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At least 289 records · Page 16

Declining tropical cyclone frequency under global warming

Assessing the role of anthropogenic warming from temporally inhomogeneous historical data in the presence of large natural variability is difficult and has caused conflicting conclusions on detection and attribution of tropical cyclone (TC) trends. Here, using a reconstructed long-term proxy of annual TC numbers together with high-resolution climate model experiments, we show robust declining trends in the annual number of TCs at global and regional scales during the twentieth century. The Twentieth Century Reanalysis (20CR) dataset is used for reconstruction because, compared with other reanalyses, it assimilates only sea-level pressure fields rather than utilize all available observations in the troposphere, making it less sensitive to temporal inhomogeneities in the observations. It can also capture TC signatures from the pre-satellite era reasonably well. The declining trends found are consistent with the twentieth century weakening of the Hadley and Walker circulations, which make conditions for TC formation less favourable.

54 ENVIRONMENTAL SCIENCES↗

MetaFlux: Meta-learning global carbon fluxes from sparse spatiotemporal observations

We provide a global, long-term carbon flux dataset of gross primary production and ecosystem respiration generated using meta-learning, called MetaFlux. The idea behind meta-learning stems from the need to learn efficiently given sparse data by learning how to learn broad features across tasks to better infer other poorly sampled ones. Using meta-trained ensemble of deep models, we generate global carbon products on daily and monthly timescales at a 0.25-degree spatial resolution from 2001 to 2021, through a combination of reanalysis and remote-sensing products. Site-level validation finds that MetaFlux ensembles have lower validation error by 5–7% compared to their non-meta-trained counterparts. In addition, they are more robust to extreme observations, with 4–24% lower errors. We also checked for seasonality, interannual variability, and correlation to solar-induced fluorescence of the upscaled product and found that MetaFlux outperformed other machine-learning based carbon product, especially in the tropics and semi-arids by 10–40%. Overall, MetaFlux can be used to study a wide range of biogeochemical processes.

54 ENVIRONMENTAL SCIENCES↗

CMDV (CM)4 Project - University of Washington contribution. Final report

The original goal of this project was to diagnose and improve CLUBB, the turbulence and cloud fraction parameterization used in DOE’s E3SM model. For this purpose, we planned to use large-eddy simulation (LES) and ARM observations from the NE Pacific Ocean and the SGP site, in coordination with ARM’s LASSO program. It was determined that for these cloud regimes, many of the turbulent ‘moment closures’ which underlie CLUBB’s mathematical formulation are inconsistent with LES, which is an appropriate benchmark for testing this. The research assistant found that these closures could be more accurately formulated using machine learning using the LES as a training dataset. However the resulting parameterization proved to quickly drift away from physical plausibility. A novel machine-learning based boundary layer parameterization called MARBLE based on matching the time evolution of a parameterized cloud-topped boundary layer to reanalysis was then developed and published.

54 ENVIRONMENTAL SCIENCES↗

Validation of wind resource and energy production simulations for small wind turbines in the United States

Abstract. Due to financial and temporal limitations, the small wind community relies upon simplified wind speed models and energy production simulation tools to assess site suitability and produce energy generation expectations. While efficient and user-friendly, these models and tools are subject to errors that have been insufficiently quantified at small wind turbine heights. This study leverages observations from meteorological towers and sodars across the United States to validate wind speed estimates from the Wind Integration National Dataset (WIND) Toolkit, the European Centre for Medium-Range Weather Forecasts (ECMWF) Reanalysis v5 (ERA5), and the Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2), revealing average biases within ±0.5 m s−1 at small wind hub heights. Observations from small wind turbines across the United States provide references for validating energy production estimates from the System Advisor Model (SAM), Wind Report, MyWindTurbine.com, and Global Wind Atlas 3 (GWA3), which are seen to overestimate actual annual capacity factors by 2.5, 4.2, 11.5, and 7.3 percentage points, respectively. In addition to quantifying the error metrics, this paper identifies sources of model and tool discrepancies, noting that interannual fluctuation in the wind resource, wind speed class, and loss assumptions produces more variability in estimates than different horizontal and vertical interpolation techniques. The results of this study provide small wind installers and owners with information about these challenges to consider when making performance estimates and thus possible adjustments accordingly. Looking to the future, recognizing these error metrics and sources of discrepancies provides model and tool researchers and developers with opportunities for product improvement that could positively impact small wind customer confidence and the ability to finance small wind projects.

17 WIND ENERGY↗

Subseasonal Representation and Predictability of North American Weather Regimes Using Cluster Analysis

Abstract This study focuses on assessing the representation and predictability of North American weather regimes, which are persistent large-scale atmospheric patterns, in a set of initialized subseasonal reforecasts created using the Community Earth System Model, version 2 (CESM2). The k -means clustering was used to extract four key North American (10°–70°N, 150°–40°W) weather regimes within ERA5 reanalysis, which were used to interpret CESM2 subseasonal forecast performance. Results show that CESM2 can recreate the climatology of the four main North American weather regimes with skill but exhibits biases during later lead times with overoccurrence of the West Coast high regime and underoccurrence of the Greenland high and Alaskan ridge regimes. Overall, the West Coast high and Pacific trough regimes exhibited higher predictability within CESM2, partly related to El Niño. Despite biases, several reforecasts were skillful and exhibited high predictability during later lead times, which could be partly attributed to skillful representation of the atmosphere from the tropics to extratropics upstream of North America. The high predictability at the subseasonal time scale of these case-study examples was manifested as an “ensemble realignment,” in which most ensemble members agreed on a prediction despite ensemble trajectory dispersion during earlier lead times. Weather regimes were also shown to project distinct temperature and precipitation anomalies across North America that largely agree with observational products. This study further demonstrates that unsupervised learning methods can be used to uncover sources and limits of subseasonal predictability, along with systematic biases present in numerical prediction systems. Significance Statement North American weather regimes are large-scale atmospheric patterns that can persist for several days. Their skillful subseasonal (2 weeks or greater) prediction can provide valuable lead time to prepare for temperature and precipitation anomalies that can stress energy and water resources. The purpose of this study was to assess the climatological representation and subseasonal predictability of four key North American weather regimes using a research subseasonal prediction system and clustering analysis. We found that the Pacific trough and West Coast high regimes exhibited higher predictability than other regimes and that skillful representation of conditions across the tropics and extratropics can increase predictability during later lead times. Future work will quantify causal pathways associated with high predictability.

58 GEOSCIENCES↗

Constraints on simulated past Arctic amplification and lapse rate feedback from observations

The Arctic has warmed more rapidly than the global mean during the past few decades. The lapse rate feedback (LRF) has been identified as being a large contributor to the Arctic amplification (AA) of climate change. This particular feedback arises from the vertically non-uniform warming of the troposphere, which in the Arctic emerges as strong near-surface and muted free-tropospheric warming. Stable stratification and meridional energy transport are two characteristic processes that are evoked as causes for this vertical warming structure. Our aim is to constrain these governing processes by making use of detailed observations in combination with the large climate model ensemble of the sixth Coupled Model Intercomparison Project (CMIP6). We build on the result that CMIP6 models show a large spread in AA and Arctic LRF, which are positively correlated for the historical period of 1951–2014. Thus, we present process-oriented constraints by linking characteristics of the current climate to historical climate simulations. In particular, we compare a large consortium of present-day observations to co-located model data from subsets that show a weak and strong simulated AA and Arctic LRF in the past. Our analyses suggest that the vertical temperature structure of the Arctic boundary layer is more realistically depicted in climate models with weak (w) AA and Arctic LRF (CMIP6/w) in the past. In particular, CMIP6/w models show stronger inversions in the present climate for boreal autumn and winter and over sea ice, which is more consistent with the observations. These results are based on observations from the year-long Multidisciplinary Drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition in the central Arctic, long-term measurements at the Utqiagvik site in Alaska, USA, and dropsonde temperature profiling from aircraft campaigns in the Fram Strait. In addition, the atmospheric energy transport from lower latitudes that can further mediate the warming structure in the free troposphere is more realistically represented by CMIP6/w models. In particular, CMIP6/w models systemically simulate a weaker Arctic atmospheric energy transport convergence in the present climate for boreal autumn and winter, which is more consistent with fifth generation reanalysis of the European Centre for Medium-Range Weather Forecasts (ERA5). We further show a positive relationship between the magnitude of the present-day transport convergence and the strength of past AA. With respect to the Arctic LRF, we find links between the changes in transport pathways that drive vertical warming structures and local differences in the LRF. This highlights the mediating influence of advection on the Arctic LRF and motivates deeper studies to explicitly link spatial patterns of Arctic feedbacks to changes in the large-scale circulation.

54 ENVIRONMENTAL SCIENCES↗

Radiative, Hydrologic, and Circulation Responses to Warming in Cess‐Potter Simulations Using the Global 3.25‐km SCREAM

Using the global 3.25-km Simple Cloud Resolving E3SM Atmosphere Model (SCREAM 3 km), a pair of 13-month Cess-Potter simulations are performed to quantify the radiative feedbacks and the hydrologic and circulation responses to warming. Large-scale aspects of SCREAM 3 km's top-of-atmosphere radiative fluxes, precipitation rates, and circulations are in good agreement with observations and reanalysis, with notable differences, including a drier lower free-troposphere in the Tropics, reduced precipitation and humidity over the Tropical West Pacific, and poleward shifted Southern Hemisphere midlatitude jet. In response to warming, SCREAM 3 km predicts a total radiative feedback within the top 15% of the CMIP5 and CMIP6 models, which puts it substantially higher than the feedback reported by other kilometer-scale models. SCREAM 3 km's high radiative feedback stems from a strongly positive shortwave cloud feedback, most prominent over the mid- and high-latitudes. SCREAM 3 km's high precipitation response also puts it among the highest of CMIP models, whereas its circulation response is within the spread of CMIP models. An ensemble of five perturbed initial condition Cess-Potter simulations with a 12 km version of SCREAM (SCREAM 12 km) is performed to characterize uncertainty and resolution sensitivity. It suggests that the uncertainty from analyzing a pair of 1-year simulations is small compared to the inter-model spread in feedbacks and precipitation response. SCREAM 12 km also produces a strong precipitation response to warming but a much lower cloud feedback and total radiative feedback. The results from these experiments suggest that the spread in climate feedbacks will likely persist in the next generation of kilometer-scale models.

54 ENVIRONMENTAL SCIENCES↗

Developing a simulator-based satellite dataset for using machine learning techniques to derive aerosol-cloud-precipitation interactions in models and observations in a consistent framework

Aerosol-cloud-precipitation interactions (ACPI) remain a major uncertainty in understanding the Earth’s radiation budget and water cycle (including extremes). After decades of active research, various observationally based metrics have been developed to constrain ACPI in Earth System Models (ESMs), but direct comparison of model and data estimates can confound scientific understanding because limitations and uncertainties in sampling and retrieval procedures may combine with model deficiencies in process representations of ACPI to obstruct understanding. Furthermore, conventional ACPI metrics often vary from one regime to another, and the ACPI process representation in ESMs is also typically derived based on only a limited area/regime (even though the parameterization applies globally). To bridge the gap between models and data and to correctly describe ACPI in all regimes, we propose to construct a new CALIPSO-CloudSat merged dataset that is produced by the same algorithms used in satellite simulators in ESMs, and to use machine learning techniques to derive new ACPI metrics that can be accurately estimated by satellites and can provide meaningful constraints on cloud microphysical process representations in ESMs. The dataset will include measured and retrieved variables for aerosol, cloud, and precipitation from CALIPSO and CloudSat, and environmental variables from meteorological reanalysis. The data will be used to train a neural network to construct the ACPI metrics as a function of environmental conditions. The new ACPI formula will be used to constrain the ACPI in the Energy Exascale Earth System Model (E3SM), and to augment/reformulate the ACPI process representation in the E3SM to improve the simulation of the evolution of the atmosphere under different environmental conditions.

54 ENVIRONMENTAL SCIENCES↗

Advancing Organized Convection Representation in the Unified Model: Implementing and Enhancing Multiscale Coherent Structure Parameterization

To address the effect of stratiform latent heating on meso- to large-scale circulations, an enhanced implementation of the Multiscale Coherent Structure Parameterization (MCSP) is developed for the Met Office Unified Model. MCSP represents the top-heavy stratiform latent heating from under-resolved organized convection in general circulation models. We couple the MCSP with a mass-flux convection scheme (CoMorph-A) to improve storm lifecycle continuity. The improved MCSP trigger is specifically designed for mixed-phase deep convective cloud, combined with a background vertical wind shear, both known to be crucial for stratiform development. We also test a cloud top temperature dependent convective-stratiform heating partitioning, in contrast to the earlier fixed partitioning. Assessments from ensemble weather forecasts and decadal simulations demonstrate that MCSP directly reduces cloud deepening and precipitation areas by moderating mesoscale circulations. Indirectly, it amends tropical precipitation biases, notably correcting dry and wet biases over India and the Indian Ocean, respectively. Remarkably, the scheme outperforms a climate model ensemble by improving seasonal precipitation cycle predictions in these regions. The scheme also improves Madden-Julian Oscillation (MJO) spectra, achieving better alignment with observational and reanalysis data by intensifying the simulated MJO over the Indian Ocean during phases 4 to 5. However, the scheme increases precipitation overestimation over the Western Pacific. Shifting from fixed to temperature-dependent convective-stratiform partitioning reduces the Pacific precipitation overestimation and further improves the seasonal cycle in India. Spatially correlated biases highlight the necessity for advances beyond deterministic approaches to align MCSP with environmental conditions.

54 ENVIRONMENTAL SCIENCES↗

Augmentation of WRF-Hydro to simulate overland-flow- and streamflow-generated debris flow susceptibility in burn scars

In steep wildfire-burned terrains, intense rainfall can produce large runoff that can trigger highly destructive debris flows. However, the ability to accurately characterize and forecast debris flow susceptibility in burned terrains using physics-based tools remains limited. Here, we augment the Weather Research and Forecasting Hydrological modeling system (WRF-Hydro) to simulate both overland and channelized flows and assess postfire debris flow susceptibility over a regional domain. We perform hindcast simulations using high-resolution weather-radar-derived precipitation and reanalysis data to drive non-burned baseline and burn scar sensitivity experiments. Our simulations focus on January 2021 when an atmospheric river triggered numerous debris flows within a wildfire burn scar in Big Sur – one of which destroyed California's famous Highway 1. Compared to the baseline, our burn scar simulation yields dramatic increases in total and peak discharge and shorter lags between rainfall onset and peak discharge, consistent with streamflow observations at nearby US Geological Survey (USGS) streamflow gage sites. For the 404 catchments located in the simulated burn scar area, median catchment-area-normalized peak discharge increases by ~ 450 % compared to the baseline. Catchments with anomalously high catchment-area-normalized peak discharge correspond well with post-event field-based and remotely sensed debris flow observations. We suggest that our regional postfire debris flow susceptibility analysis demonstrates WRF-Hydro as a compelling new physics-based tool whose utility could be further extended via coupling to sediment erosion and transport models and/or ensemble-based operational weather forecasts. Given the high-fidelity performance of our augmented version of WRF-Hydro, as well as its potential usage in probabilistic hazard forecasts, we argue for its continued development and application in postfire hydrologic and natural hazard assessments.

54 ENVIRONMENTAL SCIENCES↗

Integrated Hourly Meteorological Database of 20 Meteorological Stations (1981-2022) for Watershed Function SFA Hydrological Modeling

This dataset contains (a) a script “R_met_integrated_for_modeling.R”, and (b) associated input CSV files: 3 CSV files per location to create a 5-variable integrated meteorological dataset file (air temperature, precipitation, wind speed, relative humidity, and solar radiation) for 19 meteorological stations and 1 location within Trail Creek from the modeling team within the East River Community Observatory as part of the Watershed Function Scientific Focus Area (SFA). As meteorological forcings varied across the watershed, a high-frequency database is needed to ensure consistency in the data analysis and modeling. We evaluated several data sources, including gridded meteorological products and field data from meteorological stations. We determined that our modeling efforts required multiple data sources to meet all their needs. As output, this dataset contains (c) a single CSV data file (*_1981-2022.csv) for each location (20 CSV output files total) containing hourly time series data for 1981 to 2022 and (d) five PNG files of time series and density plots for each variable per location (100 PNG files). Detailed location metadata is contained within the Integrated_Met_Database_Locations.csv file for each point location included within this dataset, obtained from Varadharajan et al., 2023 doi:10.15485/1660962. This dataset also includes (e) a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata and (f) a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type. Review the (g) ReadMe_Integrated_Met_Database.pdf file for additional details on the script, methods, and structure of the dataset.The script integrates Northwest Alliance for Computational Science and Engineering’s PRISM gridded data product, National Oceanic and Atmospheric Administration’s NCEP-NCAR Reanalysis 1 gridded data product (through the `RCNEP` R package, Kemp et al., doi:10.32614/CRAN.package.RNCEP), and analytical-based calculations. Further, this script downscales the input data into hourly frequency, which is necessary for the modeling efforts.

54 ENVIRONMENTAL SCIENCES↗

Differential Credibility of Climate Modes in CMIP6

This work quantitatively evaluates the fidelity with which the northern annular mode (NAM), southern annular mode (SAM), Pacific–North American pattern (PNA), El Niño–Southern Oscillation (ENSO), Pacific decadal oscillation (PDO), Atlantic multidecadal oscillation (AMO), and the first-order mode interactions are represented in Earth system model (ESM) output from the CMIP6 archive. Several skill metrics are used as part of a differential credibility assessment (DCA) of both spatial and temporal characteristics of the modes across ESMs, ESM families, and specific ESM realizations relative to ERA5. The spatial patterns and probability distributions are generally well represented but skill scores that measure the degree to which the frequencies of maximum variance are captured are consistently lower for most ESMs and climate modes. Substantial variability in skill scores manifests across realizations from individual ESMs for the PNA and oceanic modes. Further, the ESMs consistently overestimate the strength of the NAM–PNA first-order interaction and underestimate the NAM–AMO connection. Furthermore, these results suggest that the choice of ESM and ESM realizations will continue to play a critical role in determining climate projections at the global and regional scale at least in the near term.

54 ENVIRONMENTAL SCIENCES↗

Super-Resolution for Renewable Energy Resource Data with Wind from Reanalysis Data and Application to Ukraine

With a potentially increasing share of the electricity grid relying on wind to provide generating capacity and energy, there is an expanding global need for historically accurate, spatiotemporally continuous, high-resolution wind data. Conventional downscaling methods for generating these data based on numerical weather prediction have a high computational burden and require extensive tuning for historical accuracy. In this work, we present a novel deep learning-based spatiotemporal downscaling method using generative adversarial networks (GANs) for generating historically accurate high-resolution wind resource data from the European Centre for Medium-Range Weather Forecasting Reanalysis version 5 data (ERA5). In contrast to previous approaches, which used coarsened high-resolution data as low-resolution training data, we use true low-resolution simulation outputs. We show that by training a GAN model with ERA5 as the low-resolution input and Wind Integration National Dataset Toolkit (WTK) data as the high-resolution target, we achieved results comparable in historical accuracy and spatiotemporal variability to conventional dynamical downscaling. This GAN-based downscaling method additionally reduces computational costs over dynamical downscaling by two orders of magnitude. We applied this approach to downscale 30 km, hourly ERA5 data to 2 km, 5 min wind data for January 2000 through December 2023 at multiple hub heights over Ukraine, Moldova, and part of Romania. With WTK coverage limited to North America from 2007–2013, this is a significant spatiotemporal generalization. The geographic extent centered on Ukraine was motivated by stakeholders and energy-planning needs to rebuild the Ukrainian power grid in a decentralized manner. This 24-year data record is the first member of the super-resolution for renewable energy resource data with wind from the reanalysis data dataset (Sup3rWind).

17 WIND ENERGY↗

Regime-based aerosol–cloud interactions from CALIPSO-MODIS and the Energy Exascale Earth System Model version 2 (E3SMv2) over the Eastern North Atlantic

This study investigates aerosol-cloud interactions in marine boundary layer (MBL) clouds using an advanced deep-learning-driven synoptic-regime-based framework, combining satellite data (CALIPSO vertically resolved aerosol extinction and MODIS cloud properties) with 1° nudged Energy Exascale Earth System Model version 2 (E3SMv2) simulation over the Eastern North Atlantic (ENA; ∼10°×10°, 2006–2014). The E3SMv2 captures observed seasonal variations in cloud droplet number concentrations (N d ) and liquid water path (LWP), though it systematically underestimates N d . We then partition ENA meteorology into four synoptic regimes (Pre-Trough, Post-Trough, Ridge, Trough) via a deep-learning clustering of ERA5 reanalysis fields, enabling regime-dependent aerosol-cloud interactions analyses. Both satellite and E3SMv2 exhibit an inverted-V LWP-N d relationship. In Post-Trough and Ridge regimes, the satellite shows stronger negative LWP-N d sensitivities than in Pre-Trough regime. The Trough regime displays a muted satellite LWP response. In comparison, the model predicts more exaggerated LWP responses across regimes, with LWP increasing too quickly at low N d and decreasing more sharply at high N d , especially in Pre-Trough and Trough regimes. These exaggerated model LWP sensitivities may stem from uncertainties in representing drizzle processes, entrainment, and turbulent mixing. As for N d susceptibility to aerosols, N d increases with MBL aerosol extinction in both datasets, but the simulated aerosol-cloud interactions appear oversensitive to meteorological conditions. Overall, E3SMv2 better captures aerosol effects under regimes that favor stratiform clouds (Post-Trough, Ridge), but performance deteriorates for regimes with deeper, dynamically complex clouds (Trough), highlighting the need for improved representations of those cloud processes in climate models.

Environmental sciences↗

The Influence of African Easterly Waves on Atlantic Tropical Cyclone Tracks and Landfall in Large Ensembles

African easterly waves (AEWs) are an important precursor or “seed” for Atlantic tropical cyclones (TCs), with 60%–80% of major hurricanes observed to originate from AEWs. However, climate model simulations indicate that AEWs are not necessary to maintain annual Atlantic TC frequency. Furthermore, small ensembles suggest that AEWs may impact the spatial distribution and landfall of Atlantic TCs. Here, we investigated the influence of AEWs on the spatial distribution of Atlantic TC tracks and landfall using 50-member ensembles of TC-permitting regional model simulations for five hurricane seasons characterized by different levels of TC activity. The control simulations are seasonal hindcasts in which AEWs were prescribed through the eastern lateral boundary condition using reanalysis. In the experiments, we suppressed AEWs by applying a 2–10 day filter to the eastern lateral boundary condition. In response to AEW suppression, we discovered statistically significant increases in Atlantic TC frequency (10%–26%) and landfall (16%–44%), a westward shift in TC genesis location and tracks with increased landfall over the Caribbean Islands, southwestern Gulf Coast, and southeastern US coast, and increases in mid-tropospheric relative humidity in the main development region. In addition, we evaluated TC genesis mechanisms in the absence of AEWs and found evidence that the intertropical convergence zone (ITCZ) intensified and extended northward, resulting in ITCZ wave-breaking that shed vortices which served as TC seeds. By uncovering the connections between TC seed types and the likelihood of TC landfall, this research can provide Atlantic coastal and island communities with useful information to prepare for TC impacts.

African easterly waves↗

Exploring Western North Pacific Tropical Cyclone Activity in the High‐Resolution Community Atmosphere Model

Abstract High‐resolution climate models (∼28 km grid spacing) can permit realistic simulations of tropical cyclones (TCs), thus enabling their investigation in relation to the climate system. On the global scale, previous works have demonstrated that the Community Atmosphere Model (CAM) version 5 presents a reasonable TC climatology under prescribed present‐day (1980–2005) forcing. However, for the Western North Pacific (WNP) region, known biases in simulated TC genesis frequency and location under‐represent the basin's dominant share in observations. This study addresses these model biases in WNP by evaluating WNP TCs in a decadal simulation, and exploring potential improvements through nudging experiments. Among the major environmental controls of TC genesis, the lack of mid‐level moisture is identified as the leading cause of the deficit in simulated WNP TC genesis over the Pacific Warm Pool. Subsequent seasonal experiments explore the effect of constraining the large‐scale environment on TC development by nudging WNP temperature field toward reanalysis at various strengths. Temperature nudging elicits a significant response in TC genesis and intensity development, as well as in moisture and convection over the Warm Pool. These responses are sensitive to the choice of nudging timescale. Overall, the nudging experiments demonstrate that improvements in the large‐scale environment can lead to improvements in simulated TCs, suggesting future model developments in relation to model physics. In this way, the potential improvements in model fidelity will contribute to the understanding of how the mean state of current or future climates may give rise to extremes such as TCs.

58 GEOSCIENCES↗

An Experimental and Theoretical Study of the High Temperature Reactions of the Four Butyl Radical Isomers

The high temperature gas phase chemistry of the four butyl radical isomers (n-butyl,sec-butyl, iso-butyl, andtert-butyl) was investigated in a combined experimental and theoretical study. Organic nitrites were used as convenient and clean sources of each of the butyl radical isomers. Rate coefficients for dissociation of each nitrite were obtained experimentally and are at, or close to, the high pressure limit. Low pressure experiments were performed in a diaphragmless shock tube with laser schlieren densitometry at post-shock pressures of 65, 130, and 260 Torr and post-shock temperatures of 700-1000 K. Additional experiments were conducted with iso-butyl radicals at 805 K and 8.7 bar to elucidate changes in mechanism at higher pressures. These experiments were performed in a miniature shock tube with synchrotron-based photoionization mass spectrometry. The mass spectra confirmed that scission of the O-NO bond is the primary channel by which the precursors dissociate, but they also provided evidence of a minor channel (<7.7%) through HNO loss and formation of an aldehyde. These high pressure experiments were also used to determine the disproportionation/recombination ratio for iso-butyl radicals as 0.3. Reanalysis of the lower-temperature literature and the present data yielded rate constants for the disproportionation reaction, iso-butyl + iso-butyl = iso-butene + iso-butane. A chemical kinetics model was developed for the reactions of the butyl isomers that included new paths for highly energized adducts. These adducts are formed by the addition of H, CH 3 or C 2 H 5 to the butyl radicals. Accompanying theoretical investigations show that chemically activated pathways are competitive with stabilization of the adduct by collision under the conditions of the laser schlieren experiments. These calculations also show that at 10 bar and T< 1000 K stabilization is the only important reaction, but at higher temperatures, even at 10 bar, chemically activated product channels should also be considered. Branching fractions and rate coefficients are presented for these reactions. Furthermore, this study also highlights the importance of the radical structure for determining branching ratios for disproportionation and recombination of alkyl radicals, and these were facilitated by theoretical calculations of recombination rate coefficients for the four butyl radical isomers. Overall, the results reveal previously unknown features of butyl radical chemistry under conditions that are relevant to a wide range of applications and reaction mechanisms are presented that incorporate pressure dependent rate coefficients for the key steps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Response of the Polar Vortex to Tropospheric Temperature Eddies in an Idealized General Circulation Model

Abstract A dry-core idealized general circulation model with a stratospheric polar vortex in the Northern Hemisphere is run with a combination of simplified topography and imposed tropospheric temperature perturbations, each located in the Northern Hemisphere with a zonal wavenumber of 1. The phase difference between the imposed temperature wave and the topography is varied to understand what effect this has on the occurrence of polar vortex displacements. Geometric moments are used to identify the centroid of the polar vortex for the purposes of classifying whether or not the polar vortex is displaced. Displacements of the polar vortex are a response to increased tropospheric wave activity. Compared to a model run with only topography, the likelihood of the polar vortex being displaced increases when the warm region is located west of the topography peak, and decreases when the cold region is west of the topography peak. This response from the polar vortex is due to the modulation of vertically propagating wave activity by the temperature forcing. When the southerly winds on the western side of the topographically forced anticyclone are collocated with warm- or cold-temperature forcing, the vertical wave activity flux in the troposphere becomes more positive or negative, respectively. This is in line with recent reanalysis studies that showed that anomalous warming west of the surface pressure high, in the climatological standing wave, precedes polar vortex disturbances.

54 ENVIRONMENTAL SCIENCES↗