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Two different collection kernels which include turbulence effects on the collision rate of liquid droplets are used as a basis to develop a parameterization of the warm-rain processes autoconversion, accretion, and self-collection. The new parameterization is tested and validated with the help of a 1-D bin microphysics model. Large-eddy simulations of the rain formation in shallow cumulus clouds confirm previous results that turbulence effects can significantly enhance the development of rainwater in clouds and the occurrence and amount of surface precipitation. The detailed behavior differs significantly for the two turbulence models, revealing a considerable uncertainty in our understanding of such effects. In addition, the large-eddy simulations show a pronounced sensitivity to grid resolution, which suggests that besides the effect of sub-grid small-scale isotropic turbulence which is parameterized as part of the collection kernel also the larger turbulent eddies play an important role for the formation of rain in shallow clouds.
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Different treatments of the Kelvin effect in LES modeling of early contrails are shown to cause variations in the survival rate of ice particles by up to a factor of 4 and in optical depth and mean particle size by up to 50 %. The Kelvin effect which varies exponentially with particle size, can reduce or even suppress the impact of other important ambient parameters, such as ice supersaturation, on particle survival rate. Lowering or neglecting the Kelvin effect is shown to substantially alter the evolution of the ice particle size distribution and delay the onset of particle loss. A strongly Kelvin effect dependent exponential relation between particle survival rate and particle size is shown for high <i>EI</i><sub><i>soot</i></sub> (<i>O</i>(10<sup>15</sup>)).
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In the framework of the ChArMEx (the Chemistry-Aerosol Mediterranean Experiment; <a href="http://charmex.lsce.ipsl.fr/" target="_blank">http://charmex.lsce.ipsl.fr/</a>) program, the seasonal variability of the aerosol optical, microphysical and radiative properties derived from AERONET (Aerosol Robotic Network; <a href="http://aeronet.gsfc.nasa.gov/" target="_blank">http://aeronet.gsfc.nasa.gov/</a>) is examined in two regional background insular sites in the western Mediterranean Basin: Ersa (Corsica Island, France) and Palma de Mallorca (Mallorca Island, Spain). A third site, Alborán (Alborán Island, Spain), with only a few months of data is considered for examining possible northeast–southwest (NE–SW) gradients of the aforementioned aerosol properties. The AERONET dataset is exclusively composed of level 2.0 inversion products available during the 5-year period 2011–2015. AERONET solar radiative fluxes are compared with ground- and satellite-based flux measurements. To the best of our knowledge this is the first time that AERONET fluxes are compared with measurements at the top of the atmosphere. Strong events (with an aerosol optical depth at 440 nm greater than 0.4) of long-range transport aerosols, one of the main drivers of the observed annual cycles and NE–SW gradients, are (1) mineral dust outbreaks predominant in spring and summer in the north and in summer in the south and (2) European pollution episodes predominant in autumn. A NE–SW gradient exists in the western Mediterranean Basin for the aerosol optical depth and especially its coarse-mode fraction, which all together produces a similar gradient for the aerosol direct radiative forcing. The aerosol fine mode is rather homogeneously distributed. Absorption properties are quite variable because of the many and different sources of anthropogenic particles in and around the western Mediterranean Basin: North African and European urban areas, the Iberian and Italian peninsulas, most forest fires and ship emissions. As a result, the aerosol direct forcing efficiency, more dependent to absorption than the absolute forcing, has no marked gradient.
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Future trends in Arctic springtime total column ozone, and its chemical and dynamical drivers, are assessed using a seven-member ensemble from the Met Office Unified Model with United Kingdom Chemistry and Aerosols (UM-UKCA) simulating the period 1960–2100. The Arctic mean March total column ozone increases throughout the 21st century at a rate of ∼ 11.5 DU decade<sup>−1</sup>, and is projected to return to the 1980 level in the late 2030s. However, the integrations show that even past 2060 springtime Arctic ozone can episodically drop by ∼ 50–100 DU below the corresponding long-term ensemble mean for that period, reaching values characteristic of the near-present-day average level. Consistent with the global decline in inorganic chlorine (Cl<sub><i>y</i></sub>) over the century, the estimated mean halogen-induced chemical ozone loss in the Arctic lower atmosphere in spring decreases by around a factor of 2 between the periods 2001–2020 and 2061–2080. However, in the presence of a cold and strong polar vortex, elevated halogen-induced ozone losses well above the corresponding long-term mean continue to occur in the simulations into the second part of the century. The ensemble shows a significant cooling trend in the Arctic winter mid- and upper stratosphere, but there is less confidence in the projected temperature trends in the lower stratosphere (100–50 hPa). This is partly due to an increase in downwelling over the Arctic polar cap in winter, which increases transport of ozone into the polar region as well as drives adiabatic warming that partly offsets the radiatively driven stratospheric cooling. However, individual winters characterised by significantly suppressed downwelling, reduced transport and anomalously low temperatures continue to occur in the future. We conclude that, despite the projected long-term recovery of Arctic ozone, the large interannual dynamical variability is expected to continue in the future, thereby facilitating episodic reductions in springtime ozone columns. Whilst our results suggest that the relative role of dynamical processes for determining Arctic springtime ozone will increase in the future, halogen chemistry will remain a smaller but non-negligible contributor for many decades to come.
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An accurate understanding of urban air quality requires considering a coupled behavior between the dispersion of reactive pollutants and atmospheric dynamics. Currently, urban air pollution is mostly dominated by traffic emission, where nitrogen oxides (NO<sub><i>x</i></sub>) and volatile organic compounds (VOCs) are the primary emitted pollutants. However, modeling reactive pollutants with a large set of chemical reactions, using a computational fluid dynamic (CFD) model, requires a large amount of computational (CPU) time. In this sense, the selection of the chemical reactions needed in different atmospheric conditions becomes essential in finding the best compromise between CPU time and accuracy. The purpose of this work is to assess the differences in NO and NO<sub>2</sub> concentrations by considering three chemical approaches: (a) passive tracers (non-reactive), (b) the NO<sub><i>x</i></sub>–O<sub>3</sub> photostationary state and (c) a reduced complex chemical mechanism based on 23 species and 25 reactions. The appraisal of the effects of chemical reactions focuses on studying the NO and NO<sub>2</sub> dispersion in comparison with the tracer behavior within the street. In turn, the effect of including VOC reactions is also analyzed taking into account several VOC ∕ NO<sub><i>x</i></sub> ratios of traffic emission. Given that the NO and NO<sub>2</sub> dispersion can also be affected by atmospheric conditions, such as wind flow or the background concentration from season-dependent pollutants, in this work the influence of wind speeds and background O<sub>3</sub> concentrations are studied. The results show that the presence of ozone in the street plays an important role in NO and NO<sub>2</sub> concentrations. Therefore, greater differences linked to the chemical approach used are found with higher O<sub>3</sub> concentrations and faster wind speeds. This bears relation to the vertical flux as a function of ambient wind speed since it increases the pollutant exchange between the street and the overlying air. This detailed study allows one to ascertain under which atmospheric conditions the inclusion of chemical reactions are necessary for the study of NO and NO<sub>2</sub> dispersion. The conclusions can be applied to future studies in order to establish the chemical reactions needed in terms of an accurate modeling of NO and NO<sub>2</sub> dispersion and the CPU time required in a real urban area.
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Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel <i>METEOR</i> in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr<sub>3</sub>) and dibromomethane (CH<sub>2</sub>Br<sub>2</sub>) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH<sub>3</sub>I) of up to 35.4 pmol L<sup>−1</sup>, chloroiodomethane (CH<sub>2</sub>ClI) of up to 58.1 pmol L<sup>−1</sup> and diiodomethane (CH<sub>2</sub>I<sub>2</sub>) of up to 32.4 pmol L<sup>−1</sup> in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH<sub>3</sub>I (up to 3.2 ppt), CH<sub>2</sub>ClI (up to 2.5 ppt) and CH<sub>2</sub>I<sub>2</sub> (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.
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During a cruise of R/V <i>METEOR</i> in December 2012 the oceanic sources and emissions of various halogenated trace gases and their mixing ratios in the marine atmospheric boundary layer (MABL) were investigated above the Peruvian upwelling. This study presents novel observations of the three very short lived substances (VSLSs) – bromoform, dibromomethane and methyl iodide – together with high-resolution meteorological measurements, Lagrangian transport and source–loss calculations. Oceanic emissions of bromoform and dibromomethane were relatively low compared to other upwelling regions, while those for methyl iodide were very high. Radiosonde launches during the cruise revealed a low, stable MABL and a distinct trade inversion above acting as strong barriers for convection and vertical transport of trace gases in this region. Observed atmospheric VSLS abundances, sea surface temperature, relative humidity and MABL height correlated well during the cruise. We used a simple source–loss estimate to quantify the contribution of oceanic emissions along the cruise track to the observed atmospheric concentrations. This analysis showed that averaged, instantaneous emissions could not support the observed atmospheric mixing ratios of VSLSs and that the marine background abundances below the trade inversion were significantly influenced by advection of regional sources. Adding to this background, the observed maximum emissions of halocarbons in the coastal upwelling could explain the high atmospheric VSLS concentrations in combination with their accumulation under the distinct MABL and trade inversions. Stronger emissions along the nearshore coastline likely added to the elevated abundances under the steady atmospheric conditions. This study underscores the importance of oceanic upwelling and trade wind systems on the atmospheric distribution of marine VSLS emissions.
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High-resolution in situ balloon measurements of water vapour, aerosol, methane and temperature in the upper tropical tropopause layer (TTL) and lower stratosphere are used to evaluate the processes affecting the stratospheric water budget: horizontal transport (in-mixing) and hydration by cross-tropopause overshooting updrafts. The obtained in situ evidence of these phenomena are analysed using satellite observations by Aura MLS (Microwave Limb Sounder) and CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) together with trajectory and transport modelling performed using CLaMS (Chemical Lagrangian Model of the Stratosphere) and HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory) model.<br><br> Balloon soundings were conducted during March 2012 in Bauru, Brazil (22.3° S) in the frame of the TRO-Pico campaign for studying the impact of convective overshooting on the stratospheric water budget. The balloon payloads included two stratospheric hygrometers: FLASH-B (Fluorescence Lyman-Alpha Stratospheric Hygrometer for Balloon) and Pico-SDLA instrument as well as COBALD (Compact Optical Backscatter Aerosol Detector) sondes, complemented by Vaisala RS92 radiosondes. Water vapour vertical profiles obtained independently by the two stratospheric hygrometers are in excellent agreement, ensuring credibility of the vertical structures observed.<br><br> A signature of in-mixing is inferred from a series of vertical profiles, showing coincident enhancements in water vapour (of up to 0.5 ppmv) and aerosol at the 425 K (18.5 km) level. Trajectory analysis unambiguously links these features to intrusions from the Southern Hemisphere extratropical stratosphere, containing more water and aerosol, as demonstrated by MLS and CALIPSO global observations. The in-mixing is successfully reproduced by CLaMS simulations, showing a relatively moist filament extending to 20° S. A signature of local cross-tropopause transport of water is observed in a particular sounding, performed on a convective day and revealing water vapour enhancements of up to 0.6 ppmv as high as the 404 K (17.8 km) level. These are shown to originate from convective overshoots upwind detected by an S-band weather radar operating locally in Bauru.<br><br> The accurate in situ observations uncover two independent moisture pathways into the tropical lower stratosphere, which are hardly detectable by space-borne sounders. We argue that the moistening by horizontal transport is limited by the weak meridional gradients of water, whereas the fast convective cross-tropopause transport, largely missed by global models, can have a substantial effect, at least at a regional scale.
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A total of 480 microorganisms collected from 39 clouds sampled at the Puy de Dôme station (alt. 1465 m; 45°46′19′′ N, 2°57′52′′ E; Massif Central, France) were isolated and identified. This unique collection was screened for biosurfactant (surfactants of microbial origin) production by measuring the surface tension (<i>σ</i>) of the crude extracts, comprising the supernatants of the pure cultures, using the pendant drop technique. The results showed that 41 % of the tested strains were active producers (<i>σ</i> < 55 mN m<sup>−1</sup>), with 7 % being extremely active (<i>σ</i> < 30 mN m<sup>−1</sup>). The most efficient biosurfactant producers (<i>σ</i> < 45 mN m<sup>−1</sup>) belong to a few bacterial genera (<i>Pseudomonas</i> and <i>Xanthomonas</i>) from the Υ-Proteobacteria class (78 %) and a yeast genus (<i>Udeniomyces</i>) from the Basidiomycota phylum (11 %). Some <i>Bacillus</i> strains from the Firmicutes phylum were also active but represented a small fraction of the collected population. Strains from the Actinobacteria phylum in the collection examined in the present study showed moderate biosurfactant production (45<i><</i><i>σ</i> < 55 mN m<sup>−1</sup>). <i>Pseudomonas</i> (Υ-Proteobacteria), the most frequently detected genus in clouds, with some species issued from the phyllosphere, was the dominant group for the production of biosurfactants. We observed some correlations between the chemical composition of cloud water and the presence of biosurfactant-producing microorganisms, suggesting the “biogeography” of this production. Moreover, the potential impact of the production of biosurfactants by cloud microorganisms on atmospheric processes is discussed.
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The variability of atmospheric ammonia (NH<sub>3</sub>), emitted largely from agricultural sources, is an important factor when considering how inorganic fine particulate matter (PM<sub>2.5</sub>) concentrations and nitrogen cycling are changing over the United States. This study combines new observations of ammonia concentration from the surface, aboard aircraft, and retrieved by satellite to both evaluate the simulation of ammonia in a chemical transport model (GEOS-Chem) and identify which processes control the variability of these concentrations over a 5-year period (2008–2012). We find that the model generally underrepresents the ammonia concentration near large source regions (by 26 % at surface sites) and fails to reproduce the extent of interannual variability observed at the surface during the summer (JJA). Variability in the base simulation surface ammonia concentration is dominated by meteorology (64 %) as compared to reductions in SO<sub>2</sub> and NO<sub><i>x</i></sub> emissions imposed by regulation (32 %) over this period. Introduction of year-to-year varying ammonia emissions based on animal population, fertilizer application, and meteorologically driven volatilization does not substantially improve the model comparison with observed ammonia concentrations, and these ammonia emissions changes have little effect on the simulated ammonia concentration variability compared to those caused by the variability of meteorology and acid-precursor emissions. There is also little effect on the PM<sub>2.5</sub> concentration due to ammonia emissions variability in the summer when gas-phase changes are favored, but variability in wintertime emissions, as well as in early spring and late fall, will have a larger impact on PM<sub>2.5</sub> formation. This work highlights the need for continued improvement in both satellite-based and in situ ammonia measurements to better constrain the magnitude and impacts of spatial and temporal variability in ammonia concentrations.
