the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Cluster Dynamics-based Parameterization for Sulfuric Acid-Dimethylamine Nucleation: Comparison and Selection through Box- and Three-Dimensional- Modeling
Abstract. 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 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 valuable reference for developing parameterizations for other nucleation systems.
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RC1: 'Comment on egusphere-2024-642', Anonymous Referee #2, 25 Apr 2024
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General comments:
The work conducts comprehensive comparison of different cluster dynamics-based parameterizations for SA-DMA nucleation by integrating box-model simulations, 3-D modeling, and in-situ observations. It is found that ACDC_DB performs well in modeling 3-D NPF for both winter and summer in Beijing and shows promise for application in various atmospheric environments. Furthermore, ACDC_RM_SF0.5 exhibits effective applicability at ~280 K, but has limitations in predicting J1.4 at elevated T. While Dynamic_Sim is applicable for simulating NPF in polluted atmospheres but makes significant overestimation of J1.4 under conditions of high T and low CS.The topic discussed in this paper is highly meaningful for developing parameterizations for various nucleation systems. The reported results are clearly presented and are relevant to the scope of Atmos. Chem. Phys. I recommend publication of this manuscript after consideration of the following comments.
Specific comments:
1) Lines 94-95: Please explain briefly the reason for considering such three simplifications within Dynamics_Sim.
2) Line 281: To make a clear understanding among readers, it would be better to provide the concept of the chemical initial and boundary conditions in WRF-Chem/R2D-VBS simulations.
3) Figure 6C: It can be noted that ACDC_DB and Dynamic_Sim also exhibit an underestimation of averaged PNSDs in the 2-100 nm range in comparison to observation. Can the authors account for the cause of this phenomenon?Technical corrections:
1) Lines 143-144: “n and m represent the number of SA and DMA molecules in a cluster” should be “m and n represent the number of SA and DMA molecules in a cluster”.
2) Lines 465 and 482: “ACDC_RM” should be “ACDC_RM_SF0.5”.
3) Supporting Information, lines 37 and 38: “A: ΔG = 13.5 kcal/mol; B: ΔG = 12.9 kcal/mol” should be “A: ΔG = -13.5 kcal/mol; B: ΔG = -12.9 kcal/mol”. -
CC1: 'Comment on egusphere-2024-642', Tinja Olenius, 26 Apr 2024
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The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2024/egusphere-2024-642/egusphere-2024-642-CC1-supplement.pdf
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