Cluster-dynamics-based parameterization for sulfuric acid–dimethylamine nucleation: comparison and selection through box and three-dimensional modeling

Journal Article · Wed Sep 18 00:00:00 EDT 2024 · Atmospheric Chemistry and Physics

DOI:https://doi.org/10.5194/acp-24-10261-2024· OSTI ID:2997690

Shen, Jiewen ^[1]; Zhao, Bin ^[1]; Wang, Shuxiao ^[1]; Ning, An ^[2]; Li, Yuyang ^[3]; Cai, Runlong ^[4]; Gao, Da ^[1]; Chu, Biwu ^[5]; Gao, Yang ^[6]; Shrivastava, Manish Kumar B. ^[7]; Jiang, Jingkun ^[3]; Zhang, Xiuhui ^[2]; He, Hong ^[5]

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1. Tsinghua Univ., Beijing (China); State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, Beijing (China)
2. Beijing Institute of Technology (China)
3. State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, Beijing (China)
4. Fudan Univ., Shanghai (China)
5. Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)
6. Ocean Univ. of China, Qingdao (China)
7. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Clustering of gaseous sulfuric acid (SA) enhanced by dimethylamine (DMA) is a major mechanism for new particle formation (NPF) in polluted atmospheres. However, uncertainty remains regarding the SA–DMA nucleation parameterization that reasonably represents cluster dynamics and is applicable across various atmospheric conditions. This uncertainty hinders accurate three-dimensional (3-D) modeling of NPF and the subsequent assessment of its environmental and climatic impacts. Here we extensively compare different cluster-dynamics-based parameterizations for SA–DMA nucleation and identify the most reliable one through a combination of box model simulations, 3-D modeling, and in situ observations. Results show that the parameterization derived from Atmospheric Cluster Dynamic Code (ACDC) simulations, incorporating the latest theoretical insights (DLPNO-CCSD(T)/aug-cc-pVTZ//ωB97X-D/6-311++G(3df,3pd) level of theory) and adequate representation of cluster dynamics, exhibits dependable performance in 3-D NPF simulation for both winter and summer conditions in Beijing and shows promise for application in diverse atmospheric conditions. Another ACDC-derived parameterization, replacing the level of theory with RI-CC2/aug-cc-pV(T+d)Z//M06-2X/6–311++G(3df,3pd), also performs well in NPF modeling at relatively low temperatures around 280 K but exhibits limitations at higher temperatures due to inappropriate representation of SA–DMA cluster thermodynamics. Additionally, a previously reported parameterization incorporating simplifications is applicable for simulating NPF in polluted atmospheres but tends to overestimate particle formation rates under conditions of elevated temperature (>∼300 K) and low-condensation sink (<∼3×10^-3 s⁻¹). Our findings highlight the applicability of the new ACDC-derived parameterization, which couples the latest SA–DMA nucleation theory and holistic cluster dynamics, in 3-D NPF modeling. The ACDC-derived parameterization framework provides a valuable reference for developing parameterizations for other nucleation systems.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE; National Natural Science Foundation of China (NSFC)
• Grant/Contract Number: AC05-76RL01830
• OSTI ID: 2997690
• Report Number(s): PNNL-SA--216400
• Journal Information: Atmospheric Chemistry and Physics, Journal Name: Atmospheric Chemistry and Physics Journal Issue: 18 Vol. 24; ISSN 1680-7324
• Publisher: Copernicus GmbH
• Country of Publication: United States
• Language: English