Cloud Droplet Residuals Research Articles

Physical and Chemical Properties of Cloud Droplet Residuals and Aerosol Particles During the Arctic Ocean 2018 Expedition.

Detailed knowledge of the physical and chemical properties and sources of particles that form clouds is especially important in pristine areas like the Arctic, where particle concentrations are often low and observations are sparse. Here, we present in situ cloud and aerosol measurements from the central Arctic Ocean in August–September 2018 combined with air parcel source analysis. We provide direct experimental evidence that Aitken mode particles (particles with diameters ≲70 nm) significantly contribute to cloud condensation nuclei (CCN) or cloud droplet residuals, especially after the freeze‐up of the sea ice in the transition toward fall. These Aitken mode particles were associated with air that spent more time over the pack ice, while size distributions dominated by accumulation mode particles (particles with diameters ≳70 nm) showed a stronger contribution of oceanic air and slightly different source regions. This was accompanied by changes in the average chemical composition of the accumulation mode aerosol with an increased relative contribution of organic material toward fall. Addition of aerosol mass due to aqueous‐phase chemistry during in‐cloud processing was probably small over the pack ice given the fact that we observed very similar particle size distributions in both the whole‐air and cloud droplet residual data. These aerosol–cloud interaction observations provide valuable insight into the origin and physical and chemical properties of CCN over the pristine central Arctic Ocean.

Biomass Burning Smoke and Its Influence on Clouds Over the Western U. S.

AbstractSmall cumulus clouds over the western United States were measured via airborne instruments during the wildfire season in summer of 2018. Statistics of the sampled clouds are presented and compared to smoke aerosol properties. Cloud droplet concentrations were enhanced in regions impacted by biomass burning smoke, at times exceeding 3,000 cm−3. Images and elemental composition of individual smoke particles and cloud droplet residuals are presented and show that most are dominantly organic, internally mixed with some inorganic elements. Despite their high organic content and relatively low hygroscopicity, on average about half of smoke aerosol particles >80 nm diameter formed cloud droplets. This reduced cloud droplet size in small, smoke‐impacted clouds. A number of complex and competing climatic impacts may result from wide‐spread reductions in cloud droplet size due to wildfires prevalent across the region during summer months.

The reductions of oxalate and its precursors in cloud droplets relative to wet particles

Abstract The formation mechanism of oxalate in the aqueous phase remains uncertain. Approximately 600 000 oxalate-containing particles and 450 000 its precursors-containing particles (e.g., acetate, glyoxylate, pyruvate and malonate) were obtained using a single particle aerosol mass spectrometer at a mountain site in southern China from 9 May to 4 June, 2018. The number fraction of oxalate or its precursors was compared within three representative aerosols with different liquid water contents including cloud droplet residues (RES), cloud interstitial particles (INTER) and cloud-free ambient particles (AMB). Lower number fraction of oxalate was found in the RES relative to INTER and AMB, mostly attributed to the decrease in precursors. This was conflicted with the enhancement of in-cloud oxalate formation previously reported. Further analysis indicated that the aerosol acidity had a major influence on the formation of precursors and their conversion to oxalate. With the increase of relative aerosol acidity (defined as the sum of sulfate and nitrate peak areas divided by ammonium peak area), the formation of precursors was increased while the conversion of precursors to oxalate was suppressed. Meanwhile, this influence was more pronounced in the INTER and AMB relative to RES. This work highlighted the roles of aerosol acidity and liquid water content in the aqueous phase formations of oxalate and its precursors.

Activation of intact bacteria and bacterial fragments mixed with agar as cloud droplets and ice crystals in cloud chamber experiments

Abstract. Biological particles, including bacteria and bacterial fragments, have been of much interest due to the special ability of some to nucleate ice at modestly supercooled temperatures. This paper presents results from a recent study conducted on two strains of cultivated bacteria which suggest that bacterial fragments mixed with agar, and not whole bacterial cells, serve as cloud condensation nuclei (CCN). Due to the absence of whole bacteria cells in droplets, they are unable to serve as ice nucleating particles (INPs) in the immersion mode under the experimental conditions. Experiments were conducted at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud chamber at the Karlsruhe Institute of Technology (KIT) by injecting bacteria-containing aerosol samples into the cloud chamber and inducing cloud formation by expansion over a temperature range of −5 to −12 ∘C. Cloud droplets and ice crystals were sampled through a pumped counterflow virtual impactor inlet (PCVI) and their residuals were characterized with a single particle mass spectrometer (miniSPLAT). The size distribution of the overall aerosol was bimodal, with a large particle mode composed of intact bacteria and a mode of smaller particles composed of bacterial fragments mixed with agar that were present in higher concentrations. Results from three expansions with two bacterial strains indicate that the cloud droplet residuals had virtually the same size distribution as the smaller particle size mode and had mass spectra that closely matched those of bacterial fragments mixed with agar. The characterization of ice residuals that were sampled through an ice-selecting PCVI (IS-PCVI) also shows that the same particles that activate to form cloud droplets, bacteria fragments mixed with agar, were the only particle type observed in ice residuals. These results indicate that the unavoidable presence of agar or other growth media in all laboratory studies conducted on cultivated bacteria can greatly affect the results and needs to be considered when interpreting CCN and IN activation data.

Uptake of nitric acid, ammonia, and organics in orographic clouds: mass spectrometric analyses of droplet residual and interstitial aerosol particles

Abstract. Concurrent in situ analyses of interstitial aerosol and cloud droplet residues have been conducted at the Schmücke mountain site during the Hill Cap Cloud Thuringia campaign in central Germany in September and October 2010. Cloud droplets were sampled from warm clouds (temperatures between −3 and +16 °C) by a counterflow virtual impactor and the submicron-sized residues were analyzed by a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), while the interstitial aerosol composition was measured by an high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). During cloud-free periods, the submicron out-of-cloud aerosol was analyzed using both instruments, allowing for intercomparison between the two instruments. Further instrumentation included black carbon measurements and optical particle counters for the aerosol particles as well as optical sizing instrumentation for the cloud droplets. The results show that, under cloud conditions, on average 85 % of the submicron aerosol mass partitioned into the cloud liquid phase. Scavenging efficiencies of nitrate, ammonium, sulfate, and organics ranged between 60 and 100 %, with nitrate having, in general, the highest values. For black carbon, the scavenging efficiency was markedly lower (about 24 %). The nitrate and ammonium mass fractions were found to be markedly enhanced in cloud residues, indicating uptake of gaseous nitric acid and ammonia into the aqueous phase. This effect was found to be temperature dependent: at lower temperatures, the nitrate and ammonium mass fractions in the residues were higher. Also, the oxidation state of the organic matter in cloud residues was found to be temperature dependent: the O : C ratio was lower at higher temperatures. A possible explanation for this observation is a more effective uptake and/or higher concentrations of low-oxidized water-soluble volatile organic compounds, possibly of biogenic origin, at higher temperatures. Organic nitrates were observed in cloud residuals as well as in the out-of-cloud aerosol, but no indication of a preferred partitioning of organic nitrates into the aqueous phase or into the gas phase was detected. Assuming the uptake of nitric acid and ammonia in cloud droplets will be reversible, it will lead to a redistribution of nitrate and ammonium among the aerosol particles, leading to more uniform, internally mixed particles after several cloud passages.

CCN Properties of Organic Aerosol Collected Below and within Marine Stratocumulus Clouds near Monterey, California

The composition of aerosol from cloud droplets differs from that below cloud. Its implications for the Cloud Condensation Nuclei (CCN) activity are the focus of this study. Water-soluble organic matter from below cloud, and cloud droplet residuals off the coast of Monterey, California were collected; offline chemical composition, CCN activity and surface tension measurements coupled with Köhler Theory Analysis are used to infer the molar volume and surfactant characteristics of organics in both samples. Based on the surface tension depression of the samples, it is unlikely that the aerosol contains strong surfactants. The activation kinetics for all samples examined are consistent with rapid (NH4)2SO4 calibration aerosol. This is consistent with our current understanding of droplet kinetics for ambient CCN. However, the carbonaceous material in cloud drop residuals is far more hygroscopic than in sub-cloud aerosol, suggestive of the impact of cloud chemistry on the hygroscopic properties of organic matter.

Concentrations and solubility of trace elements in fine particles at a mountain site, southern China: regional sources and cloud processing

Abstract. The concentrations and solubility of twelve trace elements in PM2.5 at Mt. Lushan, southern China, were investigated during the summer of 2011 and the spring of 2012. The average PM2.5 mass was 55.2 ± 20.1 μg m−3 during the observation period. Temporal variations of all trace elements including total and water-soluble fractions with several dust storm spikes in total fractions of Al and Fe were observed. The enrichment factor (EF) values were 1 order of magnitude higher for the water-soluble fractions versus the total fractions of trace elements. Four major emission sources, namely nonferrous metal mining and smelting (for Cr, As, Ba and parts of Zn), coal combustion (for Pb, Zn, Se, Cu and Mn), crustal materials (for Al and Fe) and municipal solid waste incineration (for Cd and Mo), were classified by principal component analysis (PCA). Trajectory cluster analysis and the potential source contribution function (PSCF) consistently identified the Yangtze River delta (YRD), the Pearl River delta (PRD), and the neighbouring provinces of Mt. Lushan as the major source regions and transport pathways for anthropogenic elements. Northern China was identified as a major source region for crustal elements. It should be noted that apart from the YRD, the area around Mt. Lushan has become the most significant contributor to the solubility of most trace elements. Element solubility can be partially determined by emission sources. However, enhanced solubility of trace elements corresponding to increased concentrations of sulfate after the occurrence of cloud events indicated significant effects of cloud processing on aerosol element dissolution. Metal particles mixed with sulfate in cloud droplet residues were further investigated through transmission electron microscopy (TEM) analysis. Irreversible alteration of particle morphology by cloud processing was confirmed to be highly responsible for the enhancement of trace element solubility. The findings from this study imply an important role of regional anthropogenic pollution and cloud processing in the evolution of aerosol trace element solubility during transport in the troposphere.

A new WRF-Chem treatment for studying regional-scale impacts of cloud processes on aerosol and trace gases in parameterized cumuli

Abstract. A new treatment of cloud effects on aerosol and trace gases within parameterized shallow and deep convection, and aerosol effects on cloud droplet number, has been implemented in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) version 3.2.1 that can be used to better understand the aerosol life cycle over regional to synoptic scales. The modifications to the model include treatment of the cloud droplet number mixing ratio; key cloud microphysical and macrophysical parameters (including the updraft fractional area, updraft and downdraft mass fluxes, and entrainment) averaged over the population of shallow clouds, or a single deep convective cloud; and vertical transport, activation/resuspension, aqueous chemistry, and wet removal of aerosol and trace gases in warm clouds. These changes have been implemented in both the WRF-Chem chemistry packages as well as the Kain–Fritsch (KF) cumulus parameterization that has been modified to better represent shallow convective clouds. Testing of the modified WRF-Chem has been completed using observations from the Cumulus Humilis Aerosol Processing Study (CHAPS). The simulation results are used to investigate the impact of cloud–aerosol interactions on regional-scale transport of black carbon (BC), organic aerosol (OA), and sulfate aerosol. Based on the simulations presented here, changes in the column-integrated BC can be as large as −50% when cloud–aerosol interactions are considered (due largely to wet removal), or as large as +40% for sulfate under non-precipitating conditions due to sulfate production in the parameterized clouds. The modifications to WRF-Chem are found to account for changes in the cloud droplet number concentration (CDNC) and changes in the chemical composition of cloud droplet residuals in a way that is consistent with observations collected during CHAPS. Efforts are currently underway to port the changes described here to the latest version of WRF-Chem, and it is anticipated that they will be included in a future public release of WRF-Chem.

Size-resolved observations of refractory black carbon particles in cloud droplets at a marine boundary layer site

Abstract. Size-resolved observations of aerosol particles and cloud droplet residuals were studied at a marine boundary layer site (251 m a.m.s.l.) in La Jolla, San Diego, California, during 2012. A counterflow virtual impactor (CVI) was used as the inlet to sample cloud residuals while a total inlet was used to sample both cloud residuals and interstitial particles. Two cloud events totaling 10 h of in-cloud sampling were analyzed. Based on bulk aerosol particle concentrations, mass concentrations of refractory black carbon (rBC), and back trajectories, the two air masses sampled were classified as polluted marine air. Since the fraction of cloud droplets sampled by the CVI was less than 100%, the measured activated fractions of rBC should be considered as lower limits to the total fraction of rBC activated during the two cloud events. Size distributions of rBC and a coating analysis showed that sub-100 nm rBC cores with relatively thick coatings were incorporated into the cloud droplets (i.e., 95 nm rBC cores with median coating thicknesses of at least 65 nm were incorporated into the cloud droplets). Measurements also show that the coating volume fraction of rBC cores is relatively large for sub-100 nm rBC cores. For example, the median coating volume fraction of 95 nm rBC cores incorporated into cloud droplets was at least 0.9, a result that is consistent with κ-Köhler theory. Measurements of the total diameter of the rBC-containing particles (rBC core and coating) suggest that the total diameter of rBC-containing particles needed to be at least 165 nm to be incorporated into cloud droplets when the core rBC diameter is ≥ 85 nm. This result is consistent with previous work that has shown that particle diameter is important for activation of non-rBC particles. The activated fractions of rBC determined from the measurements ranged from 0.01 to 0.1 for core rBC diameters ranging from 70 to 220 nm. This type of data is useful for constraining models used for predicting rBC concentrations in the atmosphere.

Airborne investigation of the aerosols–cloud interactions in the vicinity and within a marine stratocumulus over the North Sea during EUCAARI (2008)

Within the European Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) project, the Meteo France research aircraft ATR-42 was operated from Rotterdam (Netherlands) airport during May 2008, to perform scientific flights dedicated to the investigation of aerosol–cloud interactions. The objective of this study is to illustrate the impact of cloud processing on the aerosol particle physical and chemical properties. The presented results are retrieved from measurements during flight operation with two consecutive flights, first from Rotterdam to Newcastle (United Kingdom) and subsequently reverse along the same waypoints back to Rotterdam using data measured with compact Time of Flight Aerosol Mass Spectrometer (cToF-AMS) and Scanning Mobility Particle Sizer (SMPS). Cloud-related measurements during these flights were performed over the North Sea within as well as in close vicinity of a marine stratocumulus cloud layer. Particle physical and chemical properties observed in the close vicinity, below and above the stratocumulus cloud, show strong differences: (1) the averaged aerosol size distributions, observed above and below the cloud layer, are of bimodal character with pronounced minima between Aitken and accumulation mode, very likely due to cloud processing. (2) the chemical composition of aerosol particles is strongly dependent on the position relative to the cloud layer (vicinity or below/above cloud). In general, the nitrate and organic relative mass fractions decrease with decreasing distance to the cloud, in the transit from cloud–free conditions towards the cloud boundaries. This relative mass fraction decrease ranges from a factor of three to ten, thus leading to an increase of the sulfate and ammonium relative mass concentrations while approaching the cloud layer. (3), the chemical composition of cloud droplet residuals, analyzed downstream of a Counterflow virtual Impactor (CVI) inlet indicates increased fractions of mainly soluble chemical compounds such as nitrate and organics, compared to non cloud processed particles. Finally, a net overbalance of nitrate aerosol has been revealed by comparing cloud droplet residual and non cloud processed aerosol chemical compositions. Conclusively, this study highlights gaps concerning the sampling strategy that need to be addressed for the future missions.

Chemical characterization of individual particles and residuals of cloud droplets and ice crystals collected on board research aircraft in the ISDAC 2008 study

Ambient particles and the dry residuals of mixed‐phase cloud droplets and ice crystals were collected during the Indirect and Semi‐Direct Aerosol Campaign (ISDAC) near Barrow, Alaska, in spring of 2008. The collected particles were analyzed using Computer Controlled Scanning Electron Microscopy with Energy Dispersive X‐ray analysis and Scanning Transmission X‐ray Microscopy coupled with Near Edge X‐ray Absorption Fine Structure spectroscopy to identify physico‐chemical properties that differentiate cloud‐nucleating particles from the total aerosol population. A wide range of individually mixed components was identified in the ambient particles and residuals including organic carbon compounds, inorganics, carbonates, and black carbon. Our results show that cloud droplet residuals differ from the ambient particles in both size and composition, suggesting that both properties may impact the cloud‐nucleating ability of aerosols in mixed‐phase clouds. The percentage of residual particles which contained carbonates (47%) was almost four times higher than those in ambient samples. Residual populations were also enhanced in sea salt and black carbon and reduced in organic compounds relative to the ambient particles. Further, our measurements suggest that chemical processing of aerosols may improve their cloud‐nucleating ability. Comparison of results for various time periods within ISDAC suggests that the number and composition of cloud‐nucleating particles over Alaska can be influenced by episodic events bringing aerosols from both the local vicinity and as far away as Siberia.

Aerosol Chemical Composition in Cloud Events by High Resolution Time-of-Flight Aerosol Mass Spectrometry

This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

Modeling aerosols and their interactions with shallow cumuli during the 2007 CHAPS field study

AbstractThe Weather Research and Forecasting model coupled with chemistry, using 2 km horizontal grid spacing, is used to simulate two important relationships between aerosols and clouds in the vicinity of Oklahoma City during the June 2007 Cumulus Humilis Aerosol Processing Study (CHAPS). First, the model reproduces the trends of higher nitrate volume fractions in cloud droplet residuals compared to interstitial nonactivated aerosols, as measured using an aerosol mass spectrometer. Comparing simulations with cloud chemistry turned on and off, we show that nitric acid vapor uptake by cloud droplets explains the higher nitrate content of cloud droplet residuals. Second, the model reasonably represents the observations of the first aerosol indirect effect where pollutants in the vicinity of Oklahoma City increase cloud droplet number concentrations and decrease the droplet effective radius. In addition, as documented using an offline optical code, simulated aerosol optical properties depend on several compensating effects including aerosol water content, size‐resolved chemical composition, and refractory index of various particle chemical species. All of our four sensitivity test cases clearly show an increase in simulated absorption and a decrease in single scattering albedo within the Oklahoma City plume relative to conditions outside the plume. While previous studies have often focused on cloud–aerosol interactions in stratiform and deep convective clouds, this study highlights the ability of regional‐scale models to represent some of the important aspects of cloud–aerosol interactions associated with fields of short‐lived shallow cumuli.

Ship impacts on the marine atmosphere: insights into the contribution of shipping emissions to the properties of marine aerosol and clouds

Abstract. We report properties of marine aerosol and clouds measured in the shipping lanes between Monterey Bay and San Francisco off the coast of Central California. Using a suite of aerosol instrumentation onboard the CIRPAS Twin Otter aircraft, these measurements represent a unique set of data contrasting the properties of clean and ship-impacted marine air masses in dry aerosol and cloud droplet residuals. Below-cloud aerosol exhibited average mass and number concentrations of 2 μg m−3 and 510 cm−3, respectively, which are consistent with previous studies performed off the coast of California. Enhancements in vanadium and cloud droplet number concentrations are observed concurrently with a decrease in cloud water pH, suggesting that periods of high aerosol loading are primarily linked to increased ship influence. Mass spectra from a compact time-of-flight Aerodyne aerosol mass spectrometer reveal an enhancement in the fraction of organic at m/z 42 (f42) and 99 (f99) in ship-impacted clouds. These ions are well correlated to each other (R2>0.64) both in and out of cloud and constitute 14% (f44) and 3% (f99) of organic mass during periods of enhanced sulfate. High-resolution mass spectral analysis of these masses from ship measurements suggests that the ions responsible for this variation were oxidized, possibly due to cloud processing. We propose that the organic fractions of these ions be used as a metric for determining the extent to which cloud-processed ship emissions impact the marine atmosphere where (f42 > 0.15; f99 > 0.04) would imply heavy influence from shipping emissions, (0.05 < f42 < 0.15; 0.01 < f99 < 0.04) would imply moderate, but persistent, influences from ships, and (f42 < 0.05; f99 < 0.01) would imply clean, non-ship-influenced air.

Chemical composition of ambient aerosol, ice residues and cloud droplet residues in mixed-phase clouds: single particle analysis during the Cloud and Aerosol Characterization Experiment (CLACE 6)

Abstract. Two different single particle mass spectrometers were operated in parallel at the Swiss High Alpine Research Station Jungfraujoch (JFJ, 3580 m a.s.l.) during the Cloud and Aerosol Characterization Experiment (CLACE 6) in February and March 2007. During mixed phase cloud events ice crystals from 5–20 μm were separated from larger ice aggregates, non-activated, interstitial aerosol particles and supercooled droplets using an Ice-Counterflow Virtual Impactor (Ice-CVI). During one cloud period supercooled droplets were additionally sampled and analyzed by changing the Ice-CVI setup. The small ice particles and droplets were evaporated by injection into dry air inside the Ice-CVI. The resulting ice and droplet residues (IR and DR) were analyzed for size and composition by the two single particle mass spectrometers: a custom-built Single Particle Laser-Ablation Time-of-Flight Mass Spectrometer (SPLAT) and a commercial Aerosol Time-of-Flight Mass Spectrometer (ATOFMS, TSI Model 3800). During CLACE 6 the SPLAT instrument characterized 355 individual IR that produced a mass spectrum for at least one polarity and the ATOFMS measured 152 IR. The mass spectra were binned in classes, based on the combination of dominating substances, such as mineral dust, sulfate, potassium and elemental carbon or organic material. The derived chemical information from the ice residues is compared to the JFJ ambient aerosol that was sampled while the measurement station was out of clouds (several thousand particles analyzed by SPLAT and ATOFMS) and to the composition of the residues of supercooled cloud droplets (SPLAT: 162 cloud droplet residues analyzed, ATOFMS: 1094). The measurements showed that mineral dust was strongly enhanced in the ice particle residues. Close to all of the SPLAT spectra from ice residues did contain signatures from mineral compounds, albeit connected with varying amounts of soluble compounds. Similarly, close to all of the ATOFMS IR spectra show a mineral or metallic component. Pure sulfate and nitrate containing particles were depleted in the ice residues. Sulfate and nitrate was found to dominate the droplet residues (~90% of the particles). The results from the two different single particle mass spectrometers were generally in agreement. Differences in the results originate from several causes, such as the different wavelength of the desorption and ionisation lasers and different size-dependent particle detection efficiencies.

Observation of playa salts as nuclei in orographic wave clouds

During the Ice in Clouds Experiment‐Layer Clouds (ICE‐L), dry lakebed, or playa, salts from the Great Basin region of the United States were observed as cloud nuclei in orographic wave clouds over Wyoming. Using a counterflow virtual impactor in series with a single‐particle mass spectrometer, sodium‐potassium‐magnesium‐calcium‐chloride salts were identified as residues of cloud droplets. Importantly, these salts produced similar mass spectral signatures to playa salts with elevated cloud condensation nuclei (CCN) efficiencies close to sea salt. Using a suite of chemical characterization instrumentation, the playa salts were observed to be internally mixed with oxidized organics, presumably produced by cloud processing, as well as carbonate. These salt particles were enriched as residues of large droplets (>19 μm) compared to smaller droplets (>7 μm). In addition, a small fraction of silicate‐containing playa salts were hypothesized to be important in the observed heterogeneous ice nucleation processes. While the high CCN activity of sea salt has been demonstrated to play an important role in cloud formation in marine environments, this study provides direct evidence of the importance of playa salts in cloud formation in continental North America has not been shown previously. Studies are needed to model and quantify the impact of playas on climate globally, particularly because of the abundance of playas and expected increases in the frequency and intensity of dust storms in the future due to climate and land use changes.

In-cloud processes of methacrolein under simulated conditions – Part 3: Hygroscopic and volatility properties of the formed secondary organic aerosol

Abstract. The hygroscopic and volatility properties of secondary organic aerosol (SOA) produced from the nebulization of solutions after aqueous phase photooxidation of methacrolein was experimentally studied in a laboratory, using a Volatility-Hygroscopicity Tandem DMA (VHTDMA). The obtained SOA were 80% 100°C-volatile after 5 h of reaction and only 20% 100°C-volatile after 22 h of reaction. The Hygroscopic Growth Factor (HGF) of the SOA produced from the nebulization of solutions after aqueous-phase photooxidation of methacrolein is 1.34–1.43, which is significantly higher than the HGF of SOA formed by gas-phase photooxidation of terpenes, usually found almost hydrophobic. These hygroscopic properties were confirmed for SOA formed by the nebulization of the same solutions where NaCl was added. The hygroscopic properties of the cloud droplet residuals decrease with the reaction time, in parallel with the formation of more refractory compounds. This decrease was mainly attributed to the 250°C-refractive fraction (presumably representative of the highest molecular weight compounds), which evolved from moderately hygroscopic (HGF of 1.52) to less hygroscopic (HGF of 1.36). Oligomerization is suggested as a process responsible for the decrease of both volatility and hygroscopicity with time. The NaCl seeded experiments enabled us to show that 19±4 mg L−1 of SOA was produced after 9.5 h of reaction and 41±9 mg L−1 after 22 h of in-cloud reaction. Because more and more SOA is formed as the reaction time increases, our results show that the reaction products formed during the aqueous-phase OH-oxidation of methacrolein may play a major role in the properties of residual particles upon the droplet's evaporation. Therefore, the specific physical properties of SOA produced during cloud processes should be taken into account for a global estimation of SOA and their atmospheric impacts.

Cloud processing of nitrate

The role of clouds in the transport and transformation of tropospheric pollutants was investigated through airborne measurements made out of Cleveland, Ohio, from 21 July to 18 August 2004, as part of the International Consortium for Atmospheric Research on Transport and Transformation 2004 program. Observations of gas‐phase nitrate, size‐resolved particulate nitrate, cloud water nitrate, and size‐distributed cloud residual nitrate are used to examine changes in the partitioning of nitrate from precloud to postcloud as a function of particle size. The [NO3−]/[SO42−] ratio was highest in the bulk cloud water and higher in the cloud droplet residuals compared with the below‐cloud aerosols. Most of the nitrate entered the cloud water as HNO3, and in 30% of 43 size distributions examined, the nitrate in the cloud droplets was found in residual particle sizes smaller than those of sulfate. Simulations from a trace gas‐aerosol‐cloud parcel model show that this size difference results from differences in the processes by which nitrate and sulfate enter cloud water. The transfer of HNO3 to cloud droplets is governed primarily by gas‐phase mass transfer to the droplets, leading to greater accumulation in the smaller, more numerous droplets with higher total surface area. In contrast, much of the sulfate in the cloud water is the result of nucleation scavenging, which distributes the sulfate mass toward slightly larger sizes. The extent of separation between nitrate and sulfate is dependent on the cloud base sulfate size distribution and the factors that govern both HNO3 and SO2 uptake, with subsequent S(IV) oxidation.

Is atmospheric aerosol an aerosol?—A look at sources and variability

Countless observations of the atmospheric aerosol reveal large concentration variabilities. Such variability is not characteristic for a colloid. It must have a certain degree of stability and that is not seen in the atmospheric aerosol. The question then is open if the atmospheric aerosol is really a colloid, an aerosol. On the other side, the atmospheric aerosol exhibits typical properties of colloids, which mainly stem from the large surface-to-volume ratio. This discrepancy is dissolved if the residence time of the aerosol particles is taken into account. This results in a more or less dynamic equilibrium. Because the residence time of the atmospheric aerosol is size dependent, sources (and sinks) have size dependent productions (removals). For the first time the paper presents data for selected atmospheric model aerosols, at which size ranges the majority of particles (whether mass or number) are produced (and removed). The results are also pointing toward cloud droplet residues as a supplementary aerosol particle source. In addition, the size dependent variability is asking for a change in measuring strategy and instrumental design. Short residence times require good time resolution. The paper shows that size ranges below .01 and above .1 microm are most susceptible to measurements with low time resolution. Present day measuring methods often lack the necessary time resolution.

Microphysical and chemical characteristics of cloud droplet residuals and interstitial particles in continental stratocumulus clouds

During June and July 2003 the Sources and Origins of Atmospheric Cloud Droplets experiment (SOACED) was carried out on a mountain-top site in central Sweden. The main objective of the experiment was to characterise the microphysical and chemical properties of cloud droplet residuals and interstitial aerosol particles in continental clouds and to understand the processes controlling cloud properties at this location. Interstitial and residual aerosol size distributions, cloud liquid water content and species- and size-resolved aerosol mass concentrations are the main variables employed to address questions pertaining to the cloud droplet number concentration and scavenging efficiency during a stratocumulus cloud event observed on July 28, 2003. In this cloud event, about 56% of the aerosol mass was associated with organic species, whilst SO 4 accounted for 23% and NH 4 for 14%. NO 3 and Cl made up about 7% of the total mass. The partitioning of the aerosol particles between cloud droplets and interstitial air has been studied in terms of their microphysical properties. The scavenging efficiency, defined as the fraction of particles activated into cloud elements compared to the total amount of particles, was investigated as a function of size. The scavenging efficiency curves displayed different shapes during the cloud event, from an S-shaped curve, with low scavenging efficiency in the Aitken mode and larger scavenging efficiency in the accumulation mode, to more unusual shapes where Aitken-mode particles were either solely activated or activated in addition to accumulation-mode particles. This study suggests that alterations of the aerosol chemical composition occurred during the measurement period, changing the hygroscopic nature of the CCN and decreasing their activation diameter. It is also hypothesized that entrainment of drier air aloft may have introduced inhomogeneities in the supersaturation field and modified the S-shaped scavenging curves.