The important role of nitrate in iron and manganese dissolution and sulfate formation in fine particles at a coastal site in Northern China

Bioavailable transition trace elements, such as soluble iron (Fes) and soluble manganese (Mns) in aerosols, play a crucial role in atmospheric sulfate formation and marine ecosystems. In this study conducted during the spring of 2017 in Qingdao, a coastal city in Northern China, we applied a combined approach of multiple linear regression (MLR) incorporating the results of positive matrix factorization (PMF) to estimate the solubility of Fe and Mn from various sources. PMF analysis showed that dust was the largest contributor to total Fe (Fe_T) (45.5 %), followed by non-ferrous smelting (20.3 %) and secondary formation processes (17.8 %). However, secondary formation processes (33.2 %), vehicle exhaust (19.3 %) and aqueous-phase processes (19.0 %) were found to be the primary contributors to Fes. For total Mn (Mn_T) and Mns, dust (21.2 % ∼ 35.0 %), secondary formation processes (20.3 % ∼ 25.6 %) and industry (12.6 % ∼ 16.3 %) were identified as the dominant contributors. The solubilities of Fe and Mn varied significantly depending on their sources. Interestingly, nitrate played a more pronounced role than sulfate in facilitating the dissolution of Fe and Mn during the acid processing due to the high molar ratio of NO₃^-/2SO₄^2- (1.72 ± 0.54) under the average RH of 56 % ± 15 %. This phenomenon suggested that the acid processing was primarily triggered by nitrate formation due to the low deliquescence relative humidity (DRH) of nitrate. Additionally, we discovered that the catalytic oxidation of SO₂ in aerosol water was primarily driven by Fe rather than Mn, serving as a more significant pathway for sulfate formation within a pH range of 2.0 to 4.4. These findings provide valuable insights into the impact of acidification on the dissolution of Fe and Mn under conditions of moderate RH in the real ambient atmosphere with the increasing of NO₃^-/2SO₄^2- molar ratio.