Showing papers by "Harald Saathoff published in 2021"

High homogeneous freezing onsets of sulfuric acid aerosol at cirrus temperatures

Abstract: . Homogeneous freezing of aqueous solution aerosol particles is an important process for cloud ice formation in the upper troposphere. There the air temperature is low, the ice supersaturation can be high and the concentration of ice-nucleating particles is too low to initiate and dominate cirrus cloud formation by heterogeneous ice nucleation processes. The most common description to quantify homogeneous freezing processes is based on the water activity criterion (WAC) as proposed by Koop et al. ( 2000 ) . The WAC describes the homogeneous nucleation rate coefficients only as a function of the water activity, which makes this approach well applicable in numerical models. In this study, we investigate the homogeneous freezing behavior of aqueous sulfuric acid aerosol particles by means of a comprehensive collection of laboratory-based homogeneous freezing experiments conducted at the AIDA (Aerosol Interaction and Dynamics in the Atmosphere) cloud simulation chamber, which were conducted as part of 17 measurement campaigns since 2007. The most recent experiments were conducted during October 2020 with special emphasis on temperatures below 200 K . Aqueous sulfuric acid aerosol particles of high purity were generated by particle nucleation in a gas flow composed of clean synthetic air and sulfuric acid vapor, which was added to the AIDA chamber. The resulting chamber aerosol had number concentrations from 30 cm−3 up to several thousand per cubic centimeter with particle diameters ranging from about 30 nm to 1.1 µm . Homogeneous freezing of the aerosol particles was measured at simulated cirrus formation conditions in a wide range of temperatures between 185 and 230 K with a steady increase of relative humidity during each experiment. At temperatures between about 205 K and about 230 K , the AIDA results agree well with the WAC-based predictions of homogeneous freezing onsets. At lower temperatures, however, the AIDA results show an increasing deviation from the WAC-based predictions towards higher freezing onsets. For temperatures between 185 and 205 K , the WAC-based ice saturation ratios for homogeneous freezing onsets increase from about 1.6 to 1.7, whereas the AIDA measurements show an increase from about 1.7 to 2.0 in the same temperature range. Based on the experimental results of our direct measurements, we suggest a new fit line to formulate the onset conditions of homogeneous freezing of sulfuric acid aerosol particles as an isoline for nucleation rate coefficients between 5×108 and 1013 cm −3 s −1 . The potential significant impacts of the higher homogeneous freezing thresholds, as directly observed in the AIDA experiments under simulated cirrus formation conditions, on the model prediction of cirrus cloud occurrence and related cloud radiative effects are discussed.

Sources and nature of ice-nucleating particles in the free troposphere at Jungfraujoch in winter 2017

Abstract: . Primary ice formation in mixed-phase clouds is initiated by a minute subset of the ambient aerosol population, called ice-nucleating particles (INPs). The knowledge about their atmospheric concentration, composition, and source in cloud-relevant environments is still limited. During the 2017 joint INUIT/CLACE (Ice Nuclei research UnIT/CLoud–Aerosol Characterization Experiment) field campaign, observations of INPs as well as of aerosol physical and chemical properties were performed, complemented by source region modeling. This aimed at investigating the nature and sources of INPs. The campaign took place at the High-Altitude Research Station Jungfraujoch (JFJ), a location where mixed-phase clouds frequently occur. Due to its altitude of 3580 m a.s.l., the station is usually located in the lower free troposphere, but it can also receive air masses from terrestrial and marine sources via long-range transport. INP concentrations were quasi-continuously detected with the Horizontal Ice Nucleation Chamber (HINC) under conditions representing the formation of mixed-phase clouds at −31 ∘C . The INP measurements were performed in parallel to aerosol measurements from two single-particle mass spectrometers, the Aircraft-based Laser ABlation Aerosol MAss Spectrometer (ALABAMA) and the laser ablation aerosol particle time-of-flight mass spectrometer (LAAPTOF). The chemical identity of INPs is inferred by correlating the time series of ion signals measured by the mass spectrometers with the time series of INP measurements. Moreover, our results are complemented by the direct analysis of ice particle residuals (IPRs) by using an ice-selective inlet (Ice-CVI) coupled with the ALABAMA. Mineral dust particles and aged sea spray particles showed the highest correlations with the INP time series. Their role as INPs is further supported by source emission sensitivity analysis using atmospheric transport modeling, which confirmed that air masses were advected from the Sahara and marine environments during times of elevated INP concentrations and ice-active surface site densities. Indeed, the IPR analysis showed that, by number, mineral dust particles dominated the IPR composition ( ∼58 %), and biological and metallic particles are also found to a smaller extent ( ∼10 % each). Sea spray particles are also found as IPRs (17 %), and their fraction in the IPRs strongly varied according to the increased presence of small IPRs, which is likely due to an impact from secondary ice crystal formation. This study shows the capability of combining INP concentration measurements with chemical characterization of aerosol particles using single-particle mass spectrometry, source region modeling, and analysis of ice residuals in an environment directly relevant for mixed-phase cloud formation.

The SALTENA experiment: Comprehensive observations of aerosol sources, formation and processes in the South American Andes

Abstract: This paper presents an introduction to the Southern hemisphere high altitude experiment on particle nucleation and growth (SALTENA). This field campaign took place between December 2017 and June 2018 (wet to dry season) at Chacaltaya (CHC), a GAW (Global Atmosphere Watch) station located at 5240 m a.s.l. in the Bolivian Andes. Concurrent measurements were conducted at two additional sites in El Alto (4000 m a.s.l.) and La Paz (3600 m a.s.l.). The overall goal of the campaign was to identify the sources, understand the formation mechanisms and transport, and characterize the properties of aerosol at these stations. State-of-the-art instruments were brought to the station complementing the ongoing permanent GAW measurements, to allow a comprehensive description of the chemical species of anthropogenic and biogenic origin impacting the station and contributing to new particle formation. In this overview we first provide an assessment of the complex meteorology, air mass origin, and boundary layer – free troposphere interactions during the campaign using a 6-month high-resolution WRF (Weather Research and Forecasting) simulation coupled with FLEXPART (FLEXible PARTicle dispersion model). We then show some of the research highlights from the campaign, including i) chemical transformation processes of anthropogenic pollution while the air masses are transported to the CHC station from the metropolitan area of La Paz/El Alto, ii) volcanic emissions as an important source of atmospheric sulfur compounds in the region, iii) the characterization of the compounds involved in new particle formation, and iv) the identification of long-range transported compounds from the Pacific or the Amazon basin. We conclude the article with a presentation of future research foci. The SALTENA dataset highlights the importance of comprehensive observations in strategic high-altitude locations, especially the undersampled Southern Hemisphere.

Chemical composition of nanoparticles from α -pinene nucleation and the influence of isoprene and relative humidity at low temperature

Abstract: . Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α -pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α -pinene oxidation, including in the presence of isoprene, at temperatures ( − 50 and − 30 ∘ C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C 8−10 monomers and C 18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C 5 (C 5 H 10 O 5−7 ) and C 15 compounds (C 15 H 24 O 5−10 ) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C 5 and C 15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm ( J1.7 nm ) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α -pinene and ozone mixing ratios used in the present study.

High-resolution optical constants of crystalline ammonium nitrate for infrared remote sensing of the Asian Tropopause Aerosol Layer

Abstract: . Infrared spectroscopic observations have shown that crystalline ammonium nitrate (AN) particles are an abundant constituent of the upper tropospheric aerosol layer which is formed during the Asian summer monsoon period, the so-called Asian Tropopause Aerosol Layer (ATAL). At upper tropospheric temperatures, the thermodynamically stable phase of AN is different from that at 298 K, meaning that presently available room-temperature optical constants of AN, that is, the real and imaginary parts of the complex refractive index, cannot be applied for the quantitative analysis of these infrared measurements. In this work, we have retrieved the first low-temperature data set of optical constants for crystalline AN in the 800–6000 cm −1 wavenumber range with a spectral resolution of 0.5 cm −1 . The optical constants were iteratively derived from an infrared extinction spectrum of 1 µm sized AN particles suspended in a cloud chamber at 223 K. The uncertainties of the new data set were carefully assessed in a comprehensive sensitivity analysis. We show that our data accurately fit aircraft-borne infrared measurements of ammonium nitrate particles in the ATAL.

Ice nucleation ability of ammonium sulfate aerosol particles internally mixed with secondary organics

Abstract: The abundance of aerosol particles and their ability to catalyze ice nucleation are key parameters to correctly understand and describe the aerosol indirect effect on the climate Cirrus clouds strongly influence the Earth's radiative budget, but their effect is highly sensitive to their formation mechanism, which is still poorly understood Sulfate and organics are among the most abundant aerosol components in the troposphere and have also been found in cirrus ice crystal residuals Most of the studies on ice nucleation at cirrus cloud conditions looked at either purely inorganic or purely organic particles However, particles in the atmosphere are mostly found as internal mixtures, the ice nucleation ability of which is not yet fully characterized In this study, we investigated the ice nucleation ability of internally mixed particles composed of crystalline ammonium sulfate (AS) and secondary organic material (SOM) at temperatures between −50 and −65 ∘ C The SOM was generated from the ozonolysis of α -pinene The experiments were conducted in a large cloud chamber, which also allowed us to simulate various aging processes that the particles may experience during their transport in the atmosphere, like cloud cycling and redistribution of the organic matter We found that the ice nucleation ability of the mixed AS / SOM particles is strongly dependent on the particle morphology Small organic mass fractions of 5 wt %–8 wt % condensed on the surface of AS crystals are sufficient to completely suppress the ice nucleation ability of the inorganic component, suggesting that the organic coating is evenly distributed on the surface of the seed particles In this case, the ice nucleation onset increased from a saturation ratio with respect to ice Sice∼130 for the pure AS crystals to ≥145 for the SOM-coated AS crystals However, if such SOM-coated AS crystals are subjected to the mentioned aging processes, they show an improved ice nucleation ability with the ice nucleation onset at Sice∼135 We suggest that the aging processes change the particle morphology The organic matter might redistribute on the surface to form a partially engulfed structure, where the ice-nucleation-active sites of the AS crystals are no longer completely masked by the organic coating, or the morphology of the organic coating layer might transform from a compact to a porous structure Our results underline the complexity in representing the ice nucleation ability of internally mixed particles in cloud models They also demonstrate the need to further investigate the impact of atmospheric aging and cloud processing on the morphology and related ice nucleation ability of internally mixed particles

Laboratory and field studies of ice-nucleating particles from open-lot livestock facilities in Texas

Abstract: . In this work, an abundance of ice-nucleating particles (INPs) from livestock facilities was studied through laboratory measurements from cloud-simulation chamber experiments and field investigation in the Texas Panhandle. Surface materials from two livestock facilities, one in the Texas Panhandle and another from McGregor, Texas, were selected as dust proxies for laboratory analyses. These two samples possessed different chemical and biological properties. A combination of aerosol interaction and dynamics in the atmosphere (AIDA) measurements and offline ice spectrometry was used to assess the immersion freezing mode ice nucleation ability and efficiency of these proxy samples at temperatures above −29 ∘ C. A dynamic filter processing chamber was also used to complement the freezing efficiencies of submicron and supermicron particles collected from the AIDA chamber. For the field survey, periodic ambient particle sampling took place at four commercial livestock facilities from July 2017 to July 2019. INP concentrations of collected particles were measured using an offline freezing test system, and the data were acquired for temperatures between −5 and −25 ∘ C. Our AIDA laboratory results showed that the freezing spectra of two livestock dust proxies exhibited higher freezing efficiency than previously studied soil dust samples at temperatures below −25 ∘ C. Despite their differences in composition, the freezing efficiencies of both proxy livestock dust samples were comparable to each other. Our dynamic filter processing chamber results showed on average approximately 50 % supermicron size dominance in the INPs of both dust proxies. Thus, our laboratory findings suggest the importance of particle size in immersion freezing for these samples and that the size might be a more important factor for immersion freezing of livestock dust than the composition. From a 3-year field survey, we measured a high concentration of ambient INPs of 1171.6 ± 691.6 L −1 (average ± standard error) at −25 ∘ C for aerosol particles collected at the downwind edges of livestock facilities. An obvious seasonal variation in INP concentration, peaking in summer, was observed, with the maximum at the same temperature exceeding 10 000 L −1 on 23 July 2018. The observed high INP concentrations suggest that a livestock facility is a substantial source of INPs. The INP concentration values from our field survey showed a strong correlation with measured particulate matter mass concentration, which supports the importance of size in ice nucleation of particles from livestock facilities.

Investigation of a Saharan dust plume in Western Europe by remote sensing and transport modelling

Abstract: . The evolution and the properties of a Saharan dust plume were studied near the city of Karlsruhe in south-west Germany (8.4298° E, 49.0953° N) from April 7 to 9, 2018 combining a scanning LIDAR (90°, 30°), a vertical LIDAR (90°), a sun photometer, and the transport model ICON-ART. The LIDAR measurements show that the dust particles had backscatter coefficients of 0.86 ± 0.14 Mm−1 Sr−1, an extinction coefficient of 40 ± 0.8 Mm−1, a LIDAR ratio of 46 ± 5 sr, and a particle depolarization ratio of 0.33 ± 0.07. These values are in good agreement with those obtained in previous studies of Saharan dust plumes in Western Europe. Compared to the remote sensing measurements, the model simulation predicts the plume arrival time, its layer height, and structure very well but overestimates the backscatter coefficient. In this manuscript, we discuss the complementarity and advantages of the different measurement methods as well model simulations to predict Saharan dust plumes. Main conclusions are that the ICON-ART model can predict the structure of Saharan dust plumes very well but overestimates the backscatter coefficients by a factor of 2.2 ± 0.16 at 355 nm and underestimates the aerosol optical depth (AOD) by a factor of 1.5 ± 0.11 at 340 nm for this Saharan dust plume event. Employing a scanning aerosol LIDAR allows determining backscatter coefficient, particle depolarization ratio and especially LIDAR ratio of Saharan dust both for daytime and nighttime independently. Combining LIDAR with sun photometer data allows constraining aerosol optical depth in different ways and determining column integrated LIDAR ratios. These comprehensive datasets allow for a better understanding of Saharan dust plumes in Western Europe.