Journal of Atmospheric Chemistry 31: 205–225, 1998.
© 1998 Kluwer Academic Publishers. Printed in the Netherlands.
205
Highly Time Resolved Measurements of OH
during POPCORN Using Laser-Induced
Fluorescence Spectroscopy
F. HOLLAND, U. ASCHMUTAT, M. HEßLING, A. HOFZUMAHAUS and
D. H. EHHALT
Forschungszentrum Jülich, Inst. für Atmosphärische Chemie, Jülich, Germany
(Received: 24 October 1996; in final form: 10 July 1997)
Abstract. Tropospheric hydroxyl radical (OH) concentrations were measured by laser-induced fluo-
rescence (LIF) during the POPCORN field campaign in August 1994 at a rural site in the North East
of Germany. Ambient air spectra were recorded by tuning the laser wavelength over a spectral region
covering the Q
11
(3), Q
21
(3), and P
11
(1) rotational transitions of the (0-0) band in the A-X system
of OH around 308 nm. The observed spectra clearly identify the OH radical in the atmosphere.
Besides the OH absorption lines there was no sign of any other narrow-band spectral structure
nearby demonstrating the high specificity of the method. For OH measurements with a typical time
resolution of 60–100 seconds per data point the laser wavelength was tuned repetitively over small
spectral intervals covering the peak position of the P
11
(1) OH-line and background positions. A
total of 2300 measurements were recorded including diurnal cycles of OH with more than 300 data
points. The OH as well as the LIF background signal data will be presented. In a first analysis the
background signal will be characterized and the correlation between OH and the ozone photolysis
frequency will be derived.
Key words: OH instrument, laser-induced fluorescence, OH measurements, photochemistry.
1. Introduction
This paper reports measurements of tropospheric OH radical concentrations made
during the POPCORN field campaign with an instrument based on the detection
of laser-induced fluorescence photons of OH excited at 308 nm and low pressure.
The applicability of this highly sensitive and very selective technique for the direct
measurement of ambient OH in the troposphere has already been demonstrated by
different groups (Stevens et al., 1994; Brune et al., 1995; Hard et al., 1995; Holland
et al., 1995). Data obtained so far by this technique, however, are still sparse and
have shown a relative low time resolution only. First tests of the newly developed
LIF instrument at the KFA Jülich (Holland et al., 1995) demonstrated its high de-
tection sensitivity and its capability to identify atmospheric OH spectroscopically,
but at that time no diurnal profiles were measured. The deployment of the KFA LIF
instrument during POPCORN therefore served several purposes: