Peroxy radicals from photostationary state deviations and steady state calculations during the Tropospheric OH Photochemistry Experiment at Idaho Hill, Colorado, 1993

Concentrations of peroxy radicals and a number of other trace gases were measured during the Tropospheric OH Photochemistry Experiment in August and September, 1993. The trace gas concentrations were used to derive two estimates of peroxy radical levels: deviations from the photostationary state, and theoretical calculations with the assumption of steady state radical concentrations. As in many previous studies, the photostationary state method yielded midday peroxy radical levels about twice those measured. Calculations were performed to assess the expected uncertainty in the photostationary state derived peroxy radical concentrations from the uncertainty of the input parameters. The agreement between measurements and steady state determinations was better than the photostationary state estimates, with the measurements slightly higher on average. Radical formation and destruction rates for clear sky conditions with low and high NOx were derived from the steady state calculations and the results demonstrate the processes that control peroxy radical levels in clean and polluted continental atmospheres.