The oxidation field is generated by the reaction of ozone with oils and fats on our skin, especially the unsaturated triterpene squalene, which constitutes about 10 percent of the skin lipids that protect our skin and keep it supple. The reaction releases a host of gas phase chemicals containing double bonds that react further in the air with ozone to generate substantial levels of OH radicals. These squalene degradation products were characterized and quantified individually using Proton Transfer reaction Mass Spectrometry and fast gas chromatograph-mass spectrometry systems. In addition, the total OH reactivity was determined in parallel enabling the OH levels to be quantified empirically.

The experiments were conducted at the Technical University of Denmark (DTU) in Copenhagen. Four test subjects stayed in a special climate-controlled chamber under standardized conditions. Ozone was added to the chamber air inflow in a quantity that was not harmful to humans but representative of higher indoor levels. The team determined the OH values before and during the volunteers' stay both with and without ozone present.

In order to understand how the human-generated OH field looked like in space and time during the experiments, results from a detailed multiphase chemical kinetic model from the University of California, Irvine were combined with a computational fluid dynamics model from Pennsylvania State University, both based in the USA. After validating the models against the experimental results, the modeling team examined how the human-generated OH field varied under different conditions of ventilation and ozone, beyond those tested in the laboratory. From the results, it was clear that the OH radicals were present, abundant, and forming strong spatial gradients.

"Our modeling team is the first and currently the only group that can integrate chemical processes between the skin and indoor air, from molecular scales to room scales," said Manabu Shiraiwa, a professor at UC Irvine who led the modeling part of the new work. "The model makes sense of the measurements -- why OH is generated from the reaction with the skin."

Shiraiwa added that there remain unanswered questions, like the way humidity levels impact the reactions the team traced. "I think this study opens up a new avenue for indoor air research," he said.

Adapt test methods for furniture and building materials

"We need to rethink indoor chemistry in occupied spaces because the oxidation field we create will transform many of the chemicals in our immediate vicinity. OH can oxidize many more species than ozone, creating a multitude of products directly in our breathing zone with as yet unknown health impacts." This oxidation field will also impact the chemical signals we emit and receive," says project leader Jonathan Williams, "and possibly help explain the recent finding that our sense of smell is generally more sensitive to molecules that react faster with OH."

The new finding also has implications for our health: Currently, chemical emissions of many materials and furnishings are being tested in isolation before they are approved for sale. However, it would be advisable to also conduct tests in the presence of people and ozone, says atmospheric chemist Williams. This is because oxidation processes can lead to the generation of respiratory irritants such as 4-oxopentanal (4-OPA) and other OH radical-generated oxygenated species, and small particles in the immediate vicinity of the respiratory tract. These can have adverse effects, especially in children and the infirm.

These findings are part of the project ICHEAR (Indoor Chemical Human Emissions and Reactivity Project) which brought together a group of collaborating international scientists from Denmark (DTU), the USA (Rutgers University), and Germany (MPI). The modeling was part of the MOCCIE project based at the University of California Irvine and the Pennsylvania State University. Both projects were funded by grants from the A. P. Sloan foundation.