Search for: All records

Wildfires have become larger and more frequent because of climate change, increasing their impact on air pollution. Air quality forecasts and climate models do not currently account for changes in the composition of wildfire emissions during the commonly observed progression from more flaming to smoldering combustion. Laboratory measurements have consistently shown decreased nitrogen dioxide (NO₂) relative to carbon monoxide (CO) over time, as they transitioned from more flaming to smoldering combustion, while formaldehyde (HCHO) relative to CO remained constant. Here, we show how daily ratios between column densities of NO₂versus those of CO and HCHO versus CO from the Tropospheric Monitoring Instrument (TROPOMI) changed for large wildfires in the Western United States. TROPOMI‐derived emission ratios were lower than those from the laboratory. We discuss reasons for the discrepancies, including how representative laboratory burns are of wildfires, the effect of aerosols on trace gas retrievals, and atmospheric chemistry in smoke plumes.

 

Iodine is an atmospheric trace element emitted from oceans that efficiently destroys ozone (O 3 ). Low O 3 in airborne dust layers is frequently observed but poorly understood. We show that dust is a source of gas-phase iodine, indicated by aircraft observations of iodine monoxide (IO) radicals inside lofted dust layers from the Atacama and Sechura Deserts that are up to a factor of 10 enhanced over background. Gas-phase iodine photochemistry, commensurate with observed IO, is needed to explain the low O 3 inside these dust layers (below 15 ppbv; up to 75% depleted). The added dust iodine can explain decreases in O 3 of 8% regionally and affects surface air quality. Our data suggest that iodate reduction to form volatile iodine species is a missing process in the geochemical iodine cycle and presents an unrecognized aeolian source of iodine. Atmospheric iodine has tripled since 1950 and affects ozone layer recovery and particle formation. 

Oceanic emissions of iodine destroy ozone, modify oxidative capacity, and can form new particles in the troposphere. However, the impact of iodine in the stratosphere is highly uncertain due to the lack of previous quantitative measurements. Here, we report quantitative measurements of iodine monoxide radicals and particulate iodine (I_y,part) from aircraft in the stratosphere. These measurements support that 0.77 ± 0.10 parts per trillion by volume (pptv) total inorganic iodine (I_y) is injected to the stratosphere. These high I_yamounts are indicative of active iodine recycling on ice in the upper troposphere (UT), support the upper end of recent I_yestimates (0 to 0.8 pptv) by the World Meteorological Organization, and are incompatible with zero stratospheric iodine injection. Gas-phase iodine (I_y,gas) in the UT (0.67 ± 0.09 pptv) converts to I_y,partsharply near the tropopause. In the stratosphere, IO radicals remain detectable (0.06 ± 0.03 pptv), indicating persistent I_y,partrecycling back to I_y,gasas a result of active multiphase chemistry. At the observed levels, iodine is responsible for 32% of the halogen-induced ozone loss (bromine 40%, chlorine 28%), due primarily to previously unconsidered heterogeneous chemistry. Anthropogenic (pollution) ozone has increased iodine emissions since preindustrial times (ca. factor of 3 since 1950) and could be partly responsible for the continued decrease of ozone in the lower stratosphere. Increasing iodine emissions have implications for ozone radiative forcing and possibly new particle formation near the tropopause.

 

We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O₃) concentrations, except in polar regions where the model now underestimates O₃ concentrations. Halogen chemistry reduces the global tropospheric O₃ burden by 18.6 %, with the O₃ lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  10⁶ molecules cm⁻³ are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH₄ lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH₄ by Cl is small (∼  2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼  15–27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.