During use of sodium hypochlorite bleach, gas-phase hypochlorous acid (HOCl) and chlorine (Cl2) are released, which can react with organic compounds present in indoor air. Reactivity between HOCl/Cl2 and limonene, a common constituent of indoor air, has been observed. The purpose of this study was to characterize the chemical species generated from gas-phase reactions between HOCl/Cl2 and limonene. Gas-phase reactions were prepared in Teflon chambers housing HOCl, Cl2, and limonene. The resulting chemical products were analyzed using gas-phase preconcentration, followed by gas chromatography and high-resolution mass spectrometry. Several chlorinated products were detected, including limonene species containing one, two, and three chlorines and limonene chlorohydrin. Product concentrations and yields were estimated for the most abundant products, and greater than 80% of transformed limonene was represented in the detected products. Temporal sampling of the reactions allowed time courses to be plotted for limonene decay and chlorinated limonene product generation under different conditions, including the treatments of HOCl/Cl2, Cl2 only, high vs low relative humidity, and +/- ozone. These experiments add product speciation, yield estimates, and an understanding of environmental factors affecting product formation to previous studies, further highlighting the chemical transformations initiated by sodium hypochlorite bleach in indoor air.

Peracetic acid is a disinfection agent used in medical and food processing facilities, and occupational exposures have been documented. To facilitate characterization of daily occupational exposures, the current work describes the development of a personal sampling technique to quantify the peracetic acid concentration in air samples. Peracetic acid atmospheres were generated in 100 L Teflon chambers, and samples were collected on 350 mg XAD-7 solid sorbent tubes for 4 h at a flow rate of 250 mL/min using a personal sampling pump. Indirect measurement of peracetic acid was achieved by desorption from the sorbent and subsequent treatment with cyclohexene to initiate an epoxidation reaction, formally known as the Prilezhaev reaction. The epoxidation product, cyclohexene oxide, was quantified by gas chromatography-mass spectrometry. The reaction enabled quantification of peracetic acid with high specificity over the common co-contaminants hydrogen peroxide and acetic acid, which were introduced in 10-fold and 100-fold excess to challenge the reaction. The technique also demonstrated an overall estimate of bias and precision of 11 and 8%, respectively, and a limit of detection of 60 ppbv was estimated. Preliminary storage experiments indicate that unreacted peracetic acid is stable on the sorbent tubes for 72 h when stored at -20 °C following collection. Overall, the specificity of the reaction and capability to sample for longer time periods than current methods, in addition to the use of safer personal sampling materials, demonstrate the utility of this technique for peracetic acid measurement in air. © 2022 Elsevier Inc.. All rights reserved.