ABSTRACT
In the polar tropospheric boundary layer, reactive halogen species (RHS) are responsible for ozone depletion as well as the oxidation of elemental mercury and dimethyl sulphide. After polar sunrise, air masses enriched in reactive bromine cover areas of several million square kilometers. Still, the source and release mechanisms of halogens are not completely understood. We report measurements of halogen oxides performed in the Amundsen Gulf, Arctic, during spring 2008. Active long-path differential optical absorption spectroscopy (LP-DOAS) measurements were set up offshore, several kilometers from the coast, directly on the sea ice, which was never done before. High bromine oxide concentrations were detected frequently during sunlight hours with a characteristic daily cycle showing morning and evening maxima and a minimum at noon. The, so far, highest observed average mixing ratio in the polar boundary layer of 41 pmol/mol (equal to pptv) was detected. Only short sea ice contact is required to release high amounts of bromine. An observed linear decrease of maximum bromine oxide levels with ambient temperature during sunlight, between -24 degrees C and -15 degrees C, provides indications on the conditions required for the emission of RHS. In addition, the data indicate the presence of reactive chlorine in the Arctic boundary layer. In contrast to Antarctica, iodine oxide was not detected above a detection limit of 0.3 pmol/mol.
Subject(s)
Environmental Monitoring/instrumentation , Spectrum Analysis/methods , Arctic Regions , Bromine/chemistry , Chlorine/chemistry , Environmental Monitoring/methods , Halogens/chemistry , Models, Chemical , Oceans and Seas , Oxides/chemistry , Ozone/chemistry , Salts/chemistry , Temperature , Time FactorsABSTRACT
The development of a new concurrent multiaxis (CMAX) sky viewing spectrometer to monitor rapidly changing urban concentrations of nitrogen dioxide is detailed. The CMAX differential optical absorption spectroscopy (DOAS) technique involves simultaneous spectral imaging of the zenith and off-axis measurements of spatially resolved scattered sunlight. Trace-gas amounts are retrieved from the measured spectra using the established DOAS technique. The potential of the CMAX DOAS technique to derive information on rapidly changing concentrations and the spatial distribution of NO2 in an urban environment is demonstrated. Three example data sets are presented from measurements during 2004 of tropospheric NO2 over Leicester, UK (52.62 degrees N, 1.12 degrees W). The data demonstrate the current capabilities and future potential of the CMAX DOAS method in terms of the ability to measure real-time spatially disaggregated urban NO2.