Refractory black carbon (rBC) is a primary aerosol species, produced through incomplete combustion, that absorbs sunlight and contributes to positive radiative forcing. The overall climate effect of rBC depends on its spatial distribution and atmospheric lifetime, both of which are impacted by the efficiency with which rBC is transported or removed by convective systems. These processes are poorly constrained by observations. It is especially interesting to investigate rBC transport efficiency through the Asian Summer Monsoon (ASM) since this meteorological pattern delivers vast quantities of boundary layer air from Asia, where rBC emissions are high, to the upper troposphere/lower stratosphere (UT/LS) where the lifetime of rBC is expected to be long. Here we present in-situ observations of rBC made during the Asian Summer Monsoon Chemistry and Climate Impact Project (ACCLIP) of summer, 2022. We use observed relationships between rBC and CO in ASM outflow to show that rBC is removed nearly completely (>98%) from uplifted air, and that rBC concentrations in ASM outflow are statistically indistinguishable from the UT/LS background. We compare observed rBC and CO concentrations to those expected based on two chemical transport models and find that the models reproduce CO to within a factor of 2 at all altitudes while rBC is overpredicted by a factor of 20-100 at altitudes associated with ASM outflow. We find that the rBC particles in recently convected air have thinner coatings than those found in the UTLS background, suggesting non-zero transport of rBC number that is not relevant to concentration.

Heterogeneous chemical cycles of pyrogenic nitrogen and halides influence tropospheric ozone and affect the stratosphere during extreme pyrocumulonimbus (PyroCB) events. We report field-derived N2O5 uptake coefficients, γ(N2O5), and ClNO2 yields, φ(ClNO2), from two aircraft campaigns observing fresh smoke in the lower and mid troposphere and processed/aged smoke in the upper troposphere and lower stratosphere (UTLS). Derived φ(ClNO2) varied across the full 0–1 range but was typically < 0.5 and smallest in a PyroCB (< 0.05). Derived γ(N2O5) was low in agricultural smoke (0.2–3.6 ×10-3), extremely low in mid-tropospheric wildfire smoke (0.1 × 10-3), but larger in PyroCB processed smoke (0.7–5.0 × 10–3). Aged BB aerosol in the UTLS had a higher median γ(N2O5) of 17 × 10–3 that increased with sulfate and liquid water, but that was nevertheless 1–2 orders of magnitude lower than values for aqueous sulfuric aerosol used in stratospheric models.

The influence of clouds on photochemistry remains a significant uncertainty in global chemistry models. Variability in cloud fraction, morphology, phase and optical properties provides significant challenges to models with horizontal resolutions that far exceed the scale of most clouds. Measured photolysis frequencies derived from the Charged-coupled device Actinic Flux Spectroradiometers (CAFS) on board the NASA DC-8 during the Atmospheric Tomography (ATom) mission in 2016 provide an extensive set of statistics on how clouds alter the photolytic rates throughout remote ocean basins. Here we focus on north and tropical pacific transects during the first deployment (ATom-1) in August 2016 including regular profiles through cloudy, partly cloudy and clear conditions. Nine global chemistry–climate or –transport models provide similar statistics on J-values for regional domains encompassing the measured flight path. The statistical picture of the impact of clouds on J-values emerges through the distribution of the ratio of the cloud influenced models and measurement to corresponding cloud free model runs (J-cloudy/J-clear). The models all reproduce general patterns of enhancement above and shading below cloud, but diverge in distribution patterns and clear sky prevalence.

Wildfire emissions affect downwind air quality and human health. Predictions of these impacts using models are limited by uncertainties in emissions and chemical evolution of smoke plumes. Using high-time-resolution aircraft measurements, we illustrate spatial variations that can exist horizontally and vertically within a plume due to differences in the photochemical environment. Dilution-corrected mixing ratio gradients were observed for reactive compounds and their oxidation products, such as nitrous acid, catechol, and ozone, likely due to faster photochemistry in optically-thinner plume edges relative to darker plume cores. Mixing ratio gradients in midday plumes, driven by jHONO gradients, are often steepest in the freshest transects, and become flatter with chemical aging. Gradients in plumes emitted close to sunset are characterized by titration of O3 in the plume and little to no gradient formation. We show how gradients can lead to underestimated emission ratios for reactive compounds and overestimated emission ratios for oxidation products.

Wildland fires involve complicated processes that are challenging to represent in chemical transport models. Recent airborne measurements reveal remarkable chemical tomography in fresh wildland fire plumes, which remain yet to be fully explored using models. Here we present a high-resolution large eddy simulation (LES) model coupled to chemistry to study the chemical evolution in fresh wildland fire plume. The model is configured for a large fire heavily sampled during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) field campaign, and a variety of airborne measurements are used to evaluate the chemical heterogeneity revealed by the model. We show that the model captures the observed cross-transect variations of a number of compounds quite well, including ozone (O3), nitrous acid (HONO), and peroxyacetyl nitrate (PAN), etc. The combined observational and modeling results suggest that the top and edges of fresh plume drive the photochemistry, while dark chemistry is also present but in the lower part of the plume. The model spatial resolution is shown to be very important as it may shift the chemical regime, leading to biases in O3 and NOx chemistry. Based on findings in this work, we speculate that the impact of small fires on air quality may be largely underestimated in models with coarse spatial resolutions.

Reactive chlorine and bromine species emitted from snow and aerosols can significantly alter the oxidative capacity of the polar boundary layer. However, halogen production mechanisms from snow remain highly uncertain, making it difficult for most models to include descriptions of halogen snow emissions and to understand the impact on atmospheric chemistry. We investigate the influence of Arctic halogen emissions from snow on boundary layer oxidation processes using a one-dimensional atmospheric chemistry and transport model (PACT-1D). To understand the combined impact of snow emissions and boundary layer dynamics on atmospheric chemistry, we model \ch{Cl2} and \ch{Br2} primary emissions from snow and include heterogeneous recycling of halogens on both snow and aerosols. We focus on a two-day case study from the 2009 Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) campaign at Utqia\.gvik, Alaska. The model reproduces both the diurnal cycle and high quantity of \ch{Cl2} observed, along with the measured concentrations of \ch{Br2}, \ch{BrO}, and \ch{HOBr}. Due to the combined effects of emissions, recycling, vertical mixing, and atmospheric chemistry, reactive chlorine is confined to the lowest 15 m of the atmosphere, while bromine impacts chemistry up to the boundary layer height. Upon including halogen emissions and recycling, the concentration of \ch{HO_x} (\ch{HO_x} = \ch{OH}+\ch{HO2}) at the surface increases by as much as a factor of 30 at mid-day. The change in \ch{HO_x} due to halogen chemistry, as well as chlorine atoms derived from snow emissions, significantly reduce volatile organic compound (VOC) lifetimes within a shallow layer near the surface.