Understanding aerosol microphysical properties from 10 years of data collected at Cabo Verde based on an unsupervised machine learning classification

The Cape Verde Atmospheric Observatory (CVAO), which is influenced by both marine and desert dust air masses, has been used for long-term measurements of different properties of the atmospheric aerosol from 2008 to 2017. These properties include particle number size distributions (PNSD), light-absorbing carbon (LAC) and concentrations of cloud condensation nuclei (CCN) together with their hygroscopicity. Here we summarize the results obtained for these properties and use an unsupervised machine learning algorithm for the classification of aerosol types. Five types of aerosols, i.e., marine, freshly formed, mixture, moderate dust and heavy dust, were classified. Air masses during marine periods are from the Atlantic Ocean and during dust periods are from the Sahara Desert. Heavy dust was more frequently present during wintertime, whereas the clean marine periods were more frequently present during springtime. It was observed that during the dust periods CCN number concentrations at a supersaturation of 0.30g% were roughly 2.5 times higher than during marine periods, but the hygroscopicity (κ) of particles in the size range from g1/4g30 to g1/4g175gnm during marine and dust periods were comparable. The long-term data presented here, together with the aerosol classification, can be used as a basis to improve our understanding of annual cycles of the atmospheric aerosol in the eastern tropical Atlantic Ocean and on aerosol-cloud interactions and it can be used as a basis for driving, evaluating and constraining atmospheric model simulations

Ice Nucleating Particles in Northern Greenland: annual cycles, biological contribution and parameterizations

Ice nucleating particles (INPs) can initiate ice formation in clouds at temperatures above &minus;38 &deg;C through heterogeneous ice nucleation. As a result, INPs affect cloud microphysical and radiative properties, cloud life time and precipitation behavior and thereby ultimately the Earth&rsquo;s climate. Yet, little is known regarding the sources, abundance and properties of INPs especially in remote regions such as the Arctic. In this study, two-year-long INP measurements (from July 2018 to September 2020) at Villum 5 Research Station (VRS) in Northern Greenland are presented. A low-volume filter sampler was deployed to collect filter samples for off-line INP analysis. An annual cycle of INP concentration (NINP) was observed and the fraction of biogenic INPs was found to be higher in snow-free months and lower in months when the surface was snow-covered. Samples were categorized into three different types based only on the slope of their INP spectra, namely into summer, winter and mix type. For each of the types a temperature dependent INP parameterization was derived, clearly different depending on the time 10 of the year. Winter and summer type occurred only during their respective seasons and were seen 60 % of the time. The mixed type occurred in the remaining 40 % of the time throughout the year. April, May and November were found to be transition months. A case study comparing April 2019 and April 2020 was performed. The month of April was selected because a significant difference in NINP was observed during these two periods, with clearly higher NINP in April 2020. NINP in the case study period revealed no clear dependency on either meteorological parameters or different surface types which were passed 15 by the collected air masses. Overall, the results suggest that the coastal regions of Greenland were main sources of INPs in April 2019 and 2020, most likely including both local terrestrial and marine sources. In parallel to the observed differences in NINP, also a higher cloud ice fraction was observed in satellite data for April 2020, compared to April 2019.</p

The immersion freezing behavior of ash particles from wood and brown coal burning

It is generally known that ash particles from coal combustion can trigger ice nucleation when they interact with water vapor and/or supercooled droplets. However, data on the ice nucleation of ash particles from different sources, including both anthropogenic and natural combustion processes, are still scarce. As fossil energy sources still fuel the largest proportion of electric power production worldwide, and biomass burning contributes significantly to the global aerosol loading, further data are needed to better assess the ice nucleating efficiency of ash particles. In the framework of this study, we found that ash particles from brown coal (i.e., lignite) burning are up to 2 orders of magnitude more ice active in the immersion mode below −32 °C than those from wood burning. Fly ash from a coal-fired power plant was shown to be the most efficient at nucleating ice. Furthermore, the influence of various particle generation methods on the freezing behavior was studied. For instance, particles were generated either by dispersion of dry sample material, or by atomization of ash–water suspensions, and then led into the Leipzig Aerosol Cloud Interaction Simulator (LACIS) where the immersion freezing behavior was examined. Whereas the immersion freezing behavior of ashes from wood burning was not affected by the particle generation method, it depended on the type of particle generation for ash from brown coal. It was also found that the common practice of treating prepared suspensions in an ultrasonic bath to avoid aggregation of particles led to an enhanced ice nucleation activity. The findings of this study suggest (a) that ash from brown coal burning may influence immersion freezing in clouds close to the source and (b) that the freezing behavior of ash particles may be altered by a change in sample preparation and/or particle generation

Significant continental source of ice-nucleating particles at the tip of Chile's southernmost Patagonia region

The sources and abundance of ice-nucleating particles (INPs) that initiate cloud ice formation remain understudied, especially in the Southern Hemisphere. In this study, we present INP measurements taken close to Punta Arenas, Chile, at the southernmost tip of South America from May 2019 to March 2020, during the Dynamics, Aerosol, Cloud, And Precipitation Observations in the Pristine Environment of the Southern Ocean (DACAPO-PESO) campaign. The highest ice nucleation temperature was observed at −3◦C, and from this temperature down to ∼ −10◦C, a sharp increase of INP number concentration (NINP) was observed. Heating of the samples revealed that roughly 90 % and 80 % of INPs are proteinaceous-based biogenic particles at > −10 and −15◦C, respectively. The NINP at Punta Arenas is much higher than that in the Southern Ocean, but it is comparable with an agricultural area in Argentina and forestry environment in the US. Ice active surface site density (ns) is much higher than that for marine aerosol in the Southern Ocean, but comparable to English fertile soil dust. Parameterization based on particle number concentration in the size range larger than 500 nm (N>500 nm) from the global average (DeMott et al., 2010) overestimates the measured INP, but the parameterization representing biological particles from a forestry environment (Tobo et al., 2013) yields NINP comparable to this study. No clear seasonal variation of NINP was observed. High precipitation is one of the most important meteorological parameters to enhance the NINP in both cold and warm seasons. A comparison of data from in situ and lidar measurements showed good agreement for concentrations of large aerosol particles (> 500 nm) when assuming continental conditions for retrieval of the lidar data, suggesting that these particles were well mixed within the planetary boundary layer (PBL). This corroborates the continental origin of these particles, consistent with the results from our INP source analysis. Overall, we suggest that a high NINP of biogenic INPs originated from terrestrial sources and were added to the marine air masses during the overflow of a maximum of roughly 150 km of land before arriving at the measurement station

Arctic haze over Central Europe

An extraordinary aerosol situation over Leipzig, Germany in April 2002 was investigated with a comprehensive set of ground-based volumetric and columnar aerosol data, combined with aerosol profiles from lidar, meteorological data from radiosondes and air mass trajectory calculations. Air masses were identified to stem from the Arctic, partly influenced by the greater Moscow region. An evaluation of ground-based measurements of aerosol size distributions during these periods showed that the number concentrations below about 70 nm in diameter were below respective long-term average data, while number, surface and volume concentrations of the particles larger than about 70 nm in diameter were higher than the long-term averages. The lidar aerosol profiles showed that the imported aerosol particles were present up to about 3 km altitude. The particle optical depth was up to 0.45 at 550 nm wavelength. With a one-dimensional spectral radiative transfer model top of the atmosphere (TOA) radiative forcing of the aerosol layer was estimated for a period with detailed vertical information. Solar aerosol radiative forcing values between −23 and −38 W m−2 were calculated, which are comparable to values that have been reported in heavily polluted continental plumes outside the respective source regions. The present report adds weight to previous findings of aerosol import to Europe, pointing to the need for attributing the three-dimensional aerosol burden to natural and anthropogenic sources as well as to aerosol imports from adjacent or distant source regions. In the present case, the transport situation is further complicated by forward trajectories, indicating that some of the observed Arctic haze may have originated in Central Europe. This aerosolwas transported to the European Arctic before being re-imported in the modified and augmented form to its initial source region

Characterization of aerosol properties at Cyprus, focusing on cloud condensation nuclei and ice-nucleating particles

As part of the A-LIFE (Absorbing aerosol layers in a changing climate: aging, LIFEtime and dynamics) campaign, ground-based measurements were carried out in Paphos, Cyprus, to characterize the abundance, properties, and sources of aerosol particles in general and cloud condensation nuclei (CCN) and ice-nucleating particles (INP) in particular. New particle formation (NPF) events with subsequent growth of the particles into the CCN size range were observed. Aitken mode particles featured κ values of 0.21 to 0.29, indicating the presence of organic materials. Accumulation mode particles featured a higher hygroscopicity parameter, with a median κ value of 0.57, suggesting the presence of sulfate and maybe sea salt particles mixed with organic carbon. A clear downward trend of κ with increasing supersaturation and decreasing dcrit was found. Super-micron particles originated mainly from sea-spray aerosol (SSA) and partly from mineral dust. INP concentrations (NINP) were measured in the temperature range from -6.5 to -26.5 °C, using two freezing array-type instruments. NINP at a particular temperature span around 1 order of magnitude below -20 °C and about 2 orders of magnitude at warmer temperatures (T > -18 °C). Few samples showed elevated concentrations at temperatures > -15 °C, which suggests a significant contribution of biological particles to the INP population, which possibly could originate from Cyprus. Both measured temperature spectra and NINP probability density functions (PDFs) indicate that the observed INP (ice active in the temperature range between -15 and -20 °C) mainly originate from long-range transport. There was no correlation between NINP and particle number concentration in the size range> 500 nm (N>500 nm). Parameterizations based on N>500 nm were found to overestimate NINP by about 1 to 2 orders of magnitude. There was also no correlation between NINP and particle surface area concentration. The ice active surface site density (ns) for the polluted aerosol encountered in the eastern Mediterranean in this study is about 1 to 3 orders of magnitude lower than the ns found for dust aerosol particles in previous studies. This suggests that observed NINP PDFs such as those derived here could be a better choice for modeling NINP if the aerosol particle composition is unknown or uncertain

Experimental study of the role of physicochemical surface processing on the IN ability of mineral dust particles

During the measurement campaign FROST 2 (FReezing Of duST 2), the Leipzig Aerosol Cloud Interaction Simulator (LACIS) was used to investigate the influence of various surface modifications on the ice nucleating ability of Arizona Test Dust (ATD) particles in the immersion freezing mode. The dust particles were exposed to sulfuric acid vapor, to water vapor with and without the addition of ammonia gas, and heat using a thermodenuder operating at 250 °C. Size selected, quasi monodisperse particles with a mobility diameter of 300 nm were fed into LACIS and droplets grew on these particles such that each droplet contained a single particle. Temperature dependent frozen fractions of these droplets were determined in a temperature range between −40 °C ≤T≤−28 °C. The pure ATD particles nucleated ice over a broad temperature range with their freezing behavior being separated into two freezing branches characterized through different slopes in the frozen fraction vs. temperature curves. Coating the ATD particles with sulfuric acid resulted in the particles' IN potential significantly decreasing in the first freezing branch (T>−35 °C) and a slight increase in the second branch (T≤−35 °C). The addition of water vapor after the sulfuric acid coating caused the disappearance of the first freezing branch and a strong reduction of the IN ability in the second freezing branch. The presence of ammonia gas during water vapor exposure had a negligible effect on the particles' IN ability compared to the effect of water vapor. Heating in the thermodenuder led to a decreased IN ability of the sulfuric acid coated particles for both branches but the additional heat did not or only slightly change the IN ability of the pure ATD and the water vapor exposed sulfuric acid coated particles. In other words, the combination of both sulfuric acid and water vapor being present is a main cause for the ice active surface features of the ATD particles being destroyed. A possible explanation could be the chemical transformation of ice active metal silicates to metal sulfates. The strongly enhanced reaction between sulfuric acid and dust in the presence of water vapor and the resulting significant reductions in IN potential are of importance for atmospheric ice cloud formation. Our findings suggest that the IN concentration can decrease by up to one order of magnitude for the conditions investigated

Concerted measurements of lipids in seawater and on submicrometer aerosol particles at the Cabo Verde islands: biogenic sources, selective transfer and high enrichments

In the marine environment, measurements of lipids as representative species within different lipid classes have been performed to characterize their oceanic sources and their transfer from the ocean into the atmosphere to marine aerosol particles. The set of lipid classes includes hydrocarbons (HC); fatty acid methyl esters (ME); free fatty acids (FFA); alcohols (ALC); 1,3-diacylglycerols (1,3 DG); 1,2-diacylglycerols (1,2 DG); monoacylglycerols (MG); wax esters (WE); triacylglycerols (TG); and phospholipids (PP) including phosphatidylglycerols (PG), phosphatidylethanolamine (PE), phosphatidylcholines (PC), as well as glycolipids (GL) which cover sulfoquinovosyldiacylglycerols (SQDG), monogalactosyl-diacylglycerols (MGDG), digalactosyldiacylglycerols (DGDG) and sterols (ST). These introduced lipid classes have been analyzed in the dissolved and particulate fraction of seawater, differentiating between underlying water (ULW) and the sea surface microlayer (SML) on the one hand. On the other hand, they have been examined on ambient submicrometer aerosol particle samples (PM1) which were collected at the Cape Verde Atmospheric Observatory (CVAO) by applying concerted measurements. These different lipids are found in all marine compartments but in different compositions. Along the campaign, certain variabilities are observed for the concentration of dissolved (∑DLULW: 39.8–128.5 µg L−1, ∑DLSML: 55.7–121.5 µg L−1) and particulate (∑PLULW: 36.4–93.5 µg L−1, ∑PLSML: 61.0–118.1 µg L−1) lipids in the seawater of the tropical North Atlantic Ocean. Only slight SML enrichments are observed for the lipids with an enrichment factor EFSML of 1.1–1.4 (DL) and 1.0–1.7 (PL). On PM1 aerosol particles, a total lipid concentration between 75.2–219.5 ng m−3 (averaged: 119.9 ng m−3) is measured. As also bacteria – besides phytoplankton sources – influence the lipid concentrations in seawater and on the aerosol particles, the lipid abundance cannot be exclusively explained by the phytoplankton tracer (chlorophyll a). The concentration and enrichment of lipids in the SML are not related to physicochemical properties which describe the surface activity. On the aerosol particles, an EFaer (the enrichment factor on the submicrometer aerosol particles compared to the SML) between 9×104–7×105 is observed. Regarding the individual lipid groups on the aerosol particles, a statistically significant correlation (R2=0.45, p=0.028) was found between EFaer and lipophilicity (expressed by the KOW value), which was not present for the SML. But simple physicochemical descriptors are overall not sufficient to fully explain the transfer of lipids. As our findings show that additional processes such as formation and degradation influence the ocean–atmosphere transfer of both OM in general and of lipids in particular, they have to be considered in OM transfer models. Moreover, our data suggest that the extent of the enrichment of the lipid class constituents on the aerosol particles might be related to the distribution of the lipid within the bubble–air–water interface. The lipids TG and ALC which are preferably arranged within the bubble interface are transferred to the aerosol particles to the highest extent. Finally, the connection between ice nucleation particles (INPs) in seawater, which are already active at higher temperatures (−10 to −15 ∘C), and the lipid classes PE and FFA suggests that lipids formed in the ocean have the potential to contribute to (biogenic) INP activity when transferred into the atmosphere

Characterization of aerosol particles at Cabo Verde close to sea level and at the cloud level – Part 2: Ice-nucleating particles in air, cloud and seawater

Ice-nucleating particles (INPs) in the troposphere can form ice in clouds via heterogeneous ice nucleation. Yet, atmospheric number concentrations of INPs (NINP) are not well characterized, and, although there is some understanding of their sources, it is still unclear to what extend different sources contribute or if all sources are known. In this work, we examined properties of INPs at Cabo Verde (a.k.a. Cape Verde) from different environmental compartments: the oceanic sea surface microlayer (SML), underlying water (ULW), cloud water and the atmosphere close to both sea level and cloud level. Both enrichment and depletion of NINP in SML compared to ULW were observed. The enrichment factor (EF) varied from roughly 0.4 to 11, and there was no clear trend in EF with ice-nucleation temperature. NINP values in PM10 sampled at Cape Verde Atmospheric Observatory (CVAO) at any particular ice-nucleation temperature spanned around 1 order of magnitude below −15 ∘C, and about 2 orders of magnitude at warmer temperatures (>−12  ∘C). Among the 17 PM10 samples at CVAO, three PM10 filters showed elevated NINP at warm temperatures, e.g., above 0.01 L−1 at −10 ∘C. After heating samples at 95 ∘C for 1 h, the elevated NINP at the warm temperatures disappeared, indicating that these highly ice active INPs were most likely biological particles. INP number concentrations in PM1 were generally lower than those in PM10 at CVAO. About 83±22 %, 67±18 % and 77±14 % (median±standard deviation) of INPs had a diameter >1 µm at ice-nucleation temperatures of −12, −15 and −18 ∘C, respectively. PM1 at CVAO did not show such elevated NINP at warm temperatures. Consequently, the difference in NINP between PM1 and PM10 at CVAO suggests that biological ice-active particles were present in the supermicron size range. NINP in PM10 at CVAO was found to be similar to that on Monte Verde (MV, at 744 m a.s.l.) during noncloud events. During cloud events, most INPs on MV were activated to cloud droplets. When highly ice active particles were present in PM10 filters at CVAO, they were not observed in PM10 filters on MV but in cloud water samples instead. This is direct evidence that these INPs, which are likely biological, are activated to cloud droplets during cloud events. For the observed air masses, atmospheric NINP values in air fit well to the concentrations observed in cloud water. When comparing concentrations of both sea salt and INPs in both seawater and PM10 filters, it can be concluded that sea spray aerosol (SSA) only contributed a minor fraction to the atmospheric NINP. This latter conclusion still holds when accounting for an enrichment of organic carbon in supermicron particles during sea spray generation as reported in literature

Optimizing the detection, ablation, and ion extraction efficiency of a single-particle laser ablation mass spectrometer for application in environments with low aerosol particle concentrations

The aim of this study is to show how a newly developed aerodynamic lens system (ALS), a delayed ion extraction (DIE), and better electric shielding improve the efficiency of the Aircraft-based Laser ABlation Aerosol MAss spectrometer (ALABAMA). These improvements are applicable to single-particle laser ablation mass spectrometers in general. To characterize the modifications, extensive sizeresolved measurements with spherical polystyrene latex particles (PSL; 150-6000 nm) and cubic sodium chloride particles (NaCl; 400-1700 nm) were performed. Measurements at a fixed ALS position show an improved detectable particle size range of the new ALS compared to the previously used Liu-type ALS, especially for supermicron particles. At a lens pressure of 2.4 hPa, the new ALS achieves a PSL particle size range from 230 to 3240 nm with 50% detection efficiency and between 350 and 2000 nm with 95% detection efficiency. The particle beam divergence was determined by measuring the detection efficiency at variable ALS positions along the laser cross sections and found to be minimal for PSL at about 800 nm. Compared to measurements by singleparticle mass spectrometry (SPMS) instruments using Liutype ALSs, the minimum particle beam divergence is shifted towards larger particle sizes. However, there are no disadvantages compared to the Liu-type lenses for particle sizes down to 200 nm. Improvements achieved by using the DIE and an additional electric shielding could be evaluated by size-resolved measurements of the hit rate, which is the ratio of laser pulses yielding a detectable amount of ions to the total number of emitted laser pulses. In particular, the hit rate for multiply charged particles smaller than 500 nm is significantly improved by preventing an undesired deflection of these particles in the ion extraction field. Moreover, it was found that by using the DIE the ion yield of the ablation, ionization, and ion extraction process could be increased, resulting in up to 7 times higher signal intensities of the cation spectra. The enhanced ion yield results in a larger effective width of the ablation laser beam, which in turn leads to a hit rate of almost 100% for PSL particles in the size range from 350 to 2000 nm. Regarding cubic NaCl particles the modifications of the ALABAMA result in an up to 2 times increased detection efficiency and an up to 5 times increased hit rate. The need for such instrument modifications arises in particular for measurements of particles that are present in low number concentrations such as ice-nucleating particles (INPs) in general, but also aerosol particles at high altitudes or in pristine environments. Especially for these low particle number concentrations, improved efficiencies help to overcome the statistical limitations of single-particle mass spectrometer measurements. As an example, laboratory INP measurements carried out in this study show that the appli- cation of the DIE alone increases the number of INP mass spectra per time unit by a factor of 2 to 3 for the sampled substances. Overall, the combination of instrument modifications presented here resulted in an increased measurement efficiency of the ALABAMA for different particle types and particles shape as well as for highly charged particles. © 2020 Copernicus GmbH. All rights reserved