RESUMEN
New particle formation (NPF) substantially affects the global radiation balance and climate. Iodic acid (IA) is a key marine NPF driver that recently has also been detected inland. However, its impact on continental particle nucleation remains unclear. Here, we provide molecular-level evidence that IA greatly facilitates clustering of two typical land-based nucleating precursors: dimethylamine (DMA) and sulfuric acid (SA), thereby enhancing particle nucleation. Incorporating this mechanism into an atmospheric chemical transport model, we show that IA-induced enhancement could realize an increase of over 20% in the SA-DMA nucleation rate in iodine-rich regions of China. With declining anthropogenic pollution driven by carbon neutrality and clean air policies in China, IA could enhance nucleation rates by 1.5 to 50 times by 2060. Our results demonstrate the overlooked key role of IA in continental NPF nucleation and highlight the necessity for considering synergistic SA-IA-DMA nucleation in atmospheric modeling for correct representation of the climatic impacts of aerosols.
RESUMEN
New particle formation via the ion-mediated sulfuric acid and ammonia molecular clustering mechanism remains the most widely observed and experimentally verified pathway. Recent laboratory and molecular level observations indicate iodine-driven nucleation as a potentially important source of new particles, especially in coastal areas. In this study, we assess the role of iodine species in particle formation using the best available molecular thermochemistry data and coupled to a detailed 1-d column model which is run along air mass trajectories over the Southern Ocean and the coast of Antarctica. In the air masses traversing the open ocean, ion-mediated SA-NH3 clustering appears insufficient to explain the observed particle size distribution, wherein the simulated Aitken mode is lacking. Including the iodine-assisted particle formation improves the modeled Aitken mode representation with an increase in the number of freshly formed particles. This implies that more particles survive and grow to Aitken mode sizes via condensation of gaseous precursors and heterogeneous reactions. Under certain meteorological conditions, iodine-assisted particle formation can increase cloud condensation nuclei concentrations by 20%-100%.
Asunto(s)
Aerosoles , Yodo , Regiones Antárticas , Yodo/química , Tamaño de la Partícula , Contaminantes Atmosféricos , Material ParticuladoRESUMEN
Iodine oxoacids (HIO3 and HIO2)-driven nucleation has been suggested to efficiently contribute to new particle formation (NPF) in marine atmospheres. Abundant atmospheric nucleation precursors may further enhance HIO3-HIO2-driven nucleation through various multicomponent nucleation mechanisms. However, the specific enhancing potential (EP) of different precursors remains largely unknown. Herein, the EP-based screening model of precursors and enhancing mechanism of the precursor with the highest EP on HIO3-HIO2 nucleation were investigated. The formation free energies (ΔG), as critical parameters for evaluating EP, were calculated for the dimers of 63 selected precursors with HIO2. Based on the ΔG values, (1) a quantitative structure-activity relationship model was developed for evaluating ΔG of other precursors and (2) atmospheric concentrations of 63 (precursor)1(HIO2)1 dimer clusters were assessed to identify the precursors with the highest EP for HIO3-HIO2-driven nucleation by combining with earlier results for the nucleation with HIO3 as the partner. Methanesulfonic acid (MSA) was found to be one of the precursors with the highest EP. Finally, we found that MSA can effectively enhance HIO3-HIO2 nucleation at atmospheric conditions by studying larger MSA-HIO3-HIO2 clusters. These results augment our current understanding of HIO3-HIO2 and MSA-driven nucleation and may suggest a larger impact of HIO2 in atmospheric aerosol nucleation.
Asunto(s)
Atmósfera , Clima , MesilatosRESUMEN
Iodic acid (IA) has recently been recognized as a key driver for new particle formation (NPF) in marine atmospheres. However, the knowledge of which atmospheric vapors can enhance IA-induced NPF remains limited. The unique halogen bond (XB)-forming capacity of IA makes it difficult to evaluate the enhancing potential (EP) of target compounds on IA-induced NPF based on widely studied sulfuric acid systems. Herein, we employed a three-step procedure to evaluate the EP of potential atmospheric nucleation precursors on IA-induced NPF. First, we evaluated the EP of 63 precursors by simulating the formation free energies (ΔG) of the IA-containing dimer clusters. Among all dimer clusters, 44 contained XBs, demonstrating that XBs are frequently formed. Based on the calculated ΔG values, a quantitative structure-activity relationship model was developed for evaluating the EP of other precursors. Second, amines and O/S-atom-containing acids were found to have high EP, with diethylamine (DEA) yielding the highest potential to enhance IA-induced nucleation by combining both the calculated ΔG and atmospheric concentration of considered 63 precursors. Finally, by studying larger (IA)1-3(DEA)1-3 clusters, we found that the IA-DEA system with merely 0.1 ppt (2.5×106 cm-3) DEA yields comparable nucleation rates to that of the IA-iodous acid system.
Asunto(s)
Atmósfera , Yodatos , Atmósfera/química , Aminas , GasesRESUMEN
Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce.
RESUMEN
Iodic acid (HIO3) was exploited as the effective source to build an artificial solid-electrolyte interphase (SEI) on the surface of Li anode. On one hand, HIO3 is a weak solid-state acid and can be easily handled to remove most ion-insulating residues like Li2CO3 and/or LiOH from the pristine Li surface; on the other hand, both the products of LiI and LiIO3 resulted from the chemical reactions between Li metal and HIO3 are reported to be the ion-conductive components. As a result, the lower voltage polarization and impedance, longer cycling lifetime and higher Coulombic efficiency have been successfully achieved in the HIO3-treated Li-Li and Li-Cu cells. By further using the HIO3-treated Li anode into practical Li-S batteries, the impressive results also have been obtained, with average discharge capacities of 719 mAh g-1 for 200 cycles (0.2 C) and 506 mAh g-1 for 500 cycles (0.5 C), which were better than the Li-S batteries using the pristine Li anode (552 and 401 mAh g-1, respectively) under the same conditions.