Chao Yan

Ion-induced nucleation of pure biogenic particles

Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours. It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere, and that ions have a relatively minor role. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded. Here we present evidence for the formation of aerosol particles from highly oxidized biogenic vapours in the absence of sulfuric acid in a large chamber under atmospheric conditions. The highly oxygenated molecules (HOMs) are produced by ozonolysis of α-pinene. We find that ions from Galactic cosmic rays increase the nucleation rate by one to two orders of magnitude compared with neutral nucleation. Our experimental findings are supported by quantum chemical calculations of the cluster binding energies of representative HOMs. Ion-induced nucleation of pure organic particles constitutes a potentially widespread source of aerosol particles in terrestrial environments with low sulfuric acid pollution.

The role of low-volatility organic compounds in initial particle growth in the atmosphere

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer. Although recent studies predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory), has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.

Reduced anthropogenic aerosol radiative forcing caused by biogenic new particle formation

Significance A mechanism for the formation of atmospheric aerosols via the gas to particle conversion of highly oxidized organic molecules is found to be the dominant aerosol formation process in the preindustrial boundary layer over land. The inclusion of this process in a global aerosol model raises baseline preindustrial aerosol concentrations and could lead to a reduction of 27% in estimates of anthropogenic aerosol radiative forcing. The magnitude of aerosol radiative forcing caused by anthropogenic emissions depends on the baseline state of the atmosphere under pristine preindustrial conditions. Measurements show that particle formation in atmospheric conditions can occur solely from biogenic vapors. Here, we evaluate the potential effect of this source of particles on preindustrial cloud condensation nuclei (CCN) concentrations and aerosol–cloud radiative forcing over the industrial period. Model simulations show that the pure biogenic particle formation mechanism has a much larger relative effect on CCN concentrations in the preindustrial atmosphere than in the present atmosphere because of the lower aerosol concentrations. Consequently, preindustrial cloud albedo is increased more than under present day conditions, and therefore the cooling forcing of anthropogenic aerosols is reduced. The mechanism increases CCN concentrations by 20–100% over a large fraction of the preindustrial lower atmosphere, and the magnitude of annual global mean radiative forcing caused by changes of cloud albedo since 1750 is reduced by 0.22 W m−2 (27%) to −0.60 W m−2. Model uncertainties, relatively slow formation rates, and limited available ambient measurements make it difficult to establish the significance of a mechanism that has its dominant effect under preindustrial conditions. Our simulations predict more particle formation in the Amazon than is observed. However, the first observation of pure organic nucleation has now been reported for the free troposphere. Given the potentially significant effect on anthropogenic forcing, effort should be made to better understand such naturally driven aerosol processes.

Causes and importance of new particle formation in the present‐day and preindustrial atmospheres

New particle formation has been estimated to produce around half of cloud-forming particles in the present-day atmosphere, via gas-to-particle conversion. Here we assess the importance of new particle formation (NPF) for both the present-day and the preindustrial atmospheres. We use a global aerosol model with parametrizations of NPF from previously published CLOUD chamber experiments involving sulfuric acid, ammonia, organic molecules, and ions. We find that NPF produces around 67% of cloud condensation nuclei at 0.2% supersaturation (CCN0.2%) at the level of low clouds in the preindustrial atmosphere (estimated uncertainty range 45–84%) and 54% in the present day (estimated uncertainty range 38–66%). Concerning causes, we find that the importance of biogenic volatile organic compounds (BVOCs) in NPF and CCN formation is greater than previously thought. Removing BVOCs and hence all secondary organic aerosol from our model reduces low-cloud-level CCN concentrations at 0.2% supersaturation by 26% in the present-day atmosphere and 41% in the preindustrial. Around three quarters of this reduction is due to the tiny fraction of the oxidation products of BVOCs that have sufficiently low volatility to be involved in NPF and early growth. Furthermore, we estimate that 40% of preindustrial CCN0.2% are formed via ion-induced NPF, compared with 27% in the present day, although we caution that the ion-induced fraction of NPF involving BVOCs is poorly measured at present. Our model suggests that the effect of changes in cosmic ray intensity on CCN is small and unlikely to be comparable to the effect of large variations in natural primary aerosol emissions.

Oxidizing capacity of the rural atmosphere in Hong Kong, Southern China

Atmospheric oxidizing capacity (AOC), dominated by the hydroxyl radical (OH), is an important index of the self-cleaning capacity of atmosphere and plays a vital role in the tropospheric chemistry. To better understand the key processes governing the chemistry of rural atmosphere of southern China, we analyzed the oxidation capacity and radical chemistry at a regional background site in Hong Kong from 23 August to 22 December 2012, which covered the summer, autumn and winter seasons. A chemical box model built on the latest Master Chemical Mechanism (v3.3) was used to elucidate the OH reactivity and sources of ROX radicals (ROX=OH+HO2+RO2). The AOC showed a clear seasonal pattern with stronger intensity in late summer compared to autumn and winter. Reactions with NO2 (30%) and oxygenated volatile organic compounds (OVOCs) (31%) together dominated the OH loss in summer, while reactions with CO (38% in autumn and 39% in winter) and OVOCs (34% in autumn and 25% in winter) made larger contributions in autumn and winter. Photolysis of O3 (36%-47%) presented the major ROX source during all three seasons. The second largest ROx source was HONO photolysis (25%) in summer compared to HCHO photolysis in autumn (20%) and winter (21%). Besides, photolysis of other OVOCs was another important primary source of ROx radicals with average contributions of 14%, 13% and 20% for the summer, autumn and winter cases, respectively. Overall, the present study evaluates the oxidizing capacity of the rural atmosphere of South China and elucidates the varying characteristics of photochemical processes in different air masses.

Solar eclipse demonstrating the importance of photochemistry in new particle formation

Solar eclipses provide unique possibilities to investigate atmospheric processes, such as new particle formation (NPF), important to the global aerosol load and radiative balance. The temporary absence of solar radiation gives particular insight into different oxidation and clustering processes leading to NPF. This is crucial because our mechanistic understanding on how NPF is related to photochemistry is still rather limited. During a partial solar eclipse over Finland in 2015, we found that this phenomenon had prominent effects on atmospheric on-going NPF. During the eclipse, the sources of aerosol precursor gases, such as sulphuric acid and nitrogen- containing highly oxidised organic compounds, decreased considerably, which was followed by a reduced formation of small clusters and nanoparticles and thus termination of NPF. After the eclipse, aerosol precursor molecule concentrations recovered and re-initiated NPF. Our results provide direct evidence on the key role of the photochemical production of sulphuric acid and highly oxidized organic compounds in maintaining atmospheric NPF. Our results also explain the rare occurrence of this phenomenon under dark conditions, as well as its seemingly weak connection with atmospheric ions.

Observations of biogenic ion-induced cluster formation in the atmosphere.

On the ability of biogenic vapors to initiate ion-induced cluster formation in the boreal forest. A substantial fraction of aerosols, which affect air quality and climate, is formed from gaseous precursors. Highly oxygenated organic molecules (HOMs) are essential to grow the newly formed particles and have been evidenced to initiate ion-induced nucleation in chamber experiments in the absence of sulfuric acid. We investigate this phenomenon in the real atmosphere using an extensive set of state-of-the-art ion and mass spectrometers deployed in a boreal forest environment. We show that within a few hours around sunset, HOMs resulting from the oxidation of monoterpenes are capable of forming and growing ion clusters even under low sulfuric acid levels. In these conditions, we hypothesize that the lack of photochemistry and essential vapors prevents the organic clusters from growing past 6 nm. However, this phenomenon might have been a major source of particles in the preindustrial atmosphere and might also contribute to particle formation in the future and consequently affect the climate.

Heterogeneous N 2 O 5 uptake coefficient and production yield of ClNO 2 in polluted northern China: Roles of aerosol water content and chemical composition

Heterogeneous uptake of dinitrogen pentoxide (N2O5) and production of nitryl chloride (ClNO2) are important nocturnal atmospheric processes that have significant implications for the production of secondary pollutants. However, the understanding of N2O5 uptake processes and ClNO2 production remains limited, especially in China. This study presents a field investigation of the N2O5 heterogeneous uptake coefficient (γ (N2O5)) and ClNO2 production yield (φ) in a polluted area of northern China during the summer of 2014. The N2O5 uptake coefficient and ClNO2 yield were estimated by using the simultaneously measured ClNO2 and total nitrate in 10 selected cases, which have concurrent increases in the ClNO2 and nitrate concentrations and relatively stable environmental conditions. The determined γ (N2O5) and φ values varied greatly, with an average of 0.022 for γ (N2O5) (±0.012, standard deviation) and 0.34 for φ (±0.28, standard deviation). The variations in γ (N2O5) could not be fully explained by the previously derived parameterizations of N2O5 uptake that consider nitrate, chloride, and the organic coating. Heterogeneous uptake of N2O5 was found to have a strong positive dependence on the relative humidity and aerosol water content. This result suggests that the heterogeneous uptake of N2O5 in Wangdu is governed mainly by the amount of water in the aerosol, and is strongly water limited, which is different from most of the field observations in the US and Europe. The ClNO2 yield estimated from the parameterization was also overestimated comparing to that derived from the observation. The observation-derived φ showed a decreasing trend with an increasing ratio of acetonitrile to carbon monoxide, an indicator of biomass burning emissions, which suggests a possible suppressive effect on the production yield of ClNO2 in the plumes influenced by biomass burning in this region. The findings of this study illustrate the need to improve our understanding and to parameterize the key factors for γ (N2O5) and φ to accurately assess photochemical and haze pollution.

Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene: A Combined Theoretical and Experimental Study

It is generally assumed that isoprene-derived secondary organic aerosol (SOA) precursors are mainly formed from the secondary reactions of intermediate products with OH radicals in the gas phase and multiphase oxidation in particles. In this paper, we predicted a theoretical mechanism for the primary formation of highly oxygenated molecules (HOM) in the gas phase through successive intramolecular H-shifts and O2 addition in the specific Z-δ isomer of hydroxyl-peroxy radicals and alkoxy radicals. The position of O2 addition is different from that in forming hydroperoxy aldehydes. The prediction was further supported experimentally by successfully identifying a few highly oxidized peroxy radicals and closed-shell products such as C5H9O7,9, C5H10O6,7,8, and C4H8O5 in a flow reactor by chemical ionization mass spectrometry at air pressure. These HOM products could serve as important precursors to isoprene-derived SOA. Further modeling studies on the effect of NO concentration suggested that HOM formation could account for up to ∼11% of the branching ratio (∼9% from the 4-OH channel and ∼2% from the 1-OH channel) in the reaction of isoprene with OH when the lifetimes of peroxy radicals due to bimolecular reactions are ∼100 s, which is typical in forest regions.