Publications

Abstract As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream‐V (GV) and NASA DC‐8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NO x (LNO x ) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14 ppbv of O 3 , respectively, downwind of the storm over 2 days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNO x . Normalized excess mixing ratios, Δ X /ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0 ± 0.5 and 2.3 ± 0.5 pptv ppbv −1 , respectively, and 1.4 ± 0.3 pptv ppbv −1 for acrolein in the outflow only.

Abstract. The Kathmandu Valley in Nepal is a bowl-shaped urban basin that experiences severe air pollution that poses health risks to its 3.5 million inhabitants. As part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE), ambient air quality in the Kathmandu Valley was investigated from 11 to 24 April 2015, during the pre-monsoon season. Ambient concentrations of fine and coarse particulate matter (PM2.5 and PM10, respectively), online PM1, inorganic trace gases (NH3, HNO3, SO2, and HCl), and carbon-containing gases (CO2, CO, CH4, and 93 non-methane volatile organic compounds; NMVOCs) were quantified at a semi-urban location near the center of the valley. Concentrations and ratios of NMVOC indicated origins primarily from poorly maintained vehicle emissions, biomass burning, and solvent/gasoline evaporation. During those 2 weeks, daily average PM2.5 concentrations ranged from 30 to 207 µg m−3, which exceeded the World Health Organization 24 h guideline by factors of 1.2 to 8.3. On average, the non-water mass of PM2.5 was composed of organic matter (48 %), elemental carbon (13 %), sulfate (16 %), nitrate (4 %), ammonium (9 %), chloride (2 %), calcium (1 %), magnesium (0.05 %), and potassium (1 %). Large diurnal variability in temperature and relative humidity drove corresponding variability in aerosol liquid water content, the gas–aerosol phase partitioning of NH3, HNO3, and HCl, and aerosol solution pH. The observed levels of gas-phase halogens suggest that multiphase halogen-radical chemistry involving both Cl and Br impacted regional air quality. To gain insight into the origins of organic carbon (OC), molecular markers for primary and secondary sources were quantified. Levoglucosan (averaging 1230±1154 ng m−3), 1,3,5-triphenylbenzene (0.8±0.6 ng m−3), cholesterol (2.9±6.6 ng m−3), stigmastanol (1.0 ±0.8 ng m−3), and cis-pinonic acid (4.5±1.9 ng m−3) indicate contributions from biomass burning, garbage burning, food cooking, cow dung burning, and monoterpene secondary organic aerosol, respectively. Drawing on source profiles developed in NAMaSTE, chemical mass balance (CMB) source apportionment modeling was used to estimate contributions to OC from major primary sources including garbage burning (18±5 %), biomass burning (17±10 %) inclusive of open burning and biomass-fueled cooking stoves, and internal-combustion (gasoline and diesel) engines (18±9 %). Model sensitivity tests with newly developed source profiles indicated contributions from biomass burning within a factor of 2 of previous estimates but greater contributions from garbage burning (up to three times), indicating large potential impacts of garbage burning on regional air quality and the need for further evaluation of this source. Contributions of secondary organic carbon (SOC) to PM2.5 OC included those originating from anthropogenic precursors such as naphthalene (10±4 %) and methylnaphthalene (0.3±0.1 %) and biogenic precursors for monoterpenes (0.13±0.07 %) and sesquiterpenes (5±2 %). An average of 25 % of the PM2.5 OC was unapportioned, indicating the presence of additional sources (e.g., evaporative and/or industrial emissions such as brick kilns, food cooking, and other types of SOC) and/or underestimation of the contributions from the identified source types. The source apportionment results indicate that anthropogenic combustion sources (including biomass burning, garbage burning, and fossil fuel combustion) were the greatest contributors to PM2.5 and, as such, should be considered primary targets for controlling ambient PM pollution.

We discuss two techniques based on mixed‐layer scaling for estimating trace gas surface emission fluxes from aircraft using instruments that do not have sufficient frequency response for direct eddy correlation measurements. The first is the mixed‐layer gradient technique, which requires accurate measurements of mean concentrations at several heights in the clear convective planetary boundary layer (CBL) to resolve gradients from even strong surface sources of short‐lived trace gases. The flux‐gradient relationship is obtained from large‐eddy numerical simulations of the CBL. We show that this technique is limited to trace gases with lifetimes of about a day or less. An example is dimethylsulfide (DMS), which is emitted from the ocean and has a lifetime of about a day. Surface DMS flux was estimated from data collected from the NASA P‐3B research aircraft during the Pacific Exploratory Mission‐Tropics (PEM‐Tropics) flight 7 (August 24, 1996), when the aircraft flew a sequence of constant altitude circles about 50 km in diameter at different heights in and above the boundary layer, following the boundary layer air trajectory. The flight took place between 0530 and 1330 local solar time, providing a good opportunity to observe diurnal changes within a Lagrangian framework under nearly clear‐sky conditions. The resulting DMS flux of 2.5±0.8 pptv m s −1 (6.1±1.9)×10 13 molecules m −2 s −1 , or 8.8±2.8 μmols m −2 d −1 is on the high end of previous measurements in this milieu. The second technique is the mixed‐layer variance technique, which uses measurements of the variance at several heights in the CBL to estimate the surface flux. A major problem with the variance technique is accounting for the contribution of mesoscale variability to the measured variance. Several sources of mesoscale variability were identified: clusters of small cumulus clouds rising through the top of the boundary layer, mesoscale variations in the horizontal wind leading to inaccurate tracking of the air mass and, to a lesser extent, the presence of horizontal roll vortices in some areas of the boundary layer. We show that the variance technique should be applicable to estimating surface fluxes of short‐lived trace gases in cumulus‐free boundary layers that are horizontally uniform, if sample‐collection times of about 10 s or less are used. We also show that it may be possible to utilize mesoscale variance measurements to estimate surface fluxes and lifetimes of species which have lifetimes of perhaps a week or more.

Abstract. Ozone (O3) is an important secondary pollutant that impacts air quality and human health. Eastern Asia has high regional O3 background due to the numerous sources and increasing and rapid industrial growth, which also impacts the Seoul Metropolitan Area (SMA). However, the SMA has also been experiencing increasing O3 driven by decreasing NOx emissions, highlighting the role of the local in situ O3 production on the SMA. Here, comprehensive gas-phase measurements collected on the NASA DC-8 during the National Institute of Environmental Research (NIER)/NASA Korea–United States Air Quality (KORUS-AQ) study are used to constrain the instantaneous O3 production rate over the SMA. The observed NOx oxidized products support the importance of non-measured peroxy nitrates (PNs) in the O3 chemistry in the SMA, as they accounted for ∼49 % of the total PNs. Using the total measured PNs (ΣPNs) and alkyl and multifunctional nitrates (ΣANs), unmeasured volatile organic compound (VOC) reactivity (R(VOC)) is constrained and found to range from 1.4–2.1 s−1. Combining the observationally constrained R(VOC) with the other measurements on the DC-8, the instantaneous net O3 production rate, which is as high as ∼10 ppbv h−1, along with the important sinks of O3 and radical chemistry, is constrained. This analysis shows that ΣPNs play an important role in both the sinks of O3 and radical chemistry. Since ΣPNs are assumed to be in a steady state, the results here highlight the role that ΣPNs play in urban environments in altering the net O3 production, but ΣPNs can potentially lead to increased net O3 production downwind due to their short lifetime (∼1 h). The results provide guidance for future measurements to identify the missing R(VOCs) and ΣPN production.

Abstract. The details of aerosol processes and size distributions in the stratosphere are important for both heterogeneous chemistry and aerosol-radiation interactions. Using in-situ, global-scale measurements of the size distribution of particles with diameters > 3 nm from the NASA Atmospheric Tomography Mission (ATom), we identify a mode of ultrafine aerosol in the lowermost stratosphere (LMS) at mid and high latitudes. This mode is substantial only in the northern hemisphere (NH), and was observed in all four seasons. We also observe elevated SO2, an important precursor for new particle formation (NPF) and growth, in the NH LMS. We use box modelling and thermodynamic calculations to show that NPF can occur in the LMS conditions observed on ATom. Aircraft emissions are shown as likely sources of this SO2, as well as a potential source of ultrafine particles directly emitted by, or formed in the plume of the engines. These ultra-fine particles have the potential to grow to larger sizes, and to coagulate with larger aerosol, affecting heterogeneous chemistry and aerosol-radiation interactions. Understanding all sources and characteristics of stratospheric aerosol is important in the context of anthropogenic climate change as well as proposals for climate intervention via stratospheric sulphur injection. This analysis not only adds to the, currently sparse, observations of the global impact of aviation, but also introduces another aspect of climate influence, namely a size distribution shift of the background aerosol distribution in the LMS.

Abstract Correction to: The ISME Journal advance online publication, 16 December 2014; doi:10.1038/ismej.2014.234 Since the publication of this article, the authors have identified an error concerning the acknowledgements, namely that ‘Cystic Fibrosis Research Inc.’ was incorrectly listed as ‘Cystic FibrosisResearch Foundation’.

Abstract. Ozone is a greenhouse gas and air pollutant that is harmful to human health and plants. During the summer in the southeastern U.S., many regional and global models are biased high for surface ozone compared to observations. Past studies have suggested different solutions including the need for updates to model representation of clouds, chemistry, ozone deposition, and emissions of nitrogen oxides (NOx) or biogenic hydrocarbons. Here due to the high biogenic emissions in the southeastern U.S., more comprehensive and updated isoprene and terpene chemistry is added into CESMTM/CAM-chem (Community Earth System Model/Community Atmosphere Model with chemistry) to evaluate the impact of chemistry on simulated ozone. Comparisons of the model results with data collected during the Studies of Emissions Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) field campaign and U.S. EPA CASTNET monitoring stations confirm the updated chemistry improves simulated surface ozone, ozone precursors, and NOx reservoir compounds. The isoprene and terpene chemistry updates reduce the bias in the daily maximum 8-hr average (MDA8) surface ozone by up to 7 ppb. In the past, terpene oxidation in particular has been ignored or heavily reduced in chemical schemes used in many regional and global models, and this study demonstrates comprehensive isoprene and terpene chemistry is needed to reduce surface ozone model biases. Sensitivity tests were performed in order to evaluate the impact of lingering uncertainties in isoprene and terpene oxidation on ozone. Results suggest that even though isoprene emissions are higher than terpene emissions in the southeastern U.S., remaining uncertainties in isoprene and terpene oxidation have similar impacts on ozone due to lower uncertainties in isoprene oxidation. Additionally, this study identifies the need for further constraints on aerosol uptake of organic nitrates derived from isoprene and terpenes in order to reduce uncertainty in simulated ozone.

The airways of cystic fibrosis (CF) patients are chronically colonized by patient-specific polymicrobial communities. The conditions and nutrients available in CF lungs affect the physiology and composition of the colonizing microbes. Recent work in bioreactors has shown that the fermentation product 2,3-butanediol mediates cross-feeding between some fermenting bacteria and Pseudomonas aeruginosa, and that this mechanism increases bacterial current production. To examine bacterial fermentation in the respiratory tract, breath gas metabolites were measured and several metagenomes were sequenced from CF and non-CF volunteers. 2,3-butanedione was produced in nearly all respiratory tracts. Elevated levels in one patient decreased during antibiotic treatment, and breath concentrations varied between CF patients at the same time point. Some patients had high enough levels of 2,3-butanedione to irreversibly damage lung tissue. Antibiotic therapy likely dictates the activities of 2,3-butanedione-producing microbes, which suggests a need for further study with larger sample size. Sputum microbiomes were dominated by P. aeruginosa, Streptococcus spp. and Rothia mucilaginosa, and revealed the potential for 2,3-butanedione biosynthesis. Genes encoding 2,3-butanedione biosynthesis were disproportionately abundant in Streptococcus spp, whereas genes for consumption of butanedione pathway products were encoded by P. aeruginosa and R. mucilaginosa. We propose a model where low oxygen conditions in CF lung lead to fermentation and a decrease in pH, triggering 2,3-butanedione fermentation to avoid lethal acidification. We hypothesize that this may also increase phenazine production by P. aeruginosa, increasing reactive oxygen species and providing additional electron acceptors to CF microbes.

Airborne measurements of formaldehyde (CH 2 O) were acquired employing tunable diode laser absorption spectroscopy (TDLAS) during the 2000 Tropospheric Ozone Production About the Spring Equinox (TOPSE) study. This study consisted of seven deployments spanning the time period from 4 February to 23 May 2000 and covered a wide latitudinal band from 40°N to 85°N. The median measured CH 2 O concentrations, with a few exceptions, did not show any clear temporal trends from February to May in each of five altitude and three latitude bins examined. Detailed measurement–model comparisons were carried out using a variety of approaches employing two different steady state models. Because recent emissions of CH 2 O and/or its precursors often result in model underpredictions, background conditions were identified using a number of chemical tracers. For background conditions at temperatures warmer than −45°C, the measurement–model agreement on average ranged between −13% and +5% (measurement–model/measurement), which corresponded to mean and median (measurement–model) differences of 3 ± 69 and −6 parts per trillion by volume (pptv), respectively. At very low temperatures starting at around −45°C, significant and persistent (measurement–model) differences were observed from February to early April from southern Canada to the Arctic Ocean in the 6–8 km altitude range. In such cases, measured CH 2 O was as much as 392 pptv higher than modeled, and the median difference was 132 pptv (83%). Low light conditions as well as cold temperatures may be important in this effect. A number of possible mechanisms involving the reaction of CH 3 O 2 with HO 2 to produce CH 2 O directly were investigated, but in each case the discrepancy was only minimally reduced. Other possibilities were also considered but in each case there was no compelling evidence to support any of the hypotheses. Whatever the cause, the elevated CH 2 O concentrations significantly impact upper tropospheric HO x levels at high latitudes (>57°N) in the February–April time frame.

This dataset provides information on greenhouse gases and human-produced air pollution, including atmospheric concentrations of carbon dioxide (CO2), methane (CH4), tropospheric ozone (O3), and black carbon (BC) aerosols, collected during airborne campaigns conducted by NASA's Atmospheric Tomography (ATom) mission. This dataset includes merged data from all instruments plus additional data such as numbered profiles and distance flown. Merged data have been created for seven different sampling intervals. In the case of data obtained over longer time intervals (e.g. flask data), the merge files provide (weighted) averages to match the sampling intervals. ATom deploys an extensive gas and aerosol payload on the NASA DC-8 aircraft for a systematic, global-scale sampling of the atmosphere, profiling continuously from 0.2 to 12 km altitude. Flights occurred in each of 4 seasons from 2016 to 2018. Flights originate from the Armstrong Flight Research Center in Palmdale, California, fly north to the western Arctic, south to the South Pacific, east to the Atlantic, north to Greenland, and return to California across central North America. ATom establishes a single, contiguous, global-scale dataset. This comprehensive dataset will be used to improve the representation of chemically reactive gases and short-lived climate forcers in global models of atmospheric chemistry and climate. Profiles of the reactive gases will also provide critical information for the validation of satellite data, particularly in remote areas where in situ data is lacking. Complete aircraft flight information including, but not limited to, latitude, longitude, and altitude are also provided. This data release provides results from all instruments on all four ATom flight campaigns.