Sources and formation of carbonaceous aerosols in Xi'an, China: primary emissions and secondary formation constrained by radiocarbon

To investigate the sources and formation mechanisms of carbonaceous aerosols, a major contributor to severe particulate air pollution, radiocarbon (14C) measurements were conducted on aerosols sampled from November 2015 to November 2016 in Xi'an, China. Based on the 14C content in elemental carbon (EC), organic carbon (OC) and water-insoluble OC (WIOC), contributions of major sources to carbonaceous aerosols are estimated over a whole seasonal cycle: primary and secondary fossil sources, primary biomass burning, and other non-fossil carbon formed mainly from secondary processes. Primary fossil sources of EC were further sub-divided into coal and liquid fossil fuel combustion by complementing 14C data with stable carbon isotopic signatures. The dominant EC source was liquid fossil fuel combustion (i.e., vehicle emissions), accounting for 64 % (median; 45 %–74 %, interquartile range) of EC in autumn, 60 % (41 %–72 %) in summer, 53 % (33 %–69 %) in spring and 46 % (29 %–59 %) in winter. An increased contribution from biomass burning to EC was observed in winter (#approx#28 %) compared to other seasons (warm period; #approx#15 %). In winter, coal combustion (#approx#25 %) and biomass burning equally contributed to EC, whereas in the warm period, coal combustion accounted for a larger fraction of EC than biomass burning. The relative contribution of fossil sources to OC was consistently lower than that to EC, with an annual average of 47#+-#4 %. Non-fossil OC of secondary origin was an important contributor to total OC (35#+-#4 %) and accounted for more than half of non-fossil OC (67#+-#6 %) throughout the year. Secondary fossil OC (SOCfossil) concentrations were higher than primary fossil OC (POCfossil) concentrations in winter but lower than POCfossil in the warm period. Fossil WIOC and water-soluble OC (WSOC) have been widely used as proxies for POCfossil and SOCfossil, respectively. This assumption was evaluated by (1) comparing their mass concentrations with POCfossil and SOCfossil and (2) comparing ratios of fossil WIOC to fossil EC to typical primary OC-to-EC ratios from fossil sources including both coal combustion and vehicle emissions. The results suggest that fossil WIOC and fossil WSOC are probably a better approximation for primary and secondary fossil OC, respectively, than POCfossil and SOCfossil estimated using the EC tracer method.