Browsing by Subject "GAS-PHASE OZONOLYSIS"

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  • Berndt, Torsten; Mender, Bernhard; Scholz, Wiebke; Fischer, Lukas; Herrmann, Hartmut; Kulmala, Markku; Hansel, Armin (2018)
    alpha-Pinene (C10H16) represents one of the most important biogenic emissions in the atmosphere. Its oxidation products can significantly contribute to the secondary organic aerosol (SOA) formation. Here, we report on the formation mechanism of C-19 and C-20 accretion products from alpha-pinene oxidation, which are believed to be efficient SOA precursors. Measurements have been performed in a free-jet flow system. Detection of RO2 radicals and accretion products was carried out by recent mass spectrometric techniques using different ionization schemes. Observed C-10-RO2 radicals from alpha-pinene ozonolysis were O,O-C10H15(O-2)(x)O-2 with x = 0, 1, 2, 3 and from the OH radical reaction HO-C10H16(O-2)(alpha)O-2 with alpha = 0, 1, 2. All detected C 20 accretion products can be explained via the accretion reaction RO2 + R'O-2 -> ROOR' + O-2 starting from the measured C-10-RO2 radicals. We speculate that C-19 accretion products are formed in an analogous way assuming CH2O elimination. Addition of isoprene (C5H8), producing C-5-RO2 radicals, leads to C-15 accretion products formed via cross-reactions with C-10-RO2 radicals. This process is competing with the formation of C-19/C-20 products from the pure alpha-pinene oxidation. A similar behavior has been observed for ethylene additives that form C-12 accretion products. In the atmosphere, a complex accretion product spectrum from self- and cross-reactions of available RO2 radicals can be expected. Modeling atmospheric conditions revealed that C-19/C-20 product formation is only reduced by a factor of 1.2 or 3.6 in isoprene-dominated environments assuming a 2- or 15-fold isoprene concentration over alpha-pinene, respectively, as present in different forested areas.
  • Berndt, Torsten; Scholz, Wiebke; Mentler, Bernhard; Fischer, Lukas; Herrmann, Hartmut; Kulmala, Markku; Hansel, Armin (2018)
    Hydrocarbons are emitted into the Earth's atmosphere in very large quantities by human and biogenic activities. Their atmospheric oxidation processes almost exclusively yield RO2 radicals as reactive intermediates whose atmospheric fate is not yet fully unraveled. Herein, we show that gas-phase reactions of two RO2 radicals produce accretion products composed of the carbon backbone of both reactants. The rates for accretion product formation are very high for RO2 radicals bearing functional groups, competing with those of the corresponding reactions with NO and HO2. This pathway, which has not yet been considered in the modelling of atmospheric processes, can be important, or even dominant, for the fate of RO2 radicals in all areas of the atmosphere. Moreover, the vapor pressure of the formed accretion products can be remarkably low, characterizing them as an effective source for the secondary organic aerosol.
  • Iyer, Siddharth; He, Xucheng; Hyttinen, Noora; Kurten, Theo; Rissanen, Matti P. (2017)
    The HO2 radical is an important atmospheric molecule that can potentially influence the termination of autoxidation processes of volatile organic compounds (VOCs) that lead to the formation of highly oxygenated multifunctional compounds (HOMs). In this work, we demonstrate the direct detection of the HO2 radical using an iodide-based chemical ionization mass spectrometer (iodide-CIMS). Expanding on the previously established correlation between molecule-iodide binding enthalpy and iodide-CIMS instrument sensitivity, the experimental detection of the HO2 radical was preceded by the quantum chemical calculation of the HO2*I- cluster (PBE/aug-cc-pVTZ-PP level), which showed a reasonably strong binding enthalpy of 21.60 kcal/mol. Cyclohexene ozonolysis intermediates and closed-shell products were next detected by the iodide-CIMS. The ozone-initiated cyclohexene oxidation mechanism was perturbed by the introduction of the HO2 radical, leading to the formation of closed-shell hydroperoxides. The experimental investigation once again followed the initial computational molecule-iodide binding enthalpy calculations. The quantum chemical calculations were performed at the PBE/aug-cc-pVTZ-PP level for radicals and DLPNO-CCSD(T)/def2-QZVPP//PBE/aug-cc-pVTZ-PP level for the closed-shell products. A comparison between the iodide-CIMS and nitrate-CIMS spectra with identical measurement steps revealed that the iodide-CIMS was able to detect the low-oxidized (O/C ratio 0.5 and 0.66) cyclohexene ozonolysis monomer products more efficiently than nitrate-CIMS. Higher-oxidized monomers (O/C ratio 1 to 1.5) were detected equally well by both methods. An investigation of dimers showed that both iodide- and nitrate-CIMS were able to detect the dimer compositions possibly formed from reactions between the peroxy radical monomers considered in this study. Additionally, iodide-CIMS detected organic ions that were formed by a previously suggested mechanism of dehydroxylation of peroxy acids (and deoxygenation of acyl peroxy radicals) by H2O*I- clusters. These mechanisms were computationally verified.
  • Hyttinen, Noora; Rissanen, Matti P.; Kurten, Theo (2017)
    During the past few years nitrate chemical ionization has been used to detect highly oxidized products from OH-and O-3-initiated alkene autoxidation. These have been speculated to play a significant role in atmospheric aerosol formation. As less oxidized autoxidation products have not been detected using nitrate chemical ionization, and the absolute concentrations of the highly oxidized species are as yet unknown, other reagent ions, such as acetate, are needed both to verify the detection efficiency of nitrate chemical ionization and to measure the less oxidized compounds. Here we compare the formation free energies of the acetate and nitrate clusters of several atmospherically relevant RO2 intermediates and products derived from cyclohexene ozonolysis, calculated at the omega B97xD/aug-cc-pVTZ level of theory. We found that, for the molecules with one hydrogen bonding peroxy acid group, the binding with nitrate is on average 7.5 kcal/mol weaker than with acetate and the binding is on average 10.5 kcal/mol weaker for molecules with two hydrogen bonding peroxy acid groups. We also calculated the deprotonation energies of the RO2 intermediates and the closed-shell products and found that acetate is able to deprotonate almost all of these molecules, while deprotonation with nitrate is (as expected for the conjugate base of a strong acid) not favorable.
  • Eskola, Arkke J.; Döntgen, Malte; Rotavera, Brandon; Caravan, Rebecca L.; Welz, Oliver; Savee, John D.; Osborn, David L.; Shallcross, Dudley E.; Percival, Carl J.; Taatjes, Craig A. (2018)
    Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-alpha (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH(2)l(2) in the presence of excess O-2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 +/- 0.4) x 10(-13) cm(3) s(-1) and k(CH2OO + MACR) = (4.4 +/- 1.0) x 10(-13) cm(3) s(-1), where the stated +/- 2 sigma uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) <2 x 10(-16) cm(3) s(-1). For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) <2 x 10(-14) cm(3) s(-1) is obtained.
  • Novelli, Anna; Hens, Korbinian; Ernest, Cheryl Tatum; Martinez, Monica; Noelscher, Anke C.; Sinha, Vinayak; Paasonen, Pauli; Petäjä, Tuukka; Sipilä, Mikko; Elste, Thomas; Plass-Duelmer, Christian; Phillips, Gavin J.; Kubistin, Dagmar; Williams, Jonathan; Vereecken, Luc; Lelieveld, Jos; Harder, Hartwig (2017)
    We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of similar to 5.0 x 10(4) molecules cm(-3) (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.
  • Riva, Matthieu; Rantala, Pekka; Krechmer, Jordan E.; Peräkylä, Otso; Zhang, Yanjun; Heikkinen, Liine; Garmash, Olga; Yan, Chao; Kulmala, Markku; Worsnop, Douglas; Ehn, Mikael (2019)
    The impact of aerosols on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated products, generated from the gas-phase oxidation of volatile organic compounds (VOCs), to aerosol formation. Indeed, atmospheric gaseous chemical processes yield thousands of (highly) oxygenated species, spanning a wide range of chemical formulas, functional groups and, consequently, volatilities. While recent mass spectrometric developments have allowed extensive on-line detection of a myriad of oxygenated organic species, playing a central role in atmospheric chemistry, the detailed quantification and characterization of this diverse group of compounds remains extremely challenging. To address this challenge, we evaluated the capability of current state-of-the-art mass spectrometers equipped with different chemical ionization sources to detect the oxidation products formed from alpha-Pinene ozonolysis under various conditions. Five different mass spectrometers were deployed simultaneously for a chamber study. Two chemical ionization atmospheric pressure interface time-of-flight mass spectrometers (CI-APi-TOF) with nitrate and amine reagent ion chemistries and an iodide chemical ionization time-of-flight mass spectrometer (TOF-CIMS) were used. Additionally, a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF 8000) and a new "vocus" PTR-TOF were also deployed. In the current study, we compared around 1000 different compounds between each of the five instruments, with the aim of determining which oxygenated VOCs (OVOCs) the different methods were sensitive to and identifying regions where two or more instruments were able to detect species with similar molecular formulae. We utilized a large variability in conditions (including different VOCs, ozone, NOx and OH scavenger concentrations) in our newly constructed atmospheric simulation chamber for a comprehensive correlation analysis between all instruments. This analysis, combined with estimated concentrations for identified molecules in each instrument, yielded both expected and surprising results. As anticipated based on earlier studies, the PTR instruments were the only ones able to measure the precursor VOC, the iodide TOF-CIMS efficiently detected many semi-volatile organic compounds (SVOCs) with three to five oxygen atoms, and the nitrate CI-APi-TOF was mainly sensitive to highly oxygenated organic (O > 5) molecules (HOMs). In addition, the vocus showed good agreement with the iodide TOF-CIMS for the SVOC, including a range of organonitrates. The amine CI-APi-TOF agreed well with the nitrate CI-APi-TOF for HOM dimers. However, the loadings in our experiments caused the amine reagent ion to be considerably depleted, causing nonlinear responses for monomers. This study explores and highlights both benefits and limitations of currently available chemical ionization mass spectrometry instrumentation for characterizing the wide variety of OVOCs in the atmosphere. While specifically shown for the case of alpha-Pinene ozonolysis, we expect our general findings to also be valid for a wide range of other VOC-oxidant systems. As discussed in this study, no single instrument configuration can be deemed better or worse than the others, as the optimal instrument for a particular study ultimately depends on the specific target of the study.
  • Molteni, Ugo; Simon, Mario; Heinritzi, Martin; Hoyle, Christopher R.; Bernhammer, Anne-Kathrin; Bianchi, Federico; Breitenlechner, Martin; Brilke, Sophia; Dias, António; Duplissy, Jonathan; Frege, Carla; Gordon, Hamish; Heyn, Claudia; Jokinen, Tuija; Kürten, Andreas; Lehtipalo, Katrianne; Makhmutov, Vladimir; Petäjä, Tuukka; Pieber, Simone M.; Praplan, Arnaud P.; Schobesberger, Siegfried; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Wagner, Andrea C.; Wagner, Robert; Williamson, Christina; Yan, Chao; Baltensperger, Urs; Curtius, Joachim; Donahue, Neil M.; Hansel, Armin; Kirkby, Jasper; Kulmala, Markku; Worsnop, Douglas R.; Dommen, Josef (2019)
    Terpenes are emitted by vegetation, and their oxidation in the atmosphere is an important source of secondary organic aerosol (SOA). A part of this oxidation can proceed through an autoxidation process, yielding highly oxygenated organic molecules (HOMs) with low saturation vapor pressure. They can therefore contribute, even in the absence of sulfuric acid, to new particle formation (NPF). The understanding of the autoxidation mechanism and its kinetics is still far from complete. Here, we present a mechanistic and kinetic analysis of mass spectrometry data from α-pinene (AP) ozonolysis experiments performed during the CLOUD 8 campaign at CERN. We grouped HOMs in classes according to their identified chemical composition and investigated the relative changes of these groups and their components as a function of the reagent concentration. We determined reaction rate constants for the different HOM peroxy radical reaction pathways. The accretion reaction between HOM peroxy radicals was found to be extremely fast. We developed a pseudo-mechanism for HOM formation and added it to the AP oxidation scheme of the Master Chemical Mechanism (MCM). With this extended model, the observed concentrations and trends in HOM formation were successfully simulated.
  • Ehn, Mikael; Berndt, Torsten; Wildt, Juergen; Mentel, Thomas (2017)
    Recent advances in chemical ionization mass spectrometry have allowed the detection of a new group of compounds termed highly oxygenated molecules (HOM). These are atmospheric oxidation products of volatile organic compounds (VOC) retaining most of their carbon backbone, and with O/C ratios around unity. Owing to their surprisingly high yields and low vapor pressures, the importance of HOM for aerosol formation has been easy to verify. However, the opposite can be said concerning the exact formation pathways of HOM from major aerosol precursor VOC. While the role of peroxy radical autoxidation, i.e., consecutive intramolecular H-shifts followed by O-2 addition, has been recognized, the detailed formation mechanisms remain highly uncertain. A primary reason is that the autoxidation process occurs on sub-second timescales and is extremely sensitive to environmental conditions like gas composition, temperature, and pressure. This, in turn, poses a great challenge for chemical kinetics studies to be able to mimic the relevant atmospheric reaction pathways, while simultaneously using conditions suitable for studying the short-lived radical intermediates. In this perspective, we define six specific challenges for this community to directly observe the initial steps of atmospherically relevant autoxidation reactions and thereby facilitate vital improvements in the understanding of VOC degradation and organic aerosol formation. (C) 2017 Wiley Periodicals, Inc.
  • Sarnela, Nina; Jokinen, Tuija; Duplissy, Jonathan; Yan, Chao; Nieminen, Tuomo; Ehn, Mikael; Schobesberger, Siegfried; Heinritzi, Martin; Ehrhart, Sebastian; Lehtipalo, Katrianne; Tröstl, Jasmin; Simon, Mario; Kürten, Andreas; Leiminger, Markus; Lawler, Michael J.; Rissanen, Matti P.; Bianchi, Federico; Praplan, Arnaud P.; Hakala, Jani; Amorim, Antonio; Gonin, Marc; Hansel, Armin; Kirkby, Jasper; Dommen, Josef; Curtius, Joachim; Smith, James N.; Petäjä, Tuukka; Worsnop, Douglas R.; Kulmala, Markku; Donahue, Neil M.; Sipilä, Mikko (2018)
    Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate alpha-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H-2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5-6.5% for HOM formation and 22-32% for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20-50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.
  • Rissanen, Matti P.; Mikkilä, Jyri; Iyer, Siddharth; Hakala, Jani (2019)
    A novel chemical ionization inlet named the Multi-scheme chemical IONization inlet (MION), Karsa Ltd., Helsinki, Finland) capable of fast switching between multiple reagent ion schemes is presented, and its performance is demonstrated by measuring several known oxidation products from much-studied cyclohexene and alpha-pinene ozonolysis systems by applying consecutive bromide (Br-) and nitrate (NO3-) chemical ionization. Experiments were performed in flow tube reactors under atmospheric pressure and room temperature (22 degrees C) utilizing an atmospheric pressure interface time-of-flight mass spectrometer (APi-ToF-MS, Tofwerk Ltd., Thun, Switzerland) as the detector. The application of complementary ion modes in probing the same steady-state reaction mixture enabled a far more complete picture of the detailed autoxidation process; the HO2 radical and the least-oxidized reaction products were retrieved with Br- ionization, whereas the highest-oxidized reaction products were detected in the NO3- mode, directly providing information on the first steps and on the ultimate endpoint of oxidation, respectively. While chemical ionization inlets with multiple reagent ion capabilities have been reported previously, an application in which the charging of the sample occurs at atmospheric pressure with practically no sample pretreatment, and with the potential to switch the reagent ion scheme within a second timescale, has not been introduced previously. Also, the ability of bromide ionization todetect highly oxygenated organic molecules (HOM) from atmospheric autoxidation reactions has not been demonstrated prior to this investigation.
  • Iyer, Siddharth; Rissanen, Matti P.; Kurtén, Theo (2019)
    Peroxy (RO2) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO2 + OH reaction for previously unexplored “R” structures (R = CH(O)CH2 and R = CH3C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R′O2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R′OOOR adducts, respectively. The former decomposes to RO + HO2 and R(O)OH + O2 products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R′OOOR adducts varied between 103 and 0.015 s–1 at 298 K and 1 atm. The most long-lived R′OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.
  • Drozd, Greg T.; Kurten, Theo; Donahue, Neil M.; Lester, Marsha I. (2017)
    We used the steady-state master equation to model unimolecular decay of the Criegee intermediate formed from ozonolysis of 2,3-dimethyl-2-butene (tetramethylethylene, TME). Our results show the relative importance and time scales for both the prompt and thermal unimolecular decay of the dimethyl-substituted Criegee intermediate, (CH3)(2)COO. Calculated reactive fluxes show the importance of quantum mechanical tunneling for both prompt and thermal decay to OH radical products. We constrained the initial energy distribution of chemically activated (CH3)(2)COO formed in TME ozonolysis by combining microcanonical rates k(E) measured experimentally under collision-free conditions and modeled using semiclassical transition-state theory (SCTST) with pressure dependent yields of stabilized Criegee intermediates measured with scavengers in flow-tube experiments. Thermal decay rates under atmospheric conditions k(298 K, 1 atm) increase by more than 1 order of magnitude when tunneling is included. Accounting for tunneling has important consequences for interpreting pressure dependent yields of stabilized Criegee intermediates, particularly with regard to the fraction of Criegee intermediates formed in the zero-pressure limit.