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Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO₃-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO₃ radical, the difficulty of characterizing the spatial distributions of BVOC and NO₃ within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO₃-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO₃-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

 

Atmospheric organic aerosols play a major role in climate, demanding a better understanding of their formation mechanisms by contributing multiphase chemical reactions with the participation of water. The sunlight driven aqueous photochemistry of small 2-oxocarboxylic acids is a potential major source of organic aerosol, which prompted the investigations into the mechanisms of glyoxylic acid and pyruvic acid photochemistry reviewed here. While 2-oxocarboxylic acids can be contained or directly created in the particles, the majorities of these abundant and available molecules are in the gas phase and must first undergo the surface uptake process to react in, and on the surface, of aqueous particles. Thus, the work also reviews the acid-base reaction that occurs when gaseous pyruvic acid meets the interface of aqueous microdroplets, which is contrasted with the same process for acetic acid. This work classifies relevant information needed to understand the photochemistry of aqueous pyruvic acid and glyoxylic acid and motivates future studies based on reports that use novel strategies and methodologies to advance this field. 

The structure of zymonic acid (systematic name: 4-hydroxy-2-methyl-5-oxo-2,5-dihydrofuran-2-carboxylic acid), C 6 H 6 O 5 , which had previously eluded crystallographic determination, is presented here for the first time. It forms by intramolecular condensation of parapyruvic acid, which is the product of aldol condensation of pyruvic acid. A redetermination of the crystal structure of pyruvic acid (systematic name: 2-oxopropanoic acid), C 3 H 4 O 3 , at low temperature (90 K) and with increased precision, is also presented [for the previous structure, see: Harata et al. (1977). Acta Cryst. B 33 , 210–212]. In zymonic acid, the hydroxylactone ring is close to planar (r.m.s. deviation = 0.0108 Å) and the dihedral angle between the ring and the plane formed by the bonds of the methyl and carboxylic acid carbon atoms to the ring is 88.68 (7)°. The torsion angle of the carboxylic acid group relative to the ring is 12.04 (16)°. The pyruvic acid molecule is almost planar, having a dihedral angle between the carboxylic acid and methyl-ketone groups of 3.95 (6)°. Intermolecular interactions in both crystal structures are dominated by hydrogen bonding. The common R 2 2 (8) hydrogen-bonding motif links carboxylic acid groups on adjacent molecules in both structures. In zymonic acid, this results in dimers about a crystallographic twofold of space group C 2/ c , which forces the carboxylic acid group to be disordered exactly 50:50, which scrambles the carbonyl and hydroxyl groups and gives an apparent equalization of the C—O bond lengths [1.2568 (16) and 1.2602 (16) Å]. The other hydrogen bonds in zymonic acid (O—H...O and weak C—H...O), link molecules across a 2 1 -screw axis, and generate an R 2 2 (9) motif. These hydrogen-bonding interactions propagate to form extended pleated sheets in the ab plane. Stacking of these zigzag sheets along c involves only van der Waals contacts. In pyruvic acid, inversion-related molecules are linked into R 2 2 (8) dimers, with van der Waals interactions between dimers as the only other intermolecular contacts. 

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O2(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O2(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. In addition, the rate of O2(aq) consumption is studied at air flow rates from 30.0 to 900.0 mL min−1. For the range of [PA]0 covered under air saturated conditions and 30 mL min−1 flow of air in this setup, the estimated half-lives of O2(aq) consumed by the photolytic radicalsfall within the interval from 22 to 3 min. Therefore, the corresponding depths of penetration of O2(g) into water (x = 4.3 and 1.6 µm) are determined, suggesting that accumulation and small coarse mode aqueous particles should not be O2-depleted in the presence of sunlight photons impinging this kind of chromophore. These photochemical results are of major tropospheric relevance for understanding the formation and growth of secondary organic aerosol. 

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic light. In this regard, an astonishing number of recent research articles include claims of highly efficient (photo)catalysts or similar terms about materials with superior or enhanced efficiency for a given reaction without proper experimental support. Consequently, the comparison of the efficiencies of photocatalysts may result as being meaningless, especially when reports are only based on expressions determining (1) a reaction rate per weight of catalyst or its surface area, (2) quantum efficiencies or quantum yields, and (3) turnover frequencies or turnover numbers. Herein, we summarize the standards needed for reporting valuable data in photocatalysis and highlight some common discrepancies found in the literature. This work should inform researchers interested in reporting photocatalysis projects about the correct procedures for collecting experimental data and properly characterizing the materials by providing examples and key supporting literature. 

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. The resulting complex mixture of organic aerosol has variable physical and chemical properties that contribute further to the uncertainty of these species modifying the radiative budget. Correlations between oxidative processing and increased absorptivity, hygroscopicity, and cloud condensation nuclei activity have been observed, but the mechanisms behind these phenomena have remained unexplored. Herein, we review environmentally relevant heterogeneous mechanisms occurring on interfaces that contribute to the processing of aerosols. Recent laboratory studies exploring processes at the aerosol–air interface are highlighted as capable of generating the complexity observed in the environment. Furthermore, a variety of laboratory methods developed specifically to study these processes under environmentally relevant conditions are introduced. Remarkably, the heterogeneous mechanisms presented might neither be feasible in the gas phase nor in the bulk particle phase of aerosols at the fast rates enabled on interfaces. In conclusion, these surface mechanisms are important to better understand how organic aerosols are transformed in the atmosphere affecting the environment.