Central role of nitric oxide in ozone production in the upper tropical troposphere over the Atlantic Ocean and western Africa

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, CH$_{4}$, OH, HO$_{2}$ and H$_{2}$O 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 O$_{3}$ 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 NO$_{x}$ limited

Modification of a conventional photolytic converter for improving aircraft measurements of NO2_{2} via chemiluminescence

Nitrogen oxides (NO$_{x}$≡NO+NO$_{2}$) are centrally involved in the photochemical processes taking place in the Earth\u27s atmosphere. Measurements of NO$_{2}$, 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 NO$_{2}$ 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 NO$_{2}$ 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, NO$_{2}$ artifacts, which are amplified by low conversion efficiencies, and a varying instrumental background adversely affect the NO$_{2}$ measurements. We test and characterize an alternative photolytic converter (type 2) made from quartz glass, which improves the reliability of NO$_{2}$ measurements in laboratory and field studies

In-situ observations of young contrails – overview and selected results from the CONCERT campaign

Lineshaped contrails were detected with the research aircraft Falcon during the CONCERT – CONtrail and Cirrus ExpeRimenT – campaign in October/November 2008. The Falcon was equipped with a set of instruments to measure the particle size distribution, shape, extinction and chemical composition as well as trace gas mixing ratios of sulfur dioxide (SO<sub>2</sub>), reactive nitrogen and halogen species (NO, NO<sub>y</sub>, HNO<sub>3</sub>, HONO, HCl), ozone (O<sub>3</sub>) and carbon monoxide (CO). During 12 mission flights over Europe, numerous contrails, cirrus clouds and a volcanic aerosol layer were probed at altitudes between 8.5 and 11.6 km and at temperatures above 213 K. 22 contrails from 11 different aircraft were observed near and below ice saturation. The observed NO mixing ratios, ice crystal and soot number densities are compared to a process based contrail model. On 19 November 2008 the contrail from a CRJ-2 aircraft was penetrated in 10.1 km altitude at a temperature of 221 K. The contrail had mean ice crystal number densities of 125 cm<sup>−3</sup> with effective radii <i>r</i><sub>eff</sub> of 2.6 μm. The presence of particles with <i>r</i>>50 μm in the less than 2 min old contrail suggests that natural cirrus crystals were entrained in the contrail. Mean HONO/NO (HONO/NO<sub>y</sub>) ratios of 0.037 (0.024) and the fuel sulfur conversion efficiency to H<sub>2</sub>SO<sub>4</sub> (ε<sub><i>S</i>↓</sub>) of 2.9 % observed in the CRJ-2 contrail are in the range of previous measurements in the gaseous aircraft exhaust. On 31 October 2010 aviation NO emissions could have contributed by more than 40% to the regional scale NO levels in the mid-latitude lowest stratosphere. The CONCERT observations help to better quantify the climate impact from contrails and will be used to investigate the chemical processing of trace gases on contrails

A new airborne broadband radiometer system and an efficient method to correct dynamic thermal offsets

The instrumentation of the High Altitude and Long Range (HALO) research aircraft is extended by the new Broadband AirCrAft RaDiometer Instrumentation (BACARDI) to quantify the radiative energy budget. Two sets of pyranometers and pyrgeometers are mounted to measure upward and downward solar (0.3–3 µm) and thermal–infrared (3–100 µm) irradiances. The radiometers are installed in a passively ventilated fairing to reduce the effects of the dynamic environment, e.g., fast changes in altitude and temperature. The remaining thermal effects range up to 20 W m−2 for the pyranometers and 10 W m−2 for the pyrgeometers. Using data collected by BACARDI during a night flight, it is demonstrated that the dynamic components of the offsets can be parameterized by the rate of change of the radiometer sensor temperatures, providing a greatly simplifying correction of the dynamic thermal effects. The parameterization provides a linear correction function (200–500 W m−2 K−1 s) that depends on the radiometer type and the mounting position of the radiometer on HALO. Furthermore, BACARDI measurements from the EUREC4A (Elucidating the Role of Clouds—Circulation Coupling in Climate) field campaign are analyzed to characterize the performance of the radiometers and to evaluate all corrections applied in the data processing. Vertical profiles of irradiance measurements up to 10 km altitude show that the thermal offset correction limits the bias due to temperature changes to values below 10 W m−2. Measurements with BACARDI during horizontal, circular flight patterns in cloud-free conditions demonstrate that the common geometric attitude correction of the solar downward irradiance provides reliable measurements in this typical flight section of EUREC4A, even without active stabilization of the radiometer.</p

Measurement report: Hydrogen peroxide in the upper tropical troposphere over the Atlantic Ocean and western Africa during the CAFE-Africa aircraft campaign

This study focuses on the distribution of hydrogen peroxide (H2O2) in the upper tropical troposphere at altitudes between 8 and 15 km based on in situ observations during the Chemistry of the Atmosphere: Field Experiment in Africa (CAFE-Africa) campaign conducted in August–September 2018 over the tropical Atlantic Ocean and western Africa. The measured hydrogen peroxide mixing ratios in the upper troposphere show no clear trend in the latitudinal distribution with locally increased levels (up to 1 ppbv​​​​​​​) within the Intertropical Convergence Zone (ITCZ), over the African coastal area, as well as during measurements performed in proximity to the tropical storm Florence (later developing into a hurricane). The observed H2O2 distribution suggests that mixing ratios in the upper troposphere seem to be far less dependent on latitude than assumed previously and the corresponding factors influencing the photochemical production and loss of H2O2. The observed levels of H2O2 in the upper troposphere indicate the influence of convective transport processes on the distribution of the species not only in the tropical but also in the subtropical regions. The measurements are compared to observation-based photostationary steady-state (PSS) calculations and numerical simulations by the global ECHAM/MESSy Atmospheric Chemistry (EMAC) model. North of the ITCZ, PSS calculations produce mostly lower H2O2 mixing ratios relative to the observations. The observed mixing ratios tend to exceed the PSS calculations by up to a factor of 2. With the exception of local events, the comparison between the calculated PSS values and the observations indicates enhanced H2O2 mixing ratios relative to the expectations based on PSS calculations in the north of the ITCZ. On the other hand, PSS calculations tend to overestimate the H2O2 mixing ratios in most of the sampled area in the south of the ITCZ by a factor of up to 3. The significant influence of convection in the ITCZ and the enhanced presence of clouds towards the Southern Hemisphere indicate contributions of atmospheric transport and cloud scavenging in the sampled region. Simulations performed by the EMAC model also overestimate hydrogen peroxide levels particularly in the Southern Hemisphere, most likely due to underestimated cloud scavenging. EMAC simulations and PSS calculations both indicate a latitudinal gradient from the Equator towards the subtropics. In contrast, the measurements show no clear gradient with latitude in the mixing ratios of H2O2 in the upper troposphere with a slight decrease from the ITCZ towards the subtropics, indicating a relatively low dependency on the solar radiation intensity and the corresponding photolytic activity. The largest model deviations relative to the observations correspond with the underestimated hydrogen peroxide loss due to enhanced cloud presence, scavenging, and rainout in the ITCZ and towards the south.</p

Ice particle sampling from aircraft – influence of the probing position on the ice water content

The ice water content (IWC) of cirrus clouds is an essential parameter determining their radiative properties and thus is important for climate simulations. Therefore, for a reliable measurement of IWC on board research aircraft, it is important to carefully design the ice crystal sampling and measuring devices. During the ML-CIRRUS field campaign in 2014 with the German Gulfstream GV HALO (High Altitude and Long Range Research Aircraft), IWC was recorded by three closed-path total water together with one gas-phase water instrument. The hygrometers were supplied by inlets mounted on the roof of the aircraft fuselage. Simultaneously, the IWC is determined by a cloud particle spectrometer attached under an aircraft wing. Two more examples of simultaneous IWC measurements by hygrometers and cloud spectrometers are presented, but the inlets of the hygrometers were mounted at the fuselage side (M-55 Geophysica, StratoClim campaign 2017) and bottom (NASA WB57, MacPex campaign 2011). This combination of instruments and inlet positions provides the opportunity to experimentally study the influence of the ice particle sampling position on the IWC with the approach of comparative measurements. As expected from theory and shown by computational fluid dynamics (CFD) calculations, we found that the IWCs provided by the roof inlets deviate from those measured under the aircraft wing. As a result of the inlet position in the shadow zone behind the aircraft cockpit, ice particle populations with mean mass sizes larger than about 25 µm radius are subject to losses, which lead to strongly underestimated IWCs. On the other hand, cloud populations with mean mass sizes smaller than about 12 µm are dominated by particle enrichment and thus overestimated IWCs. In the range of mean mass sizes between 12 and 25 µm, both enrichment and losses of ice crystals can occur, depending on whether the ice crystal mass peak of the size distribution – in these cases bimodal – is on the smaller or larger mass mode. The resulting deviations of the IWC reach factors of up to 10 or even more for losses as well as for enrichment. Since the mean mass size of ice crystals increases with temperature, losses are more pronounced at higher temperatures, while at lower temperatures IWC is more affected by enrichment. In contrast, in the cases where the hygrometer inlets were mounted at the fuselage side or bottom, the agreement of IWCs is most frequently within a factor of 2.5 or better – due to less disturbed ice particle sampling, as expected from theory – independently of the mean ice crystal sizes. The rather large scatter between IWC measurements reflects, for example, cirrus cloud inhomogeneities and instrument uncertainties as well as slight sampling biases which might also occur on the side or bottom of the fuselage and under the wing. However, this scatter is in the range of other studies and represent the current best possible IWC recording on fast-flying aircraft.</p

Self evaluation of communication experiences after laryngeal cancer – A longitudinal questionnaire study in patients with laryngeal cancer

<p>Abstract</p> <p>Background</p> <p>Aim of this longitudinal study was to investigate the sensitivity to change of the Swedish Self Evaluation of Communication Experiences after Laryngeal Cancer questionnaire (the S-SECEL), addressing communication dysfunction in patients treated for laryngeal cancer. Previous studies have highlighted the need for more specific questionnaires for this purpose.</p> <p>Methods</p> <p>100 patients with Tis-T4 laryngeal cancer were included prior to treatment onset. Patients answered four questionnaires at six occasions during one year; the S-SECEL, the European Organisation for Research and Treatment of Cancer (EORTC) Core Quality of Life Core Questionnaire (QLQ-C30) supplemented by the Head and Neck cancer module (QLQ-H&N35) and the Hospital Anxiety and Depression (HAD) scale. In addition, performance status was assessed. Differences within groups were tested with the Wilcoxon paired signed ranks test and between-group analyses were carried out using the Mann-Whitney <it>U </it>test. Magnitude of group differences was analyzed by means of effect sizes.</p> <p>Results</p> <p>The S-SECEL was well accepted with a response rate of 76%. Communication dysfunction increased at 1 month, followed by a continuous decrease throughout the year. Changes were statistically significant at most measurement, demonstrating the sensitivity of the S-SECEL to changes in communication over time. The S-SECEL and the EORTC QLQ-C30 with the QLQ-H&N35 demonstrated similar results; however the S-SECEL was more sensitive regarding communication dysfunction. The largest changes were found in the most diagnose specific items concerning voice and speech.</p> <p>Conclusion</p> <p>The S-SECEL was investigated in the largest Scandinavian longitudinal study concerning health-related quality of life (HRQL) in laryngeal cancer patients. The questionnaire was responsive to change and showed convergent results when compared to established HRQL questionnaires. Our findings also indicate that the S-SECEL could be a more suitable instrument than the EORTC QLQ-C30 with QLQ-H&N35 when measuring communication experiences in patients with laryngeal cancer; it is more sensitive, shorter and can be used on an individual basis. As a routine screening instrument the S-SECEL could be a valuable tool for identifying patients at risk for psychosocial problems and to help plan rehabilitation. It is therefore recommended for clinical use in evaluation of communication dysfunction for all patients with laryngeal cancer irrespective of treatment.</p

Tinnitus: Distinguishing between Subjectively Perceived Loudness and Tinnitus-Related Distress

OBJECTIVES: Overall success of current tinnitus therapies is low, which may be due to the heterogeneity of tinnitus patients. Therefore, subclassification of tinnitus patients is expected to improve therapeutic allocation, which, in turn, is hoped to improve therapeutic success for the individual patient. The present study aims to define factors that differentially influence subjectively perceived tinnitus loudness and tinnitus-related distress. METHODS: In a questionnaire-based cross-sectional survey, the data of 4705 individuals with tinnitus were analyzed. The self-report questionnaire contained items about subjective tinnitus loudness, type of onset, awareness and localization of the tinnitus, hearing impairment, chronic comorbidities, sleep quality, and psychometrically validated questionnaires addressing tinnitus-related distress, depressivity, anxiety, and somatic symptom severity. In a binary step-wise logistic regression model, we tested the predictive power of these variables on subjective tinnitus loudness and tinnitus-related distress. RESULTS: The present data contribute to the distinction between subjective tinnitus loudness and tinnitus-related distress. Whereas subjective loudness was associated with permanent awareness and binaural localization of the tinnitus, tinnitus-related distress was associated with depressivity, anxiety, and somatic symptom severity. CONCLUSIONS: Subjective tinnitus loudness and the potential presence of severe depressivity, anxiety, and somatic symptom severity should be assessed separately from tinnitus-related distress. If loud tinnitus is the major complaint together with mild or moderate tinnitus-related distress, therapies should focus on auditory perception. If levels of depressivity, anxiety or somatic symptom severity are severe, therapies and further diagnosis should focus on these symptoms at first

Tropopause and hygropause variability over the equatorial Indian Ocean during February and March 1999.

Measurements of temperature, water vapor, total water, ozone, and cloud properties were made above the western equatorial Indian Ocean in February and March 1999. The cold-point tropopause was at a mean pressure-altitude of 17 km, equivalent to a potential temperature of 380 K, and had a mean temperature of 190 K. Total water mixing ratios at the hygropause varied between 1.4 and 4.1 ppmv. The mean saturation water vapor mixing ratio at the cold point was 3.0 ppmv. This does not accurately represent the mean of the measured total water mixing ratios because the air was unsaturated at the cold point for about 40% of the measurements. As well as unsaturation at the cold point, saturation was observed above the cold point on almost 30% of the profiles. In such profiles the air was saturated with respect to water ice but was free of clouds (i.e., backscatter ratio <2) at potential temperatures more than 5 K above the tropopause and hygropause. Individual profiles show a great deal of variability in the potential temperatures of the cold point and hygropause. We attribute this to short timescale and space-scale perturbations superimposed on the seasonal cycle. There is neither a clear and consistent “setting” of the tropopause and hygropause to the same altitude by dehydration processes nor a clear and consistent separation of tropopause and hygropause by the Brewer-Dobson circulation. Similarly, neither the tropopause nor the hygropause provides a location where conditions consistently approach those implied by a simple “tropopause freeze drying” or “stratospheric fountain” hypothesis