Measurement of tropospheric OH by long‐path laser absorption at Fritz Peak Observatory, Colorado, during the OH Photochemistry Experiment, fall 1993

Abstract

The determination of the concentration of hydroxyl (OH) in the Earth's troposphere is of fundamental importance to an understanding of the chemistry of the lower atmosphere. This paper describes the results from the laser long‐path spectroscopic OH experiment used in the Tropospheric OH Photochemistry Experiment (TOHPE) held at Fritz Peak, Colorado, in fall 1993. A primary goal of TOHPE was to compare the OH concentrations measured using a variety of different techniques: a long‐path spectroscopic instrument [Mount, 1992], an in situ ion‐assisted chemical conversion instrument (Eisele and Tanner, 1991, 1993), a laser resonance fluorescence instrument [Stevens et al., 1994), and a liquid scrubber instrument (X. Chen and K. Mopper, unpublished data,; 1996), all with sensitivities at or below 1×106 molecules cm−3. In addition to the OH measurements, a nearly complete suite of trace gas species that affect the OH concentration were measured simultaneously, using both in situ and/or long‐path techniques, to provide the information necessary to understand the OH variation and concentration differences observed. Measurements of OH, NO2, CH2O, SO2, H2O, and O3 were made using long‐path spectroscopic absorption of white light or laser light and OH, NO, NO2, NOy, O3, CO, SO2, CH2O, j(O3), j(NO2), RO2/HO2, HO2, H2O, SO2, PAN, PPN, HNO3, and aerosols (size and composition) and ozone and nitrogen dioxide j‐values were measured using in situ instruments. Meteorological parameters at each end of the long path and at the Idaho Hill in situ site were also measured. The comparison of the long‐path and in situ species from this set of complementary measurements provides an effective way of interpreting air masses over the long path with those at the in situ site; this is a critical issue since the long‐path spectroscopic OH determinations provide a nonchemical and well‐calibrated measurement of OH which must be compared in a meaningful manner with the in situ determinations. Over the period of the TOHPE experiment, OH concentrations were typically low during periods of clean and clear airflow, averaging about 4×106 molecules cm−3 at noon. In contrast, during the well‐defined pollution episodes which occurred during the campaign, OH concentrations rose as high as 15×106 molecules cm−3.