Naphthalene Secondary Organic Aerosol Research Articles

Iron and Copper Alter the Oxidative Potential of Secondary Organic Aerosol: Insights from Online Measurements and Model Development.

The oxidative potential (OP) of particulate matter has been widely suggested as a key metric for describing atmospheric particle toxicity. Secondary organic aerosol (SOA) and redox-active transition metals, such as iron and copper, are key drivers of particle OP. However, their relative contributions to OP, as well as the influence of metal-organic interactions and particulate chemistry on OP, remains uncertain. In this work, we simultaneously deploy two novel online instruments for the first time, providing robust quantification of particle OP. We utilize online AA (OPAA) and 2,7-dichlorofluoroscein (ROSDCFH) methods to investigate the influence of Fe(II) and Cu(II) on the OP of secondary organic aerosol (SOA). In addition, we quantify the OH production (OPOH) from these particle mixtures. We observe a range of synergistic and antagonistic interactions when Fe(II) and Cu(II) are mixed with representative biogenic (β-pinene) and anthropogenic (naphthalene) SOA. A newly developed kinetic model revealed key reactions among SOA components, transition metals, and ascorbate, influencing OPAA. Model predictions agree well with OPAA measurements, highlighting metal-ascorbate and -naphthoquinone-ascorbate reactions as important drivers of OPAA. The simultaneous application of multiple OP assays and a kinetic model provides new insights into the influence of metal and SOA interactions on particle OP.

Effects of Nitrogen Oxides on the Production of Reactive Oxygen Species and Environmentally Persistent Free Radicals from α-Pinene and Naphthalene Secondary Organic Aerosols.

Reactive oxygen species (ROS) and environmentally persistent free radicals (EPFR) play an important role in chemical transformation of atmospheric aerosols and adverse aerosol health effects. This study investigated the effects of nitrogen oxides (NOx) during photooxidation of α-pinene and naphthalene on the EPFR content and ROS formation from secondary organic aerosols (SOA). Electron paramagnetic resonance (EPR) spectroscopy was applied to quantify EPFR content and ROS formation. While no EPFR were detected in α-pinene SOA, we found that naphthalene SOA contained about 0.7 pmol μg–1 of EPFR, and NOx has little influence on EPFR concentrations and oxidative potential. α-Pinene and naphthalene SOA generated under low NOx conditions form OH radicals and superoxide in the aqueous phase, which was lowered substantially by 50–80% for SOA generated under high NOx conditions. High-resolution mass spectrometry analysis showed the substantial formation of nitroaromatics and organic nitrates in a high NOx environment. The modeling results using the GECKO-A model that simulates explicit gas-phase chemistry and the radical 2D-VBS model that treats autoxidation predicted reduced formation of hydroperoxides and enhanced formation of organic nitrates under high NOx due to the reactions of peroxy radicals with NOx instead of their reactions with HO2. Consistently, the presence of NOx resulted in the decrease of peroxide contents and oxidative potential of α-pinene SOA.

Exposure to naphthalene and β-pinene-derived secondary organic aerosol induced divergent changes in transcript levels of BEAS-2B cells.

The health effects of exposure to secondary organic aerosols (SOAs) are still limited. Here, we investigated and compared the toxicities of soot particles (SP) coated with β-pinene SOA (SOAβPin-SP) and SP coated with naphthalene SOA (SOANap-SP) in a human bronchial epithelial cell line (BEAS-2B) residing at the air-liquid interface. SOAβPin-SP mostly contained oxygenated aliphatic compounds from β-pinene photooxidation, whereas SOANap-SP contained a significant fraction of oxygenated aromatic products under similar conditions. Following exposure, genome-wide transcriptome responses showed an Nrf2 oxidative stress response, particularly for SOANap-SP. Other signaling pathways, such as redox signaling, inflammatory signaling, and the involvement of matrix metalloproteinase, were identified to have a stronger impact following exposure to SOANap-SP. SOANap-SP also induced a stronger genotoxicity response than that of SOAβPin-SP. This study elucidated the mechanisms that govern SOA toxicity and showed that, compared to SOAs derived from a typical biogenic precursor, SOAs from a typical anthropogenic precursor have higher toxicological potency, which was accompanied with the activation of varied cellular mechanisms, such as aryl hydrocarbon receptor. This can be attributed to the difference in chemical composition; specifically, the aromatic compounds in the naphthalene-derived SOA had higher cytotoxic potential than that of the β-pinene-derived SOA.

Formation of secondary organic aerosol tracers from anthropogenic and biogenic volatile organic compounds under varied NO and oxidant conditions

For source apportionment by tracer method of secondary organic aerosol (SOA), the ratios of aerosol tracer to total SOA mass ( f SOA ) were determined during the oxidation of toluene, naphthalene, α-pinene, and isoprene by a series of laboratory experiments. Seven anthropogenic SOA tracers maintaining an aromatic ring structure, including 4-nitrophthalic acid and 3,5-dinitrosalicylic, were newly investigated as a chamber study together with 21 traditional aerosol tracers of anthropogenic and biogenic SOA. Experiments of the OH-initiated oxidation of anthropogenic VOCs were conducted as a function of the initial VOC/NO x ratio. No significant dependence on the VOC/NO x ratio was observed for the f SOA of 2,3-dihydroxy-4-oxopentanoic acid from toluene and phthalic acid from naphthalene, whereas the f SOA of nitroaromatic compounds such as 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 4-nitrophthalic acid increased with decreasing VOC/NO x ratio. Among seven newly evaluated anthropogenic SOA tracers, we concluded that 3,5-dinitronsalicylic can be used as a toluene SOA tracer, whereas 4-nitrophthalic acid can be used as a naphthalene SOA tracer. Results of kinetic calculations suggest that naphthalene is a major source of 5-nitrosalicylic acid under urban and rural conditions of previous observation studies. The ozonolysis and NO 3 -initiated oxidation of biogenic VOCs were investigated in addition to OH-initiated oxidation of biogenic VOCs. As for biogenic SOA tracers such as pinic acid and 2-methyltetrols, the f SOA value measured for the NO 3 -intiated reaction was lower than that of the OH-initiated oxidation and the f SOA value measured for the ozonolysis was not necessarily close to that of the OH-initiated oxidation. These results suggest that daytime and nighttime biogenic SOA formation events are interpreted by using different sets of the f SOA values. • Ratios of SOA tracer to aerosol mass were measured for aerosol source analysis. • Twenty-eight SOA tracers including new ones formed from four VOCs were measured. • Anthropogenic SOA tracers were studied as a function of initial VOC/NO x ratio. • Biogenic SOA tracers were studied by changing the oxidant of SOA formation.

Evaluation of the Toxicity on Lung Cells of By-Products Present in Naphthalene Secondary Organic Aerosols.

In 2018, seven million people died prematurely due to exposure to pollution. Polycyclic aromatic hydrocarbons (PAHs) are a significant source of secondary organic aerosol (SOA) in urban areas. We investigated the toxic effects of by-products of naphthalene SOA on lung cells. These by-products were 1,4-naphthoquinone (1,4-NQ), 2-hydroxy-1,4-naphthoquinone (2-OH-NQ), phthalic acid (PA) and phthaldialdehyde (OPA). Two different assessment methodologies were used to monitor the toxic effects: real-time cell analysis (RTCA) and the Holomonitor, a quantitative phase contrast microscope. The chemicals were tested in concentrations of 12.5 to 100 µM for 1,4-NQ and 1 to 10 mM for 2-OH-NQ, PA and OPA. We found that 1,4-NQ is toxic to cells from 25 to 100 µM (EC50: 38.7 µM ± 5.2); 2-OH-NQ is toxic from 1 to 10mM (EC50: 5.3 mM ± 0.6); PA is toxic from 5 to 10 mM (EC50: 5.2 mM ± 0.3) and OPA is toxic from 2.5 to 10 mM (EC50: 4.2 mM ± 0.5). Only 1,4-NQ and OPA affected cell parameters (migration, motility, motility speed and optical volume). Furthermore, 1,4-NQ is the most toxic by-product of naphthalene, with an EC50 value that was one hundred times higher than those of the other compounds. RTCA and Holomonitor analysis showed a complementarity when studying the toxicity induced by chemicals.

Reactive Oxygen Species Formed by Secondary Organic Aerosols in Water and Surrogate Lung Fluid.

Reactive oxygen species (ROS) play a central role in adverse health effects of air pollutants. Respiratory deposition of fine air particulate matter can lead to the formation of ROS in epithelial lining fluid, potentially causing oxidative stress and inflammation. Secondary organic aerosols (SOA) account for a large fraction of fine particulate matter, but their role in adverse health effects is unclear. Here, we quantify and compare the ROS yields and oxidative potential of isoprene, β-pinene, and naphthalene SOA in water and surrogate lung fluid (SLF). In pure water, isoprene and β-pinene SOA were found to produce mainly OH and organic radicals, whereas naphthalene SOA produced mainly H2O2 and O2•-. The total molar yields of ROS of isoprene and β-pinene SOA were 11.8% and 8.2% in water and decreased to 8.5% and 5.2% in SLF, which can be attributed to ROS removal by lung antioxidants. A positive correlation between the total peroxide concentration and ROS yield suggests that organic (hydro)peroxides may play an important role in ROS formation from biogenic SOA. The total molar ROS yields of naphthalene SOA was 1.7% in water and increased to 11.3% in SLF. This strong increase is likely due to redox reaction cycles involving environmentally persistent free radicals (EPFR) or semiquinones, antioxidants, and oxygen, which may promote the formation of H2O2 and the adverse health effects of anthropogenic SOA from aromatic precursors.

Exposure of Lung Epithelial Cells to Photochemically Aged Secondary Organic Aerosol Shows Increased Toxic Effects

Adverse health effects due to exposure to particulate matter (PM) are among the most important global environmental health risks. However, the effects of exposure to secondary organic aerosols (SOA), a major component of the global aerosol, are largely unknown. Here we exposed lung epithelial cells (A549) to fresh and aged SOA particles and investigated the effect of SOA atmospheric aging on cell viability and gene expression. Naphthalene- and α-pinene-derived SOA were formed in an oxidation flow reactor that simulates atmospheric SOA formation and aging dominated by OH radical oxidation under NOx-free conditions. The SOA mass and chemical composition were characterized on-line using a scanning mobility particle sizer and aerosol mass spectrometer. Fresh and aged SOA were directed to an air–liquid interface cell exposure system. Aged naphthalene- and α-pinene-derived SOA were somewhat more toxic than fresh SOA. Aged naphthalene SOA contained peroxide levels that were higher than those of fresh SOA. The le...

Relationship between chemical composition and oxidative potential of secondary organic aerosol from polycyclic aromatic hydrocarbons

Abstract. Owing to the complex nature and dynamic behaviors of secondary organic aerosol (SOA), its ability to cause oxidative stress (known as oxidative potential, or OP) and adverse health outcomes remains poorly understood. In this work, we probed the linkages between the chemical composition of SOA and its OP, and investigated impacts from various SOA evolution pathways, including atmospheric oligomerization, heterogeneous oxidation, and mixing with metal. SOA formed from photooxidation of the two most common polycyclic aromatic hydrocarbons (naphthalene and phenanthrene) were studied as model systems. OP was evaluated using the dithiothreitol (DTT) assay. The oligomer-rich fraction separated by liquid chromatography dominates DTT activity in both SOA systems (52 ± 10 % for naphthalene SOA (NSOA), and 56 ± 5 % for phenanthrene SOA (PSOA)). Heterogeneous ozonolysis of NSOA was found to enhance its OP, which is consistent with the trend observed in selected individual oxidation products. DTT activities from redox-active organic compounds and metals were found to be not additive. When mixing with highly redox-active metal (Cu), OP of the mixture decreased significantly for 1,2-naphthoquinone (42 ± 7 %), 2,3-dihydroxynaphthalene (35 ± 1 %), NSOA (50 ± 6 %), and PSOA (43 ± 4 %). Evidence from proton nuclear magnetic resonance (1H NMR) spectroscopy illustrates that such OP reduction upon mixing can be ascribed to metal–organic binding interactions. Our results highlight the role of aerosol chemical composition under atmospheric aging processes in determining the OP of SOA, which is needed for more accurate and explicit prediction of the toxicological impacts from particulate matter.

Chemical and cellular oxidant production induced by naphthalene secondary organic aerosol (SOA): effect of redox-active metals and photochemical aging

Exposure to air pollution is a leading global health risk. Secondary organic aerosol (SOA) constitute a large portion of ambient particulate matter (PM). In this study, the water-soluble oxidative potential (OP) determined by dithiothreitol (DTT) consumption and intracellular reactive oxygen and nitrogen species (ROS/RNS) production was measured for SOA generated from the photooxidation of naphthalene in the presence of iron sulfate and ammonium sulfate seed particles. The measured intrinsic OP varied for aerosol formed using different initial naphthalene concentrations, however, no trends were observed between OP and bulk aerosol composition or seed type. For all experiments, aerosol generated in the presence of iron-containing seed induced higher ROS/RNS production compared to that formed in the presence of inorganic seed. This effect was primarily attributed to differences in aerosol carbon oxidation state {boldsymbol{(}}{bar{{bf{O}}{bf{S}}}}_{{bf{c}}}{boldsymbol{)}}. In the presence of iron, radical concentrations are elevated via iron redox cycling, resulting in more oxidized species. An exponential trend was also observed between ROS/RNS and {boldsymbol{(}}{bar{{bf{O}}{bf{S}}}}_{{bf{c}}}{boldsymbol{)}} for all naphthalene SOA, regardless of seed type or aerosol formation condition. This may have important implications as aerosol have an atmospheric lifetime of a week, over which {boldsymbol{(}}{bar{{bf{O}}{bf{S}}}}_{{bf{c}}}{boldsymbol{)}} increases due to continued photochemical aging, potentially resulting in more toxic aerosol.

Inflammatory responses to secondary organic aerosols (SOA) generated from biogenic and anthropogenic precursors

Abstract. Cardiopulmonary health implications resulting from exposure to secondary organic aerosols (SOA), which comprise a significant fraction of ambient particulate matter (PM), have received increasing interest in recent years. In this study, alveolar macrophages were exposed to SOA generated from the photooxidation of biogenic and anthropogenic precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different formation conditions (RO2 + HO2 vs. RO2 + NO dominant, dry vs. humid). Various cellular responses were measured, including reactive oxygen and nitrogen species (ROS/RNS) production and secreted levels of cytokines, tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6). SOA precursor identity and formation condition affected all measured responses in a hydrocarbon-specific manner. With the exception of naphthalene SOA, cellular responses followed a trend where TNF-α levels reached a plateau with increasing IL-6 levels. ROS/RNS levels were consistent with relative levels of TNF-α and IL-6, due to their respective inflammatory and anti-inflammatory effects. Exposure to naphthalene SOA, whose aromatic-ring-containing products may trigger different cellular pathways, induced higher levels of TNF-α and ROS/RNS than suggested by the trend. Distinct cellular response patterns were identified for hydrocarbons whose photooxidation products shared similar chemical functionalities and structures, which suggests that the chemical structure (carbon chain length and functionalities) of photooxidation products may be important for determining cellular effects. A positive nonlinear correlation was also detected between ROS/RNS levels and previously measured DTT (dithiothreitol) activities for SOA samples. In the context of ambient samples collected during summer and winter in the greater Atlanta area, all laboratory-generated SOA produced similar or higher levels of ROS/RNS and DTT activities. These results suggest that the health effects of SOA are important considerations for understanding the health implications of ambient aerosols.

Characterizing source fingerprints and ageing processes in laboratory-generated secondary organic aerosols using proton-nuclear magnetic resonance (<sup>1</sup>H-NMR) analysis and HPLC HULIS determination

Abstract. The study of secondary organic aerosol (SOA) in laboratory settings has greatly increased our knowledge of the diverse chemical processes and environmental conditions responsible for the formation of particulate matter starting from biogenic and anthropogenic volatile compounds. However, characteristics of the different experimental setups and the way they impact the composition and the timescale of formation of SOA are still subject to debate. In this study, SOA samples were generated using a potential aerosol mass (PAM) oxidation flow reactor using α-pinene, naphthalene and isoprene as precursors. The PAM reactor facilitated exploration of SOA composition over atmospherically relevant photochemical ageing timescales that are unattainable in environmental chambers. The SOA samples were analyzed using two state-of-the-art analytical techniques for SOA characterization – proton nuclear magnetic resonance (1H-NMR) spectroscopy and HPLC determination of humic-like substances (HULIS). Results were compared with previous Aerodyne aerosol mass spectrometer (AMS) measurements. The combined 1H-NMR, HPLC, and AMS datasets show that the composition of the studied SOA systems tend to converge to highly oxidized organic compounds upon prolonged OH exposures. Further, our 1H-NMR findings show that only α-pinene SOA acquires spectroscopic features comparable to those of ambient OA when exposed to at least 1 × 1012 molec OH cm−3 × s OH exposure, or multiple days of equivalent atmospheric OH oxidation. Over multiple days of equivalent OH exposure, the formation of HULIS is observed in both α-pinene SOA and in naphthalene SOA (maximum yields: 16 and 30 %, respectively, of total analyzed water-soluble organic carbon, WSOC), providing evidence of the formation of humic-like polycarboxylic acids in unseeded SOA.

Chemical oxidative potential of secondary organic aerosol (SOA) generated from the photooxidation of biogenic and anthropogenic volatile organic compounds

Abstract. Particulate matter (PM), of which a significant fraction is comprised of secondary organic aerosols (SOA), has received considerable attention due to its health implications. In this study, the water-soluble oxidative potential (OPWS) of SOA generated from the photooxidation of biogenic and anthropogenic hydrocarbon precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different reaction conditions (RO2+ HO2 vs. RO2+ NO dominant, dry vs. humid) was characterized using dithiothreitol (DTT) consumption. The measured intrinsic OPWS-DTT values ranged from 9 to 205 pmol min−1 µg−1 and were highly dependent on the specific hydrocarbon precursor, with naphthalene and isoprene SOA generating the highest and lowest OPWS-DTT values, respectively. Humidity and RO2 fate affected OPWS-DTT in a hydrocarbon-specific manner, with naphthalene SOA exhibiting the most pronounced effects, likely due to the formation of nitroaromatics. Together, these results suggest that precursor identity may be more influential than reaction condition in determining SOA oxidative potential, demonstrating the importance of sources, such as incomplete combustion, to aerosol toxicity. In the context of other PM sources, all SOA systems, with the exception of naphthalene SOA, were less DTT active than ambient sources related to incomplete combustion, including diesel and gasoline combustion as well as biomass burning. Finally, naphthalene SOA was as DTT active as biomass burning aerosol, which was found to be the most DTT-active OA source in a previous ambient study. These results highlight a need to consider SOA contributions (particularly from anthropogenic hydrocarbons) to health effects in the context of hydrocarbon emissions, SOA yields, and other PM sources.

Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in the Anthropocene.

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (<3) conditions. ROS formation can be explained by the decomposition of organic hydroperoxides, which are a prominent fraction of SOA, through interactions with water and Fenton-like reactions with dissolved transition metal ions. Our findings imply that the chemical reactivity and aging of SOA particles can be enhanced upon interaction with mineral dust in deliquesced particles or cloud/fog droplets. SOA decomposition could be comparably important to the classical Fenton reaction of H2O2 with Fe2+ and that SOA can be the main source of OH radicals in aqueous droplets at low concentrations of H2O2 and Fe2+. In the human respiratory tract, the inhalation and deposition of SOA and mineral dust can also lead to the release of ROS, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols in the Anthropocene.

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (Tg) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective Tg and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

Competition between water uptake and ice nucleation by glassy organic aerosol particles

Abstract. Organic aerosol particles play a key role in climate by serving as nuclei for clouds and precipitation. Their sources and composition are highly variable, and their phase state ranges from liquid to solid under atmospheric conditions, affecting the pathway of activation to cloud droplets and ice crystals. Due to slow diffusion of water in the particle phase, organic particles may deviate in phase and morphology from their thermodynamic equilibrium state, hampering the prediction of their influence on cloud formation. We overcome this problem by combining a novel semi-empirical method for estimation of water diffusivity with a kinetic flux model that explicitly treats water diffusion. We estimate timescales for particle deliquescence as well as various ice nucleation pathways for a wide variety of organic substances, including secondary organic aerosol (SOA) from the oxidation of isoprene, α-pinene, naphthalene, and dodecane. The simulations show that, in typical atmospheric updrafts, glassy states and solid/liquid core-shell morphologies can persist for long enough that heterogeneous ice nucleation in the deposition and immersion mode can dominate over homogeneous ice nucleation. Such competition depends strongly on ambient temperature and relative humidity as well as humidification rate and particle size. Due to differences in glass transition temperature, hygroscopicity and atomic O / C ratio of the different SOA, naphthalene SOA particles have the highest potential to act as heterogeneous ice nuclei. Our findings demonstrate that kinetic limitations of water diffusion into organic aerosol particles are likely to be encountered under atmospheric conditions and can strongly affect ice nucleation pathways. For the incorporation of ice nucleation by organic aerosol particles into atmospheric models, our results demonstrate a demand for model formalisms that account for the effects of molecular diffusion and not only describe ice nucleation onsets as a function of temperature and relative humidity but also include updraft velocity, particle size and composition.

Naphthalene SOA: redox activity and naphthoquinone gas–particle partitioning

Abstract. Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10−4 m3 μg−1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

Secondary Organic Aerosol Coating Formation and Evaporation: Chamber Studies Using Black Carbon Seed Aerosol and the Single-Particle Soot Photometer

We report a protocol for using black carbon (BC) aerosol as the seed for secondary organic aerosol (SOA) formation in an environmental chamber. We employ a single-particle soot photometer (SP2) to probe single-particle SOA coating growth dynamics and find that SOA growth on nonspherical BC aerosol is diffusion-limited. Aerosol composition measurements with an Aerodyne high resolution time-of-flight aerosol mass spectrometer (AMS) confirm that the presence of BC seed does not alter the composition of SOA as compared to self-nucleated SOA or condensed SOA on ammonium sulfate seed. We employ a 3-wavelength photoacoustic soot spectrometer (PASS-3) to measure optical properties of the systems studied, including fullerene soot as the surrogate BC seed, nucleated naphthalene SOA from high-NO_x photooxidation, and nucleated α-pinene SOA from low-NO_x photooxidation. A core-and-shell Mie scattering model of the light absorption enhancement is in good agreement with measured enhancements for both the low- and high-NO_x α-pinene photooxidation systems, reinforcing the assumption of a core-shell morphology for coated BC particles. A discrepancy between measured and modeled absorption enhancement factors in the naphthalene photooxidation system is attributed to the wavelength-dependence of refractive index of the naphthalene SOA. The coating of high-NO_x α-pinene SOA decreases after reaching a peak thickness during irradiation, reflecting a volatility change in the aerosol, as confirmed by the relative magnitudes of f_(43) and f_(44) in the AMS spectra. The protocol described here provides a framework by which future studies of SOA optical properties and single-particle growth dynamics may be explored in environmental chambers.

Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer

Abstract. The elemental composition of laboratory chamber secondary organic aerosol (SOA) from glyoxal uptake, α-pinene ozonolysis, isoprene photooxidation, single-ring aromatic photooxidation, and naphthalene photooxidation is evaluated using Aerodyne high-resolution time-of-flight mass spectrometer data. SOA O/C ratios range from 1.13 for glyoxal uptake experiments to 0.30–0.43 for α-pinene ozonolysis. The elemental composition of α-pinene and naphthalene SOA is also confirmed by offline mass spectrometry. The fraction of organic signal at m/z 44 is generally a good measure of SOA oxygenation for α-pinene/O3, isoprene/high-NOx, and naphthalene SOA systems. The agreement between measured and estimated O/C ratios tends to get closer as the fraction of organic signal at m/z 44 increases. This is in contrast to the glyoxal uptake system, in which m/z 44 substantially underpredicts O/C. Although chamber SOA has generally been considered less oxygenated than ambient SOA, single-ring aromatic- and naphthalene-derived SOA can reach O/C ratios upward of 0.7, well within the range of ambient PMF component OOA, though still not as high as some ambient measurements. The spectra of aromatic and isoprene-high-NOx SOA resemble that of OOA, but the spectrum of glyoxal uptake does not resemble that of any ambient organic aerosol PMF component.

Chemical Composition of Gas- and Aerosol-Phase Products from the Photooxidation of Naphthalene

The current work focuses on the detailed evolution of the chemical composition of both the gas- and aerosol-phase constituents produced from the OH-initiated photooxidation of naphthalene under low- and high-NO(x) conditions. Under high-NO(x) conditions ring-opening products are the primary gas-phase products, suggesting that the mechanism involves dissociation of alkoxy radicals (RO) formed through an RO(2) + NO pathway, or a bicyclic peroxy mechanism. In contrast to the high-NO(x) chemistry, ring-retaining compounds appear to dominate the low-NO(x) gas-phase products owing to the RO(2) + HO(2) pathway. We are able to chemically characterize 53-68% of the secondary organic aerosol (SOA) mass. Atomic oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios measured in bulk samples by high-resolution electrospray ionization time-of-flight mass spectrometry (HR-ESI-TOFMS) are the same as the ratios observed with online high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), suggesting that the chemical compositions and oxidation levels found in the chemically-characterized fraction of the particle phase are representative of the bulk aerosol. Oligomers, organosulfates (R-OSO(3)), and other high-molecular-weight (MW) products are not observed in either the low- or high-NO(x) SOA; however, in the presence of neutral ammonium sulfate seed aerosol, an organic sulfonic acid (R-SO(3)), characterized as hydroxybenzene sulfonic acid, is observed in naphthalene SOA produced under both high- and low-NO(x) conditions. Acidic compounds and organic peroxides are found to account for a large fraction of the chemically characterized high- and low-NO(x) SOA. We propose that the major gas- and aerosol-phase products observed are generated through the formation and further reaction of 2-formylcinnamaldehyde or a bicyclic peroxy intermediate. The chemical similarity between the laboratory SOA and ambient aerosol collected from Birmingham, Alabama (AL) and Pasadena, California (CA) confirm the importance of PAH oxidation in the formation of aerosol within the urban atmosphere.