Piperazine Enhancing Sulfuric Acid-Based New Particle Formation: Implications for the Atmospheric Fate of Piperazine

Piperazine (PZ), a cyclic diamine, is one of 160 detected atmospheric amines and an alternative solvent to the widely used monoethanolamine in post-combustion CO2 capture. Participating in H2SO4 (sulfuric acid, SA)-based new particle formation (NPF) could be an important removal pathway for PZ. Here, we employed quantum chemical calculations and kinetics modeling to evaluate the enhancing potential of PZ on SA-based NPF by examining the formation of PZ-SA clusters. The results indicate that PZ behaves more like a monoamine in stabilizing SA and can enhance SA-based NPF at the parts per trillion (ppt) level. The enhancing potential of PZ is less than that of the chainlike diamine putrescine and greater than that of dimethylamine, which is one of the strongest enhancing agents confirmed by ambient observations and experiments. After the initial formation of the (PZ)(1)(SA)(1) cluster, the cluster mainly grows by gradual addition of SA or PZ monomer, followed by addition of (PZ)(1)(SA)(1) cluster. We find that the ratio of PZ removal by NPF to that by the combination of NPF and oxidations is 0.5-0.97 at 278.15 K. As a result, we conclude that participation in the NPF pathway could significantly alter the environmental impact of PZ compared to only considering oxidation pathways.