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Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with chemical transport model (GEOS-Chem CTM) and back trajectory analyses to provide the first global in-situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing non-fire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation HCOOH is not consistently depleted in the remote marine boundary layer. Over fifty fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.

We report airborne measurements of acetaldehyde (CH3CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH3CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH3CHO is estimated to be 34 Tg a-1 (42 Tg a-1 if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH3CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH3CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH3CHO production in the remote troposphere. The higher-than-expected CH3CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models.

Reactive halogens catalytically destroy O3 and therefore affect (1) stratospheric O3 depletion, and (2) the oxidative capacity of the troposphere. Reactive halogens also partition into the aerosol phase, but what governs halogen-aerosol partitioning is poorly constrained in models. In this work, we present global-scale measurements of non-sea-salt aerosol (nSSA) bromine and iodine taken during the NASA Atmospheric Tomography Mission (ATom). Using the Particle Analysis by Laser Mass Spectrometry instrument, we found that bromine and iodine are present in 8-26 % (interquartile range, IQR) and 12-44 % (IQR) of accumulation-mode nSSA, respectively. Despite being commonly found in nSSA, the mass concentrations of bromine and iodine in nSSA were low, 0.11-0.57 pmol mol-1 (IQR) and 0.04–0.24 pmol mol-1 (IQR), respectively. In the troposphere, we find two distinct sources of bromine and iodine to nSSA: (1) a primary source from biomass burning, and (2) a pervasive secondary source. In the stratosphere, nSSA bromine and iodine mass increased with increasing O3 concentrations; however, higher concentrations of stratospheric nSSA bromine and iodine were found in organic-rich particles that originated in the troposphere. Finally, we compared our ATom nSSA iodine measurements to the global chemical transport model GEOS-Chem; nSSA bromine concentrations could not be compared because they were not tracked in the model. We found that the model compared well to our ATom nSSA iodine measurements in the background atmosphere, but not in the marine boundary layer, biomass burning plumes, or in the stratosphere. [ABSTRACT FROM AUTHOR]

Observational monitoring of the stratospheric transport circulation, the Brewer–Dobson circulation (BDC), is crucial to estimate any decadal to long-term changes therein, a prerequisite to interpret trends in stratospheric composition and to constrain the consequential impacts on climate. The transport time along the BDC (i.e. the mean stratospheric age of air, AoA) can best be deduced from trace gas measurements of tracers which increase linearly with time and are chemically passive. The gas sulfur hexafluoride (SF 6) is often used to deduce AoA because it has been increasing monotonically since the ∼ 1950s, and previously its chemical sinks in the mesosphere have been assumed to be negligible for AoA estimates. However, recent studies have shown that the chemical sinks of SF 6 are stronger than assumed and become increasingly relevant with rising SF 6 concentrations. To adjust biases in AoA that result from the chemical SF 6 sinks, we here propose a simple correction scheme for SF 6 -based AoA estimates accounting for the time-dependent effects of chemical sinks. The correction scheme is based on theoretical considerations with idealized assumptions, resulting in a relation between ideal AoA and apparent AoA which is a function of the tropospheric reference time series of SF 6 and of the AoA-dependent effective lifetime of SF 6. The correction method is thoroughly tested within a self-consistent data set from a climate model that includes explicit calculation of chemical SF 6 sinks. It is shown within the model that the correction successfully reduces biases in SF 6 -based AoA to less than 5 % for mean ages below 5 years. Tests using only subsampled data for deriving the fit coefficients show that applying the correction scheme even with imperfect knowledge of the sink is far superior to not applying a sink correction. Furthermore, we show that based on currently available measurements, we are not able to constrain the fit parameters of the correction scheme based on observational data alone. However, the model-based correction curve lies within the observational uncertainty, and we thus recommend using the model-derived fit coefficients until more high-quality measurements are able to further constrain the correction scheme. The application of the correction scheme to AoA from satellites and in situ data suggests that it is highly beneficial to reconcile different observational estimates of mean AoA. [ABSTRACT FROM AUTHOR]

The Montreal Protocol was designed to protect the stratospheric ozone layer by enabling reductions in the abundance of ozone-depleting substances such as chlorofluorocarbons (CFCs) in the atmosphere.sup.1-3. The reduction in the atmospheric concentration of trichlorofluoromethane (CFC-11) has made the second-largest contribution to the decline in the total atmospheric concentration of ozone-depleting chlorine since the 1990s.sup.1. However, CFC-11 still contributes one-quarter of all chlorine reaching the stratosphere, and a timely recovery of the stratospheric ozone layer depends on a sustained decline in CFC-11 concentrations.sup.1. Here we show that the rate of decline of atmospheric CFC-11 concentrations observed at remote measurement sites was constant from 2002 to 2012, and then slowed by about 50 per cent after 2012. The observed slowdown in the decline of CFC-11 concentration was concurrent with a 50 per cent increase in the mean concentration difference observed between the Northern and Southern Hemispheres, and also with the emergence of strong correlations at the Mauna Loa Observatory between concentrations of CFC-11 and other chemicals associated with anthropogenic emissions. A simple model analysis of our findings suggests an increase in CFC-11 emissions of 13 [plus or minus] 5 gigagrams per year (25 [plus or minus] 13 per cent) since 2012, despite reported production being close to zero.sup.4 since 2006. Our three-dimensional model simulations confirm the increase in CFC-11 emissions, but indicate that this increase may have been as much as 50 per cent smaller as a result of changes in stratospheric processes or dynamics. The increase in emission of CFC-11 appears unrelated to past production; this suggests unreported new production, which is inconsistent with the Montreal Protocol agreement to phase out global CFC production by 2010.Atmospheric CFC-11 concentrations have been declining less rapidly since 2012; evidence suggests that this finding is explained by an increase in the emission of CFC-11during these years., Author(s): Stephen A. Montzka [sup.1] , Geoff S. Dutton [sup.1] [sup.2] , Pengfei Yu [sup.2] [sup.3] , Eric Ray [sup.2] [sup.3] , Robert W. Portmann [sup.3] , John S. Daniel [...]

Observational monitoring of the stratospheric transport circulation, the Brewer-Dobson-Circulation (BDC), is crucial to estimate any decadal to long-term changes therein, a prerequisite to interpret trends in stratospheric composition and to constrain the consequential impacts on climate. The transport time along the BDC (i.e., the mean age of stratospheric air, AoA) can best be deduced from trace gas measurements of tracers which increase linearly in time and are chemically passive. The gas SF 6 is often used to deduce AoA, because it has been increasing monotonically since the ~1950s, and previously its chemical sinks in the mesosphere have been assumed to be negligible for AoA estimates. However, recent studies have shown that the chemical sinks of SF 6 are stronger than assumed, and become increasingly relevant with rising SF 6 concentrations. To adjust biases in AoA that result from the chemical SF 6 sinks, we here propose a simple correction scheme for SF 6-based AoA estimates accounting for the time-dependent effects of chemical sinks. The correction scheme is based on theoretical considerations with idealized assumptions, resulting in a relation between ideal AoA and apparent AoA which is a function of the tropospheric reference time-series of SF 6 and of the AoA-dependent effective lifetime of SF 6. The correction method is thoroughly tested within a self-consistent data set from a climate model that includes explicit calculation of chemical SF 6 sinks. It is shown within the model that the correction successfully reduces biases in SF 6-based AoA to less than 5 % for mean ages below 5 years. Tests with using only sub-sampled data for deriving the fit coefficients show that applying the correction scheme even with imperfect knowledge of the sink is far superior to not applying a sink correction. Further, we show that based on currently available measurements, we are not able to constrain the fit parameters of the correction scheme based on observational data alone. However, the model-based correction curve lies within the observational uncertainty, and we thus recommend to use the model-derived fit coefficients until more high-quality measurements will be able to further constrain the correction scheme. The application of the correction scheme to AoA from satellites and in-situ data suggests that it is highly beneficial to reconcile different observational estimates of mean AoA. [ABSTRACT FROM AUTHOR]

Several analyses of satellite-based ozone measurements have reported that lower-stratospheric ozone has declined since the late 1990s. In contrast to this, lower-stratospheric ozone was found to be increasing in specified-dynamics (SD) simulations from the Whole Atmosphere Community Climate Model (WACCM-SD) despite the fact that these simulations are expected to represent the real-world dynamics and chemistry relevant to stratospheric ozone changes. This paper seeks to explain this specific model and observational discrepancy and to more generally examine the relationship between tropical lower-stratospheric upwelling and lower-stratospheric ozone. This work shows that, in general, the standard configuration of WACCM-SD fails to reproduce the tropical upwelling changes present in its input reanalysis fields. Over the period 1998 to 2016, WACCM-SD has a spurious negative upwelling trend that induces a positive near-global lower-stratospheric column ozone trend and that accounts for much of the apparent discrepancy between modeled and observed ozone trends. Using a suite of SD simulations with alternative nudging configurations, it is shown that short-term (∼ 2-decade) lower-stratospheric ozone trends scale linearly with short-term trends in tropical lower-stratospheric upwelling near 85 hPa. However, none of the simulations fully capture the recent ozone decline, and the ozone and upwelling scaling in the WACCM simulations suggests that a large short-term upwelling trend (∼ 6 % decade -1) would be needed to explain the observed satellite trends. The strong relationship between ozone and upwelling, coupled with both the large range of reanalysis upwelling trend estimates and the inability of WACCM-SD simulations to reproduce upwelling from their input reanalyses, severely limits the use of SD simulations for accurately reproducing recent ozone variability. However, a free-running version of WACCM using only surface boundary conditions and a nudged quasi-biennial oscillation produces a positive decadal-scale lower-stratospheric upwelling trend and a negative near-global lower-stratospheric column ozone trend that is in closest agreement with the ozone observations. [ABSTRACT FROM AUTHOR]

Several analyses of satellite-based ozone measurements have reported that lower stratospheric ozone has declined since the late 1990s. In contrast to this, lower stratospheric ozone was found to be increasing in specified dynamics (SD) simulations from version 4 of the Whole Atmosphere Community Climate Model (WACCM-SD) where the model was nudged using reanalysis wind/temperature fields. This paper demonstrates that the standard configuration of WACCM-SD fails to reproduce the underlying tropical upwelling changes present in the reanalysis fields used to drive the model. Over the period since the late 1990s, WACCM-SD has a spurious negative upwelling trend that induces a positive quasi-global lower stratospheric column ozone trend and accounts for much of the apparent discrepancy between modeled and observed ozone trends. Using a suite of SD simulations with alternative nudging configurations, it is shown that short-term (~2 decade) ozone trends scale linearly with short-term trends in tropical upwelling. However, none of the simulations capture the recent ozone decline, and the ozone/upwelling scaling in the WACCM simulations suggests that a large short-term upwelling trend (~6 % decade-1) would be needed to explain the observed satellite trends. The strong relationship between ozone and upwelling, coupled with both the large range of reanalysis upwelling trend estimates and the inability of WACCM-SD simulations to reproduce upwelling from their input reanalyses, severely limits the use of these simulations for accurately reproducing recent ozone variability. Contrary to expectations, a free-running version of WACCM using only surface boundary conditions and a nudged QBO more closely captures both interannual variability and decadal-scale ozone "trends" than the SD simulations. [ABSTRACT FROM AUTHOR]