Cellulose in atmospheric particulate matter at rural and urban sites across France and Switzerland

Abstract

The spatiotemporal variations in free-cellulose concentrations in atmospheric particles, as a proxy for plant debris, were investigated using an improved protocol with a high-performance liquid chromatography with pulsed amperometric detection (HPLC-PAD) method. Filter samples were taken from nine sites of varying characteristics across France and Switzerland, with sampling covering all seasons. Concentrations of cellulose, as well as carbonaceous aerosol and other source-specific chemical tracers (e.g. elemental carbon, EC; levoglucosan; polyols; trace metals; and glucose), were quantified. Annual mean free-cellulose concentrations within PM10 (particulate matter) ranged from 29 ± 38 ng m−3 at Basel (urban site) to 284 ± 225 ng m−3 at Payerne (rural site). Concentrations were considerably higher during episodes, with spikes exceeding 1150 and 2200 ng m−3 at Payerne and ANDRA-OPE (Agence nationale pour la gestion des déchets radioactifs Observatoire Pérenne de l'Environnement; rural site), respectively. A clear seasonality, with highest cellulose concentrations during summer and autumn, was observed at all rural and some urban sites. However, some urban locations exhibited a weakened seasonality. Contributions of cellulose carbon to total organic carbon are moderate on average (0.7 %–5.9 %) but much greater during “episodes”, reaching close to 20 % at Payerne. Cellulose concentrations correlated poorly between sites, even at ranges of about 10 km, indicating the localised nature of the sources of atmospheric plant debris. With regards to these sources, correlations between cellulose and typical biogenic chemical tracers (polyols and glucose) were moderate to strong (Rs = 0.28–0.78, p < 0.0001) across the nine sites. Seasonality was strongest at sites with stronger biogenic correlations, suggesting the main source of cellulose arises from biogenic origins. A second input to ambient plant debris concentrations was suggested via resuspension of plant matter at several urban sites, due to moderate cellulose correlations with mineral dust tracers, Ca2+, and Ti metal (Rs = 0.28–0.45, p < 0.007). No correlation was obtained with the biomass burning tracer (levoglucosan), an indication that this is not a source of atmospheric cellulose. Finally, an investigation into the interannual variability in atmospheric cellulose across the Grenoble metropole was completed. It was shown that concentrations and sources of ambient cellulose can vary considerably between years. All together, these results deeply improve our knowledge on the phenomenology of plant debris within ambient air.