Observations of ozone-poor air in the tropical tropopause layer

Ozonesondes reaching the tropical tropopause layer (TTL) over the west Pacific have occasionally measured layers of very low ozone concentrations - less than 15 ppbv - raising the question of how prevalent such layers are and how they are formed. In this paper, we examine aircraft measurements from the Airborne Tropical Tropopause Experiment (ATTREX), the Coordinated Airborne Studies in the Tropics (CAST) and the Convective Transport of Active Species in the Tropics (CONTRAST) experiment campaigns based in Guam in January-March 2014 for evidence of very low ozone concentrations and their relation to deep convection. The study builds on results from the ozonesonde campaign conducted from Manus Island, Papua New Guinea, as part of CAST, where ozone concentrations as low as 12 ppbv were observed between 100 and 150 hPa downwind of a deep convective complex. TTL measurements from the Global Hawk unmanned aircraft show a marked contrast between the hemispheres, with mean ozone concentrations in profiles in the Southern Hemisphere between 100 and 150 hPa of between 10.7 and 15.2 ppbv. By contrast, the mean ozone concentrations in profiles in the Northern Hemisphere were always above 15.4 ppbv and normally above 20 ppbv at these altitudes. The CAST and CONTRAST aircraft sampled the atmosphere between the surface and 120 hPa, finding very low ozone concentrations only between the surface and 700 hPa; mixing ratios as low as 7 ppbv were regularly measured in the boundary layer, whereas in the free troposphere above 200 hPa concentrations were generally well in excess of 15 ppbv. These results are consistent with uplift of almost-unmixed boundary-layer air to the TTL in deep convection. An interhemispheric difference was found in the TTL ozone concentrations, with values < 15 ppbv measured extensively in the Southern Hemisphere but seldom in the Northern Hemisphere. This is consistent with a similar contrast in the low-level ozone between the two hemispheres found by previous measurement campaigns. Further evidence of a boundary-layer origin for the uplifted air is provided by the anticorrelation between ozone and halogenated hydrocarbons of marine origin observed by the three aircraft

Global Atmospheric Budget of Acetone: Air-Sea Exchange and the Contribution to Hydroxyl Radicals

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both model simulations are compared to airborne observations from a recent global‐scale, multiseasonal campaign, the NASA Atmospheric Tomography Mission (ATom). We find that both CAM‐chem and GEOS‐Chem capture the measured acetone vertical distributions in the remote atmosphere reasonably well. The combined observational and modeling analysis suggests that (i) the ocean strongly regulates the atmospheric budget of acetone. The tropical and subtropical oceans are mostly a net source of acetone, while the high‐latitude oceans are a net sink. (ii) CMIP6 anthropogenic emission inventory may underestimate acetone and/or its precursors in the Northern Hemisphere. (iii) The MEGAN biogenic emissions model may overestimate acetone and/or its precursors, and/or the biogenic oxidation mechanisms may overestimate the acetone yields. (iv) The models consistently overestimate acetone in the upper troposphere‐lower stratosphere over the Southern Ocean in austral winter. (v) Acetone contributes up to 30–40% of hydroxyl radical production in the tropical upper troposphere/lower stratosphere

Global Atmospheric Budget of Acetone: Air‐Sea Exchange and the Contribution to Hydroxyl Radicals

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both model simulations are compared to airborne observations from a recent global‐scale, multiseasonal campaign, the NASA Atmospheric Tomography Mission (ATom). We find that both CAM‐chem and GEOS‐Chem capture the measured acetone vertical distributions in the remote atmosphere reasonably well. The combined observational and modeling analysis suggests that (i) the ocean strongly regulates the atmospheric budget of acetone. The tropical and subtropical oceans are mostly a net source of acetone, while the high‐latitude oceans are a net sink. (ii) CMIP6 anthropogenic emission inventory may underestimate acetone and/or its precursors in the Northern Hemisphere. (iii) The MEGAN biogenic emissions model may overestimate acetone and/or its precursors, and/or the biogenic oxidation mechanisms may overestimate the acetone yields. (iv) The models consistently overestimate acetone in the upper troposphere‐lower stratosphere over the Southern Ocean in austral winter. (v) Acetone contributes up to 30–40% of hydroxyl radical production in the tropical upper troposphere/lower stratosphere

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January–February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO + NO2) by a factor of two, resulting in OHCOL ~30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January–February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP

Use of Airborne In Situ VOC Measurements to Estimate Transit Time Spectrum: An Observation‐Based Diagnostic of Convective Transport

Convective transport from the marine boundary layer to the upper troposphere (UT) is investigated using airborne in situ measurements of chemical species over the tropical western Pacific. Using 42 volatile organic compounds with photochemical lifetimes ranging from shorter than a day to multiple decades, we derive a transit time spectrum G(t) and the associated modal and mean transit times for the UT air mass over the convectively dominant tropical western Pacific region. G(t) describes relative contributions of air masses transported from the marine boundary layer to the UT via all transport paths with different transit times. We further demonstrate that the volatile organic compound‐derived transit time scale is broadly comparable to that estimated from convective mass flux. The observation‐based transit time spectrum not only provides insights into convective transport pathways, but also has the potential to serve as an effective diagnostic for evaluating the representation of convective transport in global models. Plain Language Summary Tropical deep convection is an important mechanism whereby air mass and chemical species are transported from near the surface to the upper troposphere and lower stratosphere. This transport process is difficult to quantify by observations or represent in models because of the small spatial scales and short temporal scales involved. In this study, we present a method to characterize convective transport using the framework of transit time spectrum, which describes the relative contributions of different transport paths with different transit times. We demonstrate that convective transport transit time spectrum can be derived using airborne in situ measurements of chemical species with a wide range of lifetimes, and we illustrate the wealth of information they provide for quantifying transport processes. This analysis method has the potential to serve as a unique diagnostic for evaluating the representation of convective transport in global models. Key Points Airborne in situ measurements of VOCs with a wide range of lifetimes are used to quantify a convective‐transport transit time spectrum The transit time scale derived from VOC measurements is broadly comparable to that estimated from convective mass flux The estimated transit time spectrum has the potential to serve as an effective diagnostic for evaluating convective transport in CCM

Deriving Tropospheric Transit Time Distributions Using Airborne Trace Gas Measurements: Uncertainty and Information Content

This study investigates the use of airborne in situ measurements to derive transit time distributions (TTD) from the boundary layer (BL) to the upper troposphere (UT) over the highly convective tropical western Pacific (TWP). The feasibility of this method is demonstrated using 42 volatile organic compounds (VOCs) measured during the Convective Transport of Active Species in the Tropics (CONTRAST) experiment. Two important approximations necessary for the application are the constant chemical lifetimes for each compound and the representation of the BL source by the local CONTRAST data. To characterize uncertainties associated with the first approximation, we quantify the changes in derived TTDs when chemical lifetimes are estimated using conditions of the BL, UT, and tropospheric average. With the support of a trajectory model study in a companion paper, we characterize the BL source region contributing to the transport to the sampled UT. In addition to the TTDs derived using a regional average, we analyze the potential information content in locally averaged measurements to represent the dynamical variability of the region. Around 150 TTDs, derived using measurements on a ∼100 km spatial scale, show a distribution of mean and mode transit times consistent with the wide range of convective conditions encountered during the campaign. Two extreme cases, with the shortest and the near‐longest TTD, are examined using the dynamical background of the measurements and back trajectory analyses. The result provides physical consistency supporting the hypothesis that sufficient information can be obtained from measurements to resolve dynamical variability of the region. Plain Language Summary In this study, we use measurements of the atmospheric chemical composition to derive vertical transport timescales over the tropical western Pacific, where convective processes dominate. A large suite of trace gases with a wide range of chemical lifetimes are measured from a research aircraft. The trace gas measurements are used to construct “transit time distributions,” which capture the relative contributions of various transport pathways to the chemical composition of the upper troposphere in the study region. Results highlight the wealth of information in atmospheric chemical composition measurements, which is important not only for understanding chemistry of the atmosphere but also for quantifying aspects of atmospheric dynamics and circulation. Key Points The approximations and uncertainties in deriving airborne chemical observation‐based tropospheric transit time distributions are examined The necessary approximation of trace gas lifetimes is found to be the largest source of uncertainty The method successfully identified a range of dynamical transport variability from aircraft measurement

Assessment of Observational Evidence for Direct Convective Hydration of the Lower Stratosphere

In situ and remote sensing observations of water vapor are analyzed to assess the evidence for direct convective hydration of the lower stratosphere. We have examined several hundred balloon‐borne and airborne in situ measurements of lower stratospheric humidity in the tropics and northern midlatitudes. We find that the tropical lower stratospheric H2O enhancements above the background occur quite infrequently, and the height of the enhancements is within about 1 km of the cold‐point tropopause. Following Schwartz et al. (2013, https://doi.org/10.1002/grl.50421), we examine the anomalously high (above 8 ppmv) water vapor mixing ratios retrieved by the Aura Microwave Limb Sounder (MLS) at 100‐ and 82‐hPa pressure levels, and we determine their vertical location relative to the local tropopause based on both Global Forecast System (GFS) operational analysis and the ERA5 reanalysis temperature data. We find that essentially all of the >8‐ppmv MLS water vapor measurements over the extratropical North American monsoon region are above the relatively low lapse‐rate tropopause in the region, and most are above the local cold‐point tropopause. Over the Asian monsoon region, most (80/90%) of the high H2O values occur below the relatively high‐altitude local lapse‐rate/cold‐point tropopause. Anomalously high MLS water vapor retrievals at 100 and 82 hPa almost never occur in the deep tropics. We show that this result is consistent with the in situ observations given the broad vertical averaging kernel of the MLS measurement. The available evidence suggests that direct hydration of the lower stratosphere is important over North America during the monsoon season but likely has limited impact in the tropics

Assessment of Observational Evidence for Direct Convective Hydration of the Lower Stratosphere

In situ and remote sensing observations of water vapor are analyzed to assess the evidence for direct convective hydration of the lower stratosphere. We have examined several hundred balloon‐borne and airborne in situ measurements of lower stratospheric humidity in the tropics and northern midlatitudes. We find that the tropical lower stratospheric H2O enhancements above the background occur quite infrequently, and the height of the enhancements is within about 1 km of the cold‐point tropopause. Following Schwartz et al. (2013, https://doi.org/10.1002/grl.50421), we examine the anomalously high (above 8 ppmv) water vapor mixing ratios retrieved by the Aura Microwave Limb Sounder (MLS) at 100‐ and 82‐hPa pressure levels, and we determine their vertical location relative to the local tropopause based on both Global Forecast System (GFS) operational analysis and the ERA5 reanalysis temperature data. We find that essentially all of the >8‐ppmv MLS water vapor measurements over the extratropical North American monsoon region are above the relatively low lapse‐rate tropopause in the region, and most are above the local cold‐point tropopause. Over the Asian monsoon region, most (80/90%) of the high H2O values occur below the relatively high‐altitude local lapse‐rate/cold‐point tropopause. Anomalously high MLS water vapor retrievals at 100 and 82 hPa almost never occur in the deep tropics. We show that this result is consistent with the in situ observations given the broad vertical averaging kernel of the MLS measurement. The available evidence suggests that direct hydration of the lower stratosphere is important over North America during the monsoon season but likely has limited impact in the tropics

Upward transport into and within the Asian monsoon anticyclone as inferred from StratoClim trace gas observations

Every year during the Asian summer monsoon season from about mid-June to early September, a stable anticyclonic circulation system forms over the Himalayas. This Asian summer monsoon (ASM) anticyclone has been shown to promote transport of air into the stratosphere from the Asian troposphere, which contains large amounts of anthropogenic pollutants. Essential details of Asian monsoon transport, such as the exact timescales of vertical transport, the role of convection in cross-tropopause exchange, and the main location and level of export from the confined anticyclone to the stratosphere are still not fully resolved. Recent airborne observations from campaigns near the ASM anticyclone edge and centre in 2016 and 2017, respectively, show a steady decrease in carbon monoxide (CO) and increase in ozone (O3) with height starting from tropospheric values of around 100 ppb CO and 30–50 ppb O3 at about 365 K potential temperature. CO mixing ratios reach stratospheric background values below ∼25 ppb at about 420 K and do not show a significant vertical gradient at higher levels, while ozone continues to increase throughout the altitude range of the aircraft measurements. Nitrous oxide (N2O) remains at or only marginally below its 2017 tropospheric mixing ratio of 333 ppb up to about 400 K, which is above the local tropopause. A decline in N2O mixing ratios that indicates a significant contribution of stratospheric air is only visible above this level. Based on our observations, we draw the following picture of vertical transport and confinement in the ASM anticyclone: rapid convective uplift transports air to near 16 km in altitude, corresponding to potential temperatures up to about 370 K. Although this main convective outflow layer extends above the level of zero radiative heating (LZRH), our observations of CO concentration show little to no evidence of convection actually penetrating the tropopause. Rather, further ascent occurs more slowly, consistent with isentropic vertical velocities of 0.7–1.5 K d−1. For the key tracers (CO, O3, and N2O) in our study, none of which are subject to microphysical processes, neither the lapse rate tropopause (LRT) around 380 K nor the cold point tropopause (CPT) around 390 K marks a strong discontinuity in their profiles. Up to about 20 to 35 K above the LRT, isolation of air inside the ASM anticyclone prevents significant in-mixing of stratospheric air (throughout this text, the term in-mixing refers specifically to mixing processes that introduce stratospheric air into the predominantly tropospheric inner anticyclone). The observed changes in CO and O3 likely result from in situ chemical processing. Above about 420 K, mixing processes become more significant and the air inside the anticyclone is exported vertically and horizontally into the surrounding stratosphere