Reservoirs of atmospheric chlorine: Prospects for HOCl revisted

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We have re-examined the prospects of HOCl as an inert reservoir for atmospheric chlorine in the light of new theoretical calculations and available experimental measurements of its photodissociation cross-sections. The theoretical calculations and most recent laboratory studies imply that the broad maxima 3200 Å observed in two other experimental spectra may not belong to HOCl. On the basis of this implication HOCl could have a long lifetime against photodissociation in the stratosphere, and could, thereby, become a reservoir for atmospheric chlorine comparable to ClONO2 or even HCl. In this capacity HOCl could reduce the predicted ozone destruction due to any given level of total chlorine burden. We have also examined the difficulties in laboratory measurements of the HOCl absorption spectrum with particular emphasis on identifying the impurities which may be present in the experimental system. It appears that specialized new experiments are needed to clearly establish the nature and strength of HOCl absorption in the neighbourhood of 3200 Å. Some refinements in the theoretical calculations also seem desirable. In view of the difficulties involved in the laboratory determination of HOCl photodissociation cross-sections, it is suggested that a search for possible stratospheric HOCl by atmospheric spectroscopists would be worthwhile.

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