CO₂ ice structure and density under Martian atmospheric conditions

Clouds composed of CO2 ice form throughout the Martian atmosphere. In the mesosphere, CO2 ice clouds are thought to form via heterogeneous ice nucleation on nanoparticles of meteoric origin at temperatures often below 100 K. Lower altitude CO2 ice clouds in the wintertime polar regions form up to around 145 K and lead to the build-up of the polar ice caps. However, the crystal structure and related fundamental properties of CO2 ice under Martian conditions are poorly characterised. Here we present X-ray diffraction (XRD) measurements of CO2 ice, grown via deposition from the vapour phase under temperature and pressure conditions analogous to the Martian mesosphere. A crystalline cubic structure was determined, consistent with the low-pressure polymorph (CO2-I, space group Pa-3 (No. 205)). CO2 deposited at temperatures of 80 - 130 K and pressures of 0.01 – 1 mbar was consistent with dry ice and previous literature measurements, thus removing the possibility of a more complicated phase diagram for CO2 in this region. At 80 K, a lattice parameter of 5.578 ± 0.002 Å, cell volume of 173.554 ± 0.19 Å3 and density of 1.684 ± 0.002 g cm−3 was determined. Using these measurements, we determined the thermal expansion of CO2 across 80 – 130 K that allowed for a fit of CO2 ice density measurements across a larger temperature range (80 – 195 K) when combined with literature data (CO2 density = 1.72391 - 2.53×10−4 T - 2.87×10−6 T2). Temperature-dependent CO2 density values are used to estimate sedimentation velocities and heterogeneous ice nucleation rates, showing an increase in nucleation rate of up to a factor of 1000 when compared to commonly used literature values. This temperature-dependent equation of state is therefore suggested for use in future studies of Martian mesospheric CO2 clouds. Finally, we discuss the possible shapes of crystals of CO2 ice in the Martian atmosphere and show that a range of shapes including cubes and octahedra as well as a combination of the two in the form of cubo-octahedra are likely

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1°C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3°C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10°C, which corresponds to a change in active site density of more than a factor of 105. This concentration was chosen for a survey across multiple solutes-nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these ‘solute effects’, to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature

Volcanic ash ice-nucleating activity can be enhanced or depressed by ash-gas interaction in the eruption plume

Volcanic ash can trigger ice nucleation when immersed in supercooled water. This will impact several processes (e.g., electrification, aggregation, precipitation) in the eruption plume and cloud and in the wider atmosphere upon ash dispersal. Previous studies show that ash bulk properties, reflecting the chemistry and phase state of the source magma, likely contribute to the ice-nucleating activity (INA) of ash. However, it remains unexplored how interaction with magmatic gases in the hot eruption plume, which inevitably leads to altered ash surface properties, affects the ash INA. Here we demonstrate that the INA of tephra is raised by exposure to H2O(g) mixed with SO2(g) at both 800 and 400 °C, but is substantially reduced by exposure to H2O(g) alone or mixed with HCl(g) at the same temperatures. In contrast, the INA of K-feldspar and quartz is reduced by all three eruption plume processing treatments. The decrease in INA of all silicates after heating with H2O(g) might relate to a loss of ice-active sites by surface dehydroxylation and/or oxidation. In the presence of HCl(g) or SO2(g), respectively, metal chloride or sulphate salts form on the tephra surfaces only. While NaCl and CaCl2 seem to have no effect on the tephra INA, CaSO4 is inferred to create ice-active sites, potentially through a particular combination of surface chemistry and topography. Overall, our findings suggest a complex interplay of bulk mineralogy and surface alteration in influencing ice nucleation by volcanic ash, and highlight the general sensitivity (enhancement or depression) of ash INA to interaction with magmatic gases in the eruption plume

Nucleation of nitric acid hydrates in polar stratospheric clouds by meteoric material

Heterogeneous nucleation of crystalline nitric acid hydrates in polar stratospheric clouds (PSCs) enhances ozone depletion. However, the identity and mode of action of the particles responsible for nucleation remains unknown. It has been suggested that meteoric material may trigger nucleation of nitric acid trihydrate (NAT, or other nitric acid phases), but this has never been quantitatively demonstrated in the laboratory. Meteoric material is present in two forms in the stratosphere: smoke that results from the ablation and re-condensation of vapours, and fragments that result from the break-up of meteoroids entering the atmosphere. Here we show that analogues of both materials have a capacity to nucleate nitric acid hydrates. In combination with estimates from a global model of the amount of meteoric smoke and fragments in the polar stratosphere we show that meteoric material probably accounts for NAT observations in early season polar stratospheric clouds in the absence of water ice

Strong control of Southern Ocean cloud reflectivity by ice-nucleating particles

Large biases in climate model simulations of cloud radiative properties over the Southern Ocean cause large errors in modeled sea surface temperatures, atmospheric circulation, and climate sensitivity. Here, we combine cloud-resolving model simulations with estimates of the concentration of ice-nucleating particles in this region to show that our simulated Southern Ocean clouds reflect far more radiation than predicted by global models, in agreement with satellite observations. Specifically, we show that the clouds that are most sensitive to the concentration of ice-nucleating particles are low-level mixed-phase clouds in the cold sectors of extratropical cyclones, which have previously been identified as a main contributor to the Southern Ocean radiation bias. The very low ice-nucleating particle concentrations that prevail over the Southern Ocean strongly suppress cloud droplet freezing, reduce precipitation, and enhance cloud reflectivity. The results help explain why a strong radiation bias occurs mainly in this remote region away from major sources of ice-nucleating particles. The results present a substantial challenge to climate models to be able to simulate realistic ice-nucleating particle concentrations and their effects under specific meteorological conditions

Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosol–cloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D2O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, Dwater, as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 °C, and demonstrate that water diffusion is slow (Dwater ~5 × 10−17 m2 s−1), but not arrested, just below the glass transition at a water activity of 0.2. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes–Einstein equation to determine diffusion timescales from viscosity leads to values which are more than 5 orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the diffusion timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion

Modulation of the virus-receptor interaction by mutations in the V5 loop of feline immunodeficiency virus (FIV) following in vivo escape from neutralising antibody

&lt;b&gt;BACKGROUND:&lt;/b&gt; In the acute phase of infection with feline immunodeficiency virus (FIV), the virus targets activated CD4+ T cells by utilising CD134 (OX40) as a primary attachment receptor and CXCR4 as a co-receptor. The nature of the virus-receptor interaction varies between isolates; strains such as GL8 and CPGammer recognise a "complex" determinant on CD134 formed by cysteine-rich domains (CRDs) 1 and 2 of the molecule while strains such as PPR and B2542 require a more "simple" determinant comprising CRD1 only for infection. These differences in receptor recognition manifest as variations in sensitivity to receptor antagonists. In this study, we ask whether the nature of the virus-receptor interaction evolves in vivo.&lt;p&gt;&lt;/p&gt; &lt;b&gt;RESULTS:&lt;/b&gt; Following infection with a homogeneous viral population derived from a pathogenic molecular clone, a quasispecies emerged comprising variants with distinct sensitivities to neutralising antibody and displaying evidence of conversion from a "complex" to a "simple" interaction with CD134. Escape from neutralising antibody was mediated primarily by length and sequence polymorphisms in the V5 region of Env, and these alterations in V5 modulated the virus-receptor interaction as indicated by altered sensitivities to antagonism by both anti-CD134 antibody and soluble CD134.&lt;p&gt;&lt;/p&gt; &lt;b&gt;CONCLUSIONS:&lt;/b&gt; The FIV-receptor interaction evolves under the selective pressure of the host humoral immune response, and the V5 loop contributes to the virus-receptor interaction. Our data are consistent with a model whereby viruses with distinct biological properties are present in early versus late infection and with a shift from a "complex" to a "simple" interaction with CD134 with time post-infection.&lt;p&gt;&lt;/p&gt

Opinion: Cloud-phase climate feedback and the importance of ice-nucleating particles

Shallow clouds covering vast areas of the world's middle- and high-latitude oceans play a key role in dampening the global temperature rise associated with CO2. These clouds, which contain both ice and supercooled water, respond to a warming world by transitioning to a state with more liquid water and a greater albedo, resulting in a negative “cloud-phase” climate feedback component. Here we argue that the magnitude of the negative cloud-phase feedback component depends on the amount and nature of the small fraction of aerosol particles that can nucleate ice crystals. We propose that a concerted research effort is required to reduce substantial uncertainties related to the poorly understood sources, concentration, seasonal cycles and nature of these ice-nucleating particles (INPs) and their rudimentary treatment in climate models. The topic is important because many climate models may have overestimated the magnitude of the cloud-phase feedback, and those with better representation of shallow oceanic clouds predict a substantially larger climate warming. We make the case that understanding the present-day INP population in shallow clouds in the cold sector of cyclone systems is particularly critical for defining present-day cloud phase and therefore how the clouds respond to warming. We also need to develop a predictive capability for future INP emissions and sinks in a warmer world with less ice and snow and potentially stronger INP sources

Resolving the size of ice-nucleating particles with a balloon deployable aerosol sampler: the SHARK

Ice-nucleating particles (INPs) affect cloud development, lifetime, and radiative properties, hence it is important to know the abundance of INPs throughout the atmosphere. A critical factor in determining the lifetime and transport of INPs is their size; however very little size-resolved atmospheric INP concentration information exists. Here we present the development and application of a radio-controlled payload capable of collecting size-resolved aerosol from a tethered balloon for the primary purpose of offline INP analysis. This payload, known as the SHARK (Selective Height Aerosol Research Kit), consists of two complementary cascade impactors for aerosol size-segregation from 0.25 to 10 µm, with an after-filter and top stage to collect particles below and above this range at flow rates of up to 100 L min−1. The SHARK also contains an optical particle counter to quantify aerosol size distribution between 0.38 and 10 µm, and a radiosonde for the measurement of temperature, pressure, GPS altitude, and relative humidity. This is all housed within a weatherproof box, can be run from batteries for up to 11 h, and has a total weight of 9 kg. The radio control and live data link with the radiosonde allow the user to start and stop sampling depending on meteorological conditions and height, which can, for example, allow the user to avoid sampling in very humid or cloudy air, even when the SHARK is out of sight. While the collected aerosol could, in principle, be studied with an array of analytical techniques, this study demonstrates that the collected aerosol can be analysed with an offline droplet freezing instrument to determine size-resolved INP concentrations, activated fractions, and active site densities, producing similar results to those obtained using a standard PM10 aerosol sampler when summed over the appropriate size range. Test data, where the SHARK was sampling near ground level or suspended from a tethered balloon at 20 m altitude, are presented from four contrasting locations having very different size-resolved INP spectra: Hyytiälä (southern Finland), Leeds (northern England), Longyearbyen (Svalbard), and Cardington (southern England)