Reactive uptake of ozone to azo dyes in a coated-wall flow tube

Azo dyes are the most common colorants in consumer products, including clothing and cosmetics. Some azo dyes and their products from reductive degradation are known to be mutagenic, so dermal exposure to these species has been studied extensively. In contrast, oxidative degradation of azo dyes in consumer products has not been studied so thoroughly. In the indoor environment, ozone is ubiquitous, so reactive uptake of ozone to azo dyes could lead to dermal exposure to other classes of degradation products. Here, we report the first measurements of the reactive uptake of ozone to thin films of three widely used commercial azo dyes: sunset yellow, amaranth, and tartrazine. Steady-state uptake was observed for all three dyes, under all conditions investigated, even at the lowest relative humidity (RH) of 0%. The uptake coefficients increased with RH. For sunset yellow at 100 ppb of ozone, the value at 80% RH, (2.0 ± 0.5) × 10^-7, was 2.5 times greater than that at 0% RH, (8 ± 1) × 10^-8, consistent with plasticization of the thin film due to absorption of water. The uptake coefficient of sunset yellow at 80% RH exhibited an inverse dependence on the ozone mixing ratio, approaching an asymptote of 1 × 10^-7 above 250 ppb. At 80% RH and 100 ppb of ozone, the uptake coefficients for the three dyes were similar, (2.0 ± 0.5) × 10^-7 for sunset yellow, (2.7 ± 0.6) × 10^-7 for amaranth, and (3.2 ± 0.3) × 10^-7 for tartrazine, despite differences in structural parameters related to the number of reactive sites at the surface. Together, these results are consistent with ozone diffusing into the thin film and the dye molecules mixing between the layers, such that reaction is not restricted to the surface of the film. Finally, the results are suggestive of a role for azo dyes, including the occurrence of their oxidation products, in indoor chemistry.