Metals from spacecraft reentry in stratospheric aerosol particles.

Large increases in the number of low earth orbit satellites are projected in the coming decades [L. Schulz, K.-H. Glassmeier, Adv. Space Res. 67, 1002-1025 (2021)] with perhaps 50,000 additional satellites in orbit by 2030 [GAO, Large constellations of satellites: Mitigating environmental and other effects (2022)]. When spent rocket bodies and defunct satellites reenter the atmosphere, they produce metal vapors that condense into aerosol particles that descend into the stratosphere. So far, models of spacecraft reentry have focused on understanding the hazard presented by objects that survive to the surface rather than on the fate of the metals that vaporize. Here, we show that metals that vaporized during spacecraft reentries can be clearly measured in stratospheric sulfuric acid particles. Over 20 elements from reentry were detected and were present in ratios consistent with alloys used in spacecraft. The mass of lithium, aluminum, copper, and lead from the reentry of spacecraft was found to exceed the cosmic dust influx of those metals. About 10% of stratospheric sulfuric acid particles larger than 120 nm in diameter contain aluminum and other elements from spacecraft reentry. Planned increases in the number of low earth orbit satellites within the next few decades could cause up to half of stratospheric sulfuric acid particles to contain metals from reentry. The influence of this level of metallic content on the properties of stratospheric aerosol is unknown.

Natural short-lived halogens exert an indirect cooling effect on climate.

Observational evidence shows the ubiquitous presence of ocean-emitted short-lived halogens in the global atmosphere1-3. Natural emissions of these chemical compounds have been anthropogenically amplified since pre-industrial times4-6, while, in addition, anthropogenic short-lived halocarbons are currently being emitted to the atmosphere7,8. Despite their widespread distribution in the atmosphere, the combined impact of these species on Earth's radiative balance remains unknown. Here we show that short-lived halogens exert a substantial indirect cooling effect at present (-0.13 ± 0.03 watts per square metre) that arises from halogen-mediated radiative perturbations of ozone (-0.24 ± 0.02 watts per square metre), compensated by those from methane (+0.09 ± 0.01 watts per square metre), aerosols (+0.03 ± 0.01 watts per square metre) and stratospheric water vapour (+0.011 ± 0.001 watts per square metre). Importantly, this substantial cooling effect has increased since 1750 by -0.05 ± 0.03 watts per square metre (61 per cent), driven by the anthropogenic amplification of natural halogen emissions, and is projected to change further (18-31 per cent by 2100) depending on climate warming projections and socioeconomic development. We conclude that the indirect radiative effect due to short-lived halogens should now be incorporated into climate models to provide a more realistic natural baseline of Earth's climate system.

Kinetics of O3 with Ca+ and Its Higher Oxides CaOn+ (n = 1-3) and Updates to a Model of Meteoric Calcium in the Mesosphere and Lower Thermosphere.

The room-temperature rate constants and product branching fractions of CaOn+ (n = 0-3) + O3 are measured using a selected ion flow tube apparatus. Ca+ + O3 produces CaO+ + O2 with k = 9 ± 4 × 10-10 cm3 s-1, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values. Most likely, those values were underestimated due to the reformation of Ca+ from the sequential chemistry of higher calcium oxide cations with O3, as explored here. A rate constant of 8 ± 3 × 10-10 cm3 s-1 is recommended. Both CaO+ and CaO2+ react near the capture rate constant with ozone. The CaO+ reaction yields both CaO2+ + O2 (0.80 ± 0.15 branching) and Ca+ + 2O2. Similarly, the CaO2+ reaction yields both CaO3+ + O2 (0.85 ± 0.15 branching) and CaO+ + 2O2. CaO3+ + O3 yield CaO2+ + 2O2 at 2 ± 1 × 10-11 cm3 s-1, about 2% of the capture rate constant. The results are supported using density functional calculations and statistical modeling. In general, CaOn+ + O3 yield CaOn+1+ + O2, the expected oxidation. Some fraction of CaOn+1+ is produced with sufficient internal energy to further dissociate to CaOn-1+ + O2, yielding the same products as the oxidation of O3 by CaOn+. Mesospheric Ca and Ca+ concentrations are modeled as functions of day, latitude, and altitude using the Whole Atmosphere Community Climate Model (WACCM); incorporating the updated rate constants improves agreement with concentrations derived from lidar measurements.

Reply to the 'Comment on "Theoretical study of the NO3 radical reaction with CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2"' by C. J. Nielsen and Y. Tang, Phys. Chem. Chem. Phys., 2022, 24, DOI: 10.1039/D2CP03013F.

In this Reply, we answer the main argument raised in the Comment about the energy of the NO3 radical and its influence in the reaction profiles of the reaction of the NO3 radical with CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2 by C. J. Nielsen and Y. Tang. The optimized geometry of the NO3 radical has been obtained using 49 DFT functionals: 26 functionals predict a minimum with D3h symmetry and 23 with C2v symmetry. The former functionals have been used to calculate the thermodynamic values of three reactions (X + HNO3 → XH + NO3, X= OH, CH3 and CCl3) and compared with experimental data. Those functionals with smaller errors have been used to recalculate the barriers of the reaction of NO3 with CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2. The results show differences of 10.5 kJ mol-1 when compared to those obtained with the M08HX functional.

The Chemistry of Mercury in the Stratosphere.

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.

Master equation modelling of non-equilibrium chemistry in stellar outflows.

A current challenge in astrochemistry is to explain the formation of Fe-Mg silicate dust around evolved stars. The dust is observed to form within 2 to 3 stellar radii of oxygen-rich AGB stars, where the typical conditions are kinetic (translational) temperatures between 1200 and 1600 K, and total gas densities below 1011 cm-3. At these high temperatures, molecules with bond energies < 400 kJ mol-1 should be short-lived, and this results in kinetic bottlenecks in postulated mechanisms for converting the observed Fe, Mg, SiO and H2O into silicate. Here we show that, in the very low pressure regime of a stellar outflow, molecules can exhibit significant vibrational disequilibrium because optical transitions - both spontaneous and stimulated by the stellar radiation field - occur on a much faster timescale than collisions. As a result, relatively less stable molecules can form and survive long enough to provide building blocks to silicate formation. Here we use the molecule OSi(OH)2, formed by the recombination of SiO2 and H2O, as an example. When vibrational disequilibrium is accounted for in a master equation treatment which includes optical transitions, the quantity of metal silicates produced in a low mass loss rate evolved star (R Dor) is increased by 6 orders of magnitude.

Theoretical study of the NO3 radical reaction with CH2ClBr, CH2ICl, CH2BrI, CHCl2Br, and CHClBr2.

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 NO3 + CH2BrI 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.

The reaction between HgBr and O3: kinetic study and atmospheric implications.

The rate constants of many reactions currently considered to be important in the atmospheric chemistry of mercury remain to be measured in the laboratory. Here we report the first experimental determination of the rate constant of the gas-phase reaction between the HgBr radical and ozone, for which a value at room temperature of k(HgBr + O3) = (7.5 ± 0.6) × 10-11 cm3 molecule s-1 (1σ) has been obtained. The rate constants of two reduction side reactions were concurrently determined: k(HgBr + O) = (5.3 ± 0.4) × 10-11 cm3 molecule s-1 and k(HgBrO + O) = (9.1 ± 0.6) × 10-11 cm3 molecule s-1. The value of k(HgBr + O3) is slightly lower than the collision number, confirming the absence of a significant energy barrier. Considering the abundance of ozone in the troposphere, our experimental rate constant supports recent modelling results suggesting that the main atmospheric fate of HgBr is reaction with ozone to form BrHgO.

Reaction of SO3 with HONO2 and Implications for Sulfur Partitioning in the Atmosphere.

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 SO3 + HONO2 reaction are pronounced below 1 bar. The SO3 + HONO2 reaction can be a potential removal reaction for SO3 in the stratosphere and for HONO2 in the troposphere, because the reaction can potentially compete well with the SO3 + 2H2O reaction between 25 and 35 km, as well as the OH + HONO2 reaction. The present findings also suggest an unexpected new product from the SO3 + HONO2 reaction, which, although very short-lived, would have broad implications for understanding the partitioning of sulfur in the stratosphere and the potential for the SO3 reaction with organic acids to generate organosulfates without the need for heterogeneous chemistry.

Insights into the Chemistry of Iodine New Particle Formation: The Role of Iodine Oxides and the Source of Iodic Acid.

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.

First Simultaneous Lidar Observations of Thermosphere-Ionosphere Fe and Na (TIFe and TINa) Layers at McMurdo (77.84°S, 166.67°E), Antarctica With Concurrent Measurements of Aurora Activity, Enhanced Ionization Layers, and Converging Electric Field.

We report the first simultaneous, common-volume lidar observations of thermosphere-ionosphere Fe (TIFe) and Na (TINa) layers in Antarctica. We also report the observational discovery of nearly one-to-one correspondence between TIFe and aurora activity, enhanced ionization layers, and converging electric fields. Distinctive TIFe layers have a peak density of ~384 cm-3 and the TIFe mixing ratio peaks around 123 km, ~5 times the mesospheric layer maximum. All evidence shows that Fe+ ion-neutralization is the major formation mechanism of TIFe layers. The TINa mixing ratio often exhibits a broad peak at TIFe altitudes, providing evidence for in situ production via Na+ neutralization. However, the tenuous TINa layers persist long beyond TIFe disappearance and reveal gravity wave perturbations, suggesting a dynamic background of neutral Na, but not Fe, above 110 km. The striking differences between distinct TIFe and diffuse TINa suggest differential transport between Fe and Na, possibly due to mass separation.

Photochemistry of oxidized Hg(I) and Hg(II) species suggests missing mercury oxidation in the troposphere.

Mercury (Hg), a global contaminant, is emitted mainly in its elemental form Hg0 to the atmosphere where it is oxidized to reactive HgII compounds, 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 HgI and HgII species postulate their photodissociation back to Hg0 as 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 Hg0, HgI, and HgII species in a global model and evaluate the results against atmospheric Hg observations. We find that the photochemistry of HgI and HgII leads to insufficient Hg oxidation globally. The combined efficient photoreduction of HgI and HgII to Hg0 competes with thermal oxidation of Hg0, resulting in a large model overestimation of 99% of measured Hg0 and underestimation of 51% of oxidized Hg and ∼66% of HgII wet 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 HgI and HgII photoreduction processes largely offset the efficiency of bromine-initiated Hg0 oxidation and reveal missing Hg oxidation processes in the troposphere.

Water Photolysis and Its Contributions to the Hydroxyl Dayglow Emissions in the Atmospheres of Earth and Mars.

Airglow is a well-known phenomenon in the Earth's upper atmosphere, which arises from the emissions of energetic atoms and molecules. The Meinel band emission from high vibrationally excited OH(X) radicals is one of the more important contributors to the airglow from the mesosphere/lower thermosphere. The H + O3 reaction has long been regarded as the dominant source of these OH(X, high v) radicals. Here we demonstrate that vacuum ultraviolet (VUV) photolysis of water vapor at λ ∼ 112.8 nm represents another source of exceptionally highly vibrationally excited OH(X) radicals, with a nascent vibrational state population distribution that maximizes at v = 9 and extends to at least the v = 15 level. Atmospheric chemistry modeling indicates that OH(X, high v) radicals from H2O photolysis might be detectable in the OH Meinel band dayglow in the upper atmosphere of Earth and should dominate the corresponding emission from the Martian atmosphere. VUV photolysis of H2O also produces electronically excited OH(A) radicals, and simultaneous detection of emissions from OH(X, high v) and OH(A) is shown to offer a route to identifying high-oxygen exoplanetary atmospheres.

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.

Kinetic Study of the Reactions PO + O2 and PO2 + O3 and Spectroscopy of the PO Radical.

The kinetics of the reactions of PO with O2 and PO2 with O3 were studied at temperatures ranging from ∼190 to 340 K, using a pulsed laser photolysis-laser induced fluorescence technique. For the reaction of PO + O2, there is evidence of both a two- and three-body exit channel, producing PO2 + O and PO3, respectively. Potential energy surfaces of both the PO + O2 and PO2 + O3 systems were calculated using electronic structure theory and combined with RRKM calculations to explain the observed pressure and temperature dependences. For PO + O2, at pressures typical of a planetary upper atmosphere where meteoric ablation of P will occur, the reaction is effectively pressure independent with a yield of PO2 + O of >99%; the rate coefficient can be expressed by log10(k, 120-500 K, cm3 molecule-1 s-1) = -13.915 + 2.470 log10(T) - 0.5020(log10(T))2, with an uncertainty of ±10% over the experimental temperature range (191-339 K). With increasing pressure, the yield of PO3 increases, reaching ∼90% at a pressure of 1 atm and T = 300 K. For PO2 + O3, k(188-339 K) = 3.7 × 10-11 exp(-1131/T) cm3 molecule-1 s-1, with an uncertainty of ±26% over the stated temperature range. Laser-induced fluorescence spectra of PO over the wavelength range 245-248 nm were collected and simulated using pgopher to obtain new spectroscopic constants for the ground and v = 1 vibrational levels of the X2Π and A2Σ+ states of PO.

A study of the reactions of Ni+ and NiO+ ions relevant to planetary upper atmospheres.

The reactions between Ni+(2D) and O3, O2, N2, CO2 and H2O were studied at 294 K using the pulsed laser ablation at 532 nm of a nickel metal target in a fast flow tube, with mass spectrometric detection of Ni+ and NiO+. The rate coefficient for the reaction of Ni+ with O3 is k(294 K) = (9.7 ± 2.1) × 10-10 cm3 molecule-1 s-1; the reaction proceeds at the ion-permanent dipole enhanced Langevin capture rate with a predicted T-0.16 dependence. Electronic structure theory calculations were combined with Rice-Ramsperger-Kassel-Markus theory to extrapolate the measured recombination rate coefficients to the temperature and pressure conditions of planetary upper atmospheres. The following low-pressure limiting rate coefficients were obtained for T = 120-400 K and He bath gas (in cm6 molecule-2 s-1, uncertainty ±σ at 180 K): log10(k, Ni+ + N2) = -27.5009 + 1.0667log10(T) - 0.74741(log10(T))2, σ = 29%; log10(k, Ni+ + O2) = -27.8098 + 1.3065log10(T) - 0.81136(log10(T))2, σ = 32%; log10(k, Ni+ + CO2) = -29.805 + 4.2282log10(T) - 1.4303(log10(T))2, σ = 28%; log10(k, Ni+ + H2O) = -24.318 + 0.20448log10(T) - 0.66676(log10(T))2, σ = 28%). Other rate coefficients measured (at 294 K, in cm3 molecule-1 s-1) were: k(NiO+ + O) = (1.7 ± 1.2) × 10-10; k(NiO+ + CO) = (7.4 ± 1.3) × 10-11; k(NiO+ + O3) = (2.7 ± 1.0) × 10-10 with (29 ± 21)% forming Ni+ as opposed to NiO2+; k(NiO2+ + O3) = (2.9 ± 1.4) × 10-10, with (16 ± 9)% forming NiO+ as opposed to ONiO2+; and k(Ni+·N2 + O) = (7 ± 4) × 10-12. The chemistry of Ni+ and NiO+ in the upper atmospheres of Earth and Mars is then discussed.

Experimental Study of the Removal of Ground- and Excited-State Phosphorus Atoms by Atmospherically Relevant Species.

The reaction kinetics of the ground and first two excited states of atomic phosphorus, P, with atmospherically relevant species were studied at temperatures ranging from ∼200 to 750 K using a pulsed laser photolysis-laser-induced fluorescence technique. The temperature dependence of the rate coefficients is parametrized as follows (units: cm3 molecule-1 s-1, 1σ errors): k(P(2P)+O2)(189 ≤ T/K ≤ 701) = (7.10 ± 1.03) × 10-12 × (T/298)1.42±0.13 × exp[(374 ± 41)/T]; k(P(2D)+O2)(188 ≤ T/K ≤ 714) = (1.20 ± 0.29) × 10-11 × (T/298)0.821±0.207 × exp[(177 ± 70)/T]; k(P(2D)+CO2)(296 ≤ T/K ≤ 748) = (5.68 ± 0.36) × 10-12 × (T/298)0.800±0.103; k(P(2D)+N2)(188 ≤ T/K ≤ 748) = (1.42 ± 0.03) × 10-12 × (T/298)1.36±0.04; k(P(4S)+O2)(187 ≤ T/K ≤ 732) = (3.08 ± 0.31) × 10-13 × (T/298)2.24±0.29. Electronic structure theory combined with RRKM calculations have been used to explain the unusual temperature dependence of P(4S) + O2. The small pre-exponential factor for the reaction results from a tight steric constraint, together with the requirement that the reaction occurs on doublet rather than sextet electronic surfaces.