Characterization and sources of trace elements in PM₁ during autumn and winter in Qingdao, Northern China

Atmospheric sub-micrometer particles (PM₁, particles with an aerodynamic diameter ≤ 1.0 μm) monitoring in Qingdao, a coastal city in Northern China, was conducted for two consecutive years from November 1, 2018 to January 31, 2019 (hereafter referred to as OP_2018-2019) and from October 28, 2019 to January 20, 2020 (hereafter referred to as OP_2019-2020). The results showed that compared with OP_2018-2019, the concentrations of V, Ni, As, Pb, and Cd in PM₁ in OP_2019-2020 decreased by 61.9%, 31.4%, 49.2%, 25.4%, and 27.1%, respectively. For the indicators of ship emission sources, a significant reduction in V (73.3%) and Ni (22.1%) concentrations were observed after the implementation of the updated Domestic Emission Control Area (DECA 2.0) policy for ships since January 1, 2019 proposed by the Ministry of Transportation. This result demonstrated that the implementation of the DECA 2.0 policy had a significant effect on reducing ship emissions. The Field Emission Scanning Electron Microscope analysis identified the impact of ship emission sources, while the inconsistent distribution of V and Ni revealed other potential sources of Ni. The V/Ni ratios during the pre-policy and post-policy periods decreased by 40.7%. Along with the further implementation of the domestic coastal ship pollution control zone policy, V/Ni ratio should be cautiously used as a parameter for ship emission sources. The positive matrix factorization method identified five source factors: coal combustion/biomass burning (47.8%), crustal sources (21.2%), vehicle exhaust/road dust (15.1%), industrial emissions (11.1%), and ship emissions (4.9%). The contribution rates of ship emission sources before and after the DECA 2.0 policy were analyzed and found to be 5.6% and 3.4%. The potential source contribution factor analysis of As showed that the potential emission source areas were significantly reduced in OP_2019-2020, which might be related to the coal fired cleanup operations conducted in Beijing-Tianjin-Hebei and surrounding areas.