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At least 1,027 records · Page 57

Modeling the Photoelectrochemical Evolution of Lead-Based, Mixed-Halide Perovskites Due to Photosegregation

Lead-based, mixed-halide perovskites such as methylammonium lead iodide-bromide [MAPb(I 1-x Br x ) 3 ] undergo anion photosegregation under illumination. This is observed as low band gap photoluminescence from photogenerated iodine-rich domains due to favorable band offsets that induce carrier funneling into them. Unfortunately, theoretical rationalizations of mixed-halide photosegregation are complicated by biases inherent to photoluminescence-based observations. Recent compositionally-weighted X-ray diffraction (XRD) measurements now reveal broad distributions of photosegregated stoichiometries not captured by existing photosegregation models. To better bridge experiment and theory, we perform kinetic Monte Carlo (KMC) simulations of photosegregation within the context of a band gap-based thermodynamic model, which has previously accounted for numerous experimental observations. Our KMC simulations are modified to consider high carrier density Fermi-Dirac statistics that result from carrier funneling and accumulation within photosegregated I-rich domains. Obtained KMC results reproduce broad x terminal distributions seen experimentally and illustrate how they are characterized by a central, heavily I-enriched stoichiometry. I-rich domain “drifting” during photosegregation rationalizes the long photosegregation timescales seen experimentally with drifting simultaneously producing a wake of variable stoichiometry I-rich inclusions that form the lion’s share of stoichiometric heterogeneities seen in compositionally-weighted XRD measurements. These simulations and accompanying rationalizations further reveal a general criterion for realizing favorable free energies to induce demixing. Central to the criterion is the statistical occupation of low gap inclusions in the parent alloy by excitations. Furthermore, the resulting model thus provides a general framework for conceptualizing mixed-halide perovskite light and temperature sensitivities, mediated by photocarriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Real-Time Ammonia and Humidity Monitoring with Ultra-Fast Conductometric Sensors Based on Porphyrin and Phthalocyanine Complexes

Organic semiconductors like porphyrins and phthalocyanines are attracting a wide range of researchers due to their versatile electrical properties and sensing performances in conductometric sensors. In this study, we investigate two types of π-extended porphyrins, which share the same macrocyclic structure but differ in their central metal. These porphyrins are employed as sublayers in bilayer heterojunction devices, with the lutetium bisphthalocyanine complex, LuPc 2 , serving as the common top layer. Remarkably, the central metal in the porphyrin macrocycle significantly influences the solubility of the materials and, consequently, the surface topography of the resulting bilayer heterojunction devices. This structural variation translates into distinct electrical and sensing performances. The device incorporating nickel as metal centre (AM2) demonstrates superior sensitivity towards NH3, with a relative response (RR) of ca. -7% at 90 ppm, an ultra-fast response time of about 9 s, and an impressive limit of detection (LOD) of 250 ppb, whereas, the device that has zinc as metal centre in sublayer (AM3) exhibits RR value of ca. -0.9% at 90 ppm with t 90 of ca. 120 s and LOD of 2 ppm. Both devices are evaluated under randomly varying NH 3 concentration and RH value. The results shows that the AM2-based sensor allows following NH 3 in real-time, while the AM3-based sensor delivers an average concentration over time. On the other hand, the AM2-based sensor exhibits slow kinetics under RH exposure, while the AM3-based sensor precisely mirrors the pattern of random RH changes generated by the software, demonstrating its exceptional responsiveness and accuracy in tracking humidity fluctuations. In conclusion, these findings underscore the critical role of the metal centre in tuning the electrical and sensing properties of the heterojunction devices.

99 GENERAL AND MISCELLANEOUS↗

Carbon Dioxide Fluxes to the Atmosphere From Waters Within Flooded Forests in the Amazon Basin

Aquatic habitats in the lowland Amazon emit large quantities of carbon dioxide (CO 2 ). However, information on CO 2 fluxes from seasonally flooded forests that constitute 80% of the surface area of aquatic environments in the lowland Amazon basin is sparse. We provide the first multi-year measurements of CO 2 exchanges within flooded forests of the central Amazon basin. Our approach combines measurement of dissolved CO 2 concentrations and fluxes between the water and atmosphere and ecological data. Although the rates of CO 2 emission by flooded forests are lower than other aquatic habitats, such as open waters in rivers and lakes, the combination of high CO 2 concentrations and a large area results in an appreciable regional out gassing of carbon dioxide from flooded forests. These fluxes can represent about half of the net primary production of flooded forests in the central Amazon basin.

54 ENVIRONMENTAL SCIENCES↗

Low Molecular Weight Dissolved Organic Carbon: Aging, Compositional Changes, and Selective Utilization During Global Ocean Circulation

The composition and cycling dynamics of marine dissolved organic carbon (DOC) have received increased interest in recent years; however, little research has focused on the refractory, low molecular weight (LMW) component that makes up the majority of this massive C pool. In this study, we measured stable isotopic (δ 13 C), radioisotopic (Δ 14 C), and compositional (C/N, 13 C solid-state NMR) properties of separately isolated high molecular weight (HMW) and LMW DOC fractions collected using a coupled ultrafiltration and solid phase extraction approach from throughout the water column in the North Central Pacific and Central North Atlantic. The selective isolation of LMW DOC material allowed the first investigation of the composition and cycling of a previously elusive fraction of the DOC pool. The structural composition of the LMW DOC material was homogeneous throughout the water column and closely matched carboxylic-rich alicyclic material that has been proposed as a major component of the marine refractory DOC pool. Examination of offsets in the measured parameters between the deep waters of the two basins provides the first direct assessment of changes in the properties of this material with aging and utilization during ocean circulation. While our direct measurements largely confirm hypotheses regarding the relative recalcitrance of HMW and LMW DOC, we also demonstrate a number of novel observations regarding the removal and addition of DOC during global ocean circulation, including additions of fresh carbohydrate-like HMW DOC to the deep ocean and large-scale removal of both semilabile HMW and recalcitrant LMW DOC.

58 GEOSCIENCES↗

Spatiotemporal Characteristics and Propagation of Summer Extreme Precipitation Events over United States: A Complex Network Analysis

Complex Network (CN) is a graph-theory based depiction of relation shared by various elements of a complex-dynamical system such as the atmosphere. Here we applied the concept of CN to understand the directionality and topological structure of summer extreme precipitation events (SEPEs) over the conterminous United States (CONUS). The SEPEs are calculated based on the 95th percentile daily rainfall at 0.5ox0.5o spatial resolution for CONUS to investigate the multi-dimensional characteristics of precipitation extremes. The derived CN coefficients (e.g., betweenness centrality, clustering coefficient, orientation, and network divergence) reveal important structural and dynamical information about the topology of the SEPEs and improve understanding of the dominant meteorological patterns. The initiation and propagation of SEPEs from the source-zones to the sink-zones are identified. The SEPEs are influenced by topography, dominant wind patterns, and moisture sources in terms of their topological structure and spatial dynamics.

Mondal, Somnath↗

Climate-Driven Limits to Future Carbon Storage in California's Wildland Ecosystems

Enhanced ecosystem carbon storage is a key component of many climate mitigation pathways. The State of California has set an ambitious goal of carbon neutrality by 2045, relying in part on enhanced carbon sequestration in natural and working lands. We used statistical modeling, including random forest and climate analog approaches, to explore the climate-driven challenges and uncertainties associated with the goal of long-term carbon sequestration in forests and shrublands. We found that seasonal patterns of temperature and precipitation are strong controllers of the spatial distribution of aboveground live carbon. RCP8.5 projections of temperature and precipitation are estimated to drive decreases of 16.1% ± 7.5% in aboveground live carbon by the end of the century, with coastal areas of central and northern California and low/mid-elevation mountain areas being most vulnerable. With RCP4.5 projections, declines are less severe, with 8.8% ± 5.3% carbon loss. In either scenario, increases in temperature systematically cause biomass declines, and the spread of projected precipitation across 32 CMIP5 models contributes to substantial uncertainty in the magnitude of that decline. Projected changes in the environmental niche for the 20 most biomass-dominant tree species revealed widespread replacement of conifers by oak species in low elevation regions of central and northern California, with a corresponding decline in carbon storage depending on expected migration rates. The spatial patterns of vulnerability we identify may allow policymakers to assess where carbon sequestration in aboveground biomass is an appropriate part of a climate mitigation portfolio, and where future climate-driven carbon losses may be a liability.

54 ENVIRONMENTAL SCIENCES↗

MultiSector Dynamics: Advancing the Science of Complex Adaptive Human-Earth Systems

The field of MultiSector Dynamics (MSD) explores the dynamics and co-evolutionary pathways of human and Earth systems with a focus on critical goods, services, and amenities delivered to people through interdependent sectors. This commentary lays out core definitions and concepts, identifies MSD science questions in the context of the current state of knowledge, and describes ongoing activities to expand capacities for open science, leverage revolutions in data and computing, and grow and diversify the MSD workforce. Central to our vision is the ambition of advancing the next generation of complex adaptive human-Earth systems science to better address interconnected risks, increase resilience, and improve sustainability. This will require convergent research and the integration of ideas and methods from multiple disciplines. Understanding the tradeoffs, synergies, and complexities that exist in coupled human-Earth systems is particularly important in the context of energy transitions and increased future shocks.

Reed, Patrick↗

Linear Response Function Reveals the Most Effective Remote Forcing in Causing September Arctic Sea Ice Melting in CESM

We apply the linear response function method to investigate the most excitable mode of the September Arctic sea ice and its corresponding remote oceanic forcing in climate models. The method is useful in identifying the fundamental, dynamical and causal relationship between the remote forcing and sea ice response. We find that the most excitable mode of the September Arctic sea ice preferentially takes place over the Pacic side of the Arctic and its remote forcing corresponds to a dipole pattern of precipitation anomaly in the tropics with an increase of precipitation over the western and central tropical and subtropical Pacic ocean while a decrease over the Maritime Continent. The tropical precipitation anomaly likely drives a Rossby wave train propagating toward higher latitudes and leads to a ridge anomaly over the Pacic side of the Arctic, resulting in poleward atmospheric heat transport, enhanced downward longwave radiation and thus melting of the sea ice. In addition, a good agreement is found with the leading tropical Arctic teleconnection mode detected in a pre-industrial control simulation, which supports the usefulness and robustness of the linear response function method and the importance of tropical forcing in shaping the sea ice variability.

Wu, Yutian↗

Adjoint-Based Inversion of Geodetic Data for Sources of Deformation and Strain

An adjoint-based formulation leads to a particularly efficient approach for inverting geodetic measurements for the source of the deformation. Specifically, the quantities necessary to iteratively improve the fit to the observations can be computed with just three forward calculations, one to obtain the current residuals, another to solve the adjoint problem, and a third to compute the step length. An inversion algorithm utilizing the adjoint-based gradient is applied to a set of Interferometric Synthetic Aperture Radar (InSAR) data gathered between 2016 and 2018 over the Tulare Basin in California's Central Valley. Because the measured deformation is due to groundwater withdrawal, a penalty function is included in the inversion to avoid placing aquifer volume change in locations that are far from any documented wells. The solution of the inverse problem provides estimates of aquifer compaction that provide a match to the observed range changes while honoring the well data. The solution indicates an average aquifer volume loss of 2.17 km 3 /year over the two year period from January 2016 to January 2018, encompassing one drought year (2016) and one wet year (2017). Finally, this magnitude of lost volume is compatible with the 3.1 km 3 /year decrease in water volume for the entire Central Valley, estimated from GRACE satellite gravity data.

58 GEOSCIENCES↗

Summer mean and extreme precipitation over the Mid-Atlantic region: climatological characteristics and contributions from different precipitation types

Based on a long-term observational dataset from the tracking of mesoscale convective systems (MCSs), isolated deep convection (IDC), and tropical cyclones (TCs), we examine the climatological characteristics of summer mean and extreme precipitation during 2004 – 2017 and their respective contributions from MCS, IDC, TC, and non-convective (NC) systems and the local vs. remote influence of MCS and IDC over the MAR. On average, MCS, IDC, TC, and NC contribute 22%, 29%, 4%, and 45% to the total summer mean precipitation in the region. While MCS and TC precipitation primarily occurs in the coastal areas east of the Appalachian Mountains, IDC precipitation is more concentrated in the southern MAR and near the mountain windward slopes. Each summer, ~41 MCSs with an average lifetime of 19.6 hours influence the MAR, with 80% initiated outside and traveling on average 10 hours to the region. Around 13 MCSs initiated in the Great Plains and Midwest propagate across the Appalachian Mountains and contribute 20-40% to summer MCS precipitation in the central Mid-Atlantic coastal areas. In contrast, more than 2000 IDCs with an average lifetime of 2.0 hours influence the MAR each summer, and 77% are initiated locally. MCS, IDC, TC, and NC contribute 31% (30%), 26% (31%), 18% (7%), and 26% (32%) to the top 1% (5%) extreme daily precipitation, respectively. Considering extreme hourly precipitation, however, the IDC contributions increase to 41% (top 1%) and 38% (top 5%) due to the shorter duration of IDC events than the other precipitation types.

Li, Jianfeng↗

Mesoscale Convective Systems in a Superparameterized E3SM Simulation at High Resolution

Accurately representing mesoscale convective systems (MCSs) is crucial to simulating the energy and water cycles in global climate models. Using a novel MCS identification and tracking algorithm applied to observations and model simulations, we evaluate how well the Energy Exascale Earth System Model simulates MCSs over the central US. Simulations performed by E3SM at 25 km grid spacing with (SP-E3SM) and without (E3SM) superparameterization are compared and evaluated against observations using multiple metrics highlighting important MCS characteristics. Compared to E3SM, SP-E3SM better simulates MCS number and MCS precipitation amount, diurnal cycle, propagation, and the probability distribution of precipitation rate in both spring and summer. The improvement from SP is partly contributed by improvement in simulating the large-scale environments, featuring enhanced atmospheric low-level moisture and larger moisture transport to the central US relative to E3SM. However, SP-E3SM still underestimates MCS precipitation amount, particularly in summer. This underestimation is closely related to the negative bias in MCS precipitation intensity, although the drier environments simulated during summer also contributes to underestimation of MCS frequency. Without SP, the larger bias in MCS precipitation amount is closely related to the negative bias in MCS frequency, while the substantial dry bias in the large-scale environments also contributes to underestimation of MCS intensity. Our results suggest that SP improves MCS simulation by improving modeling of the large-scale environments and convection initiation, which are both major limiting factors in E3SM even at 25 km grid spacing where deep convection is represented by a cumulus parameterization.

54 ENVIRONMENTAL SCIENCES↗

Wetter California Projected by CMIP6 Models With Observational Constraints Under a High GHG Emission Scenario

As the world's fifth-largest economy entity, California (CA) is vulnerable to climate changes especially the magnitude of winter (wet season) precipitation that is closely linked to regional drought severity, vegetation growth, and wildfire activities. However, the fate of CA precipitation in the future remains highly uncertain, for example, the state-of-the-art Earth system models (ESMs) from the Coupled Model Intercomparison Project Phase 6 (CMIP6) projected –3% to +42% and –27% to +63% precipitation changes in northern and central-southern CA, respectively, under the high greenhouse gas (GHG) emission scenario (SSP585). In this work, we applied the Pareto optimality concept and used observed teleconnection patterns (causal relationships between ocean regions and CA precipitation) to mechanistically constrain CMIP6 projected CA precipitations. We estimated that precipitation will robustly increase by 0.4–1.3 mm d –1 (10–34%) over northern CA and increase by 0.1–0.5 mm d –1 (7–32%) over central-southern CA by the end of the 21st century compared with present-day. Up to 71% of ESM projection uncertainties were reduced mainly due to the strong and consistent causal relationship between North American west coast sea level pressure and CA precipitation in both observations and CMIP6 models. Our results suggest that teleconnection patterns are powerful mechanistic constraints that can help explain and reduce uncertainties in ESM projections.

54 ENVIRONMENTAL SCIENCES↗

Whistler Waves Associated With Electron Beams in Magnetopause Reconnection Diffusion Regions

Abstract Whistler waves are often observed in magnetopause reconnection associated with electron beams. We analyze seven MMS crossings surrounding the electron diffusion region (EDR) to study the role of electron beams in whistler excitation. Waves have two major types: (a) Narrow‐band waves with high ellipticities and (b) broad‐band waves that are more electrostatic with significant variations in ellipticities and wave normal angles. While both types of waves are associated with electron beams, the key difference is the anisotropy of the background population, with perpendicular and parallel anisotropies, respectively. The linear instability analysis suggests that the first type of wave is mainly due to the background anisotropy, with the beam contributing additional cyclotron resonance to enhance the wave growth. The second type of broadband waves are excited via Landau resonance, and as seen in one event, the beam anisotropy induces an additional cyclotron mode. The results are supported by particle‐in‐cell simulations. We infer that the first type occurs downstream of the central EDR, where background electrons experience Betatron acceleration to form the perpendicular anisotropy; the second type occurs in the central EDR of guide field reconnection. A parametric study is conducted with linear instability analysis. A beam anisotropy alone of above ∼3 likely excites the cyclotron mode waves. Large beam drifts cause Doppler shifts and may lead to left‐hand polarizations in the ion frame. Future studies are needed to determine whether the observation covers a broader parameter regime and to understand the competition between whistler and other instabilities.

79 ASTRONOMY AND ASTROPHYSICS↗

Systematic Underestimation of Canopy Conductance Sensitivity to Drought by Earth System Models

The response of vegetation canopy conductance (g c ) to changes in moisture availability ($γ^{m}_{gc}$) is a major source of uncertainty in climate projections. While vegetation typically reduces stomatal conductance during drought, accurately modeling how and to what degree stomata respond to changes in moisture availability at global scales is particularly challenging, because no global scale g c observations exist. Here, we leverage a collection of satellite, reanalysis and station-based near-surface air and surface temperature estimates, which are physically and statistically linked to $γ^{m}_{gc}$ due to the local cooling effect of g c through transpiration, to develop a novel emergent constraint of $γ^{m}_{gc}$ in an ensemble of Earth System Models (ESMs). We find that ESMs systematically underestimate $γ^{m}_{gc}$ by ~33%, particularly in grasslands, croplands, and savannas in semi-arid and bordering regions of the Central United States, Central Europe, Southeastern South America, Southern Africa, Eastern Australia, and parts of East Asia. We show that this underestimation occurs because ESMs inadequately reduce g c when soil moisture decreases. As g c controls carbon, water and energy fluxes, the misrepresentation of modeled $γ^{m}_{gc}$ contributes to biases in ESM projections of gross primary production, transpiration, and temperature during droughts. Our results suggest that the severity and duration of droughts may be misrepresented in ESMs due to the impact of sustained g c on both soil moisture dynamics and the biosphere-atmosphere feedbacks that affect local temperatures and regional weather patterns.

54 ENVIRONMENTAL SCIENCES↗

The GFDL Variable-Resolution Global Chemistry-Climate Model for Research at the Nexus of US Climate and Air Quality Extremes

We present a variable-resolution global chemistry-climate model (AM4VR) developed at NOAA's Geophysical Fluid Dynamics Laboratory (GFDL) for research at the nexus of US climate and air quality extremes. AM4VR has a horizontal resolution of 13 km over the US, allowing it to resolve urban-to-rural chemical regimes, mesoscale convective systems, and land-surface heterogeneity. With the resolution gradually reducing to 100 km over the Indian Ocean, we achieve multi-decadal simulations driven by observed sea surface temperatures at 50% of the computational cost for a 25-km uniform-resolution grid. In contrast with GFDL's AM4.1 contributing to the sixth Coupled Model Intercomparison Project at 100 km resolution, AM4VR features much improved US climate mean patterns and variability. In particular, AM4VR shows improved representation of: precipitation seasonal-to-diurnal cycles and extremes, notably reducing the central US dry-and-warm bias; western US snowpack and summer drought, with implications for wildfires; and the North American monsoon, affecting dust storms. AM4VR exhibits excellent representation of winter precipitation, summer drought, and air pollution meteorology in California with complex terrain, enabling skillful prediction of both extreme summer ozone pollution and winter haze events in the Central Valley. AM4VR also provides vast improvements in the process-level representations of biogenic volatile organic compound emissions, interactive dust emissions from land, and removal of air pollutants by terrestrial ecosystems. We highlight the value of increased model resolution in representing climate–air quality interactions through land-biosphere feedbacks. AM4VR offers a novel opportunity to study global dimensions to US air quality, especially the role of Earth system feedbacks in a changing climate.

54 ENVIRONMENTAL SCIENCES↗

The Role of Vapor Pressure Deficit in the CLM Simulated Interaction Between Urban Heat Islands and Heat Waves Over CONUS

Abstract Although both urban and rural temperatures are expected to increase under heat waves (HWs), whether the urban heat island (UHI) intensity becomes stronger under HWs remains unknown especially at the daily mean and large spatial scales. Using an urbanized land surface model, we quantify the interactions between UHIs and HWs over the Contiguous United States (CONUS). Synergistic interactions (i.e., increased UHI intensities under HWs) are observed over the eastern and western U.S. However, negative interactions are found in the Central U.S. due to the stronger inhibition of rural evapotranspiration by vapor pressure deficit (VPD) stresses. The interactions between UHIs and HWs in the Central U.S. will be further reduced along with the elevated VPD stresses in a hotter future. The results highlight the importance of properly parameterizing the sensitivity of urban and rural evapotranspiration to various environmental stresses in climate and earth system models.

Wang, Linying [National Key Laboratory of Earth Sy↗

Mechanisms Behind the Long‐Distance Diurnal Offshore Precipitation Propagation in Northwestern South America

Abstract Northwestern South America (NWSA) is the rainiest region on Earth, with diurnal precipitation exhibiting extensive westward offshore propagation of up to about 1,200 km in boreal spring (March‐May). The diurnal offshore precipitation propagation begins slowly (3–10 m s −1 ) near the coast of NWSA (<200 km) but accelerates significantly (∼20 m s −1 ) and shows an afternoon enhancement far from the coast (>400 km). However, the driving mechanisms behind this long‐distance precipitation propagation remain unclear. Using a new cloud tracking and classification data set, we found that mesoscale convective systems (MCSs) are the dominant precipitation contributors in the offshore region of NWSA. Cloud tracking shows that the long‐distance propagation and the afternoon enhancement of diurnal precipitation primarily originate from MCSs initiated in the early morning, either over open oceans or from the coast of Central America. Composite tendency analysis shows that MCSs initiated near the coast of Central America have significant upward cooling and moistening signals starting from the surface before initiation. Further analysis of surface diurnal perturbation fields indicates that the land breeze is the primary driving mechanism for MCS initiation. Conversely, for MCSs initiated over open oceans, a significant downward cooling signal from 400 hPa is observed ∼7 hr before initiation, corresponding to the passage of diurnal gravity waves emitted from the Andes. Additionally, our findings highlight the critical role of lower and mid‐level moisture conditions in MCS initiation, alongside the influence of gravity waves.

Hu, Jingyi [Department of Meteorology and Atmosphe↗

Autotrophic and mixotrophic metabolism of an anammox bacterium revealed by in vivo 13 C and 2 H metabolic network mapping

Anaerobic ammonium-oxidizing (anammox) bacteria mediate a key step in the biogeochemical nitrogen cycle and have been applied worldwide for the energy-efficient removal of nitrogen from wastewater. However, outside their core energy metabolism, little is known about the metabolic networks driving anammox bacterial anabolism and use of different carbon and energy substrates beyond genome-based predictions. Here, we experimentally resolved the central carbon metabolism of the anammox bacterium Candidatus ‘Kuenenia stuttgartiensis’ using time-series 13 C and 2 H isotope tracing, metabolomics, and isotopically nonstationary metabolic flux analysis. Our findings confirm predicted metabolic pathways used for CO 2 fixation, central metabolism, and amino acid biosynthesis in K. stuttgartiensis , and reveal several instances where genomic predictions are not supported by in vivo metabolic fluxes. This includes the use of the oxidative branch of an incomplete tricarboxylic acid cycle for alpha-ketoglutarate biosynthesis, despite the genome not having an annotated citrate synthase. We also demonstrate that K. stuttgartiensis is able to directly assimilate extracellular formate via the Wood–Ljungdahl pathway instead of oxidizing it completely to CO 2 followed by reassimilation. In contrast, our data suggest that K. stuttgartiensis is not capable of using acetate as a carbon or energy source in situ and that acetate oxidation occurred via the metabolic activity of a low-abundance microorganism in the bioreactor’s side population. Together, these findings provide a foundation for understanding the carbon metabolism of anammox bacteria at a systems-level and will inform future studies aimed at elucidating factors governing their function and niche differentiation in natural and engineered ecosystems.

54 ENVIRONMENTAL SCIENCES↗