This review focuses on the observed characteristics of atmospheric new particle formation (NPF) in different environments of the global troposphere. After a short introduction, we will present a ...theoretical background that discusses the methods used to analyze measurement data on atmospheric NPF and the associated terminology. We will update on our current understanding of regional NPF, i.e. NPF taking simultaneously place over large spatial scales, and complement that with a full review on reported NPF and growth rates during regional NPF events. We will shortly review atmospheric NPF taking place at sub-regional scales. Since the growth of newly-formed particles into larger sizes is of great current interest, we will briefly discuss our observation-based understanding on which gaseous compounds contribute to the growth of newly-formed particles, and what implications this will have on atmospheric cloud condensation nuclei formation. We will finish the review with a summary of our main findings and future outlook that outlines the remaining research questions and needs for additional measurements.
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.
China is one of the regions with highest PM2.5 concentration in the world. In this study, we review the spatio-temporal distribution of PM2.5 mass concentration and components in China and the effect ...of control measures on PM2.5 concentrations. Annual averaged PM2.5 concentrations in Central-Eastern China reached over 100μgm−3, in some regions even over 150μgm−3. In 2013, only 4.1% of the cities attained the annual average standard of 35μgm−3. Aitken mode particles tend to dominate the total particle number concentration. Depending on the location and time of the year, new particle formation (NPF) has been observed to take place between about 10 and 60% of the days. In most locations, NPF was less frequent at high PM mass loadings. The secondary inorganic particles (i.e., sulfate, nitrate and ammonium) ranked the highest fraction among the PM2.5 species, followed by organic matters (OM), crustal species and element carbon (EC), which accounted for 6–50%, 15–51%, 5–41% and 2–12% of PM2.5, respectively. In response to serious particulate matter pollution, China has taken aggressive steps to improve air quality in the last decade. As a result, the national emissions of primary PM2.5, sulfur dioxide (SO2), and nitrogen oxides (NOX) have been decreasing since 2005, 2006, and 2011, respectively. The emission control policies implemented in the last decade could result in noticeable reduction in PM2.5 concentrations, contributing to the decreasing PM2.5 trends observed in Beijing, Shanghai, and Guangzhou. However, the control policies issued before 2010 are insufficient to improve PM2.5 air quality notably in future. An optimal mix of energy-saving and end-of-pipe control measures should be implemented, more ambitious control policies for NMVOC and NH3 should be enforced, and special control measures in winter should be applied. 40–70% emissions should be cut off to attain PM2.5 standard.
Display omitted
•In 2013, only 4.1% of the Chinese cities attained the annual average PM2.5 standard.•Secondary inorganic aerosol ranked the highest fraction among PM2.5 species.•National emissions of primary PM2.5 and SO2 have been decreasing since 2005/2006, so as NOX since 2011.•Emission controls make important contributions to decreasing trends in PM2.5 concentrations in megacities.•40–70% emission reduction in the future is needed to attain the PM2.5 standard.
This study investigates the contribution of high-molecular weight dimer esters to laboratory-generated α-pinene gas- and particle-phase secondary organic aerosol (SOA) and particulate matter (PM) ...collected at the Nordic boreal forest site of Hyytiälä, Finland. Laboratory flow reactor experiments (25 °C) show that dimer esters from ozonolysis of α-pinene contribute between 5 and 16% of the freshly formed α-pinene particle-phase SOA mass. An increased level of formation is observed at a higher relative humidity of ∼40%, and the presence of a hydroxyl radical (OH) scavenger is shown to affect the formation of dimer esters. Of the 28 dimer esters identified in laboratory α-pinene SOA, 15 are also observed in ambient PM samples, contributing between 0.5 and 1.6% of the total PM1. The observed esters show good correlation with known α-pinene SOA tracers in collected PM samples. This work reveals an, until now, unrecognized contribution of dimer esters from α-pinene oxidation to boreal forest PM.
The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C6H10) was investigated by means of laboratory experiments together with quantum chemical calculations. The ...experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3 –)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO2) isomerization through intramolecular hydrogen shift reactions, followed by sequential O2 addition steps, that is, RO2 autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 ± 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H2O or D2O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.
Atmospheric new particle formation in China Chu, Biwu; Kerminen, Veli-Matti; Bianchi, Federico ...
Atmospheric chemistry and physics,
01/2019, Letnik:
19, Številka:
1
Journal Article
Recenzirano
Odprti dostop
New particle formation (NPF) studies in China were summarized comprehensively in this paper. NPF frequency, formation rate, and particle growth rate were closely compared among the observations ...carried out at different types of sites in different regions of China in different seasons, with the aim of exploring the nucleation and particle growth mechanisms. The interactions between air pollution and NPF are discussed, emphasizing the properties of NPF under heavy pollution conditions. The current understanding of NPF cannot fully explain the frequent occurrence of NPF at high aerosol loadings in China, and possible reasons for this phenomenon are proposed. The effects of NPF and some aspects of NPF research requiring further investigation are also summarized in this paper.
The concentrations of terpenoids (isoprene; monoterpenes, MTs; and sesquiterpenes, SQTs) and oxygenated volatile organic compounds (OVOCs; i.e. aldehydes, alcohols, acetates and volatile organic ...acids, VOAs) were investigated during 2 years at a boreal forest site in Hyytiälä, Finland, using in situ gas chromatograph mass spectrometers (GC-MSs). Seasonal and diurnal variations of terpenoid and OVOC concentrations as well as their relationship with meteorological factors were studied.
Atmospheric new particle formation (NPF), which is observed in many environments globally, is an important source of boundary-layer aerosol particles and cloud condensation nuclei, which affect both ...the climate and human health. To better understand the mechanisms behind NPF, chamber experiments can be used to simulate this phenomenon under well-controlled conditions. Recent advancements in instrumentation have made it possible to directly detect the first steps of NPF of molecular clusters (~1-2 nm in diameter) and to calculate quantities such as the formation and growth rates of these clusters. Whereas previous studies reported particle formation rates as the flux of particles across a specified particle diameter or calculated them from measurements of larger particle sizes, this protocol outlines methods to directly quantify particle dynamics for cluster sizes. Here, we describe the instrumentation and analysis methods needed to quantify particle dynamics during NPF of sub-3-nm aerosol particles in chamber experiments. The methods described in this protocol can be used to make results from different chamber experiments comparable. The experimental setup, collection and post-processing of the data, and thus completion of this protocol, take from months up to years, depending on the chamber facility, experimental plan and level of expertise. Use of this protocol requires engineering capabilities and expertise in data analysis.
Atmospheric new particle formation significantly affects global climate and air quality after newly formed particles grow above ∼50 nm. In polluted urban atmospheres with 1–3 orders of magnitude ...higher new particle formation rates than those in clean atmospheres, particle growth rates are comparable or even lower for reasons that were previously unclear. Here, we address the slow growth in urban Beijing with advanced measurements of the size-resolved molecular composition of nanoparticles using the thermal desorption chemical ionization mass spectrometer and the gas precursors using the nitrate CI-APi-ToF. A particle growth model combining condensational growth and particle-phase acid–base chemistry was developed to explore the growth mechanisms. The composition of 8–40 nm particles during new particle formation events in urban Beijing is dominated by organics (∼80%) and sulfate (∼13%), and the remainder is from base compounds, nitrate, and chloride. With the increase in particle sizes, the fraction of sulfate decreases, while that of the slow-desorbed organics, organic acids, and nitrate increases. The simulated size-resolved composition and growth rates are consistent with the measured results in most cases, and they both indicate that the condensational growth of organic vapors and H2SO4 is the major growth pathway and the particle-phase acid–base reactions play a minor role. In comparison to the high concentrations of gaseous sulfuric acid and amines that cause high formation rates, the concentration of condensable organic vapors is comparably lower under the high NO x levels, while those of the relatively high-volatility nitrogen-containing oxidation products are higher. The insufficient condensable organic vapors lead to slow growth, which further causes low survival of the newly formed particles in urban environments. Thus, the low growth rates, to some extent, counteract the impact of the high formation rates on air quality and global climate in urban environments.
Marine dimethyl sulfide (DMS) emissions are the dominant source of natural sulfur in the atmosphere. DMS oxidizes to produce low-volatility acids that potentially nucleate to form particles that may ...grow into climatically important cloud condensation nuclei (CCN). In this work, we utilize the chemistry transport model ADCHEM to demonstrate that DMS emissions are likely to contribute to the majority of CCN during the biological active period (May-August) at three different forest stations in the Nordic countries. DMS increases CCN concentrations by forming nucleation and Aitken mode particles over the ocean and land, which eventually grow into the accumulation mode by condensation of low-volatility organic compounds from continental vegetation. Our findings provide a new understanding of the exchange of marine precursors between the ocean and land, highlighting their influence as one of the dominant sources of CCN particles over the boreal forest.
PDF
