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Secondary organic aerosol (SOA) particles, formed from gas-phase biogenic volatile organic compounds (BVOCs), contribute large uncertainties to the radiative forcing that is associated with aerosols in the climate system. Reactive uptake of surface-active organic oxidation products of BVOCs at the gas–aerosol interface can potentially decrease the overall aerosol surface tension and therefore influence their propensity to act as cloud condensation nuclei (CCN). Here, we synthesize and measure some climate-relevant physical properties of SOA particle constituents consisting of the isoprene oxidation products α-, δ-, and <i>cis</i>- and <i>trans</i>-β-IEPOX (isoprene epoxide), as well as <i>syn</i>- and <i>anti</i>-2-methyltetraol. Following viscosity measurements, we use octanol–water partition coefficients to quantify the relative hydrophobicity of the oxidation products while dynamic surface tension measurements indicate that aqueous solutions of α- and <i>trans</i>-β-IEPOX exhibit significant surface tension depression. We hypothesize that the surface activity of these compounds may enhance aerosol CCN activity, and that <i>trans</i>-β-IEPOX may be highly relevant for surface chemistry of aerosol particles relative to other IEPOX isomers.
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A wave-number-frequency spectral decomposition technique is used to analyze the high-resolution NOAA/Climate Prediction Center morphing technique (CMORPH) precipitation data set and to explore the differences and similarities of the diurnal variation of warm-season precipitation in the East Asia and North America downstream of big topography. The predominant phase speed of precipitation at different time scales for North America, averaged over all warm-season months (May–August) for 2003–2010, is ~20 ms<sup>−1</sup>, which is faster than the speed of ~14 ms<sup>−1</sup> calculated for East Asia. Consistent with the recent studies of the precipitation diurnal cycles for these two regions, the difference in the diurnal phase propagation is likely due to the difference in the mean steering level wind speed for these two regions. The wave-number-frequency spectral analysis further reveals the complex, multi-scale, multi-modal nature of the warm-season precipitation variation embedded within the diurnal cycle over both continents, with phase speeds varying from 10 to 30 ms<sup>−1</sup> and wave periods varying from diurnal to a few hours. At the diurnal frequency regulated by the thermodynamically driven mountains–plains solenoids (MPSs), increased precipitation for both continents first originates in the afternoon from the eastern edge of big topography and subsequently moves downslope in the evening and reaches the broad plains area at night. More complex diurnal evolutions are observed in East Asia due to the more complex, multistep terrains east of the Tibetan Plateau and the associated localized MPS circulations. Nevertheless, increased variation of precipitation at smaller spatial and temporal scales is evident in the active phase of the dominant diurnal cycle for both continents.
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Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O<sub>3</sub> in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid–water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.
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Oxidation in the atmospheric aqueous phase (cloud droplets and deliquesced particles) has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. Most laboratory studies of aqueous-phase oxidation, however, are carried out in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation of polyols (water-soluble species with chemical formula C<sub>n</sub>H<sub>2n+2</sub>O<sub>n</sub>) is carried out within submicron particles in an environmental chamber, allowing for significant gas–particle partitioning of reactants, intermediates, and products. Dark Fenton chemistry is used as a source of hydroxyl radicals, and oxidation is monitored using a high-resolution aerosol mass spectrometer (AMS). Aqueous oxidation is rapid, and results in the formation of particulate oxalate; this is accompanied by substantial loss of carbon to the gas phase, indicating the formation of volatile products. Results are compared to those from analogous oxidation reactions carried out in bulk solution. The bulk-phase chemistry is similar to that in the particles, but with substantially less carbon loss. This is likely due to differences in partitioning of early-generation products, which evaporate out of the aqueous phase under chamber conditions (in which liquid water content is low), but remain in solution for further aqueous processing in the bulk phase. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different from those in bulk oxidation experiments. This highlights the need for aqueous oxidation studies to be carried out under atmospherically relevant partitioning conditions, with liquid water contents mimicking those of cloud droplets or aqueous aerosol.
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An evaluation of water vapor in the upper troposphere and lower stratosphere (UTLS) of the ERA-Interim, the global atmospheric reanalysis produced by the European Centre for Medium-Range Weather Forecasts (ECMWF), is presented. Water vapor measurements are derived from the Fast In situ Stratospheric Hygrometer (FISH) during a large set of airborne measurement campaigns from 2001 to 2011 in the tropics, midlatitudes and polar regions, covering isentropic layers from 300 to 400K (5–18km). <br><br> The comparison shows around 87% of the reanalysis data are within a factor of 2 of the FISH water vapor measurements and around 30% have a nearly perfect agreement with an over- and underestimation lower than 10%. Nevertheless, strong over- and underestimations can occur both in the UT and LS, in particularly in the extratropical LS and in the tropical UT, where severe over- and underestimations up to 10 times can occur. <br><br> The analysis data from the evolving ECMWF operational system is also evaluated, and the FISH measurements are divided into time periods representing different cycles of the Integrated Forecast System (IFS). The agreement with FISH improves over the time, in particular when comparing water vapor fields for time periods before 2004 and after 2010. It appears that influences of tropical tropospheric and extratropical UTLS processes, e.g., convective and quasi-isentropic exchange processes, are particularly challenging for the simulation of the UTLS water vapor distribution. Both the reanalysis and operational analysis data show the tendency of an overestimation of low water vapor mixing ratio (⪅10ppmv) in the LS and underestimation of high water vapor mixing ratio (⪆300ppmv) in the UT.
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It has been claimed for more than a century that atmospheric new particle formation is primarily influenced by the presence of sulfuric acid. However, the activation process of sulfuric acid related clusters into detectable particles is still an unresolved topic. In this study we focus on the PARADE campaign measurements conducted during August/September 2011 at Mt Kleiner Feldberg in central Germany. During this campaign a set of radicals, organic and inorganic compounds and oxidants and aerosol properties were measured or calculated. We compared a range of organic and inorganic nucleation theories, evaluating their ability to simulate measured particle formation rates at 3 nm in diameter (<i>J</i><sub>3</sub>) for a variety of different conditions. Nucleation mechanisms involving only sulfuric acid tentatively captured the observed noon-time daily maximum in <i>J</i><sub>3</sub>, but displayed an increasing difference to <i>J</i><sub>3</sub> measurements during the rest of the diurnal cycle. Including large organic radicals, i.e. organic peroxy radicals (RO<sub>2</sub>) deriving from monoterpenes and their oxidation products, in the nucleation mechanism improved the correlation between observed and simulated <i>J</i><sub>3</sub>. This supports a recently proposed empirical relationship for new particle formation that has been used in global models. However, the best match between theory and measurements for the site of interest was found for an activation process based on large organic peroxy radicals and stabilised Criegee intermediates (sCI). This novel laboratory-derived algorithm simulated the daily pattern and intensity of <i>J</i><sub>3</sub> observed in the ambient data. In this algorithm organic derived radicals are involved in activation and growth and link the formation rate of smallest aerosol particles with OH during daytime and NO<sub>3</sub> during night-time. Because the RO<sub>2</sub> lifetime is controlled by HO<sub>2</sub> and NO we conclude that peroxy radicals and NO seem to play an important role for ambient radical chemistry not only with respect to oxidation capacity but also for the activation process of new particle formation. This is supposed to have significant impact of atmospheric radical species on aerosol chemistry and should be taken into account when studying the impact of new particles in climate feedback cycles.
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The physical properties of rain spectra are generally modeled using an analytical distribution. It is common for the gamma distribution and, to a lesser extent, the lognormal distribution to be used. The majority of studies in the literature focusing on the characterization of raindrop distribution are based on deep convective cloud observations, mostly at ground level. This study focuses on shallow-cumulus rain distributions throughout the depth of the cloud layer and subcloud layer using airborne in situ measurements made with both the Particle Measuring Systems (PMS) Optical Array Probe 260X (OAP-260-X) and the PMS two-Dimensional Precipitation (2DP) instruments during the Rain in Cumulus over the Ocean (RICO) field experiment. Sampled spectra analyzed on the scale of large-eddy simulation resolution (100 m) are found to be relatively broad, with values of the shape parameter – υ for the gamma law and σ<sub>g</sub> for the lognormal law – on the order of 1–3 and 1.5–2, respectively. The dependence of the shape parameters on the main rain variables (number concentration, water content, mean volume diameter, sedimentation fluxes and radar reflectivity) is examined, and a parameterization of the shape parameters υ and σ<sub>g</sub> as a function of a power law of the rainwater content and raindrop number concentration is proposed.
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The Aerosol Optical Depth (AOD) spatial resolution effect is investigated for the linear correlation between satellite retrieved AOD and ground level particulate matter concentrations (PM<sub>2.5</sub>). The Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm was developed for the Moderate Resolution Imaging Spectroradiometer (MODIS) for obtaining AOD with a high spatial resolution of 1 km and provides a good dataset for the study of the AOD spatial resolution effect on the particulate matter concentration prediction. 946 Environmental Protection Agency (EPA) ground monitoring stations across the contiguous US have been used to investigate the linear correlation between AOD and PM<sub>2.5</sub> using AOD at different spatial resolutions (1, 3 and 10 km) and for different spatial scales (urban scale, meso-scale and continental scale). The main conclusions are: (1) for both urban, meso- and continental scale the correlation between PM<sub>2.5</sub> and AOD increased significantly with increasing spatial resolution of the AOD, (2) the correlation between AOD and PM<sub>2.5</sub> decreased significantly as the scale of study region increased for the eastern part of the US while vice versa for the western part of the US, (3) the correlation between PM<sub>2.5</sub> and AOD is much more stable and better over the eastern part of the US compared to western part due to the surface characteristics and atmospheric conditions like the fine mode fraction.
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We present in situ measurements of particle-phase liquid water. Measurements were conducted from 3 June to 15 July 2013 during the Southern Oxidant and Aerosol Study (SOAS) in the southeastern US. The region is photochemically active, humid, dominated by biogenic emissions, impacted by anthropogenic pollution, and known to contain high concentrations of organic aerosol mass. Measurements characterized mobility number size distributions of ambient atmospheric aerosols in three states: unperturbed, dry, and dry-humidified. Unperturbed measurements describe the aerosol distribution at ambient temperature and relative humidity. For the dry state, the sample was routed through a cold trap upstream of the inlet then reheated, while for the dry-humidified state the sample was rehumidified after drying. The total volume of water and semi-volatile compounds lost during drying was quantified by differencing dry and unperturbed volumes from the integrated size spectra, while semi-volatile volumes lost during drying were quantified differencing unperturbed and dry-humidified volumes. Results indicate that particle-phase liquid water was always present. Throughout the SOAS campaign, median water mass concentrations at the relative humidity (RH) encountered in the instrument typically ranged from 1 to 5 μg m<sup>−3</sup> but were as high as 73 μg m<sup>−3</sup>. On non-raining days, morning time (06:00–09:00) median mass concentrations exceeded 15 μg m<sup>−3</sup>. Hygroscopic growth factors followed a diel cycle and exceed 2 from 07:00 to 09:00 local time. The hygroscopicity parameter kappa ranged from 0.14 to 0.46 and hygroscopicity increased with increasing particle size. An observed diel cycle in kappa is consistent with changes in aerosol inorganic content and a dependency of the hygroscopicity parameter on water content. Unperturbed and dry-humidified aerosol volumes did not result in statistically discernible differences, demonstrating that drying did not lead to large losses in dry particle volume. We anticipate that our results will help improve the representation of aerosol water content and aqueous-phase-mediated partitioning of atmospheric water-soluble gases in photochemical models.
