Characterizing PM2.5 Emissions and Temporal Evolution of Organic Composition from Incense Burning in a California Residence.

The chemical composition of incense-generated organic aerosol in residential indoor air has received limited attention in Western literature. In this study, we conducted incense burning experiments in a single-family California residence during vacancy. We report the chemical composition of organic fine particulate matter (PM2.5), associated emission factors (EFs), and gas-particle phase partitioning for indoor semivolatile organic compounds (SVOCs). Speciated organic PM2.5 measurements were made using two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC×GC-HR-ToF-MS) and semivolatile thermal desorption aerosol gas chromatography (SV-TAG). Organic PM2.5 EFs ranged from 7 to 31 mg g-1 for burned incense and were largely comprised of polar and oxygenated species, with high abundance of biomass-burning tracers such as levoglucosan. Differences in PM2.5 EFs and chemical profiles were observed in relation to the type of incense burned. Nine indoor SVOCs considered to originate from sources other than incense combustion were enhanced during incense events. Time-resolved concentrations of these SVOCs correlated well with PM2.5 mass (R2 > 0.75), suggesting that low-volatility SVOCs such as bis(2-ethylhexyl)phthalate and butyl benzyl phthalate partitioned to incense-generated PM2.5. Both direct emissions and enhanced partitioning of low-volatility indoor SVOCs to incense-generated PM2.5 can influence inhalation exposures during and after indoor incense use.

Changes in light absorption and composition of chromophoric marine-dissolved organic matter across a microbial bloom.

Marine chromophoric dissolved organic matter (m-CDOM) mediates many vital photochemical processes at the ocean's surface. Isolating m-CDOM within the chemical complexity of marine dissolved organic matter has remained an analytical challenge. The SeaSCAPE campaign, a large-scale mesocosm experiment, provided a unique opportunity to probe the in situ production of m-CDOM across phytoplankton and microbial blooms. Results from mass spectrometry coupled with UV-VIS spectroscopy reveal production of a chemodiverse set of compounds well-correlated with increases in absorbance after a bacterial bloom, indicative of autochthonous m-CDOM production. Notably, many of the absorbing compounds were found to be enriched in nitrogen, which may be essential to chromophore function. From these results, quinoids, porphyrins, flavones, and amide-like compounds were identified via structural analysis and may serve as important photosensitizers in the marine boundary layer. Overall, this study demonstrates a step forward in identifying and characterizing m-CDOM using temporal mesocosm data and integrated UV-VIS spectroscopy and mass spectrometry analyses.

Nanoscopic Study of Water Uptake on Glass Surfaces with Organic Thin Films and Particles from Exposure to Indoor Cooking Activities: Comparison to Model Systems.

Water uptake by thin organic films and organic particles on glass substrates at 80% relative humidity was investigated using atomic force microscopy-infrared (AFM-IR) spectroscopy. Glass surfaces exposed to kitchen cooking activities show a wide variability of coverages from organic particles and organic thin films. Water uptake, as measured by changes in the volume of the films and particles, was also quite variable. A comparison of glass surfaces exposed to kitchen activities to model systems shows that they can be largely represented by oxidized oleic acid and carboxylate groups on long and medium hydrocarbon chains (i.e., fatty acids). Overall, we demonstrate that organic particles and thin films that cover glass surfaces can take up water under indoor-relevant conditions but that the water content is not uniform. The spatial heterogeneity of the changes in these aged glass surfaces under dry (5%) and wet (80%) conditions is quite marked, highlighting the need for studies at the nano- and microscale.

The Sea Spray Chemistry and Particle Evolution study (SeaSCAPE): overview and experimental methods.

Marine aerosols strongly influence climate through their interactions with solar radiation and clouds. However, significant questions remain regarding the influences of biological activity and seawater chemistry on the flux, chemical composition, and climate-relevant properties of marine aerosols and gases. Wave channels, a traditional tool of physical oceanography, have been adapted for large-scale ocean-atmosphere mesocosm experiments in the laboratory. These experiments enable the study of aerosols under controlled conditions which isolate the marine system from atmospheric anthropogenic and terrestrial influences. Here, we present an overview of the 2019 Sea Spray Chemistry and Particle Evolution (SeaSCAPE) study, which was conducted in an 11 800 L wave channel which was modified to facilitate atmospheric measurements. The SeaSCAPE campaign sought to determine the influence of biological activity in seawater on the production of primary sea spray aerosols, volatile organic compounds (VOCs), and secondary marine aerosols. Notably, the SeaSCAPE experiment also focused on understanding how photooxidative aging processes transform the composition of marine aerosols. In addition to a broad range of aerosol, gas, and seawater measurements, we present key results which highlight the experimental capabilities during the campaign, including the phytoplankton bloom dynamics, VOC production, and the effects of photochemical aging on aerosol production, morphology, and chemical composition. Additionally, we discuss the modifications made to the wave channel to improve aerosol production and reduce background contamination, as well as subsequent characterization experiments. The SeaSCAPE experiment provides unique insight into the connections between marine biology, atmospheric chemistry, and climate-relevant aerosol properties, and demonstrates how an ocean-atmosphere-interaction facility can be used to isolate and study reactions in the marine atmosphere in the laboratory under more controlled conditions.

Atmospheric Benzothiazoles in a Coastal Marine Environment.

Organic emissions from coastal waters play an important but poorly understood role in atmospheric chemistry in coastal regions. A mesocosm experiment focusing on facilitated biological blooms in coastal seawater, SeaSCAPE (Sea Spray Chemistry and Particle Evolution), was performed to study emission of volatile gases, primary sea spray aerosol, and formation of secondary marine aerosol as a function of ocean biological and chemical processes. Here, we report observations of aerosol-phase benzothiazoles in a marine atmospheric context with complementary measurements of dissolved-phase benzothiazoles. Though previously reported dissolved in polluted coastal waters, we report the first direct evidence of the transfer of these molecules from seawater into the atmosphere. We also report the first gas-phase observations of benzothiazole in the environment absent a direct industrial, urban, or rubber-based source. From the identities and temporal dynamics of the dissolved and aerosol species, we conclude that the presence of benzothiazoles in the coastal water (and thereby their emissions into the atmosphere) is primarily attributable to anthropogenic sources. Oxidation experiments to explore the atmospheric fate of gas-phase benzothiazole show that it produces secondary aerosol and gas-phase SO2, making it a potential contributor to secondary marine aerosol formation in coastal regions and a participant in atmospheric sulfur chemistry.

Toward a microscopic model of light absorbing dissolved organic compounds in aqueous environments: theoretical and experimental study.

Water systems often contain complex macromolecular systems that absorb light. In marine environments, these light absorbing components are often at the air-water interface and can participate in the chemistry of the atmosphere in ways that are poorly understood. Understanding the photochemistry and photophysics of these systems represents a major challenge since their composition and structures are not unique. In this study, we present a successful microscopic model of this light absorbing macromolecular species termed "marine derived chromophoric dissolved organic matter" or "m-CDOM" in water. The approach taken involves molecular dynamics simulations in the ground state using on the fly Density Functional Tight-Binding (DFTB) electronic structure theory; Time Dependent DFTB (TD-DFTB) calculations of excited states, and experimental measurements of the optical absorption spectra in aqueous solution. The theoretical hydrated model shows key features seen in the experimental data for a collected m-CDOM sample. As will be discussed, insights from the model are: (i) the low-energy A-band (at 410 nm) is due to the carbon chains combined with the diol- and the oxy-groups present in the structure; (ii) the weak B-band (at 320-360 nm) appears due to the contribution of the ionized speciated form of m-CDOM; and (iii) the higher-energy C-band (at 280 nm) is due to the two fused ring system. Thus, this is a two-speciated formed model. Although a relatively simple system, these calculations represent an important step in understanding light absorbing compounds found in nature and the search for other microscopic models of related materials remains of major interest.

Glass surface evolution following gas adsorption and particle deposition from indoor cooking events as probed by microspectroscopic analysis.

Indoor surfaces are extremely diverse and their interactions with airborne compounds and aerosols influence the lifetime and reactivity of indoor emissions. Direct measurements of the physical and chemical state of these surfaces provide insights into the underlying physical and chemical processes involving surface adsorption, surface partitioning and particle deposition. Window glass, a ubiquitous indoor surface, was placed vertically during indoor activities throughout the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign and then analyzed to measure changes in surface morphology and surface composition. Atomic force microscopy-infrared (AFM-IR) spectroscopic analyses reveal that deposition of submicron particles from cooking events is a contributor to modifying the chemical and physical state of glass surfaces. These results demonstrate that the deposition of glass surfaces can be an important sink for organic rich particles material indoors. These findings also show that particle deposition contributes enough organic matter from a single day of exposure equivalent to a uniform film up to two nanometers in thickness, and that the chemical distinctness of different indoor activities is reflective of the chemical and morphological changes seen in these indoor surfaces. Comparison of the experimental results to physical deposition models shows variable agreement, suggesting that processes not captured in physical deposition models may play a role in the sticking of particles on indoor surfaces.

Liquid Sampling-Atmospheric Pressure Glow Discharge Ionization as a Technique for the Characterization of Salt-Containing Organic Samples.

Typical ionization techniques used for mass spectrometry (MS) analysis face challenges when trying to analyze organic species in a high-salt environment. Here, we present results using a recently developed ionization source, liquid sampling-atmospheric pressure glow discharge (LS-APGD), for marine-relevant salt-containing organic samples. Using two representative sample types, a triglyceride mixture and dissolved organic matter, this method is compared to traditional electrospray ionization (ESI) under saline and neat conditions. LS-APGD produced equal or higher (15%+) ion intensities than those of ESI for both salt-containing and neat samples, although important differences linked with adduct formation in high-salt conditions explain the molecular species observed. For all sample types, LS-APGD observed a higher diversity of molecules under optimized settings (0.25 mm electrode spacing at 20 mA) compared to traditional ESI. Furthermore, because the LS-APGD source ionizes molecular species in a ∼1 mm3 volume plasma using a low-power source, there is the potential for this method to be applied in field studies, eliminating desalting procedures, which can be time-consuming and nonideal for low-concentration species.

Impact of pH and NaCl and CaCl2 Salts on the Speciation and Photochemistry of Pyruvic Acid in the Aqueous Phase.

Recent studies have shown that pyruvic acid can produce higher-molecular-weight compounds upon irradiation in the aqueous phase. These compounds can contribute to the formation of secondary organic aerosols. There have been several previous studies on the effect of ionic strength on the photochemistry of pyruvic acid; however, few of them investigated the effects of marine relevant salts such as NaCl and CaCl2. In this study, we examine the effect of NaCl and CaCl2, namely, containing the coordinating cations Na+ and Ca2+, on the speciation, absorption properties, and photoreactivity of pyruvic acid in aqueous solutions of varying pH. NMR shows that both Ca2+ and Na+ further deprotonate pyruvic acid and decrease the diol to ketone ratio of pyruvic acid than in pure water at the same pH, especially at more acidic pH (pH less than 4). The absorption spectrum shows a strong red shift in the peak maxima for the n → π* transition of pyruvic acid in NaCl/CaCl2 solutions. This dependence is much more pronounced for divalent cations (Ca2+) compared to monovalent cations (Na+). Vertical excitation energy calculations of the anionic ketone form of pyruvic acid confirm the same red shift on the n → π* transition peak in the presence of Ca2+. In addition, the presence of NaCl/CaCl2 suppresses the photolysis rate of pyruvic acid, which could be due to the deprotonation of pyruvic acid by the cations and the lower photochemical reactivity for pyruvate, the deprotonated form.

Chemistry and Photochemistry of Pyruvic Acid Adsorbed on Oxide Surfaces.

The surface chemistry and photochemistry of gas-phase pyruvic acid (CH3COCOOH) on two oxides, Al2O3 and TiO2, have been investigated using transmission Fourier transform infrared spectroscopy and mass spectrometry. At 298 K, the carboxylic acid group within pyruvic acid is found to react with surface hydroxyl groups (M-OH, M = Al, Ti) to yield pyruvate as a predominant adsorbed organic species. Upon broad-band UV irradiation (λ > 280 nm), there is a loss of adsorbed pyruvate with the concomitant formation of new products. The photochemical loss of pyruvate is higher on TiO2 than on Al2O3 indicating that the photochemistry is enhanced on the surface of a semiconductor oxide, TiO2, compared with an insulator oxide, Al2O3. Analysis of products extracted from the surface with mass spectrometry shows the formation of several new compounds. This includes zymonic acid, which is found to be present under both dark and light conditions, and other higher-molar-mass oligomeric species such as parapyruvic acid, acetolactic acid, and 2,4-dihydroxy-2-methyl-5-oxohexanoic acid that form only under irradiation. Although this study shows that there are some parallels between the aqueous-phase photochemistry of pyruvic acid and the photochemistry of adsorbed pyruvic acid in terms of the products that form, there are also distinct differences, with several other new photoproducts observed on these oxide surfaces, including lactic acid dimers and trimers as well as significant amounts of even larger oligomeric species not seen in the aqueous phase. Because of the role of pyruvic acid, the simplest of the α-keto acids, in the atmosphere and in metabolic pathways, these results have implications for the chemistry that occurs in both indoor and outdoor environments and under prebiotic Earth conditions. Overall, this study provides insights into the surface chemistry and photochemistry of pyruvic acid on different oxides (Al2O3 and TiO2).

Linking hygroscopicity and the surface microstructure of model inorganic salts, simple and complex carbohydrates, and authentic sea spray aerosol particles.

Individual airborne sea spray aerosol (SSA) particles show diversity in their morphologies and water uptake properties that are highly dependent on the biological, chemical, and physical processes within the sea subsurface and the sea surface microlayer. In this study, hygroscopicity data for model systems of organic compounds of marine origin mixed with NaCl are compared to data for authentic SSA samples collected in an ocean-atmosphere facility providing insights into the SSA particle growth, phase transitions and interactions with water vapor in the atmosphere. In particular, we combine single particle morphology analyses using atomic force microscopy (AFM) with hygroscopic growth measurements in order to provide important insights into particle hygroscopicity and the surface microstructure. For model systems, a range of simple and complex carbohydrates were studied including glucose, maltose, sucrose, laminarin, sodium alginate, and lipopolysaccharides. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM). It is shown here that the E-AIM model describes well the deliquescence transition and hygroscopic growth at low mass ratios but not as well for high ratios, most likely due to a high organic volume fraction. AFM imaging reveals that the equilibrium morphology of these single-component organic particles is amorphous. When NaCl is mixed with the organics, the particles adopt a core-shell morphology with a cubic NaCl core and the organics forming a shell similar to what is observed for the authentic SSA samples. The observation of such core-shell morphologies is found to be highly dependent on the salt to organic ratio and varies depending on the nature and solubility of the organic component. Additionally, single particle organic volume fraction AFM analysis of NaCl : glucose and NaCl : laminarin mixtures shows that the ratio of salt to organics in solution does not correspond exactly for individual particles - showing diversity within the ensemble of particles produced even for a simple two component system.