheric oxygen on water chemistry, mineral precipitation/dissolution, porosity, and permeability changes associated with an ATES system at Stockton University (New Jersey, USA). The THC model builds on a Thermal-Hydrological-Mechanical (THM) model of the site that evaluated system failure owing to possible fracturing in the caprock or around the wellbore. The causes of the system failure are not known – potential causes include hydraulic fracturing owing to elevated pump pressures that took place, a flow pathway created by one of the boreholes, or a pre-existing natural hydrologic connection between the upper unconfined aquifer and the ATES aquifer, any of which could have led to oxygenated water entering the reservoir and causing the observed Fe-oxide fouling on well screens. The THC model is used to evaluate some of the hypotheses and observations regarding system failure owing to geochemical processes. The reactive-transport code TOUGHREACT V4 was used to model the THC processes during seasonal heating and cooling operations at the Stockton ATES site over 6 years of operation. In the THC simulations, the primary effects on geochemistry were observed when the injection water is saturated with atmospheric oxygen. Simulations show greater precipitation of goethite near the cold wells as compared to the warm wells. Although volume fractions of Fe-hydroxides were relatively small, the model was aimed at processes in the aquifer at the scale of meters and larger rather than at the scale of mm or cm (i.e., a well screen). Kaolinite is the dominant precipitating phase, also around the cold wells. Illite dissolves near the cold wells and precipitates near the warm wells. There is a net decrease in the porosity near the cold wells and increase near the warm wells, although a slight amount of thermal contraction near the cold wells and expansion near the warm wells is responsible for a significant proportion of the porosity change. Owing to the coarse discretization of the numerical grid near the wells (compared to the screen thickness) the magnitude of permeability changes at the wellbore are likely underestimated. The reactive transport model in this study can be used for characterization of aquifers, optimizing the operational parameters (temperature, pressure, pH etc.), and planning of mitigation strategies for ATES systems.

15 GEOTHERMAL ENERGY↗

Efficiency-Optimized Dual Fuel Engine with In-Cylinder Gasoline/CNG Blending

The objective of the proposed project is to demonstrate targeted blending of gasoline and natural gas as a means to reduce petroleum consumption of light-duty spark-ignition engine vehicles by at least 50%. This goal will be achieved through petroleum displacement with natural gas (NG) combined with a relative engine efficiency improvement in excess of 10% while meeting retrofitability requirements with an anticipated payback period of less than 36 months. Further through NG direct injection (DI) a 10% improvement in power density over the PFI baseline will be demonstrated. The proposed project employs a sound R&D approach and combines experimental work with state-of-the-art computational modeling to be able to demonstrate the ambitious project goals. The project spans a 30 month period and is divided in 3 phases with the initial phase focused on experimental characterization of the gaseous jet structure of the high-pressure NG DI injector which is used to validate the 3D-CFD simulation tool. The phase also includes an experimental demonstration of the fundamental feasibility of the proposed dual-fuel approach on an automotive single-cylinder research engine. The scope of the second phase includes optimization of the combustion system by means of virtual design combined with 3D-CFD analysis. The resulting optimized combustion system will be built and experimentally evaluated by the end of the 12 month period. The third and final phase expands the scope by integrating the engine results in a vehicle level simulation tool with the objective of developing an optimized engine control strategy that maximizes the efficiency benefits attainable with the limited on-board NG supplies. A detailed cost analysis to verify that the 36 month amortization period requirement is met will conclude the proposed effort.

42 ENGINEERING↗

A protocol for model intercomparison of impacts of marine cloud brightening climate intervention

A modeling protocol (defined by a series of climate model simulations with specified model output) is introduced. Studies using these simulations are designed to improve the understanding of climate impacts using a strategy for climate intervention (CI) known as marine cloud brightening (MCB) in specific regions; therefore, the protocol is called MCB-REG (where REG stands for region). The model simulations are not intended to assess consequences of a realistic MCB deployment intended to achieve specific climate targets but instead to expose responses to interventions in six regions with pervasive cloud systems that are often considered candidates for such a deployment. A calibration step involving simulations with fixed sea surface temperatures (SSTs) is first used to identify a common forcing, and then coupled simulations with forcing in individual regions and combinations of regions are used to examine climate impacts. Synthetic estimates constructed by superposing responses from simulations with forcing in individual regions are considered a means of approximating the climate impacts produced when MCB interventions are introduced in multiple regions. A few results comparing simulations from three modern climate models (CESM2, E3SMv2, and UKESM1) are used to illustrate the similarities and differences between model behavior and the utility of estimates of MCB climate responses that were synthesized by summing responses introduced in individual regions. Cloud responses to aerosol injections differ substantially between models (CESM2 clouds appear much more susceptible to aerosol emissions than the other models), but patterns in precipitation and surface temperature responses were similar when forcing is imposed with similar amplitudes in the same regions. A previously identified La Niña-like response to forcing introduced in the Southeast Pacific is evident in this study, but the amplitude of the response was shown to markedly differ across the three models. Other common response patterns were also found and are discussed. Forcing in the Southeast Atlantic consistently (across all three models) produces weaker global cooling than that in other regions, and the Southeast Pacific and South Pacific show the strongest cooling. This indicates that the efficiency of a given intervention depends on not only the susceptibility of the clouds to aerosol perturbations, but also the strength of the underlying radiative feedbacks and ocean responses operating within each region. These responses were generally robust across models, but more studies and an examination of responses with ensembles would be beneficial.

54 ENVIRONMENTAL SCIENCES↗

NLRP1 deficiency attenuates diabetic retinopathy (DR) in mice through suppressing inflammation response

Highlights: • NLRP1 expression was increased in retina of diabetic mice. • NLRP1 deletion attenuates STZ-induced diabetic retinopathy. • Knockout of NLRP1 reduces inflammation and alleviates diabetic retinopathy in STZ mice. • Suppression of NLRP1 restrains inflammation in high fructose-incubated retinal ganglion cells. Diabetic retinopathy (DR) is the common cause of diabetic vascular complications. The NOD-like receptor (NLR) family, pyrin domain containing 1 (NLRP1), also known as NALP1, inflammasome is the first member of the NLR family to be discovered, playing an important role in inflammatory response. However, its effect on DR development has not been reported. In the study, the wild type (WT) and NLRP1{sup −/−} mice were injected with streptozotocin (STZ) to induce DR. The results indicated that NLRP1{sup −/−} significantly increased bodyweight reduction and decreased blood glucose levels induced by STZ. WT/DR mice exhibited higher levels of NLRP1 in retinas. NLRP1{sup −/−} ameliorated retinal abnormalities in DR mice using H&E staining. In addition, attenuated avascular areas and neovascular tufts were also observed in NLRP1{sup −/−}/DR mice. The levels of pro-inflammatory cytokines in serum and retinas were highly induced in WT/DR mice, whereas being markedly reduced by NLRP1{sup −/−}. In addition, vascular endothelial growth factor (VEGF) and Iba1 expressions induced by STZ in serum or retinas were significantly down-regulated in NLRP1{sup −/−}/DR mice. Consistently, NLRP1{sup −/−} attenuated ASC and Caspase-1 expressions in retinas of DR mice. Compared to WT/DR group, NLRP1{sup −/−} markedly decreased retina p-nuclear factor-κB (NF-κB), interleukin-1β (IL-1β) and IL-18 levels. And similar results were confirmed in vitro that suppressing NLRP1/ASC inflammasome ameliorated inflammatory response in fructose-treated retinal ganglion cells. The results above indicated that the modulation of NLRP1 inflammasome might be a promising strategy for DR therapy.

60 APPLIED LIFE SCIENCES↗

Pre-clinical therapeutic development of a series of metalloporphyrins for Parkinson's disease

Reactive oxygen species are a well-defined therapeutic target for Parkinson's disease (PD) and pharmacological agents that catalytically scavenge reactive species are promising neuroprotective strategies for treatment. Metalloporphyrins are synthetic catalytic antioxidants that mimic the body's own antioxidant enzymes i.e. superoxide dismutases and catalase. The goal of this study was to determine if newly designed metalloporphyrins have enhanced pharmacodynamics including oral bioavailability, longer plasma elimination half-lives, penetrate the blood brain barrier, and show promise for PD treatment. Three metalloporphyrins (AEOL 11216, AEOL 11203 and AEOL 11114) were identified in this study as potential candidates for further pre-clinical development. Each of these compounds demonstrated blood brain barrier permeability by the i.p. route and two of three compounds (AEOL 11203 and AEOL 11114) were orally bioavailable. All of these compounds protected against 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-induced neurotoxicity, including dopamine depletion in the striatum, dopaminergic neuronal loss in the substantial nigra, and increased oxidative/nitrative stress indices (glutathione disulfide and 3-nitrotyrosine) in the ventral midbrain of the mice without inhibiting MPTP metabolism. Daily therapeutic dosing of these metalloporphyrins were well tolerated without accumulation of brain manganese levels or behavioral alterations assessed by open field and rotarod tests. The study identified two orally active metalloporphyrins and one injectable metalloporphyrin as clinical candidates for further development in PD. - Highlights: • A series of metalloporphyrins were optimized in a mouse model of parkinsonism. • Two novel orally active, brain permeable antioxidant metalloporphyrins were identified. • The identified metalloporphyrins were well tolerated.

60 APPLIED LIFE SCIENCES↗

Production, fuel properties and combustion testing of an iso-olefins blendstock for modern vehicles

With the increasing pressure to decarbonize the transportation sector, exploring strategies that can reduce emissions from light-duty vehicles (LDV) has become critical. Bioblendstocks that allow for higher engine efficiency and fuel economy could complement vehicle electrification and help reach carbon neutrality by 2050. In this context, the potential of a mixture of iso-olefins as a bioblendstock was investigated for multimode boosted spark-ignition (SI)/advanced compression ignition (ACI) engine operation designed to achieve higher overall vehicle fuel economy. By establishing the relationship between the molecular structure of iso-olefins and research octane number (RON), octane sensitivity (S) (i.e., the difference between RON and motor octane number [MON]), and phi-sensitivity a dimethyl-hexenes rich olefins mixture (DMHROM) was identified as a preferred blendstock for SI/ACI combustion engines. Here, a pathway for DMHROM production from biomass-derived ethanol was developed and scaled up. More than 1 gallon of DMHROM blendstock was produced for fuel properties assessment including engine testing. Measurements in a Cooperative Fuel Research Engine showed that the DMHROM blendstock possesses a RON of 94 and S of 13.5, and blends synergistically. Rapid compression machine tests coupled with single-cylinder gasoline direct injection engine measurements demonstrated the 20 vol.% DMHROM blend has higher phi-sensitivity than an olefin-free gasoline base fuel and a typical California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) gasoline fuel. These results demonstrate the potential of DMHROM for improving gasoline fuel performance and quality for operation under ACI conditions. The effectiveness of the aftertreatment system in mitigating emissions was verified and showed that the pure DMHROM blendstock and 20 vol.% blend would not increase non-methane organic gases, NO x , and carbon monoxide (CO) emissions. The DMHROM blendstock was found to slightly decrease sooting tendency when added to a gasoline-base fuel (i.e., ~6% reduction at 20 vol.% blending level). Oxidation stability and lubricant compatibility were both confirmed for the 20 vol.% blend. Overall, these results demonstrate that dimethyl-hexenes have potential for improving engine efficiency and fuel economy while meeting emissions regulations and ASTM specifications for gasoline fuel.

09 BIOMASS FUELS↗

Microwave-Assisted Hydrogen Generation from Hydrocarbon-Bearing Reservoir Rocks: Stage-Dependent Thermal Runaway and In-Situ Carbonate Engineering

Microwave-assisted hydrogen generation from hydrocarbon-bearing reservoir rocks is strongly influenced by mineralogy, methane activation, carbonate reactions, and thermal runaway behavior. This study investigates a new approach in which carbonate phases are generated in-situ through the reaction of internally produced CO2 with Ca(OH)2 under microwave heating conditions. The objective is to evaluate how rock mineralogy, methane injection, and Ca(OH)2 addition influence hydrogen generation, carbon redistribution, and stage-dependent reaction pathways during microwave exposure. Microwave heating experiments were conducted using Permian Basin reservoir rocks under three experimental conditions: rock-only experiments under Ar atmosphere, CH4–Ar experiments without additive, and CH4–Ar experiments containing 5 wt% Ca(OH)2. Methane-assisted experiments were performed under continuous injection of 30 standard cubic centimeters per minute (sccm) CH4 and 30 sccm Ar. Based on thermal runaway behavior, each experiment was divided into three operational stages: Before Thermal Runaway (BR), After Thermal Runaway–Decrease in Microwave Power (ARD), and After Thermal Runaway– Increase in Microwave Power (ARI). Temperature and gas composition were continuously monitored throughout the experiments. The rock-only experiments demonstrated that hydrogen generation can occur intrinsically from hydrocarbon-bearing rocks under microwave heating, even without externally injected methane. However, hydrogen production did not correlate solely with kerogen content, indicating that mineralogy strongly influences hydrogen-generation pathways. Correlation analyses suggested that kerogen decomposition initially generated CH4, CO, and CO2, followed by secondary hydrocarbon reactions associated with H2 and C2 hydrocarbon formation. Methane-assisted experiments substantially increased hydrogen production; however, identical methane injection rates produced significantly different hydrogen yields among the rock samples, confirming that mineralogical composition controls methaneconversion behavior under microwave heating conditions. The addition of Ca(OH)2 significantly altered carbon evolution behavior in a stage-dependent manner. During the BR stage, Ca(OH)2 reduced gas-phase CO2 production, particularly in carbonate-rich rocks, indicating favorable conditions for in-situ carbonation and carbonate deposition prior to extensive thermal decomposition. The suppression of CO2 during BR became more pronounced with increasing carbonate content of the rock system. After thermal runaway, carbonate-containing systems exhibited enhanced hydrogen generation behavior, suggesting that carbonatederived mineral transformations and carbonate-mediated reactions contribute to high-temperature hydrogen-generation pathways. In carbonate-poor rocks, Ca(OH)2 addition enabled simultaneous URTeC 4493775 2 enhancement of hydrogen production and partial suppression of CO2 release during the post-runaway stages. Overall, the results demonstrate that microwave-assisted hydrogen generation is governed by dynamically evolving interactions among kerogen decomposition, methane activation, mineral transformations, carbonate formation/decomposition, and thermal runaway behavior. This work introduces in-situ carbonate engineering with Ca(OH)2 as a strategy for coupling hydrogen generation with partial insitu carbon management under microwave heating conditions.

03 NATURAL GAS↗

Time-resolved 3D imaging of two-phase fluid flow inside a steel fuel injector using synchrotron X-ray tomography

The multiphase flow inside a diesel injection nozzle is imaged using synchrotron X-rays from the Advanced Photon Source at Argonne National Laboratory. Through acquisitions performed at several viewing angles and subsequent tomographic reconstruction, in-situ 3D visualization is achieved for the first time inside a steel injector at engine-like operating conditions. The morphology of the internal flow reveals strong flow separation and vapor-filled cavities (cavitation), the degree of which correlates with the nozzle's asymmetric inlet corner profile. Micron-scale surface features, which are artifacts of manufacturing, are shown to influence the morphology of the resulting liquid-gas interface. The data obtained at 0.1 ms time resolution exposes transient flow features and the flow development timescales are shown to be correlated with in-situ imaging of the fuel injector's hydraulically-actuated valve (needle). As more than 98.5% of the X-ray photon flux is attenuated within the steel injector body itself, we are posed with a unique challenge for imaging the flow within. Time-resolved imaging under these low-light conditions is achieved by exploiting both the refractive and absorptive properties of X-ray photons. The data-processing strategy converted these images with a signal-to-noise ratio of similar to 10 into a meaningful dataset for understanding internal flow and cavitation in a nozzle of diameter 200 mu m enclosed within 1-2 millimeters of steel.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Stacked Greenfield and Brownfield ROZ Fairways in the Illinois Basin Geo-Laboratory: Co-Optimization of EOR and Associated CO 2 Storage

Residual oil zones (ROZs) are economically viable targets for carbon dioxide enhanced oil recovery (CO 2 -EOR); thick, carbonate ROZs in the San Andres Formation in the Wasson Field of the Permian Basin are an example. Incremental oil produced from CO 2 -EOR can be carbon negative via associated storage of injected CO 2 . Given the regional extent of ROZ fairways and generally higher net utilization of CO 2 (compared to conventional CO 2 -EOR), ROZs provide the opportunity for significant carbon neutral to carbon negative oil production with associated CO 2 storage, and therefore should be a priority target for exploration. However, ROZs have not been widely recognized or identified due to poor or no conventional oil production. Hence, in places like the Illinois Basin (ILB), exploratory analyses are required to recognize the existence of an ROZ. As part of this study, four formations were selected for detailed regional characterization and analysis: Carper Sandstone (part of the Borden Siltstone), Tar Springs Sandstone, Cypress Sandstone, and Middle Devonian (Geneva Dolomite and associated Dutch Creek Sandstone). The four formations underwent regional geological characterization to develop a regional geologic framework for the ROZs and their overlying seals. Findings of this study are supported by data from two field laboratory sites, one with stacked greenfield ROZs and the other with a stacked complex that includes a brownfield ROZ and depleted conventional reservoirs. The field laboratory sites were used to collect data and conduct tests to validate ROZ detection methodologies and identify economic field-deployable strategies to co-optimize CO 2 -EOR and associated storage in stacked ROZs. Findings from these field sites were extrapolated to characterize the basin-wide stacked ROZ fairway resource.

01 COAL, LIGNITE, AND PEAT↗

Mid-Atlantic U.S. Offshore Carbon Storage Resource Assessment Project (Final Technical Report)

The greatest potential for carbon storage in the northeastern United States lies in the offshore geologic formations comprising the outer continental shelf (Monteverde et al., 2011). Offshore storage can be linked to large point-sources of carbon dioxide (CO 2 ) while avoiding many of the logistical difficulties and potential risks encountered when siting onshore projects, especially in densely populated areas of the East Coast. Offshore CO 2 storage assessment and research in the United States is underway to address uncertainty in potential storage resources, particularly in the mid- and north-Atlantic offshore area. Given the current knowledge base and access to publicly available data, the objectives of the Mid-Atlantic U.S. Offshore Carbon Storage Resource Assessment Project (MAOCSRAP) were fourfold: (1) complete a systematic carbon storage resource assessment of the mid-Atlantic offshore coastal region from the Georges Bank Basin (GBB) through the Long Island Platform (LIP) to the southern Baltimore Canyon Trough (BCT); (2) define key input parameters to reduce uncertainty for offshore storage resource and efficiency estimates; (3) perform a preliminary assessment of risk factors, uncertainties, and data gaps; and (4) engage industry and regulatory stakeholders through development of a Road Map to assist future project planning and implementation. The MAOCSRAP project has compiled, inventoried, and assimilated various publicly available data sets to provide a strong technical basis on which future carbon storage studies and applications can be built. The knowledge infrastructure necessary to support the development of full-scale offshore carbon storage include: Defining the geologic characteristics of candidate storage sites (Chapter 2). Using existing seismic data to better define the continuity of the storage zones and seals (Chapter 3). Cataloguing the hydrogeologic properties of mid-Atlantic offshore storage sites (Chapter 4). Calculating prospective CO 2 storage resources using net effective pore volumes and fluid displacement properties specific to offshore lithologies (Chapter 5). Examining risk factors related to offshore storage (Chapter 6). Communicating with industry and other stakeholders about the future prospects for offshore storage (Chapter 7). Ensuring technology transfer to industry and other stakeholders (Chapter 8). Led by Battelle, this project was conducted by public and private entities with expertise in offshore geology and resources for the study region, including state geological surveys of Delaware, Maryland, and Pennsylvania; United States Geological Survey-Woods Hole Coastal and Marine Science Center and Haifa University; Rutgers University; Harvard University; and Lamont-Doherty Earth Observatory (LDEO) at Columbia University. The storage resource assessment was completed for a broad region offshore of the U.S. East Coast, from Massachusetts to Virginia. The results include high-level storage resource estimates for areas not previously characterized and improved storage resource estimates for geographically expansive portions of offshore geologic units. Results of the project provide a foundation for developing CO 2 storage along offshore areas of the mid-Atlantic United States. A combination of information was used to provide confidence in project results. Key findings of the major project tasks are summarized as follows. Subsurface Data Analysis: Legacy seismic, well-log, core, and biostratigraphic data were digitized, reprocessed, and analyzed using modern techniques, augmenting previous characterization efforts. The sequence stratigraphic framework for the Cretaceous and Jurassic strata was developed by correlating well-log depositional sequences to seismic reflectors identified in the BCT, LIP, and GBB. The integration of well-log stratigraphy with seismic stratigraphy and petrophysical analysis helped to identify and map potential storage zones within sequences of the Logan Canyon (LC), Missisauga, and Mohawk formations, as well as the regionally extensive caprock comprised of the Dawson Canyon shale. Approximately 4,000 kilometers (km) of seismic data was reprocessed to create a structural framework that was used to tie together all available well data, constrain sequence stratigraphic interpretations, and make regional assessments of offshore carbon storage resources. Prospective storage resource estimates were 150 to 1136 megatons (Mt) for the combined storage zones. This suggests mid-Atlantic U.S. offshore formations can store decades of CO 2 from industrial sources in the region. Preliminary local reservoir simulations suggest that injection rates of 1 Mt CO 2 /year may be sustained for 30 years in single injection wells in the BCT. Advanced geologic modeling and new data acquisition are needed to address data gaps and advance carbon capture and storage (CCS) in key offshore areas selected for further investigation. Offshore Risk Factors: Offshore geologic risk factors include soft sediment deformation, unit continuity, sedimentological and structural features, seismicity and hydrates. CO 2 storage risks include inadequate seals, migration/leakage, and chemical interactions leading to decreased storage. Sensitive habitats, environmental impacts, disturbance to seafloor, and other risks need to be identified in advance of project activities and integrated into detailed mitigation plans for all project phases. Stakeholder Engagement: Input and participation from government, industry, and environmental groups provided input into the Road Map and address next steps needed for project deployment. Early engagement and ongoing communication, as well as policy framework development, is key to large-scale deployment of CCS. Next Steps: This project represents an important first step by completing a high-level CO 2 storage resource assessment and building the knowledge infrastructure necessary to improve quantitative storage resource estimates. The data sets that have been curated under this project provide an opportunity to conduct research and development (R&D) needed to address data gaps and reduce risk and uncertainty. Offshore characterization and validation strategies that are systematically designed to provide data and infrastructure that can be upscaled to meet commercial requirements could be developed off of this foundation.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

A W-Geometry Ortho-TOF MS with High Resolution and Up to 100% Duty Cycle for MS/MS

Orthogonal injection time-of-flight (orthoTOF) mass spectrometry (MS) is the most prevalent form of TOFMS, owing to its greater control over incoming ion energy, the ability to correct for aberrations in incoming ion velocity and position, and its ability to provide an entire mass spectrum within a single scan. However, the duty cycle of orthoTOFMS is low compared with scanning analyzers, which can have 100% duty cycle when measuring a single type of ion. Typical duty cycles for orthoTOFMS range from 1% to 30%, depending on instrument geometry. Generally, as instrument resolution increases, duty cycle decreases. Additionally, the greatest duty cycle is achieved for the highest m/z ion recorded in the spectrum, and decreases for all other ions as a function of m/z. In a prior publication [Loboda, A.V.; Chernushevich, I.V. J. Am. Soc. Mass Spectrom. 20, 1342–1348 (20)], a novel trapping/release method for restoring the duty cycle of a V-geometry orthoTOFMS to near 100% (referred to as “Zeno pulsing”) was presented. Here, we apply that method to a W-TOF geometry analyzer with analog detection. Across a m/z range of 100–2000, sensitivity gains of ~5–20 are observed, for total ion currents approaching ~10{sup 7} ions·s{sup −1}. Zeno pulsing, or similar strategies for restoring duty cycle, will continue to be important as instrument resolution in orthoTOFMS is increased through the use of ion mirrors. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Towards time-resolved MicroED grid preparation using mix-and-inject gas dynamic virtual nozzles

Recent progress in gas dynamic virtual nozzle (GDVN) technologies in combination with high-brilliance synchrotron and X-ray free-electron lasers (XFELs) has allowed the visualization of protein dynamics in crystallo by mixing macromolecular protein crystals with a substrate using tunable mixing times on the order of milliseconds to seconds prior to serial X-ray diffraction data collection. This has become the method of choice for high-resolution structure determination of intermediate states. However, such experiments require large counts of crystals of proper sizes for high-resolution data collection, and premium beam times for screening efforts. Cryogenic microcrystal electron diffraction (MicroED) represents a complementary technique that may be a more accessible avenue for time-resolved nanocrystallography compared with serial X-ray diffraction experiments. MicroED can produce full diffraction datasets from just a few submicrometre-thick crystals, and the approach is more readily accessible, requiring standard cryogenic transmission electron microscopy (TEM) equipment available at many universities and institutes. Cryogenic MicroED, like other forms of cryo-EM, begins with rapidly freezing biological material on electron microscopy grids. In the case of MicroED, micro- to nano-crystals (<500 nm thick) are deposited onto electron microscopy grids and plunge-frozen for subsequent electron diffraction data collection. Here, we have incorporated GDVN technology developed originally for XFEL experiments into the freezing process as a first step towards time-resolved studies. We describe the limited deposition efficiency of the model MicroED protein proteinase K on TEM grids using GDVNs, preceding sample vitrification and successful MicroED data collection. We discuss both the initial results from such experiments and the methodological challenges in developing this approach into a reliable workflow for millisecond-to-second time-resolved structural studies of macromolecules. Our results promise a strategy to deposit crystals on grids using GDVNs and determine high-resolution structures by MicroED, constituting a first step towards development of time-resolved MicroED experiments.

MicroED↗

Flexible Natural Gas/Hydrogen CHP System

This project included design, development, and demonstration of a cost-effective and scalable, unique-to-the-industry 2.0 MWe fuel-flexible Caterpillar G3516 CHP genset that can run on 100% hydrogen, 100% natural gas, and up to 25% blends of hydrogen in natural gas (volume basis). This was accomplished based on over two years of extensive R&D work done on a single-cylinder engine for developing innovative hydrogen fueling, combustion, air, and electronic control systems design and strategies. Findings from the single-cylinder engine work were scaled up and applied for modifications of and lab testing and development of a 2.0 MWe 16-cylinder G3516 fuel-flexible engine-genset and electronic controls systems. During this testing and development in the engine lab, the genset was run on 100% hydrogen, 100% natural gas, and up to 25% blends of hydrogen in natural gas (volume basis) and its steady-state and transient performance and emission were documented.

03 NATURAL GAS↗

Influence of Compression Ratio on High Load Performance and Knock Behavior for Gasoline Port-Fuel Injection, Natural Gas Direct Injection and Blended Operation in a Spark Ignition Engine

Natural Gas (NG) is an alternative fuel which has attracted a lot of attention recently, in particular in the US due to shale gas availability. The higher hydrogen-to-carbon (H/C) ratio, compared to gasoline, allows for decreasing carbon dioxide emissions throughout the entire engine map. Furthermore, the high knock resistance of NG allows increasing the efficiency at high engine loads compared to fuels with lower knock resistance. NG direct injection (DI) allows for fuel to be added after intake valve closing (IVC) resulting in an increase in power density compared to an injection before IVC. Steady-state engine tests were performed on a single-cylinder research engine equipped with gasoline (E10) port-fuel injection (PFI) and NG DI to allow for in-cylinder blending of both fuels. Knock investigations were performed at two discrete compression ratios (CR), 10.5 and 12.5. Operating conditions span mid-load, wide-open-throttle and boosted conditions, depending on the knock response of the fuel blend. Blended operation was performed using E10 gasoline and NG. An additional gasoline type fuel (E85) with higher knock resistance than E10 was used as a high-octane reference fuel, since the octane rating of E10-NG fuel blends is unknown. Spark timing was varied at different loads under stoichiometric conditions in order to study the knock response as well as the effects on performance and efficiency. As anticipated, results suggest that the knock resistance can be increased significantly by increasing the NG amount. Comparing the engine operation with the least knock resistant fuel, E10 PFI, and the fuel blend with the highest knock resistance, 75% NG DI, shows an increase in indicated mean effective pressure of about 9 bar at CR 12.5. The usage of reference fuels with known knock characteristics allowed an assessment of knock characteristic of intermediate E10-NG blend levels. Mathematical correlations were developed allowing characterizing the occurrence of knocking combustion by using the Livengood-Wu knock integral. For most of the fueling strategies and operating conditions, the mathematical correlations show good agreement when compared to experimental data.

combustion↗

Preheating and premixing effects on NO x emissions in a high-pressure axially staged combustor

NO x emissions remain a primary concern for modern and future gas turbines, particularly as we progress towards a net-zero carbon future. It is critical to identify novel strategies to mitigate environmental pollutants for both modern turbines operated on natural gas and future turbines projected to use carbon-free fuels (such as hydrogen). In the current study, NO x emissions of a reacting methane-air jet in a vitiated crossflow are experimentally investigated in a model axially staged combustor at 5 atm. The combustion products from the main stage combustor flow into the axial stage at temperatures ranging from 1580 to 1650 °C. The axial stage contains a reacting jet in crossflow, which provides an overall temperature rise ranging from 50 to 220 °C to generate exit temperatures similar to gas turbine engines. The focus of this paper is to explore the effects of flame liftoff and ignition timescales on the NO x contribution of this secondary jet. This is done by varying the premixed level and preheat temperature of the axial jet. The effects are explored at different momentum flux ratios (J), jet equivalence ratios (φ jet ), exit temperatures (T exit ), and main stage (headend) temperatures (T HE ). High-speed CH* chemiluminescence imaging is employed for each test case to determine the flame stabilization point. For a given temperature rise and combustor exit temperature, an increase in ignition delay was observed with a decrease in jet temperature. This provided a NO x benefit, particularly for jets that are injected at or close to an ignitable mixture fraction. Similarly, the coaxial injector caused a significant ignition delay compared to the fully premixed injector; this also led to a NO x benefit. Overall, the results show that a thermally driven delay in the axial stage provides a greater NO x reduction than a mixing delay.

03 NATURAL GAS↗