Air pollution is growing fastest in monsoon-affected South Asia. During the dry winter monsoon, the fumes disperse toward the Indian Ocean, creating a vast pollution haze, but their fate during the wet summer monsoon has been unclear. We performed atmospheric chemistry measurements by aircraft in the Oxidation Mechanism Observations campaign, sampling the summer monsoon outflow in the upper troposphere between the Mediterranean and the Indian Ocean. The measurements, supported by model calculations, show that the monsoon sustains a remarkably efficient cleansing mechanism by which contaminants are rapidly oxidized and deposited to Earth's surface. However, some pollutants are lofted above the monsoon clouds and chemically processed in a reactive reservoir before being redistributed globally, including to the stratosphere.

Abstract. During the OMO (Oxidation Mechanism Observation) mission, trace gas measurements were performed on board the HALO (High Altitude Long Range) research aircraft in summer 2015 in order to investigate the outflow of the South Asian summer monsoon and its influence on the composition of the Asian monsoon anticyclone (AMA) in the upper troposphere over the eastern Mediterranean and the Arabian Peninsula. This study focuses on in situ observations of hydrogen peroxide (H2O2obs) and organic hydroperoxides (ROOHobs) as well as their precursors and loss processes. Observations are compared to photostationary-state (PSS) calculations of H2O2PSS and extended by a separation of ROOHobs into methyl hydroperoxide (MHPPSS) and inferred unidentified hydroperoxide (UHPPSS) mixing ratios using PSS calculations. Measurements are also contrasted to simulations with the general circulation ECHAM–MESSy for Atmospheric Chemistry (EMAC) model. We observed enhanced mixing ratios of H2O2obs (45 %), MHPPSS (9 %), and UHPPSS (136 %) in the AMA relative to the northern hemispheric background. Highest concentrations for H2O2obs and MHPPSS of 211 and 152 ppbv, respectively, were found in the tropics outside the AMA, while for UHPPSS, with 208 pptv, highest concentrations were found within the AMA. In general, the observed concentrations are higher than steady-state calculations and EMAC simulations by a factor of 3 and 2, respectively. Especially in the AMA, EMAC underestimates the H2O2EMAC (medians: 71 pptv vs. 164 pptv) and ROOHEMAC (medians: 25 pptv vs. 278 pptv) mixing ratios. Longitudinal gradients indicate a pool of hydroperoxides towards the center of the AMA, most likely associated with upwind convection over India. This indicates main contributions of atmospheric transport to the local budgets of hydroperoxides along the flight track, explaining strong deviations from steady-state calculations which only account for local photochemistry. Underestimation of H2O2EMAC by approximately a factor of 2 in the Northern Hemisphere (NH) and the AMA and overestimation in the Southern Hemisphere (SH; factor 1.3) are most likely due to uncertainties in the scavenging efficiencies for individual hydroperoxides in deep convective transport to the upper troposphere, corroborated by a sensitivity study. It seems that the observed excess UHPPSS is excess MHP transported to the west from an upper tropospheric source related to convection in the summer monsoon over Southeast Asia.

Abstract. Mechanisms of tropospheric ozone (O3) formation are generally well understood. However, studies reporting on net ozone production rates (NOPRs) directly derived from in situ observations are challenging and are sparse in number. To analyze the role of nitric oxide (NO) in net ozone production in the upper tropical troposphere above the Atlantic Ocean and western Africa, we present in situ trace gas observations obtained during the CAFE-Africa (Chemistry of the Atmosphere: Field Experiment in Africa) campaign in August and September 2018. The vertical profile of in situ measured NO along the flight tracks reveals lowest NO mixing ratios of less than 20 pptv between 2 and 8 km altitude and highest mixing ratios of 0.15–0.2 ppbv above 12 km altitude. Spatial distribution of tropospheric NO above 12 km altitude shows that the sporadically enhanced local mixing ratios (>0.4 ppbv) occur over western Africa, which we attribute to episodic lightning events. Measured O3 shows little variability in mixing ratios at 60–70 ppbv, with slightly decreasing and increasing tendencies towards the boundary layer and stratosphere, respectively. Concurrent measurements of CO, CH4, OH, HO2 and H2O enable calculations of NOPRs along the flight tracks and reveal net ozone destruction at −0.6 to −0.2 ppbv h−1 below 6 km altitude and balance of production and destruction around 7–8 km altitude. We report vertical average NOPRs of 0.2–0.4 ppbv h−1 above 12 km altitude with NOPRs occasionally larger than 0.5 ppbv h−1 over western Africa coincident with enhanced NO. We compare the observational results to simulated data retrieved from the general circulation model ECHAM/MESSy Atmospheric Chemistry (EMAC). Although the comparison of mean vertical profiles of NO and O3 indicates good agreement, local deviations between measured and modeled NO are substantial. The vertical tendencies in NOPRs calculated from simulated data largely reproduce those from in situ experimental data. However, the simulation results do not agree well with NOPRs over western Africa. Both measurements and simulations indicate that ozone formation in the upper tropical troposphere is NOx limited.

Abstract. Mechanisms of tropospheric ozone (O3) formation are generally well understood. However, studies reporting on net ozone production rates (NOPRs) directly derived from in-situ observations are challenging, and are sparse in number. To analyze the role of nitric oxide (NO) in net ozone production in the upper tropical troposphere above the Atlantic Ocean and the West African continent, we present in situ trace gas observations obtained during the CAFE-Africa (Chemistry of the Atmosphere: Field Experiment in Africa) campaign in August and September 2018. The vertical profile of in situ measured NO along the flight tracks reveals lowest NO mixing ratios of less than 20 pptv between 2 and 8 km altitude and highest mixing ratios of 0.15–0.2 ppbv above 12 km altitude. Spatial distribution of tropospheric NO above 12 km altitude shows that the sporadically enhanced local mixing ratios (> 0.4 ppbv) occur over the West African continent, which we attribute to episodic lightning events. Measured O3 shows little variability in mixing ratios at 60–70 ppbv, with slightly decreasing and increasing tendencies towards the boundary layer and stratosphere, respectively. Concurrent measurements of CO, CH4, OH and HO2 and H2O enable calculations of NOPRs along the flight tracks and reveal net ozone destruction at −0.6 to −0.2 ppbv h−1 below 6 km altitude and balance of production and destruction around 7–8 km altitude. We report vertical average NOPRs of 0.2–0.4 ppbv h−1 above 12 km altitude with NOPRs occasionally larger than 0.5 ppbv h−1 over West Africa coincident with enhanced NO. We compare the observational results to simulated data retrieved from the general circulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model. Although the comparison of mean vertical profiles of NO and O3 indicates good agreement, local deviations between measured and modelled NO are substantial. The vertical tendencies in NOPRs calculated from simulated data largely reproduce those from in situ experimental data. However, the simulation results do not agree well with NOPRs over the West African continent. Both measurements and simulations indicate that ozone formation in the upper tropical troposphere is NOx-limited.

Abstract. Laser-induced fluorescence (LIF) is a widely used technique for both laboratory-based and ambient atmospheric chemistry measurements. However, LIF instruments require calibrations in order to translate instrument response into concentrations of chemical species. Calibration of LIF instruments measuring OH and HO2 (HOx) typically involves the photolysis of water vapor by 184.9 nm light, thereby producing quantitative amounts of OH and HO2. For ground-based HOx instruments, this method of calibration is done at one pressure (typically ambient pressure) at the instrument inlet. However, airborne HOx instruments can experience varying cell pressures, internal residence times, temperatures, and humidity during flight. Therefore, replication of such variances when calibrating in the lab is essential to acquire the appropriate sensitivities. This requirement resulted in the development of the APACHE (All Pressure Altitude-based Calibrator for HOx Experimentation) chamber to characterize the sensitivity of the airborne LIF-FAGE (fluorescence assay by gas expansion) HOx instrument, HORUS, which took part in an intensive airborne campaign, OMO-Asia 2015. It utilizes photolysis of water vapor but has the additional ability to alter the pressure at the nozzle of the HORUS instrument. With APACHE, the HORUS instrument sensitivity towards OH (26.1–7.8 cts s−1 pptv−1 mW−1, ±22.6 % 1σ; cts stands for counts by the detector) and HO2 (21.2–8.1 cts s−1 pptv−1 mW−1, ±22.1 % 1σ) was characterized to the external pressure range at the instrument nozzle of 227–900 mbar. Measurements supported by a computational fluid dynamics model, COMSOL Multiphysics, revealed that, for all pressures explored in this study, APACHE is capable of initializing a homogenous flow and maintaining near-uniform flow speeds across the internal cross section of the chamber. This reduces the uncertainty regarding average exposure times across the mercury (Hg) UV ring lamp. Two different actinometrical approaches characterized the APACHE UV ring lamp flux as 6.37×1014(±1.3×1014) photons cm−2 s−1. One approach used the HORUS instrument as a transfer standard in conjunction with a calibrated on-ground calibration system traceable to NIST standards, which characterized the UV ring lamp flux to be 6.9(±1.1)×1014 photons cm−2 s−1. The second approach involved measuring ozone production by the UV ring lamp using an ANSYCO O3 41 M ozone monitor, which characterized the UV ring lamp flux to be 6.11(±0.8)×1014 photons cm−2 s−1. Data presented in this study are the first direct calibrations of an airborne HOx instrument, performed in a controlled environment in the lab using APACHE.

Abstract. Laser induced fluorescence (LIF) is a widely used technique for both laboratory-based and ambient atmospheric chemistry measurements. However, LIF instruments require calibrations in order to translate instrument response into concentrations of chemical species. Calibration of LIF instruments measuring OH and HO2 (HOX), typically involves the photolysis of water vapor by 184.9 nm light thereby producing quantitative amounts of OH and HO2. For ground-based systems HOX instruments, this method of calibration is done at one pressure (typically ambient pressure) at the instrument inlet. However, airborne HOX instruments can experience varying cell pressures, internal residence times, temperatures, and humidity during flight. Therefore, replication of such variances when calibrating are essential to acquire the appropriate sensitivities. This requirement resulted in the development of the APACHE (All Pressure Altitude-based Calibrator for HOX Experimentation) chamber. It utilizes photolysis of water vapor, but has the additional ability to alter the pressure at the inlet of the HOX instrument thus relating instrument sensitivity to the external pressure ranges experienced during flight (275 to 1000 mbar). Measurements supported by COMSOL multiphysics and its computational fluid dynamics calculations revealed that, for all pressures explored in this study, APACHE is capable of initializing homogenous flow and maintain near uniform flow speeds across the internal cross-section of the chamber. This reduces the uncertainty regarding average exposure times across the mercury (Hg) UV ring lamp. Two different actinometrical approaches characterized the APACHE UV ring lamp flux as 6.3 x 1014 (± 0.9 x 1014) s-1 depending on pressure. Data presented in this study are the first direct calibrations, performed in a controlled environment using APACHE of an airborne HOX system instrument.

Abstract. Nitrogen oxides (NOx≡NO+NO2) are centrally involved in the photochemical processes taking place in the Earth's atmosphere. Measurements of NO2, particularly in remote areas where concentrations are of the order of parts per trillion by volume (pptv), are still a challenge and subject to extensive research. In this study, we present NO2 measurements via photolysis–chemiluminescence during the research aircraft campaign CAFE Africa (Chemistry of the Atmosphere – Field Experiment in Africa) 2018 around Cabo Verde and the results of laboratory experiments to characterize the photolytic converter used. We find the NO2 reservoir species MPN (methyl peroxy nitrate) to produce the only relevant thermal interference in the converter under the operating conditions during CAFE Africa. We identify a memory effect within the conventional photolytic converter (type 1) associated with high NO concentrations and rapidly changing water vapor concentrations, accompanying changes in altitude during aircraft measurements, which is due to the porous structure of the converter material. As a result, NO2 artifacts, which are amplified by low conversion efficiencies, and a varying instrumental background adversely affect the NO2 measurements. We test and characterize an alternative photolytic converter (type 2) made from quartz glass, which improves the reliability of NO2 measurements in laboratory and field studies.

<p><strong>Abstract.</strong> In the atmospheric boundary layer (ABL), incomplete mixing (i.e., segregation) results in reduced chemical reaction rates compared to those expected from mean values and rate constants derived under well mixed conditions. Recently, segregation has been suggested as a potential cause of discrepancies between modelled and measured OH radical concentrations, especially under high isoprene conditions. Therefore, the influence of segregation on the reaction of OH radicals with isoprene has been investigated by modelling studies and one ground-based and one aircraft campaign.</p> <p>In this study, we measured isoprene and OH radicals with high time resolution in order to directly calculate the influence of segregation in a low-NO<sub>x</sub> and high-isoprene environment in the central Amazon basin. The calculated intensities of segregation (<i>I</i><sub>s</sub>) at the Amazon Tall Tower Observatory (ATTO) above canopy top are in the range of values determined at a temperate deciduous forest (ECHO-campaign) in a high-NO<sub>x</sub> low-isoprene environment, but stay below 10 %. To establish a more general idea about the causes of segregation and their potential limits, further analysis was based on the budget equations of isoprene mixing ratios, the variance of mixing ratios, and the balance of the intensity of segregation itself. Furthermore, it was investigated if a relation of <i>I</i><sub>s</sub> to the turbulent isoprene surface flux can be established theoretically and empirically, as proposed previously. A direct relation is not given and the amount of variance in <i>I</i><sub>s</sub> explained by the isoprene flux will be higher the less the influence from other processes (e.g., vertical advection) is and will therefore be greater near the surface. Although ground based values of <i>I</i><sub>s</sub> from ATTO and ECHO are in the same range, we could identify different dominating processes driving <i>I</i><sub>s</sub>. For ECHO the normalized variance of isoprene had the largest contribution, whereas for ATTO the different transport terms expressed as a residual were dominating. To get a more general picture of <i>I</i><sub>s</sub> and its potential limits in the ABL, we also compared these ground based measurements to ABL modelling studies and results from an aircraft campaign. The ground based measurements show the lowest values of the degree of inhomogenous mixing (< 20 %, mostly below 10 %). These values increase if the contribution of lower frequencies is added. Values integrated over the whole boundary layer (modelling studies) are in the range from 10 % to 30 % and aircraft measurements integrating over different landscapes are amongst the largest reported. This presents evidence that larger scale heterogeneities in land surface properties contribute substantially to <i>I</i><sub>s</sub>.</p>