scholarly journals The ice-nucleating ability of quartz immersed in water and its atmospheric importance compared to K-feldspar

Author(s):  
Alexander D. Harrison ◽  
Katherine Lever ◽  
Alberto Sanchez-Marroquin ◽  
Mark A. Holden ◽  
Thomas F. Whale ◽  
...  

Abstract. Mineral dust particles are thought to be an important type of ice-nucleating particle (INP) in the mixed-phase cloud regime around the globe. While K-feldspar has been identified as being a particularly important component of mineral dust for ice nucleation, it has been shown that quartz is also relatively ice nucleation active. Given quartz typically makes up a substantial proportion of atmospheric desert dust it could potentially be important for cloud glaciation. Here, we survey the ice-nucleating ability of 10 α-quartz samples (the most common quartz polymorph) when immersed in microlitre supercooled water droplets. Despite all samples being α-quartz, the temperature at which they induce freezing varies by around 12 °C for a constant active site density. We find that some quartz samples are very sensitive to ageing in both aqueous suspension and air, resulting in a loss of ice-nucleating activity, while other samples are insensitive to exposure to air and water over many months. The sensitivity to water and air is perhaps surprising as quartz is thought of as a chemically resistant material, but this observation suggests that the active sites responsible for nucleation are less stable than the bulk of the material. We find that the quartz group of minerals are generally less active than K-feldspars, although the most active quartz samples are of a similar activity to some K-feldspars. We also find that the quartz samples are generally more active than the plagioclase feldspar group of minerals and the albite end-member has an intermediate activity. Using both the new and literature data, active site density parameterisations have been proposed for quartz, K-feldspar, plagioclase and albite. Combining these parameterisations with the typical atmospheric abundance of each mineral and comparing the results with atmospheric ice-nucleating particle concentrations, supports previous work that suggests that K-feldspar dominates, rather than quartz (or other minerals), the ice nucleation particle population in desert dust aerosol.

2019 ◽  
Vol 19 (17) ◽  
pp. 11343-11361 ◽  
Author(s):  
Alexander D. Harrison ◽  
Katherine Lever ◽  
Alberto Sanchez-Marroquin ◽  
Mark A. Holden ◽  
Thomas F. Whale ◽  
...  

Abstract. Mineral dust particles are thought to be an important type of ice-nucleating particle (INP) in the mixed-phase cloud regime around the globe. While K-rich feldspar (K-feldspar) has been identified as being a particularly important component of mineral dust for ice nucleation, it has been shown that quartz is also relatively ice-nucleation active. Given quartz typically makes up a substantial proportion of atmospheric desert dust, it could potentially be important for cloud glaciation. Here, we survey the ice-nucleating ability of 10 α-quartz samples (the most common quartz polymorph) when immersed in microlitre supercooled water droplets. Despite all samples being α-quartz, the temperature at which they induce freezing varies by around 12 ∘C for a constant active site density. We find that some quartz samples are very sensitive to ageing in both aqueous suspension and air, resulting in a loss of ice-nucleating activity, while other samples are insensitive to exposure to air and water over many months. For example, the ice-nucleation temperatures for one quartz sample shift down by ∼2 ∘C in 1 h and 12 ∘C after 16 months in water. The sensitivity to water and air is perhaps surprising, as quartz is thought of as a chemically resistant mineral, but this observation suggests that the active sites responsible for nucleation are less stable than the bulk of the mineral. We find that the quartz group of minerals is generally less active than K-feldspars by roughly 7 ∘C, although the most active quartz samples are of a similar activity to some K-feldspars with an active site density, ns(T), of 1 cm−2 at −9 ∘C. We also find that the freshly milled quartz samples are generally more active by roughly 5 ∘C than the plagioclase feldspar group of minerals and the albite end member has an intermediate activity. Using both the new and literature data, active site density parameterizations have been proposed for freshly milled quartz, K-feldspar, plagioclase and albite. Combining these parameterizations with the typical atmospheric abundance of each mineral supports previous work that suggests that K-feldspar is the most important ice-nucleating mineral in airborne mineral dust.


2019 ◽  
Vol 19 (2) ◽  
pp. 1059-1076 ◽  
Author(s):  
Yvonne Boose ◽  
Philipp Baloh ◽  
Michael Plötze ◽  
Johannes Ofner ◽  
Hinrich Grothe ◽  
...  

Abstract. Mineral dust particles from deserts are amongst the most common ice nucleating particles in the atmosphere. The mineralogy of desert dust differs depending on the source region and can further fractionate during the dust emission processes. Mineralogy to a large extent explains the ice nucleation behavior of desert aerosol, but not entirely. Apart from pure mineral dust, desert aerosol particles often exhibit a coating or are mixed with small amounts of biological material. Aging on the ground or during atmospheric transport can deactivate nucleation sites, thus strong ice nucleating minerals may not exhibit their full potential. In the partner paper of this work, it was shown that mineralogy determines most but not all of the ice nucleation behavior in the immersion mode found for desert dust. In this study, the influence of semi-volatile organic compounds and the presence of crystal water on the ice nucleation behavior of desert aerosol is investigated. This work focuses on the deposition and condensation ice nucleation modes at temperatures between 238 and 242 K of 18 dust samples sourced from nine deserts worldwide. Chemical imaging of the particles' surface is used to determine the cause of the observed differences in ice nucleation. It is found that, while the ice nucleation ability of the majority of the dust samples is dominated by their quartz and feldspar content, in one carbonaceous sample it is mostly caused by organic matter, potentially cellulose and/or proteins. In contrast, the ice nucleation ability of an airborne Saharan sample is found to be diminished, likely by semi-volatile species covering ice nucleation active sites of the minerals. This study shows that in addition to mineralogy, other factors such as organics and crystal water content can alter the ice nucleation behavior of desert aerosol during atmospheric transport in various ways.


2018 ◽  
Author(s):  
Yvonne Boose ◽  
Philipp Baloh ◽  
Michael Plötze ◽  
Johannes Ofner ◽  
Hinrich Grothe ◽  
...  

Abstract. Mineral dust particles from deserts are amongst the most common ice-nucleating particles in the atmosphere. The mineralogy of desert dust differs depending on the source region and can further fractionate during the dust emission processes. Mineralogy to a large extent explains the ice nucleation behavior of desert aerosol, but not entirely. Apart from pure mineral dust, desert aerosol particles are often mixed with small amounts of biological material or particles exhibit a coating. Aging on the ground or during atmospheric transport can deactivate nucleation sites and thus strong ice-nucleating minerals may not exhibit their full potential. In the partner paper of this work, it was shown that mineralogy determines most but not all of the ice nucleation behavior in the immersion mode found for desert dust. In this study, the influence of semi-volatile organic compounds and the presence of crystal water on the ice nucleation behavior of desert aerosol in addition to mineralogy is investigated. This work focuses on the deposition and condensation ice nucleation modes at temperatures between 238 to 242 K of 18 dust samples sources from 9 deserts worldwide. Chemical imaging of the particles' surface is used to determine the cause of the observed differences in ice nucleation. It is found that while the ice nucleation ability of the majority of the dust samples is dominated by their quartz and feldspar content, in one carbonaceous sample it is mostly caused by organic matter, potentially cellulose and/or proteins. On the other hand, the ice nucleation ability of an airborne Saharan sample is found to be diminished likely by semi-volatile species covering ice nucleation active sites of the minerals. This study shows that in addition to mineralogy, other factors such as organics and crystal water content can alter the ice nucleation behavior of desert aerosol during atmospheric transport in various ways.


2010 ◽  
Vol 10 (23) ◽  
pp. 11471-11487 ◽  
Author(s):  
R. C. Sullivan ◽  
M. D. Petters ◽  
P. J. DeMott ◽  
S. M. Kreidenweis ◽  
H. Wex ◽  
...  

Abstract. During the FROST-2 (FReezing Of duST) measurement campaign conducted at the Leipzig Aerosol Cloud Interaction Simulator (LACIS), we investigated changes in the ice nucleation properties of 300 nm Arizona Test Dust mineral particles following thermochemical processing by varying amounts and combinations of exposure to sulphuric acid vapour, ammonia gas, water vapour, and heat. The processed particles' heterogeneous ice nucleation properties were determined in both the water subsaturated and supersaturated humidity regimes at −30 °C and −25 °C using Colorado State University's continuous flow diffusion chamber. The amount of sulphuric acid coating material was estimated by an aerosol mass spectrometer and from CCN-derived hygroscopicity measurements. The condensation of sulphuric acid decreased the dust particles' ice nucleation ability in proportion to the amount of sulphuric acid added. Heating the coated particles in a thermodenuder at 250 °C – intended to evaporate the sulphuric acid coating – reduced their freezing ability even further. We attribute this behaviour to accelerated acid digestion of ice active surface sites by heat. Exposing sulphuric acid coated dust to ammonia gas produced particles with similarly poor freezing potential; however a portion of their ice nucleation ability could be restored after heating in the thermodenuder. In no case did any combination of thermochemical treatments increase the ice nucleation ability of the coated mineral dust particles compared to unprocessed dust. These first measurements of the effect of identical chemical processing of dust particles on their ice nucleation ability under both water subsaturated and mixed-phase supersaturated cloud conditions revealed that ice nucleation was more sensitive to all coating treatments in the water subsaturated regime. The results clearly indicate irreversible impairment of ice nucleation activity in both regimes after condensation of concentrated sulphuric acid. This implies that the sulphuric acid coating caused permanent chemical and/or physical modification of the ice active surface sites; the possible dissolution of the coating during droplet activation did not restore all immersion/condensation-freezing ability.


2010 ◽  
Vol 10 (7) ◽  
pp. 16901-16940 ◽  
Author(s):  
R. C. Sullivan ◽  
M. D. Petters ◽  
P. J. DeMott ◽  
S. M. Kreidenweis ◽  
H. Wex ◽  
...  

Abstract. During the FROST-2 (FReezing Of duST) measurement campaign conducted at the Leipzig Aerosol Cloud Interaction Simulator (LACIS), we investigated changes in the ice nucleation properties of 300 nm Arizona test dust mineral particles following thermochemical processing by varying amounts and combinations of exposure to sulphuric acid vapour, ammonia gas, water vapour, and heat. The processed aerosol's heterogeneous ice nucleation properties were determined in both the water subsaturated and supersaturated humidity regimes at −30 °C and −25 °C using Colorado State University's continuous flow diffusion chamber. The amount of sulphuric acid coating material was estimated by an aerosol mass spectrometer and from CCN-derived hygroscopicity measurements. The condensation of sulphuric acid decreased the dust particles' ice nucleation ability in proportion to the amount of sulphuric acid added. Heating the coated particles in a thermodenuder at 250 °C – intended to evaporate the sulphuric acid coating – reduced their freezing ability even further. We attribute this behaviour to accelerated acid digestion of ice active surface sites by heat. Exposing sulphuric acid coated dust to ammonia gas produced particles with similarly poor freezing potential; however a portion of their ice nucleation ability could be restored after heating in the thermodenuder. In no case did any combination of thermochemical treatments increase the ice nucleation ability of the coated mineral dust particles compared to unprocessed dust. These first measurements of the effect of identical chemical processing of dust particles on their ice nucleation ability in both water subsaturated and mixed-phase supersaturated cloud conditions revealed that ice nucleation was more sensitive to all coating treatments in the water subsaturated regime. The results clearly indicate irreversible impairment of ice nucleation activity in both regimes after condensation of concentrated sulphuric acid. This implies that the sulphuric acid coating caused permanent chemical and/or physical modification of the ice active surface sites; the possible dissolution of the coating during droplet activation did not restore all immersion/condensation-freezing ability.


2020 ◽  
Author(s):  
Olli Pakarinen ◽  
Golnaz Roudsari ◽  
Bernhard Reischl ◽  
Hanna Vehkamäki

<p>Understanding the formation of ice is of great importance to many fields of science. Sufficiently pure water droplets can remain in the supercooled liquid phase to nearly -40 ºC. Crystallization of ice in the atmosphere therefore typically occurs in the presence of ice nucleating particles (INPs), such as mineral dust or organic particles. These can trigger heterogeneous ice nucleation at clearly higher temperatures. Therefore, a better understanding of how the various types of aerosol particles present in the atmosphere affect ice nucleation (IN) in clouds would be an important advance in the field of atmospheric science.</p><p>Experiments have shown in great detail what is the IN activity of different types of compounds, and recently also clarified the importance of small surface features such as surface defects, which function as active sites for ice nucleation. On most mineral dust particles, there may be only a few active sites for ice nucleation, typically around defects or pits (Holden et al., 2019). Simulations also showed enhanced ice nucleation efficiency in confined geometry such as wedges or pits (Bi, Cao and Li, 2017).</p><p>We systematically study the effect of water confining defects with different surface geometries; pyramidal pits, wedge-shaped cracks and slits with water confined between two parallel walls, using molecular dynamics simulations with both all-atom and monatomic water models, and show that that these defects enhance ice nucleation both at large supercooling and at very low supercooling.</p><p>Results of simulations on pyramidal pits on Si (100) surfaces, realizable experimentally, show a clear (∆T > 10 ºC) enhancement of ice nucleation compared to the very weakly IN active flat Si (100) or Si (111) surfaces. To show that water confinement can enhance IN also at very low supercooling, at temperatures above −10 ºC, we constructed wedge shaped structures with β-AgI (0001) surface as one of the two side walls, and slit systems by positioning two β-AgI (0001) slabs to mirror each other to cancel the dipole field from the polar surfaces. Depending on the wedge angle or the relation of the width of the gap between two slabs in the slit systems with the thickness of ice bilayers, ice nucleation can be clearly enhanced or hindered. We also clarify the different mechanisms behind IN enhancement at different geometries.</p><p>Understanding the enhanced activity at surface features may enable characterization of ice nucleation active sites on some atmospheric particles, creation of IN active sites at otherwise poorly active materials such as silicon, and also enable enhancing very active IN materials such as AgI, to nucleate ice at nearly zero supercooling.</p><p>This work was supported by the Academy of Finland Center of Excellence programme (grant no. 307331) and ARKTIKO project 285067 ICINA, by University of Helsinki, Faculty of Science ATMATH project, by the National Center for Meteorology (NCM), Abu Dhabi, UAE, under the UAE Research Program for Rain Enhancement Science, as well as ERC Grant 692891-DAMOCLES. Supercomputing resources were provided by CSC–IT Center for Science, Ltd, Finland.</p>


2014 ◽  
Vol 14 (15) ◽  
pp. 22045-22116 ◽  
Author(s):  
N. Hiranuma ◽  
S. Augustin-Bauditz ◽  
H. Bingemer ◽  
C. Budke ◽  
J. Curtius ◽  
...  

Abstract. Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice nucleating particles (INPs). However, an inter-comparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nucleation research UnIT), we distributed an illite rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. Seventeen measurement methods were involved in the data inter-comparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while ten other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing dataset was evaluated using the ice nucleation active surface-site density (ns) to develop a representative ns(T) spectrum that spans a wide temperature range (−37 °C < T < −11 °C) and covers nine orders of magnitude in ns. Our inter-comparison results revealed a discrepancy between suspension and dry-dispersed particle measurements for this mineral dust. While the agreement was good below ~ −26 °C, the ice nucleation activity, expressed in ns, was smaller for the wet suspended samples and higher for the dry-dispersed aerosol samples between about −26 and −18 °C. Only instruments making measurement techniques with wet suspended samples were able to measure ice nucleation above −18 °C. A possible explanation for the deviation between −26 and −18 °C is discussed. In general, the seventeen immersion freezing measurement techniques deviate, within the range of about 7 °C in terms of temperature, by three orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency (i.e., ns) of illite NX particles is relatively independent on droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature-dependence and weak time- and size-dependence of immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns (T) spectra, and identified a section with a steep slope between −20 and −27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below −27 °C. A multiple exponential distribution fit is expressed as ns(T) = exp(23.82 × exp(−exp(0.16 × (T + 17.49))) + 1.39) based on the specific surface area and ns(T) = exp(25.75 × exp(−exp(0.13 × (T + 17.17))) + 3.34) based on the geometric area (ns and T in m−2 and °C, respectively). These new fits, constrained by using an identical reference samples, will help to compare IN measurement methods that are not included in the present study and, thereby, IN data from future IN instruments.


2018 ◽  
Vol 18 (19) ◽  
pp. 14609-14622 ◽  
Author(s):  
Zechen Yu ◽  
Myoseon Jang

Abstract. To improve the simulation of the heterogeneous oxidation of SO2 and NOx in the presence of authentic mineral dust particles under ambient environmental conditions, the explicit kinetic mechanisms were constructed in the Atmospheric Mineral Aerosol Reaction (AMAR) model. The formation of sulfate and nitrate was divided into three phases: the gas phase, the non-dust aqueous phase, and the dust phase. In particular, AMAR established the mechanistic role of dust chemical characteristics (e.g., photoactivation, hygroscopicity, and buffering capacity) in heterogeneous chemistry. The photoactivation kinetic process of different dust particles was built into the model by measuring the photodegradation rate constant of an impregnated surrogate (malachite green dye) on a dust filter sample (e.g., Arizona test dust – ATD – and Gobi Desert dust – GDD) using an online reflective UV–visible spectrometer. The photoactivation parameters were integrated with the heterogeneous chemistry to predict the formation of reactive oxygen species on dust surfaces. A mathematical equation for the hygroscopicity of dust particles was also included in the AMAR model to process the multiphase partitioning of trace gases and in-particle chemistry. The buffering capacity of dust, which is related to the neutralization of dust alkaline carbonates with inorganic acids, was included in the model to dynamically predict the hygroscopicity of aged dust. The AMAR model simulated the formation of sulfate and nitrate using experimental data obtained in the presence of authentic mineral dust under ambient sunlight using a large outdoor smog chamber (University of Florida Atmospheric Photochemical Outdoor Reactor, UF-APHOR). Overall, the influence of GDD on the heterogeneous chemistry was much greater than that of ATD. Based on the model analysis, GDD enhanced the sulfate formation mainly via its high photoactivation capability. In the case of NO2 oxidation, dust-phase nitrate formation is mainly regulated by the buffering capacity of dust. The measured buffering capacity of GDD was 2 times greater than that of ATD, and consequently, the maximum nitrate concentration with GDD was nearly 2 times higher than that with ATD. The model also highlights that in urban areas with high NOx concentrations, hygroscopic nitrate salts quickly form via titration of the carbonates in the dust particles, but in the presence of SO2, the nitrate salts are gradually depleted by the formation of sulfate.


2015 ◽  
Vol 15 (1) ◽  
pp. 393-409 ◽  
Author(s):  
P. J. DeMott ◽  
A. J. Prenni ◽  
G. R. McMeeking ◽  
R. C. Sullivan ◽  
M. D. Petters ◽  
...  

Abstract. Data from both laboratory studies and atmospheric measurements are used to develop an empirical parameterization for the immersion freezing activity of natural mineral dust particles. Measurements made with the Colorado State University (CSU) continuous flow diffusion chamber (CFDC) when processing mineral dust aerosols at a nominal 105% relative humidity with respect to water (RHw) are taken as a measure of the immersion freezing nucleation activity of particles. Ice active frozen fractions vs. temperature for dusts representative of Saharan and Asian desert sources were consistent with similar measurements in atmospheric dust plumes for a limited set of comparisons available. The parameterization developed follows the form of one suggested previously for atmospheric particles of non-specific composition in quantifying ice nucleating particle concentrations as functions of temperature and the total number concentration of particles larger than 0.5 μm diameter. Such an approach does not explicitly account for surface area and time dependencies for ice nucleation, but sufficiently encapsulates the activation properties for potential use in regional and global modeling simulations, and possible application in developing remote sensing retrievals for ice nucleating particles. A calibration factor is introduced to account for the apparent underestimate (by approximately 3, on average) of the immersion freezing fraction of mineral dust particles for CSU CFDC data processed at an RHw of 105% vs. maximum fractions active at higher RHw. Instrumental factors that affect activation behavior vs. RHw in CFDC instruments remain to be fully explored in future studies. Nevertheless, the use of this calibration factor is supported by comparison to ice activation data obtained for the same aerosols from Aerosol Interactions and Dynamics of the Atmosphere (AIDA) expansion chamber cloud parcel experiments. Further comparison of the new parameterization, including calibration correction, to predictions of the immersion freezing surface active site density parameterization for mineral dust particles, developed separately from AIDA experimental data alone, shows excellent agreement for data collected in a descent through a Saharan aerosol layer. These studies support the utility of laboratory measurements to obtain atmospherically relevant data on the ice nucleation properties of dust and other particle types, and suggest the suitability of considering all mineral dust as a single type of ice nucleating particle as a useful first-order approximation in numerical modeling investigations.


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