Study of In/GaAs nanodroplet formation in conditions of non-stationary supersaturation during droplet epitaxy

In this paper, we present the results of kinetic Monte Carlo study of the In/GaAs growth by droplet epitaxy in conditions of non-stationary vapor supersaturation. These conditions allow achievement of the independent control of size and surface density of nanostructures. The material redistribution is realized on the surface when indium deposition is interrupted and leads to a decrease in the critical thickness of droplet formation. An average droplet size increases with increase in interruption time whereas the surface density decreases. However, additional nucleation within the wetting layer can also be observed during the growth interruptions, which makes it possible to increase the surface density of droplets.

Is the water vapor supersaturation distribution Gaussian?

Water vapor supersaturation in the atmosphere is produced in a variety of ways, including the lifting of a parcel or via isobaric mixing of parcels. However, irrespective of the mechanism of production, the water vapor supersaturation in the atmosphere has typically been modeled as a Gaussian distribution. In the current theoretical and numerical study, the nature of supersaturation produced by mixing processes is explored. The results from large eddy simulation and a Gaussian mixing model reveal the distribution of supersaturations produced by mixing to be negatively skewed. Further, the causes of skewness are explored using large eddy simulations (LES) and the Gaussian mixing model (GMM). The correlation in forcing of temperature and water vapor fields is recognized as playing a key role.

Cloud condensation nuclei (CCN) measurements with the HALO aircraft during EMeRGe in European and Asian airspace

<p>During the EMeRGe campaign we employed a cloud condensation nuclei counter (CCNC) on board the research aircraft HALO. The instrument was located in the CCN-Rack probing together with a single particle soot photometer (SP2) and a multi-impactor for sampling different air masses on silica nitrate substrates. The aerosol particles were sampled through the HALO Aerosol Submicrometer Inlet (HASI). The measurements have been performed with a two column continuous-flow longitudinal thermal-gradient instrument (CCN-200) manufactured by DMT. The CCN-200 measures the CCN number concentration as a function of water vapor supersaturation (S). These measurements are performed by changing S within one column from 0.10 % up to 1.00 % using 12 different supersaturations and keeping S constant within the second column (S = 0.38 %) to ensure baseline data with 1 Hz time resolution. The different supersaturations are created by changing the flow while setting a fixed temperature difference.</p><p>Purpose of EMeRGe is to quantify and qualify outflows of megacities, as well as their transport and transformation in the atmosphere. Therefore, measurement flights were performed in the European airspace in 2017, probing aerosol properties over cities like London, Barcelona and Rome. In March 2018, the same set of instruments was probing the outflows of Asian megacities like Taipei, Manila and aged pollution from China Mainland. Furthermore, Japanese and South Korean outflows could be probed. The measurements took place in altitudes between 0.3 km and 13 km ASL. The scientific objective is to investigate the effect of different pollution states on aerosol and CCN properties.</p>

Long-term observations of cloud condensation nuclei over the Amazon rain forest – Part 2: Variability and characteristics of biomass burning, long-range transport, and pristine rain forest aerosols

Size-resolved measurements of atmospheric aerosol and cloud condensation nuclei (CCN) concentrations and hygroscopicity were conducted over a full seasonal cycle at the remote Amazon Tall Tower Observatory (ATTO, March 2014–February 2015). In a preceding companion paper, we presented annually and seasonally averaged data and parametrizations (Part 1; Pöhlker et al., 2016a). In the present study (Part 2), we analyze key features and implications of aerosol and CCN properties for the following characteristic atmospheric conditions: Empirically pristine rain forest (PR) conditions, where no influence of pollution was detectable, as observed during parts of the wet season from March to May. The PR episodes are characterized by a bimodal aerosol size distribution (strong Aitken mode with DAit ≈ 70 nm and NAit ≈ 160 cm−3, weak accumulation mode with Dacc ≈ 160 nm and Nacc≈ 90 cm−3), a chemical composition dominated by organic compounds, and relatively low particle hygroscopicity (κAit≈ 0.12, κacc ≈ 0.18). Long-range-transport (LRT) events, which frequently bring Saharan dust, African biomass smoke, and sea spray aerosols into the Amazon Basin, mostly during February to April. The LRT episodes are characterized by a dominant accumulation mode (DAit ≈ 80 nm, NAit ≈ 120 cm−3 vs. Dacc ≈ 180 nm, Nacc ≈ 310 cm−3), an increased abundance of dust and salt, and relatively high hygroscopicity (κAit≈ 0.18, κacc ≈ 0.35). The coarse mode is also significantly enhanced during these events. Biomass burning (BB) conditions characteristic for the Amazonian dry season from August to November. The BB episodes show a very strong accumulation mode (DAit ≈ 70 nm, NAit ≈ 140 cm−3 vs. Dacc ≈ 170 nm, Nacc ≈ 3400 cm−3), very high organic mass fractions (∼ 90 %), and correspondingly low hygroscopicity (κAit≈ 0.14, κacc ≈ 0.17). Mixed-pollution (MPOL) conditions with a superposition of African and Amazonian aerosol emissions during the dry season. During the MPOL episode presented here as a case study, we observed African aerosols with a broad monomodal distribution (D ≈ 130 nm, NCN,10 ≈ 1300 cm−3), with high sulfate mass fractions (∼ 20 %) from volcanic sources and correspondingly high hygroscopicity (κ< 100 nm ≈ 0.14, κ>100nm≈ 0.22), which were periodically mixed with fresh smoke from nearby fires (D ≈ 110 nm, NCN,10 ≈ 2800 cm−3) with an organic-dominated composition and sharply decreased hygroscopicity (κ<150nm≈ 0.10, κ>150nm≈ 0.20). Insights into the aerosol mixing state are provided by particle hygroscopicity (κ) distribution plots, which indicate largely internal mixing for the PR aerosols (narrow κ distribution) and more external mixing for the BB, LRT, and MPOL aerosols (broad κ distributions). The CCN spectra (CCN concentration plotted against water vapor supersaturation) obtained for the different case studies indicate distinctly different regimes of cloud formation and microphysics depending on aerosol properties and meteorological conditions. The measurement results suggest that CCN activation and droplet formation in convective clouds are mostly aerosol-limited under PR and LRT conditions and updraft-limited under BB and MPOL conditions. Normalized CCN efficiency spectra (CCN divided by aerosol number concentration plotted against water vapor supersaturation) and corresponding parameterizations (Gaussian error function fits) provide a basis for further analysis and model studies of aerosol–cloud interactions in the Amazon.

Mass-based hygroscopicity parameter interaction model and measurement of atmospheric aerosol water uptake

In this study we derive and apply a mass-based hygroscopicity parameter interaction model for efficient description of concentration-dependent water uptake by atmospheric aerosol particles with complex chemical composition. The model approach builds on the single hygroscopicity parameter model of Petters and Kreidenweis (2007). We introduce an observable mass-based hygroscopicity parameter κm which can be deconvoluted into a dilute hygroscopicity parameter (κm0) and additional self- and cross-interaction parameters describing non-ideal solution behavior and concentration dependencies of single- and multi-component systems. For reference aerosol samples of sodium chloride and ammonium sulfate, the κm-interaction model (KIM) captures the experimentally observed concentration and humidity dependence of the hygroscopicity parameter and is in good agreement with an accurate reference model based on the Pitzer ion-interaction approach (Aerosol Inorganic Model, AIM). Experimental results for pure organic particles (malonic acid, levoglucosan) and for mixed organic-inorganic particles (malonic acid – ammonium sulfate) are also well reproduced by KIM, taking into account apparent or equilibrium solubilities for stepwise or gradual deliquescence and efflorescence transitions. The mixed organic-inorganic particles as well as atmospheric aerosol samples exhibit three distinctly different regimes of hygroscopicity: (I) a quasi-eutonic deliquescence &amp; efflorescence regime at low-humidity where substances are just partly dissolved and exist also in a non-dissolved phase, (II) a gradual deliquescence &amp; efflorescence regime at intermediate humidity where different solutes undergo gradual dissolution or solidification in the aqueous phase; and (III) a dilute regime at high humidity where the solutes are fully dissolved approaching their dilute hygroscopicity. For atmospheric aerosol samples collected from boreal rural air and from pristine tropical rainforest air (secondary organic aerosol) we present first mass-based measurements of water uptake over a wide range of relative humidity (1–99.4%) obtained with a new filter-based differential hygroscopicity analyzer (FDHA) technique. For these samples the concentration dependence of κm can be described by a simple KIM model equation based on observable mass growth factors and a total of only six fit parameters summarizing the combined effects of the dilute hygroscopicity parameters, self- and cross-interaction parameters, and solubilities of all involved chemical components. One of the fit parameters represents κm0 and can be used to predict critical dry diameters for the activation of cloud condensation nuclei (CCN) as a function of water vapor supersaturation according to Köhler theory. For sodium chloride and ammonium sulfate reference particles as well as for pristine rainforest aerosols consisting mostly of secondary organic matter, we obtained good agreement between the KIM predictions and measurement data of CCN activation. The application of KIM and mass-based measurement techniques shall help to bridge gaps in the current understanding of water uptake by atmospheric aerosols: (1) the gap between hygroscopicity parameters determined by hygroscopic growth measurements under sub-saturated conditions and by CCN activation measurements at water vapor supersaturation, and (2) the gap between the results of simplified single parameter models widely used in atmospheric or climate science and the results of complex multi-parameter ion- and molecule-interaction models frequently used in physical chemistry and solution thermodynamics (e.g., AIM, E-AIM, ADDEM, UNIFAC, AIOMFAC).

Mass-based hygroscopicity parameter interaction model and measurement of atmospheric aerosol water uptake

In this study we derive and apply a mass-based hygroscopicity parameter interaction model for efficient description of concentration-dependent water uptake by atmospheric aerosol particles. The model approach builds on the single hygroscopicity parameter model of Petters and Kreidenweis (2007). We introduce an observable mass-based hygroscopicity parameter κm, which can be deconvoluted into a dilute intrinsic hygroscopicity parameter (κm,∞) and additional self- and cross-interaction parameters describing non-ideal solution behavior and concentration dependencies of single- and multi-component systems. For sodium chloride, the κm-interaction model (KIM) captures the observed concentration and humidity dependence of the hygroscopicity parameter and is in good agreement with an accurate reference model based on the Pitzer ion-interaction approach (Aerosol Inorganic Model, AIM). For atmospheric aerosol samples collected from boreal rural air and from pristine tropical rainforest air (secondary organic aerosol) we present first mass-based measurements of water uptake over a wide range of relative humidity (1–99%) obtained with a new filter-based differential hygroscopicity analyzer (FDHA) technique. By application of KIM to the measurement data we can distinguish three different regimes of hygroscopicity in the investigated aerosol samples: (I) A quasi-eutonic regime at low relative humidity (~60% RH) where the solutes co-exist in an aqueous and non-aqueous phase; (II) a gradually deliquescent regime at intermediate humidity (~60%–90% RH) where different solutes undergo gradual dissolution in the aqueous phase; and (III) a dilute regime at high humidity (≳90% RH) where the solutes are fully dissolved approaching their dilute intrinsic hygroscopicity. The characteristic features of the three hygroscopicity regimes are similar for both samples, while the RH threshold values vary as expected for samples of different chemical composition. In each regime, the concentration dependence of κm can be described by a simple KIM model equation based on observable mass growth factors and six fit parameters summarizing the combined effects of the dilute intrinsic hygroscopicity and interaction parameters of all involved chemical components. One of the fit parameters represents κm,∞ and can be used to predict CCN activation diameters as a function of water vapor supersaturation. For sodium chloride reference particles as well as for pristine rainforest aerosols consisting mostly of secondary organic matter, we obtained good agreement between the predicted and measured critical diameters of CCN activation. The application of KIM and mass-based measurement techniques shall help to bridge gaps in the current understanding of water uptake by atmospheric aerosols: (1) the gap between hygroscopicity parameters determined by HTDMA (hygroscopicity tandem differential mobility analyzer) or FDHA measurements under sub-saturated conditions and by CCN measurements at water vapor supersaturation, and (2) the gap between the results of simplified single parameter models widely used in atmospheric or climate science and the results of complex multi-parameter ion- and molecule-interaction models frequently used in physical chemistry and thermodynamics (AIM, E-AIM, UNIFAC, AIOMFAC etc.).

Chinese SO₂ pollution over Europe – Part 2: Simulation of aerosol and cloud condensation nuclei formation

We report on sulfur dioxide (SO2) induced formation of aerosols and cloud condensation nuclei in an SO2 rich aged (9 days) pollution plume of Chinese origin, which we have detected at 5–7 km altitude during a research aircraft mission over the East Atlantic off the West coast of Ireland. Building on our measurements of SO2 and other trace gases along with plume trajectory simulations, we have performed model simulations of SO2 induced formation of gaseous sulfuric acid (GSA, H2SO4) followed by GSA induced formation and growth of aerosol particles. We find that efficient photochemical SO2 conversion to GSA took place in the plume followed by efficient formation and growth of H2SO4-H2O aerosol particles. Most particles reached sufficiently large sizes to act as cloud condensation nuclei whenever water vapor supersaturation exceeded 0.1–0.2%. As a consequence, smaller but more numerous cloud droplets are formed, which tend to increase the cloud albedo and to decrease the rainout efficiency. The detected plume represents an interesting example of the environmental impact of long range transport of fossil fuel combustion generated SO2.

Technical note: A method for measuring size-resolved CCN in the atmosphere

We present a method to investigate cloud condensation nuclei (CCN) concentrations and activation efficiencies as a function of two independent variables, aerosol particle size and water vapor supersaturation. To date, most ambient CCN measurements have been made as the integral (total) CCN concentration as a function of water vapor supersaturation only. However, since CCN properties of aerosol particles are strongly dependent on particle size, as well as on chemical composition, which commonly varies with particle size, more detailed measurements can provide additional important information about the CCN activation. With size-resolved measurements, the effect of particle size on CCN activity can be kept constant, which makes it possible to directly assess the influence of particle chemistry. The instrumental set-up consists of a differential mobility analyzer (DMA) to select particles of a known size, within a narrow size range. A condensation nuclei (CN) counter (condensation particle counter, CPC) is used to count the total number of particles in that size range, and a CCN counter is used to count the number of CCN as a function of supersaturation, in that same size range. The activation efficiency, expressed as CCN/CN ratios, can thus directly be calculated as a function of particle size and supersaturation. We present examples of the application of this technique, using salt and smoke aerosols produced in the laboratory as well as ambient aerosols.