Molecular investigation of the multi-phase photochemistry of Fe(III)-citrate in aqueous solution.

Iron (Fe) is ubiquitous in nature and found as FeII or FeIII in minerals or as dissolved ions Fe2+ or Fe3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of FeIII into natural aquatic systems, organic carboxylic acids efficiently chelate FeIII to form [FeIII-carboxylate]2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of FeIII-carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of FeIII-citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of (φ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe3+-citrates (aq) were expressed as two generalized consecutive reactions of with the experimental rate constants of j1 ∼ 0.12 min-1 and j2 ∼ 0.05 min-1, respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe-organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe-carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of FeIII-citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments.

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.

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.

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.

Response of the Aerodyne Aerosol Mass Spectrometer to Inorganic Sulfates and Organosulfur Compounds: Applications in Field and Laboratory Measurements.

Organosulfur compounds are important components of secondary organic aerosols (SOA). While the Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) has been extensively used in aerosol studies, the response of the AMS to organosulfur compounds is not well-understood. Here, we investigated the fragmentation patterns of organosulfurs and inorganic sulfates in the AMS, developed a method to deconvolve total sulfate into components of inorganic and organic origins, and applied this method in both laboratory and field measurements. Apportionment results from laboratory isoprene photooxidation experiment showed that with inorganic sulfate seed, sulfate functionality of organic origins can contribute ∼7% of SOA mass at peak growth. Results from measurements in the Southeastern U.S. showed that 4% of measured sulfate is from organosulfur compounds. Methanesulfonic acid was estimated for measurements in the coastal and remote marine boundary layer. We explored the application of this method to unit mass-resolution data, where it performed less well due to interferences. Our apportionment results demonstrate that organosulfur compounds could be a non-negligible source of sulfate fragments in AMS laboratory and field data sets. A reevaluation of previous AMS measurements over the full range of atmospheric conditions using this method could provide a global estimate/constraint on the contribution of organosulfur compounds.

Water Uptake and Hygroscopic Growth of Organosulfate Aerosol.

Organosulfates (OS) are important components of secondary organic aerosol (SOA) that have been identified in numerous field studies. This class of compounds within SOA can potentially affect aerosol physicochemical properties such as hygroscopicity because of their polar and hydrophilic nature as well as their low volatility. Currently, there is a dearth of information on how aerosol particles that contain OS interact with water vapor in the atmosphere. Herein we report a laboratory investigation on the hygroscopic properties of a structurally diverse set of OS salts at varying relative humidity (RH) using a Hygroscopicity-Tandem Differential Mobility Analyzer (H-TDMA). The OS studied include the potassium salts of glycolic acid sulfate, hydroxyacetone sulfate, 4-hydroxy-2,3-epoxybutane sulfate, and 2-butenediol sulfate and the sodium salts of benzyl sulfate, methyl sulfate, ethyl sulfate, and propyl sulfate. In addition, mixtures of OS and sodium chloride were also studied. The results showed gradual deliquescence of these aerosol particles characterized by continuous uptake and evaporation of water in both hydration and dehydration processes for the OS, while the mixture showed prompt deliquescence and effloresce transitions, albeit at a lower relative humidity relative to pure sodium chloride. Hygroscopic growth of these OS at 85% RH were also fit to parameterized functional forms. This new information provided here has important implications about the atmospheric lifetime, light scattering properties, and the role of OS in cloud formation. Moreover, results of these studies can ultimately serve as a basis for the development and evaluation of thermodynamic models for these compounds in order to consider their impact on the atmosphere.