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Evaluating stratospheric ozone and water vapour changes in CMIP6 models from 1850 to 2100
Stratospheric ozone and water vapour are key components of the Earth system, and past and future changes to both have important impacts on global and regional climate. Here, we evaluate long-term changes in these species from the pre-industrial period (1850) to the end of the 21st century in Coupled Model Intercomparison Project phase 6 (CMIP6) models under a range of future emissions scenarios. There is good agreement between the CMIP multi-model mean and observations for total column ozone (TCO), although there is substantial variation between the individual CMIP6 models. For the CMIP6 multi-model mean, global mean TCO has increased from ∼300 DU in 1850 to ∼ 305 DU in 1960, before rapidly declining in the 1970s and 1980s following the use and emission of halogenated ozone-depleting substances (ODSs). TCO is projected to return to 1960s values by the middle of the 21st century under the SSP2-4.5, SSP3-7.0, SSP4-3.4, SSP4-6.0, and SSP5-8.5 scenarios, and under the SSP3-7.0 and SSP5-8.5 scenarios TCO values are projected to be ∼ 10 DU higher than the 1960s values by 2100. However, under the SSP1-1.9 and SSP1-1.6 scenarios, TCO is not projected to return to the 1960s values despite reductions in halogenated ODSs due to decreases in tropospheric ozone mixing ratios. This global pattern is similar to regional patterns, except in the tropics where TCO under most scenarios is not projected to return to 1960s values, either through reductions in tropospheric ozone under SSP1-1.9 and SSP1-2.6, or through reductions in lower stratospheric ozone resulting from an acceleration of the Brewer-Dobson circulation under other Shared Socioeconomic Pathways (SSPs). In contrast to TCO, there is poorer agreement between the CMIP6 multi-model mean and observed lower stratospheric water vapour mixing ratios, with the CMIP6 multi-model mean underestimating observed water vapour mixing ratios by ∼ 0.5 ppmv at 70 hPa. CMIP6 multi-model mean stratospheric water vapour mixing ratios in the tropical lower stratosphere have increased by ∼ 0.5 ppmv from the pre-industrial to the present-day period and are projected to increase further by the end of the 21st century. The largest increases (∼ 2 ppmv) are simulated under the future scenarios with the highest assumed forcing pathway (e.g. SSP5-8.5). Tropical lower stratospheric water vapour, and to a lesser extent TCO, shows large variations following explosive volcanic eruptions. © Author(s) 2021.
High-molecular-weight esters in α-pinene ozonolysis secondary organic aerosol: Structural characterization and mechanistic proposal for their formation from highly oxygenated molecules
Stable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C19H28O7) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C17H26O8). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on high-molecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MWg368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MWg358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C19H28O11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012, 2014). It is suggested that an acyl peroxy radical related to cis-pinic acid (RO2•) and an alkoxy radical related to 7- or 5-hydroxypinonic acid (R′O•) serve as key gas-phase radicals and combine according to a RO2g+gR′O•→ gRO3R′ radical termination reaction. Subsequently, the unstable C19H28O11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C19H28O7 (MWg368) and C17H26O8 (MWg358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO2g+gR′O•→ gRO3R′ chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.
Ozone–gravity wave interaction in the upper stratosphere/lower mesosphere
The increase in amplitudes of upward propagating gravity waves (GWs) with height due to decreasing density is usually described by exponential growth. Recent measurements show some evidence that the upper stratospheric/lower mesospheric gravity wave potential energy density (GWPED) increases more strongly during the daytime than during the nighttime. This paper suggests that ozone-gravity wave interaction can principally produce such a phenomenon. The coupling between ozone-photochemistry and temperature is particularly strong in the upper stratosphere where the time-mean ozone mixing ratio decreases with height. Therefore, an initial ascent (or descent) of an air parcel must lead to an increase (or decrease) in ozone and in the heating rate compared to the environment, and, hence, to an amplification of the initial wave perturbation. Standard solutions of upward propagating GWs with linear ozone-temperature coupling are formulated, suggesting amplitude amplifications at a specific level during daytime of 5ĝ€¯% to 15ĝ€¯% for low-frequency GWs (periods ≥4ĝ€¯h), as a function of the intrinsic frequency which decreases if ozone-temperature coupling is included. Subsequently, the cumulative amplification during the upward level-by-level propagation leads to much stronger GW amplitudes at upper mesospheric altitudes, i.e., for single low-frequency GWs, up to a factor of 1.5 to 3 in the temperature perturbations and 3 to 9 in the GWPED increasing from summer low to polar latitudes. Consequently, the mean GWPED of a representative range of mesoscale GWs (horizontal wavelengths between 200 and 1100ĝ€¯km, vertical wavelengths between 3 and 9ĝ€¯km) is stronger by a factor of 1.7 to 3.4 (2 to 50ĝ€¯Jĝ€¯kg-1, or 2ĝ€¯% to 50ĝ€¯% in relation to the observed order of 100ĝ€¯Jĝ€¯kg-1, assuming initial GW perturbations of 1 to 2ĝ€¯K in the middle stratosphere). Conclusively, the identified process might be an important component in the middle atmospheric circulation, which has not been considered up to now.
Longitude-dependent decadal ozone changes and ozone trends in boreal winter months during 1960-2000
This study examines the longitude-dependent decadal changes and trends of ozone for the boreal winter months during the period of 1960–2000. These changes are caused primarily by changes in the planetary wave structure in the upper troposphere and lower stratosphere. The decadal changes and trends over 4 decades of geopotential perturbations, defined as a deviation from the zonal mean, are estimated by linear regression with time. The decadal changes in longitude-dependent ozone were calculated with a simple transport model of ozone based on the known planetary wave structure changes and prescribed zonal mean ozone gradients. For December of the 1960s and 1980s a statistically significant Rossby wave track appeared over the North Atlantic and Europe with an anticyclonic disturbance over the Eastern North Atlantic and Western Europe, flanked by cyclonic disturbances. In the 1970s and 1990s statistically significant cyclonic disturbances appeared over the Eastern North Atlantic and Europe, surrounded by anticyclonic anomalies over Northern Africa, Central Asia and Greenland. Similar patterns have been found for January. The Rossby wave track over the North Atlantic and Europe is stronger in the 1980s than in the 1960s. For February, the variability of the regression patterns is higher. For January we found a strong alteration in the modelled decadal changes in total ozone over Central and Northern Europe, showing a decrease of about 15 DU in the 1960s and 1980s and an increase of about 10 DU in the 1970s and 1990s. Over Central Europe the positive geopotential height trend (increase of 2.3 m/yr) over 40 years is of the same order (about 100 m) as the increase in the 1980s alone. This is important to recognize because it implies a total ozone decrease over Europe of the order of 14 DU for the 1960–2000 period, for January, if we use the standard change regression relation that about a 10-m geopotential height increase at 300 hPa is related to about a 1.4-DU total ozone decrease.
Diurnal variation of midlatitudinal NO3 column abundance over table mountain facility, California
The column abundance of NO3 was measured over Table Mountain Facility, CA (34.4° 117.7° W) from May 2003 through September 2004, using lunar occultation near full moon with a grating spectrometer. The NO 3 column retrieval was performed with the differential optical absorption spectroscopy (DOAS) technique using both the 623 and 662 nm NO 3 absorption bands. Other spectral features such as Fraunhofer lines and absorption from water vapor and oxygen were removed using solar spectra obtained at different airmass factors. We observed a seasonal variation, with nocturnally averaged NO3 columns between 5-7 × 1013 molec cm-2 during October through March, and 5-22 × 10 13 molec cm-2 during April through September. A subset of the data, with diurnal variability vastly different from the temporal profile obtained from one-dimensional stratospheric model calculations, clearly has boundary layer contributions; this was confirmed by simultaneous long-path DOAS measurements. However, even the NO3 columns that did follow the modeled time evolution were often much larger than modeled stratospheric partial columns constrained by realistic temperatures and ozone concentrations. This discrepancy is attributed to substantial tropospheric NO3 in the free troposphere, which may have the same time dependence as stratospheric NO 3.
Long-term wintertime trend of zonally asymmetric ozone in boreal extratropics during 1979-2016
Strong zonally asymmetric ozone (ZAO) changes are observed in the boreal extratropics for winter. During the TOMS (Total Ozone Mapping Spectrometer) period (1979-1992) the decrease of zonally asymmetric total ozone (ZATO) was twice as large as the observed zonal mean total ozone trend over Europe in January mainly caused by ultra-long wave transport. Recent studies have demonstrated that the ozone evolution reveals three different quasi-bidecadal trend stages: (i) Decline, (ii) leveling, and (ii) healing. This study focuses on the ZAO structure in boreal extratropics and on ozone transport changes by ultra-long waves during winter months. ERA-Interim data together with a linearized transport model are used. During the healing stage ZATO increases significantly over the North Atlantic/European region for January. The ZATO increase (healing stage) and ZATO decrease (decline stage) are caused by different monthly mean ozone transport characteristics of ultra-long planetary waves over the North Atlantic/European region. Furthermore, the vertical advection (ageostrophic transport) of ozone versus its horizontal component dominates in the lower and middle stratosphere during the healing stage. It is hypothesized that these ageostrophic wind changes are mainly caused by a wave train directed northeastwards which seems to be directly linked to the Arctic warming. © 2018 by the authors.
Zonal asymmetries in middle atmospheric ozone and water vapour derived from Odin satellite data 2001-2010
Stationary wave patterns in middle atmospheric ozone (O3) and water vapour (H2O) are an important factor in the atmospheric circulation, but there is a strong gap in diagnosing and understanding their configuration and origin. Based on Odin satellite data from 2001 to 2010 we investigate the stationary wave patterns in O3 and H2O as indicated by the seasonal long-term means of the zonally asymmetric components O3* Combining double low line O3-[O3] and H2O* Combining double low line H2O-[H2O] ([O3], [H2O]: zonal means). At mid-and polar latitudes we find a pronounced wave one pattern in both constituents. In the Northern Hemisphere, the wave patterns increase during autumn, maintain their strength during winter and decay during spring, with maximum amplitudes of about 10-20 % of the zonal mean values. During winter, the wave one in O3* shows a maximum over the North Pacific/Aleutians and a minimum over the North Atlantic/Northern Europe and a double-peak structure with enhanced amplitude in the lower and in the upper stratosphere. The wave one in H2O* extends from the lower stratosphere to the upper mesosphere with a westward shift in phase with increasing height including a jump in phase at upper stratosphere altitudes. In the Southern Hemisphere, similar wave patterns occur mainly during southern spring. By comparing the observed wave patterns in O 3* and H2O3* with a linear solution of a steady-state transport equation for a zonally asymmetric tracer component we find that these wave patterns are primarily due to zonally asymmetric transport by geostrophically balanced winds, which are derived from observed temperature profiles. In addition temperature-dependent photochemistry contributes substantially to the spatial structure of the wave pattern in O 3* . Further influences, e.g., zonal asymmetries in eddy mixing processes, are discussed.
Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics
The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate) parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O 2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl 2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS) data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007) are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO + ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen emissions and climate. Further laboratory, theoretical, and possibly atmospheric studies are needed.
Results from the validation campaign of the ozone radiometer GROMOS-C at the NDACC station of Réunion island
Ozone performs a key role in the middle atmosphere and its monitoring is thus necessary. At the Institute of Applied Physics of the University of Bern, Switzerland, we built a new ground-based microwave radiometer, GROMOS-C (GRound based Ozone MOnitoring System for Campaigns). It has a compact design and can be operated remotely with very little maintenance requirements, being therefore suitable for remote deployments. It has been conceived to measure the vertical distribution of ozone in the middle atmosphere, by observing pressure-broadened emission spectra at a frequency of 110.836 GHz. In addition, meridional and zonal wind profiles can be retrieved, based on the Doppler shift of the ozone line measured in the four directions of observation (north, east, south and west). In June 2014 the radiometer was installed at the Maïdo observatory, on Réunion island (21.2° S, 55.5° E). High-resolution ozone spectra were recorded continuously over 7 months. Vertical profiles of ozone have been retrieved through an optimal estimation inversion process, using the Atmospheric Radiative Transfer Simulator ARTS2 as the forward model. The validation is performed against ozone profiles from the Microwave Limb Sounder (MLS) on the Aura satellite, the ozone lidar located at the observatory and with ozone profiles from weekly radiosondes. Zonal and meridional winds retrieved from GROMOS-C data are validated against another wind radiometer located in situ, WIRA. In addition, we compare both ozone and winds with ECMWF (European Centre for Medium-Range Weather Forecasts) model data. Results show that GROMOS-C provides reliable ozone profiles between 30 and 0.02 hPa. The comparison with lidar profiles shows a very good agreement at all levels. The accordance with the MLS data set is within 5 % for pressure levels between 25 and 0.2 hPa. GROMOS-C's wind profiles are in good agreement with the observations by WIRA and with the model data, differences are below 5 m s−1 for both.
Hydroxyl layer: trend of number density and intra-annual variability
The layer of vibrationally excited hydroxyl (OH*) near the mesopause in Earth's atmosphere is widely used to derive the temperature at this height and to observe dynamical processes such as gravity waves. The concentration of OH* is controlled by the product of atomic hydrogen, with ozone creating a layer of enhanced concentration in the mesopause region. However, the basic influences on the OH* layer are atomic oxygen and temperature. The long-term monitoring of this layer provides information on a changing atmosphere. It is important to know which proportion of a trend results from anthropogenic impacts on the atmosphere and which proportion reflects natural variations. In a previous paper (Grygalashvyly et al., 2014), the trend of the height of the layer and the trend in temperature were investigated particularly in midlatitudes on the basis of our coupled dynamic and chemical transport model LIMA (Leibniz Institute Middle Atmosphere). In this paper we consider the trend for the number density between the years 1961 and 2009 and analyze the reason of the trends on a global scale. Further, we consider intra-annual variations. Temperature and wind have the strongest impacts on the trend. Surprisingly, the increase in greenhouse gases (GHGs) has no clear influence on the chemistry of OH*. The main reason for this lies in the fact that, in the production term of OH*, if atomic hydrogen increases due to increasing humidity of the middle atmosphere by methane oxidation, ozone decreases. The maximum of the OH* layer is found in the mesopause region and is very variable. The mesopause region is a very intricate domain marked by changeable dynamics and strong gradients of all chemically active minor constituents determining the OH* chemistry. The OH* concentration responds, in part, very sensitively to small changes in these parameters. The cause for this behavior is given by nonlinear reactions of the photochemical system being a nonlinear enforced chemical oscillator driven by the diurnal-periodic solar insolation. At the height of the OH* layer the system operates in the vicinity of chemical resonance. The solar cycle is mirrored in the data, but the long-term behavior due to the trend in the Lyman-α radiation is very small. The number density shows distinct hemispheric differences. The calculated OH* values show sometimes a step around a certain year. We introduce a method to find out the date of this step and discuss a possible reason for such behavior.