Hydroperoxides in the Marine Troposphere over the Atlantic Ocean

Hydrogen peroxide (H2O2) and organic hydroperoxides (ROOH) were measured on board of the RV Polarstern during its cruise across the Atlantic Ocean from 20 October to 12 November 1990 (54 deg N to 51 deg S latitude) by the enzyme fluorometric method. The H2O2 mixing ratio varied from below the detection limit of about 0.12 ppbv up to 3.89 ppbv, showing a latitudinal dependence with generally higher values around the equator and decreasing values poleward. The shape of the latitudinal H2O2 distribution agrees well with an analytical steady state expression for H2O2 using the measured H2O and O3 distribution and a wind dependent H2O2 deposition rate. The ROOH mixing ratio varied from below the detection limit of about 0.08 ppbv up to 1.25 ppbv with qualitatively the same latitudinal dependence as H2O2. The observed ratio ROOH/(ROOH + H2O2) varied between 0.17 and 0.98 showing higher values at the lowest H2O2 mixing ratios at high latitudes. The measured H2O2 mixing ratio shows a significa nt diurnal variation with a maximum around 14:00 local time, explicable by a superposition of the photochemical H2O2 production with a constant H2O2 deposition rate. Four independent estimations of the average effective H2O2 deposition rate inferred from the H2O2 decrease in the night, from the midday H2O2 production deficit (as derived from comparison with a photochemical model and from the daily ozone loss), and from the offset in the latitudinal H2O2 distribution, were consistent. An episode of maximum H2O2 concentration suggests the possibility of its formation in clouds