SIMULTANEOUS OBSERVATIONS OF NITRATE AND PEROXY-RADICALS IN THE MARINE BOUNDARY-LAYER

This paper describes the most extensive set of simultaneous measuremen ts of the concentrations of nitrate (NO3) and peroxy (sum of HO2 + RO2 , R = alkyl and acyl) radicals to date. The measurements were made in the coastal marine boundary layer over the North Sea, at the Weybourne Atmospheric Observatory on the North Norfolk coast during the spring and autumn of 1994. In spring the average nighttime concentration of N O3 measured by differential optical absorption spectroscopy, was about 10 parts per trillion (ppt) (maximum 25 ppt). The corresponding perox y radical concentration, measured by the chemical amplifier technique, averaged about 2 ppt (maximum 6 ppt), although this is likely to be a n underestimate of the total radical concentration. There is a signifi cant positive correlation between the two sets of radicals, which has not been reported previously. A box model of the marine boundary layer is used to show that this correlation arises from the processing of r eactive organic species by NO3. During spring the relatively long life time of NO3 (up to 18 min) at night is controlled by reaction with dim ethyl sulfide (DMS), and the model predicts significant production of HNO3, methyl tiomethylen (CH3SCH2O2) and other peroxy radicals, HCHO, and eventually sulfate. A nighttime production rate for the hydroxyl ( OH) of about 2 x 10(4) molecules cm(-3) s(-1) is estimated. During one night in autumn the NO3 lifetime of about 3 min is too short to be ex plained by reaction with unsaturated hydrocarbons, but is satisfactori ly accounted for by the heterogeneous loss of N2O5 on deliquesced aero sols in relatively polluted conditions.