a b s t r a c tPolychlorinated naphthalenes (PCNs) were listed as persistent organic pollutants in the Stockholm Convention in 2015. Despite numerous studies on PCNs, little is known about their occurrence in atmospheric particulate matter of different sizes. In this study, 49 PCN congeners were investigated for their concentrations and size-specific distributions in an urban atmosphere, and preliminary exposure assessments were conducted. Ambient air samples were collected using a high-volume cascade impactor for division into a gas fraction and four particle size fractions. Samples were collected from October 2013 to June 2014 at an urban site in Beijing, China. The concentration range for PCNs in the atmosphere (gas þ particle fractions) was 6.77e25.90 pg/m 3 (average 16.28 pg/m 3 ). The particle-bound concentration range was 0.17e2.78 pg/m 3 (average 1.73 pg/m 3 ). Therefore, PCNs were mainly found in the gas phase.The concentrations of PCNs in a fraction increased as the particle size decreased (d ae > 10 mm, 10 mm ! d ae > 2.5 mm, 2.5 mm ! d ae > 1.0 mm and d ae 1.0 mm). Consequently, PCNs were ubiquitous in inhalable fine particles, and the SPCNs associated with PM 1.0 and PM 2.5 reached 68.4% and 84.3%, respectively. Tetra-CNs and penta-CNs (the lower chlorinated homologues) predominated in the atmosphere. The homologue profiles in different size particles were almost similar, but the particulate profiles were different from those in the gas phase. Among the individual PCNs identified, CN38/40, CN52/60 and CN75 were the dominant compounds in the atmosphere. CN66/67 and CN73 collectively accounted for most of the total dioxin-like TEQ concentrations of the PCNs. Exposure to toxic compounds, such as PCNs present in PM 1.0 or PM 2.5 , may affect human health. This work presents the first data on size-specific distributions of PCNs in the atmosphere.