Nitrated and oxygenated derivatives of polycyclic aromatic hydrocarbons in the ambient air of two French alpine valleysPart 1: Concentrations, sources and gas/particle partitioning

Abstract

Ambient measurements (gas+particle phases) of 16 polycyclic aromatic hydrocarbons, 17 nitrated PAHs (NPAHs) and eight oxygenated PAHs (OPAHs) were carried out during the winter 2002-2003 and the summer 2003 in two French alpine valleys on various types of sites (traffic, sub-urban, altitude and rural). Atmospheric concentrations of these classes of compounds are of interest because they include potential mutagens and carcinogens. During both summer and winter campaigns, OPAH concentration levels were of the same order of magnitude as PAH ones while NPAH concentrations were one to two orders of magnitude lower. Total particulate PAH, OPAH and NPAH concentrations were higher in the Chamonix valley than in the Maurienne valley. A heavier pollutant accumulation process in the Chamonix valley and geomorphology promoting their dispersion seem to explain such differences. Despite reaching lower atmospheric concentrations, NPAHs seemed to account up to 20% of carcinogenic potency of particulates collected at the sites away from pollution sources. The formation of secondary compounds such as NPAHs increases significantly the carcinogenic risk at the sites away from pollution sources. Study with 2-nitrofluoranthene/1-nitropyrene ratio showed that NPAH gas phase formation was hindered in winter, and when relative contribution from primary sources was higher. Nevertheless, in winter under specific conditions, evidence of secondary NPAH formations was observed at sub-urban and traffic sites (snowfalls) and rural site (accumulation of pollutants and snowfalls). For all sampling sites, the daytime OH initiated reaction seemed to be the dominant gas phase formation pathway over the NO3 initiated reaction. The fraction of PAHs, OPAHs and NPAHs associated with the particle phase was strongly depending on their vapour pressure and the ambient conditions.