Formation Of New Aerosol Particles Research Articles

Impact of desert dust on new particle formation events and the cloud condensation nuclei budget in dust-influenced areas

Abstract. Detailed knowledge on the formation of new aerosol particles in the atmosphere from precursor gases, and their subsequent growth, commonly known as new particle formation (NPF) events, is one of the largest challenges in atmospheric aerosol science. High pre-existing particle loadings are expected to suppress the formation of new atmospheric aerosol particles due to high coagulation and condensation (CS) sinks. However, NPF events are regularly observed in conditions with high concentrations of pre-existing particles and even during intense desert dust intrusions that imply discrepancies between the observations and theory. In this study, we present a multi-site analysis of the occurrence of NPF events under the presence of desert dust particles in dust-influenced areas. Characterization of NPF events at five different locations highly influenced by desert dust outbreaks was done under dusty and non-dusty conditions using continuous measurements of aerosol size distribution in both fine and coarse size fractions. Contrary to common thought, our results show that the occurrence of NPF events is highly frequent during desert dust outbreaks, showing that NPF event frequencies during dusty conditions are similar to those observed during non-dusty conditions. Furthermore, our results show that NPF events also occur during intense desert dust outbreaks at all the studied sites, even at remote sites where the amounts of precursor vapours are expected to be low. Our results show that the condensation sink associated with coarse particles (CSC) represents up to the 60 % of the total CS during dusty conditions, which highlights the importance of considering coarse-fraction particles for NPF studies in desert-dust-influenced areas. However, we did not find a clear pattern of the effect of desert dust outbreaks on the strength of NPF events, with differences from site to site. The particle growth rate (GR) did not present a clear dependence on the CS during dusty and non-dusty conditions. This result, together with the fact that desert dust has different effects on the growth and formation rates at each site, suggests different formation and growth mechanisms at each site between dusty and non-dusty conditions, probably due to differences in precursor vapours' origins and concentrations as well as changes in the oxidative capacity of pre-existing particles and their effectiveness acting as CS. Further investigation based on multiplatform measurement campaigns and chamber experiments with state-of-the-art gaseous and particulate physical and chemical properties measurements is needed to better understand the role of catalyst components present in desert dust particles in NPF. Finally, our results reveal a significant impact of NPF events on the cloud condensation nuclei (CCN) budget during desert dust outbreaks at the studied sites. Therefore, since desert dust contributes to a major fraction of the global aerosol mass load, and since there is a foreseeable increase in the frequency, duration and intensity of desert dust episodes due to climate change, it is imperative to improve our understanding of the effect of desert dust outbreaks on NPF and the CCN budget for better climate change prediction.

Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere.

Dimeric accretion products have been observed both in atmospheric aerosol particles and in the gas phase. With their low volatilities, they are key contributors to the formation of new aerosol particles, acting as seeds for more volatile organic vapors to partition onto. Many particle-phase accretion products have been identified as esters. Various gas- and particle-phase formation pathways have been suggested for them, yet evidence remains inconclusive. In contrast, peroxide accretion products have been shown to form via gas-phase peroxy radical (RO2) cross reactions. Here, we show that these reactions can also be a major source of esters and other types of accretion products. We studied α-pinene ozonolysis using state-of-the-art chemical ionization mass spectrometry together with different isotopic labeling approaches and quantum chemical calculations, finding strong evidence for fast radical isomerization before accretion. Specifically, this isomerization seems to happen within the intermediate complex of two alkoxy (RO) radicals, which generally determines the branching of all RO2-RO2 reactions. Accretion products are formed when the radicals in the complex recombine. We found that RO with suitable structures can undergo extremely rapid C-C β scissions before recombination, often resulting in ester products. We also found evidence of this previously overlooked RO2-RO2 reaction pathway forming alkyl accretion products and speculate that some earlier peroxide identifications may in fact be hemiacetals or ethers. Our findings help answer several outstanding questions on the sources of accretion products in organic aerosol and bridge our knowledge of the gas phase formation and particle phase detection of accretion products. As esters are inherently more stable than peroxides, this also impacts their further reactivity in the aerosol.

Aerosols, Clusters, Greenhouse Gases, Trace Gases and Boundary-Layer Dynamics: on Feedbacks and Interactions

Turbulence is the key process transporting material and energy in the atmosphere. Furthermore, turbulence causes concentration fluctuations, influencing different atmospheric processes such as deposition, chemical reactions, formation of low-volatile vapours, formation of new aerosol particles and their growth in the atmosphere, and the effect of aerosol particles on boundary-layer meteorology. In order to analyse the connections, interactions and feedbacks relating those different processes require a deep understanding of atmospheric turbulence mechanisms, atmospheric chemistry and aerosol dynamics. All these processes will further influence air pollution and climate. The better we understand these processes and their interactions and associated feedback, the more effectively we can mitigate air pollution as well as mitigate climate forcers and adapt to climate change. We present several aspects on the importance of turbulence including how turbulence is crucial for atmospheric phenomena and feedbacks in different environments. Furthermore, we discuss how boundary-layer dynamics links to aerosols and air pollution. Here, we present also a roadmap from deep understanding to practical solutions.

The Role of Ionization in the Formation and Evolution of Submicron Aerosol Particles

Experimental studies estimating the effect of ions produced by corona discharge on the formation of new aerosol particles are analyzed. It is noted that, not only in a controlled space (aerosol chambers), independent of its volume, but also under conditions of the natural atmosphere, the generation of a corona discharge is accompanied by the formation of new nanometer-sized aerosol particles, the concentration of which exceeds the background concentration by more than an order of magnitude. The results obtained are interpreted on the basis of theoretical views about the effect the electric charge of ions has on the condensation of different admixtures. The coagulation theory and the model of a continuous growth were used to calculate the increase in the radius of aerosol particles as a function of time.

HIOx-IONO2 Dynamics at the Air-Water Interface: Revealing the Existence of a Halogen Bond at the Atmospheric Aerosol Surface.

Iodine is enriched in marine aerosols, particularly in coastal mid-latitude atmospheric environments, where it initiates the formation of new aerosol particles with iodic acid (HIO3) composition. However, particle formation in polluted and semipolluted locations is inhibited when the iodine monoxide radical (IO) is intercepted by NO2 to form the iodine nitrate (IONO2). The primary fate of IONO2 is believed to be, besides photolysis, uptake by aerosol surfaces, leading to particulate iodine activation. Herein we have performed Born-Oppenheimer molecular dynamics (BOMD) simulations and gas-phase quantum chemical calculations to study the iodine acids-iodine nitrate [HIOx (x = 2 and 3)-IONO2] dynamics at the air-water interface modeled by a water droplet of 191 water molecules. The results indicate that IONO2 does not react directly with these iodine acids, but forms an unusual kind of interaction with them within a few picoseconds, which is characterized as halogen bonding. The halogen bond-driven HIO3-IONO2 complex at the air-water interface undergoes deprotonation and exists as IO3--IONO2 anion, whereas the HIO2-IONO2 complex does not exhibit any proton loss to the interfacial water molecules. The gas-phase quantum chemical calculations suggest that the HIO3-IONO2 and HIO2-IONO2 complexes have appreciable stabilization energies, which are significantly enhanced upon deprotonation of iodine acids, indicating that these halogen bonds are fairly stable. These IONO2-induced halogen bonds explain the rapid loss of IONO2 to background aerosol. Moreover, they appear to work against iodide formation. Thus, they may play an important role in enhancing the amount of atmospherically nonrecyclable iodine (iodate) in marine aerosol.

On the influence of atmospheric super-saturation layer on China's heavy haze-fog events

With the background of global change, the air quality in Earth's atmosphere has significantly decreased. The North China Plain (NCP), Yangtze River Delta (YRD), Pearl River Delta (PRD) and Si-Chuan Basin (SCB) are the major areas suffering the decreasing air quality and frequent pollution events in recent years. Studying the effect of meteorological conditions on the concentration of pollution aerosols in these pollution sensitive regions is a hot focus now. This paper analyses the characteristics of atmospheric super-saturation and the corresponding H_PMLs (height of supersaturated pollution mixing layer), investigating their contribution to the frequently-seen heavy haze-fog weather. The results suggest that: (1) in the above-mentioned pollution sensitive regions in China, super-saturated layers repeatedly appear in the low altitude and the peak value of supersaturation S can reach 6–10%, which makes pollution particles into the wet adiabatic uplift process in the stable-static atmosphere. After low-level atmosphere reaches the super-saturation state below the H_PMLs, meteorological condition contributes to humidification and condensation of pollution particles. (2) Caculation of condensation function Fc, one of PLAM sensetive parameter, indicates that super-saturation state helps promote condensation, beneficial to the formation of Condensational Kink (CK) in the pollution sensitive areas. This favors the formation of new aerosol particles and intensities the cumulative growth of aerosol concentration. (3) By calculating the convective inhibition energy on average │CIN│ > 1.0 × 104 J kg−1, we found the value is about 100 times higher than the stable critical value. The uplifting diffusion of the particles is inhibited by the ambient airflow. So, this is the important reason for the aggravation and persistence of aerosol pollutants in local areas. (4) H_PMLs is negatively correlated to the pollution meteorological condition index PLAM which can describe the change of PM2.5 concentration. The lower the H_PMLs is, the higher the PLAM becomes, and the more conductive the air condition is to aggravation of pollutant aerosol concentration.

Aerosol Distribution in The Planetary Boundary Layer Aloft a Residential Area

Atmospheric aerosol is an omnipresent component of the Earth atmosphere. Aerosol particle of diameters < 100 nm or > 1 μm defines ultrafine or coarse aerosol particles, respectively. Aerosol particle concentrations within the planetary boundary layer - PBL are measured at the ground level while their vertical profiles in the PBL are usually estimated by modelling. The aim of this study was to construct vertical concentration profiles of ultrafine and coarse aerosol particles from airborne and ground measurements conducted in an urban airshed. Airborne measurements were done by an unmanned airship, remotely controlled with GPS 10 Hz position tracking, and electrically powered with propulsion vectoring, which allows average cruising speed of 6 m.s-1. The airship carried three aerosol monitors and a temperature sensor. The monitors acquired 1 Hz data on mass concentration of coarse and number concentration of ultrafine particles. Four flight sequences were conducted on the 2nd of March 2014 above Plesna village, up-wind suburb of Ostrava in the Moravian-Silesian region of the Czech Republic. The region is a European air pollution hot-spot. Repeated flights were carried out in several height levels up to 570 m above ground level - a.g.l. Early morning flight revealed a temperature inversion in the PBL up to 70 m a.g.l. This lead to coarse particle concentrations of 50 μgm-3 below the inversion layer and 10 μgm-3 above it. Concurrently, air masses at 90-120 m a.g.l. were enriched with ultrafine particles up to 2.5x104 cm-3, which may indicate a fanning plume from a distant emission source with high emission height. During the course of the day, concentrations of ultrafine and coarse particle gradually decreased. Nevertheless, a sudden increase of ultrafine particle concentrations up to 3.7x104 cm-3 was registered at 400 m a.g.l. at noon and also after a lag of 20 min at the ground. This may indicate formation of new aerosol particles at higher altitudes, which are then transported downward by evolved convective mixing. Detailed information acquired by the airship measurements allow us to better understand processes resulting in the increase of aerosol particle concentrations at ground level in urban air.

Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3.

Homogeneous nucleation and subsequent cluster growth leads to the formation of new aerosol particles in the atmosphere1. Nucleation of sulphuric acid and organic vapours is thought to be responsible for new particle formation over continents1,2 while iodine oxide vapours have been implicated in particle formation over coastal regions3–7. Molecular clustering pathways involved in atmospheric particle formation have been elucidated in controlled laboratory studies of chemically simple systems2,8–10. But no direct molecular-level observations of nucleation in atmospheric field conditions involving either sulphuric acid, organic or iodine oxide vapours have been reported to date11. Here we report field data from Mace Head, Ireland and supporting data from northern Greenland and Queen Maud Land, Antarctica that allow for the identification of the molecular steps involved in new particle formation in an iodine-rich, coastal atmospheric environment. We find that the formation and initial growth process is almost exclusively driven by iodine oxoacids and iodine oxide vapours with average resulting cluster O:I ratios of 2.4. Based on the high O:I ratio, together with observed high concentrations of iodic acid, HIO3, we suggest that cluster formation primarily proceeds by sequential addition of iodic acid HIO3, followed by intra-cluster restructuring to I2O5 and recycling of water in the atmosphere or upon drying. Overall, our study provides ambient atmospheric molecular-level observations of nucleation, supporting the previously suggested role of iodine containing species in new particle formation3–7, 12–18, and identifies the key nucleating compound.

Bisulfate – cluster based atmospheric pressure chemical ionization mass spectrometer for high-sensitivity (&amp;lt; 100 ppqV) detection of atmospheric dimethyl amine: proof-of-concept and first ambient data from boreal forest

Abstract. Atmospheric amines may play a crucial role in formation of new aerosol particles via nucleation with sulfuric acid. Recent studies have revealed that concentrations below 1 pptV can significantly promote nucleation of sulfuric acid particles. While sulfuric acid detection is relatively straightforward, no amine measurements to date have been able to reach the critical sub-pptV concentration range and atmospheric amine concentrations are in general poorly characterized. In this work we present a proof-of-concept of an instrument capable of detecting dimethyl amine (DMA) with concentrations even down to 70 ppqV (parts per quadrillion, 0.07 pptV) for a 15 min integration time. Detection of ammonia and amines other than dimethyl amine is discussed. We also report results from the first ambient measurements performed in spring 2013 at a boreal forest site. While minute signals above the signal-to-noise ratio that could be attributed to trimethyl or propyl amine were observed, DMA concentration never exceeded the detection threshold of ambient measurements (150 ppqV), thereby questioning, though not excluding, the role of DMA in nucleation at this location.

Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

Abstract. The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to ~ 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dôme (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.

New insights into nocturnal nucleation

Abstract. Formation of new aerosol particles by nucleation and growth is a significant source of aerosols in the atmosphere. New particle formation events usually take place during daytime, but in some locations they have been observed also at night. In the present study we have combined chamber experiments, quantum chemical calculations and aerosol dynamics models to study nocturnal new particle formation. All our approaches demonstrate, in a consistent manner, that the oxidation products of monoterpenes play an important role in nocturnal nucleation events. By varying the conditions in our chamber experiments, we were able to reproduce the very different types of nocturnal events observed earlier in the atmosphere. The exact strength, duration and shape of the events appears to be sensitive to the type and concentration of reacting monoterpenes, as well as the extent to which the monoterpenes are exposed to ozone and potentially other atmospheric oxidants.

First gaseous sulfuric acid measurements in automobile exhaust: Implications for volatile nanoparticle formation

Gaseous sulfuric acid (GSA) is thought to represent an important if not the most important nucleating gas present in modern diesel automobile exhaust. It triggers the formation of new aerosol particles, which grow by condensation and coagulation. Here we report on the first measurements of GSA in automobile exhaust. The experiment was made using a modern passenger diesel car equipped with an exhaust after-treatment system composed of an oxidation catalyst and a diesel-particle filter. The diesel fuel used had an ultra-low sulfur mass fraction of only 5×10 −6. Measured GSA number concentrations reached up to 1×10 9 cm −3. Freshly nucleated particles with diameters larger than 3 nm were also measured. The concentrations reached up to 1×10 5 cm −3 and were positively correlated with GSA for GSA exceeding a threshold value in the range of 5×10 7–2×10 8 cm −3. This suggests that GSA was involved in the formation of new volatile particles.

Determination of organic acids in aerosol particles from a coniferous forest by liquid chromatography–mass spectrometry

LC-MS methods with use of ion-trap and time-of-flight mass spectrometers were developed for the determination of organic acids in aerosol samples collected by a high-volume sampler in a Finnish coniferous forest. Comparison was made of the composition of samples collected during atmospheric formation of new aerosol particles and on days when this formation did not occur. A dynamic sonication-assisted solvent extraction system was developed for fast and quantitative extraction of the filter samples. Several organic acids, including pinonic acid, pinic acid, and homologous series of n-alkanoic acids, n-alkenoic acids, and aliphatic dicarboxylic acids, were identified. In samples collected between 08:00 and 16:00 hours the concentration of pinonic acid ranged from 0.5 ng m(-3) to 3.7 ng m(-3) and that of pinic acid from 0.2 ng m(-3) to 1.5 ng m(-3). For most of the compounds identified, the trends in concentration could be explained by the differences in temperature during collection. However, concentrations of short-chain n-alkanoic acids were clearly higher on the days when new aerosol particle formation occurred.

Vertical transport of sulfur dioxide and dimethyl sulfide in deep convection and its role in new particle formation

The NASA Pacific Exploratory Mission‐West experiment in 1991 and 1994 covered large portions of the western Pacific Ocean troposphere and transects of the troposphere of the equatorial and subtropical North Pacific Ocean. Sulfur dioxide and dimethyl sulfide were concurrently measured from the surface to 12 km. In 1991, sulfur dioxide had significant anthropogenic and volcanic sources. In 1994, sulfur dioxide aloft was significantly lower than in 1991. During both periods, deep convection was responsible for the distribution of sulfur dioxide and dimethyl sulfide. An assessment is made of the proportion of sulfur dioxide that could be made from dimethyl sulfide convected to high altitude. The subsequent formation of new aerosol particles from sulfur dioxide at high altitude is evaluated.

Anthropogenic influence on the distribution of tropospheric sulphate aerosol

HUMAN activities have increased global emissions of sulphur gases by about a factor of three during the past century, leading to increased sulphate aerosol concentrations, mainly in the Northern Hemisphere. Sulphate aerosols can affect the climate directly, by increasing the backscattering of solar radiation in cloud-free air, and indirectly, by providing additional cloud condensation nuclei1–4. Here we use a global transport–chemistry model to estimate the changes in the distribution of tropospheric sulphate aerosol and deposition of non-seasalt sulphur that have occurred since pre-industrial times. The increase in sulphate aerosol concentration is small over the Southern Hemisphere oceans, but reaches a factor of 100 over northern Europe in winter. Our calculations indicate, however, that at most 6% of the anthropogenic sulphur emissions is available for the formation of new aerosol particles. This is because about one-half of the sulphur dioxide is deposited on the Earth's surface, and most of the remainder is oxidized in cloud droplets so that the sulphate becomes associated with pre-existing particles. Even so, the rate of formation of new sulphate particles may have doubled since pre-industrial times.