Peroxy radical observations using chemical ionization mass spectrometry during TOPSE

Peroxy radicals (HO₂ + RO₂) were measured by chemical conversion-chemical ionization mass spectroscopy in the TOPSE (Tropospheric Ozone Production about the Spring Equinox) campaign that took place February through May 2000. Instrumentation for these measurements was deployed on the NCAR/NSF C-130 aircraft that flew at latitudes from 40 to 85°N, and altitudes from the surface to 7.5 km over the North American continent. The measurements demonstrate the evolution of photochemical activity as time progresses through the study period due to increases in free radical source rates. The increase in average peroxy radical concentration moves northward as the maximum solar elevation and length of sunlit days increase. HO_xRO_x (HO₂ + RO₂) concentrations are distributed lognormally with means of 11.5 and 7.8 pptv for the middle-latitude band (MLB) and high-latitude band (HLB), respectively. The observations agree well on average with steady state derived concentrations; measurement-model concentration ratios are 1.04 (MLB) and 0.94 (HLB). Concentrations within a given latitude band and altitude region sometimes appear to increase with NO_x concentrations, but this correlation nearly disappears at low and moderate NO_x levels when the data are parsed by radical production rate; lower radical levels are observed at the highest NO_x levels measured (near 1 ppbv). These data are compared with results from other recent observations utilizing a variety of platforms.