Catechol (1,2-benzenediol) is emitted from biomass burning and produced from a reaction of phenol with OH radicals. It has been suggested as an important secondary organic aerosol (SOA) precursor, but the mechanisms of gas-phase oxidation and SOA formation have not been investigated in detail. In this study, catechol was reacted with OH and NO radicals in the presence of NO in an environmental chamber to simulate daytime and nighttime chemistry. These reactions produced SOA with exceptionally high mass yields of 1.34 ± 0.20 and 1.50 ± 0.20, respectively, reflecting the low volatility and high density of reaction products. The dominant SOA product, 4-nitrocatechol, for which an authentic standard is available, was identified through thermal desorption particle beam mass spectrometry and Fourier transform infrared spectroscopy and was quantified in filter samples by liquid chromatography using UV detection. Molar yields of 4-nitrocatechol were 0.30 ± 0.03 and 0.91 ± 0.06 for reactions with OH and NO radicals, and thermal desorption measurements of volatility indicate that it is semivolatile at typical atmospheric aerosol loadings, consistent with field studies that have observed it in aerosol particles. Formation of 4-nitrocatechol is initiated by abstraction of a phenolic H atom by an OH or NO radical to form a β-hydroxyphenoxy/o-semiquinone radical, which then reacts with NO to form the final product.

Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acids (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air-seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transferreaction mass spectrometry (PTR-MS) University of Colorado light-emitting diode cavity-enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas-phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive dicarbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78 %, 29 %, 4 % and < 1 % for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples. Recent field observations indicate missing sources for oxygenated hydrocarbons from the oceans in atmospheric models (Myriokefalitakis et al., 2008; Sinreich et al., 2010). It is known that the SML is a complex organic and inorganic mixture (Pogorzelski and Kogut, 2003;Kozarac et al., 2005). The organic substances in the SML, including proteins, polysaccharides, humic-type materials and lipids, are likely produced from marine biota (Wilson and Collier, 1972;Gašparovic et al., 1998). As a main component of lipids, fatty acids (FA), including polyunsaturated FA (PUFA) have been detected in considerable amounts in sea surface water with concentrations of 3-200 µg L −1 (Marty et al., 1979;Derieux et al., 1998;André et al., 2004;Parrish et al., 2005;Blaženka et al., 2007). PUFA contribute as much as ∼43 % of the total FA measured, for example, in sub-Arctic Norwegian fjords Published by Copernicus Publications on behalf of the European Geosciences Union.

Humans spend approximately 90% of their time indoors, impacting their own air quality through occupancy and activities. Human VOC emissions indoors from exercise are still relatively uncertain, and questions remain about emissions from chlorine‐based cleaners. To investigate these and other issues, the ATHLETic center study of Indoor Chemistry (ATHLETIC) campaign was conducted in the weight room of the Dal Ward Athletic Center at the University of Colorado Boulder. Using a Vocus Proton‐Transfer‐Reaction Time‐of‐Flight Mass Spectrometer (Vocus PTR‐TOF), an Aerodyne Gas Chromatograph (GC), an Iodide‐Chemical Ionization Time‐of‐Flight Mass Spectrometer (I‐CIMS), and Picarro cavity ringdown spectrometers, we alternated measurements between the weight room and supply air, allowing for determination of VOC, NH3, H2O, and CO2 emission rates per person (emission factors). Human‐derived emission factors were higher than previous studies of measuring indoor air quality in rooms with individuals at rest and correlated with increased CO2 emission factors. Emission factors from personal care products (PCPs) were consistent with previous studies and typically decreased throughout the day. In addition, N‐chloraldimines were observed in the gas phase after the exercise equipment was cleaned with a dichlor solution. The chloraldimines likely originated from reactions of free amino acids with HOCl on gym surfaces.

Abstract. We have developed a field-deployable gas chromatograph (GC) with thermal desorption preconcentration (TDPC), which is demonstrated here with automatic detector switching between two high-resolution time-of-flight mass spectrometers (TOF-MSs) for in situ measurements of volatile organic compounds (VOCs). This system provides many analytical advances, including acquisition of fast time–response data in tandem with molecular speciation and two types of mass spectral information for each resolved GC peak: molecular ion identification from Vocus proton transfer reaction (PTR) TOF-MS and fragmentation pattern from electron ionization (EI) TOF-MS detection. This system was deployed during the 2018 ATHLETIC campaign at the University of Colorado Dal Ward Athletic Center in Boulder, Colorado, where it was used to characterize VOC emissions in the indoor environment. The addition of the TDPC-GC increased the Vocus sensitivity by a factor of 50 due to preconcentration over a 6 min GC sample time versus direct air sampling with the Vocus, which was operated with a time resolution of 1 Hz. The GC-TOF methods demonstrated average limits of detection of 1.6 ppt across a range of monoterpenes and aromatics. Here, we describe the method to use the two-detector system to conclusively identify a range of VOCs including hydrocarbons, oxygenates, and halocarbons, along with detailed results including the quantification of anthropogenic monoterpenes, where limonene accounted for 47 %–80 % of the indoor monoterpene composition. We also report the detection of dimethylsilanediol (DMSD), an organosiloxane degradation product, which was observed with dynamic temporal behavior distinct from volatile organosiloxanes (e.g., decamethylcyclopentasiloxane, D5 siloxane). Our results suggest DMSD is produced from humidity-dependent heterogeneous reactions occurring on surfaces in the indoor environment, rather than formed through gas-phase oxidation of volatile siloxanes.