Cloud Condensation Nuclei Production Research Articles

Ion-induced cloud modulation through new particle formation and runaway cloud condensation nuclei production

Abstract Cloud formation in the Pi Convection–Cloud Chamber is achieved via ionization in humid conditions, without the injection of aerosol particles to serve as cloud condensation nuclei (CCN). Abundant ions, turbulence, and supersaturated water vapor combine to produce new particles, which grow to become CCN sized and eventually are activated to form clouds. Coupling between the new particle formation and cloud droplets causes predator-prey type oscillations in aerosol and droplet concentrations under turbulent conditions. Leading terms are identified in the budgets for Aitken and accumulation mode aerosols and for cloud droplets. The cloud coupling is proposed to be a result of cloud-induced runaway CCN production through aerosol scavenging. The experiments suggest potential applications to marine cloud brightening, in which ions rather than sea-salt aerosols are generated.

New particle formation leads to enhanced cloud condensation nuclei concentrations on the Antarctic Peninsula

Abstract. Few studies have investigated the impact of new particle formation (NPF) on cloud condensation nuclei (CCN) in remote Antarctica, and none has elucidated the relationship between NPF and CCN production. To address that knowledge gap, we continuously measured the number size distribution of 2.5–300 nm particles and CCN number concentrations at King Sejong Station on the Antarctic Peninsula from 1 January to 31 December 2018. Ninety-seven NPF events were detected throughout the year. Clear annual and seasonal patterns of NPF were observed: high concentration and frequency of nucleation-mode particles in summer (December–February: 53 NPF cases) and undetected nucleation-mode particles in winter (June–August: no NPF cases). We estimated the spatial scale of NPF by multiplying the time during which a distinct nucleation mode can be observed at the sampling site by the locally measured wind speed. The estimated median spatial scale of NPF around the Antarctic Peninsula was found to be approximately 155 km, indicating the large scale of NPF events. Air back-trajectory analysis revealed that 80 cases of NPF events were associated with air masses originating over the ocean, followed by sea-ice (12 cases), multiple (3 cases), and land (2 cases) regions. We present and discuss three major NPF categories: (1) marine NPF, (2) sea-ice NPF, and (3) multiple NPF. Satellite estimates for sea-surface dimethylsulfoniopropionate (DMSP; a precursor of gaseous dimethyl sulfide) data showed that the production of oceanic biogenic precursors could be a key component in marine NPF events, whereas halogen compounds released from ice-covered areas could contribute to sea-ice NPF events. Terrestrial sources (wildlife colonies, vegetation, and meltwater ponds) from Antarctica could affect aerosol production in multiple air masses. Out of 97 observed NPF events, 83 cases were characterized by the simultaneous increase in the CCN concentration by 2 %–270 % (median 44 %) in the following 1 to 36 h (median 8 h) after NPF events. Overall, Antarctic NPF events were found to be a significant source of particles with different physical characteristics and related to biogenic sources in and around the Antarctic Peninsula, which subsequently grew to cloud condensation nuclei.

Contribution of regional aerosol nucleation to low-level CCN in an Amazonian deep convective environment: results from a regionally nested global model

Abstract. Global model studies and observations have shown that downward transport of aerosol nucleated in the free troposphere is a major source of cloud condensation nuclei (CCN) to the global boundary layer. In Amazonia, observations show that this downward transport can occur during strong convective activity. However, it is not clear from these studies over what spatial scale this cycle of aerosol formation and downward supply of CCN is occurring. Here, we aim to quantify the extent to which the supply of aerosol to the Amazonian boundary layer is generated from nucleation within a 1000 km regional domain or from aerosol produced further afield and the effectiveness of the transport by deep convection. We run the atmosphere-only configuration of the HadGEM3 climate model incorporating a 440 km × 1080 km regional domain over Amazonia with 4 km resolution. Simulations were performed over several diurnal cycles of convection. Below 2 km altitude in the regional domain, our results show that new particle formation within the regional domain accounts for only between 0.2 % and 3.4 % of all Aitken and accumulation mode aerosol particles, whereas nucleation that occurred outside the domain (in the global model) accounts for between 58 % and 81 %. The remaining aerosol is primary in origin. Above 10 km, the regional-domain nucleation accounts for up to 66 % of Aitken and accumulation mode aerosol, but over several days very few of these particles nucleated above 10 km in the regional domain are transported into the boundary layer within the 1000 km region, and in fact very little air is mixed that far down. Rather, particles transported downwards into the boundary layer originated from outside the regional domain and entered the domain at lower altitudes. Our model results show that CCN entering the Amazonian boundary layer are transported downwards gradually over multiple convective cycles on scales much larger than 1000 km. Therefore, on a 1000 km scale in the model (approximately one-third the size of Amazonia), trace gas emission, new particle formation, transport and CCN production do not form a “closed loop” regulated by the biosphere. Rather, on this scale, long-range transport of aerosol is a much more important factor controlling CCN in the boundary layer.

Effect of Sodium Dodecyl Benzene Sulfonate on the Production of Cloud Condensation Nuclei from Breaking Waves.

While sea spray particles are highly soluble by nature, and are thus excellent seeds for nascent cloud droplets, organic compounds such as surfactants have previously been identified within aerosol particles, bulk seawater, and the sea-surface microlayer in various oceans and seas. As the presence of dissolved surfactants within spray particles may limit their ability to act as cloud condensation nuclei (CCN), and since the abundance of CCN available during cloud formation is known to affect cloud albedo, the presence of surfactants in the marine environment can affect the local radiation balance. In this work, we added a model surfactant commonly used in households and industry (sodium dodecyl benzene sulfonate, SDBS) to a control solution of NaCl and observed its effects on the number of CCN produced by artificial breaking waves. We found that the addition of SDBS modified the number of CCN produced by a breaking wave analogue in three main ways: (I) by reducing the hygroscopicity of the resulting particulate; (II) by producing finer particulates than the control NaCl solution; and (III) by reducing the total number of particles produced overall. In addition, measurements of the absorption of ultraviolet light (λ = 224 nm) were used to quantify the concentration of SDBS in bulk water samples and aerosol extracts. We found that SDBS was significantly enriched in aerosol extracts relative to the bulk water even when the concentration of SDBS in the bulk water was below the limit of detection (LOD) of our quantitation methods. Thus, the surfactant studied will influence the production of CCN even when present in minute concentrations.

Secondary Organic Aerosol Formation Regulates Cloud Condensation Nuclei in the Global Remote Troposphere

AbstractFormation of secondary organic aerosols (SOA) through the atmospheric oxidation of organic vapors has potential to enable particle growth to cloud condensation nuclei (CCN)‐relevant sizes. In this work, we constrain a global aerosol model by using aircraft measurements to reveal the global importance of SOA formation in CCN production. Our improved model, with explicit size‐resolved aerosol microphysics and parametrizations of semivolatile organic oxidation products, presents a state‐of‐the‐art performance in simulating both particle number concentrations and organic aerosol concentrations dominated (80–95%) by SOA in the remote atmosphere, which have been challenges in previous modeling studies. The SOA formation in concert with aerosol nucleation contributes to more than 50% of CCN concentrations in those pristine environments featuring low background aerosol concentrations. We estimate that the SOA‐derived CCN alters the magnitude of cloud radiative forcing by ∼0.1 W m−2. Our findings underscore the necessity for aerosol‐climate models to represent controls on CCN concentrations by SOA production.

Observations of particle number size distributions and new particle formation in six Indian locations

Abstract. Atmospheric new particle formation (NPF) is a crucial process driving aerosol number concentrations in the atmosphere; it can significantly impact the evolution of atmospheric aerosol and cloud processes. This study analyses at least 1 year of asynchronous particle number size distributions from six different locations in India. We also analyze the frequency of NPF and its contribution to cloud condensation nuclei (CCN) concentrations. We found that the NPF frequency has a considerable seasonal variability. At the measurement sites analyzed in this study, NPF frequently occurs in March–May (pre-monsoon, about 21 % of the days) and is the least common in October–November (post-monsoon, about 7 % of the days). Considering the NPF events in all locations, the particle formation rate (JSDS) varied by more than 2 orders of magnitude (0.001–0.6 cm−3 s−1) and the growth rate between the smallest detectable size and 25 nm (GRSDS-25 nm) by about 3 orders of magnitude (0.2–17.2 nm h−1). We found that JSDS was higher by nearly 1 order of magnitude during NPF events in urban areas than mountain sites. GRSDS did not show a systematic difference. Our results showed that NPF events could significantly modulate the shape of particle number size distributions and CCN concentrations in India. The contribution of a given NPF event to CCN concentrations was the highest in urban locations (4.3 × 103 cm−3 per event and 1.2 × 103 cm−3 per event for 50 and 100 nm, respectively) as compared to mountain background sites (2.7 × 103 cm−3 per event and 1.0 × 103 cm−3 per event, respectively). We emphasize that the physical and chemical pathways responsible for NPF and factors that control its contribution to CCN production require in situ field observations using recent advances in aerosol and its precursor gaseous measurement techniques.

Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth's radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO2) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τHPMTF < 2 h) and terminates DMS oxidation to SO2 When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

Increased new particle yields with largely decreased probability of survival to CCN size at the summit of Mt. Tai under reduced SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; emissions

Abstract. Because anthropogenic sulfur dioxide (SO2) emissions have decreased considerably in the last decade, PM2.5 pollution in China has been alleviated to some extent. However, the effects of reduced SO2 on the particle number concentrations and subsequent contributions of grown new particles to cloud condensation nuclei (CCN) populations, particularly at high altitudes with low aerosol number loadings, are poorly understood. In contrast, the increase in provincial forest areas in China with rapid afforestation over the last few decades expectedly increases the biogenic emissions of volatile organic compounds and their oxidized products as nucleating precursors therein. In this study, we evaluated the campaign-based measurements made at the summit of Mt. Tai (1534 m a.s.l.) from 2007 to 2018. With the decrease in SO2 mixing ratios from 15 ± 13 ppb in 2007 to 1.6 ± 1.6 ppb in 2018, the apparent formation rate (FR) of new particles and the net maximum increase in the nucleation-mode particle number concentration (NMINP) in the spring campaign of 2018 was 2- to 3-fold higher than those in the spring campaign of 2007 with almost the same occurrence frequency of new particle formation (NPF) events. In contrast, the campaign-based comparison showed that the occurrence frequency, in which the maximum geometric median diameter of the grown new particles (Dpgmax) was &gt; 50 nm, decreased considerably from 43 %–78 % of the NPF events before 2015 to &lt; 12 % in 2017–2018. Assuming &gt; 50 nm as a CCN threshold size at high supersaturations, the observed net CCN production decreased from 3.7 × 103 cm−3 (on average) in the five campaigns before 2015 to 1.0 × 103 cm−3 (on average) in the two campaigns in 2017–2018. We argue that the increases in the apparent FR and NMINP are mainly determined by the availability of organic precursors that participate in nucleation and initial growth, whereas the decrease in the growth probability is caused by the reduced emissions of anthropogenic precursors. However, large uncertainties still exist because of a lack of data on the chemical composition of these smaller particles.

New particle formation at urban and high-altitude remote sites in the south-eastern Iberian Peninsula

Abstract. A substantial fraction of the atmospheric aerosols originates from secondary new particle formation (NPF), where atmospheric vapours are transformed into particles that subsequently grow to larger sizes, affecting human health and the climate. In this study, we investigate aerosol size distributions at two stations located close to each other (∼ 20 km) but at different altitudes: urban (UGR; 680 m a.s.l., metres above sea level) and high-altitude remote (SNS; 2500 m a.s.l.) sites, both in the area of Granada, Spain, and part of AGORA observatory (Andalusian Global ObseRvatory of the Atmosphere). The analysis shows a significant contribution of nucleation mode aerosol particles to the total aerosol number concentration at both sites, with a contribution of 47 % and 48 % at SNS and UGR, respectively. Due to the important contribution of NPF events to the total aerosol number concentrations and their high occurrence frequency (&gt; 70 %) during the study period, a detailed analysis of NPF events is done in order to get insight into the possible mechanisms and processes involved in NPF events at these contrastive sites. At SNS, NPF is found to be associated with the transport of gaseous precursors from lower altitudes by orographic buoyant upward flows. NPF events at the SNS site are always observed from the smallest measured sizes of the aerosol size distribution (4 nm), implying that NPF takes place in or in the vicinity of the high-altitude SNS station rather than being transported from lower altitudes. Although NPF events at the mountain site seem to be connected with those occurring at the urban site, growth rates (GRs) at SNS are higher than those at the UGR site (GR7−25 of 6.9 and 4.5 nm h−1 and GR4−7 of 4.1 and 3.6 nm h−1 at SNS and UGR, respectively). This fact could have special importance for the production of cloud condensation nuclei (CCN) and therefore for cloud formations which may affect regional/global climate, since larger GRs at mountain sites could translate to a larger survival probability of NPF particles reaching CCN sizes, due to the shorter time period needed for the growth. The analysis of sulfuric acid (H2SO4) shows that the contribution of H2SO4 is able to explain a minimal fraction contribution to the observed GRs at both sites (&lt; 1 % and &lt; 10 % for the 7–25 and 4–7 nm size ranges, respectively), indicating that other condensing vapours are responsible for the majority of particle growth, as well as the differing growth rates between the two sites. Results also show that the condensation sink (CS) does not play a relevant role in NPF processes at both sites and points to the availability of volatile organic compounds (VOCs) as one of the main factors controlling the NPF events at both sites. Finally, a closer analysis of the NPF events that were observed at the SNS site during a Saharan dust episode that occurred during the field campaign was carried out, evidencing the role of TiO2 and F2O3 together with VOCs in promoting new particle formation during this dust intrusion event. Although further investigation is needed to improve our understanding in this topic, this result suggests that climate effects of mineral dust and NPF are not disconnected from each other as it was commonly thought. Therefore, since mineral dust contributes to a major fraction of the global aerosol mass load, dust–NPF interaction should be taken into account in global aerosol-climate modelling for better climate change prediction.

A large source of cloud condensation nuclei from new particle formation in the tropics.

Cloud condensation nuclei (CCN) can affect cloud properties and therefore Earth's radiative balance1-3. New particle formation (NPF) from condensable vapours in the free troposphere has been suggested to contribute to CCN, especially in remote, pristine atmospheric regions4, but direct evidence is sparse, and the magnitude of this contribution is uncertain5-7. Here we use in situ aircraft measurements of vertical profiles of aerosol size distributions to present a global-scale survey of NPF occurrence. We observe intense NPF at high altitudes in tropical convective regions over both Pacific and Atlantic oceans. Together with the results of chemical-transport models, our findings indicate that NPF persists at all longitudes as a global-scale band in the tropical upper troposphere, covering about 40 per cent of Earth's surface. Furthermore, we find that this NPF in the tropical upper troposphere is a globally important source of CCN in the lower troposphere, where CCN can affect cloud properties. Our findings suggest that the production of CCN as new particles descend towards the surface is not adequately captured in global models, which tend to underestimate both the magnitude of tropical upper tropospheric NPF and the subsequent growth of new particles to CCN sizes.

Sulfur Dioxide Modifies Aerosol Particle Formation and Growth by Ozonolysis of Monoterpenes and Isoprene

AbstractThe effect of sulfur dioxide on particle formation and growth by ozonolysis of three monoterpenes (α‐pinene, β‐pinene, and limonene) and isoprene was investigated in the presence of monodisperse ammonium sulfate seed particles and an OH scavenger in a flow tube under dry conditions. Without sulfur dioxide, new particle formation was not observed, and seed particle growth was consistent with condensation of low‐volatility oxidation products produced from each organic precursor. With sulfur dioxide, new particle formation was observed from every precursor studied, consistent with sulfuric acid formation by reaction of sulfur dioxide with stabilized Criegee Intermediates. The presence of sulfur dioxide did not significantly affect seed particle growth rates from α‐pinene and limonene ozonolysis, although chemical composition measurements revealed the presence of organosulfates in the particles following SO2 exposure. Contrarily, the growth of seeds by β‐pinene and isoprene ozonolysis was considerably enhanced by sulfur dioxide, and chemical composition measurements revealed that the enhanced growth was not due to additional organic material, suggesting that inorganic sulfate was likely responsible. The results suggest that a previously unconsidered particle‐phase pathway to growth activated by sulfur dioxide may alter production of cloud condensation nuclei over regions with significant SO2‐alkene interactions.

Femtosecond filamentation induced particles and their cloud condensation nuclei activity

Laboratory experiments were conducted to investigate femtosecond filamentation induced particle formation and growth in particle-free air as well as in the presence of pre-existing ammonium sulfate aerosols. The ability of laser induced particles to act as cloud condensation nuclei (CCN) was explored. The influence of water vapor and the pulse energy on the production efficiency and activation properties of particles were also examined. In particle-free air, laser filaments could lead to a significant production of new particles, the number concentration of which was comparable to or larger than that in polluted ambient air, depending upon the pulse energy and humidity. Total particle number and mass concentrations within 20–708 nm were predominantly contributed by particles with a diameter smaller than 100 nm. Remarkably high NOx up to an order of ∼101 ppm was generated in the chamber, allowing sufficient production of HNO3 and probably subsequent HNO3-H2O binary nucleation. In the presence of pre-existing particles, the yield of particle number was largely enhanced in laser filaments, especially in humid air. Particle number size distribution shifted towards smaller particle size, leading to a slight increase in particle mass. It was found that a considerable portion of laser induced particles, no matter generated with or without pre-existing particles, could act as CCN. The amount of CCN at 0.80% supersaturation was in the magnitude of 104∼105 cm−3 in all experiments, nearly one order larger than the average ambient level even in severely polluted regions. Overall, increasing the pulse energy and water vapor would favor particle formation and growth as well as the production of CCN. Raising the pulse energy also resulted in a decline of the hygroscopic parameter κ, implying the modification of aerosol chemical composition. Though more investigative studies are still needed to explore mechanisms underlying some of these experimental results, laser filaments are undoubtedly capable of inducing substantial particle formation and modifying microphysical/chemical properties of pre-existing particles. By influencing these crucial properties and thereby aerosol direct/indirect climatic and environmental effects, laser filamentation would provide a promising potential for related atmospheric applications.

CCN production by new particle formation in the free troposphere

Abstract. Global models predict that new particle formation (NPF) is, in some environments, responsible for a substantial fraction of the total atmospheric particle number concentration and subsequently contributes significantly to cloud condensation nuclei (CCN) concentrations. NPF events were frequently observed at the highest atmospheric observatory in the world, on Chacaltaya (5240 m a.s.l.), Bolivia. The present study focuses on the impact of NPF on CCN population. Neutral cluster and Air Ion Spectrometer and mobility particle size spectrometer measurements were simultaneously used to follow the growth of particles from cluster sizes down to ∼ 2 nm up to CCN threshold sizes set to 50, 80 and 100 nm. Using measurements performed between 1 January and 31 December 2012, we found that 61 % of the 94 analysed events showed a clear particle growth and significant enhancement of the CCN-relevant particle number concentration. We evaluated the contribution of NPF, relative to the transport and growth of pre-existing particles, to CCN size. The averaged production of 50 nm particles during those events was 5072, and 1481 cm−3 for 100 nm particles, with a larger contribution of NPF compared to transport, especially during the wet season. The data set was further segregated into boundary layer (BL) and free troposphere (FT) conditions at the site. The NPF frequency of occurrence was higher in the BL (48 %) compared to the FT (39 %). Particle condensational growth was more frequently observed for events initiated in the FT, but on average faster for those initiated in the BL, when the amount of condensable species was most probably larger. As a result, the potential to form new CCN was higher for events initiated in the BL (67 % against 53 % in the FT). In contrast, higher CCN number concentration increases were found when the NPF process initially occurred in the FT, under less polluted conditions. This work highlights the competition between particle growth and the removal of freshly nucleated particles by coagulation processes. The results support model predictions which suggest that NPF is an effective source of CCN in some environments, and thus may influence regional climate through cloud-related radiative processes.

New particle formation in the southern Aegean Sea during the Etesians: importance for CCN production and cloud droplet number

Abstract. This study examines how new particle formation (NPF) in the eastern Mediterranean in summer affects CCN (cloud condensation nuclei) concentrations and cloud droplet formation. For this, the concentration and size distribution of submicron aerosol particles, along with the concentration of trace gases and meteorological variables, were studied over the central (Santorini) and southern Aegean Sea (Finokalia, Crete) from 15 to 28 July 2013, a period that includes Etesian events and moderate northern surface winds. Particle nucleation bursts were recorded during the Etesian flow at both stations, with those observed at Santorini reaching up to 1.5 × 104 particles cm−3; the fraction of nucleation-mode particles over Crete was relatively diminished, but a higher number of Aitken-mode particles were observed as a result of aging. Aerosol and photochemical pollutants covaried throughout the measurement period; lower concentrations were observed during the period of Etesian flow (e.g., 43–70 ppbv for ozone and 1.5–5.7 µg m−3 for sulfate) but were substantially enhanced during the period of moderate surface winds (i.e., increase of up to 32 for ozone and 140 % for sulfate). We find that NPF can double CCN number (at 0.1 % supersaturation), but the resulting strong competition for water vapor in cloudy updrafts decreases maximum supersaturation by 14 % and augments the potential droplet number only by 12 %. Therefore, although NPF events may strongly elevate CCN numbers, the relative impacts on cloud droplet number (compared to pre-event levels) is eventually limited by water vapor availability and depends on the prevailing cloud formation dynamics and the aerosol levels associated with the background of the region.

Isoprene suppression of new particle formation: Potential mechanisms and implications

AbstractSecondary aerosols formed from anthropogenic pollutants and natural emissions have substantial impacts on human health, air quality, and the Earth's climate. New particle formation (NPF) contributes up to 70% of the global production of cloud condensation nuclei (CCN), but the effects of biogenic volatile organic compounds (BVOCs) and their oxidation products on NPF processes in forests are poorly understood. Observations show that isoprene, the most abundant BVOC, suppresses NPF in forests. But the previously proposed chemical mechanism underlying this suppression process contradicts atmospheric observations. By reviewing observations made in other forests, it is clear that NPF rarely takes place during the summer when emissions of isoprene are high, even though there are sufficient concentrations of monoterpenes. But at present it is not clear how isoprene and its oxidation products may change the oxidation chemistry of terpenes and how NOx and other atmospheric key species affect NPF in forest environments. Future laboratory experiments with chemical speciation of gas phase nucleation precursors and clusters and chemical composition of particles smaller than 10 nm are required to understand the role of isoprene in NPF. Our results show that climate models can overpredict aerosol's first indirect effect when not considering the absence of NPF in the southeastern U.S. forests during the summer using the current nucleation algorithm that includes only sulfuric acid and total concentrations of low‐volatility organic compounds. This highlights the importance of understanding NPF processes as function of temperature, relative humidity, and BVOC compositions to make valid predictions of NPF and CCN at a wide range of atmospheric conditions.

Linking Meteorology, Turbulence, and Air Chemistry in the Amazon Rain Forest

Abstract We describe the salient features of a field study whose goals are to quantify the vertical distribution of plant-emitted hydrocarbons and their contribution to aerosol and cloud condensation nuclei production above a central Amazonian rain forest. Using observing systems deployed on a 50-m meteorological tower, complemented with tethered balloon deployments, the vertical distribution of hydrocarbons and aerosols was determined under different boundary layer thermodynamic states. The rain forest emits sufficient reactive hydrocarbons, such as isoprene and monoterpenes, to provide precursors of secondary organic aerosols and cloud condensation nuclei. Mesoscale convective systems transport ozone from the middle troposphere, enriching the atmospheric boundary layer as well as the forest canopy and surface layer. Through multiple chemical transformations, the ozone-enriched atmospheric surface layer can oxidize rain forest–emitted hydrocarbons. One conclusion derived from the field studies is that the rain forest produces the necessary chemical species and in sufficient amounts to undergo oxidation and generate aerosols that subsequently activate into cloud condensation nuclei.

Key features of new particle formation events at background sites in China and their influence on cloud condensation nuclei

Long-term continuous measurements of particle number size distributions with mobility diameter sizes ranging from 3 to 800 nm were performed to study new particle formation (NPF) events at Shangdianzi (SDZ), Mt. Tai (TS), and Lin’an (LAN) stations representing the background atmospheric conditions in the North China Plain (NCP), Central East China (CEC), and Yangtze River Delta (YRD) regions, respectively. The mean formation rate of 3-nm particles was 6.3, 3.7, and 5.8 cm–3∙s–1, and the mean particle growth rate was 3.6, 6.0, and 6.2 nm∙h–1 at SDZ, TS, and LAN, respectively. The NPF event characteristics at the three sites indicate that there may be a stronger source of low volatile vapors and higher condensational sink of pre-existing particles in the YRD region. The formation rate of NPF events at these sites, as well as the condensation sink, is approximately 10 times higher than some results reported at rural/urban sites in western countries. However, the growth rates appear to be 1–2 times higher. Approximately 12%–17% of all NPF events with nucleated particles grow to a climaterelevant size (>50 nm). These kinds of NPF events were normally observed with higher growth rate than the other NPF cases. Generally, the cloud condensation nuclei (CCN) number concentration can be enhanced by approximately a factor of 2–6 on these event days. The mean value of the enhancement factor is lowest at LAN (2–3) and highest at SDZ (~4). NPF events have also been found to have greater impact on CCN production in China at the regional scale than in the other background sites worldwide.

Some insights into the condensing vapors driving new particle growth to CCN sizes on the basis of hygroscopicity measurements

Abstract. New particle formation (NPF) and growth is an important source of cloud condensation nuclei (CCN). In this study, we investigated the chemical species driving new particle growth to the CCN sizes on the basis of particle hygroscopicity measurements carried out at the research station Melpitz, Germany. Three consecutive NPF events occurred during summertime were chosen as examples to perform the study. Hygroscopicity measurements showed that the (NH4)2SO4-equivalent water-soluble fraction accounts for 20 and 16 % of 50 and 75 nm particles, respectively, during the NPF events. Numerical analysis showed that the ratios of H2SO4 condensational growth to the observed particle growth were 20 and 13 % for 50 and 75 nm newly formed particles, respectively. Aerosol mass spectrometer measurements showed that an enhanced mass fraction of sulfate and ammonium in the newly formed particles was observed when new particles grew to the sizes larger than 30 nm shortly after the particle formation period. At a later time, the secondary organic species played a key role in the particle growth. Both hygroscopicity and aerosol mass spectrometer (AMS) measurements and numerical analysis confirmed that organic compounds were major contributors driving particle growth to CCN sizes. The critical diameters at different supersaturations estimated using AMS data and κ-Köhler theory increased significantly during the later course of NPF events. This indicated that the enhanced organic mass fraction caused a reduction in CCN efficiency of newly formed particles. Our results implied that the CCN production associated with atmospheric nucleation may be overestimated if assuming that newly formed particles can serve as CCN once they grow to a fixed particle size, an assumption made in some previous studies, especially for organic-rich environments. In our study, the enhancement in CCN number concentration associated with individual NPF events were 63, 66, and 69 % for 0.1, 0.4, and 0.6 % supersaturation, respectively.

Atmospheric new particle formation as a source of CCN in the eastern Mediterranean marine boundary layer

Abstract. While cloud condensation nuclei (CCN) production associated with atmospheric new particle formation (NPF) is thought to be frequent throughout the continental boundary layers, few studies on this phenomenon in marine air exist. Here, based on simultaneous measurement of particle number size distributions, CCN properties and aerosol chemical composition, we present the first direct evidence on CCN production resulting from NPF in the eastern Mediterranean atmosphere. We show that condensation of both gaseous sulfuric acid and organic compounds from multiple sources leads to the rapid growth of nucleated particles to CCN sizes in this environment during the summertime. Sub-100 nm particles were found to be substantially less hygroscopic than larger particles during the period with active NPF and growth (the value of κ was lower by 0.2–0.4 for 60 nm particles compared with 120 nm particles), probably due to enrichment of organic material in the sub-100 nm size range. The aerosol hygroscopicity tended to be at minimum just before the noon and at maximum in the afternoon, which was very likely due to the higher sulfate-to-organic ratios and higher degree of oxidation of the organic material during the afternoon. Simultaneous with the formation of new particles during daytime, particles formed during the previous day or even earlier were growing into the size range relevant to cloud droplet activation, and the particles formed in the atmosphere were possibly mixed with long-range-transported particles.

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.