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In-situ Measurements of Tropospheric Hydroxyl Radicals by Folded Long-Path Laser Absorption During the Field Campaign POPCORN
Authors:Uwe Brandenburger  Theo Brauers  Hans-Peter Dorn  Martin Hausmann  Dieter H Ehhalt
Institution:(1) Institut für Atmosphärische Chemie, Forschungszentrum Jülich GmbH, Germany
Abstract:Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1sgr-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.
Keywords:tropospheric hydroxyl radicals  laser absorption spectroscopy  OH-radical chemistry  field experiment
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