Reactive Oxygen Species Production from Secondary Organic Aerosols: The Importance of Singlet Oxygen

Manfrin, Alessandro; Nizkorodov, Sergey A.; Malecha, Kurtis T.; Getzinger, Gordon J.; McNeill, Kristopher; Borduas-Dedekind, Nadine

doi:10.1021/acs.est.9b01609

Cited by 44 publications

(103 citation statements)

References 79 publications

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“…2c and S1). This comparison suggests that our DOM samples, which are smaller than 0.20 µm, could be accounting for a subset of the IN activity previously observed in the sea surface microlayer (Irish et al, 2019;McCluskey et al, 2018;Wilson et al, 2015). Furthermore, sea spray aerosols have recently been shown to be effective INPs when enriched in organics (DeMott et al, 2016;Ladino et al, 2016;Si et al, 2018;Wilson et al, 2015), consistent with our results.…”

Section: Photochemistry Affects the Ice-nucleating Ability Of Domsupporting

confidence: 91%

Photomineralization mechanism changes the ability of dissolved organic matter to activate cloud droplets and to nucleate ice crystals

et al. 2019

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Abstract. An organic aerosol particle has a lifetime of approximately 1 week in the atmosphere during which it will be exposed to sunlight. However, the effect of photochemistry on the propensity of organic matter to participate in the initial cloud-forming steps is difficult to predict. In this study, we quantify on a molecular scale the effect of photochemical exposure of naturally occurring dissolved organic matter (DOM) and of a fulvic acid standard on its cloud condensation nuclei (CCN) and ice nucleation (IN) activity. We find that photochemical processing, equivalent to 4.6 d in the atmosphere, of DOM increases its ability to form cloud droplets by up to a factor of 2.5 but decreases its ability to form ice crystals at a loss rate of −0.04 ∘CT50 h−1 of sunlight at ground level. In other words, the ice nucleation activity of photooxidized DOM can require up to 4 ∘C colder temperatures for 50 % of the droplets to activate as ice crystals under immersion freezing conditions. This temperature change could impact the ratio of ice to water droplets within a mixed-phase cloud by delaying the onset of glaciation and by increasing the supercooled liquid fraction of the cloud, thereby modifying the radiative properties and the lifetime of the cloud. Concurrently, a photomineralization mechanism was quantified by monitoring the loss of organic carbon and the simultaneous production of organic acids, such as formic, acetic, oxalic and pyruvic acids, CO and CO2. This mechanism explains and predicts the observed increase in CCN and decrease in IN efficiencies. Indeed, we show that photochemical processing can be a dominant atmospheric ageing process, impacting CCN and IN efficiencies and concentrations. Photomineralization can thus alter the aerosol–cloud radiative effects of organic matter by modifying the supercooled-liquid-water-to-ice-crystal ratio in mixed-phase clouds with implications for cloud lifetime, precipitation patterns and the hydrological cycle.Highlights. During atmospheric transport, dissolved organic matter (DOM) within aqueous aerosols undergoes photochemistry. We find that photochemical processing of DOM increases its ability to form cloud droplets but decreases its ability to form ice crystals over a simulated 4.6 d in the atmosphere. A photomineralization mechanism involving the loss of organic carbon and the production of organic acids, CO and CO2 explains the observed changes and affects the liquid-water-to-ice ratio in clouds.

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Section: Photochemistry Affects the Ice-nucleating Ability Of Domsupporting

confidence: 91%

Photomineralization mechanism changes the ability of dissolved organic matter to activate cloud droplets and to nucleate ice crystals

et al. 2019

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“…Even less is known about the abiotic transformation pathways of these amino acids, as only some AAs have been studied in detail. Most mechanistic studies are limited to the transformation of AAs (GLY, glycine; TRP, tryptophan, ASP, aspartate; and SER, serine) into small carboxylic acids such as acetic, oxalic, malonic, or formic acids (Berger et al, 1999;Bianco et al, 2016b;Marion et al, 2018). In some cases, an amino acid can be converted into another one or into very different molecules (Bianco et al, 2016b;Mudd et al, 1969;Prasse et al, 2018;Stadtman, 1993;Stadtman and Levine, 2004).…”

Section: Introductionmentioning

confidence: 99%

Biotic and abiotic transformation of amino acids in cloud water: experimental studies and atmospheric implications

et al. 2021

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Abstract. The interest in organic nitrogen and particularly in quantifying and studying the fate of amino acids (AAs) has been growing in the atmospheric-science community. However very little is known about biotic and abiotic transformation mechanisms of amino acids in clouds. In this work, we measured the biotransformation rates of 18 amino acids with four bacterial strains (Pseudomonas graminis PDD-13b-3, Rhodococcus enclensis PDD-23b-28, Sphingomonas sp. PDD-32b-11, and Pseudomonas syringae PDD-32b-74) isolated from cloud water and representative of this environment. At the same time, we also determined the abiotic (chemical, OH radical) transformation rates within the same solutions mimicking the composition of cloud water. We used a new approach by UPLC–HRMS (ultra-performance liquid chromatography–high-resolution mass spectrometry) to quantify free AAs directly in the artificial-cloud-water medium without concentration and derivatization. The experimentally derived transformation rates were used to compare their relative importance under atmospheric conditions with loss rates based on kinetic data of amino acid oxidation in the aqueous phase. This analysis shows that previous estimates overestimated the abiotic degradation rates and thus underestimated the lifetime of amino acids in the atmosphere, as they only considered loss processes but did not take into account the potential transformation of amino acids into each other.

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“…In additional experiments, we verify the ability of 3 CDOM* to drive ROS formation, including 1 O2 and •OH (Manfrin et al, 2019). As shown in Figure 5, the result shows that the signal strength of 1 O2 decreases by 30% when the 3 CDOM* is quenched by SA (comparing Figure 5 (c) and (d)).…”

Section: Environmental Implicationmentioning

confidence: 70%

Triplet State Formation of Chromophoric Dissolved Organic Matter in Atmospheric Aerosols: Characteristics and Implications

Chen

et al. 2020

Preprint

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Abstract. There is chromophore dissolved organic matter (CDOM) in the atmosphere, which may form triplet-state chromophoric dissolved organic matter (3CDOM*) to further driving the formation of reactive oxygen species (ROS) under solar illumination. 3CDOM* contributes significantly to aerosol photochemistry and plays an important role in aerosol aging. We quantify the ability to form 3CDOM* and drive the formation of ROS by primary, secondary and ambient aerosols. Biomass combustion has the strongest 3CDOM* generation capacity and the weakest vehicle emission capacity. Ambient aerosol has a stronger ability to generate 3CDOM* in winter than in summer. Most of the triplet states generation conform to first-order reaction, but some of them do not due to the different quenching mechanism. The structural-activity relationship between the CDOM type and the 3CDOM* formation capacity shows that the two types of CDOM identified, which similar to the nitrogen-containing chromophores contributed 88&#8201;% to the formation of 3CDOM*. The estimated formation rate of 3CDOM* can reach ~&#8201;100&#8201;&#956;mol&#8201;m&#8722;3&#8201;h&#8722;1 in the atmosphere in Xi'an, China, which is approximately one hundred thousand-times the hydroxyl radical (&#8226;OH) production. This study verified that 3CDOM* drives at least 30&#8201;% of the singlet oxygen (1O2) and 31&#8201;% of the &#8226;OH formed by aerosols using the spin trapping and electron paramagnetic resonance technique.

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Reactive Oxygen Species Production from Secondary Organic Aerosols: The Importance of Singlet Oxygen

Cited by 44 publications

References 79 publications

Photomineralization mechanism changes the ability of dissolved organic matter to activate cloud droplets and to nucleate ice crystals

Photomineralization mechanism changes the ability of dissolved organic matter to activate cloud droplets and to nucleate ice crystals

Biotic and abiotic transformation of amino acids in cloud water: experimental studies and atmospheric implications

Triplet State Formation of Chromophoric Dissolved Organic Matter in Atmospheric Aerosols: Characteristics and Implications

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