Abstract
Abstract. Hydroxyl (OH) and hydroperoxy (HO2) radicals are central to the understanding of atmospheric chemistry. Owing to their short lifetimes, these species are frequently used to test the accuracy of model predictions and their underlying chemical mechanisms. In forested environments, laser-induced fluorescence–fluorescence assay by gas expansion (LIF–FAGE) measurements of OH have often shown substantial disagreement with model predictions, suggesting the presence of unknown OH sources in such environments. However, it is also possible that the measurements have been affected by instrumental artefacts, due to the presence of interfering species that cannot be discriminated using the traditional method of obtaining background signals via modulation of the laser excitation wavelength (“OHwave”). The interference hypothesis can be tested by using an alternative method to determine the OH background signal, via the addition of a chemical scavenger prior to sampling of ambient air (“OHchem”). In this work, the Leeds FAGE instrument was modified to include such a system to facilitate measurements of OHchem, in which propane was used to selectively remove OH from ambient air using an inlet pre-injector (IPI). The IPI system was characterised in detail, and it was found that the system did not reduce the instrument sensitivity towards OH (< 5 % difference to conventional sampling) and was able to efficiently scavenge external OH (> 99 %) without the removal of OH formed inside the fluorescence cell (< 5 %). Tests of the photolytic interference from ozone in the presence of water vapour revealed a small but potentially significant interference, equivalent to an OH concentration of ∼4×105 molec. cm−3 under typical atmospheric conditions of [O3] =50 ppbv and [H2O] =1 %. Laboratory experiments to investigate potential interferences from products of isoprene ozonolysis did result in interference signals, but these were negligible when extrapolated down to ambient ozone and isoprene levels. The interference from NO3 radicals was also tested but was found to be insignificant in our system. The Leeds IPI module was deployed during three separate field intensives that took place in summer at a coastal site in the UK and both in summer and winter in the megacity of Beijing, China, allowing for investigations of ambient OH interferences under a wide range of chemical and meteorological conditions. Comparisons of ambient OHchem measurements to the traditional OHwave method showed excellent agreement, with OHwave vs OHchem slopes of 1.05–1.16 and identical behaviour on a diel basis, consistent with laboratory interference tests. The difference between OHwave and OHchem (“OHint”) was found to scale non-linearly with OHchem, resulting in an upper limit interference of (5.0±1.4) ×106 molec. cm−3 at the very highest OHchem concentrations measured (23×106 molec. cm−3), accounting for ∼14 %–21 % of the total OHwave signal.
Highlights
The removal of pollutants and greenhouse gases in the troposphere is dominated by reactions with the hydroxyl radical (OH), which is closely coupled to the hydroperoxy radical (HO2)
Laser-induced fluorescence–fluorescence assay by gas expansion (LIF–FAGE) measurements of OH in forested environments have often been considerably higher than those predicted by models (Carslaw et al, 2001; Lelieveld et al, 2008; Ren et al, 2008; Hofzumahaus et al, 2009; Stone et al, 2011; Whalley et al, 2011; Wolfe et al, 2011)
The difficulty in simulating radical concentrations in such environments has prompted a multitude of theoretical (Peeters et al, 2009, 2014; da Silva et al, 2010; Nguyen et al, 2010; Peeters and Muller, 2010), laboratory (Dillon and Crowley, 2008; Hansen et al, 2017), and chamber (Paulot et al, 2009; Crounse et al, 2011, 2012; Wolfe et al, 2012; Fuchs et al, 2013, 2014, 2018; Praske et al, 2015; Teng et al, 2017) studies to help explain the sources of the measurement–model discrepancy through detailed investigations of the mechanism of isoprene oxidation under low NOx conditions, as well as other biogenic volatile organic compounds (BVOCs) (Novelli et al, 2018)
Summary
The removal of pollutants and greenhouse gases in the troposphere is dominated by reactions with the hydroxyl radical (OH), which is closely coupled to the hydroperoxy radical (HO2). The difficulty in simulating radical concentrations in such environments has prompted a multitude of theoretical (Peeters et al, 2009, 2014; da Silva et al, 2010; Nguyen et al, 2010; Peeters and Muller, 2010), laboratory (Dillon and Crowley, 2008; Hansen et al, 2017), and chamber (Paulot et al, 2009; Crounse et al, 2011, 2012; Wolfe et al, 2012; Fuchs et al, 2013, 2014, 2018; Praske et al, 2015; Teng et al, 2017) studies to help explain the sources of the measurement–model discrepancy through detailed investigations of the mechanism of isoprene oxidation under low NOx conditions, as well as other biogenic volatile organic compounds (BVOCs) (Novelli et al, 2018) Another hypothesis is that the LIF measurements have, at least in part, suffered from an instrumental bias in these environments due to interfering species. Observations of OH during the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions and Transport) field campaign in summer 1998, located in a mixed deciduous forest in Michigan, USA, revealed unusually high night-time OH concentrations (∼ 1×106 molec. cm−3) but measurement interferences were ruled out (Faloona et al, 2001)
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