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Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2)radicals play important roles in atmospheric chemistry. In the presence ofnitrogen oxides (NOx), reactions between OH and volatile organiccompounds (VOCs) can initiate a radical propagation cycle that leads to theproduction of ozone and secondary organic aerosols. Previous measurements ofthese radicals under low-NOx conditions in forested environmentscharacterized by emissions of biogenic VOCs, including isoprene andmonoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrationswere measured as part of the Program for Research on Oxidants:Photochemistry, Emissions, and Transport – Atmospheric Measurements ofOxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduousbroadleaf forest. Measurements of OH and HO2 were made by laser-inducedfluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques,and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements ofphotolysis frequencies, VOCs, NOx, O3, and meteorological datawere used to constrain a zero-dimensional box model utilizing either theRegional Atmospheric Chemical Mechanism (RACM2) or the Master ChemicalMechanism (MCM). Model simulations tested the influence of HOxregeneration reactions within the isoprene oxidation scheme from the LeuvenIsoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytimemaximum measurements by approximately 40 % for OH, 65 % for HO2,and more than a factor of 2 for XO2. Modeled XO2 mixing ratioswere also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals tothe model can partially explain the discrepancy between measurements andmodeled peroxy radical concentrations at night but cannot explain thedaytime discrepancies when OH reactivity is dominated by isoprene. Themodels also overestimated measured concentrations of isoprene-derivedhydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime,consistent with the model overestimation of peroxy radical concentrations.Constraining the model to the measured concentration of peroxy radicalsimproves the agreement with the measured ISOPOOH concentrations, suggestingthat the measured radical concentrations are more consistent with themeasured ISOPOOH concentrations. These results suggest that the models maybe missing an important daytime radical sink and could be overestimating therate of ozone and secondary product formation in this forest.

 

Abstract. Sea salt aerosols play an important role in the radiationbudget and atmospheric composition over the Arctic, where the climate israpidly changing. Previous observational studies have shown that Arctic sea ice leads are an important source of sea salt aerosols, and modeling efforts have also proposed blowing snow sublimation as a source. In this study,size-resolved atmospheric particle number concentrations and chemicalcomposition were measured at the Arctic coastal tundra site ofUtqiaġvik, Alaska, during spring (3 April–7 May 2016). Blowing snow conditions were observed during 25 % of the 5-week study period andwere overpredicted by a commonly used blowing snow parameterization based solely on wind speed and temperature. Throughout the study, open leads werepresent locally. During periods when blowing snow was observed, significantincreases in the number concentrations of 0.01–0.06 µm particles(factor of 6, on average) and 0.06–0.3 µm particles (67 %, on average) and a significant decrease (82 %, on average) in 1–4 µmparticles were observed compared to low wind speed periods. These size distribution changes were likely caused by the generation of ultrafineparticles from leads and/or blowing snow, with scavenging of supermicronparticles by blowing snow. At elevated wind speeds, both submicron andsupermicron sodium and chloride mass concentrations were enhanced,consistent with wind-dependent local sea salt aerosol production. Atmoderate wind speeds below the threshold for blowing snow as well as during observed blowing snow, individual sea spray aerosol particles were measured.These individual salt particles were enriched in calcium relative to sodiumin seawater due to the binding of this divalent cation with organic matter in the sea surface microlayer and subsequent enrichment during seawaterbubble bursting. The chemical composition of the surface snowpack alsoshowed contributions from sea spray aerosol deposition. Overall, theseresults show the contribution of sea spray aerosol production from leads onboth aerosols and the surface snowpack. Therefore, if blowing snowsublimation contributed to the observed sea salt aerosol, the snow beingsublimated would have been impacted by sea spray aerosol deposition rather than upward brine migration through the snowpack. Sea spray aerosol production from leads is expected to increase, with thinning and fracturingof sea ice in the rapidly warming Arctic. 

Abstract. The mechanisms of molecular halogen production from frozen saline surfacesremain incompletely understood, limiting our ability to predict atmosphericoxidation and composition in polar regions. In this laboratory study,condensed-phase hydroxyl radicals (OH) were photochemically generated infrozen saltwater solutions that mimicked the ionic composition of oceanwater. These hydroxyl radicals were found to oxidize Cl−, Br−, andI−, leading to the release of Cl2, Br2, I2, and IBr. Atmoderately acidic pH (buffered between 4.5 and 4.8), irradiation of icecontaining OH precursors (either of hydrogen peroxide or nitrite ion)produced elevated amounts of I2. Subsequent addition of O3produced additional I2, as well as small amounts of Br2. At lowerpH (1.7–2.2) and in the presence of an OH precursor, rapid dark conversionof I− to I2 occurred from reactions with hydrogen peroxide ornitrite, followed by substantial photochemical production of Br2 uponirradiation. Exposure to O3 under these low pH conditions alsoincreased production of Br2 and I2; this likely results fromdirect O3 reactions with halides, as well as the production ofgas-phase HOBr and HOI that subsequently diffuse to frozen solution to reactwith Br− and I−. Photochemical production of Cl2 was onlyobserved when the irradiated sample was composed of high-purity NaCl andhydrogen peroxide (acting as the OH precursor) at pH = 1.8. Thoughcondensed-phase OH was shown to produce Cl2 in this study, kineticscalculations suggest that heterogeneous recycling chemistry may be equallyor more important for Cl2 production in the Arctic atmosphere. Thecondensed-phase OH-mediated halogen production mechanisms demonstrated hereare consistent with those proposed from recent Arctic field observations ofmolecular halogen production from snowpacks. These reactions, even if slow,may be important for providing seed halogens to the Arctic atmosphere. Ourresults suggest the observed molecular halogen products are dependent on therelative concentrations of halides at the ice surface, as we only observewhat diffuses to the air–surface interface. 

Abstract. Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN),peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) weremeasured on the ground using a gas chromatograph electron capture detector(GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign(1 June to 15 July 2013) in Centreville, Alabama, in order to studybiosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were169, 5, and 9 pptv, respectively, and the sum accounts for an average of16 % of NO_y during the daytime (10:00 to 16:00 localtime). Higher concentrations were seen on average in air that came to thesite from the urban NO_x sources to the north. PAN levelswere the lowest observed in ground measurements over the past two decades inthe southeastern US. A multiple regression analysis indicates that biogenicvolatile organic compounds (VOCs) account for 66 % of PAN formationduring this study. Comparison of this value with a 0-D model simulation ofperoxyacetyl radical production indicates that at least 50 % of PANformation is due to isoprene oxidation. MPAN has a statistical correlationwith isoprene hydroxynitrates (IN). Organic aerosol mass increases withgas-phase MPAN and IN concentrations, but the mass of organic nitrates inparticles is largely unrelated to MPAN.

 

Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO₃), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO₃. Under dry conditions, the hydroxy nitrate yield  =  4(+1/−3) %, total ON yield  =  14(+3/−2) %, and SOA yield  ≤  10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO₃. Using a chemical box model, we show that the measured concentrations of NO₂ and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO₃ chemistry. This suggests that NO₃ addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.