The Impact of Volatile Organic Compounds and Oxides of Nitrogen on Ground‐Level Ozone and Secondary Organic Aerosols Formation Over the Triad Region in North Carolina
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Publications and source records attributed to Gaudet, Brian J..
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New particle formation (NPF) and growth govern cloud condensation nuclei (CCN) concentrations in many regions. The mechanisms governing the nucleation of molecular clusters vary substantially in different regions of the atmosphere. Additionally, the growth of these clusters from ~2 to 20 nm sizes is often governed by the availability of extremely low volatility organic vapours (ELVOCs). While the pathways to ELVOC formation from the oxidation of biogenic monoterpenes with ozone is better understood, the chemical and mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are not well understood. We integrate measurements and three-dimensional regional model simulations with the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to understand the processes governing new particle formation and growth and secondary organic aerosol (SOA) formation during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) field campaign at the Southern Great Plains (SGP) observatory in Oklahoma, and contrast it with a site within the Bankhead National Forest (BNF), Alabama in Southeast USA, where 5-year long measurements will begin in 2024. Simulations show that nucleation rates are at least an order of magnitude higher at SGP compared to BNF during the springtime days (April 28 and May 14, 2016), largely due to lower H2SO4 concentrations at BNF, which are needed for nucleation. In addition, the larger CS at BNF (compared to SGP) increase the loss of molecular clusters by coagulation to pre-existing particles. Among the 8 different nucleation mechanisms in WRF-Chem, we find that the amine+H2SO4 nucleation mechanism dominates at the SGP site, while the pure organic ion induced nucleation mechanism dominates over BNF. Through various WRF-Chem sensitivity simulations, we find that anthropogenic ELVOCs are critical for explaining the growth of newly formed particles and the resulting number size distribution observed near the surface at the SGP site during the daytime. In addition, we show that treating organic particles as semisolid, with strong diffusion-limited uptake of organic vapours, brings model predictions into closer agreement with the observed evolution of particle size distribution. Simulations also predict that anthropogenic SOA, formed by the oxidation of aromatic volatile organic compounds (VOCs), is the dominant organic aerosol component at SGP, while biogenic SOA dominates particle composition at the BNF site in Southeast USA on these days.
Atmospheric particles play critical roles in climate. However, significant knowledge gaps remain regarding the vertically resolved organic molecular-level composition of atmospheric particles due to aloft sampling challenges. To address this, we use a tethered balloon system at the Southern Great Plains Observatory and high-resolution mass spectrometry to, respectively, collect and characterize organic molecular formulas (MF) in the ground level and aloft (up to 750 m) samples. We show that organic MF uniquely detected aloft were dominated by organonitrates (139 MF; 54% of all uniquely detected aloft MF). Organonitrates that were uniquely detected aloft featured elevated O/C ratios (0.73 ± 0.23) compared to aloft organonitrates that were commonly observed at the ground level (0.63 ± 0.22). Unique aloft organic molecular composition was positively associated with increased cloud coverage, increased aloft relative humidity (~40% increase compared to ground level), and decreased vertical wind variance. Furthermore, 29% of extremely low volatility organic compounds in the aloft sample were truly unique to the aloft sample compared to the ground level, emphasizing potential oligomer formation at higher altitudes. Overall, this study highlights the importance of considering vertically resolved organic molecular composition (particularly for organonitrates) and hypothesizes that aqueous phase transformations and vertical wind variance may be key variables affecting the molecular composition of aloft organic aerosol.
Given the importance of offshore wind energy development to the U.S. clean energy targets, it is vital to be able to characterize the wind resource in that environment accurately. Toward that end, two Bureau of Ocean Energy Management buoys equipped with Doppler lidar are being maintained by Pacific Northwest National Laboratory on behalf of the Department of Energy and deployed to regions of potential offshore wind development. In addition to standard meteorological and oceanographic measurements, the buoys document the wind profile between about 40 m and 250 m above the sea surface through Doppler lidar retrievals. After a multiyear deployment of two buoys along the U.S. East Coast, the buoys were redeployed to the U.S. West coast from 2020 – 2022 to locations near the Humboldt and Morro Bay lease areas. The buoys provide nearly continuous, multiyear datasets that can be used to evaluate predictions of hub-height (~100 m) wind speed for standard atmospheric models in the region. In the absence of measurements at the study site, offshore wind developers rely on model-based data to assess site conditions. Potential sources of model error in this environment include under-resolution or misrepresentation of coastal topographically forced flows, marine boundary layer dynamics and the evolution of their associated cloud and turbulence fields, the role of upwelling and other currents on surface heat fluxes into the boundary layer, and the impact of wave fields on surface momentum fluxes and thus the wind speed profile. In particular, most predictive models of wind speed do not predict wave fields at all, relying on parameterizations to represent their effects. In thus study, we focus on evaluating the role of wind / wave interactions on modeled hub-height wind speed and error by using the Coupled Ocean–Atmosphere–Wave–Sediment–Transport Modeling System to capture two-way interactions between an atmospheric model (Weather Research and Forecasting (WRF)) and a wave model (WAVEWATCHIII (WW3)) and compare to both stand-alone WRF and one-way coupled WRF / WW3 configurations. Our approach is similar to that used in Gaudet et al. (2022) to evaluate wind / wave coupling over the U.S. East Coast, but applied to the very different environment of the U.S. West Coast. We show examples for two cases, a cold-season frontal case and a warm-season low-level jet case. We find that wind / wave coupling makes little impact on model error for these cases at the location of the lidar buoys, for which other misrepresentations of model physics seems to be responsible for model-observation discrepancies. However, domain-wide evaluations, which also make use of the National Buoy Data Center network, show that a two-way coupling approach is less prone to systematic errors in the hub-height wind field than the one-way coupled approach. WRF resolution of kilometer-scale or less is needed to properly capture the sharp wind speed gradients that can be found along the coastline, and WW3 simulations driven by the downscaled WRF produce better bulk and spectral wave fields when compared to observations. Implications of the results for wind resource characterization are then discussed.
Abstract. Low-level jets (LLJs) occur under a variety of atmospheric conditions and influence the available wind resource for wind energy projects. In 2020, lidar-mounted buoys owned by the US Department of Energy (DOE) were deployed off the California coast in two wind energy lease areas administered by the Bureau of Ocean Energy Management: Humboldt and Morro Bay. The wind profile observations from the lidars and collocated near-surface meteorological stations (4–240 m) provide valuable year-long analyses of offshore LLJ characteristics at heights relevant to wind turbines. At Humboldt, LLJs were associated with flow reversals and north-northeasterly winds, directions that are more aligned with terrain influences than the predominant northerly flow. At Morro Bay, coastal LLJs were observed primarily during northerly flow as opposed to the predominant north-northwesterly flow. LLJs were observed more frequently in colder seasons within the lowest 250 m a.s.l. (above sea level), in contrast with the summertime occurrence of the higher-altitude California coastal jet influenced by the North Pacific High, which typically occurs at heights of 300–400 m. The lidar buoy observations also validate LLJ representation in atmospheric models that estimate potential energy yield of offshore wind farms. The European Centre for Medium-Range Weather Forecasts Reanalysis version 5 (ERA5) was unsuccessful at identifying all observed LLJs at both buoy locations within the lowest 200 m. An extension of the National Renewable Energy Laboratory (NREL) 20-year wind resource dataset for the Outer Continental Shelf off the coast of California (CA20-Ext) yielded marginally greater captures of observed LLJs using the Mellor–Yamada–Nakanishi–Niino (MYNN) planetary boundary layer (PBL) scheme than the 2023 National Offshore Wind dataset (NOW-23), which uses the Yonsei University (YSU) scheme. However, CA20-Ext also produced the most LLJ false alarms, which are instances when a model identified an LLJ but no LLJ was observed. CA20-Ext and NOW-23 exhibited a tendency to overestimate the duration of LLJ events and underestimate LLJ core heights.
This report provides the results of a detailed analysis of the causes of high wind speed bias in the 20-year wind resource data set for offshore California that the National Renewable Energy Laboratory (NREL) released in 2020, herein called CA20. The data set was developed using the state-of-the-art Weather Research and Forecasting model. Notably, no floating lidars were available at the time in offshore California to validate offshore hub-height wind speeds. In late 2020, the Pacific Northwest National Laboratory (PNNL) deployed two floating lidars in the California Outer Continental Shelf, near the Bureau of Ocean Energy Management (BOEM) call areas of Humboldt and Morro Bay. Using these observations through 2021, NREL found considerable bias in modeled hub-height winds at both locations: up to +2 m/s at Humboldt over a 6-month period, and up to +1 m/s at Morro Bay over a 1-year period.
Accurate predictions of chemical lifetime, i.e., oxidation timescale and change in the mass of organic aerosols (OAs) in atmospheric models, are critical to quantify the impacts of OA on aerosol–cloud interactions, radiative forcing, and air quality. The heterogeneous oxidation of OA by hydroxyl (OH) radicals is a key process governing OA mass changes during their oxidation. Recently, laboratory observations of the OH uptake coefficient (γ OH ) and heterogeneous reaction rate (k het,OH ) for different OA systems with varying phase states have been combined to develop a new parameterization of γ OH and k het,OH as a function of the OA phase state, i.e., viscosity (η OA ). Here, in this work, we use a recently published viscosity prediction framework to analyze the new γ OH and k het,OH parameterization with a box model. Subsequently, we implement this box model to predict γ OH and k het,OH over the Amazon rainforest in the dry-to-wet transition season with both significant biomass burning and biogenic influences. Relevant parameters within our box model are specified based on detailed regional model simulations over the Amazon using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). η OA is predicted as a function of species volatility, OA composition (including water uptake) along with ambient relative humidity (RH), and temperature. Based on ambient conditions simulated by WRF-Chem over the entire atmospheric column, we use the box model to predict the upper bounds of the heterogeneous oxidation timescale of OA. Based on previous laboratory measurements, we assume that this heterogeneous OH oxidation causes fragmentation (carbon loss) of OA, followed by the evaporation of the fragmented molecules that results in the exponential decay of OA. We predict that the oxidation timescale of OA is ~1 month near the Earth’s surface in the pristine Amazonian background because of low OH concentrations. But OA is oxidized more rapidly within urban and wildfire plumes near the Earth’s surface with an order of magnitude higher OH concentrations compared to the pristine background, causing the simulated oxidation timescale of OA to be much shorter, ~3–4 days. At 3–5 km altitudes where biomass burning OA is predicted to be semisolid, the heterogeneous oxidation timescale is estimated as ~6 days to 3 weeks and decreases with increasing OH concentrations within plumes. We show that the simulated mass loss of OA is strongly size-dependent, where smaller particles oxidize more rapidly compared to larger particles due to their greater per-particle surface area-to-volume ratio. Increasing urbanization and deforestation in the Amazon in the future might increase OH concentrations in the background Amazon, causing faster oxidation of OA. At higher altitudes above liquid clouds, especially in the upper troposphere where temperatures approach ~250 K, future measurements are needed to reduce the uncertainties related to the mass loss of OA at colder temperatures and low relative humidity conditions due to its heterogeneous OH oxidation.
This short report provides a time-sensitive update on the 20-year wind resource data set (named “CA20”) produced in 2020 by the National Renewable Energy Laboratory (NREL) for the outer continental shelf (OCS) off the coast of California.
Abstract. The California Pacific coast is characterized by considerable wind resource and areas of dense population, propelling interest in offshore wind energy as the United States moves toward a sustainable and decarbonized energy future. Reanalysis models continue to serve the wind energy community in a multitude of ways, and the need for validation in locations where observations have been historically limited, such as offshore environments, is strong. The U.S. Department of Energy (DOE) owns two lidar buoys that collect wind speed observations across the wind turbine rotor layer along with meteorological and oceanographic data near the surface to characterize the wind resource. Lidar buoy data collected from recent deployments off the northern California coast near Humboldt County and the central California coast near Morro Bay allow for validation of commonly used reanalysis products. In this article, wind speeds from the Modern-Era Retrospective analysis for Research and Applications version 2 (MERRA-2), the Climate Forecast System version 2 (CFSv2), the North American Regional Reanalysis (NARR), the European Centre for Medium-Range Weather Forecasts Reanalysis version 5 (ERA5), and the analysis system of the Rapid Refresh (RAP) are validated at heights within the wind turbine rotor layer ranging from 50 to 100 m. The validation results offer guidance on the performance and uncertainty associated with utilizing reanalyses for offshore wind resource characterization, providing the offshore wind energy community with information on the conditions that lead to reanalysis error. At both California coast locations, the reanalyses tend to underestimate the observed rotor-level wind resource. Occasions of large reanalysis error occur in conjunction with stable atmospheric conditions, wind speeds associated with peak turbine power production (> 10 m s−1), and mischaracterization of the diurnal wind speed cycle in summer months.
From 2014 to 2017, two Department of Energy buoys equipped with Doppler lidar were deployed off the U.S. East Coast to provide long term measurements of hub-height wind speed in the marine environment. In this study, we performed simulations of selected cases from the deployment using a 5-km configuration of the Weather Research and Forecasting (WRF) model, to see if simulated hub height speeds could produce closer agreement with the observations than existing reanalysis products. For each case we performed two additional simulations: one in which marine surface roughness height was one-way coupled to forecast wave parameters from a standalone WaveWatch III (WW3) simulation, and another in which WRF and WW3 were two-way coupled using the Coupled-Ocean-Atmosphere-Wave-Sediment-Transport (COAWST) framework. It was found that all the 5-km WRF simulations improved 90-m wind speed statistics for the tropical cyclone case of 08 May 2015 and the cold frontal case of 25 Mar 2016, but not the nor-easter of 18 Jan 2016. The impact of wave coupling on buoy-level (4 m) wind speed was modest and case dependent, but when present, the impact was typically seen at 90 m as well, being as large as 10% in stable conditions. One-way wave coupling consistently reduced wind speeds, improving biases for 25 Mar 2016 but worsening them for 08 May 2015. Two-way wave coupling mitigated these negative biases, improved wave field representation and statistics, and mostly improved 4-m wind field correlation coefficients, at least at the VA buoy, largely due to greater self-consistency between wind and wave fields.
We report that throughout the troposphere over the Amazon rainforest, isoprene epoxydiol-secondary organic aerosols (IEPOX-SOA) are key components of submicrometer particle mass. IEPOX-SOA is thought to form by multiphase chemical pathways in the atmosphere, but using detailed model simulations, we show that these pathways are strongly inhibited by the solid particle phase state prevailing in the upper troposphere. We find that 2-methyltetrol gases formed by in-plant biochemical oxidation pathways, their partitioning to fine particles, and dissolution in cloud droplets can explain over 90% of IEPOX-SOA mass concentrations in the upper troposphere. In agreement with previous PM10 chiral measurements, our simulations indicate that plant biochemical processes are the dominant source of particulate 2-methyltetrols in the lower troposphere as well (>70%). Our results imply that in-plant biochemistry plays a central but previously unidentified role in aerosol processes and atmosphere-biosphere-climate interactions over the rainforest.
Two buoys equipped with lidars owned by US Department of Energy were deployed off the coast of California in fall of 2020 by Pacific Northwest National Laboratory. The buoys are scheduled to collect data for an entire annual cycle at two offshore locations proposed for offshore wind development by Bureau of Ocean Energy Management. One of the buoys was deployed approximately 50 km off the coast near Morro Bay in central California in 1100 m of water. The second buoy was deployed approximately 40 km off Humboldt County in northern California in 625 m of water. The buoys provided the first-ever measurements of hub-height winds off the coast of California. The atmospheric and oceanographic characteristics of the area and estimates of annual energy production at both Morro Bay and Humboldt lease areas show that both locations have a high wind energy yield and are prime locations for future floating offshore wind turbines.
Organic aerosol (OA) is a complex matrix of various constituents—fresh (primary organic aerosols—POA) and aged via oxidation (secondary organic aerosols—SOA), generated from biogenic, anthropogenic, and biomass burning sources. The viscosity of OA can be critical in influencing new particle formation, reactive uptake processes that impact evaporation-growth kinetics, and the lifetime of particles in the atmosphere. We report this work utilizes a well-defined relationship between volatility and viscosity for pure compounds, which we incorporated within the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to simulate the phase state and viscosity of bulk OA during the dry-to-wet transition season (September–October) in the Amazon rainforest during 2014. Our simulations indicate spatial and temporal heterogeneity in aerosol phase state often not captured by global-scale models. We show the strong role of water associated with organic aerosol ($w_s$) as the dominant factor that can be used to quantitatively estimate OA viscosity. Analysis of WRF-Chem simulations across the entire atmospheric column indicates a strong inverse log-linear relationship between $w_s$ and OA viscosity with a correlation coefficient approaching 1, in the background and biomass burning-influenced conditions. At high altitudes where relative humidity (RH) and temperatures are low, our simulations indicate that OA exists in a semisolid-/solid-like phase state, consistent with previous studies. OA hygroscopicity is strongly correlated (ca. –0.8) with OA viscosity at RH ca. 30–50%, but this RH range is found mostly at low OA concentrations and the middle troposphere (ca. 6–10 km altitudes) in our simulated domain. OA hygroscopicity is uncorrelated with viscosity at higher-RH (near surface) and lower-RH (upper troposphere) regimes. At the urban site near surface, where day–night differences in RH are significant, RH is found to drive the phase state. At the background forested site near surface, where day–night RH differences are small, biomass burning-influenced OA is semisolid and a significant OA associated with background conditions is liquid-like. Simulations indicate a long tail of OA viscosity frequency distributions extending in the semisolid/solid regimes over background biogenic-influenced conditions due to the role of low-volatility OA components such as monoterpene oxidation products.
As the offshore wind industry continues to gain momentum both in the U.S. and globally, reanalysis products remain essential tools for the lifecycle of a wind farm. From project siting and production estimates to determining construction and maintenance windows, reanalysis products play an important role. These regional and global long-term models also serve as inputs to higher resolution models. With such wide-ranging impacts on the offshore wind industry, the need for validation of reanalysis products is strong, particularly at typical turbine hub heights. Pacific Northwest National Laboratory (PNNL) operates two AXYS WindSentinelTM buoys for the U.S. Department of Energy (DOE) in order to collect meteorological and oceanographic data, including hub height wind speed, in areas of interest for offshore wind development. This work uses DOE buoy observations off the coasts of New Jersey and Virginia to evaluate the performance of Modern Era Retrospective Analysis for Research and Applications-2 (MERRA-2), the North American Regional Reanalysis (NARR), the European Center for Medium-Range Weather Forecasts (ECMWF) Reanalysis 5th generation (ERA5), and the National Oceanic and Atmospheric Administration (NOAA) assimilation system Rapid Refresh (RAP). Biases and degrees of correspondence are determined for each reanalysis product in order to provide insights on the performance and uncertainty for long-term wind resource characterization. With the baseline metrics determined, this work proceeds with an investigation into the sources of large deviations between the modeled and observed hub height wind speeds during the East Coast lidar buoy deployments. Consistent sources of reanalysis model error include stably stratified flow conditions, high wind shear, flow parallel to the coastline, and tropical and winter storms. For the near shore New Jersey location, offshore winds (i.e. blowing from land to water) tend to be associated with model overestimation of observed hub height wind speed, while winds parallel to the coastline are correlated with model underestimation of wind speed. Similarly, near the Virginia buoy, during southerly winds (parallel to the coastline) models underestimate the observed wind speed due to coastal upwelling. Reanalysis model wind speeds underestimate the hub height winds with increasing stable atmospheric stratification. Reanalysis model biases are seen when the observed wind speeds approach or exceed typical turbine cut-out speeds (around 20 m s-1). Large model errors during winter and tropical storm events, high wind speed events, and ramp events are often the result of wind speed timing and magnitude offsets. Overall, ERA5 provides the most successful representation of observed offshore hub height wind speeds at the U.S. East Coast buoy locations and is therefore best suited as an input boundary condition for model case studies. ERA5 performs well for a variety of atmospheric phenomena, including storms and sea breezes, however RAP, the next most successful reanalysis model, performs best in capturing the frequency of ramp events.
A major challenge in assessing the impact of aerosols on climate change is to understand how human activities change aerosol loading and properties relative to the pristine-preindustrial baseline. Here we combine chemical transport simulation and field measurements to investigate the effect of anthropogenic pollution from an isolated metropolis on particle number concentration over the preindustrial-like Amazon rainforest through various new-particle formation (NPF) mechanisms and primary particle emissions. To represent organic-mediated NPF, we employ a state-of-the-art model that systematically simulates the formation chemistry and thermodynamics of extremely low volatility organic compounds as well as their roles in NPF processes, and further update the model to improve organic NPF simulations under human-influenced conditions. Results show that urban pollution from the metropolis increases particle number concentration by a factor of 5–25 over the downwind region (within 200 km from city center) compared to background conditions. Overall, our model indicates that NPF contributes over 70% of the total particle number in the downwind region except immediately adjacent to the sources. Among different NPF mechanisms, the ternary NPF involving organics and sulfuric acid overwhelmingly dominates. The improved understanding of particle formation mechanisms will help better quantify anthropogenic aerosol forcing from pristine-preindustrial times to present day.
We use vertical profiles of airborne measurements of CO2 from frontal cases during the summer 2016 Atmospheric Carbon and Transport – America (ACT-America) campaign to evaluate the skill of a set of ten global CO2 inversion models participating in the Orbiting Carbon Observatory – 2 (OCO-2) Model Intercomparison Project (MIP). Model errors and biases (model minus observation) were categorized by region (Mid-Atlantic, Midwest, and South), frontal sector (warm or cold), and transport model (predominantly Tracer Model 5 (TM5) and Goddard Earth Observing System – Chemistry (GEOS-Chem)). Overall, the inversions reproduce the general structures of the observed vertical profiles and the enhanced / depleted low-level CO2 in warm / cold sectors, but tend to underestimate the magnitude of the sector difference in each region. In the Midwest and South warm sectors, inversion biases were about 1 ppm above 1500 m AGL, though model spread (quantified by interquartile range) was often even smaller; below 1500 m AGL, model biases were negative and about -2 ppm near the surface. For the Midwest and South cold sectors, models had +2-3 ppm biases below 1500 m AGL, but with comparable model spread. Uniquely, in the Mid-Atlantic there was a consistent difference between TM5 and GEOS-Chem mole fractions for both sectors up to 3000 m AGL (TM5 lower by 2 ppm), on the order of the observation-relative biases. In the MidAtlantic TM5 inversions had negative biases in warm sectors, while GEOS-Chem inversions had positive biases in cold sectors. Possible reasons for the regional variability are discussed.
Pacific Northwest National Laboratory (PNNL) operates two AXYS WindSentinel lidar buoys for the U.S. Department of Energy’s Wind Energy Technologies Office. The purpose of these buoys is to collect hub-height winds and supporting meteorological and oceanographic information to facilitate the development of wind energy in the U.S. waters. The first deployment for one buoy was off the coast of Virginia from December 2014 to May 2016, and the first deployment for the other buoy was off the coast of New Jersey from November 2015 until February 2017. This report describes recent analysis of data collected during these first two deployments. Specifically, we compare hub-height wind speed estimates using Monin-Obukhov Similarity Theory (MOST) to the lidar measurements, and examine how those errors are affected by wind direction, atmospheric stability, wind-wave direction differences, and various measures of the wave-state. The comparisons are done using standard similarity functions based on MOST; including the Businger - Dyer, the Beljaars & Holtslag and the Vickers & Mahrt similarity functions. All models produce large errors over the range of atmospheric stabilities that were observed, with the largest errors occurring for stable flows. The Vickers & Mahrt function resulted in the largest overall bias and standard deviation, while Beljaars & Holtslag function gave the smallest bias and standard deviation due to its better performance under stable conditions. The models perform best under unstable conditions, but even in this regime there is a consistent overestimation of the wind speed of between roughly 0 to 1 ms -1 compared to the lidar measurements. We identify specific metocean conditions (i.e. stability and wind and wave directions) at each of the deployment locations that lead to large errors in MOST predictions. Finally, a coupled ocean-atmosphere model framework was investigated to simulate large errors in weather research forecasting (WRF).
Our knowledge about synoptic-scale variations of atmospheric CO2 produced by interactions between mid-latitude cyclones and regional-scale surface fluxes remains limited by scarcity of observations. We synthesize observations of greenhouse gases (GHG) with respect to frontal passages to understand how GHG distributions change vertically and horizontally during a synoptic event. We use the airborne in-situ measurements of GHGs collected during the first Atmospheric Carbon and Transport–America (ACT) summer field campaign across three regions of the eastern US. We find that frontal structures are consistently and clearly associated with spatially coherent, significant changes in GHG composition. Warm sector CO2 mole fractions (henceforth, [CO2]) are significantly higher than those in the cold sector. The CO2 frontal differences (5-30 ppm) are largest in the atmospheric boundary layer (ABL) with smaller differences (3-5 ppm) in the free troposphere (FT). Bands of elevated CO2 (5-20 ppm enhancement compared to warm-sector mean [CO2]) repeatedly occurred in the ABL adjacent to the frontal boundary. Analyses of 84 vertical profiles reveal higher [CO2] in the FT than in the ABL in the cold-sector, the opposite pattern in the warm-sector. Average ABL-to-FT [CO2] differences are 12 ppm and -6 ppm in the warm and cold sectors, respectively. The same analysis for CH4 shows higher [CH4] in the ABL than in the FT in both warm and cold sectors with at least 30-ppb higher ABL-to-FT [CH4] differences in the warm-sector than in the cold-sector. The observational analyses presented here define new metrics for model evaluation of GHG transport.