Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products.

Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of α-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products C9-10H14-18O2-6. Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1-5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for C10H18O2 and C10H16O3 produced from oxidation of α-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of α-pinene.

A modelling study of OH, NO3 and H2SO4 in 2007-2018 at SMEAR II, Finland: analysis of long-term trends.

Major atmospheric oxidants (OH, O3 and NO3) dominate the atmospheric oxidation capacity, while H2SO4 is considered as a main driver for new particle formation. Although numerous studies have investigated the long-term trend of ozone in Europe, the trends of OH, NO3 and H2SO4 at specific sites are to a large extent unknown. The one-dimensional model SOSAA has been applied in several studies at the SMEAR II station and has been validated by measurements in several projects. Here, we applied the SOSAA model for the years 2007-2018 to simulate the atmospheric chemical components, especially the atmospheric oxidants OH and NO3, as well as H2SO4 at SMEAR II. The simulations were evaluated with observations from several shorter and longer campaigns at SMEAR II. Our results show that daily OH increased by 2.39% per year and NO3 decreased by 3.41% per year, with different trends of these oxidants during day and night. On the contrary, daytime sulfuric acid concentrations decreased by 2.78% per year, which correlated with the observed decreasing concentration of newly formed particles in the size range of 3-25 nm with 1.4% per year at SMEAR II during the years 1997-2012. Additionally, we compared our simulated OH, NO3 and H2SO4 concentrations with proxies, which are commonly applied in case a limited number of parameters are measured and no detailed model simulations are available.

Gas-to-Particle Partitioning of Cyclohexene- and α-Pinene-Derived Highly Oxygenated Dimers Evaluated Using COSMOtherm.

Oxidized organic compounds are expected to contribute to secondary organic aerosol (SOA) if they have sufficiently low volatilities. We estimated saturation vapor pressures and activity coefficients (at infinite dilution in water and a model water-insoluble organic phase) of cyclohexene- and α-pinene-derived accretion products, "dimers", using the COSMOtherm19 program. We found that these two property estimates correlate with the number of hydrogen bond-donating functional groups and oxygen atoms in the compound. In contrast, when the number of H-bond donors is fixed, no clear differences are seen either between functional group types (e.g., OH or OOH as H-bond donors) or the formation mechanisms (e.g., gas-phase radical recombination vs liquid-phase closed-shell esterification). For the cyclohexene-derived dimers studied here, COSMOtherm19 predicts lower vapor pressures than the SIMPOL.1 group-contribution method in contrast to previous COSMOtherm estimates using older parameterizations and nonsystematic conformer sampling. The studied dimers can be classified as low, extremely low, or ultra-low-volatility organic compounds based on their estimated saturation mass concentrations. In the presence of aqueous and organic aerosol particles, all of the studied dimers are likely to partition into the particle phase and thereby contribute to SOA formation.

Molecular mechanism for rapid autoxidation in α-pinene ozonolysis.

Aerosol affects Earth's climate and the health of its inhabitants. A major contributor to aerosol formation is the oxidation of volatile organic compounds. Monoterpenes are an important class of volatile organic compounds, and recent research demonstrate that they can be converted to low-volatility aerosol precursors on sub-second timescales following a single oxidant attack. The α-pinene + O3 system is particularly efficient in this regard. However, the actual mechanism behind this conversion is not understood. The key challenge is the steric strain created by the cyclobutyl ring in the oxidation products. This strain hinders subsequent unimolecular hydrogen-shift reactions essential for lowering volatility. Using quantum chemical calculations and targeted experiments, we show that the excess energy from the initial ozonolysis reaction can lead to novel oxidation intermediates without steric strain, allowing the rapid formation of products with up to 8 oxygen atoms. This is likely a key route for atmospheric organic aerosol formation.

Efficient alkane oxidation under combustion engine and atmospheric conditions.

Oxidation chemistry controls both combustion processes and the atmospheric transformation of volatile emissions. In combustion engines, radical species undergo isomerization reactions that allow fast addition of O2. This chain reaction, termed autoxidation, is enabled by high engine temperatures, but has recently been also identified as an important source for highly oxygenated species in the atmosphere, forming organic aerosol. Conventional knowledge suggests that atmospheric autoxidation requires suitable structural features, like double bonds or oxygen-containing moieties, in the precursors. With neither of these functionalities, alkanes, the primary fuel type in combustion engines and an important class of urban trace gases, are thought to have minor susceptibility to extensive autoxidation. Here, utilizing state-of-the-art mass spectrometry, measuring both radicals and oxidation products, we show that alkanes undergo autoxidation much more efficiently than previously thought, both under atmospheric and combustion conditions. Even at high concentrations of NOX, which typically rapidly terminates autoxidation in urban areas, the studied C6-C10 alkanes produce considerable amounts of highly oxygenated products that can contribute to urban organic aerosol. The results of this inter-disciplinary effort provide crucial information on oxidation processes in both combustion engines and the atmosphere, with direct implications for engine efficiency and urban air quality.

Unprecedented Ambient Sulfur Trioxide (SO3) Detection: Possible Formation Mechanism and Atmospheric Implications.

Sulfur trioxide (SO3) is a crucial compound for atmospheric sulfuric acid (H2SO4) formation, acid rain formation, and other atmospheric physicochemical processes. During the daytime, SO3 is mainly produced from the photo-oxidation of SO2 by OH radicals. However, the sources of SO3 during the early morning and night, when OH radicals are scarce, are not fully understood. We report results from two field measurements in urban Beijing during winter and summer 2019, using a nitrate-CI-APi-LTOF (chemical ionization-atmospheric pressure interface-long-time-of-flight) mass spectrometer to detect atmospheric SO3 and H2SO4. Our results show the level of SO3 was higher during the winter than during the summer, with high SO3 levels observed especially during the early morning (∼05:00 to ∼08:30) and night (∼18:00 to ∼05:00 the next day). On the basis of analysis of SO2, NO x , black carbon, traffic flow, and atmospheric ions, we suggest SO3 could be formed from the catalytic oxidation of SO2 on the surface of traffic-related black carbon. This previously unidentified SO3 source results in significant H2SO4 formation in the early morning and thus promotes sub-2.5 nm particle formation. These findings will help in understanding urban SO3 and formulating policies to mitigate secondary particle formation in Chinese megacities.

The role of highly oxygenated organic molecules in the Boreal aerosol-cloud-climate system.

Over Boreal regions, monoterpenes emitted from the forest are the main precursors for secondary organic aerosol (SOA) formation and the primary driver of the growth of new aerosol particles to climatically important cloud condensation nuclei (CCN). Autoxidation of monoterpenes leads to rapid formation of Highly Oxygenated organic Molecules (HOM). We have developed the first model with near-explicit representation of atmospheric new particle formation (NPF) and HOM formation. The model can reproduce the observed NPF, HOM gas-phase composition and SOA formation over the Boreal forest. During the spring, HOM SOA formation increases the CCN concentration by ~10 % and causes a direct aerosol radiative forcing of -0.10 W/m2. In contrast, NPF reduces the number of CCN at updraft velocities < 0.2 m/s, and causes a direct aerosol radiative forcing of +0.15 W/m2. Hence, while HOM SOA contributes to climate cooling, NPF can result in climate warming over the Boreal forest.

Closed Distal Dislocation of the Intermediate Cuneiform in a Complex Lisfranc Fracture-Dislocation: A Case Report.

CASE: A 21-year-old, active duty male sustained an irreducible, complex Lisfranc fracture-dislocation with distal extrusion of his intermediate cuneiform. He was treated in a staged manner with external fixator placement, followed by an extended midfoot fusion with autograft bone. At 19 months, he could perform all activities of daily living independently with minimal pain using an Intrepid Dynamic Exoskeletal Orthosis. CONCLUSIONS: Complex Lisfranc injuries are severe and often result in chronic pain and disability after operative management. To our knowledge, this is the only case report describing a Lisfranc fracture-dislocation with a distally extruded intermediate cuneiform treated with a fusion.

How well can we predict cluster fragmentation inside a mass spectrometer?

Fragmentation of molecular clusters inside mass spectrometers is a significant source of uncertainty in a wide range of chemical applications. We have measured the fragmentation of sulfuric acid clusters driving atmospheric new-particle formation, and developed a novel model, based on first principles calculations, capable of quantitatively predicting the extent of fragmentation.

Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts.

Peroxy (RO2) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO2 + OH reaction for previously unexplored "R" structures (R = CH(O)CH2 and R = CH3C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R'O2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R'OOOR adducts, respectively. The former decomposes to RO + HO2 and R(O)OH + O2 products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R'OOOR adducts varied between 103 and 0.015 s-1 at 298 K and 1 atm. The most long-lived R'OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.

Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol.

Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth's radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.

Computational Investigation of RO2 + HO2 and RO2 + RO2 Reactions of Monoterpene Derived First-Generation Peroxy Radicals Leading to Radical Recycling.

The oxidation of biogenically emitted volatile organic compounds (BVOC) plays an important role in the formation of secondary organic aerosols (SOA) in the atmosphere. Peroxy radicals (RO2) are central intermediates in the BVOC oxidation process. Under clean (low-NO x) conditions, the main bimolecular sink reactions for RO2 are with the hydroperoxy radical (HO2) and with other RO2 radicals. Especially for small RO2, the RO2 + HO2 reaction mainly leads to closed-shell hydroperoxide products. However, there exist other known RO2 + HO2 and RO2 + RO2 reaction channels that can recycle radicals and oxidants in the atmosphere, potentially leading to lower-volatility products and enhancing SOA formation. In this work, we present a thermodynamic overview of two such reactions: (a) RO2 + HO2 → RO + OH + O2 and (b) R'O2 + RO2 → R'O + RO + O2 for selected monoterpene + oxidant derived peroxy radicals. The monoterpenes considered are α-pinene, ß-pinene, limonene, trans-ß-ocimene, and Δ3-carene. The oxidants considered are the hydroxyl radical (OH), the nitrate radical (NO3), and ozone (O3). The reaction Gibbs energies were calculated at the DLPNO-CCSD(T)/def2-QZVPP//ωB97X-D/aug-cc-pVTZ level of theory. All reactions studied here were found to be exergonic in terms of Gibbs energy. On the basis of a comparison with previous mechanistic studies, we predict that reaction a and reaction b are likely to be most important for first-generation peroxy radicals from O3 oxidation (especially for ß-pinene), while being less so for most first-generation peroxy radicals from OH and NO3 oxidation. This is because both reactions are comparatively more exergonic for the O3 oxidized systems than their OH and NO3 oxidized counterparts. Our results indicate that bimolecular reactions of certain complex RO2 may contribute to an increase in radical and oxidant recycling under high HO2 conditions in the atmosphere, which can potentially enhance SOA formation.

NO2 Suppression of Autoxidation-Inhibition of Gas-Phase Highly Oxidized Dimer Product Formation.

Atmospheric autoxidation of volatile organic compounds (VOC) leads to prompt formation of highly oxidized multifunctional compounds (HOM) that have been found crucial in forming ambient secondary organic aerosol (SOA). As a radical chain reaction mediated by oxidized peroxy (RO2) and alkoxy (RO) radical intermediates, the formation pathways can be intercepted by suitable reaction partners, preventing the production of the highest oxidized reaction products, and thus the formation of the most condensable material. Commonly, NO is expected to have a detrimental effect on RO2 chemistry, and thus on autoxidation, whereas the influence of NO2 is mostly neglected. Here it is shown by dedicated flow tube experiments, how high concentration of NO2 suppresses cyclohexene ozonolysis initiated autoxidation chain reaction. Importantly, the addition of NO2 ceases covalently bound dimer production, indicating their production involving acylperoxy radical (RC(O)OO•) intermediates. In related experiments NO was also shown to strongly suppress the highly oxidized product formation, but due to possibility for chain propagating reactions (as with RO2 and HO2 too), the suppression is not as absolute as with NO2. Furthermore, it is shown how NO x reactions with oxidized peroxy radicals lead into indistinguishable product compositions, complicating mass spectral assignments in any RO2 + NO x system. The present work was conducted with atmospheric pressure chemical ionization mass spectrometry (CIMS) as the detection method for the highly oxidized end-products and peroxy radical intermediates, under ambient conditions and at short few second reaction times. Specifically, the insight was gained by addition of a large amount of NO2 (and NO) to the oxidation system, upon which acylperoxy radicals reacted in RC(O)O2 + NO2 → RC(O)O2NO2 reaction to form peroxyacylnitrates, consequently shutting down the oxidation sequence.

Theoretical kinetic study of the formic acid catalyzed Criegee intermediate isomerization: multistructural anharmonicity and atmospheric implications.

We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI + HCOOH → VHP + HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and which are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow the formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C-HO hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9 × 10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosols, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

Computational Comparison of Different Reagent Ions in the Chemical Ionization of Oxidized Multifunctional Compounds.

High pressure anion chemical ionization is commonly used for the detection of neutral molecules in the gas phase. The detection efficiency in these measurements depends on how strongly the reagent ion binds to the neutral target molecule. We have calculated the binding strength of nitrate (NO3-), acetate (CH3C(O)O-), lactate (CH3CH(OH)C(O)O-), trifluoroacetate (CF3C(O)O-), trifluoromethanolate (CF3O-), bromide (Br-), and iodide (I-) reagent ions to ten different products derived from the OH radical-initiated oxidation of butadiene. We found that the binding of these oxidation products to the reagent ions depends almost linearly on the number of oxygen atoms in the target molecule, with the precise chemical identity of the compound (e.g., the number and relative position of hydroxyl or hydroperoxy groups) playing a more minor role. For acetate, the formation free energy decreases on average by around 4 kcal/mol when the number of oxygen atoms in the sample molecule increases by one. For the other reagent ions the corresponding decrease is around 3 kcal/mol. For all of the molecules studied, acetate forms the most stable clusters and I- the least stable. We also investigated the effect of humidity on the chemical ionization by calculating how strongly water molecules bind to both the reagent ions and the ion-molecule clusters. Water binds much more strongly to the reagent ion monomers compared to the reagent ion "dimers" (defined here as a cluster of the reagent anion with the corresponding neutral conjugate acid, e.g., HNO3(NO3-)) or the ion-molecule clusters. This likely leads to a stronger humidity dependence when using reagent ions that are not able to form reagent ion dimers (such as CF3C(O)O-, CF3O-, Br-, and I-).

Computational and Experimental Investigation of the Detection of HO2 Radical and the Products of Its Reaction with Cyclohexene Ozonolysis Derived RO2 Radicals by an Iodide-Based Chemical Ionization Mass Spectrometer.

The HO2 radical is an important atmospheric molecule that can potentially influence the termination of autoxidation processes of volatile organic compounds (VOCs) that lead to the formation of highly oxygenated multifunctional compounds (HOMs). In this work, we demonstrate the direct detection of the HO2 radical using an iodide-based chemical ionization mass spectrometer (iodide-CIMS). Expanding on the previously established correlation between molecule-iodide binding enthalpy and iodide-CIMS instrument sensitivity, the experimental detection of the HO2 radical was preceded by the quantum chemical calculation of the HO2*I- cluster (PBE/aug-cc-pVTZ-PP level), which showed a reasonably strong binding enthalpy of 21.60 kcal/mol. Cyclohexene ozonolysis intermediates and closed-shell products were next detected by the iodide-CIMS. The ozone-initiated cyclohexene oxidation mechanism was perturbed by the introduction of the HO2 radical, leading to the formation of closed-shell hydroperoxides. The experimental investigation once again followed the initial computational molecule-iodide binding enthalpy calculations. The quantum chemical calculations were performed at the PBE/aug-cc-pVTZ-PP level for radicals and DLPNO-CCSD(T)/def2-QZVPP//PBE/aug-cc-pVTZ-PP level for the closed-shell products. A comparison between the iodide-CIMS and nitrate-CIMS spectra with identical measurement steps revealed that the iodide-CIMS was able to detect the low-oxidized (O/C ratio 0.5 and 0.66) cyclohexene ozonolysis monomer products more efficiently than nitrate-CIMS. Higher-oxidized monomers (O/C ratio 1 to 1.5) were detected equally well by both methods. An investigation of dimers showed that both iodide- and nitrate-CIMS were able to detect the dimer compositions possibly formed from reactions between the peroxy radical monomers considered in this study. Additionally, iodide-CIMS detected organic ions that were formed by a previously suggested mechanism of dehydroxylation of peroxy acids (and deoxygenation of acyl peroxy radicals) by H2O*I- clusters. These mechanisms were computationally verified.

Computational Comparison of Acetate and Nitrate Chemical Ionization of Highly Oxidized Cyclohexene Ozonolysis Intermediates and Products.

During the past few years nitrate chemical ionization has been used to detect highly oxidized products from OH- and O3-initiated alkene autoxidation. These have been speculated to play a significant role in atmospheric aerosol formation. As less oxidized autoxidation products have not been detected using nitrate chemical ionization, and the absolute concentrations of the highly oxidized species are as yet unknown, other reagent ions, such as acetate, are needed both to verify the detection efficiency of nitrate chemical ionization and to measure the less oxidized compounds. Here we compare the formation free energies of the acetate and nitrate clusters of several atmospherically relevant RO2 intermediates and products derived from cyclohexene ozonolysis, calculated at the ωB97xD/aug-cc-pVTZ level of theory. We found that, for the molecules with one hydrogen bonding peroxy acid group, the binding with nitrate is on average 7.5 kcal/mol weaker than with acetate and the binding is on average 10.5 kcal/mol weaker for molecules with two hydrogen bonding peroxy acid groups. We also calculated the deprotonation energies of the RO2 intermediates and the closed-shell products and found that acetate is able to deprotonate almost all of these molecules, while deprotonation with nitrate is (as expected for the conjugate base of a strong acid) not favorable.

Global atmospheric particle formation from CERN CLOUD measurements.

Fundamental questions remain about the origin of newly formed atmospheric aerosol particles because data from laboratory measurements have been insufficient to build global models. In contrast, gas-phase chemistry models have been based on laboratory kinetics measurements for decades. We built a global model of aerosol formation by using extensive laboratory measurements of rates of nucleation involving sulfuric acid, ammonia, ions, and organic compounds conducted in the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber. The simulations and a comparison with atmospheric observations show that nearly all nucleation throughout the present-day atmosphere involves ammonia or biogenic organic compounds, in addition to sulfuric acid. A considerable fraction of nucleation involves ions, but the relatively weak dependence on ion concentrations indicates that for the processes studied, variations in cosmic ray intensity do not appreciably affect climate through nucleation in the present-day atmosphere.