Abstract. Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2–O2 collision complexes (O4) were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2–0.55 pptv IO and 32–36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and aircraft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° W). At 14.5 km, 5–10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12–20 degrees of freedom (DoF) and up to 500 m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 × 1013 molec cm−2 (RF12) and at least 0.5 × 1013 molec cm−2 (RF17, 0–10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 × 1012 molec cm−2 (RF12) and 2.5 × 1012 molec cm−2 (RF17) and glyoxal VCDs of 2.6 × 1014 molec cm−2 (RF12) and 2.7 × 1014 molec cm−2 (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1–0.2 pptv; glyoxal: 52 ± 5%, 3–20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.

Abstract. New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale. In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute > 20% of glyoxal-SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. Results from the continental US simulation reveal the much larger potential to form glyoxal-SOA over the eastern continental US. Interestingly, the low concentrations of glyoxal-SOA over the western continental US are not due to the lack of a potential to form glyoxal-SOA here. Rather these small glyoxal-SOA concentrations reflect dry conditions and high salt concentrations, and the potential to form SOA mass here will strongly depend on the water associated with particles.

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O 3 ), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O 3 and methane (CH 4 ) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O 3 . The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Br y ), or model overestimated Br y wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Br y source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O 3 needs to be considered when estimating past and future ozone radiative effects.atmospheric chemistry | oxidative capacity | halogens | heterogeneous chemistry | UTLS T ropospheric halogens catalytically destroy O 3 (1−3), oxidize atmospheric mercury (4, 5), and modify the oxidative capacity of the atmosphere (6). O 3 is a potent greenhouse gas (7), and an important precursor for hydroxyl (OH) radicals (6, 8) that determine the lifetime of CH 4 another important greenhouse gas. About 75% of the global tropospheric O 3 (3) and CH 4 (8) loss occurs at tropical latitudes, where O 3 radiative forcing is also most sensitive to changes in O 3 (9). Halogen chemistry is thought responsible for ∼10% of the tropical tropospheric O 3 column loss (3), yet atmospheric models remain essentially untested due to the lack of vertically resolved halogen radical measurements in the tropical troposphere. Column observations from ground and satellites (10−18), including measurements in the tropics (14, 16−18), point to the existence of a-possibly ubiquitous-tropospheric BrO background concentration of ∼1−2 parts per trillion by volume (pptv) that currently remains unexplained by models, and would be of significant relevance for O 3 , OH, and mercury oxidation (2−6, 8). Recently, corroborating evidence is emerging from a measurement in the tropical free troposphere (FT) (19). IO has been detected in the Northern Hemisphere (NH) FT (19−21), but there is currently no vertically resolved measurement of BrO or IO in the ...

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 (Iy,part) from aircraft in the stratosphere. These measurements support that 0.77 ± 0.10 parts per trillion by volume (pptv) total inorganic iodine (Iy) is injected to the stratosphere. These high Iy amounts are indicative of active iodine recycling on ice in the upper troposphere (UT), support the upper end of recent Iy estimates (0 to 0.8 pptv) by the World Meteorological Organization, and are incompatible with zero stratospheric iodine injection. Gas-phase iodine (Iy,gas) in the UT (0.67 ± 0.09 pptv) converts to Iy,part sharply near the tropopause. In the stratosphere, IO radicals remain detectable (0.06 ± 0.03 pptv), indicating persistent Iy,part recycling back to Iy,gas as 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.

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...

The University of Colorado Airborne Multi-Axis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument uses solar stray light to detect and quantify multiple trace gases, including nitrogen dioxide (NO₂), glyoxal (CHOCHO), formaldehyde (HCHO), water vapor (H₂O), nitrous acid (HONO), iodine monoxide (IO), bromine monoxide (BrO), and oxygen dimers (O₄) at multiple wavelengths (absorption bands at 360, 477, 577, 632 nm) simultaneously in the open atmosphere. The instrument is unique as it (1) features a motion compensation system that decouples the telescope field of view from aircraft movements in real time (<0.35° accuracy), and (2) includes measurements of solar stray light photons from nadir, zenith, and multiple elevation angles forward and below the plane by the same spectrometer/detector system. Sets of solar stray light spectra collected from nadir to zenith scans provide some vertical profile information within 2 km above and below the aircraft altitude, and the vertical column density (VCD) below the aircraft is measured in nadir view. Maximum information about vertical profiles is derived simultaneously for trace gas concentrations and aerosol extinction coefficients over similar spatial scales and with a vertical resolution of typically 250 m during aircraft ascent/descent.

The instrument is described, and data from flights over California during the CalNex (California Research at the Nexus of Air Quality and Climate Change) and CARES (Carbonaceous Aerosols and Radiative Effects Study) air quality field campaigns is presented. Horizontal distributions of NO₂ VCD (below the aircraft) maps are sampled with typically 1 km resolution, and show good agreement with two ground-based MAX-DOAS instruments (slope = 0.95 ± 0.09, R² = 0.86). As a case study vertical profiles of NO₂, CHOCHO, HCHO, and H₂O concentrations and aerosol extinction coefficients, ε, at 477 nm calculated from O₄ measurements from a low approach at Brackett airfield inside the South Coast Air Basin (SCAB) are presented. These profiles contain ~12 degrees of freedom (DOF) over a 3.5 km altitude range, an independent information approximately every 250 m. The boundary layer NO₂ concentration, and the integral aerosol extinction over height (aerosol optical depth, AOD) agrees well with nearby ground-based in situ NO₂ measurement, and AERONET station. The detection limits of NO₂, CHOCHO, HCHO, H₂O₄₄₂, ϵ₃₆₀, ϵ₄₇₇ for 30 s integration time spectra recorded forward of the plane are 5 ppt, 3 ppt, 100 ppt, 42 ppm, 0.004 km⁻¹, 0.002 km⁻¹ in the free troposphere (FT), and 30 ppt, 16 ppt, 540 ppt, 252 ppm, 0.012 km⁻¹, 0.006 km⁻¹ inside the boundary layer (BL), respectively. Mobile column observations of trace gases and aerosols are complimentary to in situ observations, and help bridge the spatial...

The Convective Transport of Active Species in the Tropics (CONTRAST) experiment was conducted from Guam (13.5° N, 144.8° E) during January-February 2014. Using the NSF/NCAR Gulfstream V research aircraft, the experiment investigated the photochemical environment over the tropical western Pacific (TWP) warm pool, a region of massive deep convection and the major pathway for air to enter the stratosphere during Northern Hemisphere (NH) winter. The new observations provide a wealth of information for quantifying the influence of convection on the vertical distributions of active species. The airborne in situ measurements up to 15 km altitude fill a significant gap by characterizing the abundance and altitude variation of a wide suite of trace gases. These measurements, together with observations of dynamical and microphysical parameters, provide significant new data for constraining and evaluating global chemistry climate models. Measurements include precursor and product gas species of reactive halogen compounds that impact ozone in the upper troposphere/lower stratosphere. High accuracy, in-situ measurements of ozone obtained during CONTRAST quantify ozone concentration profiles in the UT, where previous observations from balloon-borne ozonesondes were often near or below the limit of detection. CONTRAST was one of the three coordinated experiments to observe the TWP during January-February 2014. Together, CONTRAST, ATTREX and CAST, using complementary capabilities of the three aircraft platforms as well as ground-based instrumentation, provide a comprehensive quantification of the regional distribution and vertical structure of natural and pollutant trace gases in the TWP during NH winter, from the oceanic boundary to the lower stratosphere.

We developed a new nitrogen oxide (NO x ) and carbon monoxide (CO) emission inventory for the Los Angeles-South Coast Air Basin (SoCAB) expanding the Fuel-based Inventory for motor-Vehicle Emissions and applied it in regional chemical transport modeling focused on the California Nexus of Air Quality and Climate Change (CalNex) 2010 field campaign. The weekday NO x emission over the SoCAB in 2010 is 620 t d À1 , while the weekend emission is 410 t d À1 . The NO x emission decrease on weekends is caused by reduced diesel truck activities. Weekday and weekend CO emissions over this region are similar: 2340 and 2180 t d À1 , respectively. Previous studies reported large discrepancies between the airborne observations of NO x and CO mixing ratios and the model simulations for CalNex based on the available bottom-up emission inventories. Utilizing the newly developed emission inventory in this study, the simulated NO x and CO mixing ratios agree with the observations from the airborne and the ground-based in situ and remote sensing instruments during the field study. The simulations also reproduce the weekly cycles of these chemical species. Both the observations and the model simulations indicate that decreased NO x on weekends leads to enhanced photochemistry and increase of O 3 and O x (=O 3 + NO 2 ) in the basin. The emission inventory developed in this study can be extended to different years and other urban regions in the U.S. to study the long-term trends in O 3 and its precursors with regional chemical transport models. precursors in the SoCAB may provide comprehensive knowledge of the evolving chemistry and transport KIM ET AL.