Abstract
Based on results of 11 yr of heterogeneous ice nucleation experiments at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) chamber in Karlsruhe, Germany, a new empirical ...parameterization framework for heterogeneous ice nucleation was developed. The framework currently includes desert dust and soot aerosol and quantifies the ice nucleation efficiency in terms of the ice nucleation active surface site (INAS) approach.
The immersion freezing INAS densities nS of all desert dust experiments follow an exponential fit as a function of temperature, well in agreement with an earlier analysis of AIDA experiments. The deposition nucleation nS isolines for desert dust follow u-shaped curves in the ice saturation ratio–temperature (Si–T) diagram at temperatures below about 240 K. The negative slope of these isolines toward lower temperatures may be explained by classical nucleation theory (CNT), whereas the behavior toward higher temperatures may be caused by a pore condensation and freezing mechanism. The deposition nucleation measured for soot at temperatures below about 240 K also follows u-shaped isolines with a shift toward higher Si for soot with higher organic carbon content. For immersion freezing of soot aerosol, only upper limits for nS were determined and used to rescale an existing parameterization line.
The new parameterization framework is compared to a CNT-based parameterization and an empirical framework as used in models. The comparison shows large differences in shape and magnitude of the nS isolines especially for deposition nucleation. For the application in models, implementation of this new framework is simple compared to that of other expressions.
Reactions of volatile organic compounds (VOC) with NO3 radicals and of reactive intermediates of oxidized VOC with NO x can lead to the formation of highly functionalized organonitrates (ON). We ...present quantitative and chemical information on ON contributing to high night-time organic aerosol (OA) mass concentrations measured during July–August 2016 in a rural area in southwest Germany. A filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS) was used to analyze the molecular composition of ON in both the gas and particle phase. We find larger contributions of ON to OA mass during the night. Identified ON are highly functionalized, with 4 to 12 oxygen atoms. The diel patterns of ON compounds with 5, 7, 10, or 15 carbon atoms per molecule vary, indicating a corresponding behavior of their potential precursor VOC. The temporal behavior of ON after sunset correlates with that of the number concentration of ultrafine particles, indicating a potential role of ON in night-time new particle formation (NPF) regularly observed at this location. We estimate an ON contribution of 18–25% to the mass increase of newly formed particles after sunset. Our study provides insights into the chemical composition of highly functionalized ON in the rural atmosphere and the role of anthropogenic emissions for night-time SOA formation in an area where biogenic VOC emissions dominate.
In spite of the resurgence in ice nucleation research a comparatively small number of studies deal with the phenomenon of pre-activation in heterogeneous ice nucleation. Fifty years ago, it was shown ...that various mineral dust and volcanic ash particles can be pre-activated to become nuclei for ice crystal formation even at temperatures as high as 270–271 K. Pre-activation was achieved under ice-subsaturated conditions without any preceding macroscopic ice growth by just temporarily cooling the particles to temperatures below 228 K. A two-step mechanism involving capillary condensation of supercooled water and subsequent homogeneous freezing was proposed to account for the particles' enhanced ice nucleation ability at high temperatures. This work reinvestigates the efficiency of the proposed pre-activation mechanism in temperature-cycling experiments performed in a large cloud chamber with suspended particles. We find the efficiency to be highest for the clay mineral illite as well as for highly porous materials like zeolite and diatomaceous earth, whereas most aerosols generated from desert dust surface samples did not reveal a measurable pre-activation ability. The pre-activation efficiency is linked to particle pores in a certain size range. As estimated by model calculations, only pores with diameters between about 5 and 8 nm contribute to pre-activation under ice-subsaturated conditions. This range is set by a combination of requirements from the negative Kelvin effect for condensation and a critical size of ice embryos for ice nucleation and melting. In contrast to the early study, pre-activation is only observed for temperatures below 260 K. Above that threshold, the particles' improved ice nucleation ability disappears due to the melting of ice in the pores.
The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary ...organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.
The evolution and the properties of a Saharan dust plume were studied near the city of Karlsruhe in southwest Germany (8.4298°E, 49.0953°N) from 7 to 9 April 2018, combining a scanning LiDAR (90°, ...30°), a vertically pointing LiDAR (90°), a sun photometer, and the transport model ICON-ART. Based on this Saharan dust case, we discuss the advantages of a scanning aerosol LiDAR and validate a method to determine LiDAR ratios independently. The LiDAR measurements at 355 nm showed that the dust particles had backscatter coefficients of 0.86 ± 0.14 Mm−1 sr−1, extinction coefficients of 40 ± 0.8 Mm−1, a LiDAR ratio of 46 ± 5 sr, and a linear particle depolarisation ratio of 0.27 ± 0.023. 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 transport model predicted the plume arrival time, its layer height, and its structure quite well. The comparison of dust plume backscatter values from the ICON-ART model and observations for two days showed a correlation with a slope of 0.9 ± 0.1 at 355 nm. This work will be useful for future studies to characterise aerosol particles employing scanning LiDARs.
The ice nucleation characteristics of Arizona test dust (ATD) and illite clay, surrogates for atmospheric ice nuclei, have been determined at the Aerosol Interactions and Dynamics in the Atmosphere ...(AIDA) chamber located at the Research Center Karlsruhe in Germany. The objective of this research was to determine the effect of sulfuric acid and ammonium sulfate coatings on the ability of these mineral dust surrogates to nucleate ice in an environment where particles realistically compete for water vapor. Coated ATD particles required higher saturations at all temperatures considered, from −20 to −45 °C, than did identical uncoated particles. Freezing of coated particles often required saturations approaching those for the homogeneous freezing of aqueous solutions of the coating material alone. Less pronounced effects were found for illite, although the presence of a coating consistently increased the saturation or decreased the temperature required for ice formation. Analysis of ice residue at the single particle level suggests that the first coated particles to freeze had thinner or incomplete coatings when compared to particles that froze later in the expansion. This observation highlights a need to verify coating properties since an assumption of homogeneity of a group of coated aerosols may be incorrect. The increase in saturation ratio for freezing suggests that gas-phase uptake of sulfates, a large fraction of which are due to anthropogenic emissions, will reduce the ice and mixed-phase cloud formation potential of atmospheric ice nuclei.
Investigations on adverse biological effects of nanoparticles (NPs) in the lung by in vitro studies are usually performed under submerged conditions where NPs are suspended in cell culture media. ...However, the behaviour of nanoparticles such as agglomeration and sedimentation in such complex suspensions is difficult to control and hence the deposited cellular dose often remains unknown. Moreover, the cellular responses to NPs under submerged culture conditions might differ from those observed at physiological settings at the air-liquid interface.
In order to avoid problems because of an altered behaviour of the nanoparticles in cell culture medium and to mimic a more realistic situation relevant for inhalation, human A549 lung epithelial cells were exposed to aerosols at the air-liquid interphase (ALI) by using the ALI deposition apparatus (ALIDA). The application of an electrostatic field allowed for particle deposition efficiencies that were higher by a factor of more than 20 compared to the unmodified VITROCELL deposition system. We studied two different amorphous silica nanoparticles (particles produced by flame synthesis and particles produced in suspension by the Stöber method). Aerosols with well-defined particle sizes and concentrations were generated by using a commercial electrospray generator or an atomizer. Only the electrospray method allowed for the generation of an aerosol containing monodisperse NPs. However, the deposited mass and surface dose of the particles was too low to induce cellular responses. Therefore, we generated the aerosol with an atomizer which supplied agglomerates and thus allowed a particle deposition with a three orders of magnitude higher mass and of surface doses on lung cells that induced significant biological effects. The deposited dose was estimated and independently validated by measurements using either transmission electron microscopy or, in case of labelled NPs, by fluorescence analyses. Surprisingly, cells exposed at the ALI were less sensitive to silica NPs as evidenced by reduced cytotoxicity and inflammatory responses.
Amorphous silica NPs induced qualitatively similar cellular responses under submerged conditions and at the ALI. However, submerged exposure to NPs triggers stronger effects at much lower cellular doses. Hence, more studies are warranted to decipher whether cells at the ALI are in general less vulnerable to NPs or specific NPs show different activities dependent on the exposure method.
Aerosol pollution in urban areas is highly variable due to numerous single emission sources such as automobiles, industrial and commercial activities as well as domestic heating, but also due to ...complex building structures redirecting air mass flows, producing leeward and windward turbulences and resuspension effects. In this publication, it is shown that one or even few aerosol monitoring sites are not able to reflect these complex patterns. In summer 2019, aerosol pollution was recorded in high spatial resolution during six night and daytime tours with a mobile sensor platform on a trailer pulled by a bicycle. Particle mass loadings showed a high variability with PM
10
values ranging from 1.3 to 221 μg m
−3
and PM
2.5
values from 0.7 to 69.0 μg m
−3
. Geostatistics were used to calculate respective models of the spatial distributions of PM
2.5
and PM10. The resulting maps depict the variability of aerosol concentrations within the urban space. These spatial distribution models delineate the distributions without cutting out the built-up structures. Elsewise, the overall spatial patterns do not become visible because of being sharply interrupted by those cutouts in the resulting maps. Thus, the spatial maps allow to identify most affected urban areas and are not restricted to the street space. Furthermore, this method provides an insight to potentially affected areas, and thus can be used to develop counter measures. It is evident that the spatial aerosol patterns cannot be directly derived from the main wind direction, but result far more from an interplay between main wind direction, built-up patterns and distribution of pollution sources. Not all pollution sources are directly obvious and more research has to be carried out to explain the micro-scale variations of spatial aerosol distribution patterns. In addition, since aerosol load in the atmosphere is a severe issue for health and wellbeing of city residents more attention has to be paid to these local inhomogeneities.
Potential impacts of lightning-induced plasma on cloud ice formation and precipitation have been a subject of debate for decades. Here, we report on the interaction of laser-generated plasma channels ...with water and ice clouds observed in a large cloud simulation chamber. Under the conditions of a typical storm cloud, in which ice and supercooled water coexist, no direct influence of the plasma channels on ice formation or precipitation processes could be detected. Under conditions typical for thin cirrus ice clouds, however, the plasma channels induced a surprisingly strong effect of ice multiplication. Within a few minutes, the laser action led to a strong enhancement of the total ice particle number density in the chamber by up to a factor of 100, even though only a 10 ⁻⁹ fraction of the chamber volume was exposed to the plasma channels. The newly formed ice particles quickly reduced the water vapor pressure to ice saturation, thereby increasing the cloud optical thickness by up to three orders of magnitude. A model relying on the complete vaporization of ice particles in the laser filament and the condensation of the resulting water vapor on plasma ions reproduces our experimental findings. This surprising effect might open new perspectives for remote sensing of water vapor and ice in the upper troposphere.
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