Global tropospheric halogen (Cl, Br, I) chemistry and its impact on oxidants

We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global atmospheric chemical transport model and apply it to investigate halogen radical cycling and implications for tropospheric oxidants. Improved representation of HOBr heterogeneous chemistry and its pH dependence in our simulation leads to less efficient recycling and mobilization of bromine radicals and enables the model to include mechanistic sea salt aerosol debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixing ratio is 0.19 ppt (parts per trillion), lower than previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison to surface and aircraft observations in marine air, which are often near or below the detection limit. The model underestimates the daytime measurements of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very large missing primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a global mean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled global mean tropospheric concentration of Cl atoms is 630 cm−3, contributing 0.8 % of the global oxidation of methane, 14 % of ethane, 8 % of propane, and 7 % of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11 %, NOx by 6 %, and OH by 4 %. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozone simulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere.

Iron-Catalyzed C(sp3)–H Alkylation through Ligand-to-Metal Charge Transfer

We report the FeCl3-catalyzed alkylation of nonactivated C(sp3)–H bonds. Photoinduced ligand-to-metal charge transfer at the iron center generates chlorine radicals that then preferentially abstract hydrogen atoms from electron-rich C(sp3)–H bonds distal to electron-withdrawing functional groups. The resultant alkyl radicals are trapped by electron-deficient olefins, and the catalytic cycle is closed by Fe(II) recombination and protodemetalation.

Global tropospheric halogen (Cl, Br, I) chemistry and its impact on oxidants

We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global atmospheric chemical transport model and apply it to investigate halogen radical cycling and implications for tropospheric oxidants. Improved representation of HOBr heterogeneous chemistry and its pH dependence in our simulation leads to less effective recycling and mobilization of bromine radicals, and enables the model to include mechanistic sea salt aerosol debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixing ratio is 0.19 ppt, lower than previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison to surface and aircraft observations in marine air, which are often near or below the detection limit. The model underestimates the daytime measurements of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very large missing primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a global mean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled global mean tropospheric concentration of Cl atoms is 630 cm−3, contributing 0.8 % of the global oxidation of methane, 14 % of ethane, 8 % of propane, and 7 % of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11 %, NOx by 6 %, and OH by 4 %. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozone simulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere.

Urban inland wintertime N₂O₅ and ClNO₂ influenced by snow-covered ground, air turbulence, and precipitation

The atmospheric multiphase reaction of dinitrogen pentoxide (N2O5) with chloride-containing aerosol particles produces nitryl chloride (ClNO2), which has been observed across the globe. The photolysis of ClNO2 produces chlorine radicals and nitrogen dioxide (NO2), which alter pollutant fates and air quality. However, the effects of local meteorology on near-surface ClNO2 production are not yet well understood, as most observational and modeling studies focus on periods of clear conditions. During a field campaign in Kalamazoo, Michigan from January–February 2018, N2O5 and ClNO2 were measured using chemical ionization mass spectrometry, with simultaneous measurements of atmospheric particulate matter and meteorological parameters. We examine the impacts of atmospheric turbulence, precipitation (snow, rain) and fog, and ground cover (snow-covered and bare ground) on the abundances of ClNO2 and N2O5. N2O5 mole ratios were lowest during periods of lower turbulence and were not statistically significantly different between snow-covered and bare ground. In contrast, ClNO2 mole ratios were highest, on average, over snow-covered ground, due to saline snowpack ClNO2 production. Both N2O5 and ClNO2 mole ratios were lowest, on average, during rainfall and fog because of scavenging, with N2O5 scavenging by fog droplets likely contributing to observed increased particulate nitrate concentrations. These observations, specifically those during active precipitation and with snow-covered ground, highlight important processes, including N2O5 and ClNO2 wet scavenging, fog nitrate production, and snowpack ClNO2 production, that govern the variability in observed atmospheric chlorine and nitrogen chemistry and are missed when considering only clear conditions.

Night-time NO emissions suppress large amounts of chlorine radical formation in Delhi

<p>Concentrations of particulate chloride can reach values over 100 µg m<sup>-3</sup> during the winter in Delhi, which is among the highest levels recorded across the globe. In the presence of nitrogen pentoxide (N<sub>2</sub>O<sub>5</sub>), this chloride can form nitryl chloride (ClNO<sub>2</sub>), which photolyses in sunlight and releases the Cl radical. The Cl radical is an incredibly potent oxidant, reacting with some volatile organic compounds (VOCs) orders of magnitude faster than more common oxidants such as OH. Chlorine would therefore be expected to play a significant role in the oxidation of VOCs in Delhi.</p><p>We carried out intensive measurements of particle- and gas-phase physical and chemical properties during a field campaign in Delhi in early 2019. A suite of instruments was used, including a chemical ionisation mass spectrometer fitted with a filter inlet for aerosols and gases (FIGAERO-CIMS) to measure N<sub>2</sub>O<sub>5</sub> and ClNO<sub>2</sub>. Despite N<sub>2</sub>O<sub>5</sub> typically being considered a night-time compound, we in fact observed the highest concentrations in the mid-afternoon and almost none at all during the night. Further analysis indicated that the ubiquity of night-time NO<sub>x</sub> emissions in the city suppresses night-time production of N<sub>2</sub>O<sub>5</sub>. As a result of this unusual diurnal pattern, high concentrations of ClNO<sub>2</sub> are unable to form overnight. The morning peak in ClNO2 and the subsequent release of chlorine radicals, while large compared with some other urban environments, is therefore much smaller than might have been expected given the high levels of particulate chloride.</p><p>In this presentation, I will discuss our observations and the impact of this unusual diurnal pattern on the atmospheric chemical profile. Impacts include a shift of even typically ‘night-time’ oxidation patterns to the day and a likely overall reduced oxidative capacity in the city’s atmosphere. Our results indicate that a reduction in chlorine emissions must be considered in tandem with NO<sub>x</sub> emission reductions in efforts to reduce Delhi’s pollution.</p>