The effects of indoor conditions (ozone concentration, temperature, relative humidity (RH), and the presence of NO(x)) on heterogeneous squalene oxidation were studied with Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy. The heterogeneous kinetics of squalene-ozone reaction revealed a pseudo-first-order reaction rate constant of 1.22 x 10(-5)/s at [O(3)] = 40 ppb. Oxidation kinetics were insensitive to temperature over the range of 24-58 +/- 2 degrees C as well as to RH and presence of NO(x). Products, however, were affected by the environmental parameters. As temperature was increased, fewer surface products and more low molecular weight gaseous products were observed. Lower air exchange rates also enhanced gas phase reactions, allowing for formation of secondary gas phase products. As RH increased, there was a shift in product distribution from ketones to aldehydes, and the presence of NO(x) during squalene ozonolysis resulted in the formation of nitrated oxidation products. Identified surface products included 6-methyl-5-hepten-2-one, geranyl acetone, and long chain ketones and aldehydes, while gas phase products included formaldehyde, acetone, 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid. Practical Implications Heterogeneous oxidation of squalene resulted in surface products including long chain aldehydes and ketones, and gas phase products including formaldehyde, a known human carcinogen (IARC 2006), and bicarbonyl compounds like: 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid that are characterized as asthma triggers and sensitizers (Anderson et al., 2007; Jarvis et al., 2005). In addition, ozonolysis experiments in the presence of NO(x) showed the formation of nitrated surface oxidation products. Such nitrated products may have higher mutagenicity, carcinogenicity, or allergenic potential than their nitrate free counterparts (Franze et al., 2005; Pitts, 1983). Kinetic studies determined that at moderate ozone levels of 40 ppb (Uhde and Salthammer, 2007), and an estimated skin surface density of 4 x 10(15) molecules/cm(2), surface reaction would lead to a minimum product formation flux of 4 x 10(10) molecules cm(2)/s. As squalene is naturally occurring and continually produced by the human body, its concentration in the indoor environment cannot be controlled. However, this study highlights the importance of regulating air exchange rate, temperature, and ozone level in the indoor environment on the formation of potentially harmful or irritating squalene oxidation products.

Nicotine dynamics in an indoor environment can be greatly affected by building parameters (e.g. relative humidity (RH), air exchange rate (AER), and presence of ozone), as well as surface parameters (e.g. surface area (SA) and polarity). To better understand the indoor fate of nicotine, these parameter effects on its sorption, desorption, and oxidation rates were investigated on model indoor surfaces that included fabrics, wallboard paper, and wood materials. Nicotine sorption under dry conditions was enhanced by higher SA and higher polarity of the substrate. Interestingly, nicotine sorption to cotton and nylon was facilitated by increased RH, while sorption to polyester was hindered by it. Desorption was affected by RH, AER, and surface type. Heterogeneous nicotine–ozone reaction was investigated by Fourier transform infrared spectrometry with attenuated total reflection (FTIR-ATR), and revealed a pseudo first-order surface reaction rate of 0.035 ± 0.015 min⁻¹ (at [O₃] = 6 ± 0.3 × 10¹⁵ molecules cm⁻³) that was partially inhibited at high RH. Extrapolation to a lower ozone level ([O₃] = 42 ppb) showed oxidation on the order of 10⁻⁵ min⁻¹ corresponding to a half-life of 1 week. In addition, similar surface products were identified in dry and high RH using gas chromatography-mass spectrometry (GC-MS). However, FTIR analysis revealed different product spectra for these conditions, suggesting additional unidentified products and association with surface water. Knowing the indoor fate of condensed and gas phase nicotine and its oxidation products will provide a better understanding of nicotine’s impact on personal exposures as well as overall indoor air quality.