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1
Raofie, Farhad, Graydon Snider, and Parisa A. Ariya. "Reaction of gaseous mercury with molecular iodine, atomic iodine, and iodine oxide radicals — Kinetics, product studies, and atmospheric implications." Canadian Journal of Chemistry 86, no. 8 (August 1, 2008): 811–20. http://dx.doi.org/10.1139/v08-088.
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Mercury is present in the Earth’s atmosphere mainly in elemental form. The chemical transformation of mercury in the atmosphere may influence its bioaccumulation in the human food chain as well as its global cycling. We carried out the first kinetic and product studies of the reactions of gaseous mercury with molecular iodine, atomic iodine, and iodine oxide radicals at tropospheric pressure (~740 Torr) and 296 ± 2 K in air and in N2 (1 Torr = 133.322 4 Pa; 0 °C = 273.15 K). Atomic iodine was formed using UV photolysis of CH2I2. IO radicals were formed by the UV photolysis of CH2I2 in the presence of ozone The reaction kinetics were studied using absolute rate techniques with gas chromatographic and mass spectroscopic detection (GC–MS). The measured rate coefficient for the reaction of Hg0 with I2 was ≤ (1.27 ± 0.58) × 10–19 cm3 molecule–1 s–1. The reaction products were analyzed in the gas phase from the suspended aerosols and from deposits on the walls of the reaction chambers using six complementary methods involving chemical ionization and electron impact mass spectrometry, GC–MS, a MALDI-TOF mass spectrometer, a cold vapor atomic fluorescence spectrometer (CVAFS), and a high-resolution transmission electron microscope (HRTEM) coupled to an energy dispersive spectrometer (EDS). The major reaction products identified were HgI2, HgO, and HgIO or HgOI. The implications of the results are discussed with regards to both the chemistry of atmospheric mercury and its potential implications in the biogeochemical cycling of mercury.Key words: mercury, molecular iodine, atomic iodine, iodine oxide radicals kinetics, product study, atmospheric chemistry.
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Campbell, Laurence, Dale L. Muccignat, and Michael J. Brunger. "Inclusion of Electron Interactions by Rate Equations in Chemical Models." Atoms 10, no. 2 (June 10, 2022): 62. http://dx.doi.org/10.3390/atoms10020062.
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The concept of treating subranges of the electron energy spectrum as species in chemical models is investigated. This is intended to facilitate simple modification of chemical models by incorporating the electron interactions as additional rate equations. It is anticipated that this embedding of fine details of the energy dependence of the electron interactions into rate equations will yield an improvement in computational efficiency compared to other methods. It will be applicable in situations where the electron density is low enough that the electron interactions with chemical species are significant compared to electron–electron interactions. A target application is the simulation of electron processes in the D-region of the Earth’s atmosphere, but it is anticipated that the method would be useful in other areas, including enhancement of Monte Carlo simulation of electron–liquid interactions and simulations of chemical reactions and radical generation induced by electrons and positrons in biomolecular systems. The aim here is to investigate the accuracy and practicality of the method. In particular, energy must be conserved, while the number of subranges should be small to reduce computation time and their distribution should be logarithmic in order to represent processes over a wide range of electron energies. The method is applied here to the interaction by inelastic and superelastic collisions of electrons with a gas of molecules with only one excited vibrational level. While this is unphysical, it allows the method to be validated by checking for accuracy, energy conservation, maintenance of equilibrium and evolution of a Maxwellian electron spectrum.
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Grankin, Dmitry, Irina Mironova, Galina Bazilevskaya, Eugene Rozanov, and Tatiana Egorova. "Atmospheric Response to EEP during Geomagnetic Disturbances." Atmosphere 14, no. 2 (January 30, 2023): 273. http://dx.doi.org/10.3390/atmos14020273.
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Energetic electron precipitation (EEP) is associated with solar activity and space weather and plays an important role in the Earth’s polar atmosphere. Energetic electrons from the radiation belt precipitate into the atmosphere during geomagnetic disturbances and cause additional ionization rates in the polar middle atmosphere. These induced atmospheric ionization rates lead to the formation of radicals in ion-molecular reactions at the heights of the mesosphere and upper stratosphere with the formation of reactive compounds of odd nitrogen NOy and odd hydrogen HOx groups. These compounds are involved in catalytic reactions that destroy the ozone. In this paper, we present the calculation of atmospheric ionization rates during geomagnetic disturbances using reconstructed spectra of electron precipitation from balloon observations; estimation of ozone destruction during precipitation events using one-dimensional photochemical radiation-convective models, taking into account both parameterization and ion chemistry; as well as provide an estimation of electron density during these periods.
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Keßel, Stephan, David Cabrera-Perez, Abraham Horowitz, Patrick R. Veres, Rolf Sander, Domenico Taraborrelli, Maria Tucceri, et al. "Atmospheric chemistry, sources and sinks of carbon suboxide, C<sub>3</sub>O<sub>2</sub>." Atmospheric Chemistry and Physics 17, no. 14 (July 20, 2017): 8789–804. http://dx.doi.org/10.5194/acp-17-8789-2017.
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Abstract. Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere are largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C3O2. Rate coefficients for the reactions of C3O2 with OH radicals and ozone were determined as kOH = (2.6 ± 0.5) × 10−12 cm3 molecule−1 s−1 at 295 K (independent of pressure between ∼ 25 and 1000 mbar) and kO3 < 1.5 × 10−21 cm3 molecule−1 s−1 at 295 K. A theoretical study on the mechanisms of these reactions indicates that the sole products are CO and CO2, as observed experimentally. The UV absorption spectrum and the interaction of C3O2 with water (Henry's law solubility and hydrolysis rate constant) were also investigated, enabling its photodissociation lifetime and hydrolysis rates, respectively, to be assessed. The role of C3O2 in the atmosphere was examined using in situ measurements, an analysis of the atmospheric sources and sinks and simulation with the EMAC atmospheric chemistry–general circulation model. The results indicate sub-pptv levels at the Earth's surface, up to about 10 pptv in regions with relatively strong sources, e.g. influenced by biomass burning, and a mean lifetime of ∼ 3.2 days. These predictions carry considerable uncertainty, as more measurement data are needed to determine ambient concentrations and constrain the source strengths.
5
Sipilä, M., T. Jokinen, T. Berndt, S. Richters, R. Makkonen, N. M. Donahue, R. L. Mauldin III, et al. "Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids." Atmospheric Chemistry and Physics 14, no. 22 (November 19, 2014): 12143–53. http://dx.doi.org/10.5194/acp-14-12143-2014.
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Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO2, atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) /k(sCI + SO2), was determined at relative humidities of 10 and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecules cm−3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO2.
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Sipilä, M., T. Jokinen, T. Berndt, S. Richters, R. Makkonen, N. M. Donahue, R. L. Mauldin III, et al. "Reactivity of stabilized Criegee intermediates (sCI) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids." Atmospheric Chemistry and Physics Discussions 14, no. 2 (January 29, 2014): 3071–98. http://dx.doi.org/10.5194/acpd-14-3071-2014.
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Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of stabilized Criegee intermediates (sCI), atmospheric oxidation processes were thought to be dominated by few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulphuric acid (H2SO4). The measured sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for the ozonolysis of α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) / k(sCI + SO2), was determined at relative humidities of 10% and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecule cm−3 and nearly independent on the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding suggests that sCIs can play a role in the formation and loss of several atmospheric constituents besides SO2.
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Kang, Zhiqin, Zhijing Wang, Yang Lu, Ran Cao, Dongwei Huang, and Qiaorong Meng. "Investigation on the Effect of Atmosphere on the Pyrolysis Behavior and Oil Quality of Jimusar Oil Shale." Geofluids 2022 (March 2, 2022): 1–9. http://dx.doi.org/10.1155/2022/1408690.
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High-temperature H2O and CO2 can improve the pyrolysis behavior of oil shale. Therefore, in this paper, Jimusar oil shale was selected as the research object and the effect of the reaction atmosphere (H2O, CO2, and N2) on its pyrolysis behavior, pyrolysate distribution, and pyrolysis oil quality was fully compared and studied. The results showed that compared with the N2 atmosphere, the presence of H2O and CO2 both increased the weight loss and weight loss rate during pyrolysis of oil shale and the existence of H2O advanced the initial precipitation temperature of volatiles by 17°C. The comprehensive release characteristic indices of volatiles during pyrolysis of oil shale in the CO2 and H2O atmospheres increased by 49.34% and 114.35%, respectively, which significantly improved its pyrolysis reactivity. Both H2O and CO2 atmospheres improved the pyrolysis oil yield of oil shale, and the pyrolysis oil yield in the H2O atmosphere performed better than that in the CO2 atmosphere. Especially, the H2O atmosphere could increase the pyrolysis oil yield by 41.42%. The existence of CO2 prevented methyl radicals from accepting hydrogen radicals during pyrolysis and reduced the alkane yield, while CO2 participated in the addition reaction of alkane, which increased the alkene yield. High-temperature H2O provided more hydrogen source, which increased the alkane yield and inhibited the alkene formation. Both H2O and CO2 atmospheres promoted the cracking of polycyclic aromatics and increased the yield of small-molecular aromatics in the pyrolysis oil. During the pyrolysis process of oil shale, CO2 and H2O underwent reforming reaction with the heavy oil, which increased the light component fraction, thereby increasing the H/C ratio of pyrolysis oil. Thus, the existence of H2O and CO2 atmospheres improved the quality of pyrolysis oil and the effect of H2O was better than CO2. The H2O and CO2 atmosphere promoted the formation of a well-developed pore structure, which was conducive to mass and heat transfer during pyrolysis of oil shale.
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Romanias, Manolis N., and Thanh Lam Nguyen. "Evaluating the Atmospheric Loss of H2 by NO3 Radicals: A Theoretical Study." Atmosphere 13, no. 8 (August 18, 2022): 1313. http://dx.doi.org/10.3390/atmos13081313.
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Molecular hydrogen (H2) is now considered among the most prominent substitute for fossil fuels. The environmental impacts of a hydrogen economy have received more attention in the last years, but still, the knowledge is relatively poor. In this work, the reaction of H2 with NO3 radical (the dominant night-time detergent of the atmosphere) is studied for the first time using high-level composite G3B3 and modification of high accuracy extrapolated ab initio thermochemistry (mHEAT) methods in combination with statistical kinetics analysis using non-separable semi-classical transition state theory (SCTST). The reaction mechanism is characterized, and it is found to proceed as a direct H-abstraction process to yield HNO3 plus H atom. The reaction enthalpy is calculated to be 12.8 kJ mol−1, in excellent agreement with a benchmark active thermochemical tables (ATcT) value of 12.2 ± 0.3 kJ mol−1. The energy barrier of the title reaction was calculated to be 74.6 and 76.7 kJ mol−1 with G3B3 and mHEAT methods, respectively. The kinetics calculations with the non-separable SCTST theory give a modified-Arrhenius expression of k(T) = 10−15 × T0.7 × exp(−6120/T) (cm3 s−1) for T = 200–400 K and provide an upper limit value of 10−22 cm3 s−1 at 298 K for the reaction rate coefficient. Therefore, as compared to the main consumption pathway of H2 by OH radicals, the title reaction plays an unimportant role in H2 loss in the Earth’s atmosphere and is a negligible source of HNO3.
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Klein, Frieder, Jesse D. Tarnas, and Wolfgang Bach. "Abiotic Sources of Molecular Hydrogen on Earth." Elements 16, no. 1 (February 1, 2020): 19–24. http://dx.doi.org/10.2138/gselements.16.1.19.
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The capacity for molecular hydrogen (H2) to hydrogenate oxygen and carbon is critical to the origin of life and represents the basis for all known life-forms. Major sources of H2 that strictly involve nonbiological processes and inorganic reactants include (1) the reduction of water during the oxidation of iron in minerals, (2) water splitting due to radioactive decay, (3) degassing of magma at low pressures, and (4) the reaction of water with surface radicals during mechanical breaking of silicate rocks. None of these processes seem to significantly affect the current global atmospheric budget of H2, yet there is substantial H2 cycling in a wide range of Earth’s subsurface environments, with multifaceted implications for microbial ecosystems.
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Egorov, O. V., and Yu N. Kalugina. "Analysis of radial cross sections of the potential energy of the interacting O3-O2 complex." Izvestiya vysshikh uchebnykh zavedenii. Fizika, no. 3 (2022): 10–16. http://dx.doi.org/10.17223/00213411/65/3/10.
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The article presents preliminary results for the potential energy calculations of the interacting O3-O2 complex. The study of this complex is important for modeling the reaction of the ozone formation in the stratospheric layer of the Earth's atmosphere. The calculations were carried out from the first principles ( ab initio ) of the quantum theory using the explicitly correlated spin-unrestricted coupled clusters method [UCCSD(T)-F12a] in a combination with the correlation-consistent basis set [aug-cc-pVTZ] to describe the molecular orbitals. The obtained radial dependences at the selected angular orientations are discussed in comparison with the O3-N2 complex.
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Savee, John D., Ewa Papajak, Brandon Rotavera, Haifeng Huang, Arkke J. Eskola, Oliver Welz, Leonid Sheps, Craig A. Taatjes, Judit Zádor, and David L. Osborn. "Direct observation and kinetics of a hydroperoxyalkyl radical (QOOH)." Science 347, no. 6222 (February 5, 2015): 643–46. http://dx.doi.org/10.1126/science.aaa1495.
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Oxidation of organic compounds in combustion and in Earth’s troposphere is mediated by reactive species formed by the addition of molecular oxygen (O2) to organic radicals. Among the most crucial and elusive of these intermediates are hydroperoxyalkyl radicals, often denoted “QOOH.” These species and their reactions with O2 are responsible for the radical chain branching that sustains autoignition and are implicated in tropospheric autoxidation that can form low-volatility, highly oxygenated organic aerosol precursors. We report direct observation and kinetics measurements of a QOOH intermediate in the oxidation of 1,3-cycloheptadiene, a molecule that offers insight into both resonance-stabilized and nonstabilized radical intermediates. The results establish that resonance stabilization dramatically changes QOOH reactivity and, hence, that oxidation of unsaturated organics can produce exceptionally long-lived QOOH intermediates.
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Silaev, Michael M. "KINETIC EQUATIONS FOR RADICAL-CHAIN OXIDATION INVOLVING PROCESS-INHIBITING ALKYL (OR HYDRO)TETRAOXYL FREE RADICAL." American Journal of Applied Sciences 05, no. 06 (June 30, 2023): 29–48. http://dx.doi.org/10.37547/tajas/volume05issue06-07.
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The derivation of kinetic equations for the oxidation processes by the free-radical nonbranched-chain mechanism is shown. This derivation is based on the proposed reaction scheme for the initiated addition of free radicals to the multiple bond of the molecular oxygen includes the addition reaction of the peroxyl free radical to the oxygen molecule to form the tetraoxyl free radical. This reaction competes with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which – alkyl(or hydro)tetraoxyl – is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. The rate equations (containing one to three parameters to be determined directly) are deduced using the quasi-steady-state treatment. These kinetic equations were used to describe the γ-induced nonbranched-chain processes of free-radical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing various amounts of oxygen at 296 K. The ratios of rate constants of competing reactions and rate constants of addition reactions to the molecular oxygen are defined. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoinhibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. It is shown that a maximum in these curves arises from the competition between hydrocarbon (or hydrogen) molecules and dioxygen for reacting with the emerging peroxyl 1:1 adduct radical. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule gas-phase reactions is considered.
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Khasanov, U., SS Iskhakova, and DT Usmanov. "Examination of the effect of air atmosphere on heterogeneous reactions under surface ionization of psychotropic drug molecules." European Journal of Mass Spectrometry 26, no. 6 (December 2020): 409–18. http://dx.doi.org/10.1177/1469066720976016.
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The results of mass spectrometric studies of surface ionization of molecules of psychotropic drugs such as chlorpromazine, amitriptyline and medazepam in an air atmosphere have been presented. The channels of heterogeneous reactions occurring during the molecule adsorption on the hot surface of the thermoemitter from refractory metal oxides have been revealed, as well as the influence of air atmosphere on these reactions. A strong influence of the air atmosphere on the heterogeneous association reactions with the emission of [M + H]+ ions has been found. This ion line is the main in the mass spectra of all the substances under study instead of the characteristic main line in the surface ionization mass spectra obtained in vacuum. The effect of air on the reactions of dehydrogenation and dissociation of adsorbed molecules of organic compounds has been insignificant. In the surface ionization mass spectra of all the substances studied under atmospheric conditions the adduct cluster ions М⋅[М−R]+, М⋅[М−Н]+ and М⋅[М+Н]+ (where М is the molecule, R is the radical, H is the hydrogen atom) up to М⋅[М+Н]+⋅HCl. They are probably formed by adhesion of analyte molecules to the primary ions [М−R]+, [М−Н]+ and [М+Н]+. A comparative analysis has been also performed with the data obtained by chromato-mass spectrometry with electron ionization, as well as with the surface ionization data for these preparations obtained under high vacuum.
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Lee, H., T. Rahn, and H. L. Throop. "A novel source of atmospheric H<sub>2</sub>: abiotic degradation of organic material." Biogeosciences Discussions 9, no. 7 (July 18, 2012): 8641–62. http://dx.doi.org/10.5194/bgd-9-8641-2012.
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Abstract. Molecular hydrogen (H2) plays an important role in atmospheric chemistry by competing for reactions with the hydroxyl radical (·OH) and contributing to the production of H2O in the stratosphere, indirectly influencing stratospheric ozone concentrations. The dominant pathway for loss of H2 from the atmosphere is via microbially-mediated soil uptake although the magnitude of this loss is still regarded as highly uncertain. Recent studies have shown that abiotic processes such as photochemically mediated degradation (photodegradation) of organic material result in direct emissions of carbon (C) and nitrogen (N)-based trace gases as well as H2. This H2 production has important implications on source-sink dynamics of H2 at the soil-atmosphere interface and thus it is important to quantify its variability over a range of plant types and materials. Here, we show quantitative observations of H2 production and its temperature dependence during abiotic degradation of four plant litter types as well as pure cellulose and high lignin content woody material. A greater amount of H2 was produced in the absence of solar radiation than from photodegradation alone, verifying that low temperature thermal degradation of plant litter is a source of H2. In addition, we measured a significant release of H2 in the absence of O2 in addition to H2 release in the presence of O2. Our results suggest that abiotic release of H2 during organic matter is ubiquitous in terrestrial ecosystems. We propose that because these processes occur at the soil-atmosphere interface, they provide a previously unaccounted for proximal source of H2 for microbial uptake and confound interpretation of direct measurements of atmospheric uptake that are important for constraining the global H2 budget.
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Lee, H., T. Rahn, and H. L. Throop. "A novel source of atmospheric H<sub>2</sub>: abiotic degradation of organic material." Biogeosciences 9, no. 11 (November 12, 2012): 4411–19. http://dx.doi.org/10.5194/bg-9-4411-2012.
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Abstract. Molecular hydrogen (H2) plays an important role in atmospheric chemistry by competing for reactions with the hydroxyl radical (OH·) and contributing to the production of H2O in the stratosphere, indirectly influencing stratospheric ozone concentrations. The dominant pathway for loss of H2 from the atmosphere is via microbially-mediated soil uptake, although the magnitude of this loss is still regarded as highly uncertain. Recent studies have shown that abiotic processes such as photochemically mediated degradation (photodegradation) of organic material result in direct emissions of carbon (C) and nitrogen (N)-based trace gases as well as H2. This H2 production has important implications on source-sink dynamics of H2 at the soil-atmosphere interface and thus it is important to quantify its variability over a range of plant types and materials. Here, we show laboratory observations of H2 production and its temperature dependence during abiotic degradation of four plant litter types as well as pure cellulose and high lignin content woody material. A greater amount of H2 was produced in the absence of solar radiation than from photodegradation alone, verifying that low temperature thermal degradation of plant litter is a source of H2. In addition, we measured a significant release of H2 both in the presence and absence of O2. Our results suggest that abiotic release of H2 during organic matter degradation is ubiquitous in arid ecosystems and may also occur in other terrestrial ecosystems. We propose that because these processes occur at the soil-atmosphere interface, they provide a previously unrecognized proximal source of H2 for microbial uptake and confound interpretation of direct measurements of atmospheric uptake that are important for constraining the global H2 budget.
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Silaev, Michael M. "OXYGEN AS OXIDANT AND ANTIOXIDANT." EPH - International Journal of Applied Science 1, no. 2 (June 27, 2015): 21–32. http://dx.doi.org/10.53555/eijas.v1i2.3.
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New reaction scheme is suggested for the initiated nonbranched-chain addition of free radicals to the multiple bond of the molecular oxygen. The scheme includes the addition reaction of the peroxyl free radical to the oxygen molecule to form the tetraoxyl free radical. This reaction competes with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which (tetraoxyl) is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. Based on the proposed scheme rate equations (containing one to three parameters to be determined directly) are deduced using quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the γ-induced nonbranched-chain processes of the freeradical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing different amounts of oxygen at 296 K. The ratios of rate constants of competing reactions and rate constants of addition reactions to the molecular oxygen are defined. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoingibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule gas-phase reactions is considered.
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Zhang, Yu, Bo Wei, and Rongzhi Tang. "Theoretical Study on the Mechanisms, Kinetics, and Toxicity Evaluation of OH-Initiated Atmospheric Oxidation Reactions of Coniferyl Alcohol." Atmosphere 14, no. 6 (June 3, 2023): 976. http://dx.doi.org/10.3390/atmos14060976.
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In this paper, we investigated the mechanisms, kinetics, and toxicity evaluation of the OH-initiated reaction of coniferyl alcohol (4-(3-hydroxy-1-propenyl)-2-methoxyphenol) in the atmosphere using theoretical calculations. The initial reaction of coniferyl alcohol with OH radicals had two pathways, H-abstraction and OH-addition reactions. The total reaction rate constants were 2.32 × 10−9 cm3 molecule−1 s−1 (in gas-phase) and 9.44 × 109 s−1 M−1 (in liquid-phase) for the preliminary reactions of coniferyl alcohol with OH radicals at 298 K, respectively, and the half-lives of the total reaction (including all initial H-abstraction and OH-addition reactions) of coniferyl alcohol with OH radical in the atmosphere, urban and remote clouds were 8.3 × 10−2 h, 5.83 × 103 h and 9.27 × 102 h, respectively. The temperature had a strong and positive influence on the initial reaction rate constant. The branching ratios of H-abstraction and OH-addition reactions were 3.68% and 97.69%, respectively, making the OH-addition reactions become dominant reactions. The ecotoxicity evaluation revealed that the toxicity levels of coniferyl alcohol and its products were similar and non-toxic. However, all these products have developmental toxicity, with most of them having no mutagenicity. Therefore, further attention should be paid to the oxidation process and product toxicity evaluation of coniferyl alcohol in the atmosphere.
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Shepherd, Mark, Daniela Giordano, Cinzia Verde, and Robert K. Poole. "The Evolution of Nitric Oxide Function: From Reactivity in the Prebiotic Earth to Examples of Biological Roles and Therapeutic Applications." Antioxidants 11, no. 7 (June 22, 2022): 1222. http://dx.doi.org/10.3390/antiox11071222.
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Nitric oxide was once considered to be of marginal interest to the biological sciences and medicine; however, there is now wide recognition, but not yet a comprehensive understanding, of its functions and effects. NO is a reactive, toxic free radical with numerous biological targets, especially metal ions. However, NO and its reaction products also play key roles as reductant and oxidant in biological redox processes, in signal transduction, immunity and infection, as well as other roles. Consequently, it can be sensed, metabolized and modified in biological systems. Here, we present a brief overview of the chemistry and biology of NO—in particular, its origins in geological time and in contemporary biology, its toxic consequences and its critical biological functions. Given that NO, with its intrinsic reactivity, appeared in the early Earth’s atmosphere before the evolution of complex lifeforms, we speculate that the potential for toxicity preceded biological function. To examine this hypothesis, we consider the nature of non-biological and biological targets of NO, the evolution of biological mechanisms for NO detoxification, and how living organisms generate this multifunctional gas.
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Sulay, Rehin, Anandhu Krishnan, Balasubramoniam Muralikrishna, Sudheesh Devadas, Chandralekha Rajalakshmi, Jintumol Mathew, and Vibin Ipe Thomas. "A Quantum Chemical Investigation into the Molecular Mechanism of the Atmospheric Reactions of Chemi-Ions with Nitrogen and Nitrogen Oxides." Entropy 24, no. 9 (September 7, 2022): 1257. http://dx.doi.org/10.3390/e24091257.
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Nitrogen oxides and chemi-ions are atmospheric pollutants with considerable aeronomic interest. These toxicants can react with each other, producing various ionic species and highly reactive by-products that play a crucial role in aerosol clustering and mediate several important atmospheric reactions. Understanding the chemical reactivity of these pollutants can provide essential information for controlling their excess emission into the atmosphere. Computational modeling and electronic structure studies help in predicting the structure, reactivity, and thermodynamics of transient atmospheric chemical species and can guide experimental research by providing vital mechanistic insights and data. In the present study, a computational investigation into the mechanisms of the binary associative reactions between negative ions: O2− and O3− with NO, NO2, and N2 was conducted using the Coupled-Cluster Singles and Doubles (CCSD) theory. Five model reactions between N2/NOx with On− (n = 2, 3) were considered in this work. Our calculations revealed that reactions (2) and (5) are two sequential processes involving intermediates, and all others occur in a concerted manner by direct transitions from the reactants to the products, with no isolable intermediates proceeding via single non-planar transition states. Our study revealed that the higher activation barrier required for the formation of NO3− (2) as compared to NO2− (1) could be the reason for the excess formation of NO2− ions over NO3− ions in the atmosphere. Further, all the investigated reactions except (5) are found to be feasible at room temperature. The energy required to break N-N bonds in the N2 molecule justifies the high barrier for (5). The results obtained from the study are in close agreement with the available experimental data. Moreover, the data from the study can be utilized for the evaluation of experiments and model predictions pertaining to NOx oxidation and molecular modeling of the gas-phase chemistry of pollutants/nucleation precursors formed in the Earth’s atmosphere and aircraft engines.
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Henglein, A. "Sonolysis of Carbon Dioxide, Nitrous Oxide and Methane in Aqueous Solution." Zeitschrift für Naturforschung B 40, no. 1 (January 1, 1985): 100–107. http://dx.doi.org/10.1515/znb-1985-0119.
Full textAbstract:
Water was irradiated with ultrasonic waves under an argon atmosphere which contained small amounts of carbon dioxide, nitrous oxide or methane. The yield of the products was measured as a function of the composition of the gas atmosphere. Maximum yields were observed at a few per cent of the added polyatomic gas. No chemical effects occurred in the irradiation under an atmosphere of pure CO2 , N2O or CH4. It is concluded that the gas mixture in the tiny gas bubbles, in which the chemical effects are brought about, is not in Henry’s equilibrium with the aqueous gas solution.The main product of the sonolysis of CO2 is CO, a small amount of formic acid also being formed. The sonolysis is explained by both the attack of H atoms from the sonolysis of water and direct decomposition of CO2 due to the high temperatures existing in compressed gas bubbles. The main products of the sonolysis of N2O are nitrogen, nitrite and nitrate. N2O enhances the rate of various oxidations such as that of iodide, nitrite and propanol-2. In the methane containing solution, a lot of hydrogen is produced, the main oxidation products being ethane, ethylene, C3- and C4-hydrocarbons and carbon monoxide. A mechanism is postulated which involves both the attack on methane by radicals from the decomposition of water and thermal decomposition of methane. The local radical concentrations are so high that a methane molecule may undergo multiple radical attack. The similarity between sonolytic reactions and reactions occurring in flames is emphasized
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Aschmann, Sara M., Janet Arey, and Roger Atkinson. "Reaction of OH radicals with 5-hydroxy-2-pentanone: formation yield of 4-oxopentanal and its OH radical reaction rate constant." Environmental Chemistry 10, no. 3 (2013): 145. http://dx.doi.org/10.1071/en12146.
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Environmental context Alkanes, major constituents of vehicle exhausts, are emitted to the atmosphere where they react, chiefly by gas-phase reactions with the hydroxyl radical, to form products which can also react further. In laboratory experiments, we studied the further reactions of a model first-generation alkane reaction product. Understanding alkane reaction chains is important because the toxicity, secondary aerosol formation and other properties of vehicle emissions can change as new compounds are formed. Abstract 1,4-Hydroxycarbonyls are major products of the gas-phase reactions of alkanes with OH radicals, and in the atmosphere they will react with OH radicals or undergo acid-catalysed cyclisation with subsequent dehydration to form highly reactive dihydrofurans. 3-Oxobutanal (CH3C(O)CH2CHO) and 4-oxopentanal (CH3C(O)CH2CH2CHO) are first-generation products of the OH radical-initiated reaction of 5-hydroxy-2-pentanone (CH3C(O)CH2CH2CH2OH). The behaviours of 3-oxobutanal and 4-oxopentanal have been monitored during OH+5-hydroxy-2-pentanone reactions carried out in the presence of NO, using solid phase microextraction fibres coated with O-(2,3,4,5,6,-pentafluorobenzyl)hydroxyl amine (PFBHA) for on-fibre derivatisation of carbonyl compounds and an annular denuder coated with XAD resin and further coated with PFBHA. The time-concentration data for 4-oxopentanal during OH+5-hydroxy-2-pentanone reactions were independent of relative humidity (0–50%), and were consistent with a rate constant for OH+4-oxopentanal of (1.2±0.5)×10–11cm3 molecule–1s–1 at 296±2K, a factor of 2 lower than both literature rate constants for other aldehydes and that estimated using a structure-reactivity approach. The molar formation yield for 4-oxopentanal from OH+5-hydroxy-2-pentanone in the presence of NO was determined to be 17±5%, consistent with predictions based on a structure-reactivity relationship and current knowledge of the subsequent reaction mechanisms.
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Guidry, Lily M., Courtney A. Poirier, Jordyn M. Ratliff, Ernest Antwi, Barbara Marchetti, and Tolga N. V. Karsili. "Modeling the Unimolecular Decay Dynamics of the Fluorinated Criegee Intermediate, CF3CHOO." Photochem 3, no. 3 (July 14, 2023): 327–35. http://dx.doi.org/10.3390/photochem3030020.
Full textAbstract:
When volatile alkenes are emitted into the atmosphere, they are rapidly removed by oxidizing agents such as hydroxyl radicals and ozone. The latter reaction is termed ozonolysis and is an important source of Criegee intermediates (CIs), i.e., carbonyl oxides, that are implicated in enhancing the oxidizing capacity of the troposphere. These CIs aid in the formation of lower volatility compounds that typically condense to form secondary organic aerosols. CIs have attracted vast attention over the past two decades. Despite this, the effect of their substitution on the ground and excited state chemistries of CIs is not well studied. Here, we extend our knowledge obtained from prior studies on CIs by CF3 substitution. The resulting CF3CHOO molecule is a CI that can be formed from the ozonolysis of hydrofluoroolefins (HFOs). Our results show that the ground state unimolecular decay should be less reactive and thus more persistent in the atmosphere than the non-fluorinated analog. The excited state dynamics, however, are predicted to occur on an ultrafast timescale. The results are discussed in the context of the ways in which our study could advance synthetic chemistry, as well as processes relevant to the atmosphere.
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Teng, Zhuochao, Xiaotong Wang, Mohammad Hassan Hadizadeh, Yanan Han, Xianwei Zhao, Qi Zhang, Hetong Wang, Ying Li, Fei Xu, and Yanhui Sun. "Theoretical Perspectives on the Gas-Phase Oxidation Mechanism and Kinetics of Carbazole Initiated by OH Radical in the Atmosphere." Atmosphere 13, no. 7 (July 18, 2022): 1129. http://dx.doi.org/10.3390/atmos13071129.
Full textAbstract:
Carbazole is one of the typical heterocyclic aromatic compounds (NSO-HETs) observed in polluted urban atmosphere, which has become a serious environmental concern. The most important atmospheric loss process of carbazole is the reaction with OH radical. The present work investigated the mechanism of OH-initiated atmospheric oxidation degradation of carbazole by using density functional theory (DFT) calculations at the M06-2X/6-311++G(3df,2p)//M06-2X/6-311+G(d,p) level. The rate constants were determined by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The lifetime of carbazole determined by OH was compared with other typical NSO-HETs. The theoretical results show that the degradation of carbazole initiated by OH radical includes four types of reactions: OH additions to “bend” C atoms, OH additions to “benzene ring” C atoms, H abstractions from C-H bonds and the H abstraction from N-H bond. The OH addition to C1 atom and the H abstraction from N-H bond are energetically favorable. The main oxidation products are hydroxycarbazole, dialdehyde, carbazolequinone, carbazole-ol, hydroxy-carbazole-one and hydroperoxyl-carbazole-one. The calculated overall rate constant of carbazole oxidation by OH radical is 6.52 × 10−12 cm3 molecule−1 s−1 and the atmospheric lifetime is 37.70 h under the condition of 298 K and 1 atm. The rate constant of carbazole determined by OH radical is similar with that of dibenzothiophene oxidation but lower than those of pyrrole, indole, dibenzofuran and fluorene. This work provides a theoretical investigation of the oxygenated mechanism of NSO-HETs in the atmosphere and should help to clarify their potential health risk for determining the reaction pathways and environmental influence of carbazole.
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Renard, P., F. Siekmann, A. Gandolfo, J. Socorro, G. Salque, S. Ravier, E. Quivet, et al. "Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen." Atmospheric Chemistry and Physics 13, no. 13 (July 8, 2013): 6473–91. http://dx.doi.org/10.5194/acp-13-6473-2013.
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Abstract. It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α,β-unsaturated carbonyl that can undergo radical oligomerization in the aerosol aqueous phase. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under various conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights in our experiments the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the dominance of oligomerization reactions after several minutes of reaction. These processes, together with the large range of initial concentrations investigated show the fundamental role that radical oligomerization processes likely play in polluted fogs and atmospheric aerosol.
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Zaytsev, Alexander, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch. "Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase." Atmospheric Measurement Techniques 14, no. 3 (March 31, 2021): 2501–13. http://dx.doi.org/10.5194/amt-14-2501-2021.
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Abstract. Short-lived highly reactive atmospheric species, such as organic peroxy radicals (RO2) and stabilized Criegee intermediates (SCIs), play an important role in controlling the oxidative removal and transformation of many natural and anthropogenic trace gases in the atmosphere. Direct speciated measurements of these components are extremely helpful for understanding their atmospheric fate and impact. We describe the development of an online method for measurements of SCIs and RO2 in laboratory experiments using chemical derivatization and spin trapping techniques combined with H3O+ and NH4+ chemical ionization mass spectrometry (CIMS). Using chemical derivatization agents with low proton affinity, such as electron-poor carbonyls, we scavenge all SCIs produced from a wide range of alkenes without depleting CIMS reagent ions. Comparison between our measurements and results from numeric modeling, using a modified version of the Master Chemical Mechanism, shows that the method can be used for the quantification of SCIs in laboratory experiments with a detection limit of 1.4×107 molecule cm−3 for an integration time of 30 s with the instrumentation used in this study. We show that spin traps are highly reactive towards atmospheric radicals and form stable adducts with them by studying the gas-phase kinetics of the reaction of spin traps with the hydroxyl radical (OH). We also demonstrate that spin trap adducts with SCIs and RO2 can be simultaneously probed and quantified under laboratory conditions with a detection limit of 1.6×108 molecule cm−3 for an integration time of 30 s for RO2 species with the instrumentation used in this study. Spin trapping prevents radical secondary reactions and cycling, ensuring that measurements are not biased by chemical interferences, and it can be implemented for detecting RO2 species in laboratory studies and potentially in the ambient atmosphere.
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Amedro, Damien, Arne J. C. Bunkan, Matias Berasategui, and John N. Crowley. "Kinetics of the OH + NO<sub>2</sub> reaction: rate coefficients (217–333 K, 16–1200 mbar) and fall-off parameters for N<sub>2</sub> and O<sub>2</sub> bath gases." Atmospheric Chemistry and Physics 19, no. 16 (August 23, 2019): 10643–57. http://dx.doi.org/10.5194/acp-19-10643-2019.
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Abstract. The radical terminating, termolecular reaction between OH and NO2 exerts great influence on the NOy∕NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor of 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis and laser-induced fluorescence over the pressure range 16–1200 mbar and temperature range 217–333 K in N2 bath gas, with experiments at 295 K (67–333 mbar) for O2. In situ measurement of NO2 using two optical absorption set-ups enabled generation of highly precise, accurate rate coefficients in the fall-off pressure range, appropriate for atmospheric conditions. We found, in agreement with previous work, that O2 bath gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6×10-30 cm6 molecule−2 s−1, k0(O2) = 2.0×10-30 cm6 molecule−2 s−1, m=3.6, k∞=6.3×10-11 cm3 molecule−1 s−1, and Fc=0.39 and compare our results to previous studies in N2 and O2 bath gases.
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Renard, P., F. Siekmann, A. Gandolfo, J. Socorro, G. Salque, S. Ravier, E. Quivet, et al. "Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen." Atmospheric Chemistry and Physics Discussions 13, no. 1 (January 28, 2013): 2913–54. http://dx.doi.org/10.5194/acpd-13-2913-2013.
Full textAbstract:
Abstract. It is now accepted that one of the important pathways of Secondary Organic Aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the liquid phase chemical mechanisms leading to macromolecules are still not well understood. For α-dicarbonyl precursors, such as methylglyoxal and glyoxal, radical reactions through OH-oxidation produce oligomers, irreversibly and faster than accretion reactions. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α, β-unsaturated carbonyl that can undergo such reaction pathways in the aqueous phase and forms even high molecular weight oligomers. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under atmospheric relevant conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the supremacy of oligomerization reactions after several minutes of reaction. These processes, together with the large ranges of initial concentrations investigated (60–656 μM of dissolved O2 and 0.2–20 mM of MVK) show the fundamental role that O2 likely plays in atmospheric organic aerosol.
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Jacobs, M. I., W. J. Burke, and M. J. Elrod. "Kinetics of the reactions of isoprene-derived hydroxynitrates: gas phase epoxide formation and solution phase hydrolysis." Atmospheric Chemistry and Physics Discussions 14, no. 8 (May 13, 2014): 12121–65. http://dx.doi.org/10.5194/acpd-14-12121-2014.
Full textAbstract:
Abstract. Isoprene, the most abundant non-methane volatile organic compound (VOC) emitted into the atmosphere, is known to undergo gas phase oxidation to form eight different hydroxynitrate isomers in "high NOx" environments. These hydroxynitrates are known to affect the global and regional formation of ozone and secondary organic aerosol (SOA), as well as affect the distribution of nitrogen. In the present study, we have synthesized three of the eight possible hydroxynitrates: 4-hydroxy-3-nitroxy isoprene (4,3-HNI) and E/Z-1-hydroxy-4-nitroxy isoprene (1,4-HNI). Oxidation of the 4,3-HNI isomer by the OH radical was monitored using a flow tube chemical ionization mass spectrometer (FT-CIMS), and its OH rate constant was determined to be (3.64 ± 0.41) × 10−11 cm3 molecule−1 s−1. The products of 4,3-HNI oxidation were monitored, and a mechanism to explain the products was developed. An isoprene epoxide (IEPOX) – a species important in SOA chemistry and thought to originate only from "low NOx" isoprene oxidation – was found as a minor, but significant product. Additionally, hydrolysis kinetics of the three synthesized isomers were monitored with NMR. The bulk, neutral solution hydrolysis rate constants for 4,3-HNI and the 1,4-HNI isomers were (1.59±0.03 × 10−5 s−1 and (6.76 ± 0.09) × 10−3 s−1, respectively. The hydrolysis reactions of each isomer were found to be general acid-catalyzed. The reaction pathways, product yields and atmospheric implications for both the gas phase and aerosol-phase reactions are discussed.
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Saiz-Lopez, Alfonso, John M. C. Plane, Carlos A. Cuevas, Anoop S. Mahajan, Jean-François Lamarque, and Douglas E. Kinnison. "Nighttime atmospheric chemistry of iodine." Atmospheric Chemistry and Physics 16, no. 24 (December 19, 2016): 15593–604. http://dx.doi.org/10.5194/acp-16-15593-2016.
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Abstract. Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I2 during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I2 could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO3+ HOI → IO + HNO3 is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T) = 2.7 × 10−12 (300 K/T)2.66 cm3 molecule−1 s−1. This reaction is included in two atmospheric models, along with the known reaction between I2 and NO3, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I2, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI + I2 and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO3 radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. The effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation.
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Jacobs, M. I., W. J. Burke, and M. J. Elrod. "Kinetics of the reactions of isoprene-derived hydroxynitrates: gas phase epoxide formation and solution phase hydrolysis." Atmospheric Chemistry and Physics 14, no. 17 (September 1, 2014): 8933–46. http://dx.doi.org/10.5194/acp-14-8933-2014.
Full textAbstract:
Abstract. Isoprene, the most abundant non-methane volatile organic compound (VOC) emitted into the atmosphere, is known to undergo gas phase oxidation to form eight different hydroxynitrate isomers in "high-NOx" environments. These hydroxynitrates are known to affect the global and regional formation of ozone and secondary organic aerosol (SOA), as well as affect the distribution of nitrogen. In the present study, we have synthesized three of the eight possible hydroxynitrates: 4-hydroxy-3-nitroxy isoprene (4,3-HNI) and E / Z-1-hydroxy-4-nitroxy isoprene (1,4-HNI). Oxidation of the 4,3-HNI isomer by the OH radical was monitored using a flow tube chemical ionization mass spectrometer (FT-CIMS), and its OH rate constant was determined to be (3.64 ± 0.41) × 10−11 cm3 molecule−1 s−1. The products of 4,3-HNI oxidation were monitored, and a mechanism to explain the products was developed. An isoprene epoxide (IEPOX) – a species important in SOA chemistry and thought to originate only from "low-NOx" isoprene oxidation – was found as a minor, but significant, product. Additionally, hydrolysis kinetics of the three synthesized isomers were monitored with nuclear magnetic resonance (NMR). The bulk, neutral solution hydrolysis rate constants for 4,3-HNI and the 1,4-HNI isomers were (1.59 ± 0.03) × 10−5 s−1 and (6.76 ± 0.09) × 10−3 s−1, respectively. The hydrolysis reactions of each isomer were found to be general acid-catalyzed. The reaction pathways, product yields and atmospheric implications for both the gas phase and aerosol phase reactions are discussed.
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Ferracci, Valerio, Ines Heimann, N. Luke Abraham, John A. Pyle, and Alexander T. Archibald. "Global modelling of the total OH reactivity: investigations on the “missing” OH sink and its atmospheric implications." Atmospheric Chemistry and Physics 18, no. 10 (May 24, 2018): 7109–29. http://dx.doi.org/10.5194/acp-18-7109-2018.
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Abstract. The hydroxyl radical (OH) plays a crucial role in the chemistry of the atmosphere as it initiates the removal of most trace gases. A number of field campaigns have observed the presence of a missing OH sink in a variety of regions across the planet. A comparison of direct measurements of the OH loss frequency, also known as total OH reactivity (kOH), with the sum of individual known OH sinks (obtained via the simultaneous detection of species such as volatile organic compounds and nitrogen oxides) indicates that, in some cases, up to 80 % of kOH is unaccounted for. In this work, the UM-UKCA chemistry-climate model was used to investigate the wider implications of the missing reactivity on the oxidising capacity of the atmosphere. Simulations of the present-day atmosphere were performed and the model was evaluated against an array of field measurements to verify that the known OH sinks were reproduced well, with a resulting good agreement found for most species. Following this, an additional sink was introduced to simulate the missing OH reactivity as an emission of a hypothetical molecule, X, which undergoes rapid reaction with OH. The magnitude and spatial distribution of this sink were underpinned by observations of the missing reactivity. Model runs showed that the missing reactivity accounted for on average 6 % of the total OH loss flux at the surface and up to 50 % in regions where emissions of the additional sink were high. The lifetime of the hydroxyl radical was reduced by 3 % in the boundary layer, whilst tropospheric methane lifetime increased by 2 % when the additional OH sink was included. As no OH recycling was introduced following the initial oxidation of X, these results can be interpreted as an upper limit of the effects of the missing reactivity on the oxidising capacity of the troposphere. The UM-UKCA simulations also allowed us to establish the atmospheric implications of the newly characterised reactions of peroxy radicals (RO2) with OH. Whilst the effects of this chemistry on kOH were minor, the reaction of the simplest peroxy radical, CH3O2, with OH was found to be a major sink for CH3O2 and source of HO2 over remote regions at the surface and in the free troposphere. Inclusion of this reaction in the model increased tropospheric methane lifetime by up to 3 %, depending on its product branching. Simulations based on the latest kinetic and product information showed that this reaction cannot reconcile models with observations of atmospheric methanol, in contrast to recent suggestions.
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Yu, Lu, Jeremy Smith, Alexander Laskin, Katheryn M. George, Cort Anastasio, Julia Laskin, Ann M. Dillner, and Qi Zhang. "Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation." Atmospheric Chemistry and Physics 16, no. 7 (April 13, 2016): 4511–27. http://dx.doi.org/10.5194/acp-16-4511-2016.
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Abstract. Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10−20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.
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Ferus, M., F. Pietrucci, A. M. Saitta, O. Ivanek, A. Knizek, P. Kubelík, M. Krus, et al. "Prebiotic synthesis initiated in formaldehyde by laser plasma simulating high-velocity impacts." Astronomy & Astrophysics 626 (June 2019): A52. http://dx.doi.org/10.1051/0004-6361/201935435.
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Context. It is well known that hydrogen cyanide and formamide can universally be considered as key molecules in prebiotic synthesis. Despite the fact that formamide has been detected in interplanetary and interstellar environments, other prebiotic species are far more abundant, including, for example, formaldehyde. However, several results indicate that formamide can play the role of important intermediate as well as that of a feedstock molecule in chemical abiogenesis. Diverse recently proposed scenarios of the origins of the first biopolymers show that liquid formamide environments could have been crucial for the formation of nucleobases, nucleosides, and for phosphorylation reactions, which lead to nucleotides. Aims. Here we report on a wide exploration of the formaldehyde reaction network under plasma conditions mimicking an asteroid descent in an Earth-like atmosphere and its impact. Methods. Dielectric breakdown using a high-power kJ-class laser system (PALS – Prague Asterix Laser System) along with quantum mechanical, ab initio molecular dynamics, and enhanced sampling simulations have been employed in order to mimic an asteroid impact plasma. Results. Being more abundant than formamide both in interstellar and interplanetary environments, during the era of early and late heavy bombardment of Earth and other planets, formaldehyde might have been delivered on asteroids to young planets. In the presence of nitrogen-bearing species, this molecule has been reprocessed under plasma conditions mimicking the local environment of an impacting body. We show that plasma reprocessing of formaldehyde leads to the formation of several radical and molecular species along with formamide. Conclusion. All the canonical nucleobases, the simplest amino acid (i.e., glycine), and the sugar ribose, have been detected after treatment of formaldehyde and nitrogen gas with dielectric breakdown. Our results, supported by quantum mechanical and enhanced sampling simulations, show that formaldehyde – by producing inter alia formamide – may have had the role of starting substance in prebiotic synthesis.
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Yu, L., J. Smith, A. Laskin, K. M. George, C. Anastasio, J. Laskin, A. M. Dillner, and Q. Zhang. "Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation." Atmospheric Chemistry and Physics Discussions 15, no. 20 (October 30, 2015): 29673–704. http://dx.doi.org/10.5194/acpd-15-29673-2015.
Full textAbstract:
Abstract. Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C&ast;) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ∼ 2 h irradiation under midday, winter solstice sunlight in northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated open-ring molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures C&ast;) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C&ast; values is observed, varying from < 10-20 μg m-3 for functionalized phenolic oligomers to > 10 μg m-3 for small open-ring species. The detection of abundant extremely low volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.
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Heinritzi, Martin, Lubna Dada, Mario Simon, Dominik Stolzenburg, Andrea C. Wagner, Lukas Fischer, Lauri R. Ahonen, et al. "Molecular understanding of the suppression of new-particle formation by isoprene." Atmospheric Chemistry and Physics 20, no. 20 (October 20, 2020): 11809–21. http://dx.doi.org/10.5194/acp-20-11809-2020.
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Abstract. Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene (C10H16) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene (C5H8), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms – which drive particle nucleation and early growth – while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C20 and C15, respectively) are produced by termination reactions between pairs of peroxy radicals (RO2⚫) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene ∕ monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C15 dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical (OH⚫) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO2⚫ radicals that reduce C20 formation. RO2⚫ termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C20 yield, such as NO, HO2 and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.
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Surl, Luke, Tjarda Roberts, and Slimane Bekki. "Observation and modelling of ozone-destructive halogen chemistry in a passively degassing volcanic plume." Atmospheric Chemistry and Physics 21, no. 16 (August 19, 2021): 12413–41. http://dx.doi.org/10.5194/acp-21-12413-2021.
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Abstract. Volcanoes emit halogens into the atmosphere that undergo complex chemical cycling in plumes and cause destruction of ozone. We present a case study of the Mount Etna plume in the summer of 2012, when the volcano was passively degassing, using aircraft observations and numerical simulations with a new 3D model “WRF-Chem Volcano” (WCV), incorporating volcanic emissions and multi-phase halogen chemistry. Measurements of SO2 – an indicator of plume intensity – and ozone were made in the plume a few tens of kilometres from Etna, revealing a strong negative correlation between ozone and SO2 levels. From these observations, using SO2 as a tracer species, we estimate a mean in-plume ozone loss rate of 1.3×10−5 molecules of O3 per second per molecule of SO2. This value is similar to observation-based estimates reported very close to Etna's vents, indicating continual ozone loss in the plume up to at least tens of kilometres downwind. The WCV model is run with nested grids to simulate the plume close to the volcano at 1 km resolution. The focus is on the early evolution of passively degassing plumes aged less than 1 h and up to tens of kilometres downwind. The model is able to reproduce the so-called “bromine explosion”: the daytime conversion of HBr into bromine radicals that continuously cycle in the plume. These forms include the radical BrO, a species whose ratio with SO2 is commonly measured in volcanic plumes as an indicator of halogen ozone-destroying chemistry. The species BrO is produced in the ambient-temperature chemistry, with in-plume BrO / SO2 ratios on the order of 10−4 mol/mol, similar to those observed previously in Etna plumes. Wind speed and time of day are identified as non-linear controls on this ratio. Sensitivity simulations confirm the importance of near-vent radical products from high-temperature chemistry in initiating the ambient-temperature plume halogen cycling. Heterogeneous reactions that activate bromine also activate a small fraction of the emitted chlorine; the resulting production of chlorine radical Cl strongly enhances the methane oxidation and hence the formation of formaldehyde (HCHO) in the plume. Modelled rates of ozone depletion are found to be similar to those derived from aircraft observations. Ozone destruction in the model is controlled by the processes that recycle bromine, with about three-quarters of this recycling occurring via reactions between halogen oxide radicals. Through sensitivity simulations, a relationship between the magnitude of halogen emissions and ozone loss is established. Volcanic halogen cycling profoundly impacts the overall plume chemistry in the model, notably hydrogen oxide radicals (HOx), nitrogen oxides (NOx), sulfur, and mercury chemistry. In the model, it depletes HOx within the plume, increasing the lifetime of SO2 and hence slowing sulfate aerosol formation. Halogen chemistry also promotes the conversion of NOx into nitric acid (HNO3). This, along with the displacement of nitrate out of background aerosols in the plume, results in enhanced HNO3 levels and an almost total depletion of NOx in the plume. The halogen–mercury model scheme is simple but includes newly identified photo-reductions of mercury halides. With this set-up, the mercury oxidation is found to be slow and in near-balance with the photo-reduction of the plume. Overall, the model findings demonstrate that halogen chemistry has to be considered for a complete understanding of sulfur, HOx, reactive nitrogen, and mercury chemistry and of the formation of sulfate particles in volcanic plumes.
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Sand, Maria, Ragnhild Bieltvedt Skeie, Marit Sandstad, Srinath Krishnan, Gunnar Myhre, Hannah Bryant, Richard Derwent, et al. "A multi-model assessment of the Global Warming Potential of hydrogen." Communications Earth & Environment 4, no. 1 (June 7, 2023). http://dx.doi.org/10.1038/s43247-023-00857-8.
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AbstractWith increasing global interest in molecular hydrogen to replace fossil fuels, more attention is being paid to potential leakages of hydrogen into the atmosphere and its environmental consequences. Hydrogen is not directly a greenhouse gas, but its chemical reactions change the abundances of the greenhouse gases methane, ozone, and stratospheric water vapor, as well as aerosols. Here, we use a model ensemble of five global atmospheric chemistry models to estimate the 100-year time-horizon Global Warming Potential (GWP100) of hydrogen. We estimate a hydrogen GWP100 of 11.6 ± 2.8 (one standard deviation). The uncertainty range covers soil uptake, photochemical production of hydrogen, the lifetimes of hydrogen and methane, and the hydroxyl radical feedback on methane and hydrogen. The hydrogen-induced changes are robust across the different models. It will be important to keep hydrogen leakages at a minimum to accomplish the benefits of switching to a hydrogen economy.
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Douroudgari, Hamed, Maryam Seyed Sharifi, and Morteza Vahedpour. "Impact of a single water molecule on the atmospheric oxidation of thiophene by hydroperoxyl radical." Scientific Reports 12, no. 1 (November 8, 2022). http://dx.doi.org/10.1038/s41598-022-22831-8.
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AbstractWater as an important assistant can alter the reactivity of atmospheric species. This project is designed to investigate the impact of a single water molecule on the atmospheric reactions of aromatic compounds that have not been attended to comprehensively. In the first part, the atmospheric oxidation mechanisms of thiophene initiated by hydroperoxyl radical through a multiwell-multichannel potential energy surface were studied to have useful information about the chemistry of the considered reaction. It was verified that for the thiophene plus HO2 reaction, the addition mechanism is dominant the same as other aromatic compounds. Due to the importance of the subject and the presence of water molecules in the atmosphere with a high concentration that we know as relative humidity, and also the lack of insight into the influence of water on the reactions of aromatic compounds with active atmospheric species, herein, the effect of a single water molecule on the addition pathways of the title reaction is evaluated. In another word, this research explores how water can change the occurrence of reactions of aromatic compounds in the atmosphere. For this, the presence of one water molecule is simulated by higher-level calculations (BD(T) method) through the main interactions with the stationary points of the most probable pathways. The results show that the mechanism of the reaction with water is more complicated than the bare reaction due to the formation of the ring-like structures. Also, water molecule decreases the relative energies of all addition pathways. Moreover, atoms in molecule theory (AIM) along with the kinetic study by the transition state (TST) and the Rice–Ramsperger–Kassel–Marcus (RRKM) theories demonstrate that the overall interactions of a path determine how the rate of that path changes. In this regard, our results establish that the interactions of water with HO2 (thiophene) in the initial complex 1WHA (1WTA or 1WTB) are stronger (weaker) than the sum of its interactions in transition states. Also, for the water-assisted pathways, the ratio of the partition function of the transition state to the partition functions of the reactants is similar to the respective bare reaction. Therefore, the reaction rates of the bare pathways are more than the water-assisted paths that include the 1WHA complex and are less than the paths that involve the 1WTA and 1WTB complexes.
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Silaev, Michael M. ""Derivation of Kinetic Equations for Free-Radical Nonbranched-Chain Processes of Hydrocarbon and Hydrogen Oxidation"." International Journal of Innovative Research in Computer Science & Technology, January 22, 2022, 31–42. http://dx.doi.org/10.55524/ijircst.2022.10.1.7.
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The derivation of kinetic equations for the oxidation processes by the free-radical nonbranched-chain mechanism is shown. This derivation is based on the proposed reaction scheme for the initiated addition of free radicals to the multiple bond of the molecular oxygen includes the addition reaction of the peroxyl free radical to the oxygen molecule to form the tetraoxyl free radical. This reaction competes with chain propagation reactions through a reactive free radical. The chain evolution stage in this scheme involves a few of free radicals, one of which (tetraoxyl) is relatively low-reactive and inhibits the chain process by shortening of the kinetic chain length. The rate equations (containing one to three parameters to be determined directly) are deduced using the quasi-steady-state treatment. The kinetic description with use the obtained rate equations is applied to the γ-induced nonbranched-chain processes of the free-radical oxidation of liquid o-xylene at 373 K and hydrogen dissolved in water containing different amounts of dioxygen at 296 K. The ratios of rate constants of competing reactions and rate constants of addition reactions to the molecular oxygen are defined. In these processes the oxygen with the increase of its concentration begins to act as an oxidation autoinhibitor (or an antioxidant), and the rate of peroxide formation as a function of the dissolved oxygen concentration has a maximum. It is shown that a maximum in these curves arises from the competition between hydrocarbon (or hydrogen) molecules and dioxygen for reacting with the emerging peroxyl 1:1 adduct radical. From the energetic standpoint possible nonchain pathways of the free-radical oxidation of hydrogen and the routes of ozone decay via the reaction with the hydroxyl free radical in the upper atmosphere (including the addition yielding the hydrotetraoxyl free radical, which can be an intermediate in the sequence of conversions of biologically hazardous UV radiation energy) were examined. The energetics of the key radical-molecule gas-phase reactions is considered.
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Douroudgari, Hamed, Morteza Vahedpour, and Fahime Khouini. "Atmospheric reaction of hydrazine plus hydroxyl radical." Scientific Reports 11, no. 1 (June 24, 2021). http://dx.doi.org/10.1038/s41598-021-92563-8.
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AbstractUnderstanding the mechanism of hydrazine oxidation reaction by OH radical along with the rate constants of all possible pathways leads to explain the fate of hydrazine in the atmosphere. In this article, the comprehensive mechanisms and kinetics of the hydrazine plus hydroxyl radical reaction have been investigated theoretically at different temperatures and pressures. To achieve the main goals, a series of high levels of quantum chemical calculations have been widely implemented in reliable channels of the H-abstraction, SN2, and addition/elimination reactions. The energy profile of all pathways accompanied by the molecular properties of the involved stationary points has been characterized at the MP2, M06-2X, and CCSD(T)/CBS levels. To estimate accurate barrier energies of the H-abstraction channels, large numbers of the CCSD (T) calculations in conjunction with various augmented basis sets have been implemented. The direct dynamic calculations have been carried out using the validated M06-2X/maug-cc-pVTZ level, and also by the CCSD(T) (energies) + MP2 (partition functions) level. The pressure-dependent rate constants of the barrierless pathways have been investigated by the strong collision approach. Therefore, the main behaviors of the N2H4 + OH reaction have been explored according to the influences of temperature and pressure on the computed rate coefficients within the well-behaved theoretical frameworks of the TST, VTST, and RRKM theories. It has been found that the H-abstraction mechanism (to form N2H3) is dominant relative to the SN2 reaction and OH-addition to the N center of N2H4 moiety (to form H2NOH + NH2). The computed high pressure limit rate constant of the main reaction pathway, k(298.15) = 7.31 × 10–11 cm3 molecule−1 s−1, has an excellent agreement with the experimental value (k (298.15) = (6.50 ± 1.3) × 10–11 cm3 molecule−1 s−1) recommended by Vaghjiani. Also, the atmospheric lifetime of hydrazine degradation by OH radicals has been demonstrated to be 32.80 to 1161.11 h at the altitudes of 0–50 km. Finally, the disagreement in the calculated rate constants between the previous theoretical study and experimental results has been rectified.