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 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 modelling of the CaOH + O2 kinetics is used to extrapolate to mesospheric temperatures and pressures. The results suggest that formation of O2CaOH slows down 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

On the mechanism of iodine oxide particle formation

The formation of atmospherically relevant iodine oxides IxO y (x = 1,...,3, y = 1,...,7) has been studied experimentally using time-of-flight mass spectrometry combined with a soft ionisation source, complemented with ab initio electronic structure calculations of ionisation potentials and bond energies at a high level of theory presented in detail in the accompanying paper (Galvez et al., 2013). For the first time, direct experimental evidence of the I2Oy (y = 1,...,5) molecules in the gas phase has been obtained. These chemical species are observed alongside their precursors (IO and OIO) in experiments where large amounts of aerosol are also generated. The measured relative concentrations of the I xOy molecules and their dependence on ozone concentration have been investigated by using chemical modelling and rate theory calculations. It is concluded that I2O4 is the most plausible candidate to initiate nucleation, while the contribution of I2O5 in the initial steps is likely to be marginal. The absence of large I 3Oy (y = 3,...,6) peaks in the mass spectra and the high stability of the I2O4-I2O4 dimer indicate that dimerisation of I2O4 is the key step in iodine oxide particle nucleation

Iodine chemistry in the troposphere and its effect on ozone

Despite the potential influence of iodine chemistry on the oxidizing capacity of the troposphere, reactive iodine distributions and their impact on tropospheric ozone remain almost unexplored aspects of the global atmosphere. Here we present a comprehensive global modelling experiment aimed at estimating lower and upper limits of the inorganic iodine burden and its impact on tropospheric ozone. Two sets of simulations without and with the photolysis of IxOy oxides (i.e. I2O2, I2O3 and I2O4) were conducted to define the range of inorganic iodine loading, partitioning and impact in the troposphere. Our results show that the most abundant daytime iodine species throughout the middle to upper troposphere is atomic iodine, with an annual average tropical abundance of (0.15-0.55) pptv. We propose the existence of a "tropical ring of atomic iodine" that peaks in the tropical upper troposphere (∼11-14 km) at the equator and extends to the sub-tropics (30°N-30°S). Annual average daytime I = IO ratios larger than 3 are modelled within the tropics, reaching ratios up to ∼20 during vigorous uplift events within strong convective regions. We calculate that the integrated contribution of catalytic iodine reactions to the total rate of tropospheric ozone loss (IOx Loss) is 2-5 times larger than the combined bromine and chlorine cycles. When IxOy photolysis is included, IOx Loss represents an upper limit of approximately 27, 14 and 27% of the tropical annual ozone loss for the marine boundary layer (MBL), free troposphere (FT) and upper troposphere (UT), respectively, while the lower limit throughout the tropical troposphere is ∼9 %. Our results indicate that iodine is the second strongest ozone-depleting family throughout the global marine UT and in the tropical MBL. We suggest that (i) iodine sources and its chemistry need to be included in global tropospheric chemistry models, (ii) experimental programs designed to quantify the iodine budget in the troposphere should include a strategy for the measurement of atomic I, and (iii) laboratory programs are needed to characterize the photochemistry of higher iodine oxides to determine their atmospheric fate since they can potentially dominate halogen-catalysed ozone destruction in the troposphere

A novel instrument to measure differential ablation of meteorite samples and proxies: The Meteoric Ablation Simulator (MASI)

On entering the Earth’s atmosphere, micrometeoroids partially or completely ablate, leaving behind layers of metallic atoms and ions. The relative concentration of the various metal layers is not well explained by current models of ablation. Furthermore, estimates of the total flux of cosmic dust and meteoroids entering the Earth’s atmosphere vary over two orders of magnitude. To better constrain these estimates and to better model the metal layers in the mesosphere, an experimental meteoric Ablation Simulator (MASI) has been developed. Interplanetary Dust Particle (IDP) analogs are subjected to temperature profiles simulating realistic entry heating, to ascertain the differential ablation of relevant metal species. MASI is the first ablation experiment capable of simulating detailed mass, velocity, and entry angle-specific temperature profiles whilst simultaneously tracking the resulting gas-phase ablation products in a time resolved manner. This enables the determination of elemental atmospheric entry yields which consider the mass and size distribution of IDPs. The instrument has also enabled the first direct measurements of differential ablation in a laboratory setting

A gas-to-particle conversion mechanism helps to explain atmospheric particle formation through clustering of iodine oxides

Emitted from the oceans, iodine-bearing molecules are ubiquitous in the atmosphere and a source of new atmospheric aerosol particles of potentially global significance. However, its inclusion in atmospheric models is hindered by a lack of understanding of the first steps of the photochemical gas-to-particle conversion mechanism. Our laboratory results show that under a high humidity and low HOx regime, the recently proposed nucleating molecule (iodic acid, HOIO2) does not form rapidly enough, and gas-to-particle conversion proceeds by clustering of iodine oxides (IxOy), albeit at slower rates than under dryer conditions. Moreover, we show experimentally that gas-phase HOIO2 is not necessary for the formation of HOIO2-containing particles. These insights help to explain new particle formation in the relatively dry polar regions and, more generally, provide for the first time a thermochemically feasible molecular mechanism from ocean iodine emissions to atmospheric particles that is currently missing in model calculations of aerosol radiative forcing

The first steps of iodine gas-to-particle conversion as seen in the lab: constraints on the role of iodine oxides and oxyacids

&amp;lt;p&amp;gt;The photooxidation of gas phase iodine-bearing molecules emitted by marine biota leads to intense particle nucleation events in the coastal and polar marine boundary layer&amp;lt;sup&amp;gt;1-3&amp;lt;/sup&amp;gt;. The ubiquity of iodine in the marine atmospheric environment&amp;lt;sup&amp;gt;4-7&amp;lt;/sup&amp;gt; has suggested that this may be a previously unrecognized global source of new aerosol particles&amp;lt;sup&amp;gt;8&amp;lt;/sup&amp;gt;. Atmospheric modeling is required in order to evaluate the importance of this process, but a substantial lack of understanding of the gas-to-particle conversion mechanism is hindering this effort, especially regarding the gas phase chemistry of the nucleating molecules (iodine oxides&amp;lt;sup&amp;gt;9&amp;lt;/sup&amp;gt;&amp;lt;sup&amp;gt;,&amp;lt;/sup&amp;gt;&amp;lt;sup&amp;gt;10&amp;lt;/sup&amp;gt; and/or oxyacids&amp;lt;sup&amp;gt;7&amp;lt;/sup&amp;gt;) and the formation kinetics of molecular clusters. To address this problem, we have conducted new flow tube laboratory experiments where pulsed laser photolysis or continuous broad-band photolysis of I&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;/O&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; mixtures&amp;amp;#160; in air are used to generate iodine radicals in the presence of atmospherically representative mixing ratios of water vapor. The molecular reactants and the resulting molecular products are detected by time-resolved VUV laser photo-ionization time-of-flight mass spectrometry. High-level quantum chemistry and master equation calculations and gas kinetics modelling are used to analyse the experimental data. In this presentation we discuss our results and their implications for the interpretation of field meassurements and for the implementatiion of an iodine oxide particle formation mechanism in atmospheric models.&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;References:&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;1. Hoffmann, T., O'Dowd, C. D. &amp;amp; Seinfeld, J. H. Iodine oxide homogeneous nucleation: An explanation for coastal new particle production. Geophys. Res. Lett. &amp;lt;strong&amp;gt;28&amp;lt;/strong&amp;gt;, 1949-1952 (2001).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;2. McFiggans, G. et al. Direct evidence for coastal iodine particles from Laminaria macroalgae - linkage to emissions of molecular iodine. Atmos. Chem. Phys. &amp;lt;strong&amp;gt;4&amp;lt;/strong&amp;gt;, 701-713 (2004).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;3. O'Dowd, C. D. et al. Marine aerosol formation from biogenic iodine emissions. Nature &amp;lt;strong&amp;gt;417&amp;lt;/strong&amp;gt;, 632-636 (2002).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;4. Prados-Roman, C. et al. Iodine oxide in the global marine boundary layer. Atmos. Chem. Phys. &amp;lt;strong&amp;gt;15&amp;lt;/strong&amp;gt;, 583-593, doi:10.5194/acp-15-583-2015 (2015).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;5. Sch&amp;amp;#246;nhardt, A. et al. Simultaneous satellite observations of IO and BrO over Antarctica. Atmos. Chem. Phys. &amp;lt;strong&amp;gt;12&amp;lt;/strong&amp;gt;, 6565-6580, doi:10.5194/acp-12-6565-2012 (2012).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;6. Mahajan, A. S. et al. Concurrent observations of atomic iodine, molecular iodine and ultrafine particles in a coastal environment. Atmos. Chem. Phys. &amp;lt;strong&amp;gt;10&amp;lt;/strong&amp;gt;, 27227-27253 (2010).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;7. Sipil&amp;amp;#228;, M. et al. Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3. Nature &amp;lt;strong&amp;gt;537&amp;lt;/strong&amp;gt;, 532-534, doi:10.1038/nature19314 (2016).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;8. Saiz-Lopez, A. et al. Atmospheric Chemistry of Iodine. Chem. Rev. &amp;lt;strong&amp;gt;112&amp;lt;/strong&amp;gt;, 1773&amp;amp;#8211;1804, doi:DOI: 10.1021/cr200029u (2012).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;9. G&amp;amp;#243;mez Mart&amp;amp;#237;n, J. C. et al. On the mechanism of iodine oxide particle formation. Phys. Chem. Chem. Phys. &amp;lt;strong&amp;gt;15&amp;lt;/strong&amp;gt;, 15612-15622, doi:10.1039/c3cp51217g (2013).&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;10. Saunders, R. W., Mahajan, A. S., G&amp;amp;#243;mez Mart&amp;amp;#237;n, J. C., Kumar, R. &amp;amp; Plane, J. M. C. Studies of the Formation and Growth of Aerosol from Molecular Iodine Precursor. Z. Phys. Chem. &amp;lt;strong&amp;gt;224&amp;lt;/strong&amp;gt;, 1095-1117 (2010).&amp;lt;/p&amp;gt; </jats:p

Enhanced production of oxidised mercury over the tropical Pacific Ocean: A key missing oxidation pathway

Mercury is a contaminant of global concern. It is transported in the atmosphere primarily as gaseous elemental mercury, but its reactivity and deposition to the surface environment, through which it enters the aquatic food chain, is greatly enhanced following oxidation. Measurements and modelling studies of oxidised mercury in the polar to sub-tropical marine boundary layer (MBL) have suggested that photolytically produced bromine atoms are the primary oxidant of mercury. We report year-round measurements of elemental and oxidised mercury, along with ozone, halogen oxides (IO and BrO) and nitrogen oxides (NO2), in the MBL over the Galápagos Islands in the equatorial Pacific. Elemental mercury concentration remained low throughout the year, while higher than expected levels of oxidised mercury occurred around midday. Our results show that the production of oxidised mercury in the tropical MBL cannot be accounted for by bromine oxidation only, or by the inclusion of ozone and hydroxyl. As a two-step oxidation mechanism, where the HgBr intermediate is further oxidised to Hg(II), depends critically on the stability of HgBr, an additional oxidant is needed to react with HgBr to explain more than 50% of the observed oxidised mercury. Based on best available thermodynamic data, we show that atomic iodine, NO2, or HO2 could all play the potential role of the missing oxidant, though their relative importance cannot be determined explicitly at this time due to the uncertainties associated with mercury oxidation kinetics. We conclude that the key pathway that significantly enhances atmospheric mercury oxidation and deposition to the tropical oceans is missing from the current understanding of atmospheric mercury oxidation

Radar Detectability Studies of Slow and Small Zodiacal Dust Cloud Particles. III. The Role of Sodium and the Head Echo Size on the Probability of Detection

We present a path forward on a long-standing issue concerning the flux of small and slow meteoroids, which are believed to be the dominant portion of the incoming meteoric mass flux into the Earth's atmosphere. Such a flux, which is predicted by dynamical dust models of the Zodiacal Cloud, is not evident in ground-based radar observations. For decades this was attributed to the fact that the radars used for meteor observations lack the sensitivity to detect this population, due to the small amount of ionization produced by slow-velocity meteors. Such a hypothesis has been challenged by the introduction of meteor head echo (HE) observations with High Power and Large Aperture radars, in particular the Arecibo 430 MHz radar. Janches et al. developed a probabilistic approach to estimate the detectability of meteors by these radars and initially showed that, with the current knowledge of ablation and ionization, such particles should dominate the detected rates by one to two orders of magnitude compared to the actual observations. In this paper, we include results in our model from recently published laboratory measurements, which showed that (1) the ablation of Na is less intense covering a wider altitude range; and (2) the ionization probability, βip for Na atoms in the air is up to two orders of magnitude smaller for low speeds than originally believed. By applying these results and using a somewhat smaller size of the HE radar target we offer a solution that reconciles these observations with model predictions

Determination of the atmospheric lifetime and global warming potential of sulfur hexafluoride using a three-dimensional model

We have used the Whole Atmosphere Community Climate Model (WACCM), with an updated treatment of loss processes, to determine the atmospheric lifetime of sulfur hexafluoride (SF6). The model includes the following SF6 removal processes: photolysis, electron attachment and reaction with mesospheric metal atoms. The Sodankylä Ion Chemistry (SIC) model is incorporated into the standard version of WACCM to produce a new version with a detailed D region ion chemistry with cluster ions and negative ions. This is used to determine a latitude- and altitude-dependent scaling factor for the electron density in the standard WACCM in order to carry out multi-year SF6 simulations. The model gives a mean SF6 lifetime over an 11-year solar cycle (τ) of 1278 years (with a range from 1120 to 1475 years), which is much shorter than the currently widely used value of 3200 years, due to the larger contribution (97.4 %) of the modelled electron density to the total atmospheric loss. The loss of SF6 by reaction with mesospheric metal atoms (Na and K) is far too slow to affect the lifetime. We investigate how this shorter atmospheric lifetime impacts the use of SF6 to derive stratospheric age of air. The age of air derived from this shorter lifetime SF6 tracer is longer by 9 % in polar latitudes at 20 km compared to a passive SF6 tracer. We also present laboratory measurements of the infrared spectrum of SF6 and find good agreement with previous studies. We calculate the resulting radiative forcings and efficiencies to be, on average, very similar to those reported previously. Our values for the 20-, 100- and 500-year global warming potentials are 18 000, 23 800 and 31 300, respectively

Disruption of ER-mitochondria tethering and signalling in C9orf72-associated amyotrophic lateral sclerosis and frontotemporal dementia

Hexanucleotide repeat expansions in C9orf72 are the most common cause of familial amyotrophic lateral sclerosis (ALS) and frontotemporal dementia (FTD). The mechanisms by which the expansions cause disease are not properly understood but a favoured route involves its translation into dipeptide repeat (DPR) polypeptides, some of which are neurotoxic. However, the precise targets for mutant C9orf72 and DPR toxicity are not fully clear, and damage to several neuronal functions has been described. Many of these functions are regulated by signalling between the endoplasmic reticulum (ER) and mitochondria. ER-mitochondria signalling requires close physical contacts between the two organelles that are mediated by the VAPB-PTPIP51 ‘tethering’ proteins. Here, we show that ER-mitochondria signalling and the VAPB-PTPIP51 tethers are disrupted in neurons derived from induced pluripotent stem (iPS) cells from patients carrying ALS/FTD pathogenic C9orf72 expansions and in affected neurons in mutant C9orf72 transgenic mice. In these mice, disruption of the VAPB-PTPIP51 tethers occurs prior to disease onset suggesting that it contributes to the pathogenic process. We also show that neurotoxic DPRs disrupt the VAPB-PTPIP51 interaction and ER-mitochondria contacts and that this may involve activation of glycogen synthase kinases-3β (GSK3β), a known negative regulator of VAPB-PTPIP51 binding. Finally, we show that these DPRs disrupt delivery of Ca2+ from ER stores to mitochondria, which is a primary function of the VAPB-PTPIP51 tethers. This delivery regulates a number of key neuronal functions that are damaged in ALS/FTD including bioenergetics, autophagy and synaptic function. Our findings reveal a new molecular target for mutant C9orf72-mediated toxicity