Jack E. Dibb

Nitric oxide (NO) in the remote marine atmosphere is underestimated by chemistry‐climate models. We explore the potential oceanic emissions of NO and its impacts using a global chemistry‐climate model with a newly developed oceanic NO emission inventory, considering the abiotic photochemical production of NO in the seawater. The results are evaluated using global observations from the NASA Atmospheric Tomography Mission (ATom). We propose that the photochemical production of NO from the photolysis of dissolved inorganic nitrite and nitrate in the surface seawater could lead to an oceanic NO _x source of ∼3 Tg N per year, which could explain the missing NO in the remote marine boundary layer. This potential oceanic NO source leads to a small but potentially widespread increase in surface ozone and hydroxyl radicals in the remote marine environment, altering our understanding of the role the remote marine atmosphere plays in the global system. Further, the role of the photolysis of nitrate aerosols may be overestimated in recent studies and warrants further investigation.

Nitric oxide (NO) in the remote marine atmosphere is underestimated by chemistry-climate models. We explore the potential oceanic emissions of NO and its impacts using a global chemistry-climate model with a newly developed oceanic NO emission inventory, considering the abiotic photochemical production of NO in the seawater. The results are evaluated using global observations from the NASA Atmospheric Tomography Mission (ATom). We show that the photochemical production of NO in the surface seawater could lead to an oceanic NOx source of ~3 Tg N per year, which could explain the missing NO in the remote marine boundary layer. Further, the role of the photolysis of nitrate aerosols may be overestimated in recent studies. This potential oceanic NO source leads to an increase in surface ozone and hydroxyl radicals in the remote marine environment, altering our understanding of the role the remote marine atmosphere plays in the global system.

The role of persistent snow covers in wintertime urban air pollution chemistry remains largely unexplored. The interactions of chemistry and transport processes are complex and the physicochemical structure of snow is uncertain. For instance, it is still unclear to what extent uptake and chemistry occur on ice, a disordered interface layer on the ice, or in brine pockets at grain boundaries. We use a process-based one-dimensional coupled atmosphere–snow model to gain initial insight into the interaction of snow with high concentrations of SO₂ and NO₂ in polluted wintertime Fairbanks, AK, USA. Snow can act as a reservoir for both gases, allowing for fluxes into the snow (during polluted periods) and out of the snow (during cleaner periods). The geometrical distribution of liquid on ice is varied to approximate the conceptual difference between the disordered ice interface and brine in localized pockets. The behavior of SO₂ is more sensitive to these differences, mostly due to its greater stickiness on ice and solubility in water compared to NO₂, which remains mostly in the snow interstitial air. Liquid-phase chemical processing of both compounds is almost insensitive to the distribution of the liquid phase in the snow and mostly determined by the volume of liquid. Our study highlights the value of comprehensive process-based modeling to further our understanding of snow chemistry. Our model platform can serve as a tool to inform and support future research efforts on improving our understanding of the liquid content of snow, chemical processing on ice surfaces, and, in general, the influence of snow on atmospheric chemistry.

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.

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.

Snowpack emissions are recognized as an important source of gas‐phase reactive bromine in the Arctic and are necessary to explain ozone depletion events in spring caused by the catalytic destruction of ozone by halogen radicals. Quantifying bromine emissions from snowpack is essential for interpretation of ice‐core bromine. We present ice‐core bromine records since the pre‐industrial (1750 CE) from six Arctic locations and examine potential post‐depositional loss of snowpack bromine using a global chemical transport model. Trend analysis of the ice‐core records shows that only the high‐latitude coastal Akademii Nauk (AN) ice core from the Russian Arctic preserves significant trends since pre‐industrial times that are consistent with trends in sea ice extent and anthropogenic emissions from source regions. Model simulations suggest that recycling of reactive bromine on the snow skin layer (top 1 mm) results in 9–17% loss of deposited bromine across all six ice‐core locations. Reactive bromine production from below the snow skin layer and within the snow photic zone is potentially more important, but the magnitude of this source is uncertain. Model simulations suggest that the AN core is most likely to preserve an atmospheric signal compared to five Greenland ice cores due to its high latitude location combined with a relatively high snow accumulation rate. Understanding the sources and amount of photochemically reactive snow bromide in the snow photic zone throughout the sunlit period in the high Arctic is essential for interpreting ice‐core bromine, and warrants further lab studies and field observations at inland locations.

Agricultural and prescribed burning activities emit large amounts of trace gases and aerosols on regional to global scales. We present a compilation of emission factors (EFs) and emission ratios from the eastern portion of the Fire Influence on Regional to Global Environments and Air Quality (FIREX‐AQ) campaign in 2019 in the United States, which sampled burning of crop residues and other prescribed fire fuels. FIREX‐AQ provided comprehensive chemical characterization of 53 crop residue and 22 prescribed fires. Crop residues burned at different modified combustion efficiencies (MCE), with corn residue burning at higher MCE than other fuel types. Prescribed fires burned at lower MCE (<0.90) which is typical, while grasslands burned at lower MCE (0.90) than normally observed due to moist, green, growing season fuels. Most non‐methane volatile organic compounds (NMVOCs) were significantly anticorrelated with MCE except for ethanol and NMVOCs that were measured with less certainty. We identified 23 species where crop residue fires differed by more than 50% from prescribed fires at the same MCE. Crop residue EFs were greater for species related to agricultural chemical use and fuel composition as well as oxygenated NMVOCs possibly due to the presence of metals such as potassium. Prescribed EFs were greater for monoterpenes (5×). FIREX‐AQ crop residue average EFs generally agreed with the previous agricultural fire study in the US but had large disagreements with global compilations. FIREX‐AQ observations show the importance of regionally‐specific and fuel‐specific EFs as first steps to reduce uncertainty in modeling the air quality impacts of fire emissions.

The NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality (FIREX‐AQ) experiment was a multi‐agency, inter‐disciplinary research effort to: (a) obtain detailed measurements of trace gas and aerosol emissions from wildfires and prescribed fires using aircraft, satellites and ground‐based instruments, (b) make extensive suborbital remote sensing measurements of fire dynamics, (c) assess local, regional, and global modeling of fires, and (d) strengthen connections to observables on the ground such as fuels and fuel consumption and satellite products such as burned area and fire radiative power. From Boise, ID western wildfires were studied with the NASA DC‐8 and two NOAA Twin Otter aircraft. The high‐altitude NASA ER‐2 was deployed from Palmdale, CA to observe some of these fires in conjunction with satellite overpasses and the other aircraft. Further research was conducted on three mobile laboratories and ground sites, and 17 different modeling forecast and analyses products for fire, fuels and air quality and climate implications. From Salina, KS the DC‐8 investigated 87 smaller fires in the Southeast with remote and in‐situ data collection. Sampling by all platforms was designed to measure emissions of trace gases and aerosols with multiple transects to capture the chemical transformation of these emissions and perform remote sensing observations of fire and smoke plumes under day and night conditions. The emissions were linked to fuels consumed and fire radiative power using orbital and suborbital remote sensing observations collected during overflights of the fires and smoke plumes and ground sampling of fuels.

Nitrate aerosol plays an important role in affecting regional air quality as well as Earth's climate. However, it is not well represented or even neglected in many global climate models. In this study, we couple the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) module with the four‐mode version of the Modal Aerosol Module (MAM4) in DOE's Energy Exascale Earth System Model version 2 (E3SMv2) to simulate nitrate aerosol and its radiative effects. We find that nitrate aerosol simulated by E3SMv2‐MAM4‐MOSAIC is sensitive to the treatment of gaseous HNO₃ transfer to/from interstitial particles related to accommodation coefficients of HNO₃ () on dust and non‐dust particles. We compare three different treatments of HNO₃ transfer: (a) a treatment (MTC_SLOW) that uses a low in the mass transfer coefficient (MTC) calculation; (b) a dust‐weighted MTC treatment (MTC_WGT) that uses a high on non‐dust particles; and (c) a dust‐weighted MTC treatment that also splits coarse mode aerosols into the coarse dust and sea salt sub‐modes in MOSAIC (MTC_SPLC). MTC_WGT and MTC_SPLC increase the global annual mean (2005–2014) nitrate burden from 0.096 (MTC_SLOW) to 0.237 and 0.185 Tg N, respectively, mostly in the coarse mode. MTC_WGT and MTC_SPLC also produce stronger nitrate direct radiative forcing (−0.048 and −0.051 W m⁻², respectively) and indirect forcing (−0.33 and −0.35 W m⁻², respectively) than MTC_SLOW (−0.021 and −0.24 W m⁻²). MTC_WGT and MTC_SPLC improve nitrate surface concentrations over remote oceans based on limited observations and vertical profiles of nitrate concentrations against aircraft measurements below 400 hPa.

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 (a₁, a₂) 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 (a₁, a₂) 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.