Knowledge gaps related to mass transfer processes involved in passive air sampling of semivolatile organic compounds and factors potentially influencing passive sampling rates (PSRs) were addressed with controlled laboratory experiments, mass transfer modeling, and a field sampling campaign. The observed non-uniform SVOC distributions within porous passive sampling media (PSMs) contradict an assumption in an earlier passive air sampling theory and proved the existence of a kinetic resistance on the PSM side. This resistance can affect PSRs as revealed by a new PAS model which is based on fundamental laws of mass transfer in air and porous media. By considering mass transfer processes within the PSM, the model is able to explain the large variations of field calibrated PSRs with temperature and between SVOC species and the two-stage uptake process, which cannot be addressed by the earlier PAS theory. Because the PSM side kinetic resistance invalidates the assumption that depuration compounds added to the PSM prior to deployment are subject to the same kinetic resistance as the sampled SVOCs, PSRs derived from the loss rates of depuration compounds can differ from the actual PSRs of the sampled SVOCs. Using such PSRs could thus introduce additional uncertainty to PAS-derived air concentrations. Experiments using XAD-resin and silica-gel filled mesh cylinder as PSMs for the uptake of SVOCs and water vapor respectively revealed that sorbent in the inner portion of the PSM does not take part in chemical uptake; PSRs are thus proportional to the interfacial transfer area but not the amount of the sorbent. Accordingly, thinner PSM can be used to reduce the amount of sorbent while keeping or even increasing the PSRs. Optimized designs of PASs could be tested time efficiently using the gravimetrical approach based on water vapor uptake by silica gel.

Knowledge gaps related to mass transfer processes involved in passive air sampling of semivolatile organic compounds and factors potentially influencing passive sampling rates (PSRs) were addressed with controlled laboratory experiments, mass transfer modeling, and a field sampling campaign. The observed non-uniform SVOC distributions within porous passive sampling media (PSMs) contradict an assumption in an earlier passive air sampling theory and proved the existence of a kinetic resistance on the PSM side. This resistance can affect PSRs as revealed by a new PAS model which is based on fundamental laws of mass transfer in air and porous media. By considering mass transfer processes within the PSM, the model is able to explain the large variations of field calibrated PSRs with temperature and between SVOC species and the two-stage uptake process, which cannot be addressed by the earlier PAS theory. Because the PSM side kinetic resistance invalidates the assumption that depuration compounds added to the PSM prior to deployment are subject to the same kinetic resistance as the sampled SVOCs, PSRs derived from the loss rates of depuration compounds can differ from the actual PSRs of the sampled SVOCs. Using such PSRs could thus introduce additional uncertainty to PAS-derived air concentrations. Experiments using XAD-resin and silica-gel filled mesh cylinder as PSMs for the uptake of SVOCs and water vapor respectively revealed that sorbent in the inner portion of the PSM does not take part in chemical uptake; PSRs are thus proportional to the interfacial transfer area but not the amount of the sorbent. Accordingly, thinner PSM can be used to reduce the amount of sorbent while keeping or even increasing the PSRs. Optimized designs of PASs could be tested time efficiently using the gravimetrical approach based on water vapor uptake by silica gel.

The presence of complex mixtures of compounds in ambient air, many of which are either unknown or uncharacterised makes an assessment of risk associated with these exposures problematic. Bioanalytical methods can provide an integrative assessment of complex mixture potency for specific mechanisms of toxicity within these contexts. The aim of this study was to evaluate the suitability of monitoring ambient air exposures as sampled by (polyurethane foam) PUF passive air samplers (PAS) using effect based techniques (bioanalytical methods). Passive samplers have the advantage of offering a low-tech inexpensive monitoring strategy which can thereby increase sampling capacity across a broader range of scenarios simultaneously. One challenge posed by the application of passive samplers in particular for these assessments has been the expression of potency estimates in relatively non-comparable terms specific to a given dose of the sampler or for a specific deployment period. The project was therefore designed in order to address these aims and previously identified challenges by investigating the applicability of these techniques for: monitoring in both indoor and outdoor air, the determination of seasonal exposure gradients; the determination of exposure gradients in different locations (urban capitals, regional centres, background); and the application of in-situ calibration to provide comparable effect measurements in terms of equivalent reference compound air concentrations. Air sampled using PUF PAS was monitored for its capacity to induce biological responses which are mechanistically relevant to critical health endpoints in these scenarios. The mechanisms assessed included genotoxicity (DNA damage – umuC assay), Aryl hydrocarbon receptor (AhR) activity (CAFLUX assay), and estrogenicity (ESCREEN assay). The findings from this effect based monitoring revealed that the level of biological response measured changes with the exposure scenario (indoor vs. outdoor; summer vs. winter; urban capital cities vs. background locations). Estrogenicity for example assessed as estradiol equivalent air concentrations (E Eq BIO) averaged 54 pg.m-3 (1.5 - 185 pg.m-3) in indoor air, while samples from ambient air were found to be not estrogenic. Total aryl hydrocarbon receptor (AhR) activity assessed as 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalent air concentrations (TCDD Eq BIO) averaged 4.1 pg.m-3 (1.3 – 7.2 pg.m-3) in indoor air while samples from ambient air averaged 15 pg.m-3 (1.5 – 46 pg.m-3)in summer and 53 pg.m-3 (2.2 – 251 pg.m-3) in winter. The relationship for both direct (-S9) and indirect (+S9) acting genotoxicity and AhR activity were found to be relatively consistent with respect to both season (elevated in winter) and location (elevated in urban capital cities). Overall suitable techniques were developed for combining passive sampling with multiple end-point toxicity testing and it was demonstrated that these techniques may be applied across different exposure scenarios. During the course of this method development and interpretation process a range of limitations were identified relating to: the use and application of effect based techniques to monitor environmental samples; the use of passive samplers within this context specifically; and also with the application of in-situ calibration techniques to passive samplers to improve the comparability of these assessments.

This study extends the work we have previously done by reporting on both gas-phase and particulate phase PCB concentrations in Chicago air as well as giving a first report on airborne OH-PCBs in Chicago. Gas phase PCB concentrations ranged from 43.1 pg/m³ to 2250 pg/m³, with an average concentration of 594 pg/m³ ± 445 pg/m³, and exhibited strong temporal trends. Particulate phase PCBs accounted on average for 4.3% of total PCBs in a sample. OH-PCBs were detected in both the gas and particulate phase and exhibit characteristics of either emission sources or atmospheric reactions depending on the congener.

Les composés organiques semi-volatils (COSVs) regroupent un grand nombre de composés chimiques utilisés notamment comme substances actives ou additifs dans les matériaux de construction, de décoration et dans de nombreux produits de consommation. Les COSVs sont omniprésents dans les environnements intérieurs et fréquemment détectés dans les poussières sédimentées et dans le compartiment aérien. Cette thèse a permis de documenter les concentrations de 57 composés dans 30 logements français et d'utiliser ces mesures pour tester un modèle d'équilibre visant à prédire leur répartition dans les différents compartiments de l'environnement intérieur. De ce travail, il ressort une forte ubiquité des COSVs dans les logements étudiés. Les concentrations les plus élevées ont été observées pour les phtalates et dans une moindre mesure pour le bisphénol A, les muscs synthétiques et certains pesticides et HAPs. Ces résultats confirment l'intérêt de mieux caractériser l'exposition de la population générale aux COSVs dans l'habitat français. Les travaux portant sur le modèle d'équilibre ont montré que le coefficient de partage entre l'air et l'octanol (Koa) peut être un bon prédicteur pour estimer la concentration d'un composé donné dans un ensemble de logements. Cependant, certaines limites ont été identifiées et une meilleure caractérisation des paramètres utilisés est recommandée. / Semivolatile organic compounds (SVOCs) include a large number of chemicals compounds used as active substances or additives in building materials and in many consumer products. SVOCs are ubiquitous in indoor environments and frequently detected in settled dust and indoor air. This work has investigated indoor concentrations of 57 target compounds in 30 French dwellings and measurements were used to test an equilibrium model to predict their partitioning in indoor compartments. The results showed a strong ubiquity of SVOCs in French dwellings. The highest concentrations were measured for phthalates and to a lesser extent for bisphenol A, synthetic musks, some pesticides and PAHs. These results confirm the interest to assess human exposure to SVOCs in the French dwellings. The work on the predictive model showed that octanol/air partitioning coefficient (Koa) is a good predictor to estimate SVOC concentrations in a large number of buildings. However, some limits were identified and a better estimation of the parameters used in these models is required.