Seasonal differences in the photochemistry of the South Pacific: A comparison of observations and model results from PEM-Tropics A and B

A time-dependent photochemical box model is used to examine the photochemistry of the equatorial and southern subtropical Pacific troposphere with aircraft data obtained during two distinct seasons: the Pacific Exploratory Mission-Tropics A (PEM-Tropics A) field campaign in September and October of 1996 and the Pacific Exploratory Mission-Tropics B (PEM-Tropics B) campaign in March and April of 1999. Model-predicted values were compared to observations for selected species (e.g., NO2, OH, HO2) with generally good agreement. Predicted values of HO2 were larger than those observed in the upper troposphere, in contrast to previous studies which show a general underprediction of HO2 at upper altitudes. Some characteristics of the budgets of HOx, NOx, and peroxides are discussed. The integrated net tendency for O-3 is negative over the remote Pacific during both seasons, with gross formation equal to no more than half of the gross destruction. This suggests that a continual supply of O-3 into the Pacific region throughout the year must exist in order to maintain O-3 levels. Integrated net tendencies for equatorial O-3 showed a seasonality, with a net loss of 1.06 x 10(11) molecules cm(-2) s(-1) during PEM-Tropics B (March) increasing by 50% to 1.60 x 10(11) molecules cm(-2) s(-1) during PEM-Tropics A (September). The seasonality over the southern subtropical Pacific was somewhat lower, with losses of 1.21 x 10(11) molecules cm(-2) s(-1) during PEM-Tropics B (March) increasing by 25% to 1.51 x 10(11) molecules cm(-2) s(-1) during PEM-Tropics A (September). While the larger net losses during PEM-Tropics A were primarily driven by higher concentrations of O-3, the ability of the subtropical atmosphere to destroy O-3 was similar to30% less effective during the PEM-Tropics A (September) campaign due to a drier atmosphere and higher overhead O-3 column amounts.