Winter‐spring evolution and variability of HOx reservoir species, hydrogen peroxide, and methyl hydroperoxide, in the northern middle to high latitudes

Abstract

The Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiment examined the evolution of tropospheric chemical compositions from February to May 2000 over North America, 40 to 85 N. Hydrogen peroxide (H2O2) and methyl hydroperoxide (CH3OOH) were investigated using instrumental observations aboard the NCAR C‐130 research aircraft. Primary TOPSE results indicate both photochemistry and atmospheric dynamics are critical factors controlling the variability of peroxides in this region. From February to May, H2O2 and CH3OOH mixing ratios increased with the greatest relative changes at mid‐altitudes. H2O2 ranged from below the detection limit (BDL = 25 pptv) to 380 pptv in winter and from BDL to 1330 pptv during spring. Winter measurements of CH3OOH were from BDL (35 pptv) to 740 pptv with higher levels of BDL to 1400 pptv measured during spring. Peroxides also decreased with latitude at all altitudes. These findings are consistent with those expected from photochemical theory. Evidence also supports a source of CH3OOH to the Arctic from the transport of subtropical air masses. Air mass back trajectories and GOES‐derived specific humidity products indicate transport of moist tropical air to the study region coincides with elevated levels of CH3OOH up to 940 pptv. The concurrence of this transport regime with episodic elevated CH3OOH events suggests a source of HOx to the Arctic. However, evidence from this study shows CH3OOH does not greatly contribute to total HOx production which is dominated primarily by reactions of O(1D) and H2O at low latitudes and CH2O at high latitudes.