Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 5 4 2005 10.5194/acpd-5-5299-2005 http://www.atmos-chem-phys-discuss.net/5/5299/2005/ http://www.atmos-chem-phys-discuss.net/5/5299/2005/acpd-5-5299-2005.html http://www.atmos-chem-phys-discuss.net/5/5299/2005/acpd-5-5299-2005.pdf 5299 5324 2005-07-28 Application of positive matrix factorization in estimating aerosol secondary organic carbon in Hong Kong and insights into the formation mechanisms Z. B. Yuan J. Z. Yu A. K. H. Lau P. K. K. Louie J. C. H. Fung Atmospheric, Marine and Coastal Environment Program, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China Department of Mathematics, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China Environmental Protection Department of HKSAR Government, 33/F, Revenue Tower, 5 Gloucester Rd., Wanchai, Hong Kong, China Secondary organic carbon (SOC) is often a significant portion of organic carbon (OC) in ambient particulate matter (PM). The levels and seasonal patterns of SOC in Hong Kong were examined using more than 2000 PM10 measurements made over a 4.5-year period (1998–2002) in a network of ten air quality monitoring stations. The positive matrix factorization (PMF) model was used to analyze this large data set for source identification and apportioning. SOC was subsequently estimated to be the sum of OC present in the secondary sources, i.e., secondary sulfate, secondary nitrate, and secondary organic aerosol. The annual average SOC as estimated by the PMF method was 4.25 µg C/m3 while the summer average was 1.66 µg C/m3 and the winter average was 7.05 µg C/m3. In comparison, the method that uses EC as a tracer for primary carbonaceous aerosol sources to derive SOC overestimated SOC by 70–212% for the summer samples and by 4–43% for the winter samples. The overestimation by the EC tracer method resulted from the inability of obtaining a single OC/EC ratio that represented a mixture of primary sources varying in time and space. We found that SOC and secondary sulfate had synchronous seasonal variation and were correlated in individual seasons, suggesting common factors that control their formation. Considering the well-established fact that both gas phase oxidation and in-cloud processing are important formation pathways for sulfate, the synchronicity of SOC and sulfate suggests that in-cloud pathways are also important for SOC formation. Additionally, the presence of SOC was found to be enhanced more than that of secondary sulfate in the winter. We postulate this to be a combined result of favorable partitioning of semivolatile SOC species in the particle phase and more abundant SOC precursors in the winter.