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      NO 2 Suppression of Autoxidation–Inhibition of Gas-Phase Highly Oxidized Dimer Product Formation

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          Abstract

          Atmospheric autoxidation of volatile organic compounds (VOC) leads to prompt formation of highly oxidized multifunctional compounds (HOM) that have been found crucial in forming ambient secondary organic aerosol (SOA). As a radical chain reaction mediated by oxidized peroxy (RO 2) and alkoxy (RO) radical intermediates, the formation pathways can be intercepted by suitable reaction partners, preventing the production of the highest oxidized reaction products, and thus the formation of the most condensable material. Commonly, NO is expected to have a detrimental effect on RO 2 chemistry, and thus on autoxidation, whereas the influence of NO 2 is mostly neglected. Here it is shown by dedicated flow tube experiments, how high concentration of NO 2 suppresses cyclohexene ozonolysis initiated autoxidation chain reaction. Importantly, the addition of NO 2 ceases covalently bound dimer production, indicating their production involving acylperoxy radical (RC(O)OO•) intermediates. In related experiments NO was also shown to strongly suppress the highly oxidized product formation, but due to possibility for chain propagating reactions (as with RO 2 and HO 2 too), the suppression is not as absolute as with NO 2. Furthermore, it is shown how NO x reactions with oxidized peroxy radicals lead into indistinguishable product compositions, complicating mass spectral assignments in any RO 2 + NO x system. The present work was conducted with atmospheric pressure chemical ionization mass spectrometry (CIMS) as the detection method for the highly oxidized end-products and peroxy radical intermediates, under ambient conditions and at short few second reaction times. Specifically, the insight was gained by addition of a large amount of NO 2 (and NO) to the oxidation system, upon which acylperoxy radicals reacted in RC(O)O 2 + NO 2 → RC(O)O 2NO 2 reaction to form peroxyacylnitrates, consequently shutting down the oxidation sequence.

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          The role of low-volatility organic compounds in initial particle growth in the atmosphere

          Jasmin Tröstl, Wayne Chuang, Hamish Gordon … (2016)
          The growth of nucleated organic particles has been investigated in controlled laboratory experiments under atmospheric conditions; initial growth is driven by organic vapours of extremely low volatility, and accelerated by more abundant vapours of slightly higher volatility, leading to markedly different modelled concentrations of atmospheric cloud condensation nuclei when this growth mechanism is taken into account. Supplementary information The online version of this article (doi:10.1038/nature18271) contains supplementary material, which is available to authorized users. The effect of atmospheric aerosols on clouds and the radiative forcing of the climate system remains poorly understood. It is thought that nucleation of aerosol particles from atmospheric vapours rarely proceeds in the absence of sulfuric acid. Now two papers in this week’s Nature point to a previously unappreciated role for highly oxygenated molecules (HOMs) in promoting new particle formation and growth, essentially a mechanism that produces aerosols in the absence of pollution. Jasper Kirkby et al . show that aerosol particles can form as a result of ion-induced nucleation of HOMs in the absence of sulfuric acid under conditions relevant to the atmosphere in the CLOUD chamber at CERN. Jasmin Tröstl et al . examined the role of organic vapours in the initial growth of nucleated organic particles in the absence of sulfuric acid in the CERN CLOUD chamber under atmospheric conditions. They find that the organic vapours driving initial growth have extremely low volatilities. With increasing particle size, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility. Supplementary information The online version of this article (doi:10.1038/nature18271) contains supplementary material, which is available to authorized users. About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday 1 . Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres 2 , 3 . In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles 4 , thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth 5 , 6 , leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer 7 , 8 , 9 , 10 . Although recent studies 11 , 12 , 13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon 2 , and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory) 2 , 14 , has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown 15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10 −4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10 −4.5 to 10 −0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations. Supplementary information The online version of this article (doi:10.1038/nature18271) contains supplementary material, which is available to authorized users.
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            Evaluated Kinetic, Photochemical and Heterogeneous Data for Atmospheric Chemistry: Supplement V. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry

            R. Atkinson, D. Baulch, R. A. Cox … (1997)
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              Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

              Mikko Sipilä, Mikael Ehn, Tuija Jokinen … (2015)
              Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.
              Article 0 comments Cited 106 times – based on 0 reviews     Review now
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                Author and article information

                Journal
                Journal ID (nlm-ta): ACS Earth Space Chem
                Journal ID (iso-abbrev): ACS Earth Space Chem
                Journal ID (publisher-id): sp
                Journal ID (coden): aesccq
                Title: ACS Earth & Space Chemistry
                Publisher: American Chemical Society
                ISSN (Electronic): 2472-3452
                Publication date (Electronic): 12 October 2018
                Publication date (Print): 15 November 2018
                Volume: 2
                Issue: 11
                Pages: 1211-1219
                Affiliations
                [1]Institute for Atmospheric and Earth System Research (INAR), University of Helsinki , Helsinki, Finland
                Author notes
                Article
                DOI: 10.1021/acsearthspacechem.8b00123
                PMC ID: 6251564
                PubMed ID: 30488044
                SO-VID: b5528d4b-1ba8-4a03-8195-14c05c46463e
                Copyright © Copyright © 2018 American Chemical Society
                License:

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

                History
                Date received : 28 August 2018
                Date accepted : 12 October 2018
                Date revision received : 10 October 2018
                Categories
                Subject: Article
                Custom metadata
                document-id-old-9 sp8b00123
                document-id-new-14 sp-2018-00123p
                ccc-price

                Keywords: autoxidation,highly oxidized multifunctional compounds,highly oxygenated molecules,hom,acylperoxy radicals,dimers,nitrogen oxides,peroxyacylnitrate
                Data availability:
                Keywords: autoxidation, highly oxidized multifunctional compounds, highly oxygenated molecules, hom, acylperoxy radicals, dimers, nitrogen oxides, peroxyacylnitrate

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