Brown Carbon from Photo-Oxidation of Glyoxal and SO2 in Aqueous Aerosol

Aqueous-phase dark reactions during the co-oxidation of glyoxal and S(IV) were recently identified as a potential source of brown carbon (BrC). Here, we explore the effects of sunlight and oxidants on aqueous solutions of glyoxal and S(IV), and on aqueous aerosol exposed to glyoxal and SO2. We find that BrC is able to form in sunlit, bulk-phase, sulfite-containing solutions, albeit more slowly than in the dark. In more atmospherically relevant chamber experiments where suspended aqueous aerosol particles are exposed to gas-phase glyoxal and SO2, the formation of detectable amounts of BrC requires an OH radical source and occurs most rapidly after a cloud event. From these observations we infer that this photobrowning is caused by radical-initiated reactions as evaporation concentrates aqueous-phase reactants and aerosol viscosity increases. Positive-mode electrospray ionization mass spectrometric analysis of aerosol-phase products reveals a large number of CxHyOz oligomers that are reduced rather than oxidized (relative to glyoxal), with the degree of reduction increasing in the presence of OH radicals. This again suggests a radical-initiated redox mechanism where photolytically produced aqueous radical species trigger S(IV)–O2 auto-oxidation chain reactions, and glyoxal-S(IV) redox reactions especially if aerosol-phase O2 is depleted. This process may contribute to daytime BrC production and aqueous-phase sulfur oxidation in the atmosphere. The BrC produced, however, is about an order of magnitude less light-absorbing than wood smoke BrC at 365 nm

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

Complex refractive index and single scattering albedo of Icelandic dust in the shortwave part of the spectrum

Icelandic dust can impact the radiative budget in high-latitude regions directly by affecting light absorption and scattering and indirectly by changing the surface albedo after dust deposition. This tends to produce a positive radiative forcing. However, the limited knowledge of the spectral optical properties of Icelandic dust prevents an accurate assessment of these radiative effects. Here, the spectral single scattering albedo (SSA) and the complex refractive index (m=n-ik) of Icelandic dust from five major emission hotspots were retrieved between 370–950 nm using online measurements of size distribution and spectral absorption (βabs) and scattering (βsca) coefficients of particles suspended in a large-scale atmospheric simulation chamber. The SSA(λ) estimated from the measured βabs and βsca increased from 0.90–0.94 at 370 nm to 0.94–0.96 at 950 nm in Icelandic dust from the different hotspots, which falls within the range of mineral dust from northern Africa and eastern Asia. The spectral complex refractive index was retrieved by minimizing the differences between the measured βabs and βsca and those computed using the Mie theory for spherical and internally homogeneous particles, using the size distribution data as input. The real part of the complex refractive index (n(λ)) was found to be 1.60–1.61 in the different samples and be independent of wavelength. The imaginary part (k(λ)) was almost constant with wavelength and was found to be around 0.004 at 370 nm and 0.002–0.003 at 950 nm. The estimated complex refractive index was close to the initial estimates based on the mineralogical composition, also suggesting that the high magnetite content observed in Icelandic dust may contribute to its high absorption capacity in the shortwave part of the spectrum. The k(λ) values retrieved for Icelandic dust are at the upper end of the reported range for low-latitude dust (e.g., from the Sahel). Furthermore, Icelandic dust tends to be more absorbing towards the near-infrared. In Icelandic dust, k(λ) between 660–950 nm was 2–8 times higher than most of the dust samples sourced in northern Africa and eastern Asia. This suggests that Icelandic dust may have a stronger positive direct radiative forcing on climate that has not been accounted for in climate predictions.</p

Development of a parallel sampling and analysis method for the elucidation of gas/particle partitioning of oxygenated semi-volatile organics : a limonene ozonolysis study

International audienceGas/particle partitioning behaviour of secondary organic matter semi-volatile fraction and the associated multiphase chemistry are key features to accurately evaluate secondary organic aerosol climate and health impacts. However, today, oxygenated secondary species partitioning is rarely assessed in experimental SOA studies and SOA modelling is still largely based on estimated partitioning data. This paper describes a new analytical approach, solvent free and easy to use, to explore the chemical composition of the secondary organic matter at a molecular scale in both gas and particulate phases. The method is based on thermal-desorption (TD) of gas and particulate samples, coupled with gas chromatography (GC) and mass spectrometry (MS), with on sampling supports derivatisation processes. Gaseous compounds are trapped on PFBHA or MTBSTFA pre-coated Tenax TA adsorbent tubes. Particulate samples are collected onto quartz or Teflon-quartz filters and subsequently exposed to PFBHA or MTBSTFA derivatisation reagents before TD-GC-MS analysis. Method development and validation are presented from an atmospherically relevant range of organic acids and carbonyl and hydroxyl compounds. Method application to a limonene ozonolysis experiment conducted in the EUPHORE simulation chamber under close-to-real conditions of low concentrations and relative humidity provides an overview of the method abilities. 25 compounds have been positively or tentatively identified, 9 being in both gaseous and particulate phases and 11, among them tri carboxylic acids, hydroxyl dicarboxylic acids and oxodicarboxylic acids, being detected for the first time

Atmospheric Fate of a Series of Carbonyl Nitrates: Photolysis Frequencies and OH-Oxidation Rate Constants

Multifunctional organic nitrates are potential NO_<i>x</i> reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: <i>k</i>_OH = (6.7 ± 2.5) × 10^–13 cm³ molecule^–1 s^–1 for α-nitrooxyacetone, (10.6 ± 4.1) × 10^–13 cm³ molecule^–1 s^–1 for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10^–13 cm³ molecule^–1 s^–1 for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10^–5 s^–1, (5.7 ± 0.3) × 10^–5 s^–1, and (7.4 ± 0.2) × 10^–5 s^–1, respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates