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At least 199 records · Page 11

Force-Triggered, Biobased Sealants for Prefabricated Building Components: Toward Improved Efficiency and Performance

The prefabricated building construction industry has made extensive progress in expediting the manufacture of prefabricated components at off-site plants. However, the sealing of joints between these components, which is crucial to ensuring the weatherproofing of the assembly, still represents a labor-intensive, on-site effort that relies on the manual installation of tapes and caulks. Here, to reduce work at the jobsite and improve the airtightness and waterproofness of building envelopes, we developed a sealant that can be installed at the plant on prefab components and have the curing reaction triggered at the jobsite by using microencapsulation technology to separate the reactive agents. A series of force-triggered, high-strength, and fast-curing sealants derived from biobased feedstocks were developed, which consist of a biobased epoxy agent encapsulated in a polymer shell, embedded in a biobased amine curing agent. The shell of the microcapsules allows an effective separation of the reactive species in the one-part sealant, allowing shelf stability to an otherwise fast-curing system as well as improving the hydrophobicity of the whole system. When force activates and breaks the microcapsules, the highly reactive epoxy and amine mix and cure, exhibiting peel strength values of up to 143 ppi (pounds per inch). The hydrophobicity of the sealants allows them to retain up to 94% of the original peel strength after complete submersion in water for 24 h, showcasing the water resistivity of the sealant system. The open-air shelf stability of the sealant complex is demonstrated by the obtention of peel strength values of ∼16 ppi when triggering the curing reaction even after being exposed 8 months to open air and humidity. The successful on-demand triggering of curing reactions and the shelf stability provide efficacy of these force-triggered sealants for installation on prefabricated components, storage for months prior to delivery, and assembly at a jobsite. These force-triggered biobased sealants for prefabricated buildings can result in lower installation time and cost and better performance than tapes and caulks at the jobsite.

biobased↗

Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers

Transient electronics are a rapidly emerging field due to their potential applications in the environment and human health. Recently, a few studies have incorporated acid-labile imine bonds into polymer semiconductors to impart transience; however, understanding of the structure–degradation property relationships of these polymers is limited. In this work, we systematically design and characterize a series of fully degradable diketopyrrolopyrrole-based polymers with engineered sidechains to investigate the impact of several molecular design parameters on the degradation lifetimes of these polymers. By monitoring degradation kinetics via ultraviolet–visible spectroscopy, we reveal that polymer degradation in solution is aggregation-dependent based on the branching point and M n , with accelerated degradation rates facilitated by decreasing aggregation. Additionally, increasing the hydrophilicity of the polymers promotes water diffusion and therefore acid hydrolysis of the imine bonds along the polymer backbone. The aggregation properties and degradation lifetimes of these polymers rely heavily on solvent, with polymers in chlorobenzene taking six times as long to degrade as in chloroform. We develop a new method for quantifying the degradation of polymers in the thin film and observe that similar factors and considerations (e.g., interchain order, crystallite size, and hydrophilicity) used for designing high-performance semiconductors impact the degradation of imine-based polymer semiconductors. We found that terpolymerization serves as an attractive approach for achieving degradable semiconductors with both good charge transport and tuned degradation properties. This study provides crucial principles for the molecular design of degradable semiconducting polymers, and we anticipate that these findings will expedite progress toward transient electronics with controlled lifetimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying the Influences of Epoxide Binding in Epoxide/CO 2 Ring Opening Copolymerization Catalysis

Understanding and predicting the effect of epoxide structure on the rate of polymerization in epoxide/CO 2 ring opening copolymerization catalysis is a long-standing challenge. Here, a known highly active Co(III)K(I) catalyst is used to investigate the influences of six different epoxides' binding strengths on their rates of copolymerization. Since calculations and experiments indicate that studying the catalytically relevant Co(III)−epoxide adduct directly is experimentally challenging, epoxide−catalyst binding interactions are quantified using a Co(II)K(I) complex to model the key catalytic intermediate. Epoxide−catalyst coordination is investigated using UV−vis spectroscopy titrations which provide fast and effective determination of association or binding constants. The epoxide−catalyst equilibrium constants show a clear exponential correlation with copolymerization rates and a new catalyst performance linear free energy relationship is revealed. Epoxides exhibiting stronger catalyst binding constants show higher copolymerization rates. The structure−activity correlation is consistent with the polymerization kinetics, mechanism and DFT calculations. Both the methods to investigate epoxide−catalyst coordination and the linear free energy relationship are shown to apply to the series of six epoxides and a second Co(III)K(I) catalyst. These structure− performance relationships are likely applicable to other transition metal catalysts and should expedite future epoxide and catalyst selection to make useful poly(carbonate) materials.

catalysts↗

Inversion of Time-Lapse Seismic Reservoir Monitoring Data Using CycleGAN: A Deep Learning-Based Approach for Estimating Dynamic Reservoir Property Changes

Carbon capture and storage is being pursued globally as a geoengineering measure for reducing the emission of anthropogenic CO 2 the atmosphere. Comprehensive monitoring, verification, and accounting programs must be established for demonstrating the safe storage of injected CO 2 . One of the most commonly deployed monitoring techniques is time-lapse seismic reservoir monitoring (also known as 4-D seismic), which involves comparing 3-D seismic survey data taken at the same study site but over different times. Analyses of 4-D seismic data volumes can help improve the quality of storage reservoir characterization, track the movement of injected CO 2 plume, and identify potential CO 2 spillover/leakage from the storage reservoirblue. However, the derivation of high-resolution CO 2 saturation maps from 4-D seismic data is a highly nonlinear and ill-posed inverse problem, often requiring significant computational effort. In this research, we apply a physics-based deep learning method to facilitate the solution of both the forward and inverse problems in seismic inversion while honoring physical constraints. A cycle generative adversarial neural network (CycleGAN) model is trained to learn the bidirectional functional mappings between the reservoir dynamic property changes and seismic attribute changes, such that both forward and inverse solutions can be obtained efficiently from the trained model. We show that our CycleGAN-based approach not only improves the reliability of 4-D seismic inversion but also expedites the quantitative interpretation. Our deep learning-based workflow is generic and can be readily used for reservoir characterization and reservoir model updates involving the use of 4-D seismic data.

58 GEOSCIENCES↗

Frictional and Lithological Controls on Shallow Slow Slip at the Northern Hikurangi Margin

Slow slip events (SSEs) have been identified at subduction zones globally as an important link in the continuum between elastodynamic ruptures and stable creep. The northern Hikurangi margin is home to shallow SSEs which propagate to within 2 km of the seafloor and possibly to the trench, providing insights into the physical conditions conducive to SSE behavior. We report on a suite of friction experiments performed on protolith material entering the SSE source region at the Hikurangi margin, collected during the International Ocean Discovery Program Expedition 375. We performed velocity stepping and slide-hold-slide experiments over a range of fault slip rates, from plate rate (5 cm/yr or 1.6 × 10 –9 m/s) to ~1 mm/s (10 –3 m/s) and quantified the frictional velocity dependence and healing rates for a range of lithologies atdifferent stresses. The frictional velocity dependence (a-b) and critical slip distance DC increase with fault slip rate in our experiments. We observe atransition from velocity weakening to strengthening at slip rates of ~0.3 µm/s. This velocity dependence of DC could be due to a combination of dilatant strengthening and a widening of the active shear zone at higher slip rates. We document low healing rates in the clay-rich volcaniclastic conglomerates, which lie above the incoming plate basement at least locally, and relatively higher healing rates in the chalk lithology. Finally, our experimental constraints on healing rates in different input lithologies extrapolated to timescales of 1–10 years are consistent with the geodetically inferred low stress drops and healing rates characteristic of the Hikurangi SSEs.

58 GEOSCIENCES↗

Role of Intense Arctic Storm in Accelerating Summer Sea Ice Melt: An In Situ Observational Study

Abstract Intense storms have been more frequently observed in the Arctic during recent years, in coincidence with extreme sea ice loss events. However, it is still not fully understood how storms drive such events due to deficient observations and modeling discrepancies. Here we address this problem by analyzing in situ observations acquired during an Arctic expedition, which uniquely captured an intense storm in summer 2016. The result shows a pronounced acceleration of sea ice loss during the storm process. Diagnostic analysis indicates a net energy loss at the ice surface, not supporting the accelerated melting. Although the open water surface gained net heat energy, it was insufficient to increase the mixed‐layer temperature to the observed values. Dynamic analysis suggests that storm‐driven increase in ocean mixing and upward Ekman pumping of the Pacific‐origin warm water tremendously increased oceanic heat flux. The thermal advection by the Ekman pumping led to a warmed mixed layer by 0.05°C–0.12°C and, in consequence, an increased basal sea ice melt rate by 0.1–1.7 cm day −1 .

58 GEOSCIENCES↗

Root Foraging Alters Global Patterns of Ecosystem Legacy From Climate Perturbations

The response of terrestrial ecosystems to climate perturbations typically persist longer than the timescale of the forcing, a phenomenon broadly referred to as legacy. Understanding the strength of legacy is critical for predicting ecosystem sensitivity to climate extremes and the extent that persistent changes in surface-atmosphere exchange might feedback onto climate. The cause of ecosystem legacy has been associated with myriad factors such as changes in aboveground biomass, however, few studies have tested how changes in the depth distribution of fine roots in response to perturbation might alter an ecosystem's recovery time. We explore this question using an Earth System Model that includes a dynamic root module where vegetation can forage for water and nutrients by altering their root profiles. The global simulations presented here show that in response to water stress events most ecosystems deepen their root profiles. In semi-arid ecosystems, this response expedites recovery (i.e., less legacy) relative to simulations without dynamics roots because access to deeper water pools after the initial event remains favorable. In wetter ecosystems, the development of deeper root profiles slows down the recovery timescale (i.e., more legacy) because the deeper root profile reduces access to nutrients and is thus unfavorable. Here, the simulations show that while the inclusion of dynamic roots might only minimally affect global patterns of Gross Primary Productivity and Evapotranspiration, the shift in root profile alters the timescale of recovery. Studies interested in the sustained response of land surfaces fluxes to climate disturbances should consider models that include dynamic root capability.

54 ENVIRONMENTAL SCIENCES↗

Evidence of a South Asian Proto‐Monsoon During the Oligocene‐Miocene Transition

Abstract The geological history of the South Asian monsoon (SAM) before the Pleistocene is not well‐constrained, primarily due to a lack of available continuous sediment archives. Previous studies have noted an intensification of SAM precipitation and atmospheric circulation during the middle Miocene (∼14 Ma), but no records are available to test how the monsoon changed prior to this. In order to improve our understanding of monsoonal evolution, geochemical and sedimentological data were generated for the Oligocene‐early Miocene (30–20 Ma) from Indian National Gas Hydrate Expedition 01 Site NGHP‐01‐01A in the eastern Arabian Sea, at 2,674 m water depth. We find the initial glaciation phase (23.7–23.0 Ma) of the Oligocene‐Miocene transition (OMT) to be associated with an increase in water column ventilation and water mass mixing, suggesting an increase in winter monsoon type atmospheric circulation, possibly driven by a relative southward shift of the intertropical convergence zone. During the latter part of the OMT, or “deglaciation” phase (23.0–22.7 Ma), a long‐term decrease in Mn (suggestive of deoxygenation), increase in Ti/Ca and dissolution of the biogenic carbonate fraction suggest an intensification of a proto‐summer SAM system, characterized by the formation of an oxygen minimum zone in the eastern Arabian Sea and a relative increase of terrigenous material delivered by runoff to the site. With no evidence at this site for an active SAM prior to the OMT we suggest that changes in orbital parameters, as well as possibly changing Tethyan/Himalayan tectonics, caused this step change in the proto‐monsoon system at this intermediate‐depth site.

Beasley, C.↗

Salt Diapir‐Driven Recycling of Gas Hydrate

Abstract By harnessing both hypothetical, synthetic basin and gas hydrate (GH) system models and real‐world models of well‐studied salt diapir‐associated GH sites at Green Canyon (Gulf of Mexico) and Blake Ridge (U.S. Atlantic coast), we propose and demonstrate salt movement (and in particular, diapirism) to be a new mechanism for the recycling of marine GH. At Green Canyon, for example, we show that by considering this newly proposed diapir‐driven recycling mechanism in conjunction with previously proposed lithological control on sandy‐reservoir‐hosted hydrate at the base of the GH stability zone (BGHSZ; ∼bottom‐simulating reflector, BSR), modeled GH saturations match drilling data. Overall, salt diapir movement‐induced GH recycling provides a temperature‐driven mechanism by which GH saturations at the BGHSZ may reach >90 vol. % and by which GH volumes near and free gas volumes beneath the BGHSZ may be increased significantly through time. Interestingly, comparison of salt diapir‐driven recycling and sediment burial‐driven recycling scenarios suggests notably higher rates of recycling via diapir‐driven versus burial‐driven processes. Our results suggest that GH and associated free gas accumulations above salt diapir crests represent particularly attractive targets for unconventional and conventional hydrocarbon resource exploration and for scientific and academic drilling expeditions aimed at exploiting GH systems. Salt basins containing GH systems—including passive margin basins of the Gulf of Mexico, southeastern Brazil, and southwestern Africa—are therefore compelling localities for studying salt‐driven GH recycling and for salt diapir‐associated natural gas exploration.

58 GEOSCIENCES↗

Sensitivity of the Arctic Sea Ice Cover to the Summer Surface Scattering Layer

Here, the ‘surface scattering layer’ (SSL) is the highly-scattering, coarse-grained ice layer that forms on the surface of melting, drained sea ice during spring and summer. Ice of sufficient thickness with an SSL has an observed persistent broadband albedo of ~0.65, resulting in a strong influence on the regional solar partitioning. Experiments during the MOSAiC expedition showed that the SSL re-forms in approximately one day following manual removal. Coincident spectral albedo measurements provide insight into the SSL evolution, where albedo increased on sunny days with higher solar insolation. Comparison with experiments in radiative transfer and global climate models show that the sea ice albedo is greatly impacted by the SSL thickness. The presence of SSL is a significant component of the ice-albedo feedback, with an albedo impact of the same order as melt ponds. Changes in SSL and implications for Arctic sea ice within a warming climate are uncertain.

54 ENVIRONMENTAL SCIENCES↗

Envisioning U.S. Climate Predictions and Projections to Meet New Challenges

In the face of a changing climate, the understanding, predictions, and projections of natural and human systems are increasingly crucial to prepare and cope with extremes and cascading hazards, determine unexpected feedbacks and potential tipping points, inform long-term adaptation strategies, and guide mitigation approaches. Increasingly complex socio-economic systems require enhanced predictive information to support advanced practices. Such new predictive challenges drive the need to fully capitalize on ambitious scientific and technological opportunities. These include the unrealized potential for very high-resolution modeling of global-to-local Earth system processes across timescales, reduction of model biases, enhanced integration of human systems and the Earth Systems, better quantification of predictability and uncertainties; expedited science-to-service pathways, and co-production of actionable information with stakeholders. Enabling technological opportunities include exascale computing, advanced data storage, novel observations and powerful data analytics, including artificial intelligence and machine learning. Looking to generate community discussions on how to accelerate progress on U.S. climate predictions and projections, representatives of Federally-funded U.S. modeling groups outline here perspectives on a six-pillar national approach grounded in climate science that builds on the strengths of the U.S. modeling community and agency goals. This calls for an unprecedented level of coordination to capitalize on transformative opportunities, augmenting and complementing current modeling center capabilities and plans to support agency missions. Tangible outcomes include projections with horizontal spatial resolutions finer than 10 km, representing extremes and associated risks in greater detail, reduced model errors, better predictability estimates, and more customized projections to support next generation climate services.

54 ENVIRONMENTAL SCIENCES↗

The Role of Non-Local Effects on Surface Sensible Heat Flux Under Different Types of Thermal Structures Over the Arctic Sea-Ice Surface

The effects of atmospheric thermal structure on the surface energy flux are poorly understood over the Arctic sea-ice surface. Here, we explore the mechanism of sensible heat exchange under different types of thermal structures over the Arctic sea-ice surface by using data collected during the Multidisciplinary drifting Observatory for the Study of Arctic Climate expedition. The quadrant analysis indicates that strong surface temperature inversions below 100 m enhance non-local effects on the positive (upward) sensible heat flux ($\overline{w'θ'}$) through entrainment of large eddies from the convective boundary layer aloft. However, strong surface inversions restrict the contributions of large eddies to the negative (downward) $\overline{w'θ'}$ due to intensified surface stability. By inspecting the existing parameterization schemes, we found that the European Center for Medium-Range Weather Forecasts Integrated Forecasting System scheme fails to predict the impacts of non-local processes on the positive $\overline{w'θ'}$, and an adjustment term to correct the bias of parameterized $\overline{w'θ'}$ is proposed.

54 ENVIRONMENTAL SCIENCES↗

The Vertical Structure of Turbulence Kinetic Energy Near the Arctic Sea‐Ice Surface

Atmospheric turbulence over the Arctic sea-ice surface has been understudied due to the lack of observational data. In this study, we focus on the turbulence kinetic energy (TKE) over sea ice and distinguish its two different vertical structures, the “Surface” type and the “Elevated” type, using observations during the Multidisciplinary drifting Observatory for the Study of Arctic Climate expedition (MOSAiC). The “Surface” type has the maximum TKE near the surface (at 2 m), while the “Elevated” type has the maximum TKE at a higher level (6 m). The TKE budget analysis indicates that the “Elevated” type is caused by the increased shear production of TKE at 6 m. In addition, spectral analysis reveals that the contribution to TKE by horizontal large eddies is enhanced in the “Elevated” type. Finally, how the vertical structure of TKE affects the parameterization of turbulent momentum flux is discussed.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of the Planetary Boundary Layer Height From ERA5 Reanalysis With MOSAiC Observations Over the Arctic Ocean

The planetary boundary layer height (PBLH) is a crucial indicator reflecting the region of the atmosphere characterized by continuous turbulence. Here, we use radiosonde and surface meteorological observations (4–7 times per day, year-round measurements) during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition to derive the PBLH (PBLH MOSAiC ), and further evaluate the PBLH from the ERA5 reanalysis (PBLH ERA5 ). Comparisons between PBLH MOSAiC and PBLH ERA5 from different perspectives reveal that: (a) The overestimation of PBLH ERA5 when the sea ice concentration is >90% is significant with the centered root mean squared error reaching up to 201 m; (b) The difference between the two products is notably pronounced in cold seasons, while it is comparatively diminished in warm seasons; (c) In neutral boundary layers, differences in PBLH ERA5 are larger compared with stable and convective boundary layers. In addition, the analysis of error sources indicates that the bias of PBLH ERA5 is sensitive to the bias of vertical thermal structure and wind speed profiles in ERA5 data sets in all conditions. Finally, we find a Random Forest model effectively reduces the bias of PBLH ERA5 with the index of agreement reaching up to 0.71 in the test data set, while a multiple linear regression demonstrates comparable performance to the Random Forest model.

54 ENVIRONMENTAL SCIENCES↗

Air‐Ice‐Ocean Coupling During a Strong Mid‐Winter Cyclone: Observing Coupled Dynamic Interactions Across Scales

Abstract Arctic cyclones are key drivers of sea ice and ocean variability. During the 2019–2020 Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition, joint observations of the coupled air‐ice‐ocean system were collected at multiple spatial scales. Here, we present observations of a strong mid‐winter cyclone that impacted the MOSAiC site as it drifted in the central Arctic pack ice. The sea ice dynamical response showed spatial structure at the scale of the evolving and translating cyclonic wind field. Internal ice stress and ocean stress play significant roles, resulting in timing offsets between the atmospheric forcing and the ice response and post‐cyclone inertial ringing in the ice and ocean. Ice motion in response to the wind field then forces the upper ocean currents through frictional drag. The strongest impacts to the sea ice and ocean from the passing cyclone occur as a result of the surface impacts of a strong atmospheric low‐level jet (LLJ) behind the trailing cold front and changing wind directions between the warm‐sector LLJ and post cold‐frontal LLJ. Impacts of the cyclone are prolonged through the coupled ice‐ocean inertial response. Local impacts of the approximately 120 km wide LLJ occur over a 12 hr period or less and at scales of a kilometer to a few tens of kilometers, meaning that these impacts occur at combined smaller spatial scales and faster time scales than most satellite observations and coupled Earth system models can resolve.

Meteorology & Atmospheric Sciences↗

Surface Energy Balance Responses to Radiative Forcing in the Central Arctic From MOSAiC and Models

The Arctic surface energy budget (SEB) couples the atmosphere with the sea ice, making it useful for both studying surface processes as well as evaluating models. Improved understanding of atmosphere-ice interactions is required to improve models, requiring year-round observations to address seasonally dependent biases. This work uses novel observations from the MOSAiC expedition to quantify the responses of surface fluxes to radiative forcing over sea ice throughout a complete annual cycle. We identify two primary regimes of flux response: an ice growth regime in winter and an ice melt regime in summer. In the growth regime, changes in radiative forcing impact upwelling longwave, sensible heat, and subsurface heat fluxes, whereas in the melt regime changes in radiative forcing primarily alter the amount of melt and subsurface transmission because the surface temperature is fixed. These observed responses of surface fluxes to radiative forcing are used to evaluate seven weather forecast models during the ice growth regime. In most models, the responses of surface fluxes to radiative forcing do not match observations. Many models also have biased downwelling longwave. One model (the Coupled Arctic Forecast System; CAFS) adequately captures both the mean radiative forcing and the flux responses in winter. CAFS is further evaluated against observations spanning the full MOSAiC year, demonstrating sufficient agreement to provide a more generalized understanding of these SEB process relationships across the Arctic.

54 ENVIRONMENTAL SCIENCES↗

A Framework for Parametric and Predictive Uncertainty Quantification in the E3SM Land Model: Assessing Site and Observable Generalizability

Quantifying parametric uncertainty using observations from individual sites provides a critical foundation for Earth system modeling, serving as a necessary first step before scaling up to regional or global applications. This study introduces a novel computational framework designed to enhance model predictability by reducing parametric uncertainty and assessing site and observable generalizability using various observational constraints. The framework integrates five components: Model Simulation, Statistical Emulation, Global Sensitivity Analysis (GSA), Model Calibration, and Model Prediction. Using the E3SM land model, we simulated site-level land-atmosphere carbon and energy fluxes from 2003 to 2007 across five evergreen needleleaf FLUXNET sites, perturbing 26 vegetation-related model parameters. Gaussian process emulators were employed to expedite GSA and model calibration. Four critical parameters that strongly influence selected land-atmosphere fluxes were identified by GSA. Bayesian approaches were used to infer parameter probability distributions leveraging synthetic data and FLUXNET observations. The results reveal that posterior parameter distributions vary significantly across different sites and observables within the same plant functional type. Probabilistic predictions indicate that parameters calibrated at one site can enhance predictive accuracy at other sites, although site heterogeneity may sometimes outweigh parametric uncertainty. Additionally, the probabilistic predictions demonstrate that calibration for one variable can also improve predictability for other variables, thereby maximizing predictive capabilities with limited observations. This framework provides a powerful approach for reducing parametric uncertainty in Earth system models and deepening our understanding of carbon dynamics and energy cycles. Its adaptability makes it a valuable tool for broader applications in Earth system modeling.

54 ENVIRONMENTAL SCIENCES↗

Air pollution control strategies directly limiting national health damages in the US

Exposure to fine particulate matter (PM 2.5 ) from fuel combustion significantly contributes to global and US mortality. Traditional air pollution control strategies typically focus on emission reductions for specific air pollutants or sectors to maintain air pollutant concentrations within acceptable levels. Here we directly set national PM 2.5 mortality cost reduction targets within a global human-earth system model with US state-level energy systems, identifying endogenously the control actions, sectors, and locations that most cost-effectively reduce PM 2.5 mortality. Our results show that substantial health benefits can be cost-effectively achieved by using electricity to replace sources with high primary PM 2.5 emission intensities, including industrial coal, building biomass, and industrial liquids. Increasing the stringency of PM 2.5 reduction targets expedites the phaseout of high emission intensity sources, leading to larger declines in major air pollutant emissions, but very limited co-benefits in reducing CO 2 emissions. Control strategies achieve the greatest mortality cost reductions in the East North Central and Middle Atlantic states.

54 ENVIRONMENTAL SCIENCES↗