Abstract
<strong class="journal-contentHeaderColor">Abstract.</strong> Air ions are the key components for a series of atmospheric physicochemical interactions, such as ion-catalyzed reactions, ion-molecule reactions, and ion-induced new particle formation. They also control atmospheric electrical properties with effects on global climate. We performed molecular-level measurements of cluster ions at the high-altitude research station Chacaltaya (CHC; 5240 m a.s.l.), located in the Bolivian Andes, from January to May 2018 using an atmospheric pressure interface time-of-flight mass spectrometer. The negative ions mainly consisted of (H<sub>2</sub>SO<sub>4</sub>)<sub>0–3</sub>•HSO<sub>4</sub><sup>−</sup>, (HNO<sub>3</sub>)<sub>0–2</sub>•NO<sub>3</sub><sup>−</sup>, SO<sub>5</sub><sup>−</sup>, (NH<sub>3</sub>)<sub>1–6</sub>•(H<sub>2</sub>SO<sub>4</sub>)<sub>3–7</sub>•HSO<sub>4</sub><sup>−</sup>, malonic acid-derived, and CHO/CHON•(HSO<sub>4</sub><sup>−</sup>/NO<sub>3</sub><sup>−</sup>) cluster ions. Their temporal variability exhibited distinct diurnal and seasonal patterns due to the changes in the corresponding neutral species’ molecular properties (such as electron affinity and proton affinity) and concentrations resulting from the air masses arriving at CHC from different source regions. The positive ions were mainly composed of protonated amines and organic cluster ions, but exhibited no clear diurnal variation. H<sub>2</sub>SO<sub>4</sub>-NH<sub>3</sub> cluster ions likely contributed to the new particle formation process, particularly during wet-to-dry transition period and dry season when CHC was more impacted by air masses originating from source regions with elevated SO<sub>2</sub> emissions. Our study provides new insights into the chemical composition of atmospheric cluster ions and their role in new particle formation in the high-altitude mountain environment of the Bolivian Andes.
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