Implementation of a chemical background method for atmospheric OH measurements by laser-induced fluorescence: characterisation and observations from the UK and China

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 concen- tration of similar to 4 x 10(5) molec. cm(-3) under typical atmospheric conditions of [O-3] = 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 nonlinearly with OHchem, resulting in an upper limit interference of (5.0 +/- 1.4) x 10(6) molec. cm(-3) at the very highest OHchem concentrations measured (23 x 10(6) molec. cm(-3)), accounting for similar to 14 %-21% of the total OHwave signal.