Photochemical processing taking place in atmospheric aqueous phases serves as both a source and a sink of organic compounds. In aqueous environments, acid–base chemistry and, by extension, aqueous-phase pH, are an important yet often neglected factors to consider when investigating the kinetics of organic compounds. We have investigated the aqueous-phase OH-oxidation of pinic acid, cis-pinonic acid, limononic acid, and formic acid (FA) as a function of pH. We have also extended our studies to other organic acids (OAs) present in the water-soluble fraction of secondary organic aerosol (SOA) arising from the ozonolysis of α-pinene. Although all the OAs exhibited larger OH reactivities at pH 10, the pH dependence was dramatically different between FA, the smallest OA, and those that contained more than eight carbons. A kinetic box model was also employed to characterize our photoreactor and to provide confidence to our results. Our finding shows that the atmospheric lifetimes of small OAs (e.g., FA) are highly sensitive to cloud water pH. However, those of larger OAs and many other OAs in α-pinene SOA are affected to a much less extent. These results are of great importance for the simplification of cloud water chemistry models.

Microbial volatile organic compounds (MVOCs) play an essential role in many environmental fields, such as indoor air quality. Long-term exposure to odorous and toxic MVOCs can negatively affect the health of occupants. Recently, the involvement of surface reservoirs in indoor chemistry has been realized, which signifies the importance of the phase partitioning of volatile organic pollutants. However, reliable partition coefficients of many MVOCs are currently lacking. Equilibrium partition coefficients, such as Henry's law constant, H, are crucial for understanding the environmental behavior of chemicals. This study aims to experimentally determine the H values and their temperature dependence for key MVOCs under temperature relevant to the indoor environment. The H values were determined with the inert gas-stripping (IGS) method and variable phase ratio headspace (VPR-HS) technique. A two-dimensional partitioning model was applied to predict the indoor phase distribution of MVOCs and potential exposure pathways to the residences. The findings show that the MVOCs are likely distributed between the gas and weakly polar (e.g., organic-rich) reservoirs indoors. Temperature and the volume of reservoirs can sensitively affect indoor partitioning. Our results give a more comprehensive view of indoor chemical partitioning and exposure.

Peroxides (H 2 O 2 , ROOR, and ROOH) are an important reaction intermediate involved in a number of natural processes, including atmospheric autoxidation and lipid peroxidation in oils and animal tissues. Iodometry is an established spectroscopic technique that has been widely used to quantify total peroxide concentration in food, indoor, and outdoor samples. Iodometry provides selectivity toward peroxides through a quantitative reaction between I − and peroxides to form I 3 − via a molecular iodine (I 2 ) intermediate. However, equilibrium changes caused by a potential interaction between olefinic species and I 2 can suppress I 3 − formation, thereby underestimating peroxide concentration. For the first time in the current study, this unrecognized interference posed by olefins (OEs) is systematically investigated to gauge its effects on the accuracy of iodometry. A number of model molecules were investigated. The interference was observed to be unique to OEs, but universally affecting different peroxide species such as H 2 O 2 , tert-butyl hydroperoxide, and aerosol-bound peroxides. A simple kinetic box model was built to explain this chemistry. The measured rate constant for 3-octenoic acid was found to be 0.84 ± 0.02 M −1 s −1 . Overall, our results show matrix effects induced by OEs can underestimate peroxide concentration determined by iodometry for edible oils, indoor environments, and animal fat, but absent in most of the atmospheric samples. Nonetheless, our results point out the importance of this interfering chemistry in matrices enriched with OEs.

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Flavoring agents added to the e-cigarette and hookah have increased the attractiveness of novel nicotine products. Many widely used flavorings are carbonyls, which are toxic to humans. In an indoor...