Counterflow Virtual Impactor Research Articles

Contribution of fluorescent primary biological aerosol particles to low-level Arctic cloud residuals

Abstract. Mixed-phase clouds (MPCs) are key players in the Arctic climate system due to their role in modulating solar and terrestrial radiation. Such radiative interactions rely, among other factors, on the ice content of MPCs, which is regulated by the availability of ice-nucleating particles (INPs). While it appears that INPs are associated with the presence of primary biological aerosol particles (PBAPs) in the Arctic, the nuances of the processes and patterns of INPs and their association with clouds and moisture sources have not been resolved. Here, we investigated for a full year the abundance of and variability in fluorescent PBAPs (fPBAPs) within cloud residuals, directly sampled by a multiparameter bioaerosol spectrometer coupled to a ground-based counterflow virtual impactor inlet at the Zeppelin Observatory (475 m a.s.l.) in Ny-Ålesund, Svalbard. fPBAP concentrations (10−3–10−2 L−1) and contributions to coarse-mode cloud residuals (0.1 to 1 in every 103 particles) were found to be close to those expected for high-temperature INPs. Transmission electron microscopy confirmed the presence of PBAPs, most likely bacteria, within one cloud residual sample. Seasonally, our results reveal an elevated presence of fPBAPs within cloud residuals in summer. Parallel water vapor isotope measurements point towards a link between summer clouds and regionally sourced air masses. Low-level MPCs were predominantly observed at the beginning and end of summer, and one explanation for their presence is the existence of high-temperature INPs. In this study, we present direct observational evidence that fPBAPs may play an important role in determining the phase of low-level Arctic clouds. These findings have potential implications for the future description of sources of ice nuclei given ongoing changes in the hydrological and biogeochemical cycles that will influence the PBAP flux in and towards the Arctic.

Identifying the seeding signature in cloud particles from hydrometeor residuals

Abstract. Cloud seeding experiments for modifying clouds and precipitation have been underway for nearly a century; yet practically all the attempts to link precipitation enhancement or suppression to the presence of seeding materials within clouds remain elusive. In 2019, the Cloud–Aerosol Interaction and Precipitation Enhancement Experiment (CAIPEEX) investigated residuals of cloud hydrometeors in seeded and non-seeded clouds with an airborne mini aerosol mass spectrometer (mAMS). The mAMS was utilized in conjunction with a counterflow virtual impactor (CVI) inlet with a cutoff diameter size of approximately 7 µm. The evaporated cloud droplets from the CVI inlet as cloud residuals were evaluated through the mAMS. The chlorine (Cl) associated with hygroscopic materials, i.e. calcium chloride (CaCl2) and potassium (K), which serve as the oxidizing agents in the flares, is found in relatively higher concentrations in the seeded clouds compared to the non-seeded clouds. In convective clouds, Cl and K as cloud residuals were found even at a vertical distance of 2.25 km from the cloud base. Major findings from the seeding impact are an increase in the number concentration of small (< 20 µm) droplets and an indication of raindrop formation at 2.25 km above the cloud base. It is demonstrated that the seed particle signature can be traced inside clouds along with the microphysical impacts.

Airborne investigation of black carbon interaction with low-level, persistent, mixed-phase clouds in the Arctic summer

Abstract. Aerosol–cloud interaction is considered one of the largest sources of uncertainty in radiative forcing estimations. To better understand the role of black carbon (BC) aerosol as a cloud nucleus and the impact of clouds on its vertical distribution in the Arctic, we report airborne in situ measurements of BC particles in the European Arctic near Svalbard during the “Arctic CLoud Observations Using airborne measurements during polar Day” (ACLOUD) campaign held in the summer of 2017. BC was measured with a single-particle soot photometer aboard the Polar 6 research aircraft from the lowest atmospheric layer up to approximately 3500 m a.s.l (metres above sea level). During in-cloud flight transects, BC particles contained in liquid droplets (BC residuals) were sampled through a counterflow virtual impactor (CVI) inlet. Four flights, conducted in the presence of low-level, surface-coupled, inside-inversion, and mixed-phase clouds over sea ice, were selected to address the variability in BC above, below, and within the cloud layer. First, the increase in size and coating thickness of BC particles from the free troposphere to the cloud-dominated boundary layer confirmed that ground observations were not representative of upper atmospheric layers. Second, although only 1 % of liquid droplets contained a BC particle, the higher number concentration of BC residuals than BC particles sampled below cloud indicated that the totality of below-cloud BC was activated by nucleation scavenging but also that alternative scavenging processes such as the activation of free-tropospheric BC at the cloud top might occur. Third, the efficient exchange of aerosol particles at cloud bottom was confirmed by the similarity of the size distribution of BC residuals and BC particles sampled below cloud. Last, the increase in the BC residual number concentration (+31 %) and geometric mean diameter (+38 %) from the cloud top to the cloud bottom and the absolute enrichment in larger BC residuals compared with outside of the cloud supported the hypothesis of concomitant scavenging mechanisms but also suggested the formation of BC agglomerates caused by cloud processing. The vertical evolution of BC properties from inside the cloud and below the cloud indicated an efficient aerosol exchange at cloud bottom, which might include activation, cloud processing, and sub-cloud release of processed BC agglomerates. In the case of persistent low-level Arctic clouds, this cycle may reiterate multiple times, adding an additional degree of complexity to the understanding of cloud processing of BC particles in the Arctic.

Revealing the chemical characteristics of Arctic low-level cloud residuals – in situ observations from a mountain site

Abstract. The role aerosol chemical composition plays in Arctic low-level cloud formation is still poorly understood. In this study we address this issue by combining in situ observations of the chemical characteristics of cloud residuals (dried liquid cloud droplets or ice crystals) and aerosol particles from the Zeppelin Observatory in Ny-Ålesund, Svalbard (approx. 480 m a.s.l.). These measurements were part of the 1-year-long Ny-Ålesund Aerosol and Cloud Experiment 2019–2020 (NASCENT). To obtain the chemical composition of cloud residuals at molecular level, we deployed a Filter Inlet for Gases and AEROsols coupled to a Chemical Ionization Mass Spectrometer (FIGAERO-CIMS) with iodide as the reagent ion behind a ground-based counterflow virtual impactor (GCVI). The station was enshrouded in clouds roughly 15 % of the time during NASCENT, out of which we analyzed 14 cloud events between December 2019 and December 2020. During the entire year, the composition of the cloud residuals shows contributions from oxygenated organic compounds, including organonitrates, and traces of the biomass burning tracer levoglucosan. In summer, methanesulfonic acid (MSA), an oxidation product of dimethyl sulfide (DMS), shows large contributions to the sampled mass, indicating marine natural sources of cloud condensation nuclei (CCN) and ice nucleating particle (INP) mass during the sunlit part of the year. In addition, we also find contributions of the inorganic acids nitric acid and sulfuric acid, with outstanding high absolute signals of sulfuric acid in one cloud residual sample in spring and one in late summer (21 May and 12 September 2020), probably caused by high anthropogenic sulfur emissions near the Barents Sea and Kara Sea. During one particular cloud event, on 18 May 2020, the air mass origin did not change before, during, or after the cloud. We therefore chose it as a case study to investigate cloud impact on aerosol physicochemical properties. We show that the overall chemical composition of the organic aerosol particles was similar before, during, and after the cloud, indicating that the particles had already undergone one or several cycles of cloud processing before being measured as residuals at the Zeppelin Observatory and/or that, on the timescales of the observed cloud event, cloud processing of the organic fraction can be neglected. Meanwhile, there were on average fewer particles but relatively more in the accumulation mode after the cloud. Comparing the signals of sulfur-containing compounds of cloud residuals with aerosols during cloud-free conditions, we find that sulfuric acid had a higher relative contribution to the cloud residuals than to aerosols during cloud-free conditions, but we did not observe an increase in particulate MSA due to the cloud. Overall, the chemical composition, especially of the organic fraction of the Arctic cloud residuals, reflected the overall composition of the general aerosol population well. Our results thus suggest that most aerosols can serve as seeds for low-level clouds in the Arctic.

In Situ Observation of Multiphase Oxidation-Driven Secondary Organic Aerosol Formation during Cloud Processing at a Mountain Site in Southern China

Secondary organic aerosols (SOAs) account for a large fraction of atmospheric fine particles, but the mechanisms of their formation and evolution processes remain unclear. In this study, a ground-based counterflow virtual impactor was used in combination with an online time-of-flight aerosol chemical speciation monitor to investigate the multiphase (gaseous and aqueous) oxidation processes and the SOA influencing factors during cloud events at a mountain site in southern China. Our results showed that the clouds promoted the formation of low-oxidized oxygenated organic aerosol (LO-OOA) and more-oxidized oxygenated organic aerosol (MO-OOA). At night, ozone (O3) and nitrate radicals (NO3•) oxidized volatile organic compounds (VOCs, mostly biogenic VOCs) to the precursors of LO-OOA and were absorbed in the cloud droplets to form LO-OOA, while the hydroxyl radical (•OH) was the main oxidant for LO-OOA during daytime. In the cloud droplets, LO-OOA was further oxidized by •OH to form MO-OOA. We propose that isoprene can be oxidized to form products in the gas phase and then absorbed by acidic cloud droplets to form 2-methylglyceric acid (2-MG), 2-MG-organosulfate, and 2-MG-organonitrate. This study improves our understanding of SOA formation, driven by multiphase oxidation during cloud events.

In-cloud scavenging of chemically segregated particle types by individual particle observation

While aerosol plays a significant role in the formation of cloud, the in-cloud scavenging of chemically segregated particle types were still insufficiently investigated and the controlling factors remain ambiguous. Several field observations were carried out during 2018–2021 at Mt. Tianjing (1690 m a.s.l.) in southern China, based on ground-based counterflow virtual impactor (GCVI)-single particle aerosol mass spectrometer (SPAMS), to investigate the in-cloud scavenging (activation) of various particle types, including black carbon (BC), organic-containing particles (OC), mineral dust (Dust), metal-containing particles (Metal), potassium-rich particles (K-rich) and sea salt (SS). GCVI was used to sample cloud droplet residual particles (Res) while PM2.5 inlet sampled interstitial particles (Inter) during cloud events and ambient particles (Amb) on sunny days, respectively. Different types of particles were recognized based on spectral characteristics obtained by the SPAMS. Based on the coupled GCVI-SPAMS measurements, the number-based scavenging efficiencies (NSEs) of various particle types could be quantified. Besides, the influence of liquid water content (LWC), PM2.5, particle size, and mixing state on the NSEs were discussed. The NSE of SS was the highest (32.4%) while OC showed the lowest NSE (9.1%). Other particle types shared similar NSEs with all the detected particles, with an average of ∼20–25%. Apart from OC, NSEs of other types of particles increased with the increase of LWC and decreased with the increase of the concentration of PM2.5, suggesting that numerous PM2.5 suppressed particles entering cloud droplets via competing for water vapor. The annual variations of NSEs were generally in accordance with LWC and PM2.5, reflecting the certain role of these environment conditions. The NSEs typically increased with particle size in a range of 0.2–2.0 μm, reflecting the dominant nucleation mechanism during in-cloud scavenging. Particles mixed with sulfate and nitrate were easier to be scavenged than those coated with organic compounds, e.g., the discrepancy reached 11.8% for the K-rich particles.

Organic enrichment in droplet residual particles relative to out of cloud over the northwestern Atlantic: analysis of airborne ACTIVATE data

Abstract. Cloud processing is known to generate aerosol species such as sulfate and secondary organic aerosol, yet there is a scarcity of airborne data to examine this issue. The NASA Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) was designed to build an unprecedented dataset relevant to aerosol–cloud interactions with two coordinated aircraft over the northwestern Atlantic, with aerosol mass spectrometer data used from four deployments between 2020–2021 to contrast aerosol composition below, in (using a counterflow virtual impactor) and above boundary layer clouds. Consistent features in all time periods of the deployments (January–March, May–June, August–September) include the mass fraction of organics and relative amount of oxygenated organics (m/z 44) relative to total organics (f44) increasing in droplet residuals relative to below and above cloud. Detailed analysis comparing data below and in cloud suggests a possible role for in-cloud aqueous processing in explaining such results; an intriguing aspect though requiring more attention is that only approximately a quarter of the cloud cases (29 of 110) showed higher organic mass fractions either below or above cloud. Of those 29 cases, the majority (25) showed higher organic mass fraction below cloud base where the cloud processing signature is presumably more evident as compared to above cloud. These results are consistent with the few past studies analyzing droplet residuals pointing to higher organic enrichment than in adjacent cloud-free areas. The data findings are important as other datasets (e.g., reanalysis) suggest that sulfate is both more abundant than organics (in contrast to this work) and more closely related to drop number concentrations in the winter when aerosol–cloud interactions are strongest. Here we show that organics are more abundant than sulfate in the droplet residuals and that aerosol interaction with clouds potentially decreases particle hygroscopicity due to the increase in organic:sulfate ratio for droplet residuals relative to surrounding cloud-free air. These results are important in light of the growing importance of organics over the northwestern Atlantic in recent decades relative to sulfate owing to the success of regulatory activity over the eastern United States to cut sulfur dioxide emissions.

A phase separation inlet for droplets, ice residuals, and interstitial aerosol particles

Abstract. A new inlet for studying the aerosol particles and hydrometeor residuals that compose mixed-phase clouds – the phaSe seParation Inlet for Droplets icE residuals and inteRstitial aerosol particles (SPIDER) – is described here. SPIDER combines a large pumped counterflow virtual impactor (L-PCVI), a flow tube evaporation chamber, and a pumped counterflow virtual impactor (PCVI) to separate droplets, ice crystals (∼3–25 µm), and interstitial aerosol particles for simultaneous sampling. Laboratory verification tests of each individual component and the composite SPIDER system were conducted. Transmission efficiency, evaporation, and ice crystals' survival were determined to show the capability of the system. The experiments show the SPIDER system can separate distinct cloud elements and interstitial aerosol particles for subsequent analysis. As a field instrument, SPIDER will help explore the properties of different cloud elements and interstitial aerosol particles in mixed-phase clouds.

The optical properties and in-situ observational evidence for the formation of brown carbon in clouds

Abstract. Atmospheric brown carbon (BrC) makes a substantial contribution to aerosol light absorption and thus global radiative forcing. Although BrC may change the lifetime of the clouds and ultimately affect precipitation, little is known regarding the optical properties and formation of BrC in the clouds. In the present study, the light-absorption properties of cloud droplet residual (cloud RES) were measured by coupled a ground-based counterflow virtual impactor (GCVI) and an aethalometer (AE-33), in addition to the cloud interstitial (cloud INT) and ambient (cloud-free) particles by PM2.5 inlet-AE-33 at Mt. Tianjing (1690 m a.s.l.), a remote mountain site in southern China, from November to December 2020. Meanwhile, the light-absorption and fluorescence properties of water-soluble organic carbon (WSOC) in the collected cloud water and PM2.5 samples were also obtained, associated with the concentration of water-soluble ions. The mean light-absorption coefficient (Abs370) of the cloud RES, cloud INT, and cloud-free particles were 0.25 ± 0.15, 1.16 ± 1.14, and 1.47 ± 1.23 Mm−1, respectively. The Abs365 of WSOC was 0.11 ± 0.08 Mm−1 in cloud water and 0.40 ± 0.31 Mm−1 in PM2.5, and the corresponding mass absorption efficiency (MAE365) was 0.17 ± 0.07 and 0.31 ± 0.21 m2 g−1, respectively. A comparison of the light-absorption coefficient between BrC in cloud RES and cloud INT particles, and WSOC in cloud water and PM2.5 indicates a considerable contribution (48 %–75 %) of water-insoluble BrC to total BrC light absorption. Secondary BrC estimated by minimum R squared (MRS) method dominated the total BrC in cloud RES (67 %–85 %), rather than in the cloud-free (11 %–16 %) and cloud INT (9 %–23 %) particles. It may indicate the formation of secondary BrC during cloud processing. Supporting evidence includes the enhanced WSOC and dominant contribution of the secondary formation and biomass burning factor (>80 %) to Abs365 in cloud water provided by positive matrix factorization (PMF) analysis. In addition, we showed that the light absorption of BrC in cloud water was closely related to humic-like substances and tyrosine-like and/or protein-like substances (r>0.63, p<0.01), whereas only humic-like substances for PM2.5, as identified by excitation-emission matrix fluorescence spectroscopy.

Microphysics of aerosol, fog and droplet residuals on the Canadian Atlantic coast

Fog has a wide range of impacts that can include transportation disruptions and climate effects. Despite being a common phenomenon, models struggle to incorporate fog microphysical properties which can affect the visibility, formation and dissipation of fog. Results are presented from a fog microphysics study conducted in June and July of 2016 near Halifax, on the eastern coast of Canada, where droplet and aerosol size distributions were measured, as well as fog droplet residuals using a ground-based counterflow virtual impactor. In the ten distinct events that were analyzed, fog never formed when the dew-point temperature was lower than the sea-surface temperature, suggesting that advection fog was primarily observed. During fog events, the concentration of particles larger than 500 nm in diameter was observed to decrease up to 90%, suggesting that nucleation scavenging was an important loss process during fog. Maximum droplet concentration was correlated (r = 0.61) to the total pre-fog aerosol concentration, despite a large (423 nm) estimated activation diameter. From our measurements, the peak supersaturation (SS) was estimated to range from 0.015–0.046%, including uncertainties due to chemical composition, which is lower than previous estimates for continental fog, including mountain sites, and would be consistent with advection fog as well as the presence of sea salt aerosol. Using basic assumptions, we estimate that for each added aerosol per cm3 in the air mass, the maximum fog droplet concentration increases by 0.011 per cm3 and the fog albedo increases by (0.55–3.8) × 10−4. This in-situ dataset will help evaluate models to ultimately improve fog forecasts for coastal areas and further our understanding of aerosol-cloud interactions.

Physical and chemical properties of aerosol particles and cloud residuals on Mt. Åreskutan in Central Sweden during summer 2014

The size distribution, volatility and hygroscopicity of ambient aerosols and cloud residuals were measured with a differential mobility particle sizer (DMPS) and a volatility–hygroscopicity tandem differential mobility analyser (VHTDMA) coupled to a counterflow virtual impactor (CVI) inlet during the Cloud and Aerosol Experiment at Åre (CAEsAR) campaign at Mt. Åreskutan during summer 2014. The chemical composition of particulate matter (PM) and cloud water were analysed offline using thermo-optical OC/EC analysis and ion chromatography. The importance of aerosol particle size for cloud droplet activation and subsequent particle scavenging was clearly visible in the measured size distributions. Cloud residuals were shifted towards larger sizes compared to ambient aerosol, and the cloud events were followed by a size distribution dominated by smaller particles. Organics dominated both PM (62% organic mass fraction) and cloud water (63% organic mass fraction) composition. The volatility and hygroscopicity of the ambient aerosols were representative of homogeneous aged aerosol with contributions from biogenic secondary organics, with median volume fraction remaining (VFR) of 0.04–0.05, and median hygroscopicity parameter κ of 0.16–0.24 for 100–300 nm particles. The corresponding VFR and κ for the cloud residuals were 0.03–0.04 and 0.18–0.20. The chemical composition, hygroscopicity and volatility measurements thus showed no major differences between the ambient aerosol particles and cloud residuals. The VFR and κ values predicted based on the chemical composition measurements agreed well with the VHTDMA measurements, indicating the bulk chemical composition to be a reasonable approximation throughout the size distribution. There were indications, however, of some more subtle changes in time scales not achievable by the offline chemical analysis applied here. Further, online observations of aerosol and cloud residual chemical composition are therefore warranted.

Direct Online Mass Spectrometry Measurements of Ice Nucleating Particles at a California Coastal Site

AbstractThe formation of ice in clouds can strongly impact cloud properties and precipitation processes during storms, including atmospheric rivers. Sea spray aerosol (SSA) particles are relatively inefficient as ice nucleating particles (INPs) compared to mineral dust. However, due to the vast coverage of the Earth's surface by the oceans, a number of recent studies have focused on identifying sources of marine INPs, particularly in regions lacking a strong influence from dust. This study describes the integration, validation, and application of a system coupling a continuous flow diffusion chamber with a single particle mass spectrometer using a pumped counterflow virtual impactor to remove nonnucleated particles and selectively measure the composition of INPs with a detection efficiency of 3.10 × 10−4. In situ measurements of immersion freezing INP composition were made at a coastal site in California using the integrated system. Mineral dust particles were the most abundant ice crystal residual type during the sampling period and found to be ice active despite having undergone atmospheric processing. SSA were more abundant in ambient measurements but represented only a minor fraction of the ice crystal residual population at −31 °C. Notably, the SSA particles that activated were enriched with organic nitrogen species that were likely transferred from the ocean. Calculations of ice nucleation active site densities were within good agreement with previous studies of mineral dust and SSA.

Enrichment of submicron sea-salt-containing particles in small cloud droplets based on single-particle mass spectrometry

Abstract. The effects of the chemical composition and size of sea-salt-containing particles on their cloud condensation nuclei (CCN) activity are incompletely understood. We used a ground-based counterflow virtual impactor (GCVI) coupled with a single-particle aerosol mass spectrometer (SPAMS) to characterize chemical composition of submicron (dry diameter of 0.2–1.0 µm) and supermicron (1.0–2.0 µm) sea-salt-containing cloud residues (dried cloud droplets) at Mount Nanling, southern China. Seven cut sizes (7.5–14 µm) of cloud droplets were set in the GCVI system. The highest number fraction of sea-salt-containing particles was observed at the cut size of 7.5 µm (26 %, by number), followed by 14 µm (17 %) and the other cut sizes (3 %–5 %). The submicron sea-salt-containing cloud residues contributed approximately 20 % (by number) at the cut size of 7.5 µm, which was significantly higher than the percentages at the cut sizes of 8–14 µm (below 2 %). This difference was likely involved in the change in the chemical composition. At the cut size of 7.5 µm, nitrate was internally mixed with over 90 % of the submicron sea-salt-containing cloud residues, which was higher than sulfate (20 %), ammonium (below 1 %), amines (6 %), hydrocarbon organic species (2 %), and organic acids (4 %). However, at the cut sizes of 8–14 µm, nitrate, sulfate, ammonium, amines, hydrocarbon organic species, and organic acids were internally mixed with > 90 %, > 80 %, 39 %–84 %, 71 %–86 %, 52 %–90 %, and 32 %–77 % of the submicron sea-salt-containing cloud residues. The proportion of sea-salt-containing particles in the supermicron cloud residues generally increased as a function of cut size, and their CCN activity was less influenced by chemical composition. This study provided a significant contribution towards a comprehensive understanding of sea-salt CCN activity.

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.

The single-particle mixing state and cloud scavenging of black carbon: a case study at a high-altitude mountain site in southern China

Abstract. In the present study, a ground-based counterflow virtual impactor (GCVI) was used to sample cloud droplet residual (cloud RES) particles, while a parallel PM2.5 inlet was used to sample cloud-free or cloud interstitial (cloud INT) particles. The mixing state of black carbon (BC)-containing particles and the mass concentrations of BC in the cloud-free, RES and INT particles were investigated using a single-particle aerosol mass spectrometer (SPAMS) and two aethalometers, respectively, at a mountain site (1690 m a. s. l. ) in southern China. The measured BC-containing particles were extensively internally mixed with sulfate and were scavenged into cloud droplets (with number fractions of 0.05–0.45) to a similar (or slightly lower) extent as all the measured particles (0.07–0.6) over the measured size range of 0.1–1.6 µm. The results indicate the preferential activation of larger particles and/or that the production of secondary compositions shifts the BC-containing particles towards larger sizes. BC-containing particles with an abundance of both sulfate and organics were scavenged less than those with sulfate but limited organics, implying the importance of the mixing state on the incorporation of BC-containing particles into cloud droplets. The mass scavenging efficiency of BC with an average of 33 % was similar for different cloud events independent of the air mass. This is the first time that both the mixing state and cloud scavenging of BC in China have been reported. Our results would improve the knowledge on the concentration, mixing state, and cloud scavenging of BC in the free troposphere.

In situ chemical composition measurement of individual cloud residue particles at a mountain site, southern China

Abstract. To investigate how atmospheric aerosol particles interact with chemical composition of cloud droplets, a ground-based counterflow virtual impactor (GCVI) coupled with a real-time single-particle aerosol mass spectrometer (SPAMS) was used to assess the chemical composition and mixing state of individual cloud residue particles in the Nanling Mountains (1690 m a. s. l. ), southern China, in January 2016. The cloud residues were classified into nine particle types: aged elemental carbon (EC), potassium-rich (K-rich), amine, dust, Pb, Fe, organic carbon (OC), sodium-rich (Na-rich) and Other. The largest fraction of the total cloud residues was the aged EC type (49.3 %), followed by the K-rich type (33.9 %). Abundant aged EC cloud residues that mixed internally with inorganic salts were found in air masses from northerly polluted areas. The number fraction (NF) of the K-rich cloud residues increased within southwesterly air masses from fire activities in Southeast Asia. When air masses changed from northerly polluted areas to southwesterly ocean and livestock areas, the amine particles increased from 0.2 to 15.1 % of the total cloud residues. The dust, Fe, Pb, Na-rich and OC particle types had a low contribution (0.5–4.1 %) to the total cloud residues. Higher fraction of nitrate (88–89 %) was found in the dust and Na-rich cloud residues relative to sulfate (41–42 %) and ammonium (15–23 %). Higher intensity of nitrate was found in the cloud residues relative to the ambient particles. Compared with nonactivated particles, nitrate intensity decreased in all cloud residues except for dust type. To our knowledge, this study is the first report on in situ observation of the chemical composition and mixing state of individual cloud residue particles in China.

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.

Liquid–Ice Mass Partition in Tropical Maritime Convective Clouds

Abstract The liquid–ice mass partitioning in tropical maritime convective clouds is studied using data collected by the National Center for Atmospheric Research C-130 research aircraft during the Ice in Clouds Experiment–Tropical project. The clouds investigated by the C-130 in this study generally contained weak to moderate updrafts. The liquid water content (LWC) is calculated using a combination of hot-wire and imaging probes. The total condensed water content (CWC) is measured by a counterflow virtual impactor. The ice water content (IWC) is calculated as CWC minus LWC. Taking into account potential significant measurement uncertainties, the liquid fraction [i.e., LWC/(LWC + IWC)] between 0° and −15°C appears to decrease by a factor of about 3 in updrafts near (<500 m) cloud top and a factor of 2 in updrafts far below (>500 m) cloud top. The decrease in liquid fraction as a function of temperature is also correlated with cloud life cycle. In dissipating clouds, ice dominates in all temperature ranges. A comparison between this study and two parameterizations shows that at different geographic locations the liquid fraction in convective clouds differs. Because of the sampling bias and the limitations of instruments, more measurements, especially with more advanced instruments, are needed in the future.

Development and characterization of an ice-selecting pumped counterflow virtual impactor (IS-PCVI) to study ice crystal residuals

Abstract. Separation of particles that play a role in cloud activation and ice nucleation from interstitial aerosols has become necessary to further understand aerosol-cloud interactions. The pumped counterflow virtual impactor (PCVI), which uses a vacuum pump to accelerate the particles and increase their momentum, provides an accessible option for dynamic and inertial separation of cloud elements. However, the use of a traditional PCVI to extract large cloud hydrometeors is difficult mainly due to its small cut-size diameters (< 5 µm). Here, for the first time we describe a development of an ice-selecting PCVI (IS-PCVI) to separate ice in controlled mixed-phase cloud system based on the particle inertia with the cut-off diameter ≥ 10 µm. We also present its laboratory application demonstrating the use of the impactor under a wide range of temperature and humidity conditions. The computational fluid dynamics simulations were initially carried out to guide the design of the IS-PCVI. After fabrication, a series of validation laboratory experiments were performed coupled with the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) expansion cloud simulation chamber. In the AIDA chamber, test aerosol particles were exposed to the ice supersaturation conditions (i.e., RHice > 100 %), where a mixture of droplets and ice crystals was formed during the expansion experiment. In parallel, the flow conditions of the IS-PCVI were actively controlled, such that it separated ice crystals from a mixture of ice crystals and cloud droplets, which were of diameter ≥ 10 µm. These large ice crystals were passed through the heated evaporation section to remove the water content. Afterwards, the residuals were characterized with a suite of online and offline instruments downstream of the IS-PCVI. These results were used to assess the optimized operating parameters of the device in terms of (1) the critical cut-size diameter, (2) the transmission efficiency and (3) the counterflow-to-input flow ratio. Particle losses were characterized by comparing the residual number concentration to the rejected interstitial particle number concentration. Overall results suggest that the IS-PCVI enables inertial separation of particles with a volume-equivalent particle size in the range of ~ 10–30 µm in diameter with small inadvertent intrusion (~ 5 %) of unwanted particles.

In situ detection of the chemistry of individual fog droplet residues in the Pearl River Delta region, China

AbstractWe use a single‐particle aerosol mass spectrometer coupled with a ground‐based counterflow virtual impactor to measure the chemical compositions of individual submicron fog droplet residues. This is the first report on single particle mass spectrometry measurements of fog droplet residual particles at ground level in an urban area. We show that most of the fog droplet residues were composed of elemental carbon (EC) (67.7%), followed by K‐rich (19.2%) and mineral dust/metal (12.3%) particles. The predominance of EC‐containing particles demonstrated that these particles could be effective fog nuclei and highlights the important influence of anthropogenic emissions on regional climate system. Compared with interstitial and ambient aerosols, nitrate was enhanced, sulfate was depressed, and ammonium‐ and organics‐containing particles were hardly found in the fog droplet residues during fog events, suggesting that dust and metal particles containing nitrate may be preferentially activated and that ammonium and organics may not play important roles in fog formation in Guangzhou. We also present direct observational evidence that trimethylamine and hydroxymethanesulfonate are not found within fog droplet residues, although we previously observed enhanced gas‐to‐particle partitioning of these compounds by fog processing. Additionally, higher fraction or intensities of [K]+, [Fe]+, and [SiO3]− were found in fog droplet residues than in ambient and interstitial particles.