The rapidly spread coronavirus disease (COVID-19) has limited people's outdoor activities and hence caused substantial reductions in anthropogenic emissions around the world. However, the air quality ...in some megacities has not been improved as expected due to the complex responses of aerosol chemistry to the changes in precursors and meteorology. Here we demonstrate the responses of primary and secondary aerosol species to the changes in anthropogenic emissions during the COVID-19 outbreak in Beijing, China along with the Chinese New Year (CNY) holiday effects on air pollution by using six-year aerosol particle composition measurements. Our results showed large reductions in primary aerosol species associated with traffic, cooking and coal combustion emissions by 30–50% on average during the CNY, while the decreases in secondary aerosol species were much small (5–12%). These results point towards a future challenge in mitigating secondary air pollution because the reduced gaseous precursors may not suppress secondary aerosol formation efficiently under stagnant meteorological conditions. By analyzing the long-term measurements from 2012 to 2020, we found considerable increases in the ratios of nitrate to sulfate, secondary to primary OA, and sulfur and nitrogen oxidation capacity despite the overall decreasing trends in mass concentrations of most aerosol species, suggesting that the decreases in anthropogenic emissions have facilitated secondary formation processes during the last decade. Therefore, a better understanding of the mechanisms driving the chemical responses of secondary aerosol to the changes in anthropogenic emissions under complex meteorological environment is essential for future mitigation of air pollution in China.
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•Different responses of primary and secondary species to the COVID-19 outbreak•30–50% decreases in primary aerosol species during the Chinese New Year holiday•Much smaller changes in secondary species compared with primary aerosol species•Large increases in sulfur and nitrogen oxidation capacity during the last decade
Highly oxygenated organic molecules (HOM) are formed in the atmosphere via autoxidation involving peroxy radicals arising from volatile organic compounds (VOC). HOM condense on pre-existing particles ...and can be involved in new particle formation. HOM thus contribute to the formation of secondary organic aerosol (SOA), a significant and ubiquitous component of atmospheric aerosol known to affect the Earth’s radiation balance. HOM were discovered only very recently, but the interest in these compounds has grown rapidly. In this Review, we define HOM and describe the currently available techniques for their identification/quantification, followed by a summary of the current knowledge on their formation mechanisms and physicochemical properties. A main aim is to provide a common frame for the currently quite fragmented literature on HOM studies. Finally, we highlight the existing gaps in our understanding and suggest directions for future HOM research.
Secondary organic aerosol (SOA) constitutes a large fraction of OA, yet remains a source of significant uncertainties in climate models due to incomplete understanding of its formation mechanisms and ...evolutionary processes. Here we evaluated the effects of photochemical and aqueous-phase processing on SOA composition and oxidation degrees in three seasons in Beijing, China, using high-resolution aerosol mass spectrometer measurements along with positive matrix factorization. Our results show that aqueous-phase processing has a dominant impact on the formation of more oxidized SOA (MO–OOA), and the contribution of MO–OOA to OA increases substantially as a function of relative humidity or liquid water content. In contrast, photochemical processing plays a major role in the formation of less oxidized SOA (LO–OOA), as indicated by the strong correlations between LO–OOA and odd oxygen (O x = O3 + NO2) during periods of photochemical production (R2 = 0.59–0.80). Higher oxygen-to-carbon ratios of SOA during periods with higher RH were also found indicating a major role of aqueous-phase processing in changing the oxidation degree of SOA in Beijing. Episodes analyses further highlight that LO–OOA plays a more important role during the early stage of the formation of autumn/winter haze episodes while MO–OOA is more significant during the later evolution period.
A high-resolution time-of-flight chemical-ionization mass spectrometer (HR-ToF-CIMS) using Iodide-adducts has been characterized and deployed in several laboratory and field studies to measure a ...suite of organic and inorganic atmospheric species. The large negative mass defect of Iodide, combined with soft ionization and the high mass-accuracy (<20 ppm) and mass-resolving power (R > 5500) of the time-of-flight mass spectrometer, provides an additional degree of separation and allows for the determination of elemental compositions for the vast majority of detected ions. Laboratory characterization reveals Iodide-adduct ionization generally exhibits increasing sensitivity toward more polar or acidic volatile organic compounds. Simultaneous retrieval of a wide range of mass-to-charge ratios (m/Q from 25 to 625 Th) at a high frequency (>1 Hz) provides a comprehensive view of atmospheric oxidative chemistry, particularly when sampling rapidly evolving plumes from fast moving platforms like an aircraft. We present the sampling protocol, detection limits and observations from the first aircraft deployment for an instrument of this type, which took place aboard the NOAA WP-3D aircraft during the Southeast Nexus (SENEX) 2013 field campaign.
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 (H
SO
) 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 (H
SO
) and initial clusters at a molecular level in a megacity. High NPF rates were observed to coincide with several familiar markers suggestive of H
SO
-dimethylamine (DMA)-water (H
O) nucleation, including sulfuric acid dimers and H
SO
-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.
Aerosol composition and sources have been extensively studied in
developed regions in China. However, aerosol chemistry in coastal regions of
eastern China with high industrial emissions remains ...poorly characterized.
Here we present a comprehensive characterization of aerosol composition and
sources near two large steel plants in a coastal city in Shandong in fall
and spring using a PM2.5 time-of-flight aerosol chemical speciation
monitor. The average (±1σ) mass concentration of PM2.5
in spring 2019 (54±44 µg m−3) was approximately twice that
(26±23 µg m−3) in fall 2018. Aerosol composition was
substantially different between the two seasons. While organics accounted
for ∼30 % of the total PM2.5 mass in both seasons,
sulfate showed a considerable decrease from 28 % in September to 16 % in
March, which was associated with a large increase in nitrate contribution
from 17 % to 32 %. Positive matrix factorization analysis showed that
secondary organic aerosol (SOA) dominated the total OA in both seasons, accounting on average for 92 % and 86 %, respectively, while the
contribution of traffic-related hydrocarbon-like OA was comparable
(8 %–9 %). During this study, we observed significant impacts of steel plant
emissions on aerosol chemistry nearby. The results showed that aerosol
particles emitted from the steel plants were overwhelmingly dominated by
ammonium sulfate and/or ammonium bisulfate with the peak concentration reaching as
high as 224 µg m−3. Further analysis showed similar mass ratios for
NOx∕CO (0.014) and NOx∕SO2 (1.24) from the two different
steel plants, which were largely different from those during periods in the
absence of industrial plumes. Bivariate polar plot analysis also supported
the dominant source region of ammonium sulfate, CO, and SO2 from the
southwest steel plants. Our results might have significant implications for
better quantification of industrial emissions using ammonium sulfate and the
ratios of gaseous species as tracers in industrial regions and nearby in the
future.
Anthropogenic emissions in Asia have significantly increased during the last two decades; as a result, the induced air pollution and its influences on radiative forcing and public health are becoming ...increasingly prominent. The Aerodyne Aerosol Mass Spectrometer (AMS) has been widely deployed in Asia for real-time characterization of aerosol chemistry. In this paper, we review the AMS measurements in Asia, mainly in China, Korea, Japan, and India since 2001 and summarize the key results and findings. The mass concentrations of non-refractory submicron aerosol species (NR-PM
1
) showed large spatial distributions with high mass loadings occurring in India and north and northwest China (60.2-81.3 μg m
−3
), whereas much lower values were observed in Korea, Japan, Singapore and regional background sites (7.5-15.1 μg m
−3
). Aerosol composition varied largely in different regions, but was overall dominated by organic aerosols (OA, 32-75%), especially in south and southeast Asia due to the impact of biomass burning. While sulfate and nitrate showed comparable contributions in urban and suburban regions in north China, sulfate dominated inorganic aerosols in south China, Japan and regional background sites. Positive matrix factorization analysis identified multiple OA factors from different sources and processes in different atmospheric environments,
e.g.
, biomass burning OA in south and southeast Asia and agricultural seasons in China, cooking OA in urban areas, and coal combustion in north China. However, secondary OA (SOA) was a ubiquitous and dominant aerosol component in all regions, accounting for 43-78% of OA. The formation of different SOA subtypes associated with photochemical production or aqueous-phase/fog processing was widely investigated. The roles of primary emissions, secondary production, regional transport, and meteorology on severe haze episodes, and different chemical responses of primary and secondary aerosol species to source emission changes and meteorology were also demonstrated. Finally, future prospects of AMS studies on long-term and aircraft measurements, water-soluble OA, the link of OA volatility, oxidation levels, and phase state were discussed.
Aerosol mass spectrometer has been widely deployed in Asia for real-time characterization of aerosol chemistry, and has significantly improved our understanding of the sources, properties, and formation processes of aerosols in a complex environment.
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 O ₃ 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.
Significance Extremely low volatility organic compounds (ELVOC) are suggested to promote aerosol particle formation and cloud condensation nuclei (CCN) production in the atmosphere. We show that the capability of biogenic VOC (BVOC) to produce ELVOC depends strongly on their chemical structure and relative oxidant levels. BVOC with an endocyclic double bond, representative emissions from, e.g., boreal forests, efficiently produce ELVOC from ozonolysis. Compounds with exocyclic double bonds or acyclic compounds including isoprene, emission representative of the tropics, produce minor quantities of ELVOC, and the role of OH radical oxidation is relatively larger. Implementing these findings into a global modeling framework shows that detailed assessment of ELVOC production pathways is crucial for understanding biogenic secondary organic aerosol and atmospheric CCN formation.
Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol ...due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron‐sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid‐catalyzed multiphase chemistry of isoprene epoxydiols, particle‐phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process‐related interactions, so that these processes can be accurately represented in atmospheric chemistry‐climate models.
Plain Language Summary
Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, often represents a major fraction of global submicron‐sized atmospheric organic aerosol. Myriad processes affect SOA formation, several of which relate to interactions between natural biogenic emissions and predominantly anthropogenic species such as SO2, NOx, sulfate, nitrate, and ammonium. Many of these key processes are nonlinear and can be synergistic or act to compensate each other in terms of climate forcing. Current atmospheric chemistry‐climate models mostly do not treat these processes. We highlight a number of process‐level mechanisms related to the interactions between anthropogenic and biogenic SOA precursors, for which the corresponding impacts on the radiative effects of SOA need to be investigated in atmospheric chemistry‐climate models. Ultimately, climate models need to capture enough important features of the chemical and dynamic evolution of SOA, in terms of both aerosol number and aerosol mass, as a function of atmospheric variables and anthropogenic perturbations to reasonably predict the spatial and temporal distributions of SOA. A better understanding of SOA formation mechanisms and physical properties is needed to improve estimates of the extent to which anthropogenic emissions and land use changes have modified global aerosol concentrations and size distributions since preindustrial times.
Key Points
We review some important developments in secondary organic aerosol (SOA) that could impact aerosol radiative forcing and response of climate to greenhouse gases
We highlight some of the important processes that involve interactions between natural biogenic emissions and anthropogenic emissions
We discuss fundamental SOA properties volatility and viscosity and their relation to evolution of aerosol mass and number concentrations in the atmosphere
Organic species are an important but poorly characterized constituent of airborne particulate matter. A quantitative understanding of the organic fraction of particles (organic aerosol, OA) is ...necessary to reduce some of the largest uncertainties that confound the assessment of the radiative forcing of climate and air quality management policies. In recent years, aerosol mass spectrometry has been increasingly relied upon for highly time-resolved characterization of OA chemistry and for elucidation of aerosol sources and lifecycle processes. Aerodyne aerosol mass spectrometers (AMS) are particularly widely used, because of their ability to quantitatively characterize the size-resolved composition of submicron particles (PM
1
). AMS report the bulk composition and temporal variations of OA in the form of ensemble mass spectra (MS) acquired over short time intervals. Because each MS represents the linear superposition of the spectra of individual components weighed by their concentrations, multivariate factor analysis of the MS matrix has proved effective at retrieving OA factors that offer a quantitative and simplified description of the thousands of individual organic species. The sum of the factors accounts for nearly 100% of the OA mass and each individual factor typically corresponds to a large group of OA constituents with similar chemical composition and temporal behavior that are characteristic of different sources and/or atmospheric processes. The application of this technique in aerosol mass spectrometry has grown rapidly in the last six years. Here we review multivariate factor analysis techniques applied to AMS and other aerosol mass spectrometers, and summarize key findings from field observations. Results that provide valuable information about aerosol sources and, in particular, secondary OA evolution on regional and global scales are highlighted. Advanced methods, for example a-priori constraints on factor mass spectra and the application of factor analysis to combined aerosol and gas phase data are discussed. Integrated analysis of worldwide OA factors is used to present a holistic regional and global description of OA. Finally, different ways in which OA factors can constrain global and regional models are discussed.
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