Formation and growth of sub-3 nm particles in megacities : impact of background aerosols

New particle formation (NPF) occurs frequently in various atmospheric environments and contributes majorly to the aerosol number budget. In megacities, the high concentrations of gaseous precursors and background aerosols add complexity to this process. Based on long-term measurements (373 days) in urban Beijing, we examine the formation and growth of sub-3 nm particles under the effects of background aerosols, as indicated by the condensation sink (CS) or the Fuchs surface area. The median CS and the median PM2.5 mass concentration for the days with NPF events were 0.03 s(-1) and 34 mu g m(-3), respectively. The high loss rates of both molecular clusters and sub-3 nm particles to background aerosols reduce their atmospheric residence time and suppress their survival. As the key clusters for H2SO4-base nucleation, sulfuric acid dimer and trimer concentrations in Beijing decrease significantly when CS increases and the scavenging becomes stronger. The occurrence of NPF events and the formation of sub-3 nm particles in Beijing is governed by CS. 95% of the observed NPF days occurred with CS values below 0.03 s(-1). During NPF events, high concentrations of sub-3 nm particles were formed and they mostly ranged from 10(3) to 10(5) cm(-3) with a median value of 6.2 x 10(3) cm(-3). Driven by the fast H2SO4-base nucleation, the daily maximum formation rate of 1.5 nm particles in Beijing has a mean value of 77 cm(-3) s(-1) and is much higher than that in clean environments. However, the mean growth rate of sub-3 nm particles in Beijing was only 2.6 nm h(-1), not significantly different from that in clean environments. The relatively low growth rate and the high level of scavenging by background aerosols result in low survival of newly formed particles. The analyses also reinforce prior results on the need to correct conventional methods to adequately quantify the formation and growth rates when analyzing data from megacities with strong coagulation scavenging due to background aerosols. The conventional balance formula underestimates the formation rate of 1.5 nm particles, while the conventional appearance time method overestimates the growth rate of sub-3 nm particles. These findings highlight the governing role of background aerosols in urban NPF.Peer reviewe

Survival probability of new atmospheric particles : closure between theory and measurements from 1.4 to 100 nm

The survival probability of freshly nucleated particles governs the influences of new particle formation (NPF) on atmospheric environments and the climate. It characterizes the probability of a particle avoiding being scavenged by the coagulation with pre-existing particles and other scavenging processes before the particle successfully grows up to a certain diameter. Despite its importance, measuring the survival probability has been challenging, which limits the knowledge of particle survival in the atmosphere and results in large uncertainties in predicting the influences of NPF. Here we report the proper methods to retrieve particle survival probability using the measured aerosol size distributions. Using diverse aerosol size distributions from urban Beijing, the Finnish boreal forest, a chamber experiment, and aerosol kinetic simulations, we demonstrate that each method is valid for a different type of aerosol size distribution, whereas misapplying the conventional methods to banana-type NPF events may underestimate the survival probability. Using these methods, we investigate the consistency between the measured survival probability of new particles and the theoretical survival probability against coagulation scavenging predicted using the measured growth rate and coagulation sink. With case-by-case and time- and size-resolved analysis of long-term measurement data from urban Beijing, we find that although both the measured and theoretical survival probabilities are sensitive to uncertainties and variations, they are, on average, consistent with each other for new particles growing from 1.4 (the cluster size) to 100 nm.Peer reviewe

Impacts of coagulation on the appearance time method for new particle growth rate evaluation and their corrections

The growth rate of atmospheric new particles is a key parameter that determines their survival probability of becoming cloud condensation nuclei and hence their impact on the climate. There have been several methods to estimate the new particle growth rate. However, due to the impact of coagulation and measurement uncertainties, it is still challenging to estimate the initial growth rate of new particles, especially in polluted environments with high background aerosol concentrations. In this study, we explore the influences of coagulation on the appearance time method to estimate the growth rate of sub-3 nm particles. The principle of the appearance time method and the impacts of coagulation on the retrieved growth rate are clarified via derivations. New formulae in both discrete and continuous spaces are proposed to correct for the impacts of coagulation. Aerosol dynamic models are used to test the new formulae. New particle formation in urban Beijing is used to illustrate the importance of considering the impacts of coagulation on the sub-3 nm particle growth rate and its calculation. We show that the conventional appearance time method needs to be corrected when the impacts of coagulation sink, coagulation source, and particle coagulation growth are non-negligible compared to the condensation growth. Under the simulation conditions with a constant concentration of non-volatile vapors, the corrected growth rate agrees with the theoretical growth rates. However, the uncorrected parameters, e.g., vapor evaporation and the variation in vapor concentration, may impact the growth rate obtained with the appearance time method. Under the simulation conditions with a varying vapor concentration, the average bias in the corrected 1.5-3 nm particle growth rate ranges from 6 %-44 %, and the maximum bias in the size-dependent growth rate is 150 %. During the test new particle formation event in urban Beijing, the corrected condensation growth rate of sub-3 nm particles was in accordance with the growth rate contributed by sulfuric acid condensation, whereas the conventional appearance time method overestimated the condensation growth rate of 1.5 nm particles by 80 %.Peer reviewe

Measurement report : Size distributions of urban aerosols down to 1 nm from long-term measurements

The size distributions of urban atmospheric aerosols convey important information on their origins and impacts. Their long-term characteristics, especially for sub-3 nm particles, are still limited. In this study, we examined the characteristics of atmospheric aerosol size distributions down to similar to 1 nm based on 4-year measurements in urban Beijing. Using cluster analysis, three typical types of number size distributions were identified, i.e., daytime new particle formation (NPF) type, daytime non-NPF type, and nighttime type. Combining a power law distribution and multiple lognormal distributions can well represent the sharp concentration decrease of sub3 nm particles with increasing size and the modal characteristics for those above 3 nm in the submicron size range. The daytime NPF type exhibits high concentrations of sub-3 nm aerosols together with other three modes. However, both the daytime non-NPF type and the nighttime type have a low abundance of sub-3 nm aerosol particles together with only two distinct modes. In urban Beijing, the concentration of H2SO4 monomer during the daytime with NPF is similar to that during the daytime without NPF, while significantly higher than that during the nighttime. The concentration of atmospheric sub-3 nm particles on NPF days has a strong seasonality while their seasonality on non-NPF days is less pronounced. In addition to NPF as the most important source, we show that vehicles can emit sub-3 nm particles as well, although their influence on the measured aerosol population strongly depends on the distance from the road.Peer reviewe

Acid-Base Clusters during Atmospheric New Particle Formation in Urban Beijing

Molecular clustering is the initial step of atmospheric new particle formation (NPF) that generates numerous secondary particles. Using two online mass spectrometers with and without a chemical ionization inlet, we characterized the neutral clusters and the naturally charged ion clusters during NPF periods in urban Beijing. In ion clusters, we observed pure sulfuric acid (SA) clusters, SA-amine clusters, SA-ammonia (NH3) clusters, and SA-amine-NH3 clusters. However, only SA clusters and SA-amine clusters were observed in the neutral form. Meanwhile, oxygenated organic molecule (OOM) clusters charged by a nitrate ion and a bisulfate ion were observed in ion clusters. Acid-base clusters correlate well with the occurrence of sub-3 nm particles, whereas OOM clusters do not. Moreover, with the increasing cluster size, amine fractions in ion acid-base clusters decrease, while NH3 fractions increase. This variation results from the reduced stability differences between SA-amine clusters and SA-NH3 clusters, which is supported by both quantum chemistry calculations and chamber experiments. The lower average number of dimethylamine (DMA) molecules in atmospheric ion clusters than the saturated value from controlled SA-DMA nucleation experiments suggests that there is insufficient DMA in urban Beijing to fully stabilize large SA clusters, and therefore, other basic molecules such as NH3 play an important role.Peer reviewe

Size-resolved particle number emissions in Beijing determined from measured particle size distributions

The climate and air quality effects of aerosol particles depend on the number and size of the particles. In urban environments, a large fraction of aerosol particles originates from anthropogenic emissions. To evaluate the effects of different pollution sources on air quality, knowledge of size distributions of particle number emissions is needed. Here we introduce a novel method for determining size-resolved particle number emissions, based on measured particle size distributions. We apply our method to data measured in Beijing, China, to determine the number size distribution of emitted particles in a diameter range from 2 to 1000 nm. The observed particle number emissions are dominated by emissions of particles smaller than 30 nm. Our results suggest that traffic is the major source of particle number emissions with the highest emissions observed for particles around 10 nm during rush hours. At sizes below 6 nm, clustering of atmospheric vapors contributes to calculated emissions. The comparison between our calculated emissions and those estimated with an integrated assessment model GAINS (Greenhouse Gas and Air Pollution Interactions and Synergies) shows that our method yields clearly higher particle emissions at sizes below 60 nm, but at sizes above that the two methods agree well. Overall, our method is proven to be a useful tool for gaining new knowledge of the size distributions of particle number emissions in urban environments and for validating emission inventories and models. In the future, the method will be developed by modeling the transport of particles from different sources to obtain more accurate estimates of particle number emissions.Peer reviewe

Quiet New Particle Formation in the Atmosphere

Atmospheric new particle formation (NPF) has been observed to take place in practice all around the world. In continental locations, typically about 10-40% of the days are so-called NPF event days characterized by a clear particle formation and growth that continue for several hours, occurring mostly during daytime. The other days are either non-event days, or days for which it is difficult to decide whether NPF had occurred or not. Using measurement data from several locations (Hyytiala, Jarvselja, and near-city background and city center of Budapest), we were able to show that NPF tends to occur also on the days traditionally characterized as non-event days. One explanation is the instrument sensitivity towards low number concentrations in the sub-10 nm range, which usually limits our capability to detect such NPF events. We found that during such days, particle formation rates at 6 nm were about 2-20% of those observed during the traditional NPF event days. Growth rates of the newly formed particles were very similar between the traditional NPF event and non-event days. This previously overlooked phenomenon, termed as quiet NPF, contributes significantly to the production of secondary particles in the atmosphere.Peer reviewe

Responses of gaseous sulfuric acid and particulate sulfate to reduced SO2 concentration : A perspective from long-term measurements in Beijing

SO2 concentration decreased rapidly in recent years in China due to the implementation of strict control policies by the government. Particulate sulfate (pSO(4)(2-)) and gaseous H2SO4 (SA) are two major products of SO2 and they play important roles in the haze formation and new particle formation (NPF), respectively. We examined the change in pSO(4)(2-) and SA concentrations in response to reduced SO2 concentration using long-term measurement data in Beijing. Simulations from the Community Multiscale Air Quality model with a 2-D Volatility Basis Set (CMAQ/2D-VBS) were used for comparison. From 2013 to 2018, SO2 concentration in Beijing decreased by similar to 81% (from 9.1 ppb to 1.7 ppb). pSO(4)(2-) concentration in submicrometer particles decreased by similar to 60% from 2012-2013 (monthly average of similar to 10 mu g.m(-3)) to 2018-2019 (monthly average of similar to 4 mu g.m(-3)). Accordingly, the fraction of pSO(4)(2-) in these particles decreased from20-30% to b10%. Increased sulfur oxidation ratio was observed both in the measurements and the CMAQ/2D-VBS simulations. Despite the reduction in SO2 concentration, there was no obvious decrease in SA concentration based on data from several measuring periods from 2008 to 2019. This was supported by the increased SA:SO2 ratio with reduced SO2 concentration and condensation sink. NPF frequency in Beijing between 2004 and 2019 remains relatively constant. This constant NPF frequency is consistent with the relatively stable SA concentration in Beijing, while different from some other cities where NPF frequency was reported to decrease with decreased SO2 concentrations. (C) 2020 Elsevier B.V. All rights reserved.Peer reviewe

Contribution of Atmospheric Oxygenated Organic Compounds to Particle Growth in an Urban Environment

Gas-phase oxygenated organic molecules (OOMs) can contribute substantially to the growth of newly formed particles. However, the characteristics of OOMs and their contributions to particle growth rate are not well understood in urban areas, which have complex anthropogenic emissions and atmospheric conditions. We performed long-term measurement of gas-phase OOMs in urban Beijing during 2018-2019 using nitrate-based chemical ionization mass spectrometry. OOM concentrations showed clear seasonal variations, with the highest in the summer and the lowest in the winter. Correspondingly, calculated particle growth rates due to OOM condensation were highest in summer, followed by spring, autumn, and winter. One prominent feature of OOMs in this urban environment was a high fraction (similar to 75%) of nitrogen-containing OOMs. These nitrogen-containing OOMs contributed only 50-60% of the total growth rate led by OOM condensation, owing to their slightly higher volatility than non-nitrate OOMs. By comparing the calculated condensation growth rates and the observed particle growth rates, we showed that sulfuric acid and its clusters are the main contributors to the growth of sub-3 nm particles, with OOMs significantly promoting the growth of 3-25 nm particles. In wintertime Beijing, however, there are missing contributors to the growth of particles above 3 nm, which remain to be further investigated.Peer reviewe

Towards a concentration closure of sub-6 nm aerosol particles and sub-3 nm atmospheric clusters

Atmospheric clusters play a key role in atmospheric new particle formation and they are a sensitive indicator for atmospheric chemistry. Both the formation and loss of atmospheric clusters include a complex set of interlinked physical and chemical processes, and therefore their dynamics is highly non-linear. Here we derive a set of simple equations to estimate the atmospheric cluster concentrations in size ranges of 1.5–2 nm and 2–3 nm as well as 3–6 nm aerosol particles. We compared the estimated concentrations with measured ones both in a boreal forest site (the SMEAR II station in Hyytiälä, Finland) and in an urban site (the AHL/BUCT station in Beijing, China). We made this comparison first for 3–6 nm particles, since in this size range observations are more reliable than at smaller sizes, and then repeated it for the 2–3 nm size range. Finally, we estimated cluster concentrations in the 1.5–2 nm size range. Our main finding is that the present observations are able to detect a major fraction of existing atmospheric clusters.Atmospheric clusters play a key role in atmospheric new particle formation and they are a sensitive indicator for atmospheric chemistry. Both the formation and loss of atmospheric clusters include a complex set of interlinked physical and chemical processes, and therefore their dynamics is highly non-linear. Here we derive a set of simple equations to estimate the atmospheric cluster concentrations in size ranges of 1.5–2 nm and 2–3 nm as well as 3–6 nm aerosol particles. We compared the estimated concentrations with measured ones both in a boreal forest site (the SMEAR II station in Hyytiälä, Finland) and in an urban site (the AHL/BUCT station in Beijing, China). We made this comparison first for 3–6 nm particles, since in this size range observations are more reliable than at smaller sizes, and then repeated it for the 2–3 nm size range. Finally, we estimated cluster concentrations in the 1.5–2 nm size range. Our main finding is that the present observations are able to detect a major fraction of existing atmospheric clusters.Peer reviewe