Juan Carlos Gómez Martín

Atmospheric Chemistry of Iodine

Atmospheric Chemistry of Iodine Alfonso Saiz-Lopez,* John M. C. Plane,* Alex R. Baker, Lucy J. Carpenter, Roland von Glasow, Juan C. G omez Martín, Gordon McFiggans, and Russell W. Saunders Laboratory for Atmospheric and Climate Science (CIAC), CSIC, Toledo, Spain School of Chemistry, University of Leeds, Leeds, LS2 9JT, United Kingdom School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ, United Kingdom Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom School of Earth, Atmospheric & Environmental Sciences, University of Manchester, Manchester, M13 9PL, United Kingdom

Kinetic studies of atmospherically relevant silicon chemistry

Atomic silicon is generated by meteoric ablation in the Earths upper atmosphere (70-110 km). The reactions of Si(3P(J)) atoms with several atmospherically relevant species were studied by the pulsed laser photolysis of a Si atom precursor (typically PheSiH3), followed by time-resolved laser induced fluorescence at 251.43 nm (Si(3p2 3P0 --> 4s 3P1)). This yielded: k(Si + O2, 190-500 K) = 9.49 x 10(-11) + 1.80 x 10(-10) x exp(-T/115 K) cm3 molecule(-1) s(-1) (uncertainty < or = +/- 15%), in good accord with recent high-level theoretical calculations but in marked disagreement with previous experimental work; k(Si + O3, 190-293 K) = (4.0 +/- 0.5) x 10(-10) cm3 molecule(-1) s(-1); k(Si + CO2, 293 K) < or = 1.2 x 10(-14) cm3 molecule(-1) s(-1); and k(Si + H2O, 293 K) < or = 2.6 x 10(-13) cm3 molecule(-1) s(-1). These results are explained using a combination of quantum chemistry calculations and long-range capture theory. The quenching rate coefficients k(Si(1D2) + N2, 293 K) = (4.0 +/- 0.7) x 10(-11) cm3 molecule(-1) s(-1) and k(Si(1D2) + H2O, 293 K) = (2.3 +/- 0.3) x 10(-10) cm3 molecule(-1) s(-1) were also determined.

Under what conditions does (SiO)N nucleation occur? A bottom-up kinetic modelling evaluation

Silicon monoxide (SiO) is a structurally complex compound exhibiting differentiated oxide-rich and silicon-rich nano-phases at length scales covering nanoclusters to the bulk. Although nano-sized and nano-segregated SiO has great technological potential (e.g. nano-silicon for optical applications) and is of enormous astronomical interest (e.g. formation of silicate cosmic dust) an accurate general description of SiO nucleation is lacking. Avoiding the deficiencies of a bulk-averaged approach typified by classical nucleation theory (CNT) we employ a bottom-up kinetic model which fully takes into account the atomistic details involved in segregation. Specifically, we derive a new low energy benchmark set of segregated (SiO)N cluster ground state candidates for N ≤ 20 and use the accurately calculated properties of these isomers to calculate SiO nucleation rates. We thus provide a state-of-the art evaluation of the range of pressure and temperature conditions for which formation of SiO will or will not proceed. Our results, which match with available experiment, reveal significant deficiencies with CNT approaches. We employ our model to shed light on controversial issue of circumstellar silicate dust formation showing that, at variance with the predictions from CNT-based calculations, pure SiO nucleation under such conditions is not viable.

Laboratory measurements of heterogeneous CO2 ice nucleation on nanoparticles under conditions relevant to the Martian mesosphere

Clouds of CO2 ice particles have been observed in the Martian mesosphere. These clouds are believed to be formed through heterogeneous nucleation of CO2 on nanometer-sized meteoric smoke particles (MSPs) or upward propagated Martian dust particles (MDPs). Large uncertainties still exist in parameterizing the microphysical formation process of these clouds as key physicochemical parameters are not well known. We present measurements on the nucleation and growth of CO2 ice on sub-4 nm radius iron oxide and silica particles representing MSPs at conditions close to the mesosphere of Mars. For both particle materials we determine the desorption energy of CO2 to be ΔFdes = (18.5 ± 0.2) kJ mol−1 corresponding to ΔFdes = (0.192 ± 0.002) eV and obtain m = 0.78 ± 0.02 for the contact parameter that governs heterogeneous nucleation by analyzing the measurements using classical heterogeneous nucleation theory. We did not find any temperature dependence for the contact parameter in the temperature range examined (64 K to 73 K). By applying these values for MSPs in the Martian mesosphere, we derive characteristic temperatures for the onset of CO2 ice nucleation, which are 8–18 K below the CO2 frost point temperature, depending on particle size. This is in line with the occurrence of highly supersaturated conditions extending to 20 K below frost point temperature without the observation of clouds. Moreover, the sticking coefficient of CO2 on solid CO2 was determined to be near unity. We further argue that the same parameters can be applied to CO2 nucleation on upward propagated MDPs.

Mesospheric removal of very long-lived greenhouse gases SF6 and CFC-115 by metal reactions, Lyman-α photolysis, and electron attachment.

The fluorinated gases SF6 and C2F5Cl (CFC-115) are chemically inert with atmospheric lifetimes of many centuries which, combined with their strong absorption of IR radiation, results in unusually high global warming potentials. Very long lifetimes imply that mesospheric sinks could make important contributions to their atmospheric removal. In order to investigate this, the photolysis cross sections at the prominent solar Lyman-α emission line (121.6 nm), and the reaction kinetics of SF6 and CFC-115 with the neutral meteoric metal atoms Na, K, Mg, and Fe over large temperature ranges, were measured experimentally. The Na and K reactions exhibit significant non-Arrhenius behavior; quantum chemistry calculations of the potential energy surfaces for the SF6 reactions indicate that the Na and K reactions with SF6 are probably activated by vibrational excitation of the F-SF5 (v3) stretching mode. A limited set of kinetic measurements on Na + SF5CF3 are also presented. The atmospheric removal of these long-lived gases by a variety of processes is then evaluated. For SF6, the removal processes in decreasing order of importance are electron attachment, VUV photolysis, and reaction with K, Na, and H. For CFC-115, the removal processes in decreasing order of importance are reaction with O((1)D), VUV photolysis, and reaction with Na, K, and H.

A study of the dissociative recombination of CaO + with electrons: Implications for Ca chemistry in the upper atmosphere

Abstract The dissociative recombination of CaO+ ions with electrons has been studied in a flowing afterglow reactor. CaO+ was generated by the pulsed laser ablation of a Ca target, followed by entrainment in an Ar+ ion/electron plasma. A kinetic model describing the gas‐phase chemistry and diffusion to the reactor walls was fitted to the experimental data, yielding a rate coefficient of (3.0 ± 1.0) × 10−7 cm3 molecule−1 s−1 at 295 K. This result has two atmospheric implications. First, the surprising observation that the Ca+/Fe+ ratio is ~8 times larger than Ca/Fe between 90 and 100 km in the atmosphere can now be explained quantitatively by the known ion‐molecule chemistry of these two metals. Second, the rate of neutralization of Ca+ ions in a descending sporadic E layer is fast enough to explain the often explosive growth of sporadic neutral Ca layers.

Reaction Kinetics of CaOH with H and O2 and O2CaOH with O: Implications for the Atmospheric Chemistry of Meteoric Calcium

The ablation of cosmic dust particles entering the Earth’s upper atmosphere produces a layer of Ca atoms around 90 km. Here, we present a set of kinetic experiments designed to understand the nature of the Ca molecular reservoirs on the underside of the layer. CaOH was produced by laser ablation of a Ca target in the fast flow tube and detected by non-resonant laser-induced fluorescence, probing the D(2Σ+) ← X(2Σ1) transition at 346.9 nm. The following rate constants were measured (at 298 K): k(CaOH + H → Ca + H2O) = (1.04 ± 0.24) × 10–10 cm3 molecule–1 s–1, k(CaOH + O → CaO + OH) < 1 × 10–11 cm3 molecule–1 s–1, and k(CaOH + O2 → O2CaOH, 1 Torr) = (5.9 ± 1.8) × 10–11 cm3 molecule–1 s–1 (uncertainty at the 2σ level of confidence). The recycling of CaOH from reaction between O2CaOH and O proceeds with an effective rate constant of keff(O2CaOH + O → CaOH + products, 298 K) = 2.8–1.2+2.0 × 10–10 cm3 molecule–1 s–1. Master equation modeling of the CaOH + O2 kinetics is used to extrapolate to mesospheric temperatures and pressures. The results suggest that the formation of O2CaOH slows the conversion of CaOH to atomic Ca via reaction with atomic H, and O2CaOH is likely to be a long-lived reservoir species on the underside of the Ca layer and a building block of meteoric smoke particles.

A new model of meteoric calcium in the mesosphere and lower thermosphere

Meteoric ablation produces layers of metal atoms in the mesosphere and lower thermosphere (MLT). It has been known for more than 30 years that the Ca atom layer is depleted by over 2 orders of magnitude compared with Na, despite these elements having nearly the same elemental abundance in chondritic meteorites. In contrast, the Ca ion abundance is depleted by less than a factor of 10. To explain these observations, a large database of neutral and ion– molecule reaction kinetics of Ca species, measured over the past decade, was incorporated into the Whole Atmosphere Community Climate Model (WACCM). A new meteoric input function for Ca and Na, derived using a chemical ablation model that has been tested experimentally with a Meteoric Ablation Simulator, shows that Ca ablates almost 1 order of magnitude less efficiently than Na. WACCM-Ca simulates the seasonal Ca layer satisfactorily when compared with lidar observations, but tends to overestimate Ca measurements made by rocket mass spectrometry and lidar. A key finding is that CaOH and CaCO3 are very stable reservoir species because they are involved in essentially closed reaction cycles with O2 and O. This has been demonstrated experimentally for CaOH, and in this study for CaCO3 using electronic structure and statistical rate theory. Most of the neutral Ca is therefore locked in these reservoirs, enabling rapid loss through polymerization into meteoric smoke particles, and this explains the extreme depletion of Ca.

Impacts of meteoric sulfur in the Earth's atmosphere

A meteoric sulfur input function and a sulfur ion chemistry scheme have been incorporated into a chemistry-climate model, in order to study the speciation of sulfur between the stratosphere and the thermosphere (~20 – 120 km), and the impact of the sulfur input from ablation of cosmic dust. The simulations have been compared to rocket observations of SO+ between 85 and 110 km, MIPAS observations of SO2 between 20 and 45 km, and stratospheric balloon-borne measurements of H2SO4 vapor and sulfate aerosol. These observations constrain the present day global flux of meteoric sulfur to ≤ 1.0 t S d-1, i.e. 2 orders of magnitude smaller than the flux of S into the stratosphere from OCS photo-oxidation and explosive volcanic SO2 injection. However, the meteoric sulfur flux is strongly focused into the polar vortices by the meridional circulation, and therefore the contribution of SO2 of meteoric origin to the polar upper stratosphere during winter is substantial (~ 30% at 50 km for a flux of 1.0 t S d-1). The Antarctic spring sulfate aerosol layer is found to be very sensitive to a moderate increase of the input rate of meteoric sulfur, showing a factor of 2 enhancement in total sulfate aerosol number density at 30 km for an input of 3.0 t S d-1. The input rate estimate of 1.0 t S d-1 suggests an enrichment of sodium relative to sulfur of 2.7 ± 1.5 and is consistent with a total cosmic dust input rate of 44 t d-1.