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Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.

Δ3 -carene is a prominent monoterpene in the atmosphere, contributing significantly to secondary organic aerosol (SOA) formation. However, knowledge about Δ3 -carene oxidation pathways, particularly regarding their ability to form highly oxygenated organic molecules (HOMs), is still limited. In this study, we present HOM measurements during Δ3 -carene ozonolysis under various conditions in two simulation chambers. We identified numerous HOMs (monomers: C 7-10 H 10-18 O 6-14 ; dimers: C 17-20 H 24-34 O 6-18) using a chemical ionization mass spectrometer (CIMS). Δ3 -carene ozonolysis yielded higher HOM concentrations than α -pinene, with a distinct distribution, indicating differences in formation pathways. All HOM signals decreased considerably at lower temperatures, reducing the estimated molar HOM yield from ∼ 3 % at 20 °C to ∼ 0.5 % at 0 °C. Interestingly, the temperature change altered the HOM distribution, increasing the observed dimer-to-monomer ratios from roughly 0.8 at 20 °C to 1.5 at 0 °C. HOM monomers with six or seven O atoms condensed more efficiently onto particles at colder temperatures, while monomers with nine or more O atoms and all dimers condensed irreversibly even at 20 °C. Using the gas- and particle-phase chemistry kinetic multilayer model ADCHAM, we were also able to reproduce the experimentally observed HOM composition, yields, and temperature dependence. [ABSTRACT FROM AUTHOR]

Micro- and nanoplastic particles have been detected in most environmental compartments. The presence of microplastics in the remote marine atmosphere and close to large lakes suggests bubble mediated water–air transfer as a source of airborne microplastics, however, quantitative estimates of plastic emission from surface waters remain uncertain. In this work, we elucidate the emission of submicron polystyrene nanospheres by bubble bursting in a laboratory setting from low salinity waters (salinity 0–1.0 g kg−1), polystyrene particle diameter (103, 147 and 269 nm), aqueous particle number concentrations in the range 4 × 107–2 × 109 cm−3, and bubble formation rate (0.88–3.35 L min−1 of air). Production of polystyrene aerosols was demonstrated using a scanning mobility particle sizer and confirmed by analysis of filter samples using pyrolysis gas chromatography coupled to mass spectrometry. We show that production of polystyrene aerosol particles scales linearly with the number concentration of plastic particles in the water. Our results suggest that small amounts (0.01 g kg−1) of salt increase polystyrene particle production. To the best of our knowledge this is the first study of bubble mediated water–air transfer of plastic particles as small as 100 nm. [ABSTRACT FROM AUTHOR]

Biogenic volatile organic compounds (BVOCs) from the Amazon forest region represent the largest source of organic carbon emissions to the atmosphere globally. These BVOC emissions dominantly consist of volatile and intermediate-volatility terpenoid compounds that undergo chemical transformations in the atmosphere to form oxygenated condensable gases and secondary organic aerosol (SOA). We collected quartz filter samples with 12 h time resolution and performed hourly in situ measurements with a semi-volatile thermal desorption aerosol gas chromatograph (SV-TAG) at a rural site ("T3") located to the west of the urban center of Manaus, Brazil as part of the Green Ocean Amazon (GoAmazon2014/5) field campaign to measure intermediate-volatility and semi-volatile BVOCs and their oxidation products during the wet and dry seasons. We speciated and quantified 30 sesquiterpenes and 4 diterpenes with mean concentrations in the range 0.01-6.04 ngm-3 (1-670ppqv). We estimate that sesquiterpenes contribute approximately 14 and 12% to the total reactive loss of O3 via reaction with isoprene or terpenes during the wet and dry seasons, respectively. This is reduced from ~ 50-70 % for within-canopy reactive O3 loss attributed to the ozonolysis of highly reactive sesquiterpenes (e.g., β-caryophyllene) that are reacted away before reaching our measurement site. We further identify a suite of their oxidation products in the gas and particle phases and explore their role in biogenic SOA formation in the central Amazon region. Synthesized authentic standards were also used to quantify gas- and particle-phase oxidation products derived from β-caryophyllene. Using tracer-based scaling methods for these products, we roughly estimate that sesquiterpene oxidation contributes at least 0.4-5 % (median 1 %) of total submicron OA mass. However, this is likely a low-end estimate, as evidence for additional unaccounted sesquiterpenes and their oxidation products clearly exists. By comparing our field data to laboratory-based sesquiterpene oxidation experiments we confirm that more than 40 additional observed compounds produced through sesquiterpene oxidation are present in Amazonian SOA, warranting further efforts towards more complete quantification.

Δ3-carene is a prominent monoterpene in the atmosphere, contributing significantly to secondary organic aerosol (SOA) formation. However, knowledge about Δ3-carene oxidation pathways, particularly regarding its ability to form highly oxygenated organic molecules (HOM), is still limited. In this study, we present HOM measurements during Δ3-carene ozonolysis under various conditions in two simulation chambers. We identified numerous HOM (monomers: C7-10H10-18O6-14, dimers: C17-20H24-34O6-18) using a chemical ionization mass spectrometer (CIMS). Δ3-carene ozonolysis yielded higher HOM concentrations than a-pinene, with a distinct distribution, indicating differences in formation pathways. All HOM signals decreased considerably at lower temperatures, reducing the estimated molar HOM yield from ~3 % at 20 °C to ~0.5 % at 0 °C. Interestingly, temperature change altered the HOM distribution, increasing the observed dimer-to-monomer ratios from roughly 0.8 at 20 °C to 1.5 at 0 °C. HOM monomers with 6 or 7 O-atoms condensed more efficiently onto particles at colder temperatures, while monomers with nine or more O-atoms and all dimers condensed irreversibly even at 20 °C. Using the gas and particle-phase chemistry kinetic multilayer model ADCHAM, we were also able to reproduce the experimentally observed HOM composition, yields and temperature dependence. [ABSTRACT FROM AUTHOR]

Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.

Aromatic organosulfates are identified and quantified in fine particulate matter (PM2.5) from Lahore, Pakistan, Godavari, Nepal, and Pasadena, California. To support detection and quantification, authentic standards of phenyl sulfate, benzyl sulfate, 3-and 4-methylphenyl sulfate and 2-, 3-, and 4-methylbenzyl sulfate were synthesized. Authentic standards and aerosol samples were analyzed by ultra-performance liquid chromatography (UPLC) coupled to negative electrospray ionization (ESI) quadrupole time-of-flight (ToF) mass spectrometry. Benzyl sulfate was present in all three locations at concentrations ranging from 4 - 90 pg m-3. Phenyl sulfate, methylphenyl sulfates and methylbenzyl sulfates were observed intermittently with abundances of 4 pg m-3, 2-31 pg m-3, 109 pg m-3, respectively. Characteristic fragment ions of aromatic organosulfates include the sulfite radical (•SO3-, m/z 80) and the sulfate radical (•SO4-,m/z 96). Instrumental response factors of phenyl and benzyl sulfates varied by a factor of 4.3, indicating that structurally-similar organosulfates may have significantly different instrumental responses and highlighting the need to develop authentic standards for absolute quantitation organosulfates. In an effort to better understand the sources of aromatic organosulfates to the atmosphere, chamber experiments with the precursor toluene were conducted under conditions that form biogenic organosulfates. Aromatic organosulfates were not detected in the chamber samples, suggesting that they form through different pathways, have different precursors (e.g. naphthalene or methylnaphthalene), or are emitted from primary sources.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

The role of airborne nanoparticles in atmospheric chemistry and public health is largely controlled by particle size, morphology, surface composition, and coating. Aerosol mass spectrometry provides real-time chemical characterization of submicron atmospheric particles, but analysis of nanoplastics in complex aerosol mixtures such as sea spray is severely limited by challenges associated with separation and ionization of the aerosol matrix. Here we characterize the internal and external mixing state of synthetic sea spray aerosols spiked with 150 nm nanoplastics. Aerosols generated from pneumatic atomization and from a sea spray tank are compared. A humidified tandem differential mobility analyzer is used as a size and hygroscopicity filter, resulting in separation of nanoplastics from sea spray, and an inline high-resolution time-of-flight aerosol mass spectrometer is used to characterize particle composition and ionization efficiency. The separation technique amplified the detection limit of the airborne nanoplastics. A salt coating was found on the nanoplastics with coating thickness increasing exponentially with increasing bulk solution salinity, which was varied from 0 to 40 g kg−1. Relative ionization efficiencies of polystyrene and sea salt chloride were 0.19 and 0.36, respectively. The growth-factor derived hygroscopicity of sea salt was 1.4 at 75% relative humidity. These results underscore the importance of separating airborne nanoplastics from sea salt aerosol for detailed online characterization by aerosol mass spectrometry and characterization of salt coatings as a function of water composition. The surface coating of nanoplastic aerosols by salts can profoundly impact their surface chemistry, water uptake, and humidified particle size distributions in the atmosphere. [ABSTRACT FROM AUTHOR]