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Satellite-based cloud top effective radius retrieved by the CERES Science Team were combined with simulated aerosol concentrations from CCCma CanAM4 to examine relationships between aerosol and cloud that underlie the first aerosol indirect (cloud albedo) effect. Evidence of a strong negative relationship between sulphate, and organic aerosols, with cloud top effective radius was found for low clouds, indicating both aerosol types are contributing to the first indirect effect on a global scale. Furthermore, effects of aerosol on the cloud droplet effective radius are more pronounced for larger cloud liquid water paths. While CanAM4 broadly reproduces the observed relationship between sulphate aerosols and cloud droplets, it does not reproduce the dependency of cloud top droplet size on organic aerosol concentrations nor the dependency on cloud liquid water path. Simulations with a modified version of the model yield a more realistic dependency of cloud droplets on organic carbon. The robustness of the methods used in the study are investigated by repeating the analysis using aerosol simulated by the GOCART model and cloud top effective radii derived from the MODIS Science Team.
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Tropospheric aerosols emitted from biomass burning reduce solar radiation at the surface and locally heat the atmosphere. Equilibrium simulations using an atmospheric general circulation model (GFDL AGCM) indicate that strong atmospheric absorption from these particles can cool the surface and increase upward motion and low-level convergence over southern Africa during the dry season. These changes increase sea level pressure over land in the biomass burning region and spin-up the hydrologic cycle by increasing clouds, atmospheric water vapor, and, to a lesser extent, precipitation. Cloud increases serve to reinforce the surface radiative cooling tendency of the aerosol. Conversely, if the climate over southern Africa were hypothetically forced by high loadings of scattering aerosol, then the change in the low-level circulation and increased subsidence would serve to decrease clouds, precipitation, and atmospheric water vapor. Surface cooling associated with scattering-only aerosols is mitigated by warming from cloud decreases. The direct and semi-direct climate impacts of biomass burning aerosol over southern Africa are sensitive to the total amount of aerosol absorption and how clouds change in response to the aerosol-induced heating of the atmosphere.
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Biomass burning (BB) in southern Africa is the largest emission source of CO and O<sub>3</sub> precursors within Africa during the West African Monsoon (WAM) between June and August. The long range transport and chemical processing of such emissions thus has the potential to exert a dominant influence on the composition of the tropical troposphere over Equatorial Africa (EA) and the Tropical Atlantic Ocean (TAO). We have performed simulations using a three-dimensional global chemistry-transport model (CTM) to quantify the effect that continental transport of such BB plumes has on the EA region. BB emissions from southern Africa were found to exert a significant influence over the TAO and EA between 10° S–20° N. The maximum concentrations in CO and O<sub>3</sub> occur between 0–5° S near the position of the African Easterly Jet – South as placed by the European Centre for Medium range Weather Forecasts (ECMWF) meteorological analysis data. By comparing co-located model output with in-situ measurements we show that the CTM fails to capture the tropospheric profile of CO in southern Africa near the main source region of the BB emissions, as well as the "extreme" concentrations of both CO and O<sub>3</sub> seen between 600–700 hPa over EA around 6° N. For more northerly locations the model exhibits high background concentrations in both CO and O<sub>3</sub> related to BB emissions from southern Africa. By altering both the temporal resolution and the vertical distribution of BB emissions in the model we show that changes in temporal resolution have the largest influence on the transport of trace gases near the source regions, EA, and in the outflow towards the west of Central Africa. Using a set of trajectory calculations we show that the performance of the CTM is heavily constrained by the ECMWF meteorological fields used to drive the CTM, which transport biomass burning plumes from southern Africa into the lower troposphere of the TAO rather than up towards the middle troposphere at 650 hPa. Similar trajectory simulations repeated using an updated meteorological dataset, which assimilates additional measurement data taken around EA, show markedly different origins for pollution events and highlight the current limitations in modelling this tropical region.
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Stimulated by recent important developments regarding the oxidation chemistry of isoprene, this study evaluates and quantifies the impacts of different mechanism updates on the boundary layer concentrations of OH and HO<sub>2</sub> radicals using the IMAGESv2 global chemistry transport model. The model results for HO<sub>x</sub>, isoprene, NO, and ozone are evaluated against air-based observations from the GABRIEL campaign, conducted over the Guyanas in October 2005, and from the INTEX-A campaign over the Eastern US in summer 2004. The version 2 of the Mainz Isoprene Mechanism (MIM2, Taraborrelli et al., 2009) used as reference mechanism in our simulations, has been modified to test (i) the artificial OH recycling proposed by Lelieveld et al. (2008), (ii) the epoxide formation mechanism proposed by Paulot et al. (2009b), and finally (iii) the HO<sub>x</sub> regeneration of the Leuven Isoprene Mechanism (LIM0) proposed by Peeters and Müller (2010). The simulations show that the LIM0 scheme holds by far the largest potential impact on HO<sub>x</sub> concentrations over densely vegetated areas in the Tropics as well as at mid-latitudes. Strong increases, by up to a factor of 4 in the modelled OH concentrations, and by a factor of 2.5–3 in the HO<sub>2</sub> abundances are estimated through the LIM0 mechanism compared to the traditional isoprene degradation schemes. Comparatively much smaller OH increases (<25%) are associated with the implementation of the mechanism of Paulot et al. (2009b); moreover, the global production of epoxides is strongly suppressed (by a factor of 4) when the LIM0 scheme is combined with this mechanism. Hydroperoxy-aldehydes (HPALDs) are found to be major first-generation products in the oxidation of isoprene by OH, with a combined globally averaged yield of 50–60%. The use of the LIM0 chemistry in the global model allows for reconciling the model with the observed concentrations at a satisfactory level, compared to the other tested mechanisms, as the observed averaged mixing ratios of both OH and HO<sub>2</sub> in the boundary layer can be reproduced to within 30%. In spite of the remaining uncertainties in the theoretically-predicted rates of critical radical reactions leading to the formation of HPALDs, and even more in the subsequent degradation of these new compounds, the current findings make a strong case for the newly proposed chemical scheme. Experimental confirmation and quantification is urgently needed for the formation of HPALDs and for their fast OH-generating photolysis.
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Measurements of gas phase soluble bromide in the boundary layer and in firn air, and Br<sup>−</sup> in aerosol and snow, were made at Summit, Greenland (72.5° N, 38.4° W, 3200 m a.s.l.) as part of a larger investigation into the influence of Br chemistry on HO<sub>x</sub> cycling. The soluble bromide measurements confirm that photochemical activation of Br<sup>−</sup> in the snow causes release of active Br to the overlying air despite trace concentrations of Br<sup>−</sup> in the snow (means 15 and 8 nmol Br<sup>−</sup> kg<sup>−1</sup> of snow in 2007 and 2008, respectively). Mixing ratios of soluble bromide above the snow were also found to be very small (mean <1 ppt both years, with maxima of 3 and 4 ppt in 2007 and 2008, respectively), but these levels clearly oxidize and deposit long-lived gaseous elemental mercury and may perturb HO<sub>x</sub> partitioning. Concentrations of Br<sup>−</sup> in surface snow tended to increase/decrease in parallel with the specific activities of the aerosol-associated radionuclides <sup>7</sup>Be and <sup>210</sup>Pb. Earlier work has shown that ventilation of the boundary layer causes simultaneous increases in <sup>7</sup>Be and <sup>210</sup>Pb at Summit, suggesting there is a pool of Br in the free troposphere above Summit in summer time. Speciation and the source of this free tropospheric Br<sup>−</sup> are not well constrained, but we suggest it may be linked to extensive regions of active Br chemistry in the Arctic basin which are known to cause ozone and mercury depletion events shortly after polar sunrise. If this hypothesis is correct, it implies persistence of the free troposphere Br<sup>−</sup> for several months after peak Br activation in March/April. Alternatively, there may be a ubiquitous pool of Br<sup>−</sup> in the free troposphere, sustained by currently unknown sources and processes.
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Perfluorooctanoic acid (PFOA) and other perfluorinated compounds are industrial chemicals in use for decades which resist degradation in the environment and seem to accumulate in polar regions. Transport of PFOA was modeled using a spatially resolved global multicompartment model including fully coupled three-dimensional ocean and atmosphere general circulation models, and two-dimensional top soil, vegetation surfaces, and sea ice compartments. In addition to primary emissions, the formation of PFOA in the atmosphere from degradation of 8:2 fluorotelomer alcohol was included as a PFOA source. Oceanic transport, delivered 14.8±5.0 (8–23) t a<sup>−1</sup> to the Arctic, strongly influenced by changes in water transport, which determined its interannual variability. This pathway constituted the dominant source of PFOA to the Arctic. Formation of PFOA in the atmosphere led to episodic transport events (timescale of days) into the Arctic with small spatial extent. Deposition in the polar region was found to be dominated by wet deposition over land, and shows maxima in boreal winter. The total atmospheric deposition of PFOA in the Arctic in the 1990s was ≈1 t a<sup>−1</sup>, much higher than previously estimated, and is dominated by primary emissions rather than secondary formation.
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The polar stratospheric ozone loss during the Arctic winters 2004/2005–2009/2010 is investigated by using high resolution simulations from the chemical transport model Mimosa-Chim and observations from Aura Microwave Limb Sounder (MLS), by applying the passive tracer technique. The winter 2004/2005 shows the coldest temperatures, highest area of polar stratospheric clouds and strongest chlorine activation in 2004/2005–2009/2010. The ozone loss diagnosed from both simulations and measurements inside the polar vortex at 475 K ranges from 0.7 ppmv in the warm winter 2005/2006 to 1.5–1.7 ppmv in the cold winter 2004/2005. Halogenated (chlorine and bromine) catalytic cycles contribute to 75–90% of the ozone loss at this level. At 675 K the lowest loss of 0.3–0.5 ppmv is computed in 2008/2009, and the highest loss of 1.3 ppmv is estimated in 2006/2007 by the model and in 2004/2005 by MLS. Most of the ozone loss (60–75%) at this level results from nitrogen catalytic cycles rather than halogen cycles. At both 475 and 675 K levels the simulated ozone and ozone loss evolution inside the vortex is in reasonably good agreement with the MLS observations. The ozone partial column loss in 350–850 K deduced from the model calculations at the MLS sampling locations inside the polar vortex ranges between 43 DU in 2005/2006 and 109 DU in 2004/2005, while those derived from the MLS observations range between 26 DU and 115 DU for the same winters. The partial column ozone depletion derived in that vertical range is larger than that estimated in 350–550 K by 19±7 DU on average, mainly due to NO<sub>x</sub> chemistry. The column ozone loss estimates from both Mimosa-Chim and MLS in 350–850 K are generally in good agreement with those derived from ground-based ultraviolet-visible spectrometer total ozone observations for the respective winters, except in 2010.
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We examine the interannual variability in the NO<sub>2</sub> column over North America measured by the Ozone Monitoring Instrument (OMI) in 2005–2008. By comparison to a model of soil NO<sub>x</sub> emissions driven by the North American Regional Reanalysis precipitation and 0–10 cm soil temperature fields, we show the source of this observed interannual variability over much of the central United States in June is fertilizer application. We find that dry, warm conditions followed by convective precipitation induces pulsed emissions of NO<sub>x</sub> over the agricultural Great Plains. In June 2006 we infer a 50% increase in soil NO<sub>x</sub> emission and a 30% increase in the tropospheric NO<sub>2</sub> column relative to the June 2005–2008 mean. In a case-study of fertilized corn and soybean fields over SE South Dakota, we find an associated rain-induced pulsing event reaching 4.6×10<sup>15</sup> molec cm<sup>−2</sup>, equivalent to a surface concentration of ~2 ppbv. We calculate that soil NO<sub>x</sub> emissions resulted in a mean daily maximum 8-h ozone enhancement over the agricultural Great Plains of 5 ppbv in June 2006 (with predicted events reaching 16 ppbv) compared with a mean enhancement of 3 ppbv for soil NO<sub>x</sub> in the years 2005–2008.
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This study presents a synthetic model intercomparison to investigate the importance of transport model errors for estimating the sources and sinks of CO<sub>2</sub> using satellite measurements. The experiments were designed for testing the potential performance of the proposed CO<sub>2</sub> lidar A-SCOPE, but also apply to other space borne missions that monitor total column CO<sub>2</sub>. The participating transport models IFS, LMDZ, TM3, and TM5 were run in forward and inverse mode using common a priori CO<sub>2</sub> fluxes and initial concentrations. Forward simulations of column averaged CO<sub>2</sub> (<i>x</i>CO<sub>2</sub>) mixing ratios vary between the models by σ=0.5 ppm over the continents and σ=0.27 ppm over the oceans. Despite the fact that the models agree on average on the sub-ppm level, these modest differences nevertheless lead to significant discrepancies in the inverted fluxes of 0.1 PgC/yr per 10<sup>6</sup> km<sup>2</sup> over land and 0.03 PgC/yr per 10<sup>6</sup> km<sup>2</sup> over the ocean. These transport model induced flux uncertainties exceed the target requirement that was formulated for the A-SCOPE mission of 0.02 PgC/yr per 10<sup>6</sup> km<sup>2</sup>, and could also limit the overall performance of other CO<sub>2</sub> missions such as GOSAT. A variable, but overall encouraging agreement is found in comparison with FTS measurements at Park Falls, Darwin, Spitsbergen, and Bremen, although systematic differences are found exceeding the 0.5 ppm level. Because of this, our estimate of the impact of transport model uncerainty is likely to be conservative. It is concluded that to make use of the remote sensing technique for quantifying the sources and sinks of CO<sub>2</sub> not only requires highly accurate satellite instruments, but also puts stringent requirements on the performance of atmospheric transport models. Improving the accuracy of these models should receive high priority, which calls for a closer collaboration between experts in atmospheric dynamics and tracer transport.
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Crystal sublimation/loss is a dominant feature of the contrail evolution during the vortex phase and has a substantial impact on the later contrail-to-cirrus transition. Previous studies showed that the fraction of crystals surviving the vortex phase depends primarily on relative humidity, temperature and the aircraft type. An existing model for contrail vortex phase simulations (with a 2-moment bulk microphysics scheme) was upgraded with a newly developed state-of-the-art microphysics module (LCM) which uses Lagrangian particle tracking. This allows for explicit process-oriented modelling of the ice crystal size distribution in contrast to the bulk approach. We show that it is of great importance to employ an advanced microphysics scheme to determine the crystal loss during the vortex phase. The LCM-model shows even larger sensitivities to the above mentioned key parameters than previously estimated with the bulk model. The impact of the initial crystal number is studied and for the first time also the initial width of the crystal size distribution. Both are shown to be relevant. This corroborates the need for a realistic representation of microphysical processes and knowledge of the ice phase characteristics.
