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At least 847 records · Page 47

Chemical Insights into the Molecular Composition of Organic Aerosols in the Urban Region of Houston, Texas

Molecular functional groups, such as organosulfates (CHOS) and organonitrates (CHNO) are important tracers for field observations of secondary organic aerosols (SOA). While CHOS and CHNO are prevalent in the atmosphere, there is a lack of knowledge regarding daily and day- and night-time variations in these species in the urban atmosphere. Meteorological factors such as wind speed/direction, relative humidity (RH), and temperature can influence the formation of CHOS/CHNO. To investigate these trends, we utilized multimodal chemical imaging and advanced high resolution mass spectrometry techniques to acquire particle speciation and molecular formulas (MFs) associated with day and night sampling periods. Back trajectory analyses revealed the oceanic influence of southern wind airmasses in later June sampling periods with organic fractions <10%. Conversely, northern winds in early June sampling periods contributed to the episodic emergence of extremely low volatile organics (ELVOCs) and organic factions up to 41%. The observed unique MFs to June 3 (223 MFs) and to June 4 (144 MFs) were largely found to be of biogenic rather than anthropogenic origin. Finally, our findings reveal episodic prevalence and temporal distribution of SOA constituents across the urban region of Houston, Texas.

54 ENVIRONMENTAL SCIENCES↗

Quasi-Random Multimetallic Nanoparticle Arrays

Here, this paper describes a nanofabrication procedure that can generate multiscale substrates with quasi-random microregions of nanoparticle arrays having different periodicities and metals. We combine cycles of large-area nanoparticle array fabrication with solvent-assisted wrinkle lithography to mask and etch quasi-random areas of prefabricated nanoparticles to control the fill factors of the arrays. The approach is highly flexible, and parameters, including nanoparticle size and material, array geometry, and fill factor, can be tailored independently. Multimetallic nanoparticle arrays can support surface lattice resonances at fill factors as low as 20% and can function as nanoscale cavities for lasing action with as few as 10% of the nanoparticles in an array. We demonstrated that multimetallic nanoparticle substrates that combine two or three arrays with different periodicities can exhibit lasing responses over visible and near-infrared wavelengths. Our work showcases the robust optical responses of multimetallic and periodic devices for broadband light manipulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunable Metasurface External-Cavity Quantum Cascade Lasers up to 5.74 THz

Vertical-external-cavity surface-emitting lasers based on amplifying quantum-cascade metasurfaces are demonstrated in the 5–6 THz range for the first time. Enhanced parasitic coupling to lossy surface modes requires updated design guidelines, while elevated losses and lower available material gain limit the scaling of the metasurface period from previous designs. A series of metasurface devices with varying periods employing both uniform and focusing metasurfaces is fabricated and characterized. Reducing the metasurface period below 70% of the free-space wavelength enables devices with superior performance, achieving pulsed operation up to 5.74 THz with peak output powers of 1.3 mW, maximum operating temperatures up to 83 K, and continuous-wave operation up to 54 K with 23 μW of output power. In the best case, single-mode tuning from 5.23–5.73 THz, which corresponds to a 9.1% fractional tuning, is realized with near-Gaussian far-field profiles maintained across the entire range. Finally, these results establish quantum cascade vertical-external-cavity surface-emitting lasers as promising candidates for high-frequency local oscillator applications in heterodyne spectroscopy.

gallium arsenide↗

Roadmap for Deployment of Modularized Hydrothermal Liquefaction: Understanding the Impacts of Industry Learning, Optimal Plant Scale, and Delivery Costs on Biofuel Pricing

Hydrothermal liquefaction (HTL) is a promising technology for converting abundant organic wastes into fuels. Previous techno-economic analyses (TEAs) of HTL have been used to estimate the minimum fuel selling price (MFSP) of biofuel products, but these analyses often assume a bespoke plant design where each plant operates under unique process conditions and neglect transportation costs. However, transportation costs must be included in realistic TEAs, and further, a mass-produced fixed-scale modular plant design approach may be more effective than case-by-case plant design, provided that there is sufficient market capacity to benefit from modularization. This study estimates fuel price behavior in the presence of transportation costs and benefits stemming from modular plant design. This analysis indicates that a modular process capable of handling 60 dry tons per day (DTPD) is optimal, resulting in a ~25% reduction in MFSP (from $4.70/GGE, fully upgraded) at complete market feedstock utilization compared with case-by-case design. The associated cost reductions are attributable to learning benefits and modularization. Several HTL deployment “roadmaps” are then explored, with each roadmap consisting of different periods of case-by-case design followed by adoption of a modularized approach. A period of nonmodular industry growth up to market saturation of ~7% followed by implementation of modular plant design strikes a balance between the investment risk and learned cost reductions associated with modular plant design. However, if bespoke plants built during this period of nonmodular growth saturate more than 23% of available feedstock, learned cost reductions are significantly diminished. Here, this study points to the potential benefits of modularized and decentralized waste-to-energy processes when the modularization follows an optimal deployment strategy.

09 BIOMASS FUELS↗

Guest-Controlled Incommensurate Modulation in a Meta-Rigid Metal–Organic Framework Material

Structural transitions of host systems in response to guest binding dominate many chemical processes. We report an unprecedented type of structural flexibility within a meta-rigid material, MFM-520, which exhibits a reversible periodic-to-aperiodic structural transition resulting from a drastic distortion of a [ZnO 4 N] node controlled by the specific host–guest interactions. The aperiodic crystal structure of MFM-520 has no three-dimensional (3D) lattice periodicity but shows translational symmetry in higher-dimensional (3 + 2)D space. In this work, we have directly visualized the aperiodic state which is induced by incommensurate modulation of the periodic framework of MFM-520·H 2 O upon dehydration to give MFM-520. Filling MFM-520 with CO 2 and SO 2 reveals that, while CO 2 has a minimal structural influence, SO 2 can further modulate the structure incommensurately. MFM-520 shows exceptional selectivity for SO 2 under flue-gas desulfurization conditions, and the facile release of captured SO 2 from MFM-520 enabled the conversion to valuable sulfonamide products. MFM-520 can thus be used as a highly efficient capture and delivery system for SO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Persistence and Plasticity in Conifer Water–Use Strategies

The selective use of seasonal precipitation by vegetation is critical to understanding the residence time and flow path of water in watersheds, yet there are limited datasets to test how climate alters these dynamics. Here, we use measurements of the seasonal cycle of tree ring δ 18 O for two widespread conifer species in the Rocky Mountains of North America to provide a multi-decadal depiction of the seasonal origins of forest water use. The results show that while the conifer tree stands had a dominant preference for use of snowmelt, there were multi-annual periods over the last four decades when use of summer precipitation was preferential. Utilization of summer rain emerged during years with increased snowfall and tree growth, suggesting that summer rain enhanced the transpiration stream only during the periods of highest water use. We hypothesize this could be explained through shallowing of the root profile during wetter periods and/or through the influence of changing water table depths on the residence time of summer precipitation in the root zone. We suggest the tree ring proxy approach used here could be applied in other watersheds to provide critical insight into the temporal dynamics of plant water use that could not be inferred from short measurement campaigns. Furthermore, these data on the seasonal origins of forest water are critical for understanding forest vulnerability to drought, the processes that affect precipitation pathways and residence time in watersheds and the interpretation of tree ring proxy data.

59 BASIC BIOLOGICAL SCIENCES↗

Cloud and Precipitation Properties of MCSs Along the Meiyu Frontal Zone in Central and Southern China and Their Associated Large-Scale Environments

This study focuses on investigating the cloud and precipitation features of Meiyu mesoscale convective systems (MCSs) and their relation to the large-scale environments in central and southern China using satellite observations and reanalysis data during the period 2014–2018. MCSs from two different locations, the Yangtze River Basin (YRB) and Southern China (SC), are examined separately. The Meiyu MCSs have a mean precipitation rate of 3.6 mm/hr and contribute 20% to 60% of the total precipitation during the Meiyu period. The diurnal cycle of Meiyu MCSs shows a maximum precipitation amount in the morning, which is associated with the enhanced nocturnal low-level jet (LLJ) overnight. Although the synoptic setups in YRB and SC are found to be similar when normalized around the MCS initiation locations, MCSs exhibit some differences in terms of the cloud top height, precipitation rate, and duration, which are likely by the differences in the local forcing. Large interannual variations are found in MCSs' number, cloud size, lifetime, and rainfall intensity, which is found to be associated with the interannual variabilities in the large-scale environments. By comparing the large-scale environments with climatological mean states, we find that the year with the most intense MCS activity during the study period is characterized by an intensified southwesterly LLJ, which increases the moisture transport from the Indian Ocean and an enhancement of the midtropospheric westerly jet, which induces adiabatic ascent along the Meiyu front, creating more favorable conditions for convection.

54 ENVIRONMENTAL SCIENCES↗

Estimating and Forecasting Time-Varying Groundwater Recharge in Fractured Rock: A State-Space Formulation with Preferential and Diffuse Flow to the Water Table

Rapid infiltration following precipitation may result in groundwater contamination from surface contaminants or pathogens. In fractured rock, contaminants can migrate rapidly to points of groundwater withdrawals. In contrast to the temporal availability of groundwater quality chemical indicators, meteorological and groundwater level observations are available in real-time to estimate time-varying recharge, which can act as a surrogate to identify periods of rapid infiltration that may indicate contamination susceptibility. Estimating recharge using methods, such as base-flow recession, unsaturated infiltration models, or Water-Table Fluctuations (WTF), cannot capitalize on currently available technologies and telecommunication infrastructure to conduct real-time recharge estimation at scales relevant to characterizing rapid infiltration. We present a linear, physics-based State-Space (SS) model of one-dimensional infiltration to estimate recharge, which includes preferential and diffuse-flow to the water table. The model can take advantage of real-time data for water-table altitude, precipitation, and evapotranspiration. Model parameters are calibrated over an observation period, and the Kalman Filter (KF) is subsequently applied to continuously update the observed (water-table altitude) and unobserved (groundwater recharge) system states and predict future states as new data become available. The SS/KF algorithm is demonstrated at the Masser Groundwater Recharge Site in Pennsylvania, USA and comparisons are made with recharge estimates from WTF methods. Model results indicate that the frequency of observations (daily versus sub-daily) dictates the allocation between preferential and diffuse flow. Additionally, because infiltration processes encompass many nonlinearities, model parameters estimated from observation periods need to be updated at least seasonally to account for changing recharge conditions.

groundwater, Recharge, infiltration, recursive est↗

Saturn's Weather‐Driven Aurorae Modulate Oscillations in the Magnetic Field and Radio Emissions

Abstract The Cassini spacecraft revealed that Saturn's magnetic field displayed oscillations at a period originally thought to match the planetary rotation rate but later found not to. One of many proposed theories predicts that a polar twin‐cell neutral weather system drives this variation, producing observable differences in flows within Saturn's ionosphere. Here, using spectral observations of auroral emission lines taken by the Keck Observatory's Near Infrared Echelle Spectrograph (Keck‐NIRSPEC) in 2017, we derive ion line‐of‐sight velocity maps after grouping spectra into rotational quadrants matching phases of the planetary magnetic field. We measure 0.5 km s −1 wind systems in the ionosphere consistent with predicted neutral twin‐vortex flow patterns. These findings demonstrate that neutral winds in Saturn's polar regions cause the rotational period, as determined via the magnetic field, to exhibit differences and time variabilities relative to the planet's true period of rotation in a process never before seen within planetary atmospheres.

Chowdhury, M. N.↗

Convection-permitting hindcasting of diurnal variation of Mei-yu rainfall over East China with a global variable-resolution model

Two sets of 48-hr hindcast experiments for Mei-yu season using non-hydrostatic global variable-resolution model (MPAS-Atmosphere) with regional refinement at 4km resolution (V4km) and uniform 60km resolution (U60km) are first-time conducted to attempt at simulating the Mei-yu rainfall in 2015 over East China. The analysis focuses on the seasonal average of diurnal variation of precipitation amount (PA), intensity (PI), and frequency (PF). Both simulations reasonably reproduce the spatial distribution of PA. V4km is more skillful in simulating the spatial distributions and magnitudes of PF and PI. The diurnal cycle of Mei-yu rainfall shows a major early morning peak and a minor afternoon peak, contributed by precipitation during two sub-periods with distinct synoptic circulations. With strong Mei-yu in the first sub-period, the diurnal variation of PA is controlled by nocturnal southwesterly jet. V4km overestimates the morning peak mainly due to its bias in simulating boundary layer inertial oscillation. Although differences in PA between the simulations are small, U60km overestimates PF and underestimates PI. With weak Mei-yu in the second sub-period, the diurnal variation of PA is controlled by both synoptic circulation and local convection. At both resolutions, deviations in the large-scale circulation modulated by a few typhoons lead to positive biases in the morning peak of PA. After removing the typhoon impacts, V4km captures the observed diurnal cycle of PA well, while U60km significantly underestimates PA and PI particularly in the afternoon. Future studies focusing on advancing modeling of southwesterly jet and typhoons may further improve convection permitting simulation of Mei-yu rainfall.

Xu, Mingyue↗

Megadrought: A Series of Unfortunate La Niña Events?

Megadroughts are multidecadal periods of aridity more persistent than most droughts during the instrumental period. Paleoclimate evidence suggests that megadroughts occur in many parts of the world, including North America, Central America, western Europe, eastern Asia, and northern Africa. It remains unclear to what extent such megadroughts require external forcing or whether they can arise from internal climate variability alone. A novel statistical–dynamical approach is used to evaluate the possibility that such events arise solely as a function of interannual tropical sea surface temperature (SST) variations. A statistical emulator of tropical SST variations is constructed by using an empirical moving-blocks bootstrap approach that randomly samples multiyear sequences of the observational SST record. This approach preserves the power spectrum, seasonal cycle, and spatial pattern of El Niño-Southern Oscillation (ENSO) but removes longer timescale fluctuations embedded in the observational record. These resampled SST anomalies are then used to force an atmospheric model (the Community Atmosphere Model Version 5). As megadroughts emerge in this run, they should, therefore, be solely a consequence of La Niña sequences combined with internal atmospheric variability and persistence driven by soil moisture storage and other land-surface processes. We indeed find that megadroughts in this simulation have an amplitude-duration rate that is generally indistinguishable from the rate documented in paleoclimate records of the western United States. Our findings support the idea that megadroughts may occur randomly when the unforced climate system evolves freely over a sufficiently long period of time, implying that an unforced unusual but statistically plausible series of La Niña events may be sufficient to generate megadrought.

54 ENVIRONMENTAL SCIENCES↗

Temporal Trends of Racial and Socioeconomic Disparities in Population Exposures to Upstream Oil and Gas Development in California

People living near oil and gas development are exposed to multiple environmental stressors that pose health risks. Some studies suggest these risks are higher for racially and socioeconomically marginalized people, which may be partly attributable to disparities in exposures. We examined whether racially and socioeconomically marginalized people in California are disproportionately exposed to oil and gas wells and associated hazards. We longitudinally assessed exposure to wells during three time periods (2005–2009, 2010–2014, and 2015–2019) using sociodemographic data at the census block group‐level. For each block group and time period, we assessed exposure to new, active, retired, and plugged wells, and cumulative production volume. We calculated risk ratios to determine whether marginalized people disproportionately resided near wells (within 1 km). Averaged across the three time periods, we estimated that 1.1 million Californians (3.0%) lived within 1 km of active wells. Nearly 9 million Californians (22.9%) lived within 1 km of plugged wells. The proportion of Black residents near active wells was 42%–49% higher than the proportion of Black residents across California, and the proportion of Hispanic residents near active wells was 4%–13% higher than their statewide proportion. Disparities were greatest in areas with the highest oil and gas production, where the proportion of Black residents was 105%–139% higher than statewide. Socioeconomically marginalized residents also had disproportionately high exposure to wells. Though oil and gas production has declined in California, marginalized communities persistently had disproportionately high exposure to wells, potentially contributing to health disparities.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Increasing Hurricane Intensification Rate Near the US Atlantic Coast

Hurricanes often cause severe damage and loss of life, and storms that intensify close to the coast pose a particularly serious threat. While changes in hurricane intensification and environment have been examined at basin scales previously, near-coastal changes have not been adequately explored. In this study, we address this using a suite of observations and climate model simulations. Over the 40-year period of 1979–2018, the mean 24-hr hurricane intensification rate increased by ~1.2 kt 6-hr –1 near the US Atlantic coast. However, a significant increase in intensification did not occur near the Gulf coast over the same period. The enhanced hurricane intensification along the Atlantic coast is consistent with an increasingly favorable dynamic and thermodynamic environment there, which is well simulated by climate models over the historical period. Further, multi-model projections suggest a continued enhancement of the storm environment and hurricane intensification near the Atlantic coast in the future.

54 ENVIRONMENTAL SCIENCES↗

WUS256: An Adjoint Waveform Tomography Model of the Crust and Upper Mantle of the Western United States for Improved Waveform Simulations

Abstract We report a new model (WUS256) of radially anisotropic seismic wavespeeds of the crust and upper mantle of the western United States (WUS) obtained from adjoint waveform tomography for the purpose of improving synthetic waveform fits to observed data. WUS256 is based on inversion of over 94,000 waveforms from 72 earthquakes recorded by nearly 3,400 stations. We started with the SPiRaL global model (Simmons et al., 2021, https://doi.org/10.1093/gji/ggab277 ) and waveforms in the period band of 50–120 s. We followed a conservative multiscale inversion approach with eight stages and 256 total inversion iterations which enabled monotonic misfit reduction to 20‐s minimum‐period waves. WUS256 relied on time‐frequency (TF) phase misfits and a trust region limited memory Broyden–Fletcher–Goldfarb–Shanno (L‐BFGS) optimization. Hessian‐vector products were used to qualitatively assess model resolution. Results indicate that WUS256 has good coverage of the continental regions to depths of about 150 km and is able to resolve features on lateral scales of about 200 km. We quantify waveform fits by the reduction in TF and normalized amplitude difference misfits between WUS256 and the SPiRaL starting model. WUS256 significantly improves waveform fits with misfit reduction 64% for both inversion and validation data sets compared to the SPiRaL starting model and shows even better fits compared to other models. Waveform fits illustrate that WUS256 reproduces body‐waves, fundamental mode surface waves as well as late arriving dispersed and/or scattered short period surface waves. The improvement in waveform fit indicates that WUS256 can be used to reproduce path effects on regional complete waveforms and moment tensor inversions.

58 GEOSCIENCES↗

Machine Learning of Key Variables Impacting Extreme Precipitation in Various Regions of the Contiguous United States

Abstract Amplification in extreme precipitation intensity and frequency can cause severe flooding and impose significant social and economic consequences. Variations in extreme precipitation intensity, frequencies, and return periods can be attributed to many physical variables across spatial and temporal scales. Here we employ ensemble machine learning (ML) methods, namely random forest (RF), eXtreme Gradient Boosting (XGB), and artificial neural networks (ANN), to explore key contributing variables to monthly extreme precipitation intensity and frequency in six regions over the United States. We further establish emulators for return periods. Results show that the ML models for intensity perform better in regions with obvious seasonality (i.e., Northern Great Plains, Southern Great Plains, and West Coast) than the other three regions (Northeast, Southwest, and Rocky Mountains), while for frequency the models perform well for most regions. The Shapley additive explanation is used to help explain the relationships between extreme precipitation characteristics and identify top variables for RF and XGB. We find that latent heat flux, relative humidity, soil moisture, and large‐scale subsidence are key common variables across the regions for both monthly intensity and frequency, and their compound effects are non‐negligible. The developed ML models capture the probability and return period of extreme precipitation well for all regions and may be used for decision making (e.g., infrastructure planning and design).

54 ENVIRONMENTAL SCIENCES↗

Aridification of Colorado River Basin's Snowpack Regions Has Driven Water Losses Despite Ameliorating Effects of Vegetation

Abstract The Colorado River Basin is an important natural resource for the semi‐arid southwestern United States (US), where it provides water to more than 40 million people. While nearly 1.5°C of anthropogenic warming has occurred across this region from the 1880s to 2021, climate models show little agreement in the precipitation change during the same historical period, with no trend in the mean of the latest (sixth) generation of Global Climate Models. As such, here we focus on how the CO 2 increase and associated anthropogenic warming over the historical period has impacted runoff across the Colorado Basin. We find that the Colorado Basin's runoff over the historical period has decreased by 8.1% per degree Celsius of warming (°C −1 ). However, the magnitude of this sensitivity is reduced to 6.8% °C −1 when considering vegetation response to historical CO 2 . For present‐day conditions, this translates to runoff reductions of 10.3% due to anthropogenic increases in both temperature and CO 2 since 1880. We demonstrate that Colorado Basin's natural flow has been decreased by roughly the storage of Lake Mead during the 2000–2021 megadrought due to this long term anthropogenic influence, suggesting the basin's first shortage in 2021 would likely not have occurred without anthropogenic warming. We further show warming has led to disproportionate aridification in snowpack regions, causing runoff to decline at double the rate relative to non‐snowpack regions. Thus, despite only making up ∼30% of the basin's drainage area, 86% of runoff decreases in the Colorado Basin is driven by water loss in snowpack regions.

54 ENVIRONMENTAL SCIENCES↗

Using Financial Contracts to Facilitate Informal Leases Within a Western United States Water Market Based on Prior Appropriation

The ability to reallocate water to higher-value uses during drought is an increasingly important “soft-path” tool for managing water resources in an uncertain future. In most of the Western United States, state-level water market institutions that enable reallocation also impose substantial transaction costs on market participants related to regulatory approval and litigation. These transaction costs can be prohibitive for many participants in terms of both costs and lengthy approval periods, limiting transfers and reducing allocation efficiency, particularly during drought crises periods. This manuscript describes a mechanism to reduce transaction costs by adapting an existing form of informal leases to facilitate quicker and less expensive transfers among market participants. Instead of navigating the formal approval process to lease a water right, informal leases are financial contracts for conservation that enable more junior holders of existing rights to divert water during drought, thereby allowing the formal transfer approval process to be bypassed. The informal leasing approach is tested in the Upper Colorado River Basin, where drought and institutional barriers to transfers lead to frequent shortages for urban rights holders along Colorado's Front Range. Informal leases are facilitated via option contracts that include adaptive triggers and that define volumes of additional, compensatory, releases designed to mitigate impacts to instream flows and third parties. Results suggest that more rapid reallocation of water via informal leases could have resulted in up to $222 million in additional benefits for urban rights holders during the historical period 1950–2013.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

The Changing Influence of Precipitation on Soil Moisture Drought With Warming in the Mediterranean and Western North America

Abstract Anthropogenic climate change has already affected drought severity and risk across many regions, and climate models project additional increases in drought risk with future warming. Historically, droughts are typically caused by periods of below‐normal precipitation and terminated by average or above‐normal precipitation. In many regions, however, soil moisture is projected to decrease primarily through warming‐driven increases in evaporative demand, potentially affecting the ability of negative precipitation anomalies to cause drought and positive precipitation anomalies to terminate drought. Here, we use climate model simulations from Phase Six of the Coupled Model Intercomparison Project (CMIP6) to investigate how different levels of warming (1, 2, and 3°C) affect the influence of precipitation on soil moisture drought in the Mediterranean and Western North America regions. We demonstrate that the same monthly precipitation deficits (25th percentile relative to a preindustrial baseline) at a global warming level of 2°C increase the probability of both surface and rootzone soil moisture drought by 29% in the Mediterranean and 32% and 6% in Western North America compared to the preindustrial baseline. Furthermore, the probability of a dry (25th percentile relative to a preindustrial baseline) surface soil moisture month given a high (75th percentile relative to a preindustrial baseline) precipitation month is 6 (Mediterranean) and 3 (Western North America) times more likely in a 2°C world compared to the preindustrial baseline. For these regions, warming will likely increase the risk of soil moisture drought during low precipitation periods while simultaneously reducing the efficacy of high precipitation periods to terminate droughts.

Environmental Sciences & Ecology↗