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The effectiveness of aerosols as immersion freezing nuclei at the South Pole station was investigated during January and February 2009 using the FRIDGE-TAU. The analysis consisted of testing the freezing temperature of about 100–130 drops per sample containing aerosols collected at ground level and on a balloon lifted to different heights. All the drops froze between −18 °C and −27 °C. The temperature in which 50 % of the drops froze occurred at −24 °C, while nuclei concentration of 1 L<sup>−1</sup> at −23 °C was calculated. Meteorological conditions such as wind speed, ice precipitation as well as the trajectories of the air masses affected the ice nuclei concentrations. Higher concentrations were observed on days when the winds were stronger or when the air mass originated from the sea.
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This study utilizes large eddy simulation, aircraft measurements, and satellite observations to identify factors that bias the absolute magnitude of metrics of aerosol-cloud-precipitation interactions for warm clouds. The metrics considered are precipitation susceptibility <i>S</i><sub>o</sub>, which examines rain rate sensitivity to changes in drop number, and a cloud-precipitation metric, χ, which relates changes in rain rate to those in drop size. While wide ranges in rain rate exist at fixed cloud drop concentration for different cloud liquid water amounts, χ and <i>S</i><sub>o</sub> are shown to be relatively insensitive to the growth phase of the cloud for large datasets that include data representing the full spectrum of cloud lifetime. Spatial resolution of measurements is shown to influence the liquid water path-dependent behavior of <i>S</i><sub>o</sub> and χ. Other factors of importance are the choice of the minimum rain rate threshold, and how to quantify rain rate, drop size, and the cloud condensation nucleus proxy. Finally, low biases in retrieved aerosol amounts owing to wet scavenging and high biases associated with above-cloud aerosol layers should be accounted for. The paper explores the impact of these effects for model, satellite, and aircraft data.
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Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr<sup>−1</sup> of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH<sub>3</sub>CN) are highlighted and key areas requiring future research are briefly discussed.
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Biogenic volatile organic compounds (BVOCs) such as isoprene constitute a large proportion of the global atmospheric oxidant sink. Their reactions in the atmosphere contribute to processes such as ozone production and secondary organic aerosol formation. However, over the tropical rainforest, where 50 % of the global emissions of BVOCs are believed to occur, atmospheric chemistry models have been unable to simulate concurrently the measured daytime concentration of isoprene and that of its principal oxidant, hydroxyl (OH). One reason for this model-measurement discrepancy may be incomplete mixing of isoprene within the convective boundary layer, leading to patchiness or segregation in isoprene and OH mixing ratios and average concentrations that appear to be incompatible with each other. One way of capturing this effect in models of atmospheric chemistry is to use a reduced effective rate constant for their reaction. Recent studies comparing atmospheric chemistry global/box models with field measurements have suggested that this effective rate reduction may be as large as 50 %; which is at the upper limit of that calculated using large eddy simulation models. To date there has only been one field campaign worldwide that has reported co-located measurements of isoprene and OH at the necessary temporal resolution to calculate the segregation of these compounds. However many campaigns have recorded sufficiently high resolution isoprene measurements to capture the small-scale fluctuations in its concentration. Assuming uniform distributions of other OH production and loss processes, we use a box model of atmospheric chemistry, constrained by the spectrum of isoprene concentrations measured, as a virtual instrument, to estimate the variability in OH at a point and hence, to estimate the segregation intensity of isoprene and OH from high-frequency isoprene time series. The method successfully reproduces the only directly observed segregation, using measurements made in a deciduous forest in Germany. The effective rate constant reduction for the reaction of isoprene and OH over a South-East Asian rainforest is calculated to be typically <15 %. Although there are many unconstrained uncertainties, the likely nature of those processes suggests that this value represents an upper limit. The estimate is not sensitive to heterogeneities in NO at this remote site, unless they are correlated with those of isoprene, or to OH-recycling schemes in the isoprene oxidation mechanism, unless the recycling happens in the first reaction step. Segregation alone is therefore unlikely to be the sole cause of model-measurement discrepancies for isoprene and OH above a rainforest.
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Atmospheric aerosols often contain surface active organics. Surface activity can affect cloud droplet formation through both surface partitioning and surface tension reduction in activating droplets. However, a comprehensive thermodynamic account for these effects in Köhler modeling is computationally demanding and requires knowledge of both droplet composition and component molecular properties, which is generally unavailable. Here, a simple representation of activation properties for surface active organics is introduced and compared against detailed model predictions and laboratory measurements of CCN activity for mixed surfactant-salt particles from the literature. This simple organic representation is seen to work well for aerosol organic-inorganic composition ranges typically found in the atmosphere, and agreement with both experiments and detailed model predictions increases with surfactant strength. The simple representation does not require resolution of the organic aerosol composition and relies solely on properties of the organic fraction that can be measured directly with available techniques. It can thus potentially be applied to complex and ambient surface active aerosols. It is not computationally demanding, and therefore has high potential for implementation to atmospheric models accounting for cloud microphysics.
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The purpose of this study is to develop an emission inventory for major anthropogenic air pollutants and VOC species in the Yangtze River Delta (YRD) region for the year 2007. A "bottom-up" methodology was adopted to compile the inventory based on major emission sources in the sixteen cities of this region. Results show that the emissions of SO<sub>2</sub>, NO<sub>x</sub>, CO, PM<sub>10</sub>, PM<sub>2.5</sub>, VOCs, and NH<sub>3</sub> in the YRD region for the year 2007 are 2392 kt, 2293 kt, 6697 kt, 3116 kt, 1511 kt, 2767 kt, and 459 kt, respectively. Ethylene, mp-xylene, o-xylene, toluene, 1,2,4-trimethylbenzene, 2,4-dimethylpentane, ethyl benzene, propylene, 1-pentene, and isoprene are the key species contributing 77 % to the total ozone formation potential (OFP). The spatial distribution of the emissions shows the emissions and OFPs are mainly concentrated in the urban and industrial areas along the Yangtze River and around Hangzhou Bay. The industrial sources, including power plants other fuel combustion facilities, and non-combustion processes contribute about 97 %, 86 %, 89 %, 91 %, and 69 % of the total SO<sub>2</sub>, NO<sub>x</sub>, PM<sub>10</sub>, PM<sub>2.5</sub>, and VOC emissions. Vehicles take up 12.3 % and 12.4 % of the NO<sub>x</sub> and VOC emissions, respectively. Regarding OFPs, the chemical industry, domestic use of paint & printing, and gasoline vehicles contribute 38 %, 24 %, and 12 % to the ozone formation in the YRD region.
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Weekly cycles in aerosol concentration and corresponding cycles in precipitation have been reported over Europe, but results are conflicting. To obtain a large potential effect of aerosols on precipitation the focus will here be on a highly polluted region on the borders between Germany, Poland and the Czech Republic. Meteorological parameters from 30 surface stations in a mix of urban, rural and remote locations were analyzed for the time period 1983–2008, using three different tests: the Kruskal-Wallis test, a spectral analysis and a comparison of the regular 7-day week to constructed 6- and 8-day weeks. A clear and statistically significant weekly cycle will be expected to pass all three tests. Precipitation amount as well as meteorological variables associated with convective conditions, such as the frequency of heavy precipitation events and observations of rain showers, showed two-peak weekly cycles with maxima on Tuesdays and during weekends. The amplitudes of the weekly cycles were in many cases larger for the heavily polluted 1983–1987 period than for the cleaner 2004–2008 period, but were equally often largest in the cleaner period. Moreover, of all the variables, periods and seasons investigated, the weekly cycles were statistically significant only for summertime values of light precipitation frequency and cloud amount, and only by one of the three tests applied (the Kruskal-Wallis test). Conclusively, clear weekly cycles in meteorological variables were not found in this polluted region of Europe.
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Urban O<sub>3</sub> is produced by photochemical chain reactions that amplify background O<sub>3</sub> in mixtures of gaseous nitrogen oxides (NO<sub>x</sub>) and organic molecules. Current thinking treats NO<sub>x</sub> and organics as independent variables that limit O<sub>3</sub> production depending on the NO<sub>x</sub> to organic ratio; in this paradigm, reducing organics either has no effect or reduces O<sub>3</sub>. We describe a theoretical counterexample where NO<sub>x</sub> and organics are strongly coupled and reducing organics increases O<sub>3</sub> production, and illustrate the example with observations from Mexico City. This effect arises from chain termination in the HO<sub>x</sub> and NO<sub>x</sub> cycles via organic nitrate production. We show that reductions in VOC reactivity that inadvertently reduce organic nitrate production rates will be counterproductive without concurrent reductions in NO<sub>x</sub> or other organics.
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The Microwave Limb Sounder (MLS) on the Aura satellite has been used to measure temperatures in the stratosphere, mesosphere and lower thermosphere. The data used here are from August 2004 to December 2010 and latitudes 75° N to 75° S. The temperature data reveal the regular presence of a westward-propagating 16-day planetary wave with zonal wavenumber 1. The wave amplitudes maximise in winter at middle to high latitudes, where monthly-mean amplitudes can be as large as ~8 K. Significant wave amplitudes are also observed in the summer-time mesosphere and lower thermosphere (MLT) and at lower stratospheric heights of up to ~20 km at middle to high latitudes. Wave amplitudes in the Northern Hemisphere approach values twice as large as those in the Southern Hemisphere. Wave amplitudes are also closely related to mean zonal winds and are largest in regions of strongest eastward flow. There is a reduction in wave amplitudes at the stratopause. No significant wave amplitudes are observed near the equator or in the strongly westward background winds of the atmosphere in summer. This behaviour is interpreted as a consequence of wave/mean-flow interactions. Perturbations in wave amplitude summer MLT are compared to those simultaneously observed in the winter stratosphere of the opposite hemisphere and found to have a correlation coefficient of +0.22, suggesting a small degrees of inter-hemispheric coupling. We interpret this to mean that some of the summer-time MLT wave may originate in the winter stratosphere of the opposite hemisphere and have been ducted across the equator. We do not observe a significant QBO modulation of the 16-day wave amplitude in the polar summer-time MLT. Wave amplitudes were also observed to be suppressed during the major sudden stratospheric warming events of the Northern Hemisphere winters of 2006 and 2009.
