Using chemical ionization mass spectrometry to probe indoor and outdoor atmospheric chemistry
Date
2021
Authors
Mattila, James M., author
Farmer, Delphine K., advisor
Reynolds, Melissa M., committee member
Willis, Megan D., committee member
Carter, Ellison M., committee member
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Abstract
People spend the majority of their time in indoor environments. Knowledge of the sources, sinks, and chemistry of indoor pollutants is therefore imperative to indoor air quality and human health. We studied the indoor chemistry of cooking and cleaning at the House Observations of Microbial and Environmental Chemistry (HOMEChem) field campaign during summer 2018 at the University of Texas test house (UTest house) in Austin, TX. We performed measurements of several gas-phase cooking- and cleaning-related analytes using a fast (1 Hz), online chemical ionization mass spectrometry (CIMS) measurement technique utilizing iodide reagent ions. Combining these and other measurements of gas-phase analytes and particulate matter present in indoor air during HOMEChem enables us to piece together a holistic story of the indoor chemistry of cooking and cleaning. We observed enhanced levels of several chlorinated and nitrogenated compounds when cleaning indoors with a commercial bleach solution during HOMEChem. We observed production of several inorganic chlorinated and nitrogenated pollutants from bleaching, including hypochlorous acid, chlorine gas, and chloramines. Levels of hypochlorous acid and nitrogen trichloride observed during cleaning are likely detrimental to human health. Bleach cleaning indoors also lead to the production of secondary organic aerosol—a common outdoor atmospheric pollutant associated with respiratory and cardiovascular issues—as well as potentially harmful organic isocyanates, cyanogen chloride, and chlorocarbons. These results collectively demonstrate bleach cleaning as a source of indoor pollution which impacts indoor air quality and occupant health. We characterized indoor reactive organic carbon (ROC) emissions from cooking and cleaning during HOMEChem, and directly compared resultant chemical complexity of indoor air to outdoors. Cooking indoors greatly impacts ROC concentrations and physiochemical properties, and thus carbon reactivities and lifetimes. Cleaning indoors yielded relatively insubstantial changes. Consistently higher indoor ROC concentrations compared to outdoors demonstrated that indoor emissions were a net source of reactive carbon to the outdoor atmosphere, following their removal by ventilation. ROC dominated indoor and outdoor oxidant reactivity compared to other atmospheric carbon species, thereby greatly influencing secondary pollutant formation, including carbon dioxide, ozone, and secondary particulate matter. Most oxidation chemistry to produce these secondary pollutants likely took place outdoors following the ventilation of ROC species, given the low oxidant levels typical of indoor environments. Moving outdoors, we demonstrated the efficacy of a CIMS instrument utilizing acetate ionization toward quantifying various gas-phase acids in the troposphere. Here, we performed measurements during the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) field campaign in summer 2014. Diurnal increases in mixing ratios were consistent with photochemical sources of nitric, isocyanic, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m Boulder Atmospheric Observatory tower demonstrated net surface-level emissions of alkanoic acids, but net surface deposition of nitric and pyruvic acid. Nearby traffic emissions and agricultural activity were a primary source of propionic, butyric, and valeric acids, and likely contributed photochemical precursors to nitric and isocyanic acids. The combined diel and vertical profiles of the alkanoic acids and isocyanic acid were inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.
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Subject
analytical chemistry
indoor air
air pollution
mass spectrometry
atmospheric chemistry