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

Kinetic Study of Ni and NiO Reactions Pertinent to the Earth’s Upper Atmosphere

Nickel atoms are injected into the Earth’s mesosphere by meteoric ablation, producing a Ni layer between 70 and 105 km in altitude. The subsequent reactions of Ni and NiO with atmospherically relevant species were studied using the time-resolved pulsed laser photolysis-laser-induced fluorescence technique, combined with electronic structure calculations and RRKM theory where appropriate. Results for bimolecular reactions (in cm3 molecule–1 s–1): k(Ni + O3, 293 K) = (6.5 ± 0.7) × 10–10; k(NiO + O3 → Ni + 2O2, 293 K) = (1.4 ± 0.5) × 10–10; k(NiO + O3 → NiO2 + O2, 293 K) = (2.5 ± 0.7) × 10–10; k(NiO + CO, 190–377 K) = (3.2 ± 0.6) × 10–11 (T/200)−0.19±0.05. For termolecular reactions (in cm6 molecule–2 s–1, uncertainty ± σ over the stated temperature range): log10(krec,0(Ni + O2 + N2, 190–455 K)) = −37.592 + 7.168log10(T) - 1.5650(log10(T))2, σ = 11%; log10(krec,0(NiO + O2 + N2, 293–380 K)) = −41.0913 + 10.1064log10(T) – 2.2610(log10(T))2, σ = 22%; and log10(krec,0(NiO + CO2 + N2, 191–375 K)) = −41.4265 + 10.9640log10(T) – 2.5287(log10(T))2, σ = 15%. The faster recombination reaction NiO + H2O + N2, which is clearly in the falloff region over the experimental pressure range (3–10 Torr), is best described by log10(krec,0/cm6 molecule–2 s–1) = −29.7651 + 5.2064log10(T) – 1.7118(log10(T))2, krec,∞ = 6.0 × 10–10 exp(−171/T) cm3 molecule–1 s–1, broadening factor Fc = 0.84, σ = 16%. The implications of these results in the atmosphere are then discussed

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

The fate of meteoric metals in ice particles: Effects of sublimation and energetic particle bombardment

The uptake and potential reactivity of metal atoms on water ice can be an important process in planetary atmospheres and on icy bodies in the interplanetary and interstellar medium. For instance, metal atom uptake affects the gas-phase chemistry of the Earth’s mesosphere, and has been proposed to influence the agglomeration of matter into planets in protoplanetary disks. In this study the fate of Mg and K atoms, incorporated into water-ice films prepared under ultra-high vacuum conditions at temperatures of 110–140 K, was investigated. Temperature-programmed desorption experiments reveal that Mg- and K-containing species do not co-desorb when the ice sublimates, demonstrating that uptake on ice particles causes irreversible removal of the metals from the gas phase. This implies that uptake on ice particles in terrestrial polar mesospheric clouds accelerates the formation of large meteoric smoke particles (≥1 nm radius above 80 km) following sublimation of the ice. Energetic sputtering of metal-dosed ice layers by 500 eV Ar+ and Kr+ ions shows that whereas K reacts on (or within) the ice surface to form KOH, adsorbed Mg atoms are chemically inert. These experimental results are consistent with electronic structure calculations of the metals bound to an ice surface, where theoretical adsorption energies on ice are calculated to be −68 kJ mol−1 for K, −91 kJ mol−1 for Mg, and −306 kJ mol−1 for Fe. K can also insert into a surface H2O to produce KOH and a dangling H atom, in a reaction that is slightly exothermic

Chemical modelling of dust–gas chemistry within AGB outflows – I. Effect on the gas-phase chemistry

Chemical modelling of asymptotic giant branch (AGB) outflows is typically focused on either non-thermodynamic equilibrium chemistry in the inner region or photon-driven chemistry in the outer region. We include, for the first time, a comprehensive dust–gas chemistry in our AGB outflow chemical kinetics model, including both dust–gas interactions and grain-surface chemistry. The dust is assumed to have formed in the inner region, and follows an interstellar-like dust-size distribution. Using radiative transfer modelling, we obtain dust temperature profiles for different dust types in an O-rich and a C-rich outflow. We calculate a grid of models, sampling different outflow densities, drift velocities between the dust and gas, and dust types. Dust–gas chemistry can significantly affect the gas-phase composition, depleting parent and daughter species and increasing the abundance of certain daughter species via grain-surface formation followed by desorption/sputtering. Its influence depends on four factors: outflow density, dust temperature, initial composition, and drift velocity. The largest effects are for higher density outflows with cold dust and O-rich parent species, as these species generally have a larger binding energy. At drift velocities larger than ∼10 km s−1, ice mantles undergo sputtering; however, they are not fully destroyed. Models with dust–gas chemistry can better reproduce the observed depletion of species in O-rich outflows. When including colder dust in the C-rich outflows and adjusting the binding energy of CS, the depletion in C-rich outflows is also better reproduced. To best interpret high-resolution molecular line observations from AGB outflows, dust–gas interactions are needed in chemical kinetics models

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

Meteoric Metal Chemistry in the Martian Atmosphere

Recent measurements by the Imaging Ultraviolet Spectrograph (IUVS) instrument on NASA's Mars Atmosphere and Volatile EvolutioN mission show that a persistent layer of Mg⁺ ions occurs around 90 km in the Martian atmosphere but that neutral Mg atoms are not detectable. These observations can be satisfactorily modeled with a global meteoric ablation rate of 0.06 t sol⁻¹, out of a cosmic dust input of 2.7 ± 1.6 t sol⁻¹. The absence of detectable Mg at 90 km requires that at least 50% of the ablating Mg atoms ionize through hyperthermal collisions with CO₂ molecules. Dissociative recombination of MgO⁺.(CO₂)n cluster ions with electrons to produce MgCO₃ directly, rather than MgO, also avoids a buildup of Mg to detectable levels. The meteoric injection rate of Mg, Fe, and other metals—constrained by the IUVS measurements—enables the production rate of metal carbonate molecules (principally MgCO₃ and FeCO₃) to be determined. These molecules have very large electric dipole moments (11.6 and 9.2 Debye, respectively) and thus form clusters with up to six H₂O molecules at temperatures below 150 K. These clusters should then coagulate efficiently, building up metal carbonate‐rich ice particles which can act as nucleating particles for the formation of CO₂‐ice clouds. Observable mesospheric clouds are predicted to occur between 65 and 80 km at temperatures below 95 K and above 85 km at temperatures about 5 K colder

Susceptibility and Response of Human Blood Monocyte Subsets to Primary Dengue Virus Infection

Human blood monocytes play a central role in dengue infections and form the majority of virus infected cells in the blood. Human blood monocytes are heterogeneous and divided into CD16− and CD16+ subsets. Monocyte subsets play distinct roles during disease, but it is not currently known if monocyte subsets differentially contribute to dengue protection and pathogenesis. Here, we compared the susceptibility and response of the human CD16− and CD16+ blood monocyte subsets to primary dengue virus in vitro. We found that both monocyte subsets were equally susceptible to dengue virus (DENV2 NGC), and capable of supporting the initial production of new infective virus particles. Both monocyte subsets produced anti-viral factors, including IFN-α, CXCL10 and TRAIL. However, CD16+ monocytes were the major producers of inflammatory cytokines and chemokines in response to dengue virus, including IL-1β, TNF-α, IL-6, CCL2, 3 and 4. The susceptibility of both monocyte subsets to infection was increased after IL-4 treatment, but this increase was more profound for the CD16+ monocyte subset, particularly at early time points after virus exposure. These findings reveal the differential role that monocyte subsets might play during dengue disease

Reliability of Transcriptional Cycles and the Yeast Cell-Cycle Oscillator

A recently published transcriptional oscillator associated with the yeast cell cycle provides clues and raises questions about the mechanisms underlying autonomous cyclic processes in cells. Unlike other biological and synthetic oscillatory networks in the literature, this one does not seem to rely on a constitutive signal or positive auto-regulation, but rather to operate through stable transmission of a pulse on a slow positive feedback loop that determines its period. We construct a continuous-time Boolean model of this network, which permits the modeling of noise through small fluctuations in the timing of events, and show that it can sustain stable oscillations. Analysis of simpler network models shows how a few building blocks can be arranged to provide stability against fluctuations. Our findings suggest that the transcriptional oscillator in yeast belongs to a new class of biological oscillators

Pharmacological characterisation of murine α4β1δ GABAA receptors expressed in Xenopus oocytes

BACKGROUND: GABAA receptor subunit composition has a profound effect on the receptor's physiological and pharmacological properties. The receptor β subunit is widely recognised for its importance in receptor assembly, trafficking and post-translational modifications, but its influence on extrasynaptic GABAA receptor function is less well understood. Here, we examine the pharmacological properties of a potentially native extrasynaptic GABAA receptor that incorporates the β1 subunit, specifically composed of α4β1δ and α4β1 subunits. RESULTS: GABA activated concentration-dependent responses at α4β1δ and α4β1 receptors with EC50 values in the nanomolar to micromolar range, respectively. The divalent cations Zn(2+) and Cu(2+), and the β1-selective inhibitor salicylidine salicylhydrazide (SCS), inhibited GABA-activated currents at α4β1δ receptors. Surprisingly the α4β1 receptor demonstrated biphasic sensitivity to Zn(2+) inhibition that may reflect variable subunit stoichiometries with differing sensitivity to Zn(2+). The neurosteroid tetrahydro-deoxycorticosterone (THDOC) significantly increased GABA-initiated responses in concentrations above 30 nM for α4β1δ receptors. CONCLUSIONS: With this study we report the first pharmacological characterisation of various GABAA receptor ligands acting at murine α4β1δ GABAA receptors, thereby improving our understanding of the molecular pharmacology of this receptor isoform. This study highlights some notable differences in the pharmacology of murine and human α4β1δ receptors. We consider the likelihood that the α4β1δ receptor may play a role as an extrasynaptic GABAA receptor in the nervous system