-
Quasi-monochromatic gravity-wave-induced oscillations, monitored using the mesospheric OH airglow emission over Kolhapur (16.8° N, 74.2° E), India, during January to April 2010 and January to December 2011, have been characterized using the Krassovsky method. The nocturnal variability reveals prominent wave signatures with periods ranging from 5.2 to 10.8 h as the dominant nocturnal wave with embedded short-period waves having wave periods of 1.5–4.4 h. The results show that the magnitude of the Krassovsky parameter, viz. |<i>η</i>|, ranged from 2.1 to 10.2 h for principal or long nocturnal waves (5.2–10.8 h observed periods), and from 1.5 to 5.4 h for the short waves (1.5–4.4 h observed periods) during the years of 2010 and 2011, respectively. The phase (i.e., Φ) values of the Krassovsky parameters exhibited larger variability and varied from −8.1 to −167°. The deduced mean vertical wavelengths are found to be approximately −60.2 ± 20 and −42.8 ± 35 km for long- and short-period waves for the year 2010. Similarly, for 2011 the mean vertical wavelengths are found to be approximately −77.6 ± 30 and −59.2 ± 30 km for long and short wave periods, respectively, indicating that the observations over Kolhapur were dominated by upward-propagating waves. We use a full-wave model to simulate the response of OH emission to the wave motion and compare the results with observed values.
-
Continuous measurements of atmospheric gaseous elemental mercury (GEM), particulate bound mercury (PBM) and gaseous oxidized mercury (GOM) at the high-altitude Pic du Midi Observatory (PDM Observatory, 2877 m a.s.l.) in southern France were made from November 2011 to November 2012. The mean GEM, PBM and GOM concentrations were 1.86 ng m<sup>−3</sup>, 14 pg m<sup>−3</sup> and 27 pg m<sup>−3</sup>, respectively and we observed 44 high PBM (peak PBM values of 33–98 pg m<sup>−3</sup>) and 61 high GOM (peak GOM values of 91–295 pg m<sup>−3</sup>) events. The high PBM events occurred mainly in cold seasons (winter and spring) whereas high GOM events were mainly observed in the warm seasons (summer and autumn). In cold seasons the maximum air mass residence times (ARTs) associated with high PBM events were observed in the upper troposphere over North America. The ratios of high PBM ARTs to total ARTs over North America, Europe, the Arctic region and Atlantic Ocean were all elevated in the cold season compared to the warm season, indicating that the middle and upper free troposphere of the Northern Hemisphere may be more enriched in PBM in cold seasons. PBM concentrations and PBM ∕ GOM ratios during the high PBM events were significantly anti-correlated with atmospheric aerosol concentrations, air temperature and solar radiation, suggesting in situ formation of PBM in the middle and upper troposphere. We identified two distinct types of high GOM events with the GOM concentrations positively and negatively correlated with atmospheric ozone concentrations, respectively. High GOM events positively correlated with ozone were mainly related to air masses from the upper troposphere over the Arctic region and middle troposphere over the temperate North Atlantic Ocean, whereas high GOM events anti-correlated with ozone were mainly related to air masses from the lower free troposphere over the subtropical North Atlantic Ocean. The ARTs analysis demonstrates that the lower and middle free troposphere over the North Atlantic Ocean was the largest source region of atmospheric GOM at the PDM Observatory. The ratios of high GOM ARTs to total ARTs over the subtropical North Atlantic Ocean in summer were significantly higher than those over the temperate and sub-arctic North Atlantic Ocean as well as that over the North Atlantic Ocean in other seasons, indicating abundant in situ oxidation of GEM to GOM in the lower free troposphere over the subtropical North Atlantic Ocean in summer.
-
In isoprene-impacted environments, carbonyl nitrates are produced from NO<sub>3</sub>-initiated isoprene oxidation, which constitutes a potentially important NO<sub><i>x</i></sub> reservoir. To better understand the fate of isoprene carbonyl nitrates, we synthesized a model compound, <i>trans</i>-2-methyl-4-nitrooxy-2-buten-1-al (4,1-isoprene carbonyl nitrate, or 4,1-isoprene nitrooxy enal), and investigated its photochemical degradation process. The measured OH and O<sub>3</sub> oxidation rate constants (298 K) for this nitrooxy enal are 4.1(±0.7) × 10<sup>−11</sup> cm<sup>3</sup> molecules<sup>−1</sup> s<sup>−1</sup> and 4.4(±0.3) × 10<sup>−18</sup> cm<sup>3</sup> molecules<sup>−1</sup> s<sup>−1</sup>, respectively. Its UV absorption spectrum was determined, and the result is consistent with TDDFT calculations. Based on its UV absorption cross section and photolysis frequency in a reaction chamber, we estimate that the ambient photolysis frequency for this compound is 3.1(±0.8) × 10<sup>−4</sup> s<sup>−1</sup> for a solar zenith angle of 45°. The fast photolysis rate and high reactivity toward OH lead to a lifetime of less than 1 h for the isoprene nitrooxy enal, with photolysis being a dominant daytime sink. The nitrate products derived from the OH oxidation and the photolysis of the nitrooxy enal were identified with an iodide-based chemical ionization mass spectrometer. For the OH oxidation reaction, we quantified the yields of two nitrate products, methyl vinyl ketone nitrate and ethanal nitrate, which together contributed to 36(±5) % of the first-generation products.
-
We simulated the time evolution of atmospheric cluster concentrations in a one-component system where not only do clusters grow by condensation of monomers, but cluster–cluster collisions also significantly contribute to the growth of the clusters. Our aim was to investigate the consistency of the growth rates of sub-3 nm clusters determined with different methods and the validity of the common approach to use them to estimate particle formation rates. We compared the growth rate corresponding to particle fluxes (FGR), the growth rate derived from the appearance times of clusters (AGR), and the growth rate calculated based on irreversible vapor condensation (CGR). We found that the relation between the different growth rates depends strongly on the external conditions and the properties of the model substance. The difference between the different growth rates was typically highest at the smallest, sub-2 nm sizes. FGR was generally lower than AGR and CGR; at the smallest sizes the difference was often very large, while at sizes larger than 2 nm the growth rates were closer to each other. AGR and CGR were in most cases close to each other at all sizes. The difference between the growth rates was generally lower in conditions where cluster concentrations were high, and evaporation and other losses were thus less significant. Furthermore, our results show that the conventional method used to determine particle formation rates from growth rates may give estimates far from the true values. Thus, care must be taken not only in how the growth rate is determined but also in how it is applied.
-
The Weather Research and Forecasting model with Chemistry (WRF-Chem) has been used to simulate a region of Brazil heavily influenced by biomass burning. Nested simulations were run at 5 and 1 km horizontal grid spacing for three case studies in September 2012. Simulations were run with and without fire emissions, convective parameterisation on the 5 km domain, and aerosol–radiation interactions in order to explore the differences attributable to the parameterisations and to better understand the aerosol direct effects and cloud responses. Direct aerosol–radiation interactions due to biomass burning aerosol resulted in a net cooling, with an average short-wave direct effect of −4.08 ± 1.53 Wm<sup>−2</sup>. However, around 21.7 Wm<sup>−2</sup> is absorbed by aerosol in the atmospheric column, warming the atmosphere at the aerosol layer height, stabilising the column, inhibiting convection, and reducing cloud cover and precipitation. The changes to clouds due to radiatively absorbing aerosol (traditionally known as the semi-direct effects) increase the net short-wave radiation reaching the surface by reducing cloud cover, producing a secondary warming that counters the direct cooling. However, the magnitude of the semi-direct effect was found to be extremely sensitive to the model resolution and the use of convective parameterisation. Precipitation became organised in isolated convective cells when not using a convective parameterisation on the 5 km domain, reducing both total cloud cover and total precipitation. The SW semi-direct effect varied from 6.06 ± 1.46 with convective parameterisation to 3.61 ± 0.86 Wm<sup>−2</sup> without. Convective cells within the 1 km domain are typically smaller but with greater updraft velocity than equivalent cells in the 5 km domain, reducing the proportion of the domain covered by cloud in all scenarios and producing a smaller semi-direct effect. Biomass burning (BB) aerosol particles acted as cloud condensation nuclei (CCN), increasing the droplet number concentration of clouds. However, the changes to cloud properties had negligible impact on the net radiative balance in either domain, with or without convective parameterisation. The sensitivity to the uncertainties relating to the semi-direct effect was greater than any other observable indirect effects. Although the version of WRF-Chem distributed to the community currently lacks aerosol–cloud interactions in parameterised clouds, the results of this study suggest a greater priority for the development is to improve the modelling of semi-direct effects by reducing the uncertainties relating to the use of convective parameterisation and resolution before WRF-Chem can reliably quantify the regional impacts of aerosols.
-
This study evaluates the distribution and variation of carbon monoxide (CO) in the upper troposphere and lower stratosphere (UTLS) during 2004–2012 as simulated by two chemical transport models, using the latest version of Aura Microwave Limb Sounder (MLS) observations. The simulated spatial distributions, temporal variations and vertical transport of CO in the UTLS region are compared with those observed by MLS. We also investigate the impact of surface emissions and deep convection on CO concentrations in the UTLS over different regions, using both model simulations and MLS observations. Global Modeling Initiative (GMI) and GEOS-Chem simulations of UTLS CO both show similar spatial distributions to observations. The global mean CO values simulated by both models agree with MLS observations at 215 and 147 hPa, but are significantly underestimated by more than 40 % at 100 hPa. In addition, the models underestimate the peak CO values by up to 70 % at 100 hPa, 60 % at 147 hPa and 40 % at 215 hPa, with GEOS-Chem generally simulating more CO at 100 hPa and less CO at 215 hPa than GMI. The seasonal distributions of CO simulated by both models are in better agreement with MLS in the Southern Hemisphere (SH) than in the Northern Hemisphere (NH), with disagreements between model and observations over enhanced CO regions such as southern Africa. The simulated vertical transport of CO shows better agreement with MLS in the tropics and the SH subtropics than the NH subtropics. We also examine regional variations in the relationships among surface CO emission, convection and UTLS CO concentrations. The two models exhibit emission–convection–CO relationships similar to those observed by MLS over the tropics and some regions with enhanced UTLS CO.
-
National annual total CO<sub>2</sub> emissions from combustion of fossil fuels are likely known to within 5–10 % for most developed countries. However, uncertainties are inevitably larger (by unknown amounts) for emission estimates at regional and monthly scales, or for developing countries. Given recent international efforts to establish emission reduction targets, independent determination and verification of regional and national scale fossil fuel CO<sub>2</sub> emissions are likely to become increasingly important. Here, we take advantage of the fact that precise measurements of <sup>14</sup>C in CO<sub>2</sub> provide a largely unbiased tracer for recently added fossil-fuel-derived CO<sub>2</sub> in the atmosphere and present an atmospheric inversion technique to jointly assimilate observations of CO<sub>2</sub> and <sup>14</sup>CO<sub>2</sub> in order to simultaneously estimate fossil fuel emissions and biospheric exchange fluxes of CO<sub>2</sub>. Using this method in a set of Observation System Simulation Experiments (OSSEs), we show that given the coverage of <sup>14</sup>CO<sub>2</sub> measurements available in 2010 (969 over North America, 1063 globally), we can recover the US national total fossil fuel emission to better than 1 % for the year and to within 5 % for most months. Increasing the number of <sup>14</sup>CO<sub>2</sub> observations to ∼ 5000 per year over North America, as recently recommended by the National Academy of Science (NAS) (Pacala et al., 2010), we recover monthly emissions to within 5 % for all months for the US as a whole and also for smaller, highly emissive regions over which the specified data coverage is relatively dense, such as for the New England states or the NY-NJ-PA tri-state area. This result suggests that, given continued improvement in state-of-the art transport models, a measurement program similar in scale to that recommended by the NAS can provide for independent verification of bottom-up inventories of fossil fuel CO<sub>2</sub> at the regional and national scale. In addition, we show that the dual tracer inversion framework can detect and minimize biases in estimates of the biospheric flux that would otherwise arise in a traditional CO<sub>2</sub>-only inversion when prescribing fixed but inaccurate fossil fuel fluxes.
-
In this paper, we assess how daily ozone (O<sub>3</sub>) measurements from the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp-A platform can contribute to the analyses of the processes driving O<sub>3</sub> variability in the troposphere and the stratosphere and, in the future, to the monitoring of long-term trends. The temporal evolution of O<sub>3</sub> during the first 6 years of IASI (2008–2013) operation is investigated with multivariate regressions separately in four different layers (ground–300, 300–150, 150–25, 25–3 hPa), by adjusting to the daily time series averaged in 20° zonal bands, seasonal and linear trend terms along with important geophysical drivers of O<sub>3</sub> variation (e.g. solar flux, quasi-biennial oscillation (QBO)). The regression model is shown to perform generally very well with a strong dominance of the annual harmonic terms and significant contributions from O<sub>3</sub> drivers, in particular in the equatorial region where the QBO and the solar flux contribution dominate. More particularly, despite the short period of the IASI data set available up to now, two noticeable statistically significant apparent trends are inferred from the daily IASI measurements: a positive trend in the upper stratosphere (e.g. 1.74 ± 0.77 DU year<sup>−1</sup> between 30 and 50° S), which is consistent with other studies suggesting a turnaround for stratospheric O<sub>3</sub> recovery, and a negative trend in the troposphere at the mid-latitudes and high northern latitudes (e.g. −0.26 ± 0.11 DU year<sup>−1</sup> between 30 and 50° N), especially during summer and probably linked to the impact of decreasing ozone precursor emissions. The impact of the high temporal sampling of IASI on the uncertainty in the determination of O<sub>3</sub> trend has been further explored by performing multivariate regressions on IASI monthly averages and on ground-based Fourier transform infrared (FTIR) measurements.
-
Wildfires are not only a threat to human property and a vital element of many ecosystems, but also an important source of air pollution. In this study, we first review the available evidence for a past or possible future climate-driven increase in wildfire emissions in Europe. We then introduce an ensemble of model simulations with a coupled wildfire–dynamic-ecosystem model, which we combine with published spatial maps of both wildfire and anthropogenic emissions of several major air pollutants to arrive at air pollutant emission projections for several time slices during the 21st century. The results indicate moderate wildfire-driven emission increases until 2050, but there is a possibility of large increases until the last decades of this century at high levels of climate change. We identify southern and north-eastern Europe as potential areas where wildfires may surpass anthropogenic pollution sources during the summer months. Under a scenario of high levels of climate change (Representative Concentration Pathway, RCP, 8.5), emissions from wildfires in central and northern Portugal and possibly southern Italy and along the west coast of the Balkan peninsula are projected to reach levels that could affect annual mean particulate matter concentrations enough to be relevant for meeting WHO air quality targets.
-
Aerosols are often advected above cloud decks, and the amount of aerosols over cloud has been assumed to be similar to that at the same heights in nearby clear sky. In this assumption, cloud and aerosol above cloud-top height are considered randomly located with respect to each other. The Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) data are analyzed here to investigate this assumption on global scales. <br><br> The CALIPSO data reveal that the aerosol optical depth (AOD) above low cloud tends to be smaller than in nearby clear sky during the daytime, and the opposite is true during the nighttime. In particular, over oceanic regions with wide-spread low cloud, such as the tropical southeastern Atlantic Ocean and northeastern Pacific Ocean, the daytime AOD above low cloud is often 40 % smaller than in surrounding clear skies.
