Rapid growth of Aitken-mode particles during Arctic summer by fog chemical processing and its implication.

In the Arctic, new particle formation (NPF) and subsequent growth processes are the keys to produce Aitken-mode particles, which under certain conditions can act as cloud condensation nuclei (CCNs). The activation of Aitken-mode particles increases the CCN budget of Arctic low-level clouds and, accordingly, affects Arctic climate forcing. However, the growth mechanism of Aitken-mode particles from NPF into CCN range in the summertime Arctic boundary layer remains a subject of current research. In this combined Arctic cruise field and modeling study, we investigated Aitken-mode particle growth to sizes above 80 nm. A mechanism is suggested that explains how Aitken-mode particles can become CCN without requiring high water vapor supersaturation. Model simulations suggest the formation of semivolatile compounds, such as methanesulfonic acid (MSA) in fog droplets. When the fog droplets evaporate, these compounds repartition from CCNs into the gas phase and into the condensed phase of nonactivated Aitken-mode particles. For MSA, a mass increase factor of 18 is modeled. The postfog redistribution mechanism of semivolatile acidic and basic compounds could explain the observed growth of >20 nm h-1 for 60-nm particles to sizes above 100 nm. Overall, this study implies that the increasing frequency of NPF and fog-related particle processing can affect Arctic cloud properties in the summertime boundary layer.

The missing base molecules in atmospheric acid-base nucleation.

Transformation of low-volatility gaseous precursors to new particles affects aerosol number concentration, cloud formation and hence the climate. The clustering of acid and base molecules is a major mechanism driving fast nucleation and initial growth of new particles in the atmosphere. However, the acid-base cluster composition, measured using state-of-the-art mass spectrometers, cannot explain the measured high formation rate of new particles. Here we present strong evidence for the existence of base molecules such as amines in the smallest atmospheric sulfuric acid clusters prior to their detection by mass spectrometers. We demonstrate that forming (H2SO4)1(amine)1 is the rate-limiting step in atmospheric H2SO4-amine nucleation and the uptake of (H2SO4)1(amine)1 is a major pathway for the initial growth of H2SO4 clusters. The proposed mechanism is very consistent with measured new particle formation in urban Beijing, in which dimethylamine is the key base for H2SO4 nucleation while other bases such as ammonia may contribute to the growth of larger clusters. Our findings further underline the fact that strong amines, even at low concentrations and when undetected in the smallest clusters, can be crucial to particle formation in the planetary boundary layer.

Influence of Aerosol Chemical Composition on Condensation Sink Efficiency and New Particle Formation in Beijing.

Relatively high concentrations of preexisting particles, acting as a condensation sink (CS) of gaseous precursors, have been thought to suppress the occurrence of new particle formation (NPF) in urban environments, yet NPF still occurs frequently. Here, we aim to understand the factors promoting and inhibiting NPF events in urban Beijing by combining one-year-long measurements of particle number size distributions and PM2.5 chemical composition. Our results show that indeed the CS is an important factor controlling the occurrence of NPF events, with its chemical composition affecting the efficiency of the background particles in removing gaseous H2SO4 (effectiveness of the CS) driving NPF. During our observation period, the CS was found to be more effective for ammonium nitrate-rich (NH4NO3-rich) fine particles. On non-NPF event days, particles acting as CS contained a larger fraction of NH4NO3 compared to NPF event days under comparable CS levels. In particular, in the CS range from 0.02 to 0.03 s-1, the nitrate fraction was 17% on NPF event days and 26% on non-NPF event days. Overall, our results highlight the importance of considering the chemical composition of preexisting particles when estimating the CS and their role in inhibiting NPF events, especially in urban environments.

Global health burden of ambient PM2.5 and the contribution of anthropogenic black carbon and organic aerosols.

Chronic exposure to fine particulate matter (PM2.5) poses a major global health risk, commonly assessed by assuming equivalent toxicity for different PM2.5 constituents. We used a data-informed global atmospheric model and recent exposure-response functions to calculate the health burden of ambient PM2.5 from ten source categories. We estimate 4.23 (95% confidence interval 3.0-6.14) million excess deaths annually from the exposure to ambient PM2.5. We distinguished contributions and major sources of black carbon (BC), primary organic aerosols (POA) and anthropogenic secondary organic aerosols (aSOA). These components make up to ∼20% of the total PM2.5 in South and East Asia and East Africa. We find that domestic energy use by the burning of solid biofuels is the largest contributor to ambient BC, POA and aSOA globally. Epidemiological and toxicological studies indicate that these compounds may be relatively more hazardous than other PM2.5 compounds such as soluble salts, related to their high potential to inflict oxidative stress. We performed sensitivity analyses by considering these species to be more harmful compared to other compounds in PM2.5, as suggested by their oxidative potential using a range of potential relative risks. These analyses show that domestic energy use emerges as the leading cause of excess mortality attributable to ambient PM2.5, notably in Asia and Africa. We acknowledge the uncertainties inherent in our assumed enhanced toxicity of the anthropogenic organic and BC aerosol components, which suggest the need to better understand the mechanisms and magnitude of the associated health risks and the consequences for regulatory policies. However our assessment of the importance of emissions from domestic energy use as a cause of premature mortality is robust to a range of assumptions about the magnitude of the excess risk.

The effect of urban morphological characteristics on the spatial variation of PM2.5 air quality in downtown Nanjing.

The effects of the urban morphological characteristics on the spatial variation of near-surface PM2.5 air quality were examined. Unlike previous studies, we performed the analyses in real urban environments using continuous observations covering the whole scale of urban densities typically found in cities. We included data from 31 measurement stations divided into 8 different wind sectors with individually defined morphological characteristics leading to highly varying urban characteristics. The urban morphological characteristics explained up to 73% of the variance in normalized PM2.5 concentrations in street canyons, indicating that the spatial variation of the near-surface PM2.5 air quality was mostly defined by the characteristics studied. The fraction of urban trees nearby the stations was found to be the most important urban morphological characteristic in explaining the PM2.5 air quality, followed by the height-normalized roughness length as the second important parameter. An increase in the fraction of trees within 50 m of the stations from 25 percentile to 75 percentile (i.e. by the interquartile range, IQR) increased the normalized PM2.5 concentration by up to 24% in the street canyons. In open areas, an increase in the trees by the IQR actually decreased the normalized PM2.5 by 6% during the pre-COVID period. An increase in the height-normalized roughness length by the IQR increased the normalized PM2.5 by 9% in the street canyons. The results obtained in this study can help urban planners to identify the key urban characteristics affecting the near-surface PM2.5 air quality and also help researchers to evaluate how representative the existing measurement stations are compared to other parts of the cities.

Significance of the organic aerosol driven climate feedback in the boreal area.

Aerosol particles cool the climate by scattering solar radiation and by acting as cloud condensation nuclei. Higher temperatures resulting from increased greenhouse gas levels have been suggested to lead to increased biogenic secondary organic aerosol and cloud condensation nuclei concentrations creating a negative climate feedback mechanism. Here, we present direct observations on this feedback mechanism utilizing collocated long term aerosol chemical composition measurements and remote sensing observations on aerosol and cloud properties. Summer time organic aerosol loadings showed a clear increase with temperature, with simultaneous increase in cloud condensation nuclei concentration in a boreal forest environment. Remote sensing observations revealed a change in cloud properties with an increase in cloud reflectivity in concert with increasing organic aerosol loadings in the area. The results provide direct observational evidence on the significance of this negative climate feedback mechanism.

Toward Building a Physical Proxy for Gas-Phase Sulfuric Acid Concentration Based on Its Budget Analysis in Polluted Yangtze River Delta, East China.

Gaseous sulfuric acid (H2SO4) is a crucial precursor for secondary aerosol formation, particularly for new particle formation (NPF) that plays an essential role in the global number budget of aerosol particles and cloud condensation nuclei. Due to technology challenges, global-wide and long-term measurements of gaseous H2SO4 are currently very challenging. Empirical proxies for H2SO4 have been derived mainly based on short-term intensive campaigns. In this work, we performed comprehensive measurements of H2SO4 and related parameters in the polluted Yangtze River Delta in East China during four seasons and developed a physical proxy based on the budget analysis of gaseous H2SO4. Besides the photo-oxidation of SO2, we found that primary emissions can contribute considerably, particularly at night. Dry deposition has the potential to be a non-negligible sink, in addition to condensation onto particle surfaces. Compared with the empirical proxies, the newly developed physical proxy demonstrates extraordinary stability in all the seasons and has the potential to be widely used to improve the understanding of global NPF fundamentally.

Is reducing new particle formation a plausible solution to mitigate particulate air pollution in Beijing and other Chinese megacities?

Atmospheric gas-to-particle conversion is a crucial or even dominant contributor to haze formation in Chinese megacities in terms of aerosol number, surface area and mass. Based on our comprehensive observations in Beijing during 15 January 2018-31 March 2019, we are able to show that 80-90% of the aerosol mass (PM2.5) was formed via atmospheric reactions during the haze days and over 65% of the number concentration of haze particles resulted from new particle formation (NPF). Furthermore, the haze formation was faster when the subsequent growth of newly formed particles was enhanced. Our findings suggest that in practice almost all present-day haze episodes originate from NPF, mainly since the direct emission of primary particles in Beijing has considerably decreased during recent years. We also show that reducing the subsequent growth rate of freshly formed particles by a factor of 3-5 would delay the buildup of haze episodes by 1-3 days. Actually, this delay would decrease the length of each haze episode, so that the number of annual haze days could be approximately halved. Such improvement in air quality can be achieved with targeted reduction of gas-phase precursors for NPF, mainly dimethyl amine and ammonia, and further reductions of SO2 emissions. Furthermore, reduction of anthropogenic organic and inorganic precursor emissions would slow down the growth rate of newly-formed particles and consequently reduce the haze formation.

Seasonal Characteristics of New Particle Formation and Growth in Urban Beijing.

Understanding the atmospheric new particle formation (NPF) process within the global range is important for revealing the budget of atmospheric aerosols and their impacts. We investigated the seasonal characteristics of NPF in the urban environment of Beijing. Aerosol size distributions down to ∼1 nm and H2SO4 concentration were measured during 2018-2019. The observed formation rate of 1.5 nm particles (J1.5) is significantly higher than those in the clean environment, e.g., Hyytiälä, whereas the growth rate is not significantly different. Both J1.5 and NPF frequency in urban Beijing show a clear seasonal variation with maxima in winter and minima in summer, while the observed growth rates are generally within the same range around the year. We show that ambient temperature is a governing factor driving the seasonal variation of J1.5. In contrast, the condensation sink and the daily maximum H2SO4 concentration show no significant seasonal variation during the NPF periods. In all four seasons, condensation of H2SO4 and (H2SO4)n(amine)n clusters contributes significantly to the growth rates in the sub-3 nm size range, whereas it is less important for the observed growth rates of particles above 3 nm. Therefore, other species are always needed for the growth of larger particles.

Exploring the regional pollution characteristics and meteorological formation mechanism of PM2.5 in North China during 2013-2017.

In the last decade, North China (NC) has been one of the most populated and polluted regions in the world. The regional air pollution has had a serious impact on people's health; thus, all levels of government have implemented various pollution prevention measures since 2013. Based on multi-city in situ environmental and meteorological data, as well as the meteorological reanalysis dataset from 2013 to 2017, regional pollution characteristics and meteorological formation mechanisms were analyzed to provide a more comprehensive understanding of the evolution of PM2.5 in NC. The domain-averaged PM2.5 was 79 ±â€¯17 µg m-3 from 2013 to 2017, with a decreasing rate of 10 µg m-3 yr-1. Two automatic computer algorithms were established to identify 6 daily regional pollution types (DRPTs) and 48 persistent regional pollution events (PRPEs) over NC during 2014-2017. The average PM2.5 concentration for the Large-Region-Pollution type (including the Large-Moderate-Region-Pollution and Large-Severe-Region-Pollution types) was 113 ±â€¯40 µg m-3, and more than half of Large-Region-Pollution days and PRPEs occurred in winter. The PRPEs in NC mainly developed from the area south of Hebei. The number of Large-Region-Pollution days decreased notably from 2014 to 2017, the annual number of days varying between 194 and 97 days, whereas a slight decline was observed in winter. In addition, the averaged PM2.5 concentrations and the numbers and durations of the PRPEs decreased. Lamb-Jenkinson weather typing was used to reveal the impact of synoptic circulations on PM2.5 across NC. Generally, the contributions of the variations in circulation to the reduction in PM2.5 levels over NC between 2013 and 2017 were 64% and 45% in summer and winter, respectively. The three most highly polluted weather types were types C, S and E, with an average PM2.5 concentration of 137 ±â€¯40 µg m-3 in winter. Furthermore, three typical circulation dynamics were categorized in the peak stage of the PRPEs, namely, the southerly airflow pattern, the northerly airflow pattern and anticyclone pattern; the averaged relative humidity, recirculation index, wind speed and boundary layer height were 63%, 0.33, 2.0 m s-1 and 493 m, respectively. Our results imply that additional emission reduction measures should be implemented under unfavorable meteorological situations to attain ambient air quality standards in the future.

Atmospheric new particle formation from sulfuric acid and amines in a Chinese megacity.

Atmospheric new particle formation (NPF) is an important global phenomenon that is nevertheless sensitive to ambient conditions. According to both observation and theoretical arguments, NPF usually requires a relatively high sulfuric acid (H2SO4) concentration to promote the formation of new particles and a low preexisting aerosol loading to minimize the sink of new particles. We investigated NPF in Shanghai and were able to observe both precursor vapors (H2SO4) and initial clusters at a molecular level in a megacity. High NPF rates were observed to coincide with several familiar markers suggestive of H2SO4-dimethylamine (DMA)-water (H2O) nucleation, including sulfuric acid dimers and H2SO4-DMA clusters. In a cluster kinetics simulation, the observed concentration of sulfuric acid was high enough to explain the particle growth to ~3 nanometers under the very high condensation sink, whereas the subsequent higher growth rate beyond this size is believed to result from the added contribution of condensing organic species. These findings will help in understanding urban NPF and its air quality and climate effects, as well as in formulating policies to mitigate secondary particle formation in China.

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.

Rapid autoxidation forms highly oxidized RO2 radicals in the atmosphere.

Gas-phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α-pinene) form highly oxidized RO2 radicals with up to 12 O atoms, along with related closed-shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O2 addition generating a next R'OO radical, is similar to the well-known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well-known reaction principle of autoxidation is also applicable to the atmospheric gas-phase oxidation of hydrocarbons leading to extremely low-volatility products which contribute to organic aerosol mass and hence influence the aerosol-cloud-climate system.

Ultrafine particles in cities.

Ultrafine particles (UFPs; diameter less than 100 nm) are ubiquitous in urban air, and an acknowledged risk to human health. Globally, the major source for urban outdoor UFP concentrations is motor traffic. Ongoing trends towards urbanisation and expansion of road traffic are anticipated to further increase population exposure to UFPs. Numerous experimental studies have characterised UFPs in individual cities, but an integrated evaluation of emissions and population exposure is still lacking. Our analysis suggests that the average exposure to outdoor UFPs in Asian cities is about four-times larger than that in European cities but impacts on human health are largely unknown. This article reviews some fundamental drivers of UFP emissions and dispersion, and highlights unresolved challenges, as well as recommendations to ensure sustainable urban development whilst minimising any possible adverse health impacts.

Modeling regional deposited dose of submicron aerosol particles.

We developed a simple model to calculate the regional deposited dose of submicron aerosol particles in the respiratory system. This model incorporates measured outdoor and modeled indoor particle number size distributions, detailed activity patterns of three age groups (teens, adults, and the elderly), semi-empirical estimation of the regional deposition fraction, hygroscopic properties of urban aerosols, and reported breathing minute volumes. We calculated the total and regional deposited dose based on three concentration metrics: particle number (PN), mass (PM), and surface area (PSA). The 24-h total deposited dose of fine particles in adult males was around 40 µg (57×109 particles, 8×102 mm(2)) and 41 µg (40×109 particles, 8×102 mm(2)) on workdays and weekends, respectively. The total and regional 24-h deposited dose based on any of the metrics was at most 1.5 times higher in males than in females. The deposited dose values in the other age groups were slightly different than in adults. Regardless of the particle size fraction or the deposited dose metric, the pulmonary/alveolar region received the largest fraction of the deposited dose. These values represent the lowest estimate of the deposited dose and they are expected to be higher in real-life conditions after considering indoor sources of aerosol particles and spatial variability of outdoor aerosols. This model can be extended to youngsters (<12 years old) after gaining accurate information about the deposition fraction inside their respiratory system and their breathing pattern. This investigation is foreseen to bridge the gap between exposure and response in epidemiological studies.

Direct observations of atmospheric aerosol nucleation.

Atmospheric nucleation is the dominant source of aerosol particles in the global atmosphere and an important player in aerosol climatic effects. The key steps of this process occur in the sub-2-nanometer (nm) size range, in which direct size-segregated observations have not been possible until very recently. Here, we present detailed observations of atmospheric nanoparticles and clusters down to 1-nm mobility diameter. We identified three separate size regimes below 2-nm diameter that build up a physically, chemically, and dynamically consistent framework on atmospheric nucleation--more specifically, aerosol formation via neutral pathways. Our findings emphasize the important role of organic compounds in atmospheric aerosol formation, subsequent aerosol growth, radiative forcing and associated feedbacks between biogenic emissions, clouds, and climate.

Measurement of the nucleation of atmospheric aerosol particles.

The formation of new atmospheric aerosol particles and their subsequent growth have been observed frequently at various locations all over the world. The atmospheric nucleation rate (or formation rate) and growth rate (GR) are key parameters to characterize the phenomenon. Recent progress in measurement techniques enables us to measure atmospheric nucleation at the size (mobility diameter) of 1.5 (±0.4) nm. The detection limit has decreased from 3 to 1 nm within the past 10 years. In this protocol, we describe the procedures for identifying new-particle-formation (NPF) events, and for determining the nucleation, formation and growth rates during such events under atmospheric conditions. We describe the present instrumentation, best practices and other tools used to investigate atmospheric nucleation and NPF at a certain mobility diameter (1.5, 2.0 or 3.0 nm). The key instruments comprise devices capable of measuring the number concentration of the formed nanoparticles and their size, such as a suite of modern condensation particle counters (CPCs) and air ion spectrometers, and devices for characterizing the pre-existing particle number concentration distribution, such as a differential mobility particle sizer (DMPS). We also discuss the reliability of the methods used and requirements for proper measurements and data analysis. The time scale for realizing this procedure is 1 year.

Activity pattern of a selected group of school occupants and their family members in Helsinki-Finland.

The daily time-spent in different environments is an important factor in calculation of personal exposure to air pollutants. Despite this importance, the amount of research done on this topic is rather limited, especially in North Europe where the climate is rather cold. In this study, we gathered detailed information via a standard questionnaire to report the residence time and place of 167 subjects (between 2 and 93 years old) lived in Helsinki during three time periods in winter and spring 2009. Subjects spent 81%-92% of their time indoors and up to ~15% of their time outdoors. The daily time-spent in different environments was affected by several factors: ambient temperature, type of day (workday or weekend/holiday), gender, and age. Therefore, the differences occur individually and can be explained by these factors. For example, subjects spent more time at home on weekends than workdays because obviously the majority of our subjects did not have work on weekends. The time-spent at kindergarten/school/work increased with age until retirement. Females spent more time at home than males. After all, the activity pattern found in this study is rather similar to those previously reported in Germany and North America.

Experimental observation of strongly bound dimers of sulfuric acid: application to nucleation in the atmosphere.

Sulfuric acid is a key compound in atmospheric nucleation. Here we report on the observation of a close-to-collision-limited sulfuric acid dimer formation in atmospherically relevant laboratory conditions in the absence of measurable quantities of ammonia or organics. The observed dimer formation rate was clearly higher than the measured new particle formation rate at ∼1.5 nm suggesting that the rate limiting step for the nucleation takes place after the dimerization step. The quantum chemical calculations suggested that even in the ultraclean conditions there exist (a) stabilizing compound(s) with (a) concentration(s) high enough to prevent the dimer evaporation. Such a stabilizing compound should be abundant enough in any natural environment and would therefore not limit the formation of sulfuric acid dimers in the atmosphere.