Optimizing isolation protocol of organic carbon and elemental carbon for 14C analysis using fine particulate samples

- A high-vacuum setup was established to collect carbon fractions.
- Both OC and EC fractions were isolated from the Sunset carbon analyzer.
- Simple protocols for isolating OC and EC for 14C analysis were proposed.
- Seasonal 14C levels of OC and EC in a heavily polluted city were reported.

Radiocarbon (14C) analysis is a unique tool that can be used to directly apportion organic carbon (OC) and elemental carbon (EC) into fossil and non-fossil fractions. In this study, a coupled carbon analyzer and high-vacuum setup was established to collect atmospheric OC and EC. We thoroughly investigated the correlations between 14C levels and mass recoveries of OC and EC using urban PM2.5 samples collected from a city in central China and found that: (1) the 14C signal of the OC fraction collected in the helium phase of the EUSSAR_2 protocol (200 °C for 120 s, 300 °C for 150 s, 450 °C for 180 s, and 650 °C for 180 s) was representative of the entire OC fraction, with a relative error of approximately 6%, and (2) after thermal treatments of 120 s at 200 °C, 150 s at 300 °C, and 180 s at 475 °C in an oxidative atmosphere (10% oxygen, 90% helium) and 180 s at 650 °C in helium, the remaining EC fraction sufficiently represented the 14C level of the entire EC, with a relative error of <10%. The average recovery of the OC and EC fractions for 14C analysis was 64± 7% (n = 5) and 87 ± 5% (n = 5), respectively. The fraction of modern carbon in the OC and EC of reference material (RM) 8785 was 0.564 ± 0.013 and 0.238 ± 0.006, respectively. Analysis of 14C levels in four selected PM2.5 samples in Xinxiang, China revealed that the relative contribution of fossil sources in OC and EC in the PM2.5 samples were 50.5± 5.8% and 81.4± 2.6%, respectively, which are comparable to findings in previous studies conducted in other Chinese cities. We confirmed that most urban EC derives from fossil fuel combustion processes, whereas both fossil and non-fossil sources have comparable and important impacts on OC. Our results suggested that water-soluble organic carbon (WSOC) and its pyrolytic carbon can be completely removed before EC collection via the method employed in this study.