On the isolation of OC and EC and the optimal strategy of radiocarbon-based source apportionment of carbonaceous aerosols

Abstract. Radiocarbon (¹⁴C) measurements of elemental carbon (EC) and organic carbon (OC) separately (as opposed to only total carbon, TC) allow an unambiguous quantification of their non-fossil and fossil sources and represent an improvement in carbonaceous aerosol source apportionment. Isolation of OC and EC for accurate ¹⁴C determination requires complete removal of interfering fractions with maximum recovery. The optimal strategy for ¹⁴C-based source apportionment of carbonaceous aerosols should follow an approach to subdivide TC into different carbonaceous aerosol fractions for individual ¹⁴C analyses, as these fractions may differ in their origins. To evaluate the extent of positive and negative artefacts during OC and EC separation, we performed sample preparation with a commercial Thermo-Optical OC/EC Analyser (TOA) by monitoring the optical properties of the sample during the thermal treatments. Extensive attention has been devoted to the set-up of TOA conditions, in particular, heating program and choice of carrier gas. Based on different types of carbonaceous aerosols samples, an optimised TOA protocol (Swiss_4S) with four steps is developed to minimise the charring of OC, the premature combustion of EC and thus artefacts of ¹⁴C-based source apportionment of EC. For the isolation of EC for ¹⁴C analysis, the water-extraction treatment on the filter prior to any thermal treatment is an essential prerequisite for subsequent radiocarbon measurements; otherwise the non-fossil contribution may be overestimated due to the positive bias from charring. The Swiss_4S protocol involves the following consecutive four steps (S1, S2, S3 and S4): (1) S1 in pure oxygen (O₂) at 375 °C for separation of OC for untreated filters and water-insoluble organic carbon (WINSOC) for water-extracted filters; (2) S2 in O₂ at 475 °C followed by (3) S3 in helium (He) at 650 °C, aiming at complete OC removal before EC isolation and leading to better consistency with thermal-optical protocols like EUSAAR_2, compared to pure oxygen methods; and (4) S4 in O₂ at 760 °C for recovery of the remaining EC.

WINSOC was found to have a significantly higher fossil contribution than the water-soluble OC (WSOC). Moreover, the experimental results demonstrate the lower refractivity of wood-burning EC compared to fossil EC and the difficulty of clearly isolating EC without premature evolution. Hence, simplified techniques of EC isolation for ¹⁴C analysis are prone to a substantial bias and generally tend towards an overestimation of fossil sources. To obtain the comprehensive picture of the sources of carbonaceous aerosols, the Swiss_4S protocol is not only implemented to measure OC and EC fractions, but also WINSOC as well as a continuum of refractory OC and non-refractory EC for ¹⁴C source apportionment. In addition, WSOC can be determined by subtraction of the water-soluble fraction of TC from untreated TC. Last, we recommend that ¹⁴C results of EC should in general be reported together with the EC recovery.