Impact of the spectral and spatial properties of natural light on indoor gas-phase chemistry: Experimental and modeling study.

The characteristics of indoor light (intensity, spectral, spatial distribution) originating from outdoors have been studied using experimental and modeling tools. They are influenced by many parameters such as building location, meteorological conditions, and the type of window. They have a direct impact on indoor air quality through a change in chemical processes by varying the photolysis rates of indoor pollutants. Transmittances of different windows have been measured and exhibit different wavelength cutoffs, thus influencing the potential of different species to be photolysed. The spectral distribution of light entering indoors through the windows was measured under different conditions and was found to be weakly dependent on the time of day for indirect cloudy, direct sunshine, partly cloudy conditions contrary to the light intensity, in agreement with calculations of the transmittance as a function of the zenithal angle and the calculated outdoor spectral distribution. The same conclusion can be drawn concerning the position within the room. The impact of these light characteristics on the indoor chemistry has been studied using the INCA-Indoor model by considering the variation in the photolysis rates of key indoor species. Depending on the conditions, photolysis processes can lead to a significant production of radicals and secondary species.

Reactive indoor air chemistry and health-A workshop summary.

The chemical composition of indoor air changes due to the reactive nature of the indoor environment. Historically, only the stable parent compounds were investigated due to their ease of measurement by conventional methods. Today, however, scientists can better characterize oxidation products (gas and particulate-phase) formed by indoor chemistry. An understanding of occupant exposure can be developed through the investigation of indoor oxidants, the use of derivatization techniques, atmospheric pressure detection, the development of real-time technologies, and improved complex modeling techniques. Moreover, the connection between exposure and health effects is now receiving more attention from the research community. Nevertheless, a need still exists for improved understanding of the possible link between indoor air chemistry and observed acute or chronic health effects and long-term effects such as work-related asthma.

Identification of the major HOx radical pathways in an indoor air environment.

OH and HO2 profiles measured in a real environment have been compared to the results of the INCA-Indoor model to improve our understanding of indoor chemistry. Significant levels of both radicals have been measured and their profiles display similar diurnal behavior, reaching peak concentrations during direct sunlight (up to 1.6×106 and 4.0×107  cm-3 for OH and HO2 , respectively). Concentrations of O3 , NOx , volatile organic compounds (VOCs), HONO, and photolysis frequencies were constrained to the observed values. The HOx profiles are well simulated in terms of variation for both species (Pearson's coefficients: pOH =0.55, pHO2 =0.76) and concentration for OH (mean normalized bias error: MNBEOH =-30%), HO2 concentration being always underestimated (MNBEHO2 =-62%). Production and loss pathways analysis confirmed HONO photolysis role as an OH precursor (here up to 50% of the production rate). HO2 formation is linked to OH-initiated VOC oxidation. A sensitivity analysis was conducted by varying HONO, VOCs, and NO concentrations. OH, HO2 , and formaldehyde concentrations increase with HONO concentrations; OH and formaldehyde concentrations are weakly dependent on NO, whereas HO2 concentrations are strongly reduced with increasing NO. Increasing VOC concentrations decreases OH by consumption and enhances HO2 and formaldehyde.

Assessment of indoor HONO formation mechanisms based on in situ measurements and modeling.

The photolysis of HONO has been found to be the oxidation driver through OH formation in the indoor air measurement campaign SURFin, an extensive campaign carried out in July 2012 in a classroom in Marseille. In this study, the INCA-Indoor model is used to evaluate different HONO formation mechanisms that have been used previously in indoor air quality models. In order to avoid biases in the results due to the uncertainty in rate constants, those parameters were adjusted to fit one representative day of the SURFin campaign. Then, the mechanisms have been tested with the optimized parameters against other experiments carried out during the SURFin campaign. Based on the observations and these findings, we propose a new mechanism incorporating sorption of NO2 onto surfaces with possible saturation of these surfaces. This mechanism is able to better reproduce the experimental profiles over a large range of conditions.

Fast sorption measurements of volatile organic compounds on building materials: Part 1 - Methodology developed for field applications.

A Proton Transfer Reaction-Mass Spectrometer (PTR-MS) has been coupled to the outlet of a Field and Laboratory Emission Cell (FLEC), to measure volatile organic compounds (VOC) concentration during a sorption experiments (Rizk et al., this issue) [1]. The limits of detection of the PTR-MS for three VOCs are presented for different time resolution (2, 10 and 20 s). The mass transfer coefficient was calculated in the FLEC cavity for the different flow rates. The concentration profile obtained from a sorption experiment performed on a gypsum board and a vinyl flooring are also presented in comparison with the profile obtained for a Pyrex glass used as a material that do not present any sorption behavior (no sink). Finally, the correlation between the concentration of VOCs adsorbed on the surface of the gypsum board at equilibrium (Cse ) and the concentration of VOCs Ce measured in the gas phase at equilibrium is presented for benzene, C8 aromatics and toluene.

The MERMAID study: indoor and outdoor average pollutant concentrations in 10 low-energy school buildings in France.

Indoor air quality was characterized in 10 recently built energy-efficient French schools during two periods of 4.5 days. Carbon dioxide time-resolved measurements during occupancy clearly highlight the key role of the ventilation rate (scheduled or occupancy indexed), especially in this type of building, which was tightly sealed and equipped with a dual-flow ventilation system to provide air refreshment. Volatile organic compounds (VOCs) and inorganic gases (ozone and NO2 ) were measured indoors and outdoors by passive techniques during the occupied and the unoccupied periods. Over 150 VOC species were identified. Among them, 27 species were selected for quantification, based on their occurrence. High concentrations were found for acetone, 2-butanone, formaldehyde, toluene, and hexaldehyde. However, these concentrations are lower than those previously observed in conventional school buildings. The indoor/outdoor and unoccupied/occupied ratios are informative regarding emission sources. Except for benzene, ozone, and NO2 , all the pollutants in these buildings have an indoor source. Occupancy is associated with increased levels of acetone, 2-butanone, pentanal, butyl acetate, and alkanes.

Note: a laser-flash photolysis and laser-induced fluorescence detection technique for measuring total HO2 reactivity in ambient air.

A novel instrument for measuring total HO2 reactivity in the troposphere was successfully developed using a laser-flash photolysis and laser-induced fluorescence detection technique. Validation and testing were conducted through kinetic measurements of the reaction of HO2 radicals with NO2, and the results were found to be in good agreement with recent recommended values. The limit of detection (LOD) for HO2 loss rate measurement is achieved to be 0.024 s(-1) (3σ) with 60 times decay integrations. An observation of ambient air was carried out in a suburb of Tokyo to test the practical use of the developed instrument and un-expected rapid HO2 loss rate has been observed.

Atmospheric and kinetic studies of OH and HO2 by the FAGE technique.

A new FAGE setup has recently been built at the University of Lille, France. It permits the quantification of OH and HO2 in the atmosphere with a detection limit of 3 x 105 molecules/(cm3 x min) for OH and 1 x 10(6) molecules/(cm3 x min) for HO2. Its coupling to a photolysis cell enables the measurement of the total reactivity of the hydroxyl radical in ambient air and kinetic studies in laboratory. Two configurations have been considered: one with the photolysis cell at 90 degrees to the FAGE nozzle, the other on line with the FAGE nozzle. The two configurations have been tested and validated by measuring the well known rate constants of OH with CH4, C3H8 and CO. The advantages and drawbacks of each configuration have been evaluated. The "on line" configuration limits losses and permits measurements over a larger reactivity range but is affected by OH formation from the laser beam striking the FAGE nozzle, thus limiting the ability to carry out energy dependence studies which can, in contrast, be successfully performed in the 90 degrees configuration.