Solid organic-coated ammonium sulfate particles at high relative humidity in the summertime Arctic atmosphere.

SignificancePhysical and chemical properties of individual atmospheric particles determine their climate impacts. Hygroscopic inorganic salt particles mixed with trace amounts of organic material are predicted to be liquid under typical tropospheric conditions in the summertime Arctic. Yet, we unexpectedly observed a significant concentration of solid particles composed of ammonium sulfate with an organic coating under conditions of high relative humidity and low temperature. These particle properties are consistent with marine biogenic-derived new particle formation and growth, with particle collision hypothesized to result in the solid phase. This particle source is predicted to have increasing relevance in the context of declining Arctic sea ice and increasing open water, with impacts on clouds, and therefore climate.

Volatility Basis Set Distributions and Viscosity of Organic Aerosol Mixtures: Insights from Chemical Characterization Using Temperature-Programmed Desorption-Direct Analysis in Real-Time High-Resolution Mass Spectrometry.

Quantitative assessment of gas-particle partitioning of individual components within complex atmospheric organic aerosol (OA) mixtures is critical for predicting and comprehending the formation and evolution of OA particles in the atmosphere. This investigation leverages previously documented data obtained through a temperature-programmed desorption-direct analysis in real-time, high-resolution mass spectrometry (TPD-DART-HRMS) platform. This methodology facilitates the bottom-up construction of volatility basis set (VBS) distributions for constituents found in three biogenic secondary organic aerosol (SOA) mixtures produced through the ozonolysis of α-pinene, limonene, and ocimene. The apparent enthalpies (ΔH*, kJ mol-1) and saturation mass concentrations (CT*, µg·m-3) of individual SOA components, determined as a function of temperature (T, K), facilitated an assessment of changes in VBS distributions and gas-particle partitioning with respect to T and atmospheric total organic mass loadings (tOM, µg·m-3). The VBS distributions reveal distinct differences in volatilities among monomers, dimers, and trimers, categorized into separate volatility bins. At the ambient temperature of T = 298 K, only monomers efficiently partition between gas and particle phases across a broad range of atmospherically relevant tOM values of 1-100 µg·m-3. Partitioning of dimers and trimers becomes notable only at T > 360 K and T > 420 K, respectively. The viscosity of SOA mixtures is assessed using a bottom-up calculation approach, incorporating the input of elemental formulas, ΔH*, CT*, and particle-phase mass fractions of the SOA components. Through this approach, we are able to accurately estimate the variations in SOA viscosity that result from the evaporation of its components. These variations are, in turn, influenced by atmospherically relevant changes in tOM and T. Comparison of the calculated SOA viscosity and diffusivity values with literature reported experimental results shows close agreement, thereby validating the employed calculation approach. These findings underscore the significant potential for TPD-DART-HRMS measurements in enabling the untargeted analysis of organic molecules within OA mixtures. This approach facilitates quantitative assessment of their gas-particle partitioning and allows for the estimation of their viscosity and condensed-phase diffusion, thereby contributing valuable insights to atmospheric models.

Enhanced Light Absorption and Elevated Viscosity of Atmospheric Brown Carbon through Evaporation of Volatile Components.

Samples of brown carbon (BrC) material were collected from smoke emissions originating from wood pyrolysis experiments, serving as a proxy for BrC representative of biomass burning emissions. The acquired samples, referred to as "pyrolysis oil (PO1)," underwent subsequent processing by thermal evaporation of their volatile compounds, resulting in a set of three additional samples with volume reduction factors of 1.33, 2, and 3, denoted as PO1.33, PO2, and PO3. The chemical compositions of these POx samples and their BrC chromophore features were analyzed using a high-performance liquid chromatography instrument coupled with a photodiode array detector and a high-resolution mass spectrometer. The investigation revealed a noteworthy twofold enhancement of BrC light absorption observed for the progression of PO1 to PO3 samples, assessed across the spectral range of 300-500 nm. Concurrently, a decrease in the absorption Ångstrom exponent (AAE) from 11 to 7 was observed, indicating a weaker spectral dependence. The relative enhancement of BrC absorption at longer wavelengths was more significant, as exemplified by the increased mass absorption coefficient (MAC) measured at 405 nm from 0.1 to 0.5 m2/g. Molecular characterization further supports this darkening trend, manifesting as a depletion of small oxygenated, less absorbing monoaromatic compounds and the retention of relatively large, less polar, more absorbing constituents. Noteworthy alterations of the PO1 to PO3 mixtures included a reduction in the saturation vapor pressure of their components and an increase in viscosity. These changes were quantified by the mean values shifting from approximately 1.8 × 103 µg/m3 to 2.3 µg/m3 and from ∼103 Pa·s to ∼106 Pa·s, respectively. These results provide quantitative insights into the extent of BrC aerosol darkening during atmospheric aging through nonreactive evaporation. This new understanding will inform the refinement of atmospheric and chemical transport models.

Volatility Measurements of Individual Components in Organic Aerosol Mixtures Using Temperature-Programmed Desorption-Direct Analysis in Real Time-High Resolution Mass Spectrometry.

Atmospheric organic aerosols (OA) have profound effects on air quality, visibility, and radiative forcing of climate. Quantitative assessment of gas-particle equilibrium of OA components is critical to understand formation, growth, distribution, and evolution of OA in the atmosphere. This study presents a novel ambient pressure measurement approach developed and tested for untargeted screening of individual components in complex OA mixtures, followed by targeted chemical speciation of identified species and assessment of their physicochemical properties such as saturation vapor pressure and enthalpies of sublimation/evaporation. The method employs temperature-programmed desorption (TPD) experiments coupled to "direct analysis in real time" (DART) ionization source and high resolution mass spectrometry (HRMS) detection. Progression of the mass spectra is acquired in the TPD experiments over a T = 25-350 °C temperature range, and extracted ion chromatograms (EIC) of individual species are used to infer their apparent enthalpies of sublimation/evaporation (ΔHsub*) and saturation vapor pressure (pT*, Pa, or CT*, µg m-3) as a function of T. We validate application of this method for analysis of selected organic compounds with known ΔHsub and CT values, which showed excellent agreement between our results and the existing data. We then extend these experiments to interrogate individual components in complex OA samples generated in the laboratory-controlled ozonolysis of α-pinene, limonene, and ß-ocimene monoterpenes. The abundant OA species of interest are distinguished based on their accurate mass measurements, followed by quantitation of their apparent ΔHsub* and CT* values from the corresponding EIC records. Comparison of C298K* values derived from our experiments for the individual OA components with the corresponding estimates based on their elemental composition using a "molecular corridors" (MC) parametrization suggests that the MC calculations tend to overestimate the saturation vapor pressures of OA components. Presented results indicate very promising applicability of the TPD-DART-HRMS method for the untargeted analysis of organic molecules in OA and other environmental mixtures, enabling rapid detection and quantification of organic pollutants in the real-world condensed-phase samples at atmospheric pressure and without sample preparation.

Molecular and Structural Characterization of Isomeric Compounds in Atmospheric Organic Aerosol Using Ion Mobility-Mass Spectrometry.

Secondary organic aerosol (SOA) formed through multiphase atmospheric chemistry makes up a large fraction of airborne particles. The chemical composition and molecular structures of SOA constituents vary between different emission sources and aging processes in the atmosphere, which complicates their identification. In this work, we employ drift tube ion mobility spectrometry with quadrupole time-of-flight mass spectrometry (IM-MS) detection for rapid gas-phase separation and multidimensional characterization of isomers in two biogenic SOAs produced from ozonolysis of isomeric monoterpenes, d-limonene (LSOA) and α-pinene (PSOA). SOA samples were ionized using electrospray ionization (ESI) and characterized using IM-MS in both positive and negative ionization modes. The IM-derived collision cross sections in nitrogen gas (DTCCSN2 ) for individual SOA components were obtained using multifield and single-field measurements. A novel application of IM multiplexing/high-resolution demultiplexing methodology was employed to increase sensitivity, improve peak shapes, and augment mobility baseline resolution, which revealed several isomeric structures for the measured ions. For LSOA and PSOA samples, we report significant structural differences of the isomer structures. Molecular structural calculations using density functional theory combined with the theoretical modeling of CCS values provide insights into the structural differences between LSOA and PSOA constituents. The average DTCCSN2 values for monomeric SOA components observed as [M + Na]+ ions are 3-6% higher than those of their [M - H]- counterparts. Meanwhile, dimeric and trimeric isomer components in both samples showed an inverse trend with the relevant values of [M - H]- ions being 3-7% higher than their [M + Na]+ counterparts, respectively. The results indicate that the structures of Na+-coordinated oligomeric ions are more compact than those of the corresponding deprotonated species. The coordination with Na+ occurs on the oxygen atoms of the carbonyl groups leading to a compact configuration. Meanwhile, deprotonated molecules have higher DTCCSN2 values due to their elongated structures in the gas phase. Therefore, DTCCSN2 values of isomers in SOA mixtures depend strongly on the mode of ionization in ESI. Additionally, PSOA monomers and dimers exhibit larger DTCCSN2 values (1-4%) than their LSOA counterparts owing to more rigid structures. A cyclobutane ring is present with functional groups pointing in opposite directions in PSOA compounds, as compared to noncyclic flexible LSOA structures, forming more compact ions in the gas phase. Lastly, we investigated the effects of direct photolysis on the chemical transformations of selected individual PSOA components. We use IM-MS to reveal structural changes associated with aerosol aging by photolysis. This study illustrates the detailed molecular and structural descriptors for the detection and annotation of structural isomers in complex SOA mixtures.

Molecular Analysis of Secondary Brown Carbon Produced from the Photooxidation of Naphthalene.

We investigate the chemical composition of organic light-absorbing components, also known as brown carbon (BrC) chromophores, formed in a proxy of anthropogenic secondary organic aerosol generated from the photooxidation of naphthalene (naph-SOA) in the absence and presence of NOx. High-performance liquid chromatography equipped with a photodiode array detector and electrospray ionization high-resolution mass spectrometer is employed to characterize naph-SOA and its BrC components. We provide molecular-level insights into the chemical composition and optical properties of individual naph-SOA components and investigate their BrC relevance. This work reveals the formation of strongly absorbing nitro-aromatic chromophores under high-NOx conditions and describes their degradation during atmospheric aging. NOx addition enhanced the light absorption of naph-SOA while reducing wavelength-dependence, as seen by the mass absorption coefficient (MAC) and absorption Ångström exponent (AAE). Optical parameters of naph-SOA generated under low- and high-NOx conditions showed a range of values from MACOM 405nm ∼ 0.12 m2 g-1 and AAE300-450nm ∼ 8.87 (low-NOx) to MACOM 405nm ∼ 0.19 m2 g-1 and AAE300-450nm ∼ 7.59 (high-NOx), consistent with "very weak" and "weak" BrC optical classes, respectively. The weak-BrC class is commonly attributed to biomass smoldering emissions, which appear to have optical properties comparable with the naph-SOA. Molecular chromophores contributing to naphthalene BrC absorption were identified with substantial nitro-aromatics, indicating that these species may be used as source-specific markers of BrC related to the anthropogenic emissions.

Optical Properties of Secondary Organic Aerosol Produced by Photooxidation of Naphthalene under NOx Condition.

Secondary organic aerosols (SOAs) affect incoming solar radiation by interacting with light at ultraviolet and visible wavelength ranges. However, the relationship between the chemical composition and optical properties of SOA is still not well understood. In this study, the complex refractive index (RI) of SOA produced from OH oxidation of naphthalene in the presence of nitrogen oxides (NOx) was retrieved online in the wavelength range of 315-650 nm and the bulk chemical composition of the SOA was characterized by an online high-resolution time-of-flight mass spectrometer. In addition, the molecular-level composition of brown carbon chromophores was determined using high-performance liquid chromatography coupled to a photodiode array detector and a high-resolution mass spectrometer. The real part of the RI of the SOA increases with both the NOx/naphthalene ratio and aging time, likely due to the increased mean polarizability and decreased molecular weight due to fragmentation. Highly absorbing nitroaromatics (e.g., C6H5NO4, C7H7NO4, C7H5NO5, C8H5NO5) produced under higher NOx conditions contribute significantly to the light absorption of the SOA. The imaginary part of the RI linearly increases with the NOx/VOCs ratio due to the formation of nitroaromatic compounds. As a function of aging, the imaginary RI increases with the O/C ratio (slope = 0.024), mainly attributed to the achieved higher NOx/VOCs ratio, which favors the formation of light-absorbing nitroaromatics. The light-absorbing enhancement is not as significant with extensive aging as it is under a lower aging time due to the opening of aromatic rings by reactions.

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China.

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. The molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derivedcompounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ∼23-64% of the total light absorption measured by the PDA detector in the wavelength range of 300-370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet-visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

Kinetics, Products, and Brown Carbon Formation by Aqueous-Phase Reactions of Glycolaldehyde with Atmospheric Amines and Ammonium Sulfate.

Glycolaldehyde (GAld) is a C2 water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde's aqueous-phase reactions with AS, methylamine, and glycine. Reaction rate constants are smaller than those of respective glyoxal and methylglyoxal reactions in the pH range of 3-6. In follow-up cloud chamber experiments, deliquesced glycine and AS seed particles were found to take up glycolaldehyde and methylamine and form brown carbon. At very high relative humidity, these changes were more than 2 orders of magnitude faster than predicted by our bulk liquid NMR kinetics measurements, suggesting that reactions involving surface-active species at crowded air-water interfaces may play an important role. The high-resolution liquid chromatography-electrospray ionization-mass spectrometric analysis of filter extracts of unprocessed AS + GAld seed particles identified sugar-like C6 and C12 GAld oligomers, including proposed product 3-deoxyglucosone, with and without modification by reactions with ammonia to diimine and imidazole forms. Chamber exposure to methylamine gas, cloud processing, and simulated sunlight increased the incorporation of both ammonia and methylamine into oligomers. Many C4-C16 imidazole derivatives were detected in an extract of chamber-exposed aerosol along with a predominance of N-derivatized C6 and C12 glycolaldehyde oligomers, suggesting that GAld is capable of forming brown carbon SOA.

Chemical Composition and Molecular-Specific Optical Properties of Atmospheric Brown Carbon Associated with Biomass Burning.

This study provides molecular insights into the light absorption properties of biomass burning (BB) brown carbon (BrC) through the chemical characterization of tar condensates generated from heated wood pellets at oxidative and pyrolysis conditions. Both liquid tar condensates separated into "darker oily" and "lighter aqueous" immiscible phases. The molecular composition of these samples was investigated using reversed-phase liquid chromatography coupled with a photodiode array detector and a high-resolution mass spectrometer. The results revealed two sets of BrC chromophores: (1) common to all four samples and (2) specific to the "oily" fractions. The common BrC chromophores consist of polar, monoaromatic species. The oil-specific BrC chromophores include less-polar and nonpolar polyaromatic compounds. The most-light-absorbing pyrolysis oily phase (PO) was aerosolized and size-separated using a cascade impactor to compare the composition and optical properties of the bulk versus the aerosolized BrC. The mass absorption coefficient (MAC300-500 nm) of aerosolized PO increased compared to that of the bulk, due to gas-phase partitioning of more volatile and less absorbing chromophores. The optical properties of the aerosolized PO were consistent with previously reported ambient BB BrC measurements. These results suggest the darkening of atmospheric BrC following non-reactive evaporation that transforms the optical properties and composition of aged BrC aerosols.

Photosensitized Reactions of a Phenolic Carbonyl from Wood Combustion in the Aqueous Phase-Chemical Evolution and Light Absorption Properties of AqSOA.

Guaiacyl acetone (GA) is a phenolic carbonyl emitted in significant quantities by wood combustion that undergoes rapid aqueous-phase oxidation to produce aqueous secondary organic aerosol (aqSOA). We investigate the photosensitized oxidation of GA by an organic triplet excited state (3C*) and the formation and aging of the resulting aqSOA in wood smoke-influenced fog/cloud water. The chemical transformations of the aqSOA were characterized in situ using a high-resolution time-of-flight aerosol mass spectrometer. Additionally, aqSOA samples collected over different time periods were analyzed using high-performance liquid chromatography coupled with a photodiode array detector and a high-resolution Orbitrap mass spectrometer (HPLC-PDA-HRMS) to provide details on the molecular composition and optical properties of brown carbon (BrC) chromophores. Our results show efficient formation of aqSOA from GA, with an average mass yield around 80%. The composition and BrC properties of the aqSOA changed significantly over the course of reaction. Three generations of aqSOA products were identified via positive matrix factorization analysis of the aerosol mass spectrometry data. Oligomerization and functionalization dominated the production of the first-generation aqSOA, whereas fragmentation and ring-opening reactions controlled the formation of more oxidized second- and third-generation products. Significant formation of BrC was observed in the early stages of the photoreaction, while organic acids were produced throughout the experiment. High-molecular weight molecules (m/z > 180) with high aromaticity were identified via HPLC-PDA-HRMS and were found to account for a majority of the UV-vis absorption of the aqSOA.

Optical Properties of Secondary Organic Aerosol Produced by Nitrate Radical Oxidation of Biogenic Volatile Organic Compounds.

Nighttime oxidation of biogenic volatile organic compounds (BVOCs) by nitrate radicals (NO3·) represents one of the most important interactions between anthropogenic and natural emissions, leading to substantial secondary organic aerosol (SOA) formation. The direct climatic effect of such SOA cannot be quantified because its optical properties and atmospheric fate are poorly understood. In this study, we generated SOA from the NO3· oxidation of a series BVOCs including isoprene, monoterpenes, and sesquiterpenes. The SOA were subjected to comprehensive online and offline chemical composition analysis using high-resolution mass spectrometry and optical properties measurements using a novel broadband (315-650 nm) cavity-enhanced spectrometer, which covers the wavelength range needed to understand the potential contribution of the SOA to direct radiative forcing. The SOA contained a significant fraction of oxygenated organic nitrates (ONs), consisting of monomers and oligomers that are responsible for the detected light absorption in the 315-400 nm range. The SOA created from ß-pinene and α-humulene was further photochemically aged in an oxidation flow reactor. The SOA has an atmospheric photochemical bleaching lifetime of >6.2 h, indicating that some of the ONs in the SOA may serve as atmosphere-stable nitrogen oxide sinks or reservoirs and will absorb and scatter incoming solar radiation during the daytime.

Chemical Imaging of Atmospheric Particles.

Airborne particles are very dynamic and highly reactive components of the Earth's atmosphere. Their high surface area and water content provide a unique reaction environment for multiphase chemistry that continually modifies particle composition and properties that consequently impact air quality as well as concentrations of gas-phase species. By absorbing and scattering solar and terrestrial radiation, particles directly influence the planet's radiative balance. Their indirect effects include modifying the nucleation, lifetime, and physical properties of clouds. Due to the sensitivity of the atmospheric environment to all these variables, fundamental studies of chemical transformations of atmospheric particles, their sources, continuously evolving composition, and physical properties are of highest research priority. Accurate descriptions of particles and their effects in the atmosphere require comprehensive information not only on the particle-type populations and their size distributions and concentrations, but also on the diversity and the spatial heterogeneity of chemical components within individual particles. Developments and applications of modern chemical imaging approaches for off-line characterization of atmospheric particles have been at the forefront of modern experimental studies and have resulted in a transformative impact in atmospheric chemistry and physics. This Account presents a synopsis of recent advances in chemical imaging of atmospheric particles collected on substrates during field and laboratory experiments. The unique advantage of chemical imaging methods is that they simultaneously provide two analytical measurements: imaging of particles to assess variability in their individual sizes and morphology, as well as particle-specific speciation of their composition and spatial heterogeneity of different chemical components within individual particles. We also highlight analytical chemistry approaches that enable chemical imaging of particles with different levels of elemental and molecular specificity, including applications of multimodal methodologies where the same or similar groups of particles are probed by two or more complementary techniques. These approaches provide unique experimental insights on the nature and sources of particles, understanding their physical properties, atmospheric reactivity, and transformations. Chemical imaging data provide unique experimental input for atmospheric models that simulate aging and changes in particle-type populations, internal composition, and their associated optical and cloud forming properties. We highlight applications of chemical imaging in selected recent studies, discuss their existing limitations, and forecast future research directions for this area.

Laboratory Insights into the Diel Cycle of Optical and Chemical Transformations of Biomass Burning Brown Carbon Aerosols.

Transformations of biomass burning brown carbon aerosols (BB-BrC) over their diurnal lifecycle are currently not well studied. In this study, the aging of BB tar proxy aerosols processed by NO3• under dark conditions followed by the photochemical OH• reaction and photolysis were investigated in tandem flow reactors. The results show that O3 oxidation in the dark diminishes light absorption of wood tar aerosols, resulting in higher particle single-scattering albedo (SSA). NO3• reactions augment the mass absorption coefficient (MAC) of the aerosols by a factor of 2-3 by forming secondary chromophores, such as nitroaromatic compounds (NACs) and organonitrates. Subsequent OH• oxidation and direct photolysis both decompose the organic nitrates (ONs, representing bulk functionalities of NACs and organonitrates) in the NO3•-aged wood tar aerosols, thus decreasing particle absorption. Moreover, NACs degrade faster than organonitrates by photochemical aging. The NO3•-aged wood tar aerosols are more susceptible to photolysis than to OH• reactions. The photolysis lifetimes for the ONs and for the absorbance of the NO3•-aged aerosols are on the order of hours under typical solar irradiation, while the absorption and ON lifetimes toward OH• oxidation are substantially longer. Overall, nighttime aging via NO3• reactions increases the light absorption of wood tar aerosols and shortens their absorption lifetime under daytime conditions.

Particle-Phase Diffusion Modulates Partitioning of Semivolatile Organic Compounds to Aged Secondary Organic Aerosol.

The diffusivity of semivolatile organic compounds (SVOCs) in the bulk particle phase of a viscous atmospheric secondary organic aerosol (SOA) can have a profound impact on aerosol growth and size distribution dynamics. Here, we investigate the bulk diffusivity of SVOCs formed from photo-oxidation of isoprene as they partition to a bimodal aerosol consisting of an Aitken (potassium sulfate) and accumulation mode (aged α-pinene SOA) particles as a function of relative humidity (RH). The model analysis of the observed size distribution evolution shows that liquid-like diffusion coefficient values of Db > 10-10 cm2 s-1 fail to explain the growth of the Aitken mode. Instead, much lower values of Db between 2.5 × 10-15 cm2 s-1 at 32% RH and 8 × 10-15 cm2 s-1 at 82% RH were needed to successfully reproduce the growth of both modes. The diffusivity within the aged α-pinene SOA remains appreciably slow even at 80% RH, resulting in hindered partitioning of SVOCs to large viscous particles and allowing smaller and relatively less viscous particles to effectively absorb the available SVOCs and grow much faster than would be possible otherwise. These results have important implications for modeling SOA formation and growth in the ambient atmosphere.

Formation of Secondary Brown Carbon in Biomass Burning Aerosol Proxies through NO3 Radical Reactions.

Atmospheric brown carbon (BrC) is an important contributor to the radiative forcing of climate by organic aerosols. Because of the molecular diversity of BrC compounds and their dynamic transformations, it is challenging to predictively understand BrC optical properties. OH radical and O3 reactions, together with photolysis, lead to diminished light absorption and lower warming effects of biomass burning BrC. The effects of night-time aging on the optical properties of BrC aerosols are less known. To address this knowledge gap, night-time NO3 radical chemistry with tar aerosols from wood pyrolysis was investigated in a flow reactor. This study shows that the optical properties of BrC change because of transformations driven by reactions with the NO3 radical that form new absorbing species and lead to significant absorption enhancement over the ultraviolet-visible (UV-vis) range. The overnight aging increases the mass absorption coefficients of the BrC by a factor of 1.3-3.2 between 380 nm and 650 nm. Nitrated organic compounds, particularly nitroaromatics, were identified as the main products that contribute to the enhanced light absorption in the secondary BrC. Night-time aging of BrC aerosols represents an important source of secondary BrC and can have a pronounced effect on atmospheric chemistry and air pollution.

Comprehensive Molecular Characterization of Atmospheric Brown Carbon by High Resolution Mass Spectrometry with Electrospray and Atmospheric Pressure Photoionization.

Light-absorbing components of atmospheric organic aerosols, which are collectively termed "brown carbon" (BrC), are ubiquitous in the atmosphere. They affect absorption of solar radiation by aerosols in the atmosphere and human health as some of them have been identified as potential toxins. Understanding the sources, formation, atmospheric evolution, and environmental effects of BrC requires molecular identification and characterization of light-absorption properties of BrC chromophores. Identification of BrC components is challenging due to the complexity of atmospheric aerosols. In this study, we employ two complementary ionization techniques, atmospheric pressure photo ionization (APPI) and electrospray ionization (ESI), to obtain broad coverage of both polar and nonpolar BrC components using high-resolution mass spectrometry (HRMS). These techniques are combined with chromatographic separation of BrC compounds with high performance liquid chromatography (HPLC), characterization of their light absorption with a photodiode array (PDA) detector, and chemical composition with HRMS. We demonstrate that this approach enables more comprehensive characterization of BrC in biomass burning organic aerosols (BBOAs) emitted from test burns of sage brush biofuel. In particular, we found that nonpolar BrC chromophores such as PAHs are only detected using positive mode APPI. Meanwhile, negative mode ESI results in detection of polar compounds such as nitroaromatics, aromatic acids, and phenols. For the BrC material examined in this study, over 40% of the solvent-extractable BrC light absorption is attributed to water insoluble, nonpolar to semipolar compounds such as PAHs and their derivatives, which require APPI for their identification. In contrast, the polar, water-soluble BrC compounds, which are detected in ESI, account for less than 30% of light absorption by BrC.

Heating-Induced Transformations of Atmospheric Particles: Environmental Transmission Electron Microscopy Study.

Environmental transmission electron microscopy was employed to probe transformations in the size, morphology, and composition of individual atmospheric particles as a function of temperature. Two different heating devices were used and calibrated in this work: a furnace heater and a Micro Electro Mechanical System heater. The temperature calibration used sublimation temperatures of NaCl, glucose, and ammonium sulfate particles, and the melting temperature of tin. Volatilization of Suwanee River Fulvic Acid was further used to validate the calibration up to 800 °C. The calibrated furnace holder was used to examine both laboratory-generated secondary organic aerosol particles and field-collected atmospheric particles. Chemical analysis by scanning transmission X-ray microscopy and near-edge fine-structure spectroscopy of the organic particles at different heating steps showed that above 300 °C particle volatilization was accompanied by charring. These methods were then applied to ambient particles collected in the central Amazon region. Distinct categories of particles differed in their volatilization response to heating. Spherical, more-viscous particles lost less volume during heating than particles that spread on the imaging substrate during impaction, due to either being liquid upon impaction or lower viscosity. This methodology illustrates a new analytical approach to accurately measure the volume fraction remaining for individually tracked atmospheric particles at elevated temperatures.

Aerosol Emissions from Great Lakes Harmful Algal Blooms.

In freshwater lakes, harmful algal blooms (HABs) of Cyanobacteria (blue-green algae) produce toxins that impact human health. However, little is known about the lake spray aerosol (LSA) produced from wave-breaking in freshwater HABs. In this study, LSA were produced in the laboratory from freshwater samples collected from Lake Michigan and Lake Erie during HAB and nonbloom conditions. The incorporation of biological material within the individual HAB-influenced LSA particles was examined by single-particle mass spectrometry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and fluorescence microscopy. Freshwater with higher blue-green algae content produced higher number fractions of individual LSA particles that contained biological material, showing that organic molecules of biological origin are incorporated in LSA from HABs. The number fraction of individual LSA particles containing biological material also increased with particle diameter (greater than 0.5 µm), a size dependence that is consistent with previous studies of sea spray aerosol impacted by phytoplankton blooms. Similar to sea spray aerosol, organic carbon markers were most frequently observed in individual LSA particles less than 0.5 µm in diameter. Understanding the transfer of biological material from freshwater to the atmosphere via LSA is crucial for determining health and climate effects of HABs.

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol.

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. Here, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.