Estimating contributions from biomass burning, fossil fuel combustion, and biogenic carbon to carbonaceous aerosols in the Valley of Chamonix: a dual approach based on radiocarbon and levoglucosan

Atmospheric particulate matter (PM) affects the climate in various ways and has a negative impact on human health. In populated mountain valleys in Alpine regions, emissions from road traffic contribute to carbonaceous aerosols, but residential wood burning can be another source of PM during winter. We determine the contribution of fossil and non-fossil carbon sources by measuring radiocarbon in aerosols using the recently installed AixMICADAS facility. The accelerator mass spectrometer is coupled to an elemental analyzer (EA) by means of a gas interface system directly connected to the gas ion source. This system provides rapid and accurate radiocarbon measurements for small samples (10-100 mu gC) with minimal preparation from the aerosol filters. We show how the contamination induced by the EA protocol can be quantified and corrected for. Several standards and synthetic samples are then used to demonstrate the precision and accuracy of aerosol measurements over the full range of expected C-14/C-12 ratios, ranging from modern carbon to fossil carbon depleted in C-14. Aerosols sampled in Chamonix and Passy (Arve River valley, French Alps) from November 2013 to August 2014 are analyzed for both radiocarbon (124 analyses in total) and levoglucosan, which is commonly used as a specific tracer for biomass burning. NOx concentration, which is expected to be associated with traffic emissions, is also monitored. Based on C-14 measurements, we can show that the relative fraction of non-fossil carbon is significantly higher in winter than in summer. In winter, non-fossil carbon represents about 85% of total carbon, while in summer this proportion is still 75% considering all samples. The largest total carbon and levoglucosan concentrations are observed for winter aerosols with values up to 50 and 8 mu g m(-3), respectively. These levels are higher than those observed in many European cities, but are close to those for other polluted Alpine valleys. The non-fossil carbon concentrations are strongly correlated with the levoglucosan concentrations in winter samples, suggesting that almost all of the non-fossil carbon originates from wood combustion used for heating during winter. For summer samples, the joint use of C-14 and levoglucosan measurements leads to a new model to separately quantify the contributions of biomass burning and biogenic emissions in the non-fossil fraction. The comparison of the biogenic fraction with polyols (a proxy for primary soil biogenic emissions) and with the temperature suggests a major influence of the secondary biogenic aerosols. Significant correlations are found between the NOx concentration and the fossil carbon concentration for all seasons and sites, confirming the relation between road traffic emissions and fossil carbon. Overall, this dual approach combining radiocarbon and levoglucosan analyses strengthens the conclusion concerning the impact of biomass burning. Combining these geochemical data serves both to detect and quantify additional carbon sources. The Arve River valley provides the first illustration of aerosols of this model.