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Abstract: Most intensive field studies investigating aerosols have been conducted in summer, and thus, wintertime aerosol sources and chemistry are comparatively poorly understood. An aerosol mass spectrometer was flown on the National Science Foundation/National Center for Atmospheric Research C‐130 during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) 2015 campaign in the northeast United States. The fraction of boundary layer submicron aerosol that was organic aerosol (OA) was about a factor of 2 smaller than during a 2011 summertime study in a similar region. However, the OA measured in WINTER was almost as oxidized as OA measured in several other studies in warmer months of the year. Fifty‐eight percent of the OA was oxygenated (secondary), and 42% was primary (POA). Biomass burning OA (likely from residential heating) was ubiquitous and accounted for 33% of the OA mass. Using nonvolatile POA, one of two default secondary OA (SOA) formulations in GEOS‐Chem (v10‐01) shows very large underpredictions of SOA and O/C (5×) and overprediction of POA (2×). We strongly recommend against using that formulation in future studies. Semivolatile POA, an alternative default in GEOS‐Chem, or a simplified parameterization (SIMPLE) were closer to the observations, although still with substantial differences. A case study of urban outflow from metropolitan New York City showed a consistent amount and normalized rate of added OA mass (due to SOA formation) compared to summer studies, although proceeding more slowly due to lower OH concentrations. A box model and SIMPLE perform similarly for WINTER as for Los Angeles, with an underprediction at ages <6 hr, suggesting that fast chemistry might be missing from the models. [ABSTRACT FROM AUTHOR]

Lightning is one of the most important sources of upper tropospheric NO x; however, there is a large spread in estimates of the global emission rates (2-8 Tg N yr−1). We combine upper tropospheric in situ observations from the Deep Convective Clouds and Chemistry (DC3) experiment and global satellite-retrieved NO2 tropospheric column densities to constrain mean lightning NO x (LNO x) emissions per flash. Insights from DC3 indicate that the NO x lifetime is ~3 h in the region of outflow of thunderstorms, mainly due to production of methyl peroxy nitrate and alkyl and multifunctional nitrates. The lifetime then increases farther downwind from the region of outflow. Reinterpreting previous analyses using the 3 h lifetime reduces the spread among various methods that have been used to calculate mean LNO x emissions per flash and indicates a global LNO x emission rate of ~9 Tg N yr−1, a flux larger than the high end of recent estimates. [ABSTRACT FROM AUTHOR]

Chemical components of organic aerosol (OA) selectively absorb light at short wavelengths. In this study, the prevalence, sources, and optical importance of this socalled brown carbon (BrC) aerosol component are investigated throughout the North American continental tropospheric column during a summer of extensive biomass burning. Spectrophotometric absorption measurements on extracts of bulk aerosol samples collected from an aircraft over the central USA were analyzed to directly quantify BrC abundance. BrC was found to be prevalent throughout the 1 to 12 km altitude measurement range, with dramatic enhancements in biomass-burning plumes. BrC to black carbon (BC) ratios, under background tropospheric conditions, increased with altitude, consistent with a corresponding increase in the absorption Ångström exponent (AAE) determined from a three-wavelength particle soot absorption photometer (PSAP). The sum of inferred BC absorption and measured BrC absorption at 365 nm was within 3% of the measured PSAP absorption for background conditions and 22% for biomass burning. A radiative transfer model showed that BrC absorption reduced top-ofatmosphere (TOA) aerosol forcing by ~20% in the background troposphere. Extensive radiative model simulations applying this study background tropospheric conditions provided a look-up chart for determining radiative forcing efficiencies of BrC as a function of a surface-measured BrC : BC ratio and single scattering albedo (SSA). The chart is a first attempt to provide a tool for better assessment of brown carbon's forcing effect when one is limited to only surface data. These results indicate that BrC is an important contributor to direct aerosol radiative forcing. [ABSTRACT FROM AUTHOR]

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br-) was 0.9±0.1, 1.06+0.30/-0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the spaceborne observation of BrO. The good agreement (R² = 0.76; slope = 0.95; intercept =-3.4 pmol mol-1) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pmol mol-1) under unpolluted conditions (NO<10 pmol mol-1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with Due to image rights restrictions, multiple line equation(s) cannot be graphically displayed. from OMI on 17 April 2008. [ABSTRACT FROM AUTHOR]

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time, high latitude troposphere based on aircraft and satellite measurements of BrO and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometry (CIMS) instrument to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br-) was 0.9 ± 0.1, 1.06 ± 0.30, 0.4 ± 0.1, and 0.95 ± 0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R² = 0.76; slope = 0.98; intercept = -3.5 pptv) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pptv) under unpolluted conditions (NO < 100 pptv), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide. Tropospheric BrO vertical column densities (BRODue to image rights restrictions, multiple line equation(s) cannot be graphically displayed) derived from CIMS BrO observations compare well with BRODue to image rights restrictions, multiple line equation(s) cannot be graphically displayed from OMI on 17 April 2008. [ABSTRACT FROM AUTHOR]

In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr + Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200-500m altitude. In ozonedepleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere. [ABSTRACT FROM AUTHOR]

In-situ airborne measurements of trace gases, aerosol size distributions, chemistry and optical properties were conducted over Mexico and the Eastern North Pacific during MILAGRO and INTEX-B. Heterogeneous reactions between secondary aerosol precursor gases and mineral dust lead to sequestration of sulfur, nitrogen and chlorine in the supermicrometer particulate size range. Simultaneous measurements of aerosol size distributions and weak-acid soluble calcium result in an estimate of 11 wt% of CaCO3 for Asian dust. During transport across the North Pacific, ∼5-30% of the CaCO3 is converted to CaSO4 or Ca(NO3)2 with an additional ∼4% consumed through reactions with HCl. The 1996 to 2008 record from the Mauna Loa Observatory confirm these findings, indicating that, on average, 19% of the CaCO3 has reacted to form CaSO4 and 7% has reacted to form Ca(NO3)2 and ∼2% has reacted with HCl. In the nitrogen-oxide rich boundary layer near Mexico City up to 30% of the CaCO3 has reacted to form Ca(NO3)2 while an additional 8% has reacted with HCl. These heterogeneous reactions can result in a ∼3% increase in dust solubility which has an insignificant effect on their optical properties compared to their variability in-situ. However, competition between supermicrometer dust and submicrometer primary aerosol for condensing secondary aerosol species led to a 25% smaller number median diameter for the accumulation mode aerosol. A 10-25% reduction of accumulation mode number median diameter results in a 30-70% reduction in submicrometer light scattering at relative humidities in the 80-95% range. At 80% RH submicrometer light scattering is only reduced ∼3% due to a higher mass fraction of hydrophobic refractory components in the dust-affected accumulation mode aerosol. Thus reducing the geometric mean diameter of the submicrometer aerosol has a much larger effect on aerosol optical properties than changes to the hygroscopic:hydrophobic mass fractions of the accumulation mode aerosol. In the presence of dust, nitric acid concentrations are reduced to <50% of total nitrate (nitric acid plus particulate nitrate). NOy as a fraction of total nitrogen (NOy plus particulate nitrate), is reduced from >85% to 60-80% in the presence of dust. These observations support previous model studies which predict irreversible sequestration of reactive nitrogen species through heterogeneous reactions with mineral dust during long-range transport. [ABSTRACT FROM AUTHOR]

Gas-phase elemental mercury (Hg°) was measured aboard the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment Phase B (INTEXB) campaign in spring 2006. Flights were conducted around Mexico City and on two subsequent deployments over the North Pacific based out of Honolulu, Hawaii and Anchorage, Alaska. Data obtained from 0.15-12 km altitude showed that Hg° exhibited a relatively constant vertical profile centered around 100 ppqv. Highly concentrated pollution plumes emanating from the Mexico City urban agglomeration revealed that mixing ratios of Hg° as large as 500 ppqv were related to combustion tracers such as CO, but not SO2 which is presumably released locally from coal burning, refineries, and volcanoes. Our analysis of Mexico City plumes indicated that widespread multi-source urban/industrial emissions may have a more important influence on Hg° than specific point sources. Over the Pacific, correlations with CO, CO2, CH4, and C2Cl4 were diffuse overall, but recognizable on flights out of Anchorage and Honolulu. In distinct plumes originating from the Asian continent the Hg°- CO relationship yielded an average value of ~0.56 ppqv/ppbv, in good agreement with previous findings. A prominent feature of the INTEX-B dataset was frequent total depletion of Hg° in the upper troposphere when stratospherically influenced air was encountered. Ozone data obtained with the differential absorption lidar (DIAL) showed that the stratospheric impact on the tropospheric column was a common and pervasive feature on all flights out of Honolulu and Anchorage. We propose that this is likely a major factor driving large-scale seasonality in Hg° mixing ratios, especially at mid-latitudes, and an important process that should be incorporated into global chemical transport models. [ABSTRACT FROM AUTHOR]

Gas-phase elemental mercury (Hg°) was measured aboard the NASA DC-8 aircraft during the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign in spring 2006. Flights were conducted around Mexico City and on two subsequent deployments over the North Pacific based out of Honolulu, Hawaii and Anchorage, Alaska. Data obtained from 0.15-12 km altitude showed that Hg° exhibited a relatively constant vertical profile centered around 100 ppqv. Highly concentrated pollution plumes emanating from the Mexico City urban agglomeration revealed that mixing ratios of Hg° as large as 500 ppqv were related to combustion tracers such as CO, but not SO2 which is presumably released locally from coal burning, refineries, and volcanoes. Our analysis of Mexico City plumes indicated that widespread multi-source urban/industrial emissions may have a more important influence on Hg° than specific point sources. Over the Pacific, correlations with CO, CO2, CH4, and C2Cl4 were diffuse overall, but recognizable on flights out of Anchorage and Honolulu. In distinct 15 plumes originating from the Asian continent the Hg°-CO relationship yielded an average value of ∼.56 ppqv/ppbv, in good agreement with previous findings. A prominent feature of the INTEX-B dataset was frequent total depletion of Hg° in the upper troposphere when stratospherically influenced air was encountered. Ozone data obtained with the differential absorption lidar (DIAL) showed that the stratospheric impact on the tropospheric column was a common and pervasive feature on all flights out of Honolulu and Anchorage. We propose that this is likely a major factor driving large-scale seasonality in Hg° mixing ratios, especially at mid-latitudes, and an important process that should be incorporated into global chemical transport models. [ABSTRACT FROM AUTHOR]

Using a new approach that constrains thermodynamic modeling of aerosol composition with measured gas-to-particle partitioning of inorganic nitrate, we estimate the acidity levels for aerosol sampled in the South Korean planetary boundary layer during the NASA/NIER KORUS-AQ field campaign. The pH (mean ± 1σ = 2.43±0.68) and aerosol liquid water content determined were then used to determine the 'chemical regime' of the inorganic fraction of particulate matter (PM) sensitivity to ammonia and nitrate availability. We found that the aerosol formation is always sensitive to HNO3 levels, especially in highly polluted regions, while it is only exclusively sensitive to NH3 in some rural/remote regions. Nitrate levels are further promoted because dry deposition velocity is low and allows its accumulation in the boundary layer. Because of this, HNO3 reductions achieved by NOX controls prove to be the most effective approach for all conditions examined, and that NH3 emissions can only partially affect PM reduction for the specific season and region. Despite the benefits of controlling PM formation to reduce ammonium-nitrate aerosol and PM mass, changes in the acidity domain can significantly affect other processes and sources of aerosol toxicity (e.g. solubilization of Fe, Cu and other metals) as well as the deposition patterns of these trace species and reactive nitrogen., (Copyright 2024 Ifayoyinsola Ibikunle, Andreas Beyersdorf, Pedro Campuzano-Jost, Chelsea Corr, John D. Crounse, Jack Dibb, Glenn Diskin, Greg Huey, Jose-Luis Jimenez, Michelle J. Kim, Benjamin A. Nault, Eric Scheuer, Alex Teng, Paul O. Wennberg, Bruce Anderson, James Crawford, Rodney Weber, Athanasios Nenes. License: This work is licensed under a Creative Commons Attribution 4.0 International License.)

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global-scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole-to-pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7% to 48% of the top of the atmosphere clear-sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance., (©2020. The Authors.)