Kinetics, mechanisms and ionic liquids in the uptake of n-butylamine onto low molecular weight dicarboxylic acids

Atmospheric particles adversely affect visibility, health, and climate, yet the kinetics and mechanisms of particle formation and growth are poorly understood. Multiphase reactions between amines and dicarboxylic acids (diacids) have been suggested to contribute. In this study, the reactions of n-butylamine (BA) with solid C3-C8 diacids were studied at 296 ± 1 K using a Knudsen cell interfaced to a quadrupole mass spectrometer. Uptake coefficients for amines on the diacids with known geometric surface areas were measured at initial amine concentrations from (3-50) × 1011 cm-3. Uptake coefficients ranged from 0.7 ± 0.1 (2σ) for malonic acid (C3) to <10-6 for suberic acid (C8), show an odd-even carbon number effect, and decrease with increasing chain length within each series. Butylaminium salts formed from evaporation of aqueous solutions of BA with C3, C5 and C7 diacids (as well as C8) were viscous liquids, suggesting that ionic liquids (ILs) form on the surface during the reactions of gas phase amine with the odd carbon diacids. Predictions from the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) were quantitatively consistent with uptake occurring via dissolution of the underlying diacid into the IL layer and reaction with amine taken up from the gas phase. The butylaminium salts formed from the C4 and C6 diacids were solids, and their uptake coefficients were smaller. These experiments and kinetic modeling demonstrate the unexpected formation of ILs in a gas-solid reaction, and suggest that ILs should be considered under some circumstances in atmospheric processes

Organics Substantially Reduce HO2 Uptake onto Aerosols Containing Transition Metal ions

A HO2 mass accommodation coefficient of α = 0.23 ± 0.07 was measured onto submicron copper(II)-doped ammonium sulfate aerosols at a relative humidity of 60 ± 3%, at 293 ± 2 K and at an initial HO2 concentration of ∼1 × 109 molecules cm−3 by using an aerosol flow tube coupled to a sensitive fluorescence assay by gas expansion (FAGE) HO2 detection system. The effect upon the HO2 uptake coefficient γ of adding different organic species (malonic acid, citric acid, 1,2-diaminoethane, tartronic acid, ethylenediaminetetraacetic acid (EDTA), and oxalic acid) into the copper(II)-doped aerosols was investigated. The HO2 uptake coefficient decreased steadily from the mass accommodation value to γ = 0.008 ± 0.009 when EDTA was added in a one-to-one molar ratio with the copper(II) ions, and to γ = 0.003 ± 0.004 when oxalic acid was added into the aerosol in a ten-to-one molar ratio with the copper(II). EDTA binds strongly to copper(II) ions, potentially making them unavailable for catalytic destruction of HO2, and could also be acting as a surfactant or changing the viscosity of the aerosol. The addition of oxalic acid to the aerosol potentially forms low-volatility copper−oxalate complexes that reduce the uptake of HO2 either by changing the viscosity of the aerosol or by causing precipitation out of the aerosol forming a coating. It is likely that there is a high enough oxalate to copper(II) ion ratio in many types of atmospheric aerosols to decrease the HO2 uptake coefficient. No observable change in the HO2 uptake coefficient was measured when the other organic species (malonic acid, citric acid, 1,2-diaminoethane, and tartronic acid) were added in a ten-to-one molar ratio with the copper(II) ions

Unexpected formation of oxygen-free products and nitrous acid from the ozonolysis of the neonicotinoid nitenpyram.

The neonicotinoid nitenpyram (NPM) is a multifunctional nitroenamine [(R1N)(R2N)C=CHNO2] pesticide. As a nitroalkene, it is structurally similar to other emerging contaminants such as the pharmaceuticals ranitidine and nizatidine. Because ozone is a common atmospheric oxidant, such compounds may be oxidized on contact with air to form new products that have different toxicity compared to the parent compounds. Here we show that oxidation of thin solid films of NPM by gas-phase ozone produces unexpected products, the majority of which do not contain oxygen, despite the highly oxidizing reactant. A further surprising finding is the formation of gas-phase nitrous acid (HONO), a species known to be a major photolytic source of the highly reactive hydroxyl radical in air. The results of application of a kinetic multilayer model show that reaction was not restricted to the surface layers but, at sufficiently high ozone concentrations, occurred throughout the film. The rate constant derived for the O3-NPM reaction is 1 × 10-18 cm3⋅s-1, and the diffusion coefficient of ozone in the thin film is 9 × 10-10 cm2⋅s-1 These findings highlight the unique chemistry of multifunctional nitroenamines and demonstrate that known chemical mechanisms for individual moieties in such compounds cannot be extrapolated from simple alkenes. This is critical for guiding assessments of the environmental fates and impacts of pesticides and pharmaceuticals, and for providing guidance in designing better future alternatives

Within-city spatial variations in long-term average outdoor oxidant gas concentrations and cardiovascular mortality: Effect modification by oxidative potential in the Canadian Census Health and Environment Cohort.

UNLABELLED: Health effects of oxidant gases may be enhanced by components of particulate air pollution that contribute to oxidative stress. Our aim was to examine if within-city spatial variations in the oxidative potential of outdoor fine particulate air pollution (PM2.5) modify relationships between oxidant gases and cardiovascular mortality. METHODS: We conducted a retrospective cohort study of participants in the Canadian Census Health and Environment Cohort who lived in Toronto or Montreal, Canada, from 2002 to 2015. Cox proportional hazards models were used to estimate associations between outdoor concentrations of oxidant gases (Ox, a redox-weighted average of nitrogen dioxide and ozone) and cardiovascular deaths. Analyses were performed across strata of two measures of PM2.5 oxidative potential and reactive oxygen species concentrations (ROS) adjusting for relevant confounding factors. RESULTS: PM2.5 mass concentration showed little within-city variability, but PM2.5 oxidative potential and ROS were more variable. Spatial variations in outdoor Ox were associated with an increased risk of cardiovascular mortality [HR per 5 ppb = 1.028, 95% confidence interval (CI): 1.001, 1.055]. The effect of Ox on cardiovascular mortality was stronger above the median of each measure of PM2.5 oxidative potential and ROS (e.g., above the median of glutathione-based oxidative potential: HR = 1.045, 95% CI: 1.009, 1.081; below median: HR = 1.000, 95% CI: 0.960, 1.043). CONCLUSION: Within-city spatial variations in PM2.5 oxidative potential may modify long-term cardiovascular health impacts of Ox. Regions with elevated Ox and PM2.5 oxidative potential may be priority areas for interventions to decrease the population health impacts of outdoor air pollution

Multiphase reactivity of polycyclic aromatic hydrocarbons is driven by phase separation and diffusion limitations.

Benzo[a]pyrene (BaP), a key polycyclic aromatic hydrocarbon (PAH) often associated with soot particles coated by organic compounds, is a known carcinogen and mutagen. When mixed with organics, the kinetics and mechanisms of chemical transformations of BaP by ozone in indoor and outdoor environments are still not fully elucidated. Using direct analysis in real-time mass spectrometry (DART-MS), kinetics studies of the ozonolysis of BaP in thin films exhibited fast initial loss of BaP followed by a slower decay at long exposure times. Kinetic multilayer modeling demonstrates that the slow decay of BaP over long times can be simulated if there is slow diffusion of BaP from the film interior to the surface, resolving long-standing unresolved observations of incomplete PAH decay upon prolonged ozone exposure. Phase separation drives the slow diffusion time scales in multicomponent systems. Specifically, thermodynamic modeling predicts that BaP phase separates from secondary organic aerosol material so that the BaP-rich layer at the surface shields the inner BaP from ozone. Also, BaP is miscible with organic oils such as squalane, linoleic acid, and cooking oil, but its oxidation products are virtually immiscible, resulting in the formation of a viscous surface crust that hinders diffusion of BaP from the film interior to the surface. These findings imply that phase separation and slow diffusion significantly prolong the chemical lifetime of PAHs, affecting long-range transport of PAHs in the atmosphere and their fates in indoor environments

Photoenhanced Radical Formation in Aqueous Mixtures of Levoglucosan and Benzoquinone: Implications to Photochemical Aging of Biomass-Burning Organic Aerosols.

The photochemical aging of biomass-burning organic aerosols (BBOAs) by exposure to sunlight changes the chemical composition over its atmospheric lifetime, affecting the toxicological and climate-relevant properties of BBOA particles. This study used electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping agent, 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO), high-resolution mass spectrometry, and kinetic modeling to study the photosensitized formation of reactive oxygen species (ROS) and free radicals in mixtures of benzoquinone and levoglucosan, known BBOA tracer molecules. EPR analysis of irradiated benzoquinone solutions showed dominant formation of hydroxyl radicals (•OH), which are known products of reaction of triplet-state benzoquinone with water, also yielding semiquinone radicals. In addition, hydrogen radicals (H•) were also observed, which were not detected in previous studies. They were most likely generated by photochemical decomposition of semiquinone radicals. The irradiation of mixtures of benzoquinone and levoglucosan led to substantial formation of carbon- and oxygen-centered organic radicals, which became prominent in mixtures with a higher fraction of levoglucosan. High-resolution mass spectrometry permitted direct observation of BMPO-radical adducts and demonstrated the formation of •OH, semiquinone radicals, and organic radicals derived from oxidation of benzoquinone and levoglucosan. Mass spectrometry also detected superoxide radical adducts (BMPO-OOH) that did not appear in the EPR spectra. Kinetic modeling of the processes in the irradiated mixtures successfully reproduced the time evolution of the observed formation of the BMPO adducts of •OH and H• observed with EPR. The model was then applied to describe photochemical processes that would occur in mixtures of benzoquinone and levoglucosan in the absence of BMPO, predicting the generation of HO2• due to the reaction of H• with dissolved oxygen. These results imply that photoirradiation of aerosols containing photosensitizers induces ROS formation and secondary radical chemistry to drive photochemical aging of BBOA in the atmosphere