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Atmospheric chemistry and fate of C2-C5 peroxyacyl nitrates

Conference ·
OSTI ID:197479

Peroxyacyl nitrates, RC(O)OONO{sub 2} (PANs), are of major importance in atmospheric chemistry. They have also received attention as toxic air contaminants: the several PANs studied so far are eye irritants, mutagenic and phytotoxic. While the simplest compound, PAN (CH{sub 3}C(O)OONO{sub 2}), has been studied in detail, little is known regarding the ambient concentrations, atmospheric persistence and atmospheric fate of higher molecular weight PANs. In this study, the authors have investigated 12 saturated and unsaturated aliphatic PANs, R = CH{sub 3}(PAN), C{sub 2}H{sub 5}, C{sub 3}H{sub 7} (2 isomers), C{sub 4}H{sub 9} (4 isomers), CH{sub 2} = CH-, CH{sub 2} = C(CH{sub 3})-, CH{sub 2} = C(C{sub 2}H{sub 5})- and CH{sub 3}CH = CH-. These compounds have been synthesized in the liquid phase, prepared in-situ by sunlight irradiation of NO-carbonyl mixtures (e.g., CH{sub 2} = C(C{sub 2}H{sub 5})C(O)OONO{sub 2} from NO and 2-ethylacrolein), measured at ppb levels by electron capture gas chromatography, and characterized using a number of chemical and physical diagnostic tests. Thermal decomposition, a major loss process for all PANs in the atmosphere (RCO{sub 3}NO{sub 2} {yields} RCO{sub 3} + NO{sub 2}) has been studied at ambient temperature and 1 atm. of air. Other removal processes studied include reactions with OH, and, for the unsaturated PANs, reactions with ozone. These removal processes will be discussed with respect to the persistence of PANs in the atmosphere.

OSTI ID:
197479
Report Number(s):
CONF-9405167--
Country of Publication:
United States
Language:
English

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