Condensation Of Organic Vapors Research Articles

Condensation of organic-inorganic vapours governs the production of ultrafine secondary marine cloud nuclei

Ultrafine secondary marine aerosol (<100 nm), formed via gas-to-particle conversion, can make an important contribution to the number of cloud condensation nuclei in the marine boundary layer. It has long been known that the growth of ultrafine secondary marine aerosol cannot be sustained solely by condensation of the inorganic species that drive the initial nucleation, and condensation of organic vapours has been suggested as the most likely mechanism. However, the evidence from field observations had been lacking. Here we report observational evidence on the importance of the condensation of organic and inorganic vapours onto Aitken mode particles in forming cloud condensation nuclei. Further long-term analysis (over 10 years) with additional hygroscopicity growth measurements reveals that the ultrafine secondary marine aerosol growth events are driven by condensation of biogenic vapours, which leads to up to substantial increases in cloud condensation nuclei number at realistic marine cloud supersaturation.

A kinetic partitioning method for simulating the condensation mass flux of organic vapors in a wide volatility range

Organic aerosols are ubiquitous, playing important roles in various atmospheric physicochemical processes such as the formation of cloud droplets and haze. Condensation of organic vapors, as a net effect of association with particles and dissociation from the condensed phase, is a fundamental process that drives the formation of organic aerosols. Kinetic models are often used to simulate the condensation fluxes of low-volatility organic vapors and aerosol growth. However, the widely used kinetic growth models usually calculate the evaporation of a certain species based on previous particulate compositions, without including the co-condensation of other species. Here we present a new kinetic partitioning method for calculating the condensation fluxes of organic vapors in a wide volatility range with low computational cost. In this method, the organic vapors are assumed to be in a quasi-steady state, but never reach real association-dissociation equilibrium during the simultaneous condensation of multiple species. We show a good consistency between the kinetic partitioning method and kinetic models in simulating particle mass fractions and condensation fluxes. Under relevant atmospheric conditions, we reveal that the kinetic partitioning method also reproduce the trend that low-volatility species are almost non-volatile while volatile organic compounds almost reach association-dissociation equilibrium, while there is a transition regime between them. This transition regime varies with atmospheric conditions, such as temperature and vapor concentrations. Compared with previous studies combining kinetic growth methods with equilibrium partitioning theories to simplify the condensation flux calculation, this method helps to improve accuracy without a significant expense of computation cost, and it can be applied in a wider range of atmospheric conditions such as in extremely cold atmospheres and polluted exhaust plumes.

Cloud response to co-condensation of water and organic vapors over the boreal forest

Abstract. Accounting for the condensation of organic vapors along with water vapor (co-condensation) has been shown in adiabatic cloud parcel model (CPM) simulations to enhance the number of aerosol particles that activate to form cloud droplets. The boreal forest is an important source of biogenic organic vapors, but the role of these vapors in co-condensation has not been systematically investigated. In this work, the environmental conditions under which strong co-condensation-driven cloud droplet number enhancements would be expected over the boreal biome are identified. Recent measurement technology, specifically the Filter Inlet for Gases and AEROsols (FIGAERO) coupled to an iodide-adduct chemical ionization mass spectrometer (I-CIMS), is utilized to construct volatility distributions of the boreal atmospheric organics. Then, a suite of CPM simulations initialized with a comprehensive set of concurrent aerosol observations collected in the boreal forest of Finland during spring 2014 is performed. The degree to which co-condensation impacts droplet formation in the model is shown to be dependent on the initialization of temperature, relative humidity, updraft velocity, aerosol size distribution, organic vapor concentration, and the volatility distribution. The predicted median enhancements in cloud droplet number concentration (CDNC) due to accounting for the co-condensation of water and organics fall on average between 16 % and 22 %. This corresponds to activating particles 10–16 nm smaller in dry diameter that would otherwise remain as interstitial aerosol. The highest CDNC enhancements (ΔCDNC) are predicted in the presence of a nascent ultrafine aerosol mode with a geometric mean diameter of ∼ 40 nm and no clear Hoppel minimum, indicative of pristine environments with a source of ultrafine particles (e.g., via new particle formation processes). Such aerosol size distributions are observed 30 %–40 % of the time in the studied boreal forest environment in spring and fall when new particle formation frequency is the highest. To evaluate the frequencies with which such distributions are experienced by an Earth system model over the whole boreal biome, 5 years of UK Earth System Model (UKESM1) simulations are further used. The frequencies are substantially lower than those observed at the boreal forest measurement site (&lt; 6 % of the time), and the positive values, peaking in spring, are modeled only over Fennoscandia and the western parts of Siberia. Overall, the similarities in the size distributions between observed and modeled (UKESM1) are limited, which would limit the ability of this model, or any model with a similar aerosol representation, to project the climate relevance of co-condensation over the boreal forest. For the critical aerosol size distribution regime, ΔCDNC is shown to be sensitive to the concentrations of semi-volatile and some intermediate-volatility organic compounds (SVOCs and IVOCs), especially when the overall particle surface area is low. The magnitudes of ΔCDNC remain less affected by the more volatile vapors such as formic acid and extremely low- and low-volatility organic compounds (ELVOCs and LVOCs). The reasons for this are that most volatile organic vapors condense inefficiently due to their high volatility below the cloud base, and the concentrations of LVOCs and ELVOCs are too low to gain significant concentrations of soluble mass to reduce the critical supersaturations enough for droplet activation to occur. A reduction in the critical supersaturation caused by organic condensation emerges as the main driver of the modeled ΔCDNC. The results highlight the potential significance of co-condensation in pristine boreal environments close to sources of fresh ultrafine particles. For accurate predictions of co-condensation effects on CDNC, also in larger-scale models, an accurate representation of the aerosol size distribution is critical. Further studies targeted at finding observational evidence and constraints for co-condensation in the field are encouraged.

Heterogeneous Nucleation Drives Particle Size Segregation in Sequential Ozone and Nitrate Radical Oxidation of Catechol

Secondary organic aerosol formation via condensation of organic vapors onto existing aerosol transforms the chemical composition and size distribution of ambient aerosol, with implications for air quality and Earth's radiative balance. Gas-to-particle conversion is generally thought to occur on a continuum between equilibrium-driven partitioning of semivolatile molecules to the pre-existing mass size distribution and kinetic-driven condensation of low volatility molecules to the pre-existing surface area size distribution. However, we offer experimental evidence in contrast to this framework. When catechol is sequentially oxidized by O3 and NO3 in the presence of (NH4)2SO4 seed particles with a single size mode, we observe a bimodal organic aerosol mass size distribution with two size modes of distinct chemical composition with nitrocatechol from NO3 oxidation preferentially condensing onto the large end of the pre-existing size distribution (∼750 nm). A size-resolved chemistry and microphysics model reproduces the evolution of the two distinct organic aerosol size modes─heterogeneous nucleation to an independent, nitrocatechol-rich aerosol phase.

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.

Multiple new-particle growth pathways observed at the US DOE Southern Great Plains field site

Abstract. New-particle formation (NPF) is a significant source of aerosol particles into the atmosphere. However, these particles are initially too small to have climatic importance and must grow, primarily through net uptake of low-volatility species, from diameters ∼ 1 to 30–100 nm in order to potentially impact climate. There are currently uncertainties in the physical and chemical processes associated with the growth of these freshly formed particles that lead to uncertainties in aerosol-climate modeling. Four main pathways for new-particle growth have been identified: condensation of sulfuric-acid vapor (and associated bases when available), condensation of organic vapors, uptake of organic acids through acid–base chemistry in the particle phase, and accretion of organic molecules in the particle phase to create a lower-volatility compound that then contributes to the aerosol mass. The relative importance of each pathway is uncertain and is the focus of this work. The 2013 New Particle Formation Study (NPFS) measurement campaign took place at the DOE Southern Great Plains (SGP) facility in Lamont, Oklahoma, during spring 2013. Measured gas- and particle-phase compositions during these new-particle growth events suggest three distinct growth pathways: (1) growth by primarily organics, (2) growth by primarily sulfuric acid and ammonia, and (3) growth by primarily sulfuric acid and associated bases and organics. To supplement the measurements, we used the particle growth model MABNAG (Model for Acid–Base chemistry in NAnoparticle Growth) to gain further insight into the growth processes on these 3 days at SGP. MABNAG simulates growth from (1) sulfuric-acid condensation (and subsequent salt formation with ammonia or amines), (2) near-irreversible condensation from nonreactive extremely low-volatility organic compounds (ELVOCs), and (3) organic-acid condensation and subsequent salt formation with ammonia or amines. MABNAG is able to corroborate the observed differing growth pathways, while also predicting that ELVOCs contribute more to growth than organic salt formation. However, most MABNAG model simulations tend to underpredict the observed growth rates between 10 and 20 nm in diameter; this underprediction may come from neglecting the contributions to growth from semi-to-low-volatility species or accretion reactions. Our results suggest that in addition to sulfuric acid, ELVOCs are also very important for growth in this rural setting. We discuss the limitations of our study that arise from not accounting for semi- and low-volatility organics, as well as nitrogen-containing species beyond ammonia and amines in the model. Quantitatively understanding the overall budget, evolution, and thermodynamic properties of lower-volatility organics in the atmosphere will be essential for improving global aerosol models.

Influence of dielectrics with light absorption on the photonic bandgap of porous alumina photonic crystals

In this work, the influences of dielectrics with light absorption on the photonic bandgaps (PBGs) of porous alumina photonic crystals (PCs) were studied. Transmittance spectra of porous alumina PCs adsorbing ethanol showed that all the PBGs positions red-shifted; however, the transmittance of the PBG bottom showed different trends when the PBGs were located in different wavelength regions. In the near infrared region, liquid ethanol has strong light absorption, and, with the increase in adsorption, the PBG bottom transmittance of porous alumina PCs first increased and then decreased. However, in the visible light region, liquid ethanol has little light absorption, and thus, with the increase in adsorption, the PBG bottom transmittance of porous alumina PCs increased gradually all the time. Simulated results were consistent with the experimental results. The capillary condensation of organic vapors in the pores of porous alumina accounted for the change in the PBG bottom transmittance. The nonnegligible light absorption of the organic vapors was the cause of the decrease in the transmittance. The results for porous alumina PC adsorbing methanol, acetone, and toluene further confirmed the influences of light absorption on the PBG bottomed transmittance.

The role of organic condensation on ultrafine particle growth during nucleation events

Abstract. A new aerosol dynamics model (DMANx) has been developed that simulates aerosol size/composition distribution and includes the condensation of organic vapors on nanoparticles through the implementation of the recently developed volatility basis set framework. Simulations were performed for Hyytiälä (Finland) and Finokalia (Greece), two locations with different organic sources where detailed measurements were available to constrain the new model. We investigate the effect of condensation of organics and chemical aging reactions of secondary organic aerosol (SOA) precursors on ultrafine particle growth and particle number concentration during a typical springtime nucleation event in both locations. This work highlights the importance of the pathways of oxidation of biogenic volatile organic compounds and the production of extremely low volatility organics. At Hyytiälä, organic condensation dominates the growth process of new particles. The low-volatility SOA contributes to particle growth during the early growth stage, but after a few hours most of the growth is due to semi-volatile SOA. At Finokalia, simulations show that organics have a complementary role in new particle growth, contributing 45% to the total mass of new particles. Condensation of organics increases the number concentration of particles that can act as CCN (cloud condensation nuclei) (N100) by 13% at Finokalia and 25% at Hyytiälä during a typical spring day with nucleation. The sensitivity of our results to the surface tension used is discussed.

Near-unity mass accommodation coefficient of organic molecules of varying structure.

Atmospheric aerosol particles have a significant effect on global climate, air quality, and consequently human health. Condensation of organic vapors is a key process in the growth of nanometer-sized particles to climate relevant sizes. This growth is very sensitive to the mass accommodation coefficient α, a quantity describing the vapor uptake ability of the particles, but knowledge on α of atmospheric organics is lacking. In this work, we have determined α for four organic molecules with diverse structural properties: adipic acid, succinic acid, naphthalene, and nonane. The coefficients are studied using molecular dynamics simulations, complemented with expansion chamber measurements. Our results are consistent with α = 1 (indicating nearly perfect accommodation), regardless of the molecular structural properties, the phase state of the bulk condensed phase, or surface curvature. The results highlight the need for experimental techniques capable of resolving the internal structure of nanoparticles to better constrain the accommodation of atmospheric organics.

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors.

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

Introductory lecture: Atmospheric organic aerosols: insights from the combination of measurements and chemical transport models

The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile compounds to extremely low volatility compounds can explain the observed growth rates of new particles in rural environments.

Organic condensation: a vital link connecting aerosol formation to cloud condensation nuclei (CCN) concentrations

Abstract. Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health. Ultrafine (&lt;100 nm) particles often dominate aerosol numbers, and nucleation of atmospheric vapors is an important source of these particles. To have climatic relevance, however, the freshly nucleated particles need to grow in size. We combine observations from two continental sites (Egbert, Canada and Hyytiälä, Finland) to show that condensation of organic vapors is a crucial factor governing the lifetimes and climatic importance of the smallest atmospheric particles. We model the observed ultrafine aerosol growth with a simplified scheme approximating the condensing species as a mixture of effectively non-volatile and semi-volatile species, demonstrate that state-of-the-art organic gas-particle partitioning models fail to reproduce the observations, and propose a modeling approach that is consistent with the measurements. We find that roughly half of the mass of the condensing mass needs to be distributed proportional to the aerosol surface area (thus implying that the condensation is governed by gas-phase concentration rather than the equilibrium vapour pressure) to explain the observed aerosol growth. We demonstrate the large sensitivity of predicted number concentrations of cloud condensation nuclei (CCN) to these interactions between organic vapors and the smallest atmospheric nanoparticles – highlighting the need for representing this process in global climate models.

Porous silicon layer for optical sensing of organic vapor

The objective of this study is to evaluate the feasibility of porous silicon (PS) layer as a vapor sensor. We prepared three types of PS layer samples – a single layer, distributed Bragg reflector (DBR) layer, and microcavity layer – and examined their reflectance spectra before, during, and after exposure to different concentrations of various organic vapors. When the PS layer samples were exposed to the organic vapors, their reflectance spectra promptly shifted toward longer wavelengths. We determined that this redshift in the reflectance spectra could be attributed to the changes in the refractive index induced by the capillary condensation of organic vapors in the pores of the PS layers. The PS layers showed excellent sensing ability under different concentrations and types of organic vapors. Once the organic vapors were removed, the reflectance spectra of the PS layer samples promptly returned to their original states. In this study, we successfully demonstrated the rapid, sensitive, and reversible sensing of organic vapors using different PS layers.

Dispersal and morphological characteristics of smoke particulate emission from fires in the boreal forests of Siberia

About 10–14 million hectares of Siberian boreal forests burn annually. These forest fires, which amount to 300–500 million tons of biomass each year, result in smoke emission into the atmosphere. Direct measurements of smoke emissions conducted in several natural fire experiments at a taiga in Krasnoyarsk Territory between 2000–2009 have shown that the total amount of particulate emission from the fire is estimated to be 0.2–1 t/ha. These values represent 1–7% of the total biomass consumed during a typical forest fire in Siberia (15–30 t/ha); the remaining 93–99% of the burnt biomass are gaseous combustion products. Data on the disperse characteristics of particulate smokes, averaged over 16 natural fire experiments from 2007–2009, have shown that (89 ± 8)% of the total aerosol matter are in particles with aerodynamical diameters of less than 3 μm, (7 ± 6)% are in particles of 3–5 μm, and the remaining 5–10% of material is in particles larger than 7 μm. The morphological structure of the smoke particles indicates that submicron particles are formed due to condensation of organic vapors directly over a combustion zone, followed by their coagulation into particles of 1–3 μm. The elemental composition of the fine fraction of smoke emission, measured with the use of X-ray fluorescence with synchroton radiation excitation, is demonstrated to be used for discrimination between the sources of the elements.

Gas adsorption and capillary condensation in nanoporous alumina films

Gas adsorption and capillary condensation of organic vapors are studied by opticalinterferometry, using anodized nanoporous alumina films with controlled geometry(cylindrical pores with diameters in the range of 10–60 nm). The optical response of the filmis optimized with respect to the geometric parameters of the pores, for potentialperformance as a gas sensor device. The average thickness of the adsorbed film at lowrelative pressures is not affected by the pore size. Capillary evaporation of the liquid fromthe nanopores occurs at the liquid–vapor equilibrium described by the classical Kelvinequation with a hemispherical meniscus. Due to the almost complete wetting, we canquantitatively describe the condensation for isopropanol using the Cohan model with acylindrical meniscus in the Kelvin equation. This model describes the observedhysteresis and allows us to use the adsorption branch of the isotherm to calculatethe pore size distribution of the sample in good agreement with independentstructural measurements. The condensation for toluene lacks reproducibility due toincomplete surface wetting. This exemplifies the relevant role of the fluid–solid(van der Waals) interactions in the hysteretic behavior of capillary condensation.

Structure and adsorption properties of activated carbon aerogels

AbstractActivated carbon aerogels (ACAs) with excellent microporosity (e.g., 0.44 cm3/g) and mesoporosity (e.g., 1.72 cm3/g) were prepared by CO2 activation. Their structures were investigated with transmission electron microscopy and N2 adsorption–desorption analysis. Subsequently, their adsorption properties toward organic vapors were studied with static and dynamic adsorption experiments. The micropores of the ACAs had stronger adsorption ability than those of normal porous carbons. Furthermore, the condensation of organic vapors in the mesopores of ACAs greatly enhanced their equilibrium adsorption at high relative pressures. As a result, the adsorption capacities of organic vapors on the typical ACAs prepared were about 2–3 times greater than those on normal porous carbons. In addition, they also possessed excellent adsorption dynamics and outstanding desorption and regeneration properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006

Raman lidar observations of aged Siberian and Canadian forest fire smoke in the free troposphere over Germany in 2003: Microphysical particle characterization

Dual‐wavelength Raman lidar observations were regularly carried out at Leipzig (51.3°N, 12.4°E) from May to August 2003. The measurements showed that particle backscatter and extinction coefficients in the free troposphere were higher compared to values in 2000–2002. Backward dispersion modeling indicates that intense forest fires that occurred in Siberia and Canada in spring/summer 2003 were the main cause of these free tropospheric haze layers. Measurements on 3 days were selected for an optical and microphysical particle characterization of these well‐aged particle plumes. Particle lidar ratios measured at 532 nm wavelength were higher than at 355 nm. This property seems to be a characteristic feature of aged biomass‐burning particles observed over central Germany. Mean particle Ångström exponents calculated for the wavelength range from 355 to 532 nm varied from 0 to 1.3. Particle effective radii varied between 0.24 and 0.41 μm. Pollution advected from North America on 25 August 2003, in contrast, was characterized by considerably smaller particles. Mean effective radii were ≤0.2 μm, and Ångström exponents were 1.8–2.1. Lidar ratios in that case were lower at 532 nm compared to those at 355 nm. Such signatures are characteristic for anthropogenic particles. At the moment, however, it cannot be completely ruled out that extremely hot forest fires in western areas of Canada generated comparably small particles. Except for this specific case the forest fire particles were considerably larger than what is usually reported from in situ observations of biomass‐burning smoke. Possible explanations for this difference could be the kind of burning process, which could generate much larger particles in the source region, condensation of organic vapors on existing particles, and coagulation processes during the long transport time of more than a week. Relative humidity measured in these layers was very low. Hygroscopic growth of the particles therefore seemed to have little influence on the size of the particles. The forest fire smoke consisted of moderately absorbing material. Real parts of the complex refractive index of the particles were mostly &lt;1.5, and imaginary parts were &lt;0.01i. Single‐scattering albedo in all cases varied between 0.9 and 0.98 at 532 nm.

Initial steps of aerosol growth

Abstract. The formation and growth of atmospheric aerosols depend on several steps, namely nucleation, initial steps of growth and subsequent – mainly condensational – growth. This work focuses on the initial steps of growth, meaning the growth right after nucleation, where the interplay of curvature effects and thermodynamics has a significant role on the growth kinetics. More specifically, we investigate how ion clusters and aerosol particles grow from 1.5 nm to 20 nm (diameter) in atmospheric conditions using experimental data obtained by air ion and aerosol spectrometers. The measurements have been performed at a boreal forest site in Finland. The observed trend that the growth rate seems to increase as a function of size can be used to investigate possible growth mechanisms. Such a growth rate is consistent with a recently suggested nano-Köhler mechanism, in which growth is activated at a certain size with respect to condensation of organic vapors. The results also imply that charge-enhanced growth associated with ion-mediated nucleation plays only a minor role in the initial steps of growth, since it would imply a clear decrease of the growth rate with size. Finally, further evidence was obtained on the earlier suggestion that atmospheric nucleation and the subsequent growth of fresh nuclei are likely to be uncoupled phenomena via different participating vapors.

Observations of particle formation and growth in a mountainous forest region in central Europe

In the summers of 2001 and 2002, particle formation and growth were observed at a forest ecosystem research site in the “Fichtelgebirge” mountain range in NE Bavaria, Germany. Atmospheric nucleation events, identified through detailed analysis of the time evolution of submicron particle size distributions, differed considerably from nonevent days with respect to ultrafine particle concentrations and meteorological parameters. Particle diameter growth rates, as quantified through the geometric mean diameter development of the 3–60 nm particle fraction, ranged from 2.2 to 5.7 nm h−1. While H2SO4 concentrations typically explained less than 10% of the observed growth rates, a significant fraction of particle growth may be explained through condensation of organic vapors from α‐pinene oxidation. On several days, cocondensation of H2SO4 and α‐pinene oxidation products was sufficient to fully explain the observed growth dynamics. While BVOC emissions from the tree vegetation may contribute to particle formation, the forest also acts as an effective sink for particles. This is reflected in the dominance of particle deposition to the forest over emission, with the strongest deposition fluxes occurring during particle formation events.

The use of the pulse height analyser ultrafine condensation particle counter (PHA-UCPC) technique applied to sizing of nucleation mode particles of differing chemical composition

A modified white-light pulse-height analyser (PHA) TSI 3025 ultra-fine condensation particle counter (UCPC) is often used to provide fast response of aerosol size distributions between 3 and 10 nm since there is a monotonic link between initial aerosol size and nucleated droplet final size. The use of the PHA-UCPC for sizing nucleation mode particles depends on the droplet nucleation in the condenser chamber being somewhat independent of particle composition. Laboratory characterization of the PHA-UCPC for a range of chemical compositions, thought to be involved in atmospheric aerosol nucleation and growth, are presented here. Ammonium sulphate, pinic acid, cis-pinonic acid, malonic acid and an iodine oxide were studied and their PHA-UCPC calibration kernels are presented. It was found that all species possessed significantly different PHA responses. The results suggest that, unless the nano-particle chemical composition is known, then the PHA-UCPC cannot be used for measurements of aerosol size distributions. However, the PHA-UCPC, if used in parallel with mobility size distribution measurements, can help elucidate nano-particle chemical composition. Using the combination of mobility size distributions and the PHA-UCPC response during a nucleation and growth event over the boreal forest indicates that new particle formation, in this region, is driven by condensation of organic vapours.