scholarly journals Evidence for heterogeneous chlorine activation in the tropical UTLS

2011 ◽  
Vol 11 (1) ◽  
pp. 241-256 ◽  
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
G. Günther ◽  
P. Konopka ◽  
I. Gensch ◽  
...  

Abstract. Airborne in-situ observations of ClO in the tropics were made during the TROCCINOX (Aracatuba, Brazil, February 2005) and SCOUT-O3 (Darwin, Australia, November/December 2005) field campaigns. While during most flights significant amounts of ClO (≈10–20 parts per trillion, ppt) were present only in aged stratospheric air, instances of enhanced ClO mixing ratios of up to 40 ppt – significantly exceeding those expected from gas phase chemistry – were observed in air masses of a more tropospheric character. Most of these observations are associated with low temperatures or with the presence of cirrus clouds (often both), suggesting that cirrus ice particles and/or liquid aerosol at low temperatures may promote significant heterogeneous chlorine activation in the tropical upper troposphere lower stratosphere (UTLS). In two case studies, particularly high levels of ClO observed were reproduced by chemistry simulations only under the assumption that significant denoxification had occurred in the observed air. However, to reproduce the ClO observations in these simulations, O3 mixing ratios higher than observed had to be assumed, and at least for one of these flights, a significant denoxification is in contrast to the observed NO levels, suggesting that the coupling of chlorine and nitrogen compounds in the tropical UTLS may not be completely understood.

2010 ◽  
Vol 10 (7) ◽  
pp. 18063-18099
Author(s):  
M. von Hobe ◽  
J.-U. Grooß ◽  
G. Günther ◽  
P. Konopka ◽  
I. Gensch ◽  
...  

Abstract. Airborne in-situ observations of ClO in the tropics were made during the TROCCINOX (Aracatuba, Brasil, February 2005) and SCOUT-O3 (Darwin, Australia, November/December 2005) field campaigns. While during most flights significant amounts of ClO (≈10–20 parts per trillion, ppt) were present only in aged stratospheric air, instances of enhanced ClO mixing ratios of up to 40 ppt – significantly exceeding those expected from gas phase chemistry – were observed in air masses of a more tropospheric character. Most of these observations concur with low temperatures or with the presence of cirrus clouds (often both), suggesting that cirrus ice particles and/or liquid aerosol at low temperatures may promote significant heterogeneous chlorine activation in the tropical upper troposphere lower stratosphere (UTLS). In two case studies, particularly high levels of ClO observed were reproduced by chemistry simulations only under the assumption that significant denoxification had occurred in the observed air. At least for one of these flights, a significant denoxification is in contrast to the observed NO levels suggesting that the coupling of chlorine and nitrogen compounds in the tropical UTLS may not be completely understood.


2021 ◽  
Author(s):  
Victor Lannuque ◽  
Bastien Sauvage ◽  
Brice Barret ◽  
Hannah Clark ◽  
Gilles Athier ◽  
...  

Abstract. Between December 2005 and 2013, the In-service Aircraft for a Global Observing System (IAGOS) program produced almost daily in situ measurements of CO and O3 between Europe and southern Africa. IAGOS data combined with measurements from the IASI instrument onboard the Metop-A satellite (2008–2013) are used to characterize meridional distributions and seasonality of CO and O3 in the African upper troposphere (UT). The FLEXPART particle dispersion model and the SOFT-IO model which combines the FLEXPART model with CO emission inventories are used to explore the sources and origins of the observed transects of CO and O3. We focus our analysis on two main seasons: December to March (DJFM) and June to October (JJASO). These seasons have been defined according to the position of Intertropical Convergence Zone (ITCZ), determined using in situ measurements from IAGOS. During both seasons, the UT CO meridional transects are characterized by maximum mixing ratios located 10° from the position of the ITCZ above the dry regions inside the hemisphere of the strongest Hadley cell (132 to 165 ppb at 0–5° N in DJFM and 128 to 149 ppb at 3–7° S in JJASO), and decreasing values south- and north-ward. The O3 meridional transects are characterized by mixing ratio minima of ~ 42–54 ppb at the ITCZ (10–16° S in DJFM and 5–8° N in JJASO) framed by local maxima (~ 53–71 ppb) coincident with the wind shear zones North and South of the ITCZ. O3 gradients are strongest in the hemisphere of the strongest Hadley cell. IASI UT O3 distributions in DJFM have revealed that the maxima are a part of a crescent-shaped O3 plume above the Atlantic Ocean around the Gulf of Guinea. CO emitted at the surface is transported towards the ITCZ by the trade winds and then convectively uplifted. Once in the upper troposphere, CO enriched air masses are transported away from the ITCZ by the upper branches of the Hadley cells and accumulate within the zonal wind shear zones where the maximum CO mixing ratios are found. Anthropogenic and fires both contribute, by the same order of magnitude, to the CO budget of the African upper troposphere. Local fires have the highest contribution, drive the location of the observed UT CO maxima, and are related to the following transport pathway: CO emitted at the surface is transported towards the ITCZ by the trade winds and further convectively uplifted. Then UT CO enriched air masses are transported away from the ITCZ by the upper branches of the Hadley cells and accumulate within the zonal wind shear zones where the maxima are located. Anthropogenic CO contribution is mostly from Africa during the entire year, with a low seasonal variability, and is related to similar transport circulation than fire air masses. There is also a large contribution from Asia in JJASO related to the fast convective uplift of polluted air masses in the Asian monsoon region which are further westward transported by the tropical easterly jet (TEJ) and the Asian monsoon anticyclone (AMA). O3 minima correspond to air masses that were recently uplifted from the surface where mixing ratios are low at the ITCZ. The O3 maxima correspond to old high altitude air masses uplifted from either local or long distance area of high O3 precursor emissions (Africa and South America during all the year, South Asia mainly in JJASO), and must be created during transport by photochemistry. This analysis of meridional transects contribute to a better understanding of distributions of CO and O3 in the intertropical African upper troposphere and the processes which drive these distributions. Therefore, it provides a solid basis for comparison and improvement of models and satellite products in order to get the good O3 for the good reasons.


2018 ◽  
Vol 18 (20) ◽  
pp. 15363-15386 ◽  
Author(s):  
Thomas von Clarmann ◽  
Sören Johansson

Abstract. This review article compiles the characteristics of the gas chlorine nitrate and discusses its role in atmospheric chemistry. Chlorine nitrate is a reservoir of both stratospheric chlorine and nitrogen. It is formed by a termolecular reaction of ClO and NO2. Sink processes include gas-phase chemistry, photo-dissociation, and heterogeneous chemistry on aerosols. The latter sink is particularly important in the context of polar spring stratospheric chlorine activation. ClONO2 has vibrational–rotational bands in the infrared, notably at 779, 809, 1293, and 1735 cm−1, which are used for remote sensing of ClONO2 in the atmosphere. Mid-infrared emission and absorption spectroscopy have long been the only concepts for atmospheric ClONO2 measurements. More recently, fluorescence and mass spectroscopic in situ techniques have been developed. Global ClONO2 distributions have a maximum at polar winter latitudes at about 20–30 km altitude, where mixing ratios can exceed 2 ppbv. The annual cycle is most pronounced in the polar stratosphere, where ClONO2 concentrations are an indicator of chlorine activation and de-activation.


2010 ◽  
Vol 3 (3) ◽  
pp. 1359-1421
Author(s):  
R. Hommel ◽  
C. Timmreck ◽  
H. F. Graf

Abstract. In this paper we investigate results from a middle-atmosphere aerosol-climate model which has been developed to study the evolution of stratospheric aerosols. Here we focus on the stratospheric background period and evaluate several key quantities of the global dispersion of stratospheric aerosols and their precursors with observations and other model studies. It is shown that the model fairly well reproduces in situ observations of the aerosol size and number concentrations in the upper troposphere and lower stratosphere (UT/LS). Compared to measurements from the limb-sounding SAGE II satellite instrument, modelled integrated aerosol quantities are more biased the lower the moment of the aerosol population. Both findings are consistent with earlier work analysing the quality of SAGE II retrieved e.g. aerosol surface area densities from the volcanically unperturbed stratosphere (SPARC/ASAP, 2006; Thomason et al., 2008; Wurl et al., 2010). The model suggests that new particles are formed over large areas of the LS, albeit nucleation rates in the upper troposphere are at least one order of magnitude larger than those in the stratosphere. Hence, we suggest that both tropospheric sulphate aerosols and particles formed in situ in the LS are maintaining the stability of the stratospheric aerosol layer also in the absence of direct stratospheric emissions from volcanoes. Particle size distributions are clearly bimodal, except in the upper branches of the stratospheric aerosol layer where aerosols evaporate. Modelled concentrations of condensation nuclei (CN) are lesser than measured in regions of the aerosol layer where aerosol mixing ratios are largest, due to an overpredicted particle growth by coagulation. Transport regimes of tropical stratospheric aerosol have been identified from modelled aerosol mixing ratios and correspond to those deduced from satellite extinction measurements. We found that convective updraft in the Asian Monsoon region significantly contributes to both stratospheric aerosol load and size. The timing of formation and descend of layers of fine mode particles in the winter and spring polar stratosphere (CN layer) are reproduced by the model. Far above the tropopause where nucleation is inhibited due to with height increasing stratospheric temperatures, planetary wave mixing transports significant amounts of fine mode particles from the polar stratosphere to mid-latitudes. In those regions enhanced condensation rates of sulphuric acid vapour counteracts the evaporation of aerosols, hence prolonging the aerosol lifetime in the upper branches of the stratospheric aerosol layer. Measurements of the aerosol precursors SO2 and sulphuric acid vapour are fairly well reproduced by the model throughout the stratosphere.


2010 ◽  
Vol 23 (3) ◽  
pp. 542-558 ◽  
Author(s):  
Samson Hagos ◽  
Chidong Zhang ◽  
Wei-Kuo Tao ◽  
Steve Lang ◽  
Yukari N. Takayabu ◽  
...  

Abstract This study aims to evaluate the consistency and discrepancies in estimates of diabatic heating profiles associated with precipitation based on satellite observations and microphysics and those derived from the thermodynamics of the large-scale environment. It presents a survey of diabatic heating profile estimates from four Tropical Rainfall Measuring Mission (TRMM) products, four global reanalyses, and in situ sounding measurements from eight field campaigns at various tropical locations. Common in most of the estimates are the following: (i) bottom-heavy profiles, ubiquitous over the oceans, are associated with relatively low rain rates, while top-heavy profiles are generally associated with high rain rates; (ii) temporal variability of latent heating profiles is dominated by two modes, a deep mode with a peak in the upper troposphere and a shallow mode with a low-level peak; and (iii) the structure of the deep modes is almost the same in different estimates and different regions in the tropics. The primary uncertainty is in the amount of shallow heating over the tropical oceans, which differs substantially among the estimates.


2008 ◽  
Vol 8 (3) ◽  
pp. 10627-10664
Author(s):  
R. James ◽  
B. Legras

Abstract. Both in situ measurements and satellite observations indicate evidence of mixing in the upper troposphere (UT) and the lower-stratosphere (LS). In this study, the measurements performed during the Pre-AVE and Costa-Rica AVE campaigns are analysed with diffusive back-trajectories to assess mixing properties in the tropical and the subtropical UT/LS. A description of cross-tropopause pathways and mixing time scales is provided. In the subtropics, Troposphere-Stratosphere mixing processes are found to differ in the vicinity of the tropopause and at higher altitudes. Below 350 K, the mixing line observed during Pre-AVE is shown to result from fast and local cross-tropopause irreversible exchange, involving two initially distant air masses with distinct chemical compositions. For measurements located above 350 K, mixing of the tropospheric air in the subtropical stratosphere occurs over a period of a month, the origins of the tropospheric source being localised in the tropical UT and the tropical boundary layer. In the tropics, quantitative reconstructions of CO and O3 profiles above 360 K are obtained for one month back-trajectories calculations, pointing out that long term mixing is essential to determine the chemical composition in the tropical ascent. In particular, the existence of two-way meridional irreversible exchanges between 360 and 450 K is found to export tropical air in the subtropical stratosphere and to entrain old stratospheric air in the tropical ascent. Calculations of the Lagrangian mean age of air is shown to be in qualitative agreement with the CO2 observations and diabatic calculations.


2020 ◽  
Author(s):  
Eloise J. Slater ◽  
Lisa K. Whalley ◽  
Robert Woodward-Massey ◽  
Chunxiang Ye ◽  
James D. Lee ◽  
...  

Abstract. Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ~ 250 ppbv, believed to be the highest mole fraction for which there have then co-located radical observations. The daily maximum mixing ratios for radical species varied significantly day-to-day over the range 1–8 × 106 cm−3 (OH), 0.2–1.5 × 108 cm−3 (HO2) and 0.3–2.5 × 108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7 × 106 cm−3, 0.39 × 108 cm−3 and 0.88 × 108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (~ 83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted, haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ~ 1 (for all radicals) at 3 ppbv of NO to a factor of ~ 3, ~ 20 and ~ 91 for OH, HO2 and RO2, respectively, at ~ 200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) inside and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high pollution episodes, despite the reduction in photolysis rates within haze.


2020 ◽  
Vol 20 (23) ◽  
pp. 14847-14871
Author(s):  
Eloise J. Slater ◽  
Lisa K. Whalley ◽  
Robert Woodward-Massey ◽  
Chunxiang Ye ◽  
James D. Lee ◽  
...  

Abstract. Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ∼250 ppbv. The daily maximum mixing ratios for radical species varied significantly day-to-day over the ranges 1–8×106 cm−3 (OH), 0.2–1.5×108 cm−3 (HO2) and 0.3–2.5×108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7×106, 0.39×108 and 0.88×108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (∼83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ∼1 (for all radicals) at 3 ppbv of NO to a factor of ∼3, ∼20 and ∼91 for OH, HO2 and RO2, respectively, at ∼200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) in and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high-pollution episodes, despite the reduction in photolysis rates within haze.


2017 ◽  
Vol 17 (9) ◽  
pp. 6091-6111 ◽  
Author(s):  
Klaus-D. Gottschaldt ◽  
Hans Schlager ◽  
Robert Baumann ◽  
Heiko Bozem ◽  
Veronika Eyring ◽  
...  

Abstract. We present in situ measurements of the trace gas composition of the upper tropospheric (UT) Asian summer monsoon anticyclone (ASMA) performed with the High Altitude and Long Range Research Aircraft (HALO) in the frame of the Earth System Model Validation (ESMVal) campaign. Air masses with enhanced O3 mixing ratios were encountered after entering the ASMA at its southern edge at about 150 hPa on 18 September 2012. This is in contrast to the presumption that the anticyclone's interior is dominated by recently uplifted air with low O3 in the monsoon season. We also observed enhanced CO and HCl in the ASMA, which are tracers for boundary layer pollution and tropopause layer (TL) air or stratospheric in-mixing respectively. In addition, reactive nitrogen was enhanced in the ASMA. Along the HALO flight track across the ASMA boundary, strong gradients of these tracers separate anticyclonic from outside air. Lagrangian trajectory calculations using HYSPLIT show that HALO sampled a filament of UT air three times, which included air masses uplifted from the lower or mid-troposphere north of the Bay of Bengal. The trace gas gradients between UT and uplifted air masses were preserved during transport within a belt of streamlines fringing the central part of the anticyclone (fringe), but are smaller than the gradients across the ASMA boundary. Our data represent the first in situ observations across the southern part and downstream of the eastern ASMA flank. Back-trajectories starting at the flight track furthermore indicate that HALO transected the ASMA where it was just splitting into a Tibetan and an Iranian part. The O3-rich filament is diverted from the fringe towards the interior of the original anticyclone, and is at least partially bound to become part of the new Iranian eddy. A simulation with the ECHAM/MESSy Atmospheric Chemistry (EMAC) model is found to reproduce the observations reasonably well. It shows that O3-rich air is entrained by the outer streamlines of the anticyclone at its eastern flank. Back-trajectories and increased HCl mixing ratios indicate that the entrained air originates in the stratospherically influenced TL. Photochemical ageing of air masses in the ASMA additionally increases O3 in originally O3-poor, but CO-rich air. Simulated monthly mean trace gas distributions show decreased O3 in the ASMA centre only at the 100 hPa level in July and August, but at lower altitudes and in September the ASMA is dominated by increased O3. The combination of entrainment from the tropopause region, photochemistry and dynamical instabilities can explain the in situ observations, and might have a larger impact on the highly variable trace gas composition of the anticyclone than previously thought.


2011 ◽  
Vol 4 (3) ◽  
pp. 809-834 ◽  
Author(s):  
R. Hommel ◽  
C. Timmreck ◽  
H. F. Graf

Abstract. In this paper we investigate results from a three-dimensional middle-atmosphere aerosol-climate model which has been developed to study the evolution of stratospheric aerosols. Here we focus on the stratospheric background period and evaluate several key quantities of the global distribution of stratospheric aerosols and their precursors with observations and other model studies. It is shown that the model fairly well reproduces in situ observations of the aerosol size and number concentrations in the upper troposphere and lower stratosphere (UT/LS). Compared to measurements from the limb-sounding SAGE II satellite instrument, modelled integrated aerosol quantities are more biased the lower the moment of the aerosol population is. Both findings are consistent with earlier work analysing the quality of SAGE II retrieved e.g. aerosol surface area densities in the volcanically unperturbed stratosphere (SPARC/ASAP, 2006; Thomason et al., 2008; Wurl et al., 2010). The model suggests that new particles are formed over large areas of the LS, albeit nucleation rates in the upper troposphere are at least one order of magnitude larger than those in the stratosphere. Hence, we suggest that both, tropospheric sulphate aerosols and particles formed in situ in the LS are maintaining the stability of the stratospheric aerosol layer in the absence of direct stratospheric emissions from volcanoes. Particle size distributions are clearly bimodal, except in the upper branches of the stratospheric aerosol layer where aerosols evaporate. Modelled concentrations of condensation nuclei (CN) are smaller than measured in regions of the aerosol layer where aerosol mixing ratios are largest. This points to an overestimated particle growth by coagulation. Transport regimes of tropical stratospheric aerosol have been identified from modelled aerosol mixing ratios and correspond to those deduced from satellite extinction measurements. We found that convective updraft in the Asian Monsoon region significantly contributes to both stratospheric aerosol load and size. The timing of formation and descend of layers of fine mode particles in the winter and spring polar stratosphere (CN layer) are well reproduced by the model. Where temperatures in the stratosphere increase with altitude, nucleation is unlikely to occur. Nevertheless, in these regions we find a significant concentration of fine mode aerosols. The place of origin of these particles is in the polar stratosphere. They are mixed into the mid-latitudes by planetary waves. There enhanced condensation rates of sulphuric acid vapour counteract evaporation and extend aerosol lifetime in the upper branches of the stratospheric aerosol layer. Measured aerosol precursors concentrations, SO2 and sulphuric acid vapour, are fairly well reproduced by the model throughout the stratosphere.


Sign in / Sign up

Export Citation Format

Share Document