Photooxidation-Initiated Aqueous-Phase Formation of Organic Peroxides: Delving into Formation Mechanisms.

Formation of highly oxygenated molecules (HOMs) such as organic peroxides (ROOR, ROOH, and H2O2) is known to degrade food and organic matter. Gas-phase unimolecular autoxidation and bimolecular RO2 + HO2/RO2 reactions are prominently renowned mechanisms associated with the formation of peroxides. However, the reaction pathways and conditions favoring the generation of peroxides in the aqueous phase need to be evaluated. Here, we identified bulk aqueous-phase ROOHs in varying organic precursors, including a laboratory model compound and monoterpene oxidation products. Our results show that formation of ROOHs is suppressed at enhanced oxidant concentrations but exhibits complex trends at elevated precursor concentrations. Furthermore, we observed an exponential increase in the yield of ROOHs when UV light with longer wavelengths was used in the experiment, comparing UVA, UVB, and UVC. Water-soluble organic compounds represent a significant fraction of ambient cloud-water components (up to 500 µM). Thus, the reaction pathways facilitating the formation of HOMs (i.e., ROOHs) during the aqueous-phase oxidation of water-soluble species add to the climate and health burden of atmospheric particulate matter.

Unexpected electrophiles in the atmosphere - anhydride nucleophile reactions and uptake to biomass burning emissions.

Biomass burning is a significant contributor to atmospheric pollution, its emissions have been found to have adverse impacts on climate and human health. Largely, these impacts are dictated by how the composition of the emissions changes once emitted into the atmosphere. Recently, anhydrides have been identified as a significant fraction of biomass burning emissions, however, little is known about their atmospheric evolution, or their interactions within the burn plume. Without this understanding, it is challenging to predict the impact of anhydrides on biomass burning emissions, and by extension, their influence on climate and health. In this study, we investigate anhydrides as potentially unrecognized electrophiles in the atmosphere. Firstly, by exploring their reactivity towards important biomass burning emitted nucleophiles, and secondly, by measuring their uptake on the emissions themselves. Our results show that phthalic and maleic anhydride can react with a wide range of nucleophiles, including hydroxy and amino-containing compounds, such as levoglucosan or aniline. Additionally, using a coated-wall flow tube setup, we demonstrate that anhydrides reactively uptake to biomass burning films and influence their composition. The anhydride nucleophile reaction was found to be irreversible, proceeding without sunlight or free radicals and indicating it may occur during the day or nighttime. Furthermore, the reaction products were found to be water-stable and contain functional groups which enhance their mass and likely contribute to the formation of secondary organic aerosol, with knock-on climate effects. Overall, our study sheds light on the fundamental chemistry of anhydrides and their potential impacts in the atmosphere.

Particulate matter emitted from ultrasonic humidifiers-Chemical composition and implication to indoor air.

Household humidification is widely practiced to combat dry indoor air. While the benefits of household humidification are widely perceived, its implications to the indoor air have not been critically appraised. In particular, ultrasonic humidifiers are known to generate fine particulate matter (PM). In this study, we first conducted laboratory experiments to investigate the size, quantity, and chemical composition of PM generated by an ultrasonic humidifier. The mass of PM generated showed a correlation with the total alkalinity of charge water, suggesting that CaCO3 is likely making a major contribution to PM. Ion chromatography analysis revealed a large amount of SO42- in PM, representing a previously unrecognized indoor source. Preliminary results of organic compounds being present in humidifier PM are also presented. A whole-house experiment was further conducted at an actual residential house, with five low-cost sensors (AirBeam) monitoring PM in real time. Operation of a single ultrasonic humidifier resulted in PM2.5 concentrations up to hundreds of µg m-3 , and its influence extended across the entire household. The transport and loss of PM2.5 depended on the rate of air circulation and ventilation. This study emphasizes the need to further investigate the impact of humidifier operation, both on human health and on the indoor atmospheric chemistry, for example, partitioning of acidic and basic compounds.

Comprehensive analysis of emissions from wood and cow dung burning using chemometrics and two-dimensional gas chromatography.

Biomass burning is a global source of climate- and health-affecting emissions. The impacts of biomass burning emissions (BBE) are tied to their complex and variable chemical makeup. For instance, the nitrogen content of BBE influences their capacity to absorb light, and therefore affect the Earth's radiative budget. Factors such as temperature, biomass type, or air flow rate during the combustion all modify the composition of BBE, making accurate characterization challenging. Herein, for the first time, principal component analysis (PCA) was applied to emissions gathered during laboratory-based combustion of wood and cow dung biomass in a tube furnace. A thermal desorption two dimensional time-of-flight gas chromatography mass spectrometry (TD-GC × GC-ToF-MS) setup was employed to separate and identify chemical species. By combining these techniques with a feature selection algorithm, we determined that low temperature and air flow rate lead to greater feature separation on PCA scores plots. Of the 729 variables used to construct the plots, 61 were identified as significant. These species - including sugars such as d-Allose and melezitose, as well as tracers such as levoglucosan and guaiacol - significantly differentiated emissions from wood versus cow dung biomass, especially at lower temperatures. In particular, combustion of either fuel at 0.2 slpm and 500 °C, lead to 20 times the variability in levoglucosan peak area over more efficient furnace parameters. Chemical species evolved only from dung burning contained on average 0.595 nitrogen atoms versus 0.515 for wood, indicating that a higher nitrogen content of the base fuel may not necessarily translate into emission of unique nitrogen containing species, potentially causing the underestimation of dung burning impacts. Overall, TD-GC × GC-ToF-MS coupled to PCA reliably separated emissions from wood and dung biomass while simultaneously identifying significant chemical features, displaying the suitability of this combination of techniques towards characterizing complex BBE matrices in the future.