Singlet Oxygen Seasonality in Aqueous PM<sub>10</sub> is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol

Bogler, Sophie; Daellenbach, Kaspar R.; Bell, David M.; Prévôt, Andrê S. H.; Haddad, Imad El; Borduas-Dedekind, Nadine

doi:10.1021/acs.est.2c04554

Cited by 16 publications

(38 citation statements)

References 38 publications

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“…2d exhibit very similar relationships between 1 O2* and DOC, suggesting DOC 420 concentration might be a good predictor of 1 O2* concentrations in atmospheric waters. Apparent quantum yields of 1 O2* are 3.0 (± 0.2)% for WIN and 2.0 (± 0.4)% for SUM (Table S8), which are in the range of typical values for atmospheric waters (Bogler et al, 2022;Kaur and Anastasio, 2017;Kaur et al, 2019;Manfrin et al, 2019) and surface waters (Ossola et al, 2020). For WIN, 1 O2* is linearly related to DOC throughout the dilution series, but in SUM the singlet oxygen concentration exhibits a linear relationship at low DOC and then starts to level off 425 in the more concentrated extracts (Fig.…”

Section: Singlet Molecular Oxygen In Pm Extracts 410mentioning

confidence: 71%

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

Worland

Jiang

et al. 2023

Preprint

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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 radical (●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.

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Section: Singlet Molecular Oxygen In Pm Extracts 410mentioning

confidence: 71%

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

Worland

Jiang

et al. 2023

Preprint

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“…The discussions have been based on oxidative water treatment, but the kinetic data and protocols provided here also benefit understanding of the photochemical processes in sunlit surface waters − and tropospheric aqueous phase. , For example, FFA has been used to quantify 1 O 2 formation from photosensitized reactions of brown carbon in tropospheric droplets. , However, its selectivity toward 1 O 2 needs careful evaluation as the new kinetic data (Table ) shows that other reactive species such as halogen radicals (can be from photosensitized reactions of aerosol halides) are also reactive toward FFA, which might interfere with 1 O 2 quantification. For the convenience of researchers, Figure S12 presents a visualized scheme illustrating better use of probes and quenchers.…”

Section: Resultsmentioning

confidence: 99%

Assessing the Use of Probes and Quenchers for Understanding the Reactive Species in Advanced Oxidation Processes

Lei

et al. 2023

Environ. Sci. Technol.

169

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Advanced oxidation processes (AOPs) are increasingly applied in water and wastewater treatment. Understanding the role of reactive species using probes and quenchers is one of the main requirements for good process design. However, much fundamental kinetic data for the reactions of probes and quenchers with reactive species is lacking, probably leading to inappropriate probe and quencher selection and dosing. In this work, secondorder rate constants for over 150 reactions of probes and quenchers with reactive species such as • OH, SO 4•− , and Cl • and chemical oxidants such as free chlorine and persulfate were determined. Some previously ill-quantified reactions (e.g., furfuryl alcohol and methyl phenyl sulfoxide reactions with certain chemical oxidants, nitrobenzene and 1,4-dioxane reactions with certain halogen radicals) were found to be kinetically favorable. The selection of specific probes can be guided by the improved kinetic database. The criteria for properly choosing dosages of probes and quenchers were proposed along with a procedure for quantifying reactive species free of interference from probe addition. The limitations of probe and quencher approaches were explicated, and possible solutions (e.g., the combination with other tools) were proposed. Overall, the kinetic database and protocols provided in this work benefit future research in understanding the radical chemistry in AOPs as well as other radical-involved processes.

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“…A rate constant k sink of 4 × 10 8 M –1 s –1 produced the best fit to the data, combined with a [oxidants] concentration of 5 × 10 –14 M which is on the same order of magnitude as the steady-state concentration of singlet oxygen ( 1 O 2 ) in irradiated solutions (Table S4). , …”

Section: Resultsmentioning

confidence: 99%

“…A rate constant k sink of 4 × 10 8 M −1 s −1 produced the best fit to the data, combined with a [oxidants] concentration of 5 × 10 −14 M which is on the same order of magnitude as the steady-state concentration of singlet oxygen ( 1 O 2 ) in irradiated solutions (Table S4). 64,65 The kinetic box model for pyruvic acid retained the same values for [TOC], k OC and [oxidants]. The initial concentration in (NH 4 ) 2 SO 4 -methylglyoxal solutions was on average 2.1 × 10 −6 M, and a photooxidation yield of γ of 0.04% best fitted the observed production.…”

Section: Photoproductsmentioning

confidence: 99%

Tracking the Photomineralization Mechanism in Irradiated Lab-Generated and Field-Collected Brown Carbon Samples and Its Effect on Cloud Condensation Nuclei Abilities

2023

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Organic aerosols affect the planet's radiative balance by absorbing and scattering light as well as by activating cloud droplets. These organic aerosols contain chromophores, termed brown carbon (BrC), and can undergo indirect photochemistry, affecting their ability to act as cloud condensation nuclei (CCN). Here, we investigated the effect of photochemical aging by tracking the conversion of organic carbon into inorganic carbon, termed the photomineralization mechanism, and its effect on the CCN abilities in four different types of BrC samples: (1) laboratorygenerated (NH 4 ) 2 SO 4 -methylglyoxal solutions, (2) dissolved organic matter isolate from Suwannee River fulvic acid (SRFA), (3) ambient firewood smoke aerosols, and (4) ambient urban wintertime particulate matter in Padua, Italy. Photomineralization occurred in all BrC samples albeit at different rates, evidenced by photobleaching and by loss of organic carbon up to 23% over a simulated 17.6 h of sunlight exposure. These losses were correlated with the production of CO up to 4% and of CO 2 up to 54% of the initial organic carbon mass, monitored by gas chromatography. Photoproducts of formic, acetic, oxalic and pyruvic acids were also produced during irradiation of the BrC solutions, but at different yields depending on the sample. Despite these chemical changes, CCN abilities did not change substantially for the BrC samples. In fact, the CCN abilities were dictated by the salt content of the BrC solution, trumping a photomineralization effect on the CCN abilities for the hygroscopic BrC samples. Solutions of (NH 4 ) 2 SO 4 -methylglyoxal, SRFA, firewood smoke, and ambient Padua samples had hygroscopicity parameters κ of 0.6, 0.1, 0.3, and 0.6, respectively. As expected, the SRFA solution with a κ of 0.1 was most impacted by the photomineralization mechanism. Overall, our results suggest that the photomineralization mechanism is expected in all BrC samples and can drive changes in the optical properties and chemical composition of aging organic aerosols.

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Singlet Oxygen Seasonality in Aqueous PM₁₀ is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol

Cited by 16 publications

References 38 publications

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

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

Assessing the Use of Probes and Quenchers for Understanding the Reactive Species in Advanced Oxidation Processes

Tracking the Photomineralization Mechanism in Irradiated Lab-Generated and Field-Collected Brown Carbon Samples and Its Effect on Cloud Condensation Nuclei Abilities

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Singlet Oxygen Seasonality in Aqueous PM10 is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol

Cited by 16 publications

References 38 publications

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

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

Assessing the Use of Probes and Quenchers for Understanding the Reactive Species in Advanced Oxidation Processes

Tracking the Photomineralization Mechanism in Irradiated Lab-Generated and Field-Collected Brown Carbon Samples and Its Effect on Cloud Condensation Nuclei Abilities

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Product

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Singlet Oxygen Seasonality in Aqueous PM₁₀ is Driven by Biomass Burning and Anthropogenic Secondary Organic Aerosol