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At least 1,171 records · Page 65

Significance of a Solid Electrolyte Interphase on Separation of Anode and Cathode Materials from Spent Li-Ion Batteries by Froth Flotation

The separation of electrode active materials from spent Li-ion batteries (LIBs) by froth flotation is challenging due to the changes in surface properties of electrode active materials from cycling as well as the presence of organic binders. In this work, the froth flotation separation of aged anode and cathode composite materials from spent LIBs was systematically investigated after the materials were heat treated. The results show that aged anode and cathode materials from spent LIBs can be well separated from each other after a heating process in air at 400 degrees C and at which some of the PVDF binder remains intact. The underlying mechanism was investigated by X-ray photoelectron spectroscopy (XPS), contact angle measurements, and scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX). The results from the XPS and contact angle measurements show that there is a hydrophilic and oxygen-rich layer on the surface of aged anode materials. This hydrophilic surface, associated with the solid electrolyte interface (SEI) layer, impacts the froth flotation process significantly. The results also show that both the SEI layers and PVDF binder residues on the surface are removed at 400 degrees C for an hour, restoring the hydrophobicity of the anode materials, which, in turn, benefits the separation of anode and cathode materials. The STEM/EDX elemental analysis data confirms that there are 20 nm-thick oxygen-rich SEI layers on the surfaces, which can be removed after a heating process. The present result illustrates the significance of the SEI layers in flotation separation of electrode materials and sheds new lights into the future development of the recycling processes for the separation of anode and cathode composite materials from spent Li-ion batteries.

25 ENERGY STORAGE↗

Engineered Membrane Vesicle Production via oprF or oprI Deletion Has Distinct Phenotypic Effects in Pseudomonas putida

Membrane vesicle (MV) production is a natural phenomenon in Gram-negative bacteria and represents an emerging synthetic biology tool for the secretion of biomolecules or bioproducts. Manipulation of membrane components has proven successful in enhancing MV production. However, the impact of membrane disruptions on strain fitness and protein composition warrants further investigation for the use of MVs in industrial bioprocesses. Here, we identify and characterize two genetic engineering strategies for inducing hypervesiculation-deletion of genes for the outer membrane porin OprF or the lipoprotein OprI-in the commonly used platform Pseudomonas putida KT2440. Deletion of oprI generated up to a 1.5-fold increase in MVs, larger MVs with a greater proportion of outer membrane proteins, and no significant impact on strain fitness compared to wild type. In contrast, deletion of oprF, relative to wild type, generated up to a 4-fold increase in MVs but diminished growth, permeabilized membranes, and increased cytosolic protein packaging. Both hypervesiculation phenotypes increased nontargeted and MV-targeted mNeonGreen extracellular signal by up to 6-fold, demonstrating vesiculation as a mechanism for protein secretion. Despite increased blebbing of MVs from gene deletions, proteins involved in membrane biosynthesis were not elevated relative to wild type. Overexpression of gpsA, which initiates glycerophospholipid biosynthesis, in the ΔoprF background improved the membrane integrity by 37% and maintained MV formation, highlighting the importance of membrane biosynthesis in restoring the membrane in hypervesiculating strains. Together, this study provides genetic engineering strategies with corresponding phenotypic outcomes toward providing a synthetic biology toolset for MV deployment in P. putida.

59 BASIC BIOLOGICAL SCIENCES↗

A Telomerase-Activated Magnetic Resonance Imaging Probe for Consecutively Monitoring Tumor Growth Kinetics and In Situ Screening Inhibitors

Telomerase has long been considered as a biomarker for cancer diagnosis and a therapeutic target for drug discovery. Detecting telomerase activity in vivo could provide more direct information of tumor progression and response to drug treatment, which, however, is hampered by the lack of an effective probe that can generate an output signal without a tissue penetration depth limit. Here in this study, using the principle of distance-dependent magnetic resonance tuning, we constructed a telomerase-activated magnetic resonance imaging probe (TAMP) by connecting superparamagnetic ferroferric oxide nanoparticles (SPFONs) and paramagnetic Gd-DOTA (Gd(III) 1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraazacyclododecane-1,4,7,10-tet-raacetic acid) complexes via telomerase-responsive DNA motifs. Upon telomerase-catalyzed extension of the primer in TAMP, Gd-DOTA-conjugated oligonucleotides can be liberated from the surface of SPFONs through a DNA strand displacement reaction, restoring the T 1 signal of the Gd-DOTA for a direct readout of the telomerase activity. Here we show that, by tracking telomerase activity, this probe provides consistent monitoring of tumor growth kinetics during progression and in response to drug treatment and enables in situ screening of telomerase inhibitors in whole-animal models. This study provides an alternative toolkit for cancer diagnosis, treatment response assessment, and anticancer drug screening.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering

Dimeric complexes composed of d 8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir 2 (dimen) 4 ] 2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, in this work, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population—often termed the ground state hole—with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d 8 –d 8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anionic Lipids Regulate the Light-Harvesting Complex 1-Reaction Center Photocycle in Purple Bacteria

Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. Here, in this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.

bacteria↗

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗

Transitory Topochemical Tailoring of a van der Waals Superconductor

Topochemical intercalation is widely used to access metastable phases with novel electronic properties, but the reverse reaction (deintercalation) typically restores the original state, limiting practical use. Here, in this study, we present a topochemical approach that employs a sacrificial intercalant that thermally decomposes to irreversibly lock in the new electronic state. Using 2-aminobutane as the sacrificial intercalant, we convert the van der Waals (vdW) material 1T-TiSe 2 into a superconductor and the vdW superconductor 2H-NbSe 2 into a nonsuperconducting metal, while preserving the ability to exfoliate the resulting crystals. We find that this transitory intercalation increases the electron density in both materials and partially suppresses the CDW in TiSe 2 . By tuning the thermolysis temperature, we can systematically vary the carrier density in TiSe 2 , enabling us to map its phase diagram. The superconductivity in TiSe 2 is retained in exfoliated flakes, although with a lower critical temperature. This transitory topochemical strategy enables access to new electronic states with precisely tuned carrier densities that are otherwise inaccessible through direct solid-state synthesis.

36 MATERIALS SCIENCE↗

The [4Fe-4S] Cluster of HydF Is Essential for [FeFe]-Hydrogenase Maturation

The organometallic H-cluster of the [FeFe]-hydrogenase is assembled in vivo through a complex process requiring the action of three dedicated maturation enzymes, HydG, HydE, and HydF, as well as the aminomethyl-lipoyl-H-protein (H met ) of the glycine cleavage system (GCS). Here we probe the role of HydF and its [4Fe-4S] cluster in [FeFe]-hydrogenase maturation by using a defined semisynthetic approach in which [Fe I 2 (μ-SH) 2 (CO) 4 (CN) 2 ] 2– ([2Fe] E ) is used to bypass HydE and HydG, and GCS components are used in place of cell lysate. We show that inclusion of the iron–sulfur carrier protein NfuA and the high-CO-affinity myoglobin variant Mb H64L provides dramatically improved hydrogenase activities up to 828 μmol/min/mg, equivalent to the best reported activities for Chlamydomonas reinhardtii [FeFe]-hydrogenase isolated from the native organism. Apo-HydF lacking a [4Fe-4S] cluster provides very little hydrogenase activity; however, full maturation is restored with the addition of NfuA, which we demonstrate reconstitutes the [4Fe-4S] cluster of HydF. In addition, a HydF variant lacking a [4Fe-4S] cluster by changing two cysteine ligands to alanine is completely unable to support either semisynthetic maturation using [2Fe] E , or full maturation using HydG and HydE, even in the presence of NfuA, demonstrating that the HydF [4Fe-4S] cluster is absolutely essential for [FeFe]-hydrogenase maturation. The possibility that the HydF [4Fe-4S] cluster plays a role in direct binding of [2Fe] E is negated by our results with the HydF D311C variant, which demonstrate that the labile Asp311 cluster ligand is not essential for [2Fe] E binding and HydA maturation. We therefore conclude that [2Fe]E binds HydF adjacent to, but not directly coordinated to, the [4Fe-4S] cluster. The HydF [4Fe-4S] cluster is proposed to be essential due to its impact on the [2Fe] E binding orientation and the ability of the HydF/[2Fe] E complex to form productive interactions with H met or the H met /T-protein complex during DTMA ligand biosynthesis.

cluster chemistry↗

Control of Molecular Bonding Strength on Metal Catalysts with Organic Monolayers for CO 2 Reduction

The development of separate levers for controlling the bonding strength of different reactive species on catalyst surfaces is challenging but essential for the design of highly active and selective catalysts. For example, during CO 2 reduction, production of CO often requires balancing a trade-off between the adsorption strength of the reactant and product states: weak binding of CO is desirable from a selectivity perspective, but weak binding of CO 2 leads to low activity. Here in this paper, we demonstrate a new method of controlling both CO 2 adsorption and CO desorption over supported metal catalysts by employing a single self-assembly step where organic monolayer films were deposited on the catalyst support. Binding of phosphonic acid monolayers on supported Pt and Pd catalysts weakened CO binding via a through-support effect. The weakened CO adsorption was generally accompanied by decreased adsorption and reactivity of CO 2 . However, by the incorporation of basic amine functions at controlled positions in the modifying film, strong CO 2 adsorption and hydrogenation reactivity could be restored. Thus, both through-surface and through-space interactions could be manipulated by design of the organic modifiers. After surface modification, the catalysts exhibited significantly improved selectivity (up to ~99% at conversions near 50%) and activity toward CO production. Moreover, the rate of deactivation was notably reduced due to prevention of CO poisoning.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Purification of Lithium-Ion Battery Black Mass through Tailored Alkaline Corrosion

Obtaining high-purity material outputs is crucial to the viability of novel process aimed at direct recycling of lithium-ion batteries. Metallic impurities in recycled cathodes have been shown to inhibit performance, thereby threatening mainstream acceptance of recycled battery products. Thus, shredded black mass (BM) must be purified to remove metallic contaminants, and specifically Al and Cu originating from the electrode current collectors. We herein explore a process to ionize solid copper and aluminum to ionic form based on tailored alkaline chemistry, without incurring damage to the target cathode material (Li(NixMnyCo1-x-y)O2; NMC). Al and Cu corrosion may be enhanced through the addition of chloride salt, elevated temperatures, and the use of ultrasonication - all of which disrupt the formation of passivating films on the metallic surface, and thereby increase corrosion rate. We demonstrate optimized parameters for Al and Cu corrosion both from a kinetic and overall process cost perspective. Further, we analyze the impact of these conditions on the structural (XRD, SEM), chemical (EDS, ICP), and electrochemical (impedance, cycling, dQ/dV) properties of NMC, and suggest that the present purification method does not significantly disrupt NMC performance. Finally, we present preliminary results from a promising bench-scale demonstration of this purification process applied to a simulated black mass.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗

Multiscale Feature-feature Interactions Control Patterns of Hyporheic Exchange in a Simulated Headwater Mountain Stream

Recent predictions of hyporheic exchange at the basin-scale assume individual features control exchange independently of each other, which has been demonstrated in relatively uniform, low-gradient rivers. However, this assumption may not hold in steep catchments where both the type and size of individual features may vary over short distances, leading to irregular patterns of feature dominance on hyporheic exchange flows. Also, steep longitudinal gradients support substantial downvalley flows in the subsurface, which may create feedbacks between adjacent features. In this study, we test the extent to which features interact with one another and whether they can be aggregated to make reach-scale predictions in a headwater mountain stream. Using systematic manipulations of a 2-D stream centerline model and spectral analyses, we test for the presence of both feature-feature and multiscale interactions. Our results show that changing the height of individual step-pool features can alter hyporheic flow fields in neighboring, and sometimes distant, features. Spectral analyses revealed two scales of streambed topography—a local scale of single features and an intermediate scale that spanned multiple local-scale features. All features produced hyporheic exchange, but turnover of deeper hyporheic water only occurred at a few key locations where local- and intermediate-scale features amplified each other. Further, shallow bedrock increases the ratio of local- and intermediate-scale flowpaths to regional-scale flowpaths. Conceptual models portraying hyporheic exchange as a series of nested flowpaths should include the interactions among streambed topographic features in mountain streams. These results have implications for upscaling, field experiments, and stream restoration in steep catchments.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of Atmospheric Boundary Layer Height From Wind Profiling Radar and Slab Models and Its Responses to Seasonality of Land Cover, Subsidence, and Advection

In this study, we evaluated the effect of land cover, atmospheric subsidence, and advection on the annual dynamics of atmospheric boundary layer (ABL) height from two contrasting sites. The first site is the Walker Branch forest, a deciduous forest of temperate climate, complex topography, and cloudy summers. The second site is the Sacramento-San Joaquin River Delta, a site of Mediterranean climate, flat terrain on a local scale, and clear summers. After testing a new algorithm to calculate ABL heights from 915 MHz radar wind profilers, we evaluated a hierarchy of three slab models to recreate the diurnal and annual patterns of ABL growth. We found that the lower ABL heights in the Delta, particularly during late summer, are driven by the combined effects of increased atmospheric subsidence and marine air advection. In both sites, the annual pattern of ABL height was strongly correlated to total daily incoming radiation, and in the Delta, the annual pattern of ABL height closely followed the seasonal patterns of sensible heat flux from a mosaic of different land covers. A land composite of latent and sensible heat fluxes obtained through a meso-network of eddy covariance measurements and the ECOsystem Spaceborne Thermal Radiometer Experiment on Space Station (ECOSTRESS) mission resulted in higher model skill, thus showing that land cover heterogeneity is an important driver of ABL growth. To conclude, model simulations show that in the Delta, restoring agricultural land to wetlands with large open water areas could result in a reduction of ABL height during those months with low subsidence and advection.

54 ENVIRONMENTAL SCIENCES↗

How Does Flow Alteration Propagate Across a Large, Highly Regulated Basin? Dam Attributes, Network Context, and Implications for Biodiversity

Abstract Large dams are a leading cause of river ecosystem degradation. Although dams have cumulative effects as water flows downstream in a river network, most flow alteration research has focused on local impacts of single dams. Here we examined the highly regulated Colorado River Basin (CRB) to understand how flow alteration propagates in river networks, as influenced by the location and characteristics of dams as well as the structure of the river network—including the presence of tributaries. We used a spatial Markov network model informed by 117 upstream‐downstream pairs of monthly flow series (2003–2017) to estimate flow alteration from 84 intermediate‐to‐large dams representing >83% of the total storage in the CRB. Using Least Absolute Shrinkage and Selection Operator regression, we then investigated how flow alteration was influenced by local dam properties (e.g., purpose, storage capacity) and network‐level attributes (e.g., position, upstream cumulative storage). Flow alteration was highly variable across the network, but tended to accumulate downstream and remained high in the main stem. Dam impacts were explained by network‐level attributes (63%) more than by local dam properties (37%), underscoring the need to consider network context when assessing dam impacts. High‐impact dams were often located in sub‐watersheds with high levels of native fish biodiversity, fish imperilment, or species requiring seasonal flows that are no longer present. These three biodiversity dimensions, as well as the amount of dam‐free downstream habitat, indicate potential to restore river ecosystems via controlled flow releases. Our methods are transferrable and could guide screening for dam reoperation in other highly regulated basins.

54 ENVIRONMENTAL SCIENCES↗

Modeled Surface-Atmosphere Fluxes From Paired Sites in the Upper Great Lakes Region Using Neural Networks

The eddy covariance (EC) method is one of the most widely used approaches to quantify surface-atmosphere fluxes. However, scaling up from a single EC tower to the landscape remains an open challenge. To address this, we used 63 site years of data to examine simulated annual and growing season sums of carbon fluxes from three paired land-cover type sites of corn, restored-prairie, and switchgrass ecosystems. This was also done across the landscape by modeling fluxes using different land-cover type input data. An artificial neural network (ANN) approach was used to model net ecosystem exchange (NEE), ecosystem respiration (R eco ), and gross primary production (GPP) at one paired site using environmental observations from the second site only. With a mean spatial separation of 11 km between paired sites, we were able to model annual sums of NEE, R eco , and GPP with uncertainties of 20%, 22%, and 8%, respectively, relative to observation sums. When considering the growing season only, model uncertainties were 17%, 22%, and 9%, respectively for the three flux terms. We also show that ANN models can estimate sums of R eco and GPP fluxes without needing the constraint of similar land-cover-type, with annual uncertainties of 12% and 10%. These results provide new insights to scaling up observations from one EC site beyond the footprint of the EC tower to multiple land-cover types across the landscape.

54 ENVIRONMENTAL SCIENCES↗

A Hierarchy of Global Ocean Models Coupled to CESM1

Abstract We develop a hierarchy of simplified ocean models for coupled ocean, atmosphere, and sea ice climate simulations using the Community Earth System Model version 1 (CESM1). The hierarchy has four members: a slab ocean model, a mixed‐layer model (MLM) with entrainment and detrainment, an Ekman MLM, and an ocean general circulation model (OGCM). Flux corrections of heat and salt are applied to the simplified models ensuring that all hierarchy members have the same climatology. We diagnose the needed flux corrections from auxiliary simulations in which we restore the temperature and salinity to the daily climatology obtained from a target CESM1 simulation. The resulting three‐dimensional corrections contain the interannual variability fluxes that maintain the correct vertical gradients of temperature and salinity in the tropics. We find that the inclusion of mixed‐layer entrainment and Ekman flow produces sea surface temperature and surface air temperature fields whose means and variances are progressively more similar to those produced by the target CESM1 simulation. We illustrate the application of the hierarchy to the problem of understanding the response of the climate system to the loss of Arctic sea ice. We find that the shifts in the positions of the mid‐latitude westerly jet and of the Inter‐tropical Convergence Zone (ITCZ) in response to sea‐ice loss depend critically on upper ocean processes. Specifically, heat uptake associated with the mixed‐layer entrainment influences the shift in the westerly jet and ITCZ. Moreover, the shift of ITCZ is sensitive to the form of Ekman flow parameterization.

54 ENVIRONMENTAL SCIENCES↗

Detecting Hot Spots of Methane Flux Using Footprint‐Weighted Flux Maps

Abstract In this study, we propose a new technique for mapping the spatial heterogeneity in gas exchange around flux towers using flux footprint modeling and focusing on detecting hot spots of methane (CH 4 ) flux. In the first part of the study, we used a CH 4 release experiment to evaluate three common flux footprint models: the Hsieh model (Hsieh et al., 2000), the Kljun model (Kljun et al., 2015), and the K & M model (Kormann and Meixner, 2001), finding that the K & M model was the most accurate under these conditions. In the second part of the study, we introduce the Footprint‐Weighted Flux Map, a new technique to map spatial heterogeneity in fluxes. Using artificial CH 4 release experiments, natural tracer approaches and flux chambers we mapped the spatial flux heterogeneity, and detected and validated a hot spot of CH 4 flux in a oligohaline restored marsh. Through chamber measurements during the months of April and May, we found that fluxes at the hot spot were on average as high as 6589 ± 7889 nmol m −2 s −1 whereas background flux from the open water were on average 15.2 ± 7.5 nmol m −2 s −1 . This study provides a novel tool to evaluate the spatial heterogeneity of fluxes around eddy‐covariance towers and creates important insights for the interpretation of hot spots of CH 4 flux, paving the way for future studies aiming to understand subsurface biogeochemical processes and the microbiological conditions that lead to the occurrence of hot spots and hot moments of CH 4 flux.

54 ENVIRONMENTAL SCIENCES↗

A Century of Reforestation Reduced Anthropogenic Warming in the Eastern United States

Abstract Restoring and preserving the world's forests are promising natural pathways to mitigate some aspects of climate change. In addition to regulating atmospheric carbon dioxide concentrations, forests modify surface and near‐surface air temperatures through biophysical processes. In the eastern United States (EUS), widespread reforestation during the 20th century coincided with an anomalous lack of warming, raising questions about reforestation's contribution to local cooling and climate mitigation. Using new cross‐scale approaches and multiple independent sources of data, we uncovered links between reforestation and the response of both surface and air temperature in the EUS. Ground‐ and satellite‐based observations showed that EUS forests cool the land surface by 1–2°C annually compared to nearby grasslands and croplands, with the strongest cooling effect during midday in the growing season, when cooling is 2–5°C. Young forests (20–40 years) have the strongest cooling effect on surface temperature. Surface cooling extends to the near‐surface air, with forests reducing midday air temperature by up to 1°C compared to nearby non‐forests. Analyses of historical land cover and air temperature trends showed that the cooling benefits of reforestation extend across the landscape. Locations surrounded by reforestation were up to 1°C cooler than neighboring locations that did not undergo land cover change, and areas dominated by regrowing forests were associated with cooling temperature trends in much of the EUS. Our work indicates reforestation contributed to the historically slow pace of warming in the EUS, underscoring reforestation's potential as a local climate adaptation strategy in temperate regions.

Environmental Sciences & Ecology↗

Aitken Mode Aerosols Buffer Decoupled Mid‐Latitude Boundary Layer Clouds Against Precipitation Depletion

Aerosol-cloud-precipitation interactions are a leading source of uncertainty in estimating climate sensitivity. Remote marine boundary layers where accumulation mode (~100–400 nm diameter) aerosol concentrations are relatively low are very susceptible to aerosol changes. These regions also experience heightened Aitken mode aerosol (~10–100 nm) concentrations associated with ocean biology. Aitken aerosols may significantly influence cloud properties and evolution by replenishing cloud condensation nuclei and droplet number lost through precipitation (i.e., Aitken buffering). We use a large-eddy simulation with an Aitken-mode enabled microphysics scheme to examine the role of Aitken buffering in a mid-latitude decoupled boundary layer cloud regime observed on 15 July 2017 during the Aerosol and Cloud Experiments in the Eastern North Atlantic flight campaign: cumulus rising into stratocumulus under elevated Aitken concentrations (~100–200 mg -1 ). In situ measurements are used to constrain and evaluate this case study. Our simulation accurately captures observed aerosol-cloud-precipitation interactions and reveals time-evolving processes driving regime development and evolution. Aitken activation into the accumulation mode in the cumulus layer provides a reservoir for turbulence and convection to carry accumulation aerosols into the drizzling stratocumulus layer above. Further Aitken activation occurs aloft in the stratocumulus layer. Together, these activation events buffer this cloud regime against precipitation removal, reducing cloud break-up and associated increases in heterogeneity. We examine cloud evolution sensitivity to initial aerosol conditions. With halved accumulation number, Aitken aerosols restore accumulation concentrations, maintain droplet number similar to original values, and prevent cloud break-up. Without Aitken aerosols, precipitation-driven cloud break-up occurs rapidly. In this regime, Aitken buffering sustains brighter, more homogeneous clouds for longer.

54 ENVIRONMENTAL SCIENCES↗