TY - JOUR
T1 - Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument
AU - Novelli, Anna
AU - Hens, Korbinian
AU - Ernest, Cheryl Tatum
AU - Martinez, Monica
AU - Nölscher, Anke C.
AU - Sinha, Vinayak
AU - Paasonen, Pauli
AU - Petäjä, Tuukka
AU - Sipilä, Mikko
AU - Elste, Thomas
AU - Plass-Dülmer, Christian
AU - Phillips, Gavin J.
AU - Kubistin, Dagmar
AU - Williams, Jonathan
AU - Vereecken, Luc
AU - Lelieveld, Jos
AU - Harder, Hartwig
N1 - Funding Information:
Luc Vereecken was supported by the Max Planck Graduate Centre (MPGC) with the Johannes Gutenberg- Universität Mainz. Work during HUMPPA-COPEC was supported by the Hyytiälä site engineers and staff. Support of the European Community Research Infrastructure Action under the FP6 "Structuring the European Research Area" programme, EUSAAR contract no. RII3-CT-2006-026140, is gratefully acknowledged. The HUMPPACOPEC 2010 campaign measurements and analyses were supported by the ERC grant ATMNUCLE (project no. 227463), the Academy of Finland Centre of Excellence programme (project no. 1118615), the Academy of Finland Centre of Excellence in Atmospheric Science - From Molecular and Biological processes to The Global Climate (ATM, 272041), the European integrated project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI, project no. 036833-2), the EUSAAR TNA (project no. 400586), and the IMECC TA (project No. 4006261). The work during HOPE 2012 was supported by the scientists and staff of DWD Hohenpeißenberg, whom we would like to thank for providing the "platform" and opportunity to perform such a campaign. In particular, we thank Anja Werner, Jennifer Englert, and Katja Michl for the VOC measurements, Stephan Gilge for the trace gases measurements, and Georg Stange for running the CIMS.
Publisher Copyright:
© Author(s) 2017.
PY - 2017/6/29
Y1 - 2017/6/29
N2 - 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 ĝ1/4 ĝ€5.0ĝ€ × ĝ€104ĝ€moleculesĝ€cmĝ'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.
AB - 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 ĝ1/4 ĝ€5.0ĝ€ × ĝ€104ĝ€moleculesĝ€cmĝ'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.
UR - http://www.scopus.com/inward/record.url?scp=85021641039&partnerID=8YFLogxK
U2 - 10.5194/acp-17-7807-2017
DO - 10.5194/acp-17-7807-2017
M3 - Article
AN - SCOPUS:85021641039
SN - 1680-7316
VL - 17
SP - 7807
EP - 7826
JO - Atmospheric Chemistry and Physics
JF - Atmospheric Chemistry and Physics
IS - 12
ER -