• Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

      Novelli, Anna; Hens, Korbinian; Ernest, Cheryl T.; Martinez, Monica; Noelscher, Anke C.; Sinha, Vinayak; Paasonen, Pauli; Petaja, Tuukka; Sipila, Mikko; Elste, Thomas; et al. (Copernicus Publications, 2017-06-29)
      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 (SCI) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the afore-mentioned campaigns is caused at least partially by SCI. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCI, the background OH concentration can be removed through the addition of sulfur dioxide. SCI also adds to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of ~ 5.0 x 104 molecules cm-3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCI, 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.
    • Identifying Criegee intermediates as potential oxidants in the troposphere

      Novelli, Anna; Hens, Korbinian; Tatum-Ernest, Cheryl; Martinez, Monica; Noelscher, Anke C.; Sinha, Vinayak; Paasonen, Pauli; Petaja, Tuukka; Sipila, Mikko; Elste, Thomas; et al. (American Geophysical Union, 2015-10)
      Criegee intermediates (CI) are formed during the ozonolysis of unsaturated compounds and have been intensively studied in the last few years due to their possible role as oxidants in the troposphere. Stabilised CI (SCI) are now known to react very rapidly, k(298 K) = 10-12 to 10-10 cm3 molecule-1 s-1, with a large number of trace gases (SO2, NO2, organic acids, water dimers). Still, it remains challenging to assess their effective oxidative capacity, as CI chemistry is complex, spans a large range of rate coefficients for different SCI conformers reacting with water dimers and trace gases, and in addition no reliable measurement technique able to detect ambient SCI concentrations is currently available. In this study, we examine the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns, aided by literature data, to estimate the abundance of SCI in the lower troposphere. The budget of SCI is analyzed using four different approaches: 1) based on an observed yet unexplained H2SO4 production; 2) from the measured concentrations of unsaturated volatile organic compounds (VOC); 3) from OH reactivity measurements; 4) from the unexplained production rate of OH. A SCI concentration range between 5 x 103 and 2 x 106 molecule cm-3 is calculated for the two environments. The central weighted estimate of the SCI concentration over the boreal forest of ~ 5 x 104 molecules cm-3 implies a significant impact on the conversion of SO2 into H2SO4. In addition, we present measurements obtained using our inlet pre-injector laser-induced fluorescence assay by gas expansion technique (IPI-LIF-FAGE) for the above-mentioned campaigns. A recent laboratory study performed with the same instrumental setup showed that the IPI-LIF-FAGE system is sensitive to the detection of the OH formed from unimolecular decomposition of SCI. Building on these measurements, the background OH (OHbg) measured during the two field campaigns is investigated in comparison with many other trace gases to assess if the observations in controlled conditions are transferable to ambient conditions.
    • Identifying Criegee intermediates as potential oxidants in the troposphere

      Novelli, Anna; Hens, Korbinian; Tatum-Ernest, Cheryl; Martinez, Monica; Noelscher, Anke C.; Sinha, Vinayak; Paasonen, Pauli; Petaja, Tuukka; Sipila, Mikko; Elste, Thomas; et al. (Copernicus Publications, 2017-06-29)
      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 (SCI) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the afore-mentioned campaigns is caused at least partially by SCI. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. The background OH concentration also complements the previously underestimated production rate of sulfuric acid and is consistent with its scavenging through the addition of sulphur dioxide. A central estimate of the SCI concentration of ~ 5 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCI, 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.