Growth Of Atmospheric Nanoparticles Research Articles

Size-dependent chemical composition of atmospheric nanoparticles in urban Beijing during springtime

Atmospheric nanoparticle growth is a critical bridge between aerosol to clouds and climate. However, current mechanisms for nanoparticle growth are not yet fully understood due to unknown size-resolved chemical composition during the growth process. Here, we present comprehensive field measurements of the size-resolved chemical composition of the atmospheric nanoparticle growth in the size range from 10 to 100 nm using a custom-made Nanoparticle Chemical Ionization Mass Spectrometer (NPCIMS). The typical chemical compositions of nanoparticles are quantified in both positive and negative ion modes during growth processes after sensitivity calibration. The quantification results for chemical compositions show that CHO organics account for ∼80% of the newly formed particle in the growth process with diameters from 10 to 25 nm. However, the nitrate component is rarely observed during the nanoparticle growth under size-resolved mode (10–25 nm), indicating the little contribution of the nitrate component to growth at diameters below 25 nm. Different from the contribution of aminium salts to nanoparticle growth according to the previous urban observations in Mexico, the newly formed particle growth in urban Beijing is dominated by ammonium, sulfate, and organic components in the size-resolved modes (10–25 nm) in springtime.

Measurement of atmospheric nanoparticles: Bridging the gap between gas-phase molecules and larger particles

Atmospheric nanoparticles are crucial components contributing to fine particulate matter (PM2.5), and therefore have significant effects on visibility, climate, and human health. Due to the unique role of atmospheric nanoparticles during the evolution process from gas-phase molecules to larger particles, a number of sophisticated experimental techniques have been developed and employed for online monitoring and characterization of the physical and chemical properties of atmospheric nanoparticles, helping us to better understand the formation and growth of new particles. In this paper, we firstly review these state-of-the-art techniques for investigating the formation and growth of atmospheric nanoparticles (e.g., the gas-phase precursor species, molecular clusters, physicochemical properties, and chemical composition). Secondly, we present findings from recent field studies on the formation and growth of atmospheric nanoparticles, utilizing several advanced techniques. Furthermore, perspectives are proposed for technique development and improvements in measuring atmospheric nanoparticles.

Molecular identification of organic vapors driving atmospheric nanoparticle growth

Particles formed in the atmosphere via nucleation provide about half the number of atmospheric cloud condensation nuclei, but in many locations, this process is limited by the growth of the newly formed particles. That growth is often via condensation of organic vapors. Identification of these vapors and their sources is thus fundamental for simulating changes to aerosol-cloud interactions, which are one of the most uncertain aspects of anthropogenic climate forcing. Here we present direct molecular-level observations of a distribution of organic vapors in a forested environment that can explain simultaneously observed atmospheric nanoparticle growth from 3 to 50 nm. Furthermore, the volatility distribution of these vapors is sufficient to explain nanoparticle growth without invoking particle-phase processes. The agreement between observed mass growth, and the growth predicted from the observed mass of condensing vapors in a forested environment thus represents an important step forward in the characterization of atmospheric particle growth.

Formation and growth of atmospheric nanoparticles in the eastern Mediterranean: results from long-term measurements and process simulations

Abstract. Atmospheric new particle formation (NPF) is a common phenomenon all over the world. In this study we present the longest time series of NPF records in the eastern Mediterranean region by analyzing 10 years of aerosol number size distribution data obtained with a mobility particle sizer. The measurements were performed at the Finokalia environmental research station on Crete, Greece, during the period June 2008–June 2018. We found that NPF took place on 27 % of the available days, undefined days were 23 % and non-event days 50 %. NPF is more frequent in April and May probably due to the terrestrial biogenic activity and is less frequent in August. Throughout the period under study, nucleation was observed also during the night. Nucleation mode particles had the highest concentration in winter and early spring, mainly because of the minimum sinks, and their average contribution to the total particle number concentration was 8 %. Nucleation mode particle concentrations were low outside periods of active NPF and growth, so there are hardly any other local sources of sub-25 nm particles. Additional atmospheric ion size distribution data simultaneously collected for more than 2 years were also analyzed. Classification of NPF events based on ion spectrometer measurements differed from the corresponding classification based on a mobility spectrometer, possibly indicating a different representation of local and regional NPF events between these two measurement data sets. We used the MALTE-Box model for simulating a case study of NPF in the eastern Mediterranean region. Monoterpenes contributing to NPF can explain a large fraction of the observed NPF events according to our model simulations. However the adjusted parameterization resulting from our sensitivity tests was significantly different from the initial one that had been determined for the boreal environment.

The heterogeneous reaction of dimethylamine/ammonia with sulfuric acid to promote the growth of atmospheric nanoparticles

The heterogeneous reaction of dimethylamine (DMA) with sulfuric acid to promote the growth of atmospheric nanoparticle is different from ammonia.

КОСМІЧНІ ПРОМЕНІ Й АЕРОЗОЛІ В ЗЕМНІЙ АТМОСФЕРІ

КОСМІЧНІ ПРОМЕНІ Й АЕРОЗОЛІ В ЗЕМНІЙ АТМОСФЕРІ

Contributions of volatile and nonvolatile compounds (at 300°C) to condensational growth of atmospheric nanoparticles: An assessment based on 8.5 years of observations at the Central Europe background site Melpitz

AbstractLong‐term measurements of particle number size distributions in combination with thermodenuder analysis have been performed since July 2003 at the Central European station of Melpitz, Germany. Up to the end of 2011, 20% of all investigated days during the 8.5 years of measurements showed new particle formation and subsequent growth. To investigate the role of various chemical compound candidates for condensational nanoparticle growth, we focused on nucleation events in which the measured size distributions with and without thermodesorption both showed growth patterns (accounting for up to ~85% of all nucleation events). In this study, particulate compounds that volatilize at 300°C were specifically defined as “volatile,” in contrast to “nonvolatile” compounds, which remain in the particulate phase after being heated to 300°C. A strong correlation between ambient temperature and growth rate associated with volatile substances (except gaseous sulfuric acid) was found, which implies the importance of organics (possibly oxidized biogenic organic compounds) in particle growth at Melpitz. The contributions of the volatile compounds to the growth rate due to condensation of gaseous sulfuric acid and organics were found to be about 19% and 47%, respectively. The remaining ~25% was attributed to nonvolatile residuals, which appear to form gradually during the particle growth process and are characterized as extremely low‐volatility compounds. The growth rate associated with volatile components exhibited significant seasonal variation, with the highest value during summertime, whereas the growth rate associated with the nonvolatile fraction showed less fluctuation.

Nanoparticle growth in the CLOUD chamber

Atmospheric Aerosols![Figure][1] A view of the interior of the CERN CLOUD chamber PHOTO: CERN Atmospheric ions and small acid-base clusters can participate in the growth of atmospheric nanoparticles. These species generally are not considered in models of aerosol formation from sulfuric acid vapor and so have not been included in estimates of new particle growth rates. Lehtipalo et al. measured growth rates of particles smaller than 3 nm in the CLOUD chamber at CERN and found that compounds that stabilize sulfuric acid clusters can control the magnitude of these effects, leading to higher growth rates and affecting the growth mechanism. Nat. Comm. 10.1038/ncomms11594 (2016). [1]: pending:yes

Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis.

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

The effect of acid-base clustering and ions on the growth of atmospheric nano-particles.

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.

Reevaluating the contribution of sulfuric acid and the origin of organic compounds in atmospheric nanoparticle growth

AbstractAerosol particles formed in the atmosphere are important to the Earth's climate system due to their ability to affect cloud properties. At present, little is known about the atmospheric chemistry responsible for the growth of newly formed aerosol particles to climate‐relevant sizes. Here combining detailed aerosol measurements with a theoretical framework we found that depending on the gaseous precursors and size of the newly formed particles, the growth was dominated by either sulfuric acid accompanied by ammonium or organic compounds originating in either biogenic emissions or savannah fires. The contribution of sulfuric acid was larger during the early phases of the growth, but in clean conditions organic compounds dominated the growth from 1.5 nm up to climatically relevant sizes. Furthermore, our analysis indicates that in polluted environments the contribution of sulfuric acid to the growth may have been underestimated by up to a factor of 10.

Characteristics of formation and growth of atmospheric nanoparticles observed at four regional background sites in Korea

Measurements of the number concentration and size distribution of atmospheric nanoparticles were conducted at four sites on the west coast of the Korean Peninsula by using identical scanning mobility particle sizers (SMPSs) in October 2012. The new particle formation and subsequent growth (NPF) of atmospheric nanoparticles, which were identified by the cyclostationary empirical orthogonal function (CSEOF) analysis technique, was observed on 11 out of 21days at the Baengnyeong-do Comprehensive Monitoring Observatory (BCMO); and on 10 out of 21days at the Korea Global Atmosphere Watch Center (KGAWC) from October 9 to 29, 2012. We also observed NPF events for 9 out of 21days at both the Gosan Climate Observatory (GCO) and the Jeju Comprehensive Monitoring Observatory (JCMO). During the study period, NPF was simultaneously observed for five days at all four sites, which indicates that the NPF event had a spatial extent of at least 540km.A cold, dry and cloud-free continental air mass originated from northern China, formed favorable environmental conditions (e.g., increasing solar insolation at the surface) on simultaneous NPF at the four sites. These synoptic weather patterns were closely associated with an extraordinary typhoon passing over the south of Japan. The mean values of particle formation rates at BCMO (1.26cm−3s−1) and KGAWC (1.49cm−3s−1) were relatively higher than those at GCO (0.39cm−3s−1) and JCMO (0.74cm−3s−1), however, the growth rate showed a similar level among four sites. An increase in the spatial homogeneity and inter-site correlation of atmospheric particles among the four sites was apparent for small particles (diameter<30nm) on simultaneous NPF event days.

Model for acid-base chemistry in nanoparticle growth (MABNAG)

Abstract. Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapour pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapour pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organics and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.

Semi-empirical parameterization of size-dependent atmospheric nanoparticle growth in continental environments

Abstract. The capability to accurately yet efficiently represent atmospheric nanoparticle growth by biogenic and anthropogenic secondary organics is a challenge for current atmospheric large-scale models. It is, however, crucial to predict nanoparticle growth accurately in order to reliably estimate the atmospheric cloud condensation nuclei (CCN) concentrations. In this work we introduce a simple semi-empirical parameterization for sub-20 nm particle growth that distributes secondary organics to the nanoparticles according to their size and is therefore able to reproduce particle growth observed in the atmosphere. The parameterization includes particle growth by sulfuric acid, secondary organics from monoterpene oxidation (SORGMT) and an additional condensable vapor of non-monoterpene organics ("background"). The performance of the proposed parameterization was investigated using ambient data on particle growth rates in three diameter ranges (1.5–3 nm, 3–7 nm and 7–20 nm). The growth rate data were acquired from particle/air ion number size distribution measurements at six continental sites over Europe. The longest time series of 7 yr (2003–2009) was obtained from a boreal forest site in Hyytiälä, Finland, while about one year of data (2008–2009) was used for the other stations. The extensive ambient measurements made it possible to test how well the parameterization captures the seasonal cycle observed in sub-20 nm particle growth and to determine the weighing factors for distributing the SORGMT for different sized particles as well as the background mass flux (concentration). Besides the monoterpene oxidation products, background organics with a concentration comparable to SORGMT, around 6 × 107 cm−3 (consistent with an additional global SOA yield of 100 Tg yr−1) was needed to reproduce the observed nanoparticle growth. Simulations with global models suggest that the "background" could be linked to secondary biogenic organics that are formed in the presence of anthropogenic pollution.

Growth of atmospheric nano-particles by heterogeneous nucleation of organic vapor

Abstract. Atmospheric aerosols play critical roles in air quality, public health, and visibility. In addition, they strongly influence climate by scattering solar radiation and by changing the reflectivity and lifetime of clouds. One major but still poorly understood source of atmospheric aerosols is new particle formation, which consists of the formation of thermodynamically stable clusters from trace gas molecules (homogeneous nucleation) followed by growth of these clusters to a detectable size (~3 nm). Because freshly nucleated clusters are most susceptible to loss due to high rate of coagulation with pre-existing aerosol population, the initial growth rate strongly influences the rate of new particle formation and ambient aerosol population. Whereas many field observations and modeling studies indicate that organics enhance the initial growth of the clusters and therefore new particle formation, thermodynamic considerations would suggest that the strong increase of equilibrium vapor concentration due to cluster surface curvature (Kelvin effect) may prevent ambient organics from condensing on these small clusters. Here, the contribution of organics to the initial cluster growth is described as heterogeneous nucleation of organic molecules onto these clusters. We find that the strong gradient in cluster population with respect to its size leads to positive cluster number flux. This positive flux drives the growth of clusters substantially smaller than the Kelvin diameter, conventionally considered the minimum particle size that can be grown through condensation. The conventional approach neglects the contribution from the cluster concentration gradient, and underestimates the cluster survival probabilities by a factor of up to 60 if early growth of clusters is due to both condensation of sulfuric acid and heterogeneous nucleation of organic vapors.

The contribution of organics to atmospheric nanoparticle growth

The growth of the smallest atmospheric particles to sizes at which they may act as seeds for cloud droplets is a key step linking aerosols to clouds and climate. A synthesis of research indicates that the mechanisms controlling this growth depend on the size of the growing particle. Aerosols have a strong, yet poorly quantified, effect on climate. The growth of the smallest atmospheric particles from diameters in the nanometre range to sizes at which they may act as seeds for cloud droplets is a key step linking aerosols to clouds and climate. In many environments, atmospheric nanoparticles grow by taking up organic compounds that are derived from biogenic hydrocarbon emissions. Several mechanisms may control this uptake. Condensation of low-volatility vapours and formation of organic salts probably dominate the very first steps of growth in particles close to 1 nm in diameter. As the particles grow further, formation of organic polymers and effects related to the phase of the particle probably become increasingly important. We suggest that dependence of particle growth mechanisms on particle size needs to be investigated more systematically.

Laboratory Investigation on the Role of Organics in Atmospheric Nanoparticle Growth

The uptake of organic vapors by 4-20 nm H(2)SO(4) particles has been investigated to assess the role of organics in atmospheric nanoparticle growth. Sulfuric acid nanoparticles are generated from homogeneous binary nucleation of H(2)SO(4) and H(2)O vapors in a laminar flow chamber. The growth factor of H(2)SO(4) nanoparticles exposed to methyglyoxal, ethanol, 1-butanol, 1-heptanol, and 1-decanol is measured using a nanotandem differential mobility analyzer (nano-TDMA). The measured growth factor is close to unity when nanoparticles are exposed to methylglyoxal, ethanol, 1-butanol, 1-heptanol, and 1-decanol, indicating no apparent growth within the experimental uncertainty. In addition, spectroscopic evolution of functional groups in H(2)SO(4) particles of ∼40 nm diameter size, deposited on ZnSe crystal and subsequently exposed to glyoxal and 2,4-hexadienal, is studied using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR). The ATR-FT-IR measurements present the first spectroscopic signatures of high molecular weight aldol and oligomer products and show that polymerization and oligomerization reactions are partially reversible. The implications of the present results to nanoparticle growth in the atmosphere are discussed.

Observations of aminium salts in atmospheric nanoparticles and possible climatic implications

We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium-carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8-10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10-35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate.

On the formation and growth of atmospheric nanoparticles

In this paper we summarize recent experimental, theoretical and observational results on the formation and growth of atmospheric nanoparticles. During the last years significant progress has occurred to explain atmospheric nucleation and initial steps of the growth. Due to climatic and health effects of fine and ultrafine particles the formation and growth of new aerosol particles is of growing interest. The question “How and under which conditions does the formation of new atmospheric aerosol particles take place?” has exercised the minds of scientists since the time of John Aitken, who in the late 1880s built the first apparatus to measure the number of dust and fog particles. However, only during the last 15–20 years has the measurement technology developed to such a level that size distributions of nanometer-size particles and concentrations of gases participating in particle formation can be measured in the atmosphere. Also from a theoretical point of view atmospheric nucleation mechanisms have not been resolved: several mechanisms such as ion-induced (or ion mediated) nucleation, ternary and kinetic (barrier-less) nucleation have been suggested. In the most recent theory, the activation of existing neutral and/or ion clusters has been suggested.