M. M. Galloway

Glyoxal in Aqueous Ammonium Sulfate Solutions: Products, Kinetics and Hydration Effects

Reactions and interactions between glyoxal and salts in aqueous solution were studied. Glyoxal was found to react with ammonium to form imidazole, imidazole-2-carboxaldehyde, formic acid, N-glyoxal substituted imidazole, and minor products at very low concentrations. Overall reaction orders and rates for each major product were measured. Sulfate ions have a strong and specific interaction with glyoxal in aqueous solution, which shifts the hydration equilibria of glyoxal from the unhydrated carbonyl form to the hydrated form. This ion-specific effect contributes to the observed enhancement of the effective Henrys law coefficient for glyoxal in sulfate-containing solutions. The results of UV-vis absorption and NMR spectroscopy studies of solutions of glyoxal with ammonium, methylamine, and dimethylamine salts reveal that light absorbing compounds require the formation of nitrogen containing molecules. These findings have implications on the role of glyoxal in the atmosphere, both in models of the contribution of glyoxal to form secondary organic aerosol (SOA), the role of nitrogen containing species for aerosol optical properties and in predictions of the behavior of other carbonyls or dicarbonyls in the atmosphere.

Brown Carbon Formation by Aqueous-Phase Carbonyl Compound Reactions with Amines and Ammonium Sulfate

Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon.

Characterization of Vapor Wall Loss in Laboratory Chambers

Laboratory chambers used to study atmospheric chemistry and aerosol formation are subject to wall loss of vapors and particles that must be accounted for in calculating aerosol yields. While particle wall loss in chambers is relatively well-understood and routinely accounted for, that of vapor is less so. Here we address experimental measurement and modeling of vapor losses in environmental chambers. We identify two compounds that exhibit wall loss: 2,3-epoxy-1,4-butanediol (BEPOX), an analog of an important isoprene oxidation product; and glyoxal, a common volatile organic compound oxidation product. Dilution experiments show that BEPOX wall loss is irreversible on short time scales but is reversible on long time scales, and glyoxal wall loss is reversible for all time scales. BEPOX exhibits minimal uptake onto clean chamber walls under dry conditions, with increasing rates of uptake over the life of an in-use chamber. By performing periodic BEPOX wall loss experiments, it is possible to assess quantitatively the aging of chamber walls.

Hydroxycarboxylic Acid-Derived Organosulfates: Synthesis, Stability, and Quantification in Ambient Aerosol

Organosulfates have been proposed as contributors to aerosol growth and have been detected in both chamber and atmospheric aerosol samples. We present a simple method for the synthesis of quantitative analytical standards of two small hydroxycarboxylic acid-derived organosulfates, glycolic and lactic acid sulfate. Additionally, we discuss the stability of hydroxycarboxylic acid-derived organosulfates and their previously proposed sulfate hemiacetal isomers in commonly used solvents for filter extraction. The hydroxycarboxylic acid-derived organosulfates were found to be stable under acidic conditions comparable to those found in ambient aerosol. By using synthesized standards, quantitative organosulfate concentrations were measured from ambient particulate matter (PM(2.5)) collected in urban locations in the United States, Mexico City, and Pakistan. Lactic acid sulfate and glycolic acid sulfate concentrations ranged 0.4-3.8 ng/m(3) and 1.9-11.3 ng/m(3), respectively. We propose that glycolic acid sulfate represents an important tracer for atmospheric processes that form organosulfates in ambient particulate matter.

Analysis of photochemical and dark glyoxal uptake: Implications for SOA formation

The dependence of glyoxal uptake onto deliquesced ammonium sulfate seed aerosol was studied under photochemical (light + hydroxyl radical (OH)) and dark conditions. In this study, the chemical composition of aerosol formed from glyoxal is identical in the presence or absence of OH. In addition, there was no observed OH dependence on either glyoxal uptake or glyoxal-driven aerosol growth for this study. These findings demonstrate that, for the system used here, glyoxal uptake is not affected by the presence of OH. In combination with previous studies, this shows that the exact nature of the type of seed aerosol, in particular the presence of a coating, has a large influence on fast photochemical uptake of glyoxal. Due to the challenge of relating this seed aerosol dependence to ambient conditions, this work highlights the resulting difficulty in quantitatively including SOA formation from glyoxal in models.

Secondary organic aerosol formation during evaporation of droplets containing atmospheric aldehydes, amines, and ammonium sulfate.

Reactions of carbonyl compounds in cloudwater produce organic aerosol mass through in-cloud oxidation and during postcloud evaporation. In this work, postcloud evaporation was simulated in laboratory experiments on evaporating droplets that contain mixtures of common atmospheric aldehydes with ammonium sulfate (AS), methylamine, or glycine. Aerosol diameters were measured during monodisperse droplet drying experiments and during polydisperse droplet equilibration experiments at 75% relative humidity, and condensed-phase mass was measured in bulk thermogravimetric experiments. The evaporation of water from a droplet was found to trigger aldehyde reactions that increased residual particle volumes by a similar extent in room-temperature experiments, regardless of whether AS, methylamine, or glycine was present. The production of organic aerosol volume was highest from droplets containing glyoxal, followed by similar production from methylglyoxal or hydroxyacetone. Significant organic aerosol production was observed for glycolaldehyde, acetaldehyde, and formaldehyde only at elevated temperatures in thermogravimetric experiments. In many experiments, the amount of aerosol produced was greater than the sum of all solutes plus nonvolatile solvent impurities, indicating the additional presence of trapped water, likely caused by increasing aerosol-phase viscosity due to oligomer formation.

Glycolaldehyde Monomer and Oligomer Equilibria in Aqueous Solution: Comparing Computational Chemistry and NMR Data

A computational protocol utilizing density functional theory calculations, including Poisson-Boltzmann implicit solvent and free energy corrections, is applied to study the thermodynamic and kinetic energy landscape of glycolaldehyde in solution. Comparison is made to NMR measurements of dissolved glycolaldehyde, where the initial dimeric ring structure interconverts among several species before reaching equilibrium where the hydrated monomer is dominant. There is good agreement between computation and experiment for the concentrations of all species in solution at equilibrium, that is, the calculated relative free energies represent the system well. There is also relatively good agreement between the calculated activation barriers and the estimated rate constants for the hydration reaction. The computational approach also predicted that two of the trimers would have a small but appreciable equilibrium concentration (>0.005 M), and this was confirmed by NMR measurements. Our results suggest that while our computational protocol is reasonable and may be applied to quickly map the energy landscape of more complex reactions, knowledge of the caveats and potential errors in this approach need to be taken into account.

Formation of semisolid, oligomerized aqueous SOA: lab simulations of cloud processing.

Glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone form N-containing and oligomeric compounds during simulated cloud processing with small amines. Using a novel hygroscopicity tandem differential mobility analysis (HTDMA) system that allows varied humidification times, the hygroscopic growth (HG) of each of the resulting products of simulated cloud processing was measured. Continuous water uptake (gradual deliquescence) was observed beginning at ∼ 40% RH for all aldehyde-methylamine products. Particles containing ionic reaction products of either glyoxal or glycine were most hygroscopic, with HG between 1.16 and 1.20 at 80% RH. Longer humidification times (up to 20 min) produced an increase in growth factors for glyoxal-methylamine (19% by vol) and methylglyoxal-methylamine (8% by vol) aerosol, indicating that unusually long equilibration times can be required for HTDMA measurements of such particles. Glyoxal- and methylglyoxal-methylamine aerosol particles shattered in Raman microscopy impact-flow experiments, revealing that the particles were semisolid. Similar experiments on glycolaldehyde- and hydroxyacetone-methylamine aerosol found that the aerosol particles were liquid when dried for <1 h, but semisolid when dried for 20 h under ambient conditions. The RH required for flow (liquification) during humidification experiments followed the order methylglyoxal > glyoxal > glycolaldehyde = hydroxyacetone, likely caused by the speed of oligomer formation in each system.

Free Energy Map for the Co-Oligomerization of Formaldehyde and Ammonia

Density functional theory calculations, including Poisson-Boltzmann implicit solvent and free energy corrections, are applied to construct a free energy map of formaldehyde and ammonia co-oligomerization in aqueous solution at pH 7. The stepwise route to forming hexamethylenetetramine (HMTA), the one clearly identified major product in a complex mixture, involves a series of addition reactions of formaldehyde and ammonia coupled with dehydration and cyclization reactions at key steps in the pathway. The free energy map also allows us to propose the possible identity of some major peaks observed by mass spectroscopy in the reaction mixture being the result of stable species not along the pathway to HMTA, in particular those formed by intramolecular condensation of hydroxyl groups to form six-membered rings with ether linkages. Our study complements a baseline free energy map previously worked out for the self-oligomerization of formaldehyde in solution at pH 7 using the same computational protocol and published in this journal (J. Phys. Chem. A 2013, 117, 12658).

Maillard Chemistry in Clouds and Aqueous Aerosol As a Source of Atmospheric Humic-Like Substances.

The reported optical, physical, and chemical properties of aqueous Maillard reaction mixtures of small aldehydes (glyoxal, methylglyoxal, and glycolaldehyde) with ammonium sulfate and amines are compared with those of aqueous extracts of ambient aerosol (water-soluble organic carbon, WSOC) and the humic-like substances (HULIS) fraction of WSOC. Using a combination of new and previously published measurements, we examine fluorescence, X-ray absorbance, UV/vis, and IR spectra, complex refractive indices, (1)H and (13)C NMR spectra, thermograms, aerosol and electrospray ionization mass spectra, surface activity, and hygroscopicity. Atmospheric WSOC and HULIS encompass a range of properties, but in almost every case aqueous aldehyde-amine reaction mixtures are squarely within this range. Notable exceptions are the higher UV/visible absorbance wavelength dependence (Angström coefficients) observed for methylglyoxal reaction mixtures, the lack of surface activity of glyoxal reaction mixtures, and the higher N/C ratios of aldehyde-amine reaction products relative to atmospheric WSOC and HULIS extracts. The overall optical, physical, and chemical similarities are consistent with, but not demonstrative of, Maillard chemistry being a significant secondary source of atmospheric HULIS. However, the higher N/C ratios of aldehyde-amine reaction products limits the source strength to ≤50% of atmospheric HULIS, assuming that other sources of HULIS incorporate only negligible quantities of nitrogen.