Detection of iodine monoxide in the tropical free troposphere

Abstract

Atmospheric iodine monoxide (IO) is a radical that catalytically destroys heat trapping ozone and reacts further to form aerosols. Here, we report the detection of IO in the tropical free troposphere (FT). We present vertical profiles from airborne measurements over the Pacific Ocean that show significant IO up to 9.5 km altitude and locate, on average, two-thirds of the total column above the marine boundary layer. IO was observed in both recent deep convective outflow and aged free tropospheric air, suggesting a widespread abundance in the FT over tropical oceans. Our vertical profile measurements imply that most of the IO signal detected by satellites over tropical oceans could originate in the FT, which has implications for our understanding of iodine sources. Surprisingly, the IO concentration remains elevated in a transition layer that is decoupled from the ocean surface. This elevated concentration aloft is difficult to reconcile with our current understanding of iodine lifetimes and may indicate heterogeneous recycling of iodine from aerosols back to the gas phase. Chemical model simulations reveal that the iodine-induced ozone loss occurs mostly above the marine boundary layer (34%), in the transition layer (40%) and FT (26%) and accounts for up to 20% of the overall tropospheric ozone loss rate in the upper FT. Our results suggest that the halogen-driven ozone loss in the FT is currently underestimated. More research is needed to quantify the widespread impact that iodine species of marine origin have on free tropospheric composition, chemistry, and climate.atmospheric chemistry | oxidative capacity | halogens | heterogeneous chemistry | air-sea exchange R eactive iodine impacts atmospheric chemistry in several ways. Catalytic reaction cycles involving iodine atoms and iodine monoxide (IO; I x = I + IO) destroy tropospheric ozone, which is a primary source for OH radicals (1, 2). Halogens contribute ∼45% of the ozone loss in the remote tropical marine boundary layer (MBL) (2-4). IO further affects the oxidative capacity of the atmosphere through fast reactions with HO 2 radicals and the resulting changes in HO x (HO x = OH + HO 2 ) (1, 2). Iodine also affects NO x (NO x = NO + NO 2 ) by oxidizing NO to NO 2 (1-4). Additionally, bromine atom recycling by IO increases ozone destruction and mercury oxidation rates in the MBL, resulting in higher mercury deposition rates to ecosystems and increased availability to the food chain (2, 5, 6). Finally, in coastal regions, the formation of ultrafine aerosol particles from iodine oxides can be a source of cloud condensation nuclei that can modify Earth's albedo and thus, the radiative budget of the atmosphere (2, 7).Oceans are the main source of iodine to the atmosphere. Most current knowledge of iodine sources and chemistry is based on measurements in the MBL (3,(8)(9)(10)(11)(12)(13). IO observations at coastal MBL sites primarily link iodine sources to macroalgae (8-10). More recent studies have measured IO at open ocean sites (3, 11-13), suggesting that ther...

Impacts of bromine and iodine chemistry on tropospheric OH and HO<sub>2</sub>: comparing observations with box and global model perspectives

“…Vertically resolved airborne measurements of IO radicals in the free troposphere over the Pacific Ocean have also demonstrated a role for iodine chemistry throughout the free troposphere, with IO observed at a mixing ratio of ∼ 0.1 ppt in the free troposphere and found to be present in both recent deep convective outflow and aged free-tropospheric air (Dix et al, 2013). Model simulations to investigate iodine-driven ozone destruction throughout the troposphere indicated that only 34 % of the total iodine-driven ozone loss occurs within the marine boundary layer, with 40 % occurring in a transition layer and 26 % in the free troposphere (Dix et al, 2013).…”

“…Observations of BrO and IO radicals within the MBL have demonstrated widespread impacts on atmospheric composition and chemistry (Alicke et al, 1999;Sander et al, 2003;Leser et al, 2003;Saiz-Lopez and Plane, 2004;SaizLopez et al, 2004SaizLopez et al, , 2006Peters et al, 2005;Whalley et al, 2007;Mahajan et al, 2010a;Commane et al, 2011;Dix et al, 2013;Gomez Martin et al, 2013;Le Breton et al, 2017), including significant effects on HO x concentrations and on the HO 2 : OH ratio in coastal and marine locations (Bloss et al, 2005a(Bloss et al, , 2010Sommariva et al, 2006;Kanaya et al, 2007;Whalley et al, 2010).…”

Injection of iodine to the stratosphere

“…The CU AMAX-DOAS instrument, its data analysis, and profile retrieval have been described in detail elsewhere Dix et al, 2013;Volkamer et al, 2015]. Briefly, the instrument collects spectra of scattered sunlight from well-defined lines of sight above, below, and forward of the aircraft.…”

The Heidelberg Airborne Imaging DOAS Instrument (HAIDI) – a novel imaging DOAS device for 2-D and 3-D imaging of trace gases and aerosols

“…Meas. Tech., 7, 3459-3485, 2014 www Baidar et al, 2013;Dix et al, 2013). This is usually done in a two-stage process using inverse modeling of the atmospheric radiative transfer (e.g., Sinreich et al, 2005;Wagner et al, 2004;Frieß et al, 2006;Irie et al, 2008;Clémer et al, 2010;Wagner et al, 2011).…”