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Abstract. We introduce a custom-built, field-deployable, atmospheric pressure Ion-Molecule reaction Region (IMR) for use with Chemical Ionization Mass Spectrometry (CIMS), the so-called “t-IMR”. The design is described in quantitative detail and shows significant mitigation in potential measurement interference compared to other IMR configurations, particularly those operating at low pressure. The relatively large laminar flow and inner chamber diameter reduce the probability of sampled air and ion clusters interacting with the Teflon surfaces of the IMR before being detected by Time-of-Flight (ToF) mass spectrometry. This also leads to a substantial reduction in wall effects and artificial background signals for even low volatility organic products, as demonstrated in alpha-pinene ozonolysis experiments. An electric field is induced perpendicular to flow in the t-IMR to accelerate ions and consequent charged sample clusters to the MS interface. The strength of this field is modulated and optimized to simultaneously maximize total ion flux and instrument sensitivity. A sheath flow apparatus is introduced to provide small N2 flows counter to ion and sample cluster flow into the MS to reduce the likelihood of particulate buildup and clogs to the pinhole separating the IMR from the MS, ensuring uninterrupted sampling for extended periods of time. Finally, we demonstrate the capability of the t-IMR to be deployed to the field to measure down to sub-ppt level ambient concentrations of important trace gases including reactive bromine at a ground-based site in the marine boundary layer. We find that the t-IMR design considerably reduces artificial signals from surface contact and wall effects, and improves detection of very low concentration species in the ambient atmosphere, with respective limits of detection of 0.06, 0.05, and 2 ppt for Br2, HOBr, and HNO3. The relationship between instrument sensitivity and IMR water vapor concentrations is also explored and applied to in-field measurements. 

Abstract. Aerosol interactions with clouds represent a significant uncertainty in our understanding of the Earth system. Deep convective clouds may respond to aerosol perturbations in several ways that have proven difficult to elucidate with observations. Here, we leverage the two busiest maritime shipping lanes in the world, which emit aerosol particles and their precursors into an otherwise relatively clean tropical marine boundary layer, to make headway on the influence of aerosol on deep convective clouds. The recent 7-fold change in allowable fuel sulfur by the International Maritime Organization allows us to test the sensitivity of the lightning to changes in ship plume aerosol number-size distributions. We find that, across a range of atmospheric thermodynamic conditions, the previously documented enhancement of lightning over the shipping lanes has fallen by over 40 %. The enhancement is therefore at least partially aerosol-mediated, a conclusion that is supported by observations of droplet number at cloud base, which show a similar decline over the shipping lane. These results have fundamental implications for our understanding of aerosol–cloud interactions, suggesting that deep convective clouds are impacted by the aerosol number distribution in the remote marine environment. 

The first 5 hours of aging in biomass burning plumes can strongly affect ozone photochemistry. We examine how volatile organic compounds (VOCs), nitrogen oxides, and nitrous acid influence hydroxyl radical, ozone, and peroxyacetyl nitrate (PAN) based on three aircraft campaigns over the United States. Our analyses reveal variable, highly elevated hydroxyl radical concentrations in the first 2 hours, resulting in evident fire-to-fire variability in VOCs oxidation and in ozone and PAN production. About 40 to 70% of the variability is explained by chemical aging. Ozone production in the plumes is usually VOC-limited for the first 2 hours and then nitrogen oxide limited downwind. Box model results for hydroxyl radical, ozone, and most VOCs, using the full, explicit Master Chemical Mechanism (MCM) mechanism, suggest no major gaps in the current best knowledge of gas-phase chemistry. However, the MCM sometimes overestimates PAN due to underestimated nitrogen oxide sinks. GEOS-Chem, a widely used chemical transport model with a reduced mechanism, generally underperforms because of incomplete VOC representation. We identify these critical pathways to guide future model development. 

Abstract. Tropospheric reactive iodine influences the oxidizing capacity of the atmosphere and serves as an important source of ultra-fine particles. However, the paucity of observations of gas-phase and aerosol iodine, combined with incomplete understanding and representation of iodine chemistry in models, leads to substantial uncertainties in understanding iodine abundance, speciation, and impacts. Motivated by known gaps in previous modeling studies, we introduced speciated aerosol iodine and aerosol iodide recycling to the global chemical transport model, GEOS-Chem. Modeled aerosol iodine is speciated into fine and coarse mode soluble organic iodine (SOI), iodate, and iodide. Aerosol iodide is recycled into the gas phase via heterogeneous chemistry involving halogen nitrates and hypohalous acids to form I2, ICl, and IBr, which represents an additional source of gas-phase iodine to the atmosphere. Iodide dehalogenation doubles the tropospheric burden of reactive iodine (Iy) while reducing model-measurement bias for IO and aerosol iodine. The rate of aerosol iodine conversion to Iy is more than twice as fast as the combined rates of inorganic ocean emissions and the photolysis of organic iodine gases, suggesting that aerosols are important in mediating the abundance and lifetime of tropospheric Iy. The incorporation of SOI and iodate into the model prevents iodide dehalogenation by partitioning iodide into less reactive reservoirs, which has a stabilizing effect for reactive iodine chemistry. These findings have implications for reactive halogen abundances and global oxidant budgets in the troposphere. 

Abstract Exceptionally high‐energy lightning strokes >10⁶ J (X1000 stronger than average) in the very low‐frequency band between 5 and 18 kHz, also known as superbolts (SB), occur mostly during winter over the North‐East Atlantic, the Mediterranean Sea, and over the Altiplano in South America. Here we compare the World‐Wide Lightning Location Network database with meteorological and aerosol data to examine the causes of lightning stroke high energies. Our results show that the energy per stroke increases sharply as the distance between the cloud'scharging zone(where the cloud electrification occurs) and the surface decreases. Since thecharging zoneoccurs above the 0°C isotherm, this distance is shorter when the 0°C isotherm is closer to the surface. This occurs either due to cold air mass over the ocean during winter or high surface altitude in the Altiplano during summer thunderstorms. Stroke energy decreases with the warm phase of the cloud, as proxied by the cloud base temperature, and increases with a more developed cloud, as proxied by the cloud top temperature, but to a much lesser extent than the distance between the surface and 0°C isotherm. Aerosols play no significant role. It is hypothesized that a shorter distance between thecharging zoneand the ground represents less electrical resistance that allows stronger discharge currents. 

Abstract Soils are a major source of nitrogen oxides, which in the atmosphere help govern its oxidative capacity. Thus the response of soil nitric oxide (NO) emissions to forcings such as warming or forest loss has a meaningful impact on global atmospheric chemistry. We find that the soil emission rate of NO in Amazonia from a common inventory is biased low by at least an order of magnitude in comparison to tower‐based observations. Accounting for this regional bias decreases the modeled global methane lifetime by 1.4%–2.6%. In comparison, a fully deforested Amazonia, representing a 37% decrease in global emissions of isoprene, decreases methane lifetime by at most 4.6%, highlighting the sensitive response of oxidation rates to changes in emissions of NO compared to those of terpenes. Our results demonstrate that improving our understanding of soil NO emissions will yield a more accurate representation of atmospheric oxidative capacity. 

Atmospheric oxidation of monoterpenes (C₁₀H₁₆) contributes to ambient particle number and mass concentrations due, in part, to the resulting peroxy radicals undergoing auto-oxidation to low-volatility highly oxygenated molecules (HOMs). 

Abstract The known effects of thermodynamics and aerosols can well explain the thunderstorm activity over land, but fail over oceans. Here, tracking the full lifecycle of tropical deep convective cloud clusters shows that adding fine aerosols significantly increases the lightning density for a given rainfall amount over both ocean and land. In contrast, adding coarse sea salt (dry radius > 1 μm), known as sea spray, weakens the cloud vigor and lightning by producing fewer but larger cloud drops, which accelerate warm rain at the expense of mixed-phase precipitation. Adding coarse sea spray can reduce the lightning by 90% regardless of fine aerosol loading. These findings reconcile long outstanding questions about the differences between continental and marine thunderstorms, and help to understand lightning and underlying aerosol-cloud-precipitation interaction mechanisms and their climatic effects. 

Rapid production of formic acid in biomass burning smoke is not captured by the Master Chemical Mechanism (MCM) nor simplified GEOS-Chem chemistry, likely due to missing secondary chemical production.