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We use the 3-D Whole Atmospheric Community Climate Model to investigate stratospheric ozone depletion due to the launch of small satellites (e.g., CubeSats) with an iodine propulsion system. The model considers the injection of iodine from the satellites into the Earth's thermosphere and suggests a 4-yr timescale for transport of the emissions down to the troposphere. The base case scenario is 40,000 small satellite launches per year into low orbit (100–600 km), which would inject 8 tons I yr−1 above 120 km as I+ ions and increase stratospheric inorganic iodine by ∼0.1 part per trillion (pptv). The model shows that this scenario produces a negligible impact on global stratospheric ozone (∼0.05 DU column depletion). In contrast, a 100-fold increase in the launch rate, and therefore thermospheric iodine injection, is predicted to result in modeled ozone depletion of up to 14 DU (approximately 2%–7%) over the polar regions.

In this Reply, we answer the main argument raised in the Comment about the energy of the NO radical and its influence in the reaction profiles of the reaction of the NO radical with CHClBr, CHICl, CHBrI, CHClBr, and CHClBr by C. J. Nielsen and Y. Tang. The optimized geometry of the NO radical has been obtained using 49 DFT functionals: 26 functionals predict a minimum with D symmetry and 23 with C symmetry. The former functionals have been used to calculate the thermodynamic values of three reactions (X + HNO → XH + NO, X= OH, CH and CCl) and compared with experimental data. Those functionals with smaller errors have been used to recalculate the barriers of the reaction of NO with CHClBr, CHICl, CHBrI, CHClBr, and CHClBr. The results show differences of 10.5 kJ mol when compared to those obtained with the M08HX functional.

Sulfur trioxide is a critical intermediate for the sulfur cycle and the formation of sulfuric acid in the atmosphere. The traditional view is that sulfur trioxide is removed by water vapor in the troposphere. However, the concentration of water vapor decreases significantly with increasing altitude, leading to longer atmospheric lifetimes of sulfur trioxide. Here, we utilize a dual-level strategy that combines transition state theory calculated at the W2X//DF-CCSD(T)-F12b/jun′-cc-pVDZ level, with variational transition state theory with small-curvature tunneling from direct dynamics calculations at the M08-HX/MG3S level. We also report the pressure-dependent rate constants calculated using the system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory. The present findings show that falloff effects in the SO+ HONOreaction are pronounced below 1 bar. The SO+ HONOreaction can be a potential removal reaction for SOin the stratosphere and for HONOin the troposphere, because the reaction can potentially compete well with the SO+ 2HO reaction between 25 and 35 km, as well as the OH + HONOreaction. The present findings also suggest an unexpected new product from the SO+ HONOreaction, which, although very short-lived, would have broad implications for understanding the partitioning of sulfur in the stratosphere and the potential for the SOreaction with organic acids to generate organosulfates without the need for heterogeneous chemistry. © 2022 American Chemical Society

Mercury, a global contaminant, enters the stratosphere through convective uplift, but its chemical cycling in the stratosphere is unknown. We report the first model of stratospheric mercury chemistry based on a novel photosensitized oxidation mechanism. We find two very distinct Hg chemical regimes in the stratosphere: in the upper stratosphere, above the ozone maximum concentration, Hg0 oxidation is initiated by photosensitized reactions, followed by second-step chlorine chemistry. In the lower stratosphere, ground-state Hg0 is oxidized by thermal reactions at much slower rates. This dichotomy arises due to the coincidence of the mercury absorption at 253.7 nm with the ozone Hartley band maximum at 254 nm. We also find that stratospheric Hg oxidation, controlled by chlorine and hydroxyl radicals, is much faster than previously assumed, but moderated by efficient photo-reduction of mercury compounds. Mercury lifetime shows a steep increase from hours in the upper-middle stratosphere to years in the lower stratosphere. © 2022. The Authors.

Iodine chemistry is an important driver of new particle formation in the marine and polar boundary layers. There are, however, conflicting views about how iodine gas-to-particle conversion proceeds. Laboratory studies indicate that the photooxidation of iodine produces iodine oxides (IxOy), which are well-known particle precursors. By contrast, nitrate anion chemical ionization mass spectrometry (CIMS) observations in field and environmental chamber studies have been interpreted as evidence of a dominant role of iodic acid (HIO3) in iodine-driven particle formation. Here, we report flow tube laboratory experiments that solve these discrepancies by showing that both IxOy and HIO3 are involved in atmospheric new particle formation. I2Oy molecules (y = 2, 3, and 4) react with nitrate core ions to generate mass spectra similar to those obtained by CIMS, including the iodate anion. Iodine pentoxide (I2O5) produced by photolysis of higher-order IxOy is hydrolyzed, likely by the water dimer, to yield HIO3, which also contributes to the iodate anion signal. We estimate that ∼50% of the iodate anion signals observed by nitrate CIMS under atmospheric water vapor concentrations originate from I2Oy. Under such conditions, iodine-containing clusters and particles are formed by aggregation of I2Oy and HIO3, while under dry laboratory conditions, particle formation is driven exclusively by I2Oy. An updated mechanism for iodine gas-to-particle conversion is provided. Furthermore, we propose that a key iodine reservoir species such as iodine nitrate, which we observe as a product of the reaction between iodine oxides and the nitrate anion, can also be detected by CIMS in the atmosphere.

The potential reaction of the nitrate radical (NO3), the main nighttime atmospheric oxidant, with five alkyl halides, halons (CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2) has been studied theoretically. The most favorable reaction corresponds to a hydrogen atom transfer. The stationary points on the potential energy surfaces of these reactions have been characterized. The reactions can be classified into two groups based on the number of hydrogen atoms in the halon molecules (1 or 2). The reactions with halons with only one hydrogen atom show more exothermic profiles than those with two hydrogen atoms. In addition, the kinetics of the reaction of NO 3 + CH2 BrI was studied in much higher detail using a multi-well Master Equation solver as a representative example of the nitrate radical reactivity against these halocarbons. These results indicate that the chemical lifetime of the alkyl halides would not be substantially affected by nitrate radical reactions, even in the case of NO3 -polluted atmospheric conditions.

Mercury (Hg), a global contaminant, is emitted mainly in its elemental form Hgto the atmosphere where it is oxidized to reactive Hgcompounds, which efficiently deposit to surface ecosystems. Therefore, the chemical cycling between the elemental and oxidized Hg forms in the atmosphere determines the scale and geographical pattern of global Hg deposition. Recent advances in the photochemistry of gas-phase oxidized Hgand Hgspecies postulate their photodissociation back to Hgas a crucial step in the atmospheric Hg redox cycle. However, the significance of these photodissociation mechanisms on atmospheric Hg chemistry, lifetime, and surface deposition remains uncertain. Here we implement a comprehensive and quantitative mechanism of the photochemical and thermal atmospheric reactions between Hg, Hg, and Hgspecies in a global model and evaluate the results against atmospheric Hg observations. We find that the photochemistry of Hgand Hgleads to insufficient Hg oxidation globally. The combined efficient photoreduction of Hgand Hgto Hgcompetes with thermal oxidation of Hg, resulting in a large model overestimation of 99% of measured Hgand underestimation of 51% of oxidized Hg and ∼66% of Hgwet deposition. This in turn leads to a significant increase in the calculated global atmospheric Hg lifetime of 20 mo, which is unrealistically longer than the 3-6-mo range based on observed atmospheric Hg variability. These results show that the Hgand Hgphotoreduction processes largely offset the efficiency of bromine-initiated Hgoxidation and reveal missing Hg oxidation processes in the troposphere.

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. © 2020, The Author(s).

The ablation of cosmic dust injects a range of metals into planetary upper atmospheres. In addition, dust particles which survive atmospheric entry can be an important source of organic material at a planetary surface. In this study the contribution of metals and organics from three cosmic dust sources – Jupiter-Family comets (JFCs), the Asteroid belt (AST), and Halley-Type comets (HTCs) – to the atmospheres of Earth, Mars and Venus is estimated by combining a Chemical Ablation Model (CABMOD) with a Zodiacal Cloud Model (ZoDy). ZoDy provides the mass, velocity, and radiant distributions for JFC, AST, and HTC particles. JFCs are shown to be the main mass contributor in all three atmospheres (68% for Venus, 70% Earth, and 52% for Mars), providing a total input mass for Venus, Earth and Mars of 31 ± 18 t d−1, 28 ± 16 t d−1 and 2 ± 1 t d−1, respectively. The mass contribution of AST particles increases with heliocentric distance (6% for Venus, 9% for Earth, and 14% for Mars). A novel multiphase treatment in CABMOD, tested experimentally in a Meteoric Ablation Simulator, is implemented to quantify atmospheric ablation from both the silicate melt and Fe-Ni metal domains. The ratio of Fe:Ni ablation fluxes at Earth, Mars and Venus are predicted to be close to their CI chondritic ratio of 18, in agreement with mass spectrometric measurements of Fe+:Ni+ = 20−8 +13 in the terrestrial ionosphere. In contrast, lidar measurements of the neutral atoms at Earth indicate Fe:Ni = 38 ± 11, and observations by the Neutral Gas and Ion Mass Spectrometer on the MAVEN spacecraft at Mars indicate Fe+:Ni+ = 43−10 +13. Given the slower average entry velocity of cosmic dust particles at Mars, the accretion rate of unmelted particles in Mars represents 60% of the total input mass, of which a significant fraction of the total unmelted mass (22%) does not reach an organic pyrolysis temperature (~900 K), leading to a flux of intact carbon of 14 kg d−1. This is significantly smaller than previous

Anthropogenic mercury (Hg(0)) emissions oxidize to gaseous Hg(II) compounds, before deposition to Earth surface ecosystems. Atmospheric reduction of Hg(II) competes with deposition, thereby modifying the magnitude and pattern of Hg deposition. Global Hg models have postulated that Hg(II) reduction in the atmosphere occurs through aqueous-phase photoreduction that may take place in clouds. Here we report that experimental rainfall Hg(II) photoreduction rates are much slower than modelled rates. We compute absorption cross sections of Hg(II) compounds and show that fast gas-phase Hg(II) photolysis can dominate atmospheric mercury reduction and lead to a substantial increase in the modelled, global atmospheric Hg lifetime by a factor two. Models with Hg(II) photolysis show enhanced Hg(0) deposition to land, which may prolong recovery of aquatic ecosystems long after Hg emissions are lowered, due to the longer residence time of Hg in soils compared with the ocean. Fast Hg(II) photolysis substantially changes atmospheric Hg dynamics and requires further assessment at regional and local scales.

Ablation of Mg from meteoroids entering the Earth's atmosphere was studied experimentally using a Meteoric Ablation Simulator: micron-sized particles of representative meteoritic material were flash heated to simulate atmospheric entry and the ablation rate of Mg with respect to Na measured by fast time-resolved laser-induced fluorescence. Over the range of particle diameters and entry velocities studied, Mg ablates 4.3 ± 2.1 times less efficiently than Na and 2.4 ± 0.8 times less efficiently than Fe. The resulting evaporation profiles indicate that Mg mostly ablates around 84 km in the atmosphere, compared with Fe at 88 km and Na at 95 km. The chemical ablation model Chemical Ablation Model predicts satisfactorily the measured peak ablation altitudes and relative ablated fractions of Mg, Na, Fe, and Ca but does not capture the breadth of the ablation profiles, probably due to the inhomogeneity of the minerals present in meteoroids combined with experimental limitations.©2018. American Geophysical Union. All Rights Reserved.