Thomas F. Whale

The importance of feldspar for ice nucleation by mineral dust in mixed-phase clouds

The amount of ice present in mixed-phase clouds, which contain both supercooled liquid water droplets and ice particles, affects cloud extent, lifetime, particle size and radiative properties. The freezing of cloud droplets can be catalysed by the presence of aerosol particles known as ice nuclei. One of the most important ice nuclei is thought to be mineral dust aerosol from arid regions. It is generally assumed that clay minerals, which contribute approximately two-thirds of the dust mass, dominate ice nucleation by mineral dust, and many experimental studies have therefore focused on these materials. Here we use an established droplet-freezing technique to show that feldspar minerals dominate ice nucleation by mineral dusts under mixed-phase cloud conditions, despite feldspar being a minor component of dust emitted from arid regions. We also find that clay minerals are relatively unimportant ice nuclei. Our results from a global aerosol model study suggest that feldspar ice nuclei are globally distributed and that feldspar particles may account for a large proportion of the ice nuclei in Earth’s atmosphere that contribute to freezing at temperatures below about −15 °C.

A marine biogenic source of atmospheric ice-nucleating particles

The amount of ice present in clouds can affect cloud lifetime, precipitation and radiative properties. The formation of ice in clouds is facilitated by the presence of airborne ice-nucleating particles. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice. Sea-spray aerosol contains large amounts of organic material that is ejected into the atmosphere during bubble bursting at the organically enriched sea–air interface or sea surface microlayer. Here we show that organic material in the sea surface microlayer nucleates ice under conditions relevant for mixed-phase cloud and high-altitude ice cloud formation. The ice-nucleating material is probably biogenic and less than approximately 0.2 micrometres in size. We find that exudates separated from cells of the marine diatom Thalassiosira pseudonana nucleate ice, and propose that organic material associated with phytoplankton cell exudates is a likely candidate for the observed ice-nucleating ability of the microlayer samples. Global model simulations of marine organic aerosol, in combination with our measurements, suggest that marine organic material may be an important source of ice-nucleating particles in remote marine environments such as the Southern Ocean, North Pacific Ocean and North Atlantic Ocean.

The relevance of nanoscale biological fragments for ice nucleation in clouds

Most studies of the role of biological entities as atmospheric ice-nucleating particles have focused on relatively rare supermicron particles such as bacterial cells, fungal spores and pollen grains. However, it is not clear that there are sufficient numbers of these particles in the atmosphere to strongly influence clouds. Here we show that the ice-nucleating activity of a fungus from the ubiquitous genus Fusarium is related to the presence of nanometre-scale particles which are far more numerous, and therefore potentially far more important for cloud glaciation than whole intact spores or hyphae. In addition, we quantify the ice-nucleating activity of nano-ice nucleating particles (nano-INPs) washed off pollen and also show that nano-INPs are present in a soil sample. Based on these results, we suggest that there is a reservoir of biological nano-INPs present in the environment which may, for example, become aerosolised in association with fertile soil dust particles.

Stacking disorder in ice I

Traditionally, ice I was considered to exist in two well-defined crystalline forms at ambient pressure: stable hexagonal ice (ice Ih) and metastable cubic ice (ice Ic). However, it is becoming increasingly evident that what has been called cubic ice in the past does not have a structure consistent with the cubic crystal system. Instead, it is a stacking-disordered material containing cubic sequences interlaced with hexagonal sequences, which is termed stacking-disordered ice (ice Isd). In this article, we summarise previous work on ice with stacking disorder including ice that was called cubic ice in the past. We also present new experimental data which shows that ice which crystallises after heterogeneous nucleation in water droplets containing solid inclusions also contains stacking disorder even at freezing temperatures of around -15 °C. This supports the results from molecular simulations, that the structure of ice that crystallises initially from supercooled water is always stacking-disordered and that this metastable ice can transform to the stable hexagonal phase subject to the kinetics of recrystallization. We also show that stacking disorder in ice which forms from water droplets is quantitatively distinct from ice made via other routes. The emerging picture of ice I is that of a very complex material which frequently contains stacking disorder and this stacking disorder can vary in complexity depending on the route of formation and thermal history.

A technique for quantifying heterogeneous ice nucleation in microlitre supercooled water droplets

Abstract. In many clouds, the formation of ice requires the presence of particles capable of nucleating ice. Ice-nucleating particles (INPs) are rare in comparison to cloud condensation nuclei. However, the fact that only a small fraction of aerosol particles can nucleate ice means that detection and quantification of INPs is challenging. This is particularly true at temperatures above about −20 °C since the population of particles capable of serving as INPs decreases dramatically with increasing temperature. In this paper, we describe an experimental technique in which droplets of microlitre volume containing ice-nucleating material are cooled down at a controlled rate and their freezing temperatures recorded. The advantage of using large droplet volumes is that the surface area per droplet is vastly larger than in experiments focused on single aerosol particles or cloud-sized droplets. This increases the probability of observing the effect of less common, but important, high-temperature INPs and therefore allows the quantification of their ice nucleation efficiency. The potential artefacts which could influence data from this experiment, and other similar experiments, are mitigated and discussed. Experimentally determined heterogeneous ice nucleation efficiencies for K-feldspar (microcline), kaolinite, chlorite, NX-illite, Snomax® and silver iodide are presented.

Ice Nucleation Properties of Oxidized Carbon Nanomaterials.

Heterogeneous ice nucleation is an important process in many fields, particularly atmospheric science, but is still poorly understood. All known inorganic ice nucleating particles are relatively large in size and tend to be hydrophilic. Hence it is not obvious that carbon nanomaterials should nucleate ice. However, in this paper we show that four different readily water-dispersible carbon nanomaterials are capable of nucleating ice. The tested materials were carboxylated graphene nanoflakes, graphene oxide, oxidized single walled carbon nanotubes and oxidized multiwalled carbon nanotubes. The carboxylated graphene nanoflakes have a diameter of ∼30 nm and are among the smallest entities observed so far to nucleate ice. Overall, carbon nanotubes were found to nucleate ice more efficiently than flat graphene species, and less oxidized materials nucleated ice more efficiently than more oxidized species. These well-defined carbon nanomaterials may pave the way to bridging the gap between experimental and computational studies of ice nucleation.

Heterogeneous Ice Nucleation by Soufriere Hills Volcanic Ash Immersed in Water Droplets

Fine particles of ash emitted during volcanic eruptions may sporadically influence cloud properties on a regional or global scale as well as influencing the dynamics of volcanic clouds and the subsequent dispersion of volcanic aerosol and gases. It has been shown that volcanic ash can trigger ice nucleation, but ash from relatively few volcanoes has been studied for its ice nucleating ability. In this study we quantify the efficiency with which ash from the Soufriere Hills volcano on Montserrat nucleates ice when immersed in supercooled water droplets. Using an ash sample from the 11th February 2010 eruption, we report ice nucleating efficiencies from 246 to 265 K. This wide range of temperatures was achieved using two separate droplet freezing instruments, one employing nanolitre droplets, the other using microlitre droplets. Soufriere Hills volcanic ash was significantly more efficient than all other ash samples that have been previously examined. At present the reasons for these differences are not understood, but may be related to mineralogy, amorphous content and surface chemistry.

The study of atmospheric ice-nucleating particles via microfluidically generated droplets

Ice-nucleating particles (INPs) play a significant role in the climate and hydrological cycle by triggering ice formation in supercooled clouds, thereby causing precipitation and affecting cloud lifetimes and their radiative properties. However, despite their importance, INP often comprise only 1 in 103–106 ambient particles, making it difficult to ascertain and predict their type, source, and concentration. The typical techniques for quantifying INP concentrations tend to be highly labour-intensive, suffer from poor time resolution, or are limited in sensitivity to low concentrations. Here, we present the application of microfluidic devices to the study of atmospheric INPs via the simple and rapid production of monodisperse droplets and their subsequent freezing on a cold stage. This device offers the potential for the testing of INP concentrations in aqueous samples with high sensitivity and high counting statistics. Various INPs were tested for validation of the platform, including mineral dust and biological species, with results compared to literature values. We also describe a methodology for sampling atmospheric aerosol in a manner that minimises sampling biases and which is compatible with the microfluidic device. We present results for INP concentrations in air sampled during two field campaigns: (1) from a rural location in the UK and (2) during the UK’s annual Bonfire Night festival. These initial results will provide a route for deployment of the microfluidic platform for the study and quantification of INPs in upcoming field campaigns around the globe, while providing a benchmark for future lab-on-a-chip-based INP studies.

Contributions of biogenic material to the atmospheric ice-nucleating particle population in North Western Europe

A minute fraction of atmospheric particles exert a disproportionate effect on the phase of mixed-phase clouds by acting as ice-nucleating particles (INPs). To understand the effects of these particles on weather and climate, both now and into the future, we must first develop a quantitative understanding of the major INP sources worldwide. Previous work has demonstrated that aerosols such as desert dusts are globally important INPs, but the role of biogenic INPs is unclear, with conflicting evidence for their importance. Here, we show that at a temperate site all INPs active above −18 °C at concentrations >0.1 L−1 are destroyed on heating, consistent with these INPs being of biological origin. Furthermore, we show that a global model of desert dust INPs dramatically underestimates the measured INP concentrations, but is consistent with the thermally-stable component. Notably, the heat sensitive INPs are active at temperatures where shallow cloud layers in Northern Europe are frequently observed to glaciate. Hence, we suggest that biogenic material is important for primary ice production in this region. The prevalence of heat sensitive, most likely biogenic, INPs in this region highlights that, as a community, we need to quantify the sources and transport of these particles as well as determine their atmospheric abundance across the globe and at cloud altitudes.

Ice Nucleation in Mixed-Phase Clouds

Ice nucleation must, on some level, play a critical role in the formation of ice in mixed-phase clouds. Fundamentally, there must be an initial triggering of ice formation in a cloud for it contain any ice at all, or else it will remain in a supercooled state indefinitely. There has been a great deal of work aimed at understanding and quantifying ice nucleation. It is this work which this chapter seeks to review and summarize. The different modes of ice nucleation are defined, followed by a brief discussion of the role of ice nucleation in the atmosphere in general and in mixed-phase clouds in general. The various techniques used for measuring ice nucleation efficiencies are outlined followed by a detailed treatment of classical nucleation theory as applied to heterogeneous and homogeneous ice nucleation. The various descriptions of ice nucleation efficiency used by the atmospheric ice nucleation community are described. Finally the properties required for a substance to nucleate ice efficiently are discussed and the various potential atmospheric aerosol species that may nucleate ice in mixed-phase clouds are discussed and compared.