AN INTERCOMPARISON OF SPECTROSCOPIC LASER LONG-PATH AND ION-ASSISTED IN-SITU MEASUREMENTS OF HYDROXYL CONCENTRATIONS DURING THE TROPOSPHERIC OH PHOTOCHEMISTRY EXPERIMENT, FALL 1993
Gh. Mount et al., AN INTERCOMPARISON OF SPECTROSCOPIC LASER LONG-PATH AND ION-ASSISTED IN-SITU MEASUREMENTS OF HYDROXYL CONCENTRATIONS DURING THE TROPOSPHERIC OH PHOTOCHEMISTRY EXPERIMENT, FALL 1993, JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 102(D5), 1997, pp. 6437-6455
Hydroxyl plays a central role in the chemistry of the troposphere. Sin
ce the importance of OH was first recognized in the early 1970s, many
experiments have attempted to measure OH, but very few have been succe
ssful, and much controversy has surrounded the measurements made [Cros
ley, this issue]. Thus, intercomparison of OH measurements is a requir
ement for community acceptance of derived OH concentrations, and accur
ate measurements of OH are essential to provide robust modeling of tro
pospheric chemistry since models typically allow OH concentrations to
be determined within the model for lack of measurements. The Troposphe
ric OH Photochemistry Experiment held in the Colorado Rocky Mountains
in fall 1993 brought together four instruments that to measure OH. In
order to make a proper comparison, a number of other trace species and
relevant jvalues were measured simultaneously with hydroxyl to provid
e a photochemical understanding of the measurements and an understandi
ng of the airflow in the mountainous region in which this work was con
ducted. This region provided opportunities to measure both clean and p
olluted air over a wide dynamic range of species that affect the OH co
ncentration. The measurements extended over a long enough period of ti
me that a large quantity of data were collected under a variety of atm
ospheric conditions, thus allowing for a meaningful comparison of tech
niques. The long-path spectroscopic laser system and the in situ selec
ted ion chemical ionization mass spectrometry system determined OH con
centrations for 4 weeks simultaneously. Generally, the derived concent
rations from the two instruments agreed within the 2 sigma error bars
over half the observation time. One quarter of the time, OH difference
s could be explained by different air masses between the long path and
in situ site which contained different concentrations of trace specie
s that affect OH abundance. Approximately one quarter of the data disa
greed outside the observational errors with no obvious explanation. Th
e long-path experiment typically gave concentrations about 20% higher
than the ion-assisted experiment. This could be caused by inaccuracies
in the absolute calibrations of the two instruments, or by trace spec
ies variations along the long path that differed from those at the in
situ site, Generally, agreement between ion-assisted and long-path OH
measurements was good, showing that measurements of hydroxyl in the tr
oposphere can be performed with good accuracy on a routine basis.