Search

We have analyzed TROPOMI NO2 data over the Copperbelt, a mining region which straddles the Democratic Republic of Congo and Zambia. While the ore mined there is primarily copper, this region is currently of great strategic interest because it is the world’s biggest producer of cobalt. Demand for cobalt, key to clean energy technologies (e.g., electric car batteries), is increasing worldwide and cobalt control is becoming a matter of national and global energy security. The impact of increasing mining-related activities on local air quality (high NOx is harmful to respiratory systems and crops) is unknown.TROPOMI, onboard ESA’s Sentinel-5 Precursor, is an imaging spectrometer in a sun-synchronous orbit at 824 km of altitude which measures concentrations of relevant atmospheric species (trace gases, aerosols, cloud) with quasi-global daily coverage and at high spatial resolution (~ 3.5 x 5.5 km2 in the case of NO2).We show that mining-related activities (such as extraction, smelting, and refining) can be remotely detected based on their TROPOMI NO2 signature, even in the presence of high background NO2 from biomass burning. Annual TROPOMI NO2 means for 2019, 2020, and 2021 show local enrichments consistent with point sources spatially collocated with both mines and large cities where mining-related activities take place. We have identified temporal trends in NO2 from these point sources and, when possible, we have compared those to production figures from the mining companies involved. We have quantified top-down annual NOx (NO+NO2) emissions for each of the point sources identified by applying the divergence method to the TROPOMI retrievals, using ancillary ERA5 meteorological data. Because in situ NOx measurements are not available, we contrast our emission results with emissions from the CAMS-GLOB-ANT v5.1 inventory.Our results show that NOx emissions from mining-related activities can be quantified remotely, which is important in the absence of local air quality monitoring. They also demonstrate that NO2 trend analysis can be a good indicator of mine production. This is particularly relevant for non-publicly traded mining companies, which are not required to publish their production figures. Lack of TROPOMI SO2 enhancements colocated with our NO2 point sources is consistent with SO2 capture and transformation into H2SO4, which is then used in mining-related processes or commercialized.

The production of crude oil and natural gas is associated with emissions of air pollutants, such as nitrogen oxides (NOx = NO + NO2) and volatile organic compounds, which are precursors for the formation of ground-level ozone. Knowledge of these emissions is critical to the understanding and mitigation of local air quality. NOx emissions from oil and gas production activities are not well described in commonly used emission inventories, and discrepancies of several factors have been found in the past. Here we present an easy and computationally efficient method to quantify NOx emissions from satellite NO2 observations that can be applied to evaluate common emission inventories and provide timely input for chemistry transport models. Using NO2 columns from the TROPOspheric Monitoring Instrument (TROPOMI), we calculated annually averaged NOx emissions from the divergence of NO2 column fluxes for six oil and gas production regions in the United States. Derived NOx emissions for the years 2018 to 2020 range between 4.8 and 81.1 t/day, and observed trends over time are consistent with changes in industrial activity. To evaluate the method, we compared our results with the fuel-based oil and gas NOx inventory (FOG) and performed sensitivity studies using model output from the Weather Research Forecasting model with Chemistry (WRF-Chem). We found that annually averaged NOx emissions from oil and gas production activities can in most cases be calculated within an uncertainty of 50%, while simultaneously derived emission maps show the spatial distribution of NOx emissions with a high level of detail. For future use, this method can easily be applied globally.

We present an updated fuel-based oil and gas (FOG) inventory with estimates of nitrogen oxide (NOx) emissions from oil and natural gas production in the contiguous US (CONUS). We compare the FOG inventory with aircraft-derived ("top-down") emissions for NOx over footprints that account for ∼25% of US oil and natural gas production. Across CONUS, we find that the bottom-up FOG inventory combined with other anthropogenic emissions is on average within ∼10% of top-down aircraft-derived NOx emissions. We also find good agreement in the trends of NOx from drilling- and production-phase activities, as inferred by satellites and in the bottom-up inventory. Leveraging tracer-tracer relationships derived from aircraft observations, methane (CH4) and non-methane volatile organic compound (NMVOC) emissions have been added to the inventory. Our total CONUS emission estimates for 2015 of oil and natural gas are 0.45 ± 0.14 Tg NOx/yr, 15.2 ± 3.0 Tg CH4/yr, and 5.7 ± 1.7 Tg NMVOC/yr. Compared to the US National Emissions Inventory and Greenhouse Gas Inventory, FOG NOx emissions are ∼40% lower, while inferred CH4 and NMVOC emissions are up to a factor of ∼2 higher. This suggests that NMVOC/NOx emissions from oil and gas basins are ∼3 times higher than current estimates and will likely affect how air quality models represent ozone formation downwind of oil and gas fields.

The Permian basin is the largest oil and gas production region in the U.S.A. Because of the non-conventional exploration of the basin, the region is covered with hundreds of small production facilities. Observations from the surface and from aircrafts have shown that there are continuous emissions of amongst others CH4 and NOx. Although they come from the same facilities, the sources of CH4 and NOx differ: NOx is predominantly produced by engines and generators used for drilling and to run the facilities, whereas CH4 is produced from planned and accidental releases from the production, storage and transportation of oil and gas. The TROPOMI satellite instrument allows continuous monitoring of CH4 and NO2 and has confirmed the large contribution of the oil and gas industry to the CH4 and NO2 concentrations in the Permian basin.Using the divergence method, we have derived emissions for both CH4 and NO2 from the TROPOMI data, with a high spatial resolution of better than 5x5 km2 for NO2 and better than 10x10 km2 for CH4. The results show that the Permian CH4 emissions in the basin are not dominated by a few large emission events, but are also impacted by many smaller releases across the basin. The basin can therefore be seen as a large area source that varies in space and time. Mitigation of these releases is challenging, rather than solving a few large leaks in a few facilities, the equipment and management of many small sites have to be improved to reduce emissions.In this contribution we present results of the emission retrievals. Using CAMS model data, we show the potential of the divergence method and its sensitivity. Analyses will be presented of the TROPOMI derived emissions, showing the spatial variability of CH4 and NOx emissions over the region and their relation to the underlying oil and gas production and drilling activities.

The COVID‐19 outbreak in 2020 prompted strict lockdowns, reduced human activity, and reduced emissions of air pollutants. We measured volatile organic compounds (VOCs) using a proton‐transfer‐reaction mass spectrometry instrument in Changzhou, China from 8 January through 27 March, including periods of pre‐lockdown, strict measures (level 1), and more relaxed measures (level 2). We analyze the data using positive matrix factorization and resolve four factors: textile industrial emissions (62 ± 10% average reduction during level 1 relative to pre‐lockdown), pharmaceutical industrial emissions (40 ± 20%), traffic emissions (71 ± 10%), and secondary chemistry (20 ± 20%). The two industrial sources showed different responses to the lockdown, so emissions from the industrial sector should not be scaled uniformly. The quantified changes in VOCs due to the lockdowns constrain emission inventories and inform chemistry‐transport models, particularly for sectors where activity data are sparse, as the effects of lockdowns on air quality are explored., Key Points We measured and quantified volatile organic compounds (VOCs) in Changzhou, China during the COVID‐19 lockdownsTraffic‐related VOC emissions were reduced by 70%, which agrees with reductions in traffic countsTextile and pharmaceutical industry VOC emissions responded differently, so industrial emissions should not be scaled uniformly

The development of horizontal drilling and hydraulic fracturing has led to a steep increase in the U.S. production of natural gas and crude oil from shale formations since the mid 2000s. Associated with this industrial activity are emissions of ground-level ozone precursors such as nitrogen oxides (NOx). Satellite data are important in this context, because surface measurements are limited or non-existent in rural regions, where most U.S. oil and gas production operations take place. Here we use TROPOMI NO2 observations to study NOx emissions coming from oil and natural gas production sites. Applying the divergence method we quantify basin wide emissions from well pad fields and aim to push spatial and temporal resolution of this technique. The divergence was method introduced by Beirle et al. (Science Advances 2019) to quantify point source emissions. It relies on calculating the divergence of the NO2 flux to derive NOx sources and estimating the NO2 lifetime to quantify sinks. Our analysis will include an assessment of different methods to constrain the NO2 lifetime, which becomes particularly important when applying this method to larger areas. Further we will compare our results with bottom-up derived emissions. Here we use the Fuel-based Oil & Gas (FOG) inventory that calculates NOx emissions based on fuel consumption. Initial results show good agreement for the Permian Basin (NM, TX) and we will expand our analysis to other U.S. basins.

Desert dust as a source of iron and other micronutrients is recognized to fertilize oceans, but little attention has been paid to dust as a source of iodine. Empirical observations find iodate on dust measured during ship cruises downwind of the Sahara desert. However, it remains unclear whether iodine in dust is the result of marine iodine uptake on dust during transport in the marine boundary layer, or whether such iodine accumulates over geological time scales, and is emitted together with dust. Significant enhancements of iodine have been observed in Sahara dust events in form of methyl iodide (CH3I) and iodine monoxide (IO) radicals, but atmospheric models currently do not consider dust as a source of iodine. Furthermore, dust plumes are often accompanied by significant ozone loss, which is commonly attributed to reactive uptake of O3 and other odd oxygen species (i.e., N2O5, HNO3) on dust surfaces. However, laboratory experiments struggle to reproduce the large reactive uptake coefficients needed to explain field observations, and do not consider iodine chemistry. We present evidence that dust induced "mini ozone holes" in the remote (Southern Hemisphere) lower free troposphere west of South America (TORERO field campaign) are largely the result of gas-phase iodine chemistry in otherwise unpolluted (low NOx) dust layers that originate from the Atacama and Sechura Deserts. Ozone concentrations inside these elevated dust layers are often 10-20 ppb, and as low as 3 ppb, and influence entrainment of low ozone air from aloft into the marine boundary layer. Ozone depletion is found to be widespread, extending up to 6km altitude, and thousands of kilometers along the coast. Elevated IO radical concentrations inside decoupled dust layers are higher than in the marine boundary layer, and serve as a source of iodine, and vigorous ozone sink following entrainment to the marine boundary layer. The implications for our perception of iodine sources, surface air quality, oxidative capacity, and climate are briefly discussed.

Production of oil and natural gas in North America is at an all-time high due to the development and use of horizontal drilling and hydraulic fracturing. Methane emissions associated with this industrial activity are a concern because of the contribution to climate radiative forcing. We present new measurements from the space-based TROPOspheric Monitoring Instrument (TROPOMI) launched in 2017 that show methane enhancements over production regions in the United States. Using methane and NO2 column measurements from the new TROPOMI instrument, we show that emissions from oil and gas production in the Uintah and Permian Basins can be observed in the data from individual overpasses. This is a vast improvement over measurements from previous satellite instruments, which typically needed to be averaged over a year or more to quantify trends and regional enhancements in methane emissions. In the Uintah Basin in Utah, TROPOMI methane columns correlated with in-situ measurements, and the highest columns were observed over the deepest parts of the basin, consistent with the accumulation of emissions underneath inversions. In the Permian Basin in Texas and New Mexico, methane columns showed maxima over regions with the highest natural gas production and were correlated with nitrogen-dioxide columns at a ratio that is consistent with results from in-situ airborne measurements. The improved detail provided by TROPOMI will likely enable the timely monitoring from space of methane and NO2 emissions associated with regular oil and natural gas production.

U.S. oil and natural gas production volumes have grown by up to 100% in key production areas between January 2017 and August 2019. Here we show that recent trends are visible from space and can be attributed to drilling, production, and gas flaring activities. By using oil and gas activity data as predictors in a multivariate regression to satellite measurements of tropospheric NO2 columns, observed changes in NO2 over time could be attributed to NOx emissions associated with drilling, production and gas flaring for three select regions: the Permian, Bakken, and Eagle Ford basins. We find that drilling had been the dominant NOx source contributing around 80% before the downturn in drilling activity in 2015. Thereafter, NOx contributions from drilling activities and combined production and flaring activities are similar. Comparison of our top-down source attribution with a bottom-up fuel-based oil and gas NOx emission inventory shows agreement within error margins.

7 pags., 4 figs., 2 tabs., 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., The GV aircraft was operated by the NCAR’s Earth Observing Laboratory’s (EOL) Research Aviation Facility. The involvement of the NSF-sponsored Lower Atmospheric Observing Facilities, managed and operated by NCAR/EOL, is acknowledged. R.V. acknowledges funding by NSF Awards AGS-1104104 (TORERO), AGS-1261740 (CONTRAST), and AGS-1620530. ATom-1 and 2 were supported by NASA’s Earth System Science Pathfinder Program EVS-2 funding (Grants NNX15AH33A, NNX15AJ23G, and 80NSSC19K0124). This study has received funding from the European Research Council Executive Agency under the European Union’s Horizon 2020 Research and Innovation Programme (Project ERC2016-COG 726349 CLIMAHAL).

30 pags., 11 figs., 5 tabs., We quantify the stratospheric injection of brominated very short-lived substances (VSLS) based on aircraft observations acquired in winter 2014 above the Tropical Western Pacific during the CONvective TRansport of Active Species in the Tropics (CONTRAST) and the Airborne Tropical TRopopause EXperiment (ATTREX) campaigns. The overall contribution of VSLS to stratospheric bromine was determined to be 5.0 ± 2.1 ppt, in agreement with the 5 ± 3 ppt estimate provided in the 2014 World Meteorological Organization (WMO) Ozone Assessment report (WMO 2014), but with lower uncertainty. Measurements of organic bromine compounds, including VSLS, were analyzed using CFC-11 as a reference stratospheric tracer. From this analysis, 2.9 ± 0.6 ppt of bromine enters the stratosphere via organic source gas injection of VSLS. This value is two times the mean bromine content of VSLS measured at the tropical tropopause, for regions outside of the Tropical Western Pacific, summarized in WMO 2014. A photochemical box model, constrained to CONTRAST observations, was used to estimate inorganic bromine from measurements of BrO collected by two instruments. The analysis indicates that 2.1 ± 2.1 ppt of bromine enters the stratosphere via inorganic product gas injection. We also examine the representation of brominated VSLS within 14 global models that participated in the Chemistry-Climate Model Initiative. The representation of stratospheric bromine in these models generally lies within the range of our empirical estimate. Models that include explicit representations of VSLS compare better with bromine observations in the lower stratosphere than models that utilize longer-lived chemicals as a surrogate for VSLS., The CONTRAST field deployment was supported by the U.S. NSF, and the ATTREX field deployment was supported by the National Aeronautics and Space Administration (NASA). P. A. W., R. J. S., T. P. C., J. M. N., and D. C. A. received support from NSF, NASA Atmospheric Composition Modeling and Analysis Program (ACMAP), and the NASA Modeling, Analysis, and Prediction (MAP). D. C. A. also received support from the NASA Upper Atmospheric Research Program. J. M. N. was also supported by the NASA Postdoctoral Program at the NASA Goddard Space Flight Center, administered by Universities Space Research Association under contract with NASA. R. V. acknowledges funding from NSF awards AGS‐1261740 and AGS‐1620530. CONTRAST data are publicly available at “http://data.eol.ucar.edu/master_list/?project= CONTRAST.” ATTREX data are publicly available at “https://espoarchive.nasa.gov/archive/browse/attrex/id4/GHawk.” The National Center for Environmental Prediction (NCEP) meteorological data are available at “https://doi.org/10.5065/D6M043C6.” CCMI outputs from CESM1‐WACCM and CESM1‐CAM4Chem are archived by the National Center for Atmospheric Research (NCAR) at “www.earthsystemgrid.org,” and NCAR is sponsored by NSF. CCMI output from the EMAC‐L90MA‐SD simulation is available at “https://doi.org/10.5281/zenodo.1204495.” All other CCMI simulations are archived by the British Atmospheric Data Centre at “http://badc.nerc.ac.uk/”. Output from CAM‐chem‐SD is available as “NCAR/ACD CAMChem 1 Degree Forecast” at “http://catalog.eol.ucar.edu/contrast/model/CAMChem_NCAR_1deg/.” WACCM and CAM‐Chem are components of the Community Earth System Model (CESM), which is also supported by NSF. Computing resources were provided by NCAR's Climate Simulation Laboratory, sponsored by NSF and other agencies. This research was enabled by the computational and storage resources of NCAR's Computational and Information System Laboratory (CISL). R. S. and K. A. S., with ACCESS‐CCM, acknowledge support from Australian Research Council's Centre of Excellence for Climate System Science (CE110001028), the Australian Government's National Computational Merit Allocation Scheme (q90), and Australian Antarctic science grant program (FoRCES 4012). CCSRNIES research was supported by the Environment Research and Technology Development Fund (2‐1303 and 2‐1709) of the Ministry of the Environment, Japan, and computations were performed on NEC‐SX9/A(ECO) computers at the CGER, NIES. The EMAC simulations have been performed at the German Climate Computing Centre (DKRZ) through support from the Bundesministerium für Bildung und Forschung (BMBF). DKRZ and its scientific steering committee are gratefully acknowledged for providing the HPC and data archiving resources for the consortial project ESCiMo (Earth System Chemistry integrated Modelling). The TOMCAT modeling was supported by NERC NCAS and the SISLAC project (NE/R001782/1), and the simulations were performed on the Archer and Leeds HPC Systems.

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Bry) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January–February 2014). The observed BrO and inferred Bry profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBry). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1.6×1013 molec cm−2, compared to model predictions of 0.9×1013 molec cm−2 in GEOS-Chem (CBry but no SSA source), 0.4×1013 molec cm−2 in CAM-Chem (CBry and SSA), and 2.1×1013 molec cm−2 in GEOS-Chem (CBry and SSA). Neither global model fully captures the C-shape of the Bry profile. A local Bry maximum of 3.6 ppt (2.9–4.4 ppt; 95 % confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Bry decreases from the convective TTL to the aged TTL. Analysis of gas-phase Bry against multiple tracers (CFC-11, H2O ∕ O3 ratio, and potential temperature) reveals a Bry minimum of 2.7 ppt (2.3–3.1 ppt; 95 % CI) in the aged TTL, which agrees closely with a stratospheric injection of 2.6 ± 0.6 ppt of inorganic Bry (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.6–7.0 ppt; 95 % CI) in the stratospheric "middleworld" and 6.9 ppt (6.5–7.3 ppt; 95 % CI) in the stratospheric "overworld". The local Bry minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a more complex partitioning of gas-phase and aerosol Bry species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Bry) are needed to explain the gas-phase Bry budget in the upper free troposphere and TTL. They are also consistent with observations of significant bromide in Upper Troposphere–Lower Stratosphere aerosols. The total Bry budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Bry species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Bry in the upper FT, (2) test Bry partitioning, and possibly explain the gas-phase Bry minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Bry to the lower stratosphere.

Formaldehyde (HCHO) directly affects the atmospheric oxidative capacity through its effects on HOx. In remote marine environments, such as the Tropical Western Pacific (TWP), it is particularly important to understand the processes controlling the abundance of HCHO because model output from these regions is used to correct satellite retrievals of HCHO. Here, we have used observations from the CONTRAST field campaign, conducted during January and February 2014, to evaluate our understanding of the processes controlling the distribution of HCHO in the TWP as well as its representation in chemical transport/climate models. Observed HCHO mixing ratios varied from ~500 pptv near the surface to ~75 pptv in the upper troposphere. Recent convective transport of near surface HCHO and its precursors, acetaldehyde and possibly methyl hydroperoxide, increased upper tropospheric HCHO mixing ratios by ~33% (22 pptv); this air contained roughly 60% less NO than more aged air. Output from the CAM-Chem chemistry transport model (2014 meteorology) as well as nine chemistry climate models from the Chemistry-Climate Model Initiative (free-running meteorology) are found to uniformly underestimate HCHO columns derived from in situ observations by between 4 and 50%. This underestimate of HCHO likely results from a near factor of two underestimate of NO in most models, which strongly suggests errors in NOx emissions inventories and/or in the model chemical mechanisms. Likewise, the lack of oceanic acetaldehyde emissions and potential errors in the model acetaldehyde chemistry lead to additional underestimates in modeled HCHO of up to 75 pptv (~15%) in the lower troposphere.

Мета роботи складалася у виявленні фізичних та функціональних причин травматизму та ефективності застосування комплексної методики відновлення баскетболісток після травм опорно-рухового апарата. Матеріал і методи: В даному дослідженні прийняли участь 21 баскетболістка, з них 4 майстра спорту, 9 кандидатів в майстри спорту, 8 спортсменок 1 розряду. Методи дослідження: педагогічний метод суб'єктивної оцінки ваги навантаження й інтенсивності болючих відчуттів, фізіологічні методи дослідження (тест максимальної працездатності, ортостатична проба, визначення показників серцевого ритму, визначення показників роботи дихальної та серцево-судинної систем), методи педагогічного тестування, метод педагогічного експерименту, методи математичної статистики. Результати. Встановлено, що травматичність баскетболісток підвищується по мірі підвищення їх вагозростових показників. Це пов’язано з біомеханічними, функціональними, психофізіологічними, ортостатичними та вегето-судинними особливостями людей різного зросту, а також - вимогами гри, які підвищуються по мірі підвищення вагозростових показників спортсменок, що заставляє центрових та крайніх нападаючих постійно працювати на межі своїх можливостей і приводить до травматизму. Висновки. Застосування ефективних методів індивідуалізації навчально-тренувального процесу, одним з яких може служити метод контролю навантажень по суб’єктивним відчуттям, а також – ефективних методів профілактики та лікування травм.

The elevated deposition of atmospheric mercury over the southeastern United States is currently not well understood. Here we measure partial columns and vertical profiles of bromine monoxide (BrO) radicals, a key component of mercury oxidation chemistry, to better understand the processes and altitudes at which mercury is being oxidized in the atmosphere. We use data from a ground-based MAX-DOAS instrument located at a coastal site ∼ 1 km from the Gulf of Mexico in Gulf Breeze, FL, where we had previously detected tropospheric BrO (Coburn et al., 2011). Our profile retrieval assimilates information about stratospheric BrO from the WACCM chemical transport model (CTM), and uses only measurements at moderately low solar zenith angles (SZAs) to estimate the BrO slant column density contained in the reference spectrum (SCDRef). The approach has 2.6 degrees of freedom, and avoids spectroscopic complications that arise at high SZA; knowledge about SCDRef further helps to maximize sensitivity in the free troposphere (FT). A cloud-free case study day with low aerosol load (9 April 2010) provided optimal conditions for distinguishing marine boundary layer (MBL: 0–1 km) and free-tropospheric (FT: 1–15 km) BrO from the ground. The average daytime tropospheric BrO vertical column density (VCD) of ∼ 2.3 × 1013 molec cm−2 (SZA 5 molec cm−2 s−1 for bromine, while the contribution from ozone (O3) is 0.8 × 105 molec cm−2 s−1. Chlorine-induced oxidation is estimated to add 2), and to a lesser extent also HO2 radicals. Using a 3-D CTM, we find that surface GOM variations are also typical of other days, and are mainly derived from the FT. Bromine chemistry is active in the FT over Gulf Breeze, where it forms water-soluble GOM that is subsequently available for wet scavenging by thunderstorms or transport to the boundary layer.

A DOAS (Differential Optical Absorption Spectroscopy) instrument was implemented and operated onboard a long-distance passenger aircraft within the framework of the CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container). The instrument was designed to keep weight, size and power consumption low and to comply with civil aviation regulations. It records spectra of scattered light from three viewing directions (nadir, 10° above and below horizon) using a miniaturized telescope system. The telescopes are integrated in the main pylon of the inlet system which is mounted at the belly of the aircraft. Fibre bundles transmit light from the telescopes to spectrograph-detector units inside the DOAS container instrument. The latter is part of the removable CARIBIC instrument container, which is installed monthly on the aircraft for a series of measurement flights. During 30 flight operations within three years, measurements of HCHO, HONO, NO2, BrO, O3 and the oxygen dimer O4 were conducted. All of these trace gases except BrO could be analysed with a 30 s time resolution. HONO was detected for the first time in a deep convective cloud over central Asia, while BrO, NO2 and O3 could be observed in tropopause fold regions. Biomass burning signatures over South America could be seen and measurements during ascent and descent provided information on boundary layer trace gas profiles (e.g. NO2 or HCHO).

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 (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) 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 O3. 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 (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry 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 O3 needs to be considered when estimating past and future ozone radiative effects.

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.

The collision-induced O2 complex, O2O2, is a very important trace gas for understanding remote sensing measurements of aerosols, cloud properties and atmospheric trace gases. Many ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of the O2O2 optical depth require correction factors of 0.75 ± 0.1 to reproduce radiative transfer modeling (RTM) results for a nearly pure Rayleigh atmosphere. One of the potential causes of this discrepancy is uncertainty in laboratory-measured O2O2 absorption cross section temperature and pressure dependencies due to difficulties in replicating atmospheric conditions in the laboratory environment. This paper presents ground-based direct-sun (DS) and airborne multi-axis (AMAX) DOAS measurements of O2O2 absorption optical depths under actual atmospheric conditions in two wavelength regions (335–390 and 435–490 nm). DS irradiance measurements were made by the Washington State University research-grade Multi-Function Differential Spectroscopy Instrument instrument from 2007 to 2014 at seven sites with significant pressure (778 to 1013 hPa) and O2O2 profile-weighted temperature (247 to 275 K) differences. Aircraft MAX-DOAS measurements were conducted by the University of Colorado (CU) AMAX-DOAS instrument on 29 January 2012 over the Southern Hemispheric subtropical Pacific Ocean. Scattered solar radiance spectra were collected at altitudes between 9 and 13.2 km, with O2O2 profile-weighted temperatures of 231 to 244 K and nearly pure Rayleigh scattering conditions. Due to the well-defined DS air-mass factors during ground-based measurements and extensively characterized atmospheric conditions during the aircraft AMAX-DOAS measurements, O2O2 "pseudo" absorption cross sections, σ, are derived from the observed optical depths and estimated O2O2 column densities. Vertical O2O2 columns are calculated from the atmospheric sounding temperature, pressure and specific humidity profiles. Based on the ground-based atmospheric DS observations, there is no pressure dependence of the O2O2 σ within the measurement errors (3%). Two data sets are combined to derive the peak σ temperature dependence of the 360 and 477 nm dimer absorption bands from 231 to 275 K. DS and AMAX-derived peak σ ( O2O2) as a function of T can be described by a quadratic function at 360 nm and linear function at 477 nm with about 9% ± 2.5% per 44 K rate. Recent laboratory-measured O2O2 cross sections by Thalman and Volkamer (2013) agree with these "DOAS apparent" peak σ( O2O2) at 233, 253 and 273 K within 3%. Changes in the O2O2 spectral band shape at colder temperatures are observed for the first time in field data. Temperature effects on spectral band shapes can introduce errors in the retrieved O2O2 column abundances if a single room temperature σ( O2O2) is used in the DOAS analysis. Simultaneous fitting of σ( O2O2) at temperatures that bracket the ambient temperature range can reduce such errors. Our results show that laboratory-measured σ( O2O2) (Hermans, 2011, at 296 K and Thalman and Volkamer, 2013) are applicable for observations over a wide range of atmospheric conditions. Column densities derived using Hermans (2011) σ at 296 K require very small correction factors (0.94 ± 0.02 at 231 K and 0.99 ± 0.02 at 275 K) to reproduce theoretically calculated slant column densities for DS and AMAX-DOAS measurements. Simultaneous fitting of σ( O2O2) at 203 and 293 K further improved the results at UV and visible wavelengths for AMAX-DOAS.

We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box-model to infer total gas phase inorganic bromine (Bry) over the tropical Western Pacific Ocean (tWPO) during the CONTRAST field campaign (January–February 2014). The median tropospheric BrO Vertical Column Density (VCD) over the tWPO was measured as 1.6 × 1013 molec cm−2, compared to model predictions of 0.4 × 1013 in CAM-Chem, 0.9 × 1013 in GEOS-Chem, and 2.1 × 1013 in GEOS-Chem with a sea-salt aerosol (SSA) bromine source. The observed BrO and inferred Bry profiles is found to be C-shaped in the troposphere, with local maxima in the marine boundary layer (MBL) and in the upper free troposphere. Neither global model fully captures this profile shape. Between 6 and 13.5 km, the inferred Bry is highly sensitive to assumptions about the rate of heterogeneous bromine recycling (depends on the surface area of ice/aerosols), and the inclusion of a SSA bromine source. A local Bry maximum of 3.6 ppt (2.3–11.1 ppt, 95 % CI) is observed between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective TTL to the aged TTL, gas phase Bry decreases from the convective TTL to the aged TTL. Analysis of gas phase Bry against multiple tracers (CFC-11, H2O / O3 ratio, and θ) reveals a Bry minimum of 2.7 ppt (2.4–3.0 ppt, 95 % CI) in the aged TTL, which is remarkably insensitive to assumptions about heterogeneous chemistry. Bry increases to 6.3 ppt (5.9–6.7 ppt, 95 % CI) in the stratospheric middleworld, and 6.9 ppt (6.7–7.1 ppt, 95 % CI) in the stratospheric overworld. The local Bry minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-chem, and suggests a more complex partitioning of gas phase and aerosol Bry species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA derived gas phase Bry) are needed to explain the gas phase Bry budget in the TTL. They are also consistent with observations of significant bromide in UTLS aerosols. The total Bry budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas phase Bry species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. These simultaneous measurements are needed 1) to quantify SSA derived Bry aloft, 2) to test Bry partitioning, and explain the gas phase Bry minimum in the aged TTL, 3) to constrain heterogeneous reaction rates of bromine, and 4) to account for all of the sources of Bry to the lower stratosphere.

Vertical column measurements of trace gases along the direct solar beam using airborne and mobile Solar Occultation Flux provide a tool to study emissions from area sources that can be directly compared with emission inventories.

descripción no proporcionada por scopus

We are developing sensitive atmospheric vertical profile retrieval capabilities from MAX-DOAS sensors on tropical island mountaintops. Particularly, we target BrO which has significant impacts on the lifetime of greenhouse gases such as O3 and CH4.

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 ( 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 scales that are probed by satellites and ground-based observations, and predicted by atmospheric models.

Aircraft and satellite observations indicate the presence of ppt (pptpmol/mol) levels of BrO in the free troposphere with important implications for the tropospheric budgets of ozone, OH, and mercury. We can reproduce these observations with the GEOS-Chem global tropospheric chemistry model by including a broader consideration of multiphase halogen (Br-Cl) chemistry than has been done in the past. Important reactions for regenerating BrO from its nonradical reservoirs include HOBr+Br-/Cl- in both aerosols and clouds, and oxidation of Br- by ClNO3 and ozone. Most tropospheric BrO in the model is in the free troposphere, consistent with observations and originates mainly from the photolysis and oxidation of ocean-emitted CHBr3. Stratospheric input is also important in the upper troposphere. Including production of gas phase inorganic bromine from debromination of acidified sea salt aerosol increases free tropospheric Br-y by about 30%. We find HOBr to be the dominant gas-phase reservoir of inorganic bromine. Halogen (Br-Cl) radical chemistry as implemented here in GEOS-Chem drives 14% and 11% decreases in the global burdens of tropospheric ozone and OH, respectively, a 16% increase in the atmospheric lifetime of methane, and an atmospheric lifetime of 6months for elemental mercury. The dominant mechanism for the Br-Cl driven tropospheric ozone decrease is oxidation of NOx by formation and hydrolysis of BrNO3 and ClNO3.

We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and the oxygen dimer (O4) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10−6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise). Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMSNLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMSFWHM. The non-linearity of our detector is low (∼10−2) yet – unless actively controlled – is sufficiently large to create RMSNLin of up to 2 × 10−4. The optical resolution is sensitive to temperature changes (0.03 detector pixels °C−1 at 334 nm), and temperature variations of 0.1°C can cause RMSFWHM of ~1 × 10−4. Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s the instrument can reach RMS noise of 3 × 10−5, and typical RMS in field measurements ranged from 6 × 10−5 to 1.4 × 10−4. The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 1013 molec cm−2, 8 × 1012 molec cm−2 and 4 × 1014 molec cm−2, respectively. HCHO and NO2 were also detected with typical MBL VCDs of 1 × 1016 and 3 × 1015 molec cm−2. These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly discussed. The CU GMAX-DOAS has great potential to investigate RMS-limited problems, like the abundance and variability of trace gases in the MBL and possibly the free troposphere (FT).

We present the first detection of glyoxal (CHOCHO) over the remote tropical Pacific Ocean in the Marine Boundary Layer (MBL). The measurements were conducted by means of the University of Colorado Ship Multi-Axis Differential Optical Absorption Spectroscopy (CU SMAX-DOAS) instrument aboard the research vessel Ronald H. Brown. The research vessel was on a cruise in the framework of the VAMOS Ocean-Cloud-Atmosphere-Land Study – Regional Experiment (VOCALS-REx) and the Tropical Atmosphere Ocean (TAO) projects lasting from October 2008 through January 2009 (74 days at sea). The CU SMAX-DOAS instrument features a motion compensation system to characterize the pitch and roll of the ship and to compensate for ship movements in real time. We found elevated mixing ratios of up to 140 ppt CHOCHO located inside the MBL up to 3000 km from the continental coast over biologically active upwelling regions of the tropical Eastern Pacific Ocean. This is surprising since CHOCHO is very short lived (atmospheric life time ~2 h) and highly water soluble (Henry's Law constant H = 4.2 × 105 M/atm). This CHOCHO cannot be explained by transport of it or its precursors from continental sources. Rather, the open ocean must be a source for CHOCHO to the atmosphere. Dissolved Organic Matter (DOM) photochemistry in surface waters is a source for Volatile Organic Compounds (VOCs) to the atmosphere, e.g. acetaldehyde. The extension of this mechanism to very soluble gases, like CHOCHO, is not straightforward since the air-sea flux is directed from the atmosphere into the ocean. For CHOCHO, the dissolved concentrations would need to be extremely high in order to explain our gas-phase observations by this mechanism (40–70 μM CHOCHO, compared to ~0.01 μM acetaldehyde and 60–70 μM DOM). Further, while there is as yet no direct measurement of VOCs in our study area, measurements of the CHOCHO precursors isoprene, and/or acetylene over phytoplankton bloom areas in other parts of the oceans are too low (by a factor of 10–100) to explain the observed CHOCHO amounts. We conclude that our CHOCHO data cannot be explained by currently understood processes. Yet, it supports first global source estimates of 20 Tg/year CHOCHO from the oceans, which likely is a significant source of secondary organic aerosol (SOA). This chemistry is currently not considered by atmospheric models.

An airfreight container with automated instruments for measurement of atmospheric gases and trace compounds was operated on a monthly basis onboard a Boeing 767-300 ER of LTU International Airways during long-distance flights from 1997 to 2002 (CARIBIC, Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container, http://www.caribic-atmospheric.com). Subsequently a more advanced system has been developed, using a larger capacity container with additional equipment and an improved inlet system. CARIBIC phase #2 was implemented on a new long-range aircraft type Airbus A340-600 of the Lufthansa German Airlines (Star Alliance) in December 2004, creating a powerful flying observatory. The instrument package comprises detectors for the measurement of O3, total and gaseous H2O, NO and NOy, CO, CO2, O2, Hg, and number concentrations of sub-micrometer particles (>4 nm, >12 nm, and >18 nm diameter). Furthermore, an optical particle counter (OPC) and a proton transfer mass spectrometer (PTR-MS) are incorporated. Aerosol samples are collected for analysis of elemental composition and particle morphology after flight. Air samples are taken in glass containers for laboratory analyses of hydrocarbons, halocarbons and greenhouse gases (including isotopic composition of CO2) in several laboratories. Absorption tubes collect oxygenated volatile organic compounds. Three differential optical absorption spectrometers (DOAS) with their telescopes mounted in the inlet system measure atmospheric trace gases such as BrO, HONO, and NO2. A video camera mounted in the inlet provides information about clouds along the flight track. The flying observatory, its equipment and examples of measurement results are reported.

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 CU Airborne Multi AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, in situ aerosol size distributions by an Ultra High Sensitivity Aerosol Spectrometer (UHSAS), and in situ H2O by Vertical-Cavity Surface-Emitting Laser hygrometer (VCSEL). Data are presented from two research flights (RF12, RF17) aboard the NSF/NCAR GV aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project. We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols, and find O4-inferred aerosol extinction profiles at 477 nm agree within 5% with Mie calculations of extinction profiles constrained by UHSAS. 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), 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- 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 20% (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 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, and 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.

© 2015. American Geophysical Union. All Rights Reserved. We report a new estimation of the injection of iodine into the stratosphere based on novel daytime (solar zenith angle < 45°) aircraft observations in the tropical tropopause layer and a global atmospheric model with the most recent knowledge about iodine photochemistry. The results indicate that significant levels of total reactive iodine (0.25-0.7 parts per trillion by volume), between 2 and 5 times larger than the accepted upper limits, can be injected into the stratosphere via tropical convective outflow. At these iodine levels, modeled iodine catalytic cycles account for up to 30% of the contemporary ozone loss in the tropical lower stratosphere and can exert a stratospheric ozone depletion potential equivalent to, or even larger than, that of very short-lived bromocarbons. Therefore, we suggest that iodine sources and chemistry need to be considered in assessments of the historical and future evolution of the stratospheric ozone layer.

The collision induced O2 complex, O2O2, is a very important trace gas in remote sensing measurements of aerosol and cloud properties. Some ground based MAX-DOAS measurements of O2O2 slant column density require correction factors of 0.75 ± 0.1 to reproduce radiative transfer modeling (RTM) results for a near pure Rayleigh atmosphere. One of the potential causes of this discrepancy is believed to be uncertainty in laboratory measured O2O2 absorption cross section temperature and pressure dependence, due to difficulties in replicating atmospheric conditions in the laboratory environment. This paper presents direct-sun (DS) and airborne multi-axis (AMAX) DOAS measurements of O2O2 absorption optical depths under actual Earth atmospheric conditions in two wavelength regions (335–390 nm and 435–490 nm). DS irradiance measurements were made by the research grade MFDOAS instrument from 2007–2014 at seven sites with significant pressure (778–1013 hPa) and O2O2 profile weighted temperature (247–275 K) differences. Aircraft MAX-DOAS measurements were conducted by the University of Colorado AMAX-DOAS instrument on 29 January 2012 over the Southern Hemisphere subtropical Pacific Ocean. Scattered solar radiance spectra were collected at altitudes between 9 and 13.2 km, with O2O2 profile weighted temperatures of 231–244 K, and near pure Rayleigh scattering conditions. Due to the well defined DS air mass factors and extensively characterized atmospheric conditions during the AMAX-DOAS measurements, O2O2"pseudo" absorption cross sections, σ, are derived from the observed optical depths and estimated O2O2column densities. Vertical O2O2 columns are calculated from the atmospheric sounding temperature, pressure and specific humidity profiles. Based on the atmospheric DS observations, there is no pressure dependence of the O2O2 σ, within the measurement errors (3%). The two data sets are combined to derive peak σ temperature dependence of 360 and 477 nm absorption bands from 231–275 K. DS and AMAX derived peak σ(O2O2) as a function of T can be described by a quadratic function at 360 nm and linear at 477 nm with about 9 ± 2.5% per 44 K rate. Recent laboratory measured O2O2 cross sections by Thalman and Volkamer (2013) agree with these "DOAS apparent" peak σ(O2O2) at 233 K, 253 K and 273 K within 3%. Changes in the O2O2 spectral band-shape at colder temperatures are for the first time also observed in field data. Temperature effects on spectral band shapes can introduce errors in the retrieved O2O2 column abundances if a single room temperature σ(O2O2) is used in the DOAS analysis. Simultaneous fitting of σ(O2O2) at temperatures that bracket the ambient temperature range can reduce such errors. Our results suggest that laboratory measured σ(O2O2) (Hermans et al. (2011) at 296 K and Thalman and Volkamer (2013)) are applicable for observations over a wide range of atmospheric conditions. Column densities derived using Hermans et al. (2011) σ at 296 K require very small correction factors (0.94 ± 0.02 at 231 K and 0.99 ± 0.02 at 275 K) to reproduce theoretically calculated SCDs for DS and AMAX-DOAS measurements. Simultaneous fitting of σ(O2O2) at 203 and 293 K further improved results at UV and visible wavelengths for AMAX-DOAS.

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.