Quantum chemical modeling of organic enhanced atmospheric nucleation: A critical review

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2023, Volume and Issue: 13(5)

Published: May 9, 2023

Abstract Aerosol particles are important for our global climate, but the mechanisms and especially relative importance of various vapors new formation (NPF) remain uncertain. Quantum chemical (QC) studies on organic enhanced nucleation has past couple decades attracted immense attention, very little remains known about exact compounds that potentially NPF. Here we comprehensively review QC literature atmospheric cluster involving compounds. We outline potential systems should be further investigated. Cluster complex multi‐functional accretion products warrant investigations, such out reach with currently applied methodologies. suggest a “cluster functional groups” approach to address this issue, which will allow identification structure involved in This article is categorized under: Theoretical Physical Chemistry > Reaction Dynamics Kinetics Software Thermochemistry Molecular Statistical Mechanics Interactions

Language: Английский

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Trends of Full-Volatility Organic Emissions in China from 2005 to 2019 and Their Organic Aerosol Formation Potentials

Environmental Science & Technology Letters, Journal Year: 2023, Volume and Issue: 10(2), P. 137 - 144

Published: Jan. 31, 2023

Emissions of organic compounds have strong influences on the environment. Most previous emission inventories only cover emissions particulate carbon and nonmethane volatile (NMVOC) but neglect semivolatile intermediate (S/IVOC), which considerably contribute to aerosol (OA) burden. Herein, we developed a full-volatility inventory in China from 2005 2019 analyzed OA formation potential (OAFP) each volatility bin source using two-dimensional basis set (2D-VBS) box model. The low/extremely low/ultralow VOC (xLVOC) decreased substantially during 2005–2019, while SVOC showed significant decline after 2014, mainly because reduced residential biomass consumption. IVOC amounts were similar those 2005; however, major sources changed substantially. chemical products (VCP) increased significantly became dominant emissions. S/IVOC VCP contributed 1322 kt OAFP 2019, higher than total anthropogenic xLVOC Considering high S/IVOC, future air pollution control policies should prioritize VCP, burning, diesel vehicles.

Language: Английский

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Isoprene nitrates drive new particle formation in Amazon’s upper troposphere

Nature, Journal Year: 2024, Volume and Issue: 636(8041), P. 124 - 130

Published: Dec. 4, 2024

Abstract New particle formation (NPF) in the tropical upper troposphere is a globally important source of atmospheric aerosols 1–4 . It known to occur over Amazon basin, but nucleation mechanism and chemical precursors have yet be identified 2 Here we present comprehensive situ aircraft measurements showing that extremely low-volatile oxidation products isoprene, particularly certain organonitrates, drive NPF Amazonian troposphere. The organonitrates originate from OH-initiated isoprene forest emissions presence nitrogen oxides lightning. Nucleation bursts start about h after sunrise outflow nocturnal deep convection, producing high aerosol concentrations more than 50,000 particles cm − 3 We report characteristic diurnal cycles precursor gases particles. Our observations show interplay between biogenic convection with associated lightning, photochemistry low ambient temperature uniquely promotes NPF. grow time, undergo long-range transport descend through subsidence lower troposphere, which they can serve as cloud condensation nuclei (CCN) influence Earth’s hydrological cycle, radiation budget climate 1,4–8

Language: Английский

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Measurement report: Molecular composition and volatility of gaseous organic compounds in a boreal forest – from volatile organic compounds to highly oxygenated organic molecules

Atmospheric chemistry and physics, Journal Year: 2021, Volume and Issue: 21(11), P. 8961 - 8977

Published: June 14, 2021

Abstract. The molecular composition and volatility of gaseous organic compounds were investigated during April–July 2019 at the Station for Measuring Ecosystem – Atmosphere Relations (SMEAR) II situated in a boreal forest Hyytiälä, southern Finland. In order to obtain more complete picture full understanding ambient (from volatile compounds, VOCs, highly oxygenated molecules, HOMs), two different instruments used. A Vocus proton-transfer-reaction time-of-flight mass spectrometer (Vocus PTR-ToF; hereafter Vocus) was deployed measure VOCs less (i.e., OVOCs). addition, multi-scheme chemical ionization inlet coupled an atmospheric pressure interface (MION API-ToF) used detect (using Br− as reagent ion; MION-Br) (including HOMs; using NO3- MION-NO3). comparison among measurement techniques revealed that highest elemental oxygen-to-carbon ratios (O : C) observed by MION-NO3 (0.9 ± 0.1, average 1 standard deviation), followed MION-Br (0.8 0.1); lowest O C (0.2 0.1). Diurnal patterns measured found vary techniques, even with same formula, suggesting contributions isomers detected and/or fragmentation from parent inside instruments. Based on complementary information obtained Vocus, MION-Br, MION-NO3, bulk all this obtained. As expected, VOC class most abundant (about 53.2 %), intermediate-volatility (IVOCs, about 45.9 %). Although condensable (low-volatility LVOCs; extremely low ELVOCs; ultralow-volatility ULVOCs) only comprised 0.2 % total they play important role new particle formation shown previous studies forest. Our study shows characterization advantages combining MION API-ToF measuring oxidation extents HOMs). results therefore provide comprehensive well insights into interpreting measurements or testing/improving parameterizations transport climate models.

Language: Английский

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Towards understanding the characteristics of new particle formation in the Eastern Mediterranean

Atmospheric chemistry and physics, Journal Year: 2021, Volume and Issue: 21(11), P. 9223 - 9251

Published: June 16, 2021

Abstract. To quantify the contribution of new particle formation (NPF) to ultrafine number and cloud condensation nuclei (CCN) budgets, one has understand mechanisms that govern NPF in different environments its temporal extent. Here, we study Cyprus, an Eastern Mediterranean country located at crossroads three continents affected by diverse air masses originating from continental, maritime, desert-dust source areas. We performed 1-year continuous measurements aerosol particles down ∼ 1 nm diameter for first time Middle East (EMME) region. These were complemented with trace gas data, meteorological variables, retroplume analysis. show is a very frequent phenomenon this site higher frequencies occurrence during spring autumn. events both local regional origin, occurred frequently month lowest frequency. Some exhibited multiple onsets, while others apparent shrinkage size. Additionally, observed nighttime episodes high loadings. Particle rates growth comparable those urban environments, although our rural one. Meteorological variables gases played role explaining intra-monthly variability events, but they did not explain why summer months had least Similarly, pre-existing loading seasonality. The frequency associated H2SO4 concentrations lower NO2 concentrations, which indicator anthropogenic influence. Air arriving these months, could suggest precursor vapors important nucleation are transported East. Further comprehensive required prove hypothesis.

Language: Английский

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Anthropogenic Volatile Organic Compound (AVOC) Autoxidation as a Source of Highly Oxygenated Organic Molecules (HOM)

The Journal of Physical Chemistry A, Journal Year: 2021, Volume and Issue: 125(41), P. 9027 - 9039

Published: Oct. 7, 2021

Gas-phase hydrocarbon autoxidation is a rapid pathway for the production of in situ aerosol precursor compounds. It highway to molecular growth and lowering vapor pressure, it produces hydrogen-bonding functional groups that allow molecule bind into substrate. crucial process formation atmospheric secondary organic (SOA). Recently, gas-phase several volatile compounds (VOC) has been shown yield highly oxygenated molecules (HOM). Most details on HOM have obtained from biogenic monoterpenes their surrogates, with cyclic structures double bonds both found strongly facilitate formation, especially ozonolysis reactions. Similar structural features common aromatic observed high yields, despite lack appreciable O

Language: Английский

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The impacts of VOCs on PM2.5 increasing via their chemical losses estimates: A case study in a typical industrial city of China

Atmospheric Environment, Journal Year: 2022, Volume and Issue: 273, P. 118978 - 118978

Published: Jan. 30, 2022

Language: Английский

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Frequent new particle formation at remote sites in the subboreal forest of North America

Atmospheric chemistry and physics, Journal Year: 2022, Volume and Issue: 22(4), P. 2487 - 2505

Published: Feb. 24, 2022

Abstract. The frequency and intensity of new particle formation (NPF) over remote forest regions in the temperate boreal zones, thus importance NPF for aerosol budget life cycle pristine atmosphere, remains controversial. Whereas has been shown to occur relatively frequently at several sites Scandinavia, it was found be nearly absent a mid-continental site Siberia. To explore this issue further, we made measurements size distributions between 10 420 nm diameter two transition region British Columbia, Canada. covered 23 d during month June 2019, time when typically reaches its seasonal maximum midlatitude regions. These are first such near-pristine on North American continent. Although were only 150 km apart, there clear differences them. At Eagle Lake site, occurred daily, nucleation-mode concentrations reached above 5000 cm−3. In contrast, Nazko River six events 11 d, about 800 reasons difference could not conclusively resolved with available data; they may include air mass origins, preexisting aerosols, density type cover surrounding contrast observations other environments, that our nighttime just as daytime. Together lack identifiable sources sulfuric acid precursor species fetch sites, suggests nucleation extremely low volatility organics predominant mechanism. Our results indicate extended measurement campaigns more comprehensive set instrumentation investigate role America essential deeper scientific understanding important process global budget.

Language: Английский

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NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 8, 2023

The interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated molecules (HOM), key precursors secondary aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on from monoterpenes concentrations (0 - 82 pptv). We demonstrate such enhance modulating RO2 loss favoring alkoxy continue to autoxidize through isomerization. These insights suggest yields typical boreal forest emissions vary 2.5%-6.5%, will not completely inhibited high Our findings challenge notion monotonically reduces extending knowledge RO2-NO interactions low-NO regime. This represents a major advance towards an accurate assessment budgets, especially in environments, which prevails pre-industrial atmosphere, pristine areas, upper boundary layer.

Language: Английский

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Atmospheric nanoparticle growth

Reviews of Modern Physics, Journal Year: 2023, Volume and Issue: 95(4)

Published: Nov. 9, 2023

Atmospheric nanoparticles can serve as nuclei for cloud droplets, thereby inducing significant but uncertain effects on the radiative forcing of climate system. This article focuses physicochemical processes that govern growth these particles from formation molecular clusters until reach sizes where they act condensation nuclei. The review describes latest developments in measurement and modeling connects domains to large-scale simulations such Earth system models. authors recommend closer coordination among laboratory studies, atmospheric measurements, understand importance

Language: Английский

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