Much of our understanding of atmospheric secondary organic aerosol (SOA) formation from volatile organic compounds derives from laboratory chamber measurements, including mass yield and elemental ...composition. These measurements alone are insufficient to identify the chemical mechanisms of SOA production. We present here a comprehensive dataset on the molecular identity, abundance, and kinetics of α-pinene SOA, a canonical system that has received much attention owing to its importance as an organic aerosol source in the pristine atmosphere. Identified organic species account for ∼58–72% of the α-pinene SOA mass, and are characterized as semivolatile/low-volatility monomers and extremely low volatility dimers, which exhibit comparable oxidation states yet different functionalities. Features of the α-pinene SOA formation process are revealed for the first time, to our knowledge, from the dynamics of individual particle-phase components. Although monomeric products dominate the overall aerosol mass, rapid production of dimers plays a key role in initiating particle growth. Continuous production of monomers is observed after the parent α-pinene is consumed, which cannot be explained solely by gas-phase photochemical production. Additionally, distinct responses of monomers and dimers to α-pinene oxidation by ozone vs. hydroxyl radicals, temperature, and relative humidity are observed. Gas-phase radical combination reactions together with condensed phase rearrangement of labile molecules potentially explain the newly characterized SOA features, thereby opening up further avenues for understanding formation and evolution mechanisms of α-pinene SOA.
Coronavirus disease 2019 (COVID-19) patients exhaled millions of severe acute respiratory syndrome coronavirus 2 RNA copies per hour, which plays an important role in COVID-19 transmission. Exhaled ...breath had a higher positive rate (26.9%, n = 52) than surface (5.4%, n = 242) and air (3.8%, n = 26) samples.
Recent work has shown that the atmospheric oxidation of isoprene (2-methyl-1,3-butadiene, C5H8) leads to the formation of secondary organic aerosol (SOA). In this study, the mechanism of SOA ...formation by isoprene photooxidation is comprehensively investigated, by measurements of SOA yields over a range of experimental conditions, namely isoprene and NO x concentrations. Hydrogen peroxide is used as the radical precursor, substantially constraining the observed gas-phase chemistry; all oxidation is dominated by the OH radical, and organic peroxy radicals (RO2) react only with HO2 (formed in the OH + H2O2 reaction) or NO concentrations, including NO x -free conditions. At high NO x , yields are found to decrease substantially with increasing NO x , indicating the importance of RO2 chemistry in SOA formation. Under low-NO x conditions, SOA mass is observed to decay rapidly, a result of chemical reactions of semivolatile SOA components, most likely organic hydroperoxides.
Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two ...key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NOx conditions, respectively. Isoprene low-NOx SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NOx conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NOx SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO₂ and NO₂, respectively) could be a substantial source of "missing urban SOA" not included in current atmospheric models.
We demonstrate a highly sensitive nanoparticle and virus detection method by using a thermal-stabilized reference interferometer in conjunction with an ultrahigh-Q microcavity. Sensitivity is ...sufficient to resolve shifts caused by binding of individual nanobeads in solution down to a record radius of 12.5 nm, a size approaching that of single protein molecules. A histogram of wavelength shift versus nanoparticle radius shows that particle size can be inferred from shift maxima. Additionally, the signal-to-noise ratio for detection of Influenza A virus is enhanced to 38:1 from the previously reported 3:1. The method does not use feedback stabilization of the probe laser. It is also observed that the conjunction of particle-induced backscatter and optical-path-induced shifts can be used to enhance detection signal-to-noise.
The transfer functions and penetrations of five differential mobility analyzers (DMAs) for sub-2 nm particle classification were evaluated in this study. These DMAs include the TSI nanoDMA, the ...Caltech radial DMA (RDMA) and nanoRDMA, the Grimm nanoDMA, and the Karlsruhe-Vienna DMA. Measurements were done using tetra-alkyl ammonium ion standards with mobility diameters of 1.16, 1.47, and 1.70 nm. These monomobile ions were generated by electrospray followed by high resolution mobility classification. Measurements were focused at an aerosol-to-sheath flow ratio of 0.1. A data inversion routine was developed to obtain the true transfer function for each test DMA, and these measured transfer functions were compared with theory. DMA penetration efficiencies were also measured. An approximate model for diffusional deposition, based on the modified Gormley and Kennedy equation using an effective length, is given for each test DMA. These results quantitatively characterize the performance of the test DMAs in classifying sub-2 nm particles and can be readily used for DMA data inversion.
A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog
, but how it occurs in cities is often puzzling
. If the growth ...rates of urban particles are similar to those found in cleaner environments (1-10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below -15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid-base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms
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About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday. Atmospheric observations show that the growth ...rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer. Although recent studies predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory), has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10(-4.5) micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10(-4.5) to 10(-0.5) micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.
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