Atmospheric Aqueous Phase Research Articles

OH Radical Oxidation of Organosulfates in the Atmospheric Aqueous Phase.

Organosulfates (OS, ROSO3-), ubiquitous constituents of atmospheric particulate matter (PM), influence both the physicochemical and climatic properties of PM. Although the formation pathways of OS have been extensively researched, only a few studies have investigated the atmospheric fate of this class of compounds. Here, to better understand the reactivity and transformation of OS under cloudwater- and aerosol-relevant conditions, we investigate the hydroxyl radical (OH) oxidation bimolecular rate constants (kOS+OHII) and products of five atmospherically relevant OS as a function of pH and ionic strength: methyl sulfate (MeS), ethyl sulfate (EtS), propyl sulfate (PrS), hydroxyacetone sulfate (HaS) and phenyl sulfate (PhS). Our results show that OS are oxidized by OH with kOS+OHII between 108 - 109 M-1 s-1, which corresponds to atmospheric lifetimes of minutes in aqueous aerosol to days in cloudwater. We find that kOS+OHII increases with carbon chain length (MeS < EtS < PrS) and aromaticity (PrS < PhS), but does not depend on solution pH (2, 9). In addition, we find that whereas the OH reactivity of the aliphatic OS studied here decreases by ∼2× with increasing ionic strength (0-15 M), the reactivity of PhS decreases by ∼10×. The oxidation of EtS and PrS produced organic peroxides (ROOH) as first-generation oxidation products, which subsequently photolyzed; the oxidation of PhS resulted in hydroxylated aromatic products. These results highlight the need for inclusion of OS loss pathways in atmospheric models, and suggest caution in using ambient OS concentration measurements alone to estimate their production rates.

Deciphering the key drivers of oxidative potential during ammonium nitrate-mediated aqueous-phase photoreaction of methoxyphenols

Methoxyphenols are released in abundance from lignin pyrolysis during biomass burning. Apart from being atmospheric brown carbon components that absorb solar radiation and warm the climate, methoxyphenols also undergo photoreaction in the atmospheric aqueous phase and form secondary organic aerosols (aqSOA). While efforts have been devoted to understanding chemical evolutions and climate-related optical properties of aqSOA, their potential health impacts also require timely investigations. Herein, we used the dithiothreitol (DTT) assay to investigate oxidative potential of the aqSOA formed during the 8-hr aqueous-phase photoreaction of two typical methoxyphenols, vanillin and vanillic acid, under pH 2 or 8, and with or without ammonia nitrate. The highest DTT consumption rates (RDTT) were observed for vanillin aqSOA formed in the presence of ammonia nitrate and at pH 8. At pH 2, although RDTT increased rapidly during early photoreaction, it reduced after prolonged illumination. High resolution mass spectrometry and linear regression analyses were performed to correlate the photoreaction products with the observed RDTT. Results showed that three products that present quinone, lactone and dimer structures, respectively, should be the key drivers of elevated RDTT for aqSOA formed during photoreaction of vanillin and vanillic acid alone, whereas it shifted to the nitrogen-containing aromatic compounds during their photoreaction with ammonia nitrate. Our results have revealed the role of nitrogen-containing aromatic compounds in the oxidative potential and health effects of aqSOA from biomass burning, which was rarely recognized before and warrants immediate assessments.

Theoretical investigation on the oxidation mechanism of methylglyoxal in the aqueous phase

The oxidation mechanism of methylglyoxal (CH3COCHO) in the aqueous phase plays a crucial role in the formation of secondary organic aerosols (SOA). To date, the investigations of reaction mechanisms of MG in the aqueous phase still needs to be refined, and the oxidation mechanisms of MG in the existence of various oxidants (e.g., H2O2, O3, ∙NO3, etc.) are in controversy. In this paper, we investigated the hypothesis that small-molecule organic acids are the primary products in cloud water and fog droplets, while large-molecule organic acids and oligomers play crucial roles in wet aerosols. Specifically, the hydration reaction, oxidation mechanism and oligomerization reaction of MG in aqueous phase were investigated on a theoretical basis. It has been indicated that the hydration reaction is a significant initiating reaction of MG in the atmospheric aqueous phase, whose generated hydrated compounds played a critical part in the process of forming oligomers. The aqueous oxidation reaction of MG could form a variety of organic acids, including pyruvic acid, formic acid, acetic acid, and oxalic acid. In the presence of OH radicals, pyruvic acid was the main first-generation production, which undergoes further reactions to form acetic acid, oxalic acid, and mesoxalic acid. Acetic acid was mainly derived from the reaction of OH radicals with pyruvic acid, whereas oxalic and mesoxalic acids were mainly generated by the OH radical reaction for MG and pyruvic acid. Of these, the formation of acetic acid was thermodynamically most favorable. Additionally, the reactions of MG with other oxidants also provided the possible pathways for pyruvic acid production. At 298 K, we calculated the rate constants for the reaction of MGHY with NO3, OH, HO2 radicals, and O3 to be 4.48 × 108, 2.54 × 107, 1.26 × 10−2, and 4.38 × 10−4 M−1 s−1, with atmospheric aqueous phase lifetimes (τ) of 4.43, 3.12 × 103, 2.21 × 1011, and 3.17 × 108 h, respectively. The theoretical results from this work will facilitate the explanation for the MG reaction process in the aqueous phase so as to further correctly estimate the relationship between the aqueous phase chemistry of MG and the formation of SOA.

Predicting reaction rate constants of organic compounds with oxidants in the atmospheric aqueous-phase through multi-task learning

The atmospheric aqueous-phase chemistry has received increasing attention in the last decades for its non-negligible environmental significance. Yet, the insufficient experimental data on oxidative reaction rate constants (kaq) obstructs the further analysis and modeling of this system. Predictive models based on machine learning (ML) algorithms have shown potential as an effective estimation tool, however, they are restricted to the lack of training data as well. To overcome this data limitation, we developed multi-task (MT) models that could exploit the common knowledge from reactions in gas- and aqueous-phases simultaneously. Toward kaq of organic compounds with hydroxyl radical (OH), nitrate radical (NO3), and ozone (O3), the MT models showed a notably better predictive ability compared to benchmark models, while obtaining wide applicability on compounds from different chemical classes. By interpreting the models using Shapley additive explanations (SHAP), we evidenced that the MT models utilized the common knowledge in both phases and correctly identified the reaction mechanisms. This study aims to provide new insight into the estimation of necessary kinetic parameters in atmospheric aqueous-phase chemistry, as well as a reference to ML research for other predictive tasks of atmospheric interest.

Mechanistic insight into the formation of aromatic organosulfates and sulfonates through sulfoxy-radical-initiated reactions in the atmospheric aqueous phase

Despite monocyclic aromatic organosulfates (OSs) and sulfonates have been ubiquitously detected in aerosols, their formation processes need to be further analyzed. Monocyclic aromatic hydrocarbon reactions with sulfoxy radical are considered as the significant formation pathway of these monocyclic organosulfur compounds in recent studies, but the reaction mechanism remains unknown. In this work, we selected benzoic acid as a representative monocyclic aromatic hydrocarbon to study its reaction with SO3·- and SO4·- using quantum chemical calculation. The result shows that SO4·- is the main initiator for benzoic acid and its anion (benzoate). And dragging an electron from benzoate (or an H atom from benzoic acid) to produce the radical C6H5COO· is the most favorable route in SO4·--initiated benzoate (or benzoic acid) reactions due to the lowest activation free energies (5.14 or 5.47 kcal mol−1). In addition, the addition of SO4·- to benzoate (or benzoic acid) can also occur because their activation free energies are close to the value of the most favorable route. The analysis on rate constants indicates higher pH can facilitate the formation of these OSs and sulfonates. The produced OSs and sulfonates have different characteristics: only phenyl sulfonate is formed for monocyclic aromatic sulfonates, while both phenyl sulfate and carboxyphenyl sulfate are generated for monocyclic aromatic OSs. This mechanism study can extend our understanding about the formation of monocyclic aromatic OSs and sulfonates, and provide the insight into further studies on aromatic OSs and sulfonates.

Direct aqueous photochemistry of methylglyoxal and its effect on sulfate formation

In recent years, among many oxidation pathways studied for atmospheric sulfate formation, the aqueous phase oxidation pathways of H2O2 and organic hydroperoxides (ROOHs) have attracted great scientific attention. Higher concentrations of H2O2 and ubiquitous ROOHs have been observed in atmospheric aqueous phase environments (cloud water, fog droplets, etc.). However, there are still some gaps in the study of their aqueous phase generation and their influences on sulfate formation. In this study, the aqueous phase photochemical reaction of methylglyoxal, a ubiquitous organic substance in the atmospheric aqueous phase, was studied under UV irradiation, and the generation of H2O2 and ROOHs in this system was investigated. It is found for the first time that the aqueous phase photolysis of methylglyoxal not only produces H2O2 but also produces ROOHs, and UV light and O2 are necessary for the formation of H2O2 and ROOHs. Based on the experimental results, the possible mechanism of aqueous phase photochemistry of methylglyoxal and the generation of H2O2 and ROOHs were proposed. The effect of aqueous phase photolysis of methylglyoxal on sulfate formation under different conditions was also investigated. The results show that the aqueous phase photolysis of methylglyoxal significantly promoted SO2 oxidation and sulfate formation, in which SO2 oxidation was realized by the generated H2O2, ROOHs and •OH radicals, and the importance of the formed ROOHs cannot be ignored. These results fill some gaps in the field of aqueous phase H2O2 and ROOHs production, and to a certain extent confirm the important roles of the aqueous phase photolysis of methylglyoxal and the formed H2O2 and ROOHs in the production of sulfate. The study reveals the new sources of H2O2 and ROOHs, and provides a new insight into the heterogeneous aqueous phase oxidation pathways and mechanisms of SO2 in cloud and fog droplets and haze particles.

Chemical characterization and speciation of the soluble fraction of Arctic PM10

The chemical composition of the soluble fraction of atmospheric particulate matter (PM) and how these components can combine with each other to form different species affect the chemistry of the aqueous phase dispersed in the atmosphere: raindrops, clouds, fog, and ice particles. The study was focused on the analysis of the soluble fraction of Arctic PM10 samples collected at Ny-Ålesund (Svalbard Islands, Norwegian Arctic) during the year 2012. The concentration values of Na+, K+, NH4+, Ca2+, Mg2+, Mn2+, Cu2+, Zn2+, Fe3+, Al3+, Cl−, NO2−, NO3−, SO42−, PO43−, formate, acetate, malonate, and oxalate in the water-soluble fraction of PM10 were determined by atomic spectroscopy and ion chromatography. Speciation models were applied to define the major species that would occur in aqueous solution as a function of pH (2–10). The model highlights that (i) the main cations such as Na+, K+, Mg2+, and Ca2+ occur in the form of aquoions in the whole investigated pH range; (ii) Cu2+, Zn2+, and, in particular, Fe3+ and Al3+ are mostly present in their hydrolytic forms; and (iii) Al3+, Fe3+, and Cu2+ form solid hydrolytic species that precipitate at pH values slightly higher than neutrality. These latter metals show interesting interactions with oxalate and sulfate ions, too. The speciation models were also calculated considering the seasonal variability of the concentration of the components and at higher concentration levels than those found in water PM extracts, to better simulate concentrations actually found in the atmospheric aqueous phase. The results highlight the role of oxalate as the main organic ligand in solution.Graphical

Effects of copper on chemical kinetics and brown carbon formation in the aqueous ˙OH oxidation of phenolic compounds.

Many phenolic compounds (PhCs) in biomass burning and fossil fuel combustion emissions can partition into atmospheric aqueous phases (e.g., cloud/fog water and aqueous aerosols) and undergo reactions to form secondary organic aerosols (SOAs) and brown carbon (BrC). Redox-active transition metals, particularly Fe and Cu, are ubiquitous species in atmospheric aqueous phases known to participate in Fenton/Fenton-like chemistry as a source of aqueous ˙OH. However, even though the concentrations of water-soluble Cu are close to those of water-soluble Fe in atmospheric aqueous phases in some areas, unlike Fe, the effects that Cu have on SOA and BrC formation in atmospheric aqueous phases have scarcely been studied and remain poorly understood. We investigated the effects of Cu(II) on PhC reaction rates and BrC formation during the aqueous oxidation of four PhCs (guaiacol, catechol, syringol, and vanillin) by ˙OH generated from Fenton-like chemistry under different pH conditions. While the PhCs reacted when both H2O2 and Cu(II) were present in the absence (i.e., dark oxidation) and presence (i.e., photooxidation) of light, the reaction rates were at least one order of magnitude higher during photooxidation. Higher PhC reaction rates were measured at higher pH during both dark oxidation and photooxidation as a result of higher ˙OH concentrations produced by Fenton-like chemistry. Only water-soluble BrC was formed during dark oxidation and photooxidation when Cu(II) was present. Mass absorption coefficients (103 to 104 cm2 g-1) comparable to those of biomass burning BrC were measured during dark oxidation and photooxidation when Cu(II) was present. Light absorption was enhanced at higher pH during dark oxidation and photooxidation, which indicated that higher quantities and/or more absorbing BrC chromophores were formed at higher pH. The effects that Cu(II) had on the PhC reaction rates and the composition of SOAs and BrC formed depended on the PhC base structure (i.e., benzenediol vs. methoxyphenol). Overall, these results show how aqueous reactions involving Cu(II), H2O2, and PhCs can be an efficient source of daytime and nighttime water-soluble BrC and SOAs, which can have significant implications for how the atmospheric fates of PhCs are modeled for areas with substantial concentrations of water-soluble Cu in highly to moderately acidic cloud/fog water and aqueous aerosols.

Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase

Photochemical Reactions of Benzene with Chlorine Radicals in Atmospheric Aqueous Phase

Predicting photooxidant concentrations in aerosol liquid water based on laboratory extracts of ambient particles

Abstract. Aerosol liquid water (ALW) is a unique reaction medium, but its chemistry is poorly understood. For example, little is known of photooxidant concentrations – including hydroxyl radicals (⚫OH), singlet molecular oxygen (1O2*), and oxidizing triplet excited states of organic matter (3C*) – even though they likely drive much of ALW chemistry. Due to the very limited water content of particles, it is difficult to quantify oxidant concentrations in ALW directly. To predict these values, we measured photooxidant concentrations in illuminated aqueous particle extracts as a function of dilution and used the resulting oxidant kinetics to extrapolate to ALW conditions. We prepared dilution series from two sets of particles collected in Davis, California: one from winter (WIN) and one from summer (SUM). Both periods are influenced by biomass burning, with dissolved organic carbon (DOC) in the extracts ranging from 10 to 495 mg C L−1. In the winter sample, the ⚫OH concentration is independent of particle mass concentration, with an average value of 5.0 (± 2.2) × 10−15 M, while in summer ⚫OH increases with DOC in the range (0.4–7.7) × 10−15 M. In both winter and summer samples, 3C* concentrations increase rapidly with particle mass concentrations in the extracts and then plateau under more concentrated conditions, with a range of (0.2–7) × 10−13 M. WIN and SUM have the same range of 1O2* concentrations, (0.2–8.5) × 10−12 M, but in WIN the 1O2* concentration increases linearly with DOC, while in SUM 1O2* approaches a plateau. We next extrapolated the relationships of oxidant formation rates and sinks as a function of particle mass concentration from our dilute extracts to the much more concentrated condition of aerosol liquid water. Predicted ⚫OH concentrations in ALW (including mass transport of ⚫OH from the gas phase) are (5–8) × 10−15 M, similar to those in fog/cloud waters. In contrast, predicted concentrations of 3C* and 1O2* in ALW are approximately 10 to 100 times higher than in cloud/fogs, with values of (4–9) × 10−13 M and (1–5) × 10−12 M, respectively. Although ⚫OH is often considered the main sink for organic compounds in the atmospheric aqueous phase, the much higher concentrations of 3C* and 1O2* in aerosol liquid water suggest these photooxidants will be more important sinks for many organics in particle water.

Temperature-Dependent Oxidation of Hydroxylated Aldehydes by •OH, SO4•-, and NO3• Radicals in the Atmospheric Aqueous Phase.

T-dependent aqueous-phase rate constants were determined for the oxidation of the hydroxy aldehydes, glyceraldehyde, glycolaldehyde, and lactaldehyde, by the hydroxyl radicals (•OH), the sulfate radicals (SO4•-), and the nitrate radicals (NO3•). The obtained Arrhenius expressions for the oxidation by the •OH radical are: k(T,GLYCERALDEHYDE+OH•) = (3.3 ± 0.1) × 1010 × exp((-960 ± 80 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+OH•) = (4.3 ± 0.1) × 1011 × exp((-1740 ± 50 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+OH•) = (1.6 ± 0.1) × 1011 × exp((-1410 ± 180 K)/T)/L mol-1 s-1; for the SO4•- radical: k(T,GLYCERALDEHYDE+SO4•-) = (4.3 ± 0.1) × 109 × exp((-1400 ± 50 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+SO4•-) = (10.3 ± 0.3) × 109 × exp((-1730 ± 190 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+SO4•-) = (2.2 ± 0.1) × 109 × exp((-1030 ± 230 K)/T)/L mol-1 s-1; and for the NO3• radical: k(T,GLYCERALDEHYDE+NO3•) = (3.4 ± 0.2) × 1011 × exp((-3470 ± 460 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+NO3•) = (7.8 ± 0.2) × 1011 × exp((-3820 ± 240 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+NO3•) = (4.3 ± 0.2) × 1010 × exp((-2750 ± 340 K)/T)/L mol-1 s-1, respectively. Targeted simulations of multiphase chemistry reveal that the oxidation by OH radicals in cloud droplets is important under remote and wildfire influenced continental conditions due to enhanced partitioning. There, the modeled average aqueous •OH concentration is 2.6 × 10-14 and 1.8 × 10-14 mol L-1, whereas it is 7.9 × 10-14 and 3.5 × 10-14 mol L-1 under wet particle conditions. During cloud periods, the aqueous-phase reactions by •OH contribute to the oxidation of glycolaldehyde, lactaldehyde, and glyceraldehyde by about 35 and 29%, 3 and 3%, and 47 and 37%, respectively.

Polar Nitrated Aromatic Compounds in Urban Fine Particulate Matter: A Focus on Formation via an Aqueous-Phase Radical Mechanism.

Polar nitrated aromatic compounds (pNACs) are key ambient brown carbon chromophores; however, their formation mechanisms, especially in the aqueous phase, remain unclear. We developed an advanced technique for pNACs and measured 1764 compounds in atmospheric fine particulate matter sampled in urban Beijing, China. Molecular formulas were derived for 433 compounds, of which 17 were confirmed using reference standards. Potential novel species with up to four aromatic rings and a maximum of five functional groups were found. Higher concentrations were detected in the heating season, with a median of 82.6 ng m-3 for Σ17pNACs. Non-negative matrix factorization analysis indicated that primary emissions particularly coal combustion were dominant in the heating season. While in the non-heating season, aqueous-phase nitration could generate abundant pNACs with the carboxyl group, which was confirmed by their significant association with the aerosol liquid water content. Aqueous-phase formation of 3- and 5-nitrosalicylic acids instead of their isomer of 4-hydroxy-3-nitrobenzoic acid suggests the existence of an intermediate where the intramolecular hydrogen bond favors kinetics-controlled NO2• nitration. This study provides not only a promising technique for the pNAC measurement but also evidence for their atmospheric aqueous-phase formation, facilitating further evaluation of pNACs' climatic effects.

Aqueous-phase formation of N-containing secondary organic compounds affected by the ionic strength

The reaction of carbonyl-to-imine/hemiaminal conversion in the atmospheric aqueous phase is a critical pathway to produce the light-absorbing N-containing secondary organic compounds (SOC). The formation mechanism of these compounds has been wildly investigated in bulk solutions with a low ionic strength. However, the ionic strength in the aqueous phase of the polluted atmosphere may be higher. It is still unclear whether and to what extent the inorganic ions can affect the SOC formation. Here we prepared the bulk solution with certain ionic strength, in which glyoxal and ammonium were mixed to mimic the aqueous-phase reaction. Molecular characterization by High-resolution Mass Spectrometry was performed to identify the N-containing products, and the light absorption of the mixtures was measured by ultraviolet-visible spectroscopy. Thirty-nine N-containing compounds were identified and divided into four categories (N-heterocyclic chromophores, high-molecular-weight compounds with N-heterocycle, aliphatic imines/hemiaminals, and the unclassified). It was observed that the longer reaction time and higher ionic strength led to the formation of more N-heterocyclic chromophores and the increasing of the light-absorbance of the mixture. The added inorganic ions were proposed to make the aqueous phase somewhat viscous so that the molecules were prone to undergo consecutive and intramolecular reactions to form the heterocycles. In general, this study revealed that the enhanced ionic strength and prolonged reaction time had the promotion effect on the light-absorbing SOC formation. It implies that the aldehyde-derived aqueous-phase SOC would contribute more light-absorbing particulate matter in the industrial or populated area where inorganic ions are abundant.

Aqueous-phase photo-oxidation of selected green leaf volatiles initiated by [rad]OH radicals: Products and atmospheric implications

C5- and C6- unsaturated oxygenated organic compounds emitted by plants under stress like cutting, freezing or drying, known as Green Leaf Volatiles (GLVs), may clear some of the existing uncertainties in secondary organic aerosol (SOA) budget. The transformations of GLVs are a potential source of SOA components through photo-oxidation processes occurring in the atmospheric aqueous phase. Here, we investigated the aqueous photo-oxidation products from three abundant GLVs (1-penten-3-ol, (Z)-2-hexen-1-ol, and (E)-2-hexen-1-al) induced by OH radicals, carried out in a photo-reactor under simulated solar conditions. The aqueous reaction samples were analyzed using advanced hyphenated mass spectrometry techniques: capillary gas chromatography mass spectrometry (c-GC–MS); and reversed-phase liquid chromatography high resolution mass spectrometry (LC-HRMS). Using carbonyl-targeted c-GC–MS analysis, we confirmed the presence of propionaldehyde, butyraldehyde, 1-penten-3-one, and 2-hexen-1-al in the reaction samples. The LC-HRMS analysis confirmed the presence of a new carbonyl product with the molecular formula C6H10O2, which probably bears the hydroxyhexenal or hydroxyhexenone structure. Density functional theory (DFT)-based quantum calculations were used to evaluate the experimental data and obtain insight into the formation mechanism and structures of the identified oxidation products via the addition and hydrogen-abstraction pathways. DFT calculations highlighted the importance of the hydrogen abstraction pathway leading to the new product C6H10O2. Atmospheric relevance of the identified products was evaluated using a set of physical property data like Henry's law constant (HLC) and vapor pressure (VP). The unknown product of molecular formula C6H10O2 has higher HLC and lower VP than the parent GLV and thus has potential to remain in the aqueous phase leading to possible aqueous SOA formation. Other observed carbonyl products are likely first stage oxidation products and precursors of aged SOA.

Light Absorption by Cinnamaldehyde Constituents of Biomass Burning Organic Aerosol Modeled Using Time-Dependent Density Functional Theory

Organic aerosol emitted from biomass burning absorbs visible radiation. However, the impact of this light absorption on the overall climate effects of atmospheric aerosol is not well known, partly due to variability in particle composition and absorptivity. Cinnamaldehydes, which consist of an aromatic ring with an unsaturated aldehyde substituent, are an important class of chromophores in light-absorbing organic aerosol, or brown carbon. Here, light absorption by a homologous series of three cinnamaldehydes─coumaraldehyde, coniferaldehyde, and sinapaldehyde─is modeled with time-dependent density functional theory (TD-DFT) calculations, in the gas and aqueous phases. Based on a survey of hydration and acid dissociation equilibria, the neutral aldehyde is expected to be the predominant form of each species in the atmospheric aqueous phase. These species have complicated conformational landscapes compared to many other brown carbon constituents, like rigid polycyclic aromatic hydrocarbons. For coumaraldehyde, coniferaldehyde, and sinapaldehyde, a total of 8, 26, and 18 conformers were located, respectively. For each species, most of the total population is accounted for by the four most-populated conformers. The relative contributions of the conformers to the total light absorption of the respective species are dictated more by differences in the relative free energies than by differences in the molar absorption coefficients. As the functionalization increases, the absorption is red-shifted. The peaks predicted in water agree well with experimental spectra of coniferaldehyde and sinapaldehyde. No conformers have vertical transitions in the visible spectral range, so absorption above 380 nm is due to the shoulders of transitions of major conformers at ultraviolet wavelengths. These results demonstrate the importance of exploring potential energy landscapes, determining conformer stability and absorptivity, to predict the light absorption of chromophores in brown carbon.

A fast and efficient method for the analysis of α-dicarbonyl compounds in aqueous solutions: Development and application

Among the highly oxygenated species formed in situ in the atmosphere, α-dicarbonyl compounds are the most reactive species, thus contributing to the formation of secondary organic aerosols that affect both air quality and climate. They are ubiquitous in the atmosphere and are easily transferred to the atmospheric aqueous phase due to their high solubility. In addition, α-dicarbonyl compounds are toxic compounds found in food in biochemistry studies as they can be produced endogenously through various pathways and exogenously through the Maillard reaction. In this work, we take advantage of the high reactivity of α-dicarbonyl compounds in alkaline solutions (intramolecular Cannizzaro reaction) to develop an analytical method based on high performance ion chromatography. This fast and efficient method is suitable for glyoxal, methylglyoxal and phenylglyoxal which are detected as glycolate, lactate and mandelate anions respectively, with 100% conversion at pH > 12 and room temperature for exposure times to hydroxide ranging from 5 min to 4 h. Diacetyl is detected as 2,4-dihydroxy-2,4-dimethyl-5-oxohexanoate due to a base-catalysed aldol reaction that occurs before the Cannizzaro reaction. The analytical method is successfully applied to monitor glyoxal consumption during aqueous phase HO∙-oxidation, an atmospherically relevant reaction using concentrations that can be observed in fog and cloud water. The method also reveals potential analytical artifacts that can occur in the use of ion chromatography for α-hydroxy carboxylates measurements in complex matrices due to α-dicarbonyl conversion during the analysis time. An estimation of the artifact is given for each of the studied α-hydroxy carboxylates. Other polyfunctional and pH-sensitive compounds that are potentially present in environmental samples (such as nitrooxycarbonyls) can also be converted into α-hydroxy carboxylates and/or nitrite ions within the HPIC run. This shows the need for complementary analytical measurements when complex matrices are studied.

Long-term monitoring of cloud water chemistry at Whiteface Mountain: the emergence of a new chemical regime

Abstract. Atmospheric aqueous chemistry can have profound effects on our environment. The importance of chemistry within the atmospheric aqueous phase started gaining widespread attention in the 1970s as there was growing concern over the negative impacts on ecosystem health from acid deposition. Research at mountaintop observatories including Whiteface Mountain (WFM) showed that gas phase sulfur dioxide emissions react in cloud droplets to form sulfuric acid, which also impacted air quality by increasing aerosol mass loadings. The current study updates the long-term trends in cloud water composition at WFM for the period 1994–2021, with special consideration given to samples that have traditionally been excluded from analysis due to inorganic charge imbalance. We emphasize three major findings: (1) a growing abundance of total organic carbon (TOC), with annual median concentrations more than doubling since measurements began in 2009, (2) a growing imbalance between the measured inorganic cations and anions, consistent with independent rain water observations, implying that a substantial fraction of anions are no longer being measured with the historical suite of measurements, and (3) a growing number of samples exhibiting greater ammonium concentrations than sulfate plus nitrate concentrations, which now routinely describes over one-third of samples. Organic acids are identified as the most likely candidates for the missing anions, since the measured inorganic ion imbalance correlates strongly with measured TOC concentrations. An “inferred cloud droplet pH” is introduced to estimate the pH of the vast majority of cloud droplets as they reside in the atmosphere using a simple method to account for the expected mixing state of calcium and magnesium containing particles. While the inferred cloud droplet pH closely matches the measured bulk cloud water pH during the early years of the cloud water monitoring program, a growing discrepancy is found over the latter half of the record. We interpret these observations as indicating a growing fraction of cloud droplet acidity that is no longer accounted for by the measured sulfate, nitrate and ammonium concentrations. Altogether, these observations indicate that the chemical system at WFM has shifted away from a system dominated by sulfate to a system controlled by base cations, reactive nitrogen species and organic compounds. Further research is required to understand the effects on air quality, climate and ecosystem health.

PH affects the aqueous-phase nitrate-mediated photooxidation of phenolic compounds: implications for brown carbon formation and evolution.

Brown carbon (BrC) is known to have important impacts on atmospheric chemistry and climate. Phenolic compounds are a prominent class of BrC precursors that are emitted in large quantities from biomass burning and fossil fuel combustion. Inorganic nitrate is a ubiquitous component of atmospheric aqueous phases such as cloudwater, fog, and aqueous aerosols. The photolysis of inorganic nitrate can lead to BrC formation via the photonitration of phenolic compounds in the aqueous phase. However, the acidity of the atmospheric aqueous phase adds complexity to these photonitration processes and needs to be considered when investigating BrC formation from the nitrate-mediated photooxidation of phenolic compounds. In this study, we investigated the influence of pH on the formation and evolution of BrC from the aqueous-phase photooxidation of guaiacol, catechol, 5-nitroguaiacol, and 4-nitrocatechol initiated by inorganic nitrate photolysis. The reaction rates, BrC composition and quantities were found to depend on the aqueous phase pH. Guaiacol, catechol, and 5-nitroguaiacol reacted substantially faster at lower pH. In contrast, 4-nitrocatechol reacted at slower rates at lower pH. For all four phenolic compounds, the initial stages of photooxidation resulted in an increase in light absorption (i.e., photo-enhancement) in the near-UV and visible range due to the formation of light absorbing products formed via the addition of nitro and/or hydroxyl groups to the phenolic compound. Greater photo-enhancement was observed at lower pH during the nitrate-mediated photooxidation of guaiacol and catechol. In contrast, greater photo-enhancement was observed at higher pH during the nitrate-mediated photooxidation of 5-nitroguaiacol and 4-nitrocatechol. This indicated that the effect that the aqueous phase pH has on the composition and yields of BrC formed is not universal, and will depend on the initial phenolic compound. These results provide new insights into how the atmospheric aqueous phase acidity influences the reactivities of different phenolic compounds and BrC formation/evolution during photooxidation initiated by inorganic nitrate photolysis, which will have significant implications for how the atmospheric fates of phenolic compounds and BrC formation/evolution are modeled for areas with high levels of inorganic nitrate.

Kinetics of the nitrate-mediated photooxidation of monocarboxylic acids in the aqueous phase.

The photooxidation of organic compounds by hydroxyl radicals (·OH) in atmospheric aqueous phases contributes to both the formation and aging of secondary organic aerosols (SOAs), which usually include carboxylic acids. Hydrogen peroxide (H2O2) and inorganic nitrate are two important ·OH photochemical sources in atmospheric aqueous phases. The aqueous phase pH is an important factor that not only controls the dissociation of carboxylic acids and consequently their ·OH reactivities, but also the production of ·OH and other reactive species from the photolysis of some ·OH photochemical precursors, particularly inorganic nitrate. While many studies have reported on the aqueous pH-dependent photodegradation rates of carboxylic acids with ·OH produced by H2O2 photolysis, the aqueous pH-dependent photodegradation rates of carboxylic acids with ·OH produced by inorganic nitrate photolysis have not been studied. In this work, we investigated the pH-dependent (pH 2 to 7) aqueous photooxidation of formic acid (FA), glycolic acid (GA), and pyruvic acid (PA) initiated by the photolysis of ammonium nitrate (NH4NO3). The observed reaction rates of the three carboxylic acids were controlled by the [NH4NO3]/[carboxylic acid] concentration ratio. Higher [NH4NO3]/[carboxylic acid] concentration ratios resulted in faster photodegradation rates, which could be attributed to the higher concentrations of ·OH produced from the photolysis of higher concentrations of NH4NO3. In addition, the observed photodegradation rates of the three carboxylic acids strongly depended on the pH. The highest photodegradation rate was observed at pH 4 for FA, whereas the highest photodegradation rates were observed at pH 2 for GA and PA. The observed pH-dependent FA and GA photodegradation rates were due to the combined effects of the pH-dependent ·OH formation from NH4NO3 photolysis and the differences in ·OH reactivities of dissociated vs. undissociated FA and GA. In contrast, the observed pH-dependent PA photodegradation rate was due primarily to the pH-dependent decarboxylation of PA initiated by light. These results highlight how the aqueous phase pH and inorganic nitrate photolysis can combine to influence the degradation rates of carboxylic acids, which can have significant implications for how the atmospheric fates of carboxylic acids are modeled for regions with substantial concentrations of inorganic nitrate in cloud water and aqueous aerosols.

The oxidation mechanism and kinetics of limononic acid by hydroxyl radical in atmospheric aqueous phase

Limononic acid (3-isopropenyl-6-oxoheptanoic acid, LA), as an important precursor of secondary organic aerosols (SOA), has attracted extensive attention in the field of atmospheric chemistry. However, its microscopic oxidation mechanism is still unclear. In this study, the density functional theory calculations were conducted to study the oxidation mechanism of LA by ·OH in aqueous phase. The results show that the reactions of hydroxylation are more likely to occur than the dehydrogenation reaction, because of the lower free energy barrier (2.3–5.4 kcal mol−1). At 298 K, the total rate constant of the reaction initiated by ·OH is 1.06 × 1010 M−1 s−1, which fits the experimental value well. Among all reactions, the hydroxylation reaction in C9 site of LA is the most favorable pathway, and the corresponding hydroxylation intermediate (IM4) can react with ·OH, H2O, dissolved O2, and HO2·. Three important tropospheric free radicals (R·, RO· and RO2·) are generated during the subsequent reaction process. Meanwhile alcohols, ketones, aldehydes, and oxidized acids can be formed in the overall reaction scheme. These products are the precursor for the formation of SOA, and this transformation process will increase the O/C ratio of aqueous phase SOA. This study has an important significance for understanding the oxidation mechanism of monoterpenoids in the atmospheric aqueous phase.