Particulate Oxalate-To-Sulfate Ratio as an Aqueous Processing Marker: Similarity Across Field Campaigns and Limitations.

Leveraging aerosol data from multiple airborne and surface-based field campaigns encompassing diverse environmental conditions, we calculate statistics of the oxalate-sulfate mass ratio (median: 0.0217; 95% confidence interval: 0.0154-0.0296; R = 0.76; N = 2,948). Ground-based measurements of the oxalate-sulfate ratio fall within our 95% confidence interval, suggesting the range is robust within the mixed layer for the submicrometer particle size range. We demonstrate that dust and biomass burning emissions can separately bias this ratio toward higher values by at least one order of magnitude. In the absence of these confounding factors, the 95% confidence interval of the ratio may be used to estimate the relative extent of aqueous processing by comparing inferred oxalate concentrations between air masses, with the assumption that sulfate primarily originates from aqueous processing.

Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO x.

The concentration of nitrogen oxides (NO x) plays a central role in controlling air quality. On a global scale, the primary sink of NO x is oxidation to form HNO3. Gas-phase HNO3 photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO3 undergoes photolysis 10-300 times more rapidly than gas-phase HNO3. We present here constraints on the rate of particle-phase HNO3 photolysis based on observations of NO x and HNO3 collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO x to HNO3 ratios. Negligible to moderate enhancements of the HNO3 photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO3 photolysis would not significantly affect the HNO3 budget but could help explain observations of HONO and NO x in highly aged air.

Enhanced aqueous formation and neutralization of fine atmospheric particles driven by extreme cold.

The prevailing view for aqueous secondary aerosol formation is that it occurs in clouds and fogs, owing to the large liquid water content compared to minute levels in fine particles. Our research indicates that this view may need reevaluation due to enhancements in aqueous reactions in highly concentrated small particles. Here, we show that low temperature can play a role through a unique effect on particle pH that can substantially modulate secondary aerosol formation. Marked increases in hydroxymethanesulfonate observed under extreme cold in Fairbanks, Alaska, demonstrate the effect. These findings provide insight on aqueous chemistry in fine particles under cold conditions expanding possible regions of secondary aerosol formation that are pH dependent beyond conditions of high liquid water.

Overview of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) Field Experiment.

The Alaskan Layered Pollution And Chemical Analysis (ALPACA) field experiment was a collaborative study designed to improve understanding of pollution sources and chemical processes during winter (cold climate and low-photochemical activity), to investigate indoor pollution, and to study dispersion of pollution as affected by frequent temperature inversions. A number of the research goals were motivated by questions raised by residents of Fairbanks, Alaska, where the study was held. This paper describes the measurement strategies and the conditions encountered during the January and February 2022 field experiment, and reports early examples of how the measurements addressed research goals, particularly those of interest to the residents. Outdoor air measurements showed high concentrations of particulate matter and pollutant gases including volatile organic carbon species. During pollution events, low winds and extremely stable atmospheric conditions trapped pollution below 73 m, an extremely shallow vertical scale. Tethered-balloon-based measurements intercepted plumes aloft, which were associated with power plant point sources through transport modeling. Because cold climate residents spend much of their time indoors, the study included an indoor air quality component, where measurements were made inside and outside a house to study infiltration and indoor sources. In the absence of indoor activities such as cooking and/or heating with a pellet stove, indoor particulate matter concentrations were lower than outdoors; however, cooking and pellet stove burns often caused higher indoor particulate matter concentrations than outdoors. The mass-normalized particulate matter oxidative potential, a health-relevant property measured here by the reactivity with dithiothreiol, of indoor particles varied by source, with cooking particles having less oxidative potential per mass than pellet stove particles.

Beyond the Ångström Exponent: Probing Additional Information in Spectral Curvature and Variability of In Situ Aerosol Hyperspectral (0.3-0.7 µm) Optical Properties.

Ångström exponents (α) allow reconstruction of aerosol optical spectra over a broad range of wavelengths from measurements at two or more wavelengths. Hyperspectral measurements of atmospheric aerosols provide opportunities to probe measured spectra for information inaccessible from only a few wavelengths. Four sets of hyperspectral in situ aerosol optical coefficients (aerosol-phase total extinction, σ ext, and absorption, σ abs; liquid-phase soluble absorption from methanol, σ MeOH-abs, and water, σ DI-abs, extracts) were measured from biomass burning aerosols (BBAs). Hyperspectral single scattering albedo (ω), calculated from σ ext and σ abs, provide spectral resolution over a wide spectral range rare for this optical parameter. Observed spectral shifts between σ abs and σ MeOH-abs/σ DI-abs argue in favor of measuring σ abs rather than reconstructing it from liquid extracts. Logarithmically transformed spectra exhibited curvature better fit by second-order polynomials than linear α. Mapping second order fit coefficients (a 1, a 2) revealed samples from a given fire tended to cluster together, that is, aerosol spectra from a given fire were similar to each other and somewhat distinct from others. Separation in (a 1, a 2) space for spectra with the same α suggest additional information in second-order parameterization absent from the linear fit. Spectral features found in the fit residuals indicate more information in the measured spectra than captured by the fits. Above-detection σ MeOH-abs at 0.7 µm suggests assuming all absorption at long visible wavelengths is BC to partition absorption between BC and brown carbon (BrC) overestimates BC and underestimates BrC across the spectral range. Hyperspectral measurements may eventually discriminate BBA among fires in different ecosystems under variable conditions.

HCOOH in the remote atmosphere: Constraints from Atmospheric Tomography (ATom) airborne observations.

Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with chemical transport model (GEOS-Chem CTM) and back trajectory analyses to provide the first global in-situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing non-fire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation HCOOH is not consistently depleted in the remote marine boundary layer. Over fifty fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.

The Korea-United States Air Quality (KORUS-AQ) field study.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May-June 2016. The effort was jointly sponsored by the National Institute of Environmental Research of South Korea and the National Aeronautics and Space Administration of the United States. KORUS-AQ offered an unprecedented, multi-perspective view of air quality conditions in South Korea by employing observations from three aircraft, an extensive ground-based network, and three ships along with an array of air quality forecast models. Information gathered during the study is contributing to an improved understanding of the factors controlling air quality in South Korea. The study also provided a valuable test bed for future air quality-observing strategies involving geostationary satellite instruments being launched by both countries to examine air quality throughout the day over Asia and North America. This article presents details on the KORUS-AQ observational assets, study execution, data products, and air quality conditions observed during the study. High-level findings from companion papers in this special issue are also summarized and discussed in relation to the factors controlling fine particle and ozone pollution, current emissions and source apportionment, and expectations for the role of satellite observations in the future. Resulting policy recommendations and advice regarding plans going forward are summarized. These results provide an important update to early feedback previously provided in a Rapid Science Synthesis Report produced for South Korean policy makers in 2017 and form the basis for the Final Science Synthesis Report delivered in 2020.

Why do Models Overestimate Surface Ozone in the Southeastern United States?

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx ≡ NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30-60%, dependent on the assumption of the contribution by soil NOx emissions. Upper tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft, and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 8±13 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Light extinction by fine atmospheric particles in the White Mountains region of New Hampshire and its relationship to air mass transport.

Chemical, optical, and physical measurements of fine aerosols (aerodynamic diameter < or = 2.5 microm) have been performed at a mountaintop location adjacent to the White Mountain National Forest in northern NH, USA. A 1-month long sampling campaign was conducted at Cranmore Mountain during spring 2000. We report on the apportionment of light extinction by fine aerosols into its major chemical components, and relationships between variations in aerosol parameters and changes in air mass origin. Filter-based, 24-h integrated samples were collected and analyzed for major inorganic ions, as well as organic (OC), elemental (EC), and total carbon. Light scattering and light absorption coefficients were measured at 5-min intervals using an integrating nephelometer and a light absorption photometer. Fine particle number density was measured with a condensation particle counter. Air mass origins and transport patterns were investigated through the use of 3-day backward trajectories and a synoptic climate classification system. Two distinct transport regimes were observed: (1) flow from the north/northeast (N/NE) occurred during 9 out of 18 sample-days; and (2) flow from the west/southwest (W/SW) occurred 8 out of 18 sample-days. All measured and derived aerosol and meteorological parameters were separated into two categories based on these different flow scenarios. During W/SW flow, higher values of aerosol chemical concentration, absorption and scattering coefficients, number density, and haziness were observed compared to N/NE flow. The highest level of haziness was associated with the climate classification Frontal Atlantic Return, which brought polluted air into the region from the mid-Atlantic corridor. Fine particle mass scattering efficiencies of (NH4)2SO4 and OC were 5.35 +/- 0.42 m2 g(-1) and 1.56 +/- 0.40 m2 g(-1), respectively, when transport was out of the N/NE. When transport was from the W/SW the values were 4.94 +/- 0.68 m2 g(-1) for (NH4)2SO4 and 2.18 +/- 0.91 m2 g(-1) for OC. EC mass absorption efficiency when transport was from the N/NE was 9.66 +/- 1.06 m2 g(-1) and 10.80 +/- 1.76 m2 g(-1) when transport was from the W/SW. Results from this work can be used to predict visual air quality in the White Mountain National Forest based on a forecasted synoptic climate classification and its associated visibility.