Sources and formation mechanisms of carbonaceous aerosol at a regional background site in the Netherlands: Insights from a year-long radiocarbon study

Abstract

We measured the radioactive carbon isotope 14C (radiocarbon) in various fractions of the carbonaceous aerosol sampled between February 2011 and March 2012 at the Cesar Observatory in the Netherlands. Based on the radiocarbon content in total carbon (TC), organic carbon (OC), water-insoluble organic carbon (WIOC), and elemental carbon (EC), we estimated the contribution of major sources to the carbonaceous aerosol. The main source categories were fossil fuel combustion, biomass burning, and other contemporary carbon, which is mainly biogenic secondary organic aerosol material (SOA). A clear seasonal variation is seen in EC from biomass burning (ECbb), with lowest values in summer and highest values in winter, but ECbb is a minor fraction of EC in all seasons. WIOC from contemporary sources is highly correlated with ECbb, indicating that biomass burning is a dominant source of contemporary WIOC. This suggests that most biogenic SOA is water soluble and that water-insoluble carbon stems mainly from primary sources. Seasonal variations in other carbon fractions are less clear and hardly distinguishable from variations related to air mass history. Air masses originating from the ocean sector presumably contain little carbonaceous aerosol from outside the Netherlands, and during these conditions measured carbon concentrations reflect regional sources. In these situations absolute TC concentrations are usually rather low, around 1.5ĝ€μgĝ€mĝ'3, and ECbb is always very low ( ĝ1/4 ĝ€0.05ĝ€μgĝ€mĝ'3), even in winter, indicating that biomass burning is not a strong source of carbonaceous aerosol in the Netherlands. In continental air masses, which usually arrive from the east or south and have spent several days over land, TC concentrations are on average by a factor of 3.5 higher. ECbb increases more strongly than TC to 0.2ĝ€μgĝ€mĝ'3. Fossil EC and fossil WIOC, which are indicative of primary emissions, show a more moderate increase by a factor of 2.5 on average. An interesting case is fossil water-soluble organic carbon (WSOC, calculated as OC-WIOC), which can be regarded as a proxy for SOA from fossil precursors. Fossil WSOC has low concentrations when regional sources are sampled and increases by more than a factor of 5 in continental air masses. A longer residence time of air masses over land seems to result in increased SOA concentrations from fossil origin.