NSF NCAR Earth Observing Laboratory

Abstract. We use an ensemble of aircraft, satellite, sonde, and surface observations for April–May 2006 (NASA/INTEX-B aircraft campaign) to better understand the mechanisms for transpacific ozone pollution and its implications for North American air quality. The observations are interpreted with a global 3-D chemical transport model (GEOS-Chem). OMI NO2 satellite observations constrain Asian anthropogenic NOx emissions and indicate a factor of 2 increase from 2000 to 2006 in China. Satellite observations of CO from AIRS and TES indicate two major events of Asian transpacific pollution during INTEX-B. Correlation between TES CO and ozone observations shows evidence for transpacific ozone pollution. The semi-permanent Pacific High and Aleutian Low cause splitting of transpacific pollution plumes over the Northeast Pacific. The northern branch circulates around the Aleutian Low and has little impact on North America. The southern branch circulates around the Pacific High and some of that air impacts western North America. Both aircraft measurements and model results show sustained ozone production driven by peroxyacetylnitrate (PAN) decomposition in the southern branch, roughly doubling the transpacific influence from ozone produced in the Asian boundary layer. Model simulation of ozone observations at Mt. Bachelor Observatory in Oregon (2.7 km altitude) indicates a mean Asian ozone pollution contribution of 9±3 ppbv to the mean observed concentration of 54 ppbv, reflecting mostly an enhancement in background ozone rather than episodic Asian plumes. Asian pollution enhanced surface ozone concentrations by 5–7 ppbv over western North America in spring 2006. The 2000–2006 rise in Asian anthropogenic emissions increased this influence by 1–2 ppbv.

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Abstract. We have integrated observations of tropospheric ozone, very short-lived (VSL) halocarbons and reactive iodine and bromine species from a wide variety of tropical data sources with the global CAM-Chem chemistry-climate model and offline radiative transfer calculations to compute the contribution of halogen chemistry to ozone loss and associated radiative impact in the tropical marine troposphere. The inclusion of tropospheric halogen chemistry in CAM-Chem leads to an annually averaged depletion of around 10% (~2.5 Dobson units) of the tropical tropospheric ozone column, with largest effects in the middle to upper troposphere. This depletion contributes approximately −0.10 W m−2 to the radiative flux at the tropical tropopause. This negative flux is of similar magnitude to the ~0.33 W m−2 contribution of tropospheric ozone to present-day radiative balance as recently estimated from satellite observations. We find that the implementation of oceanic halogen sources and chemistry in climate models is an important component of the natural background ozone budget and we suggest that it needs to be considered when estimating both preindustrial ozone baseline levels and long term changes in tropospheric ozone.

Abstract Nocturnal dinitrogen pentoxide (N 2 O 5 ) heterogeneous chemistry impacts regional air quality and the distribution and lifetime of tropospheric oxidants. Formed from the oxidation of nitrogen oxides, N 2 O 5 is heterogeneously lost to aerosol with a highly variable reaction probability, γ (N 2 O 5 ), dependent on aerosol composition and ambient conditions. Reaction products include soluble nitrate (HNO 3 or NO 3 − ) and nitryl chloride (ClNO 2 ). We report the first‐ever derivations of γ (N 2 O 5 ) from ambient wintertime aircraft measurements in the critically important nocturnal residual boundary layer. Box modeling of the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign over the eastern United States derived 2,876 individual γ (N 2 O 5 ) values with a median value of 0.0143 and range of 2 × 10 −5 to 0.1751. WINTER γ (N 2 O 5 ) values exhibited the strongest correlation with aerosol water content, but weak correlations with other variables, such as aerosol nitrate and organics, suggesting a complex, nonlinear dependence on multiple factors, or an additional dependence on a nonobserved factor. This factor may be related to aerosol phase, morphology (i.e., core shell), or mixing state, none of which are commonly measured during aircraft field studies. Despite general agreement with previous laboratory observations, comparison of WINTER data with 14 literature parameterizations (used to predict γ (N 2 O 5 ) in chemical transport models) confirms that none of the current methods reproduce the full range of γ (N 2 O 5 ) values. Nine reproduce the WINTER median within a factor of 2. Presented here is the first field‐based, empirical parameterization of γ (N 2 O 5 ), fit to WINTER data, based on the functional form of previous parameterizations.

Abstract. A field-deployable water vapor profiling instrument that builds on the foundation of the preceding generations of diode-laser-based differential absorption lidar (DIAL) laboratory prototypes was constructed and tested. Significant advances are discussed, including a unique shared telescope design that allows expansion of the outgoing beam for eye-safe operation with optomechanical and thermal stability; multistage optical filtering enabling measurement during daytime bright-cloud conditions; rapid spectral switching between the online and offline wavelengths enabling measurements during changing atmospheric conditions; and enhanced performance at lower ranges by the introduction of a new filter design and the addition of a wide field-of-view channel. Performance modeling, testing, and intercomparisons are performed and discussed. In general, the instrument has a 150 m range resolution with a 10 min temporal resolution; 1 min temporal resolution in the lowest 2 km of the atmosphere is demonstrated. The instrument is shown capable of autonomous long-term field operation – 50 days with a > 95% uptime – under a broad set of atmospheric conditions and potentially forms the basis for a ground-based network of eye-safe autonomous instruments needed for the atmospheric sciences research and forecasting communities.

Abstract. We present a digital, freely available, searchable, and evaluated compilation of rate coefficients for the gas-phase reactions of organic compounds with OH, Cl, and NO3 radicals and with O3. Although other compilations of many of these data exist, many are out of date, most have limited scope, and all are difficult to search and to load completely into a digitized form. This compilation uses results of previous reviews, though many recommendations are updated to incorporate new or omitted data or address errors, and includes recommendations on many reactions that have not been reviewed previously. The database, which incorporates over 50 years of measurements, consists of a total of 2765 recommended bimolecular rate coefficients for the reactions of 1357 organic substances with OH, 709 with Cl, 310 with O3, and 389 with NO3, and is much larger than previous compilations. Many compound types are present in this database, including naturally occurring chemicals formed in or emitted to the atmosphere and anthropogenic compounds such as halocarbons and their degradation products. Recommendations are made for rate coefficients at 298 K and, where possible, the temperature dependences over the entire range of the available data. The primary motivation behind this project has been to provide a large and thoroughly evaluated training dataset for the development of structure–activity relationships (SARs), whose reliability depends fundamentally upon the availability of high-quality experimental data. However, there are other potential applications of this work, such as research related to atmospheric lifetimes and fates of organic compounds, or modelling gas-phase reactions of organics in various environments. This database is freely accessible at https://doi.org/10.25326/36 (McGillen et al., 2019).

Abstract The Chequamegon Heterogeneous Ecosystem Energy-Balance Study Enabled by a High-Density Extensive Array of Detectors 2019 (CHEESEHEAD19) is an ongoing National Science Foundation project based on an intensive field campaign that occurred from June to October 2019. The purpose of the study is to examine how the atmospheric boundary layer (ABL) responds to spatial heterogeneity in surface energy fluxes. One of the main objectives is to test whether lack of energy balance closure measured by eddy covariance (EC) towers is related to mesoscale atmospheric processes. Finally, the project evaluates data-driven methods for scaling surface energy fluxes, with the aim to improve model–data comparison and integration. To address these questions, an extensive suite of ground, tower, profiling, and airborne instrumentation was deployed over a 10 km × 10 km domain of a heterogeneous forest ecosystem in the Chequamegon–Nicolet National Forest in northern Wisconsin, United States, centered on an existing 447-m tower that anchors an AmeriFlux/NOAA supersite (US-PFa/WLEF). The project deployed one of the world’s highest-density networks of above-canopy EC measurements of surface energy fluxes. This tower EC network was coupled with spatial measurements of EC fluxes from aircraft; maps of leaf and canopy properties derived from airborne spectroscopy, ground-based measurements of plant productivity, phenology, and physiology; and atmospheric profiles of wind, water vapor, and temperature using radar, sodar, lidar, microwave radiometers, infrared interferometers, and radiosondes. These observations are being used with large-eddy simulation and scaling experiments to better understand submesoscale processes and improve formulations of subgrid-scale processes in numerical weather and climate models.

Abstract. Satellite and aircraft observations made during the 2006 Texas Air Quality Study (TexAQS) detected strong urban, industrial and power plant plumes in Texas. We simulated these plumes using the Weather Research and Forecasting-Chemistry (WRF-Chem) model with input from the US EPA's 2005 National Emission Inventory (NEI-2005), in order to evaluate emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs) in the cities of Houston and Dallas-Fort Worth. We compared the model results with satellite retrievals of tropospheric nitrogen dioxide (NO2) columns and airborne in-situ observations of several trace gases including NOx and a number of VOCs. The model and satellite NO2 columns agree well for regions with large power plants and for urban areas that are dominated by mobile sources, such as Dallas. However, in Houston, where significant mobile, industrial, and in-port marine vessel sources contribute to NOx emissions, the model NO2 columns are approximately 50%–70% higher than the satellite columns. Similar conclusions are drawn from comparisons of the model results with the TexAQS 2006 aircraft observations in Dallas and Houston. For Dallas plumes, the model-simulated NO2 showed good agreement with the aircraft observations. In contrast, the model-simulated NO2 is ~60% higher than the aircraft observations in the Houston plumes. Further analysis indicates that the NEI-2005 NOx emissions over the Houston Ship Channel area are overestimated while the urban Houston NOx emissions are reasonably represented. The comparisons of model and aircraft observations confirm that highly reactive VOC emissions originating from industrial sources in Houston are underestimated in NEI-2005. The update of VOC emissions based on Solar Occultation Flux measurements during the field campaign leads to improved model simulations of ethylene, propylene, and formaldehyde. Reducing NOx emissions in the Houston Ship Channel and increasing highly reactive VOC emissions from the point sources in Houston improve the model's capability of simulating ozone (O3) plumes observed by the NOAA WP-3D aircraft, although the deficiencies in the model O3 simulations indicate that many challenges remain for a full understanding of the O3 formation mechanisms in Houston.

Abstract The Cloud System Evolution in the Trades (CSET) study was designed to describe and explain the evolution of the boundary layer aerosol, cloud, and thermodynamic structures along trajectories within the North Pacific trade winds. The study centered on seven round trips of the National Science Foundation–National Center for Atmospheric Research (NSF–NCAR) Gulfstream V (GV) between Sacramento, California, and Kona, Hawaii, between 7 July and 9 August 2015. The CSET observing strategy was to sample aerosol, cloud, and boundary layer properties upwind from the transition zone over the North Pacific and to resample these areas two days later. Global Forecast System forecast trajectories were used to plan the outbound flight to Hawaii with updated forecast trajectories setting the return flight plan two days later. Two key elements of the CSET observing system were the newly developed High-Performance Instrumented Airborne Platform for Environmental Research (HIAPER) Cloud Radar (HCR) and the high-spectral-resolution lidar (HSRL). Together they provided unprecedented characterizations of aerosol, cloud, and precipitation structures that were combined with in situ measurements of aerosol, cloud, precipitation, and turbulence properties. The cloud systems sampled included solid stratocumulus infused with smoke from Canadian wildfires, mesoscale cloud–precipitation complexes, and patches of shallow cumuli in very clean environments. Ultraclean layers observed frequently near the top of the boundary layer were often associated with shallow, optically thin, layered veil clouds. The extensive aerosol, cloud, drizzle, and boundary layer sampling made over open areas of the northeast Pacific along 2-day trajectories during CSET will be an invaluable resource for modeling studies of boundary layer cloud system evolution and its governing physical processes.

Clouds over the Southern Ocean exist in a pristine environment that results in unique microphysical properties. However, in situ observations of these clouds are rare, and the dominant precipitation processes are unknown. Uncertainties in their life cycles and radiative properties make them interesting from a weather and climate perspective. Data from the standard cloud physics payload during the High‐performance Instrumented Airborne Platform for Environmental Research (HIAPER) Pole‐to‐Pole Observations global transects provide a unique snapshot the nature of low‐level clouds in the Southern Ocean. High quantities of supercooled liquid water (up to 0.47gm −3 ) were observed in clouds as cold as −22°C during two flights in different seasons and different meteorological conditions, supporting climatologies inferred from satellite observations. Cloud droplet concentrations were calculated from mean droplet size and liquid water concentrations, and were in the range of 30–120cm −3 , which is fairly typical for the pristine Southern Ocean environment. Ice in nonprecipitating or lightly precipitating clouds was found to be rare, while drizzle drops with diameter greater than 100μm formed through warm rain processes were widespread. Large, pristine crystals were commonly seen in very low concentrations below cloud base.

Abstract Nitryl chloride (ClNO 2 ) plays an important role in the budget and distribution of tropospheric oxidants, halogens, and reactive nitrogen species. ClNO 2 is formed from the heterogeneous uptake and reaction of dinitrogen pentoxide (N 2 O 5 ) on chloride‐containing aerosol, with a production yield, ϕ (ClNO 2 ), defined as the moles of ClNO 2 produced relative to N 2 O 5 lost. The ϕ (ClNO 2 ) has been increasingly incorporated into 3‐D chemical models where it is parameterized based on laboratory‐derived kinetics and currently accepted aqueous‐phase formation mechanism. This parameterization models ϕ (ClNO 2 ) as a function of the aerosol chloride to water molar ratio. Box model simulations of night flights during the 2015 Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) aircraft campaign derived 3,425 individual ϕ (ClNO 2 ) values with a median of 0.138 and range of 0.003 to 1. Comparison of the box model median to those predicted by two other field‐based ϕ (ClNO 2 ) derivation methods agreed within a factor of 1.3, within the uncertainties of each method. In contrast, the box model median was 75–84% lower than predictions from the laboratory‐based parameterization (i.e., [parameterization − box model]/parameterization). An evaluation of factors influencing this difference reveals a positive dependence of ϕ (ClNO 2 ) on aerosol water, opposite to the currently parameterized trend. Additional factors may include aqueous‐phase competition reactions for the nitronium ion intermediate and/or direct ClNO 2 loss mechanisms. Further laboratory studies of ClNO 2 formation and the impacts of aerosol water, sulfate, organics, and ClNO 2 aqueous‐phase reactions are required to elucidate and quantify these processes on ambient aerosol, critical for the development of a robust ϕ (ClNO 2 ) parameterization.

Abstract. We use the NASA Goddard Earth Observing System (GEOS) Chemistry Climate Model (GEOSCCM) to quantify the contribution of the two most important brominated very short lived substances (VSLSs), bromoform (CHBr3) and dibromomethane (CH2Br2), to stratospheric bromine and its sensitivity to convection strength. Model simulations suggest that the most active transport of VSLSs from the marine boundary layer through the tropopause occurs over the tropical Indian Ocean, the tropical western Pacific, and off the Pacific coast of Mexico. Together, convective lofting of CHBr3 and CH2Br2 and their degradation products supplies ~8 ppt total bromine to the base of the tropical tropopause layer (TTL, ~150 hPa), similar to the amount of VSLS organic bromine available in the marine boundary layer (~7.8–8.4 ppt) in the active convective lofting regions mentioned above. Of the total ~8 ppt VSLS bromine that enters the base of the TTL at ~150 hPa, half is in the form of organic source gases and half in the form of inorganic product gases. Only a small portion (<10%) of the VSLS-originated bromine is removed via wet scavenging in the TTL before reaching the lower stratosphere. On average, globally, CHBr3 and CH2Br2 together contribute ~7.7 pptv to the present-day inorganic bromine in the stratosphere. However, varying model deep-convection strength between maximum (strongest) and minimum (weakest) convection conditions can introduce a ~2.6 pptv uncertainty in the contribution of VSLSs to inorganic bromine in the stratosphere (BryVSLS). Contrary to conventional wisdom, the minimum convection condition leads to a larger BryVSLS as the reduced scavenging in soluble product gases, and thus a significant increase in product gas injection (2–3 ppt), greatly exceeds the relatively minor decrease in source gas injection (a few 10ths ppt).

We describe implementation and demonstration of a polarization technique adapted for lidar to measure all unique elements of the volume backscatter phase matrix. This capability allows for detection of preferential orientation within a scattering volume, and may improve scattering inversions on oriented ice crystals. The technique is enabled using a Mueller formalism commonly employed in polarimetry, which does not require the lidar instrument be polarization preserving. Instead, the accuracy of the polarization measurements are limited by the accuracy of the instrument characterization. A high spectral resolution lidar at the National Center for Atmospheric Research was modified to demonstrate this polarization technique. Two observations where the instrument is tilted off zenith are presented. In the first case, the lidar detects flattened large raindrops oriented along the same direction due to drag forces from falling. The second case is an ice cloud approximately 5 km above lidar base that contains preferentially oriented ice crystals in a narrow altitude band.

This study estimates the amplitude and phase of the climatological diurnal cycle of temperature, from the surface to 10 hPa. The analysis is based on four‐times‐daily radiosonde data from 53 stations in four regions in the Northern Hemisphere, equatorial soundings from the Tropical Ocean Global Atmosphere/Coupled Ocean Atmosphere Response Experiment, and more recent eight‐times‐daily radiosonde data from the Atmospheric Radiation Measurement program's Central Facility in Oklahoma. Our results are in general qualitative agreement with earlier studies, with some quantitative differences, but provide more detail about vertical, seasonal, and geographic variations. The amplitude of the diurnal cycle (half the diurnal temperature range) is largest (1 to 4 K) at the surface. At 850 hPa and above, the regional‐average amplitudes are <1 K throughout the troposphere and stratosphere. The amplitude of the diurnal cycle in the boundary layer is larger over land than over ocean, and generally larger in summer than winter (except for monsoon regions, where it is larger in the dry season). In the upper‐troposphere and stratosphere, land‐sea and seasonal differences are not prominent. The diurnal cycle peaks a few hours after local noon at the surface, a few hours later at 850 hPa, and somewhat earlier in the upper troposphere. The timing of the diurnal cycle peak in the stratosphere is more uncertain. Radiosonde data are also used to simulate deep‐layer mean temperatures that would be observed by the satellite‐borne microwave sounding unit, and the amplitude and phase of their diurnal cycles are estimated. An evaluation is made of the uncertainty in these results due to the temporal resolution of the sounding data, which is only barely adequate for resolving the first harmonic of the diurnal cycle, the precision of radiosonde temperature data, and potential biases in daytime stratospheric temperature observations.

We present a demonstration of a diode-laser-based high spectral resolution lidar. It is capable of performing calibrated retrievals of aerosol and cloud optical properties at a 150 m range resolution with less than 1 minute integration time over an approximate range of 12 km during day and night. This instrument operates at 780 nm, a wavelength that is well established for reliable semiconductor lasers and detectors, and was chosen because it corresponds to the D2 rubidium absorption line. A heated vapor reference cell of isotopic rubidium 87 is used as an effective and reliable aerosol signal blocking filter in the instrument. In principle, the diode-laser-based high spectral resolution lidar can be made cost competitive with elastic backscatter lidar systems, yet delivers a significant improvement in data quality through direct retrieval of quantitative optical properties of clouds and aerosols.

Abstract We use observations from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) aircraft campaign to constrain the proposed mechanism of Cl 2 production from ClNO 2 reaction in acidic particles. To reproduce Cl 2 concentrations observed during WINTER with a chemical box model that includes ClNO 2 reactive uptake to form Cl 2 , the model required the ClNO 2 reaction probability, γ (ClNO 2 ), to range from 6 × 10 −6 to 7 × 10 −5 , with a mean value of 2.3 × 10 −5 (±1.8 × 10 −5 ). These field‐determined γ (ClNO 2 ) are more than an order of magnitude lower than those determined in previous laboratory experiments on acidic surfaces, even when calculated particle pH is ≤2. We hypothesize this is because thick salt films in the laboratory enhanced the reactive uptake ClNO 2 compared to that which would occur in submicron aerosol particles. Using the reacto‐diffusive length‐scale framework, we show that the field and laboratory observations can be reconciled if the net aqueous‐phase reaction rate constant for ClNO 2 (aq) + Cl ‐ (aq) in acidic particles is on the order of 10 4 s −1 . We show that wet particle diameter and particulate chloride mass together explain 90% of the observed variance in the box model‐derived γ (ClNO 2 ), implying that the availability of chloride and particle volume limit the efficiency of the reaction. Despite a much lower conversion of ClNO 2 into Cl 2 , this mechanism can still be responsible for the nocturnal formation of 10–20 pptv of Cl 2 in polluted regions, yielding an atmospherically relevant concentration of Cl atoms the following morning.

Oriented particles can exhibit different polarization properties than randomly oriented particles. These properties cannot be resolved by conventional polarization lidar systems and are capable of corrupting the interpretation of depolarization ratio measurements. Additionally, the typical characteristics of backscatter phase matrices from atmospheric oriented particles are not well established. The National Center for Atmospheric Research High Spectral Resolution Lidar was outfitted in spring of 2012 to measure the backscatter phase matrix, allowing it to fully characterize the polarization properties of oriented particles. The lidar data analyzed here considers operation at 4°, 22° and 32° off zenith in Boulder, CO, USA (40.0°N,105.2°W). The HSRL has primarily observed oriented ice crystal signatures at lidar tilt angles near 32° off zenith which corresponds to an expected peak in backscatter from horizontally oriented plates. The maximum occurrence frequency of oriented ice crystals is measured at 5 km, where 2% of clouds produced significant oriented ice signatures by exhibiting diattenuation in their scattering matrices. The HSRL also observed oriented particle characteristics of rain at all three tilt angles. Oriented signatures in rain are common at all three tilt angles. As many as 70% of all rain observations made at 22° off zenith exhibited oriented signatures. The oriented rain signatures exhibit significant linear diattenuation and retardance.

A Raman shifter is optimized for generating high-energy laser pulses at a 1.54 microm wavelength. A forward-scattering design is described, including details of the multiple pass and nonfocused optical design, Stokes injection seeding, and internal gas recirculation. First-Stokes conversion efficiencies up to 43%--equivalent to 62% photon conversion efficiency--were measured. Experimental results show output average power in excess of 17.5 W, pulse energies of 350 mJ at 50 Hz, with good beam quality (M2<6). Narrow bandwidth and tunable output is produced when pumping with a single longitudinal mode Nd:YAG laser and seeding the process with a Stokes wavelength narrowband laser diode.

The application of time-correlated single photon counting hardware and techniques to atmospheric lidar is presented. The results establish the viability of adapting photon time-tagging techniques to atmospheric lidar systems, facilitating high-range resolution (millimeter-level precision) and dynamic system observing capabilities that address the variety of atmospheric scatterers often present in atmospheric lidar profiles. The technique is demonstrated through measurements made by a high repetition rate, low pulse energy, elastic scattering, photon counting lidar. Detection probabilities with a non-zero system dead-time are derived and tested using acquired data. Atmospheric point cloud generation and the statistical implications on data retrievals utilizing this approach are presented. The results show an ability to preserve backscattered intensities while generating photon detections at picosecond resolution from a variety atmospheric scatterers.

Abstract. Laboratory experiments were conducted to investigate the effects of water vapor on the reaction of nitric oxide with ozone in a gas-phase chemiluminescence instrument used for fast response and high sensitivity detection of atmospheric ozone. Water vapor was introduced into a constant level ozone standard and both ozone and water vapor signals were recorded at 10 Hz. The presence of water vapor was found to reduce, i.e. quench, the ozone signal. A dimensionless correction factor was determined to be 4.15 ± 0.14 × 10−3, which corresponds to a 4.15% increase in the corrected ozone signal per 10 mmol mol−1 of co-sampled water vapor. An ozone-inert water vapor permeable membrane (a Nafion dryer with a counterflow of dry air from a compressed gas cylinder) was installed in the sampling line and was shown to remove the bulk of the water vapor in the sample air. At water vapor mole fractions above 25 mmol mol−1, the Nafion dryer removed over 75% of the water vapor in the sample. This reduced the required ozone signal correction from over 11% to less than 2.5%. The Nafion dryer was highly effective at reducing the fast fluctuations of the water vapor signal (more than 97%) while leaving the ozone signal unaffected, which is a crucial improvement for minimizing the quenching interference of water vapor fluxes and required density correction in the determination of ozone fluxes by the eddy covariance technique.