The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 10 4 –10 5 molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅10 6 molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air.

Modeling the interaction of dust with long-wave (LW) radiation is still a challenge because of the scarcity of information on the complex refractive index of dust from different source regions. In particular, little is known about the variability of the refractive index as a function of the dust mineralogical composition, which depends on the specific emission source, and its size distribution, which is modified during transport. As a consequence, to date, climate models and remote sensing retrievals generally use a spatially invariant and time-constant value for the dust LW refractive index. In this paper, the variability of the mineral dust LW refractive index as a function of its mineralogical composition and size distribution is explored by in situ measurements in a large smog chamber. Mineral dust aerosols were generated from 19 natural soils from 8 regions: northern Africa, the Sahel, eastern Africa and the Middle East, eastern Asia, North and South America, southern Africa, and Australia. Soil samples were selected from a total of 137 available samples in order to represent the diversity of sources from arid and semi-arid areas worldwide and to account for the heterogeneity of the soil composition at the global scale. Aerosol samples generated from soils were re-suspended in the chamber, where their LW extinction spectra (3–15 µm), size distribution, and mineralogical composition were measured. The generated aerosol exhibits a realistic size distribution and mineralogy, including both the sub- and super-micron fractions, and represents in typical atmospheric proportions the main LW-active minerals, such as clays, quartz, and calcite. The complex refractive index of the aerosol is obtained by an optical inversion based upon the measured extinction spectrum and size distribution. Results from the present study show that the imaginary LW refractive index (k) of dust varies greatly both in magnitude and spectral shape from sample to sample, reflecting the differences in particle composition. In the 3–15 µm spectral range, k is between ∼ 0.001 and 0.92. The strength of the dust absorption at ∼ 7 and 11.4 µm depends on the amount of calcite within the samples, while the absorption between 8 and 14 µm is determined by the relative abundance of quartz and clays. The imaginary part (k) is observed to vary both from region to region and for varying sources within the same region. Conversely, for the real part (n), which is in the range 0.84–1.94, values are observed to agree for all dust samples across most of the spectrum within the error bars. This implies that while a constant n can be probably assumed for dust from different sources, a varying k should be used both at the global and the regional scale. A linear relationship between the magnitude of the imaginary refractive index at 7.0, 9.2, and 11.4 µm and the mass concentration of calcite and quartz absorbing at these wavelengths was found. We suggest that this may lead to predictive rules to estimate the LW refractive index of dust in specific bands based on ...