L'impact des particules fines (PM10-PM2.5) sur la santé a été largement étudié depuis de nombreuses années, notamment pour les sites de proximité automobile. De nombreux dépassements de la valeur limite en PM10 imposée par les directives européennes ont lieu en France et en Europe, en milieu urbain et plus fréquemment en proximité automobile. Les émissions véhiculaires sont une des sources majeures de particules. Ces émissions proviennent à la fois des échappements (TE) mais aussi des émissions hors échappement (TNE) (abrasion des freins, des pneus et de la route, resuspension des poussières de la chaussée dû au déplacement des véhicules…). En France, très peu d'études en proximité automobile ont été effectuées. Les études de déconvolution des sources en France et en Europe s'appuient la plupart du temps sur des parcs automobiles non adaptés (parc américain) ou trop anciens. De plus, seule la source TE est considérée, ce qui sous-estime largement la contribution véhiculaire aux PM10. La meilleure connaissance de la formation, de la caractérisation et de la quantification des particules émises par le trafic est devenue primordiale. L'objectif final étant la détermination des contributions des émissions véhiculaires TE et TNE aux sources primaires de particules, la caractérisation précise de ces sources est primordial. Pour cela, la recherche de traceurs véhiculaires en phases gaz et particulaire a constitué une grosse partie de ce travail. La combinaison de l'étude sur banc à rouleau de cinq véhicules bien représentés dans le parc automobile roulant français et de l'étude effectuée en proximité automobile (Rocade Sud de Grenoble) a constitué le socle de ce travail. Dans la première étude, certains composés chimiques sont apparus comme indicateurs des émissions TE (EC, HAP légers, profils d'alcanes typiques, quelques métaux comme Fe, Cu etc.). Des différences importantes sont observées entre les véhicules diesel sans filtre à particules (FAP) et les véhicules essence et diesel sans FAP. La seconde étude, comparant le site trafic (Grenoble-Echirolles) avec un site de fond urbain (Grenoble- Les Frênes), a mis en évidence certains composés chimiques comme spécifiques des sources TNE et TE sur la base des connaissances acquises avec les mesures sur banc et sur l'enrichissement de certains composés par rapport au site de fond (EC, Cu, Fe, Sn, Mn…). On peut souligner certains enrichissements majeurs comme EC (78%), Cu (82%), Fe (88%), etc. La résolution temporelle a été faite sur une base de 4h, permettant ainsi une caractérisation chimique détaillée en fonction des heures de pointe et "creuses". Une troisième étude, en site trafic également (Grenoble-Le Rondeau) mais sous influence du salage en hiver, est venue compléter nos recherches. Enfin, en nous appuyant sur les résultats de la première partie, nous avons cherché à déconvoluer les sources véhiculaires TE et TNE (Echirolles et Le Rondeau) au moyen d'un modèle statistique d'analyses multivariées, la PMF (Positive Matrix Factorization), apportant ainsi la contribution possible de ces sources aux PM10. Les émissions véhiculaires (TNE+ TE) y contribuent à 34% à Echirolles et à 53% au Rondeau. Quelques incertitudes sont discutées par rapport aux résultats trouvés avec ceux provenant de l'étude géochimique détaillée en première partie. / Fine particles (PM10-P2.5) are recognized to be deleterious to human health particularly in the roadway vicinity. In European countries, and in particular in France, the European daily limit value is exceeded in many sites more than 35 times a year. One of the major sources of fine particles in urban and roadside sites is road traffic. Emissions from road traffic involve exhaust and non-exhaust emissions (resuspension of road dusts, from the brakes, tyres and road-surface-wear, from the corrosion of vehicle components…). Numerous studies have been performed in order to account for exhaust emissions, however not in France. Generally, the profiles used in source apportionment models are not adapted (since they are American profiles) to the French or European fleets. In addition, the contribution of the nonexhaust fraction to total particulate matter (PM) mass is generally not accounted for in the source apportionment results. Therefore, PM10 emissions are underestimated. As a result, better knowledge about formation, characterization and quantification of particles from traffic are becoming necessary. The goals of this work are numerous because ambient air and exhaust emission measurements have been involved. The aim is to accurately discriminate exhaust and nonexhaust sources, in order to provide groundbreaking insights into the contribution and chemical composition of traffic sources. Therefore, the analyses of gas and particle tracers represent a big part of this work. The relationships between the measurements of 5 in-use vehicles well-represented in the French fleet and measurements performed in the vicinity of a suburban highway (southern ring road of Grenoble) have been firstly examined. In the first study, several chemical compounds, organics and inorganics, appeared as tracers of vehicular exhaust (EC, light PAHs, typical alkanes profiles, metals like Fe, Cu etc.). Large differences are noticeable between Diesel vehicles without DPF and petrol vehicles/diesel vehicle retrofitted with a DPF. In the second study, comparison with results from an urban background site (Grenoble-Les Frênes) and from the traffic site (Grenoble-Echirolles) highlighted several specific chemical compounds of exhaust and non-exhaust sources (EC, Cu, Fe, Sn, Mn…). Large increments due to the local traffic have been observed (EC (+78%), Cu (82%), Fe (88%), etc.). The 4-hour temporal resolution allowed for the detailed characterization of chemical species during rush hours and less busy periods. An additional field campaign was performed in another roadside site (Grenoble-Le Rondeau) but in winter during salting conditions. Supplementary information was obtained concerning non-exhaust sources. Finally, thanks to the results from the first part of this work, a Positive Matrix Factorization (PMF) analysis was applied to roadside data (Echirolles and Le Rondeau) in order to discriminate non-exhaust and exhaust traffic sources and to estimate their contribution to PM10. Major contributions for traffic sources (exhaust and non-exhaust) were 34% (Echirolles) and 53% (Le Rondeau). Uncertainties linked to these results are discussed with the results of the first part (detailed chemical study) of this work.

In this Dissertation, systematic work has been carried out to study the road-deposited sediment and its adsorbed pollutants from a stormwater pollution perspective. Solid-phase concentration, surface load, source apportionment, risk assessment, and desorption dynamics of polycyclic aromatic hydrocarbons and/or heavy metals in road-deposited sediments (RDS) were investigated. In order to provide data to assist potential strategies of stormwater pollution mitigation and integrated catchment management to minimise the adverse impacts of RDS adsorbed pollutants on stormwawter quality, the following specific topics were addressed. ⑴ The influences of traffic load and antecedent dry-weather period on pollution level and ecological risk of heavy metals in RDS were analyzed. ⑵ The build-up dynamics and chemical fractionation of metals were determined. ⑶ The potential source contributions and risk assessment of polycyclic aromatic hydrocarbons in size-fractionated RDS were firstly determined by a Principal component analysis - Multiple linear regression receptor model. ⑷ The qualitative and quantitative source apportionments of polycyclic aromatic hydrocarbons were subsequently investigated through a combined qualitative Molecular Diagnostic Ratio and quantitative Positive Matrix Factorization source apportionment with an extended data set. ⑸ The exposure risk of polycyclic aromatic hydrocarbons were evaluated and calculated by incremental lifetime cancer risk models. ⑹ Then, a novel ecological risk assessment approach to the RDS adsorbed toxic substances was developed, which was explored exclusively for the study of RDS for a water pollution aspect. ⑺ Finally, the effects of rainwater, major wastewater constituents of dissolved organic matter and surfactant on the leaching of heavy metals from RDS were carried out.

This dissertation is a collection of studies that investigates the issue of air pollution in the field of environmental chemistry. My thesis consists of research works done to measure the concentration of particulate matter (PM) and gas-phase species in ambient air. High concentrations of PM is a significant problem in Utah and in other regions of the world. Particles having an aerodynamic diameter of 2.5 micrometers and smaller play a crucial role in air pollution and pose serious health risks when inhaled. PM is composed of both organic and inorganic components. The organic fraction in PM ranges from 10-90% of the total particle mass. Several methods have been employed to measure the organic fraction of PM, but these techniques require extensive laboratory analysis, expensive bench top equipment, and do a poor job of capturing diurnal variations of the concentrations of ambient organic compounds. The Hansen Lab has developed a new instrument called the Organic Aerosol Monitor (OAM) which is based on gas chromatography followed by mass spectrometry detection platform for measuring the carbonaceous component of PM2.5 on an hourly averaged basis. Organic marker data collected in 2016 using the OAM was used in a Positive Matrix Factorization (PMF) analysis to identify the sources of PM in West Valley City, Utah. Additionally, data was collected in Richfield and Vernal, UT in 2017 - 2018 to quantitatively monitor the composition of organic markers of PM2.5. Some previously unidentified organic compounds in PM were successfully identified during this study, including terpenes, polycyclic aromatic hydrocarbons (PAHs), diethyl phthalate, some herbicides, and pesticides. Gas-phase species play a significant role in driving the formation of air pollutants in Earth's atmosphere. Traditional gas detection methods do not provide high temporally and spatially resolved data; therefore, it becomes important to detect and measure gas-phase species both qualitatively and quantitatively to better understand the sources of air pollution. An incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) combines a broadband incoherent light source, a stable optical cavity formed by two highly reflective mirrors and a charged-coupled device (CCD) detector to quantitatively measure the gas-phase compounds present in the atmosphere. The concentrations of formaldehyde (HCHO) were measured using IBBCEAS to investigate the sources of this hydrocarbon in Bountiful, Utah during 2019. Another important species is OH radical. It is one of the most predominant oxidizing species present in the atmosphere. It is found in low concentrations, 0.1 ppt. Detecting concentrations this low is challenging. A new IBBCEAS instrument has been designed and elements of this instrument were tested by measuring the OH overtones in a variety of short chained alcohols. A set of experiments were conducted to measure the absorption cross-sections for the 5th and 6th OH vibrational overtones in a series of short chained alcohols by IBBCEAS. Because OH radical's lowest energy electronic state occurs in the same wavelength region (i.e., 308 nm) that SO2 absorbs (300-310 nm), a study was conducted in which the concentrations of SO2 were measured using an IBBCEAS and compared with a commercially available SO2 monitor.

Les particules fines (PM2.5) suscitent de plus en plus l’intérêt des pouvoirs publics en raison de leurs effets néfastes sur la qualité de l’air et la santé humaine. La mise en place des politiques de réductions efficaces des émissions requière une connaissance détaillée des contributions des principales sources aux concentrations ambiantes en PM. Ainsi, cette thèse a pour objectifs de caractériser la composition chimique des PM2.5, et de quantifier leurs sources d’émissions à Marseille. Pour se faire, une campagne de mesure d’un an (2011-2012) a été conduite sur le site de fond urbain de « Cinq avenues ». La spéciation chimique complète des filtres collectés a été réalisée, et 3 modèles-récepteurs ont été utilisés: CMB (Chemical Mass Balance), PMF (Positive Matrix Factorization), et ME-2 (Multilinear Engine). Bien que basés sur des concepts sensiblement différents, l’exercice d’intercomparaison des sorties de ces modèles a montré globalement un bon accord pour l’estimation des contributions de la combustion de biomasse (entre 23 et 33% en moyenne annuelle) et du trafic véhiculaire (14-26%). En revanche, des différences significatives sont observées pour la source industrielle (1-18%) et le sulfate d’ammonium (12-30%). Cette étude a mis en évidence une contribution importante de la matière organique (OM) qui représente en moyenne 42% des PM2.5. Quant à la quantification des sources, l’un des résultats marquants est la mise en évidence de deux types d’aérosols de combustion de biomasse, dont l’un provient très probablement du brûlage à l’air libre de déchets verts. Ce dernier peut même être considéré comme un contributeur majeur des PM2.5 à l’automne et en début d’hiver. / Fine particulate matter (PM2.5) has received considerable attention due to its impact on human health and air quality. Therefore, effective plans for human health protection require a detailed knowledge of the most relevant PM emission sources and their contributions to the ambient PM levels. Thus, this thesis aims to characterize the chemical composition of PM2.5 collected in Marseille area, and quantify the impacts of the main emission sources. To meet these objectives, a one-year monitoring campaign was conducted at the urban background site of “Cinq avenues” during the period of 2011-2012. A detailed chemical characterization of the collected PM2.5 filters was performed, and 3 receptor models were applied to this database: CMB (Chemical Mass Balance), PMF (Positive Matrix Factorization), and ME-2 (Multilinear Engine). Although based on significantly different concepts, the intercomparison exercise of the output data of the used models has generally showed a good agreement in estimating the source contributions of biomass burning (representing between 23 and 33% on annual average) and vehicular traffic (between 14 and 26%). In contrast, significant differences were observed for the industrial (1-18%) and ammonium sulfate (12-30%) sources. This study highlighted the significant contribution of organic matter (OM), which represents 42% of the PM2.5 mass, on average. Regarding the source apportionment results, one of the most striking findings is the identification of two types of biomass burning aerosol, one of which probably comes from open burning of green waste. The latter can even be considered a major contributor to the PM2.5 mass during fall and early winter

Polyzyklische aromatische Kohlenwasserstoffe (PAK) sind eine Klasse krebserregender Schadstoffe. Aufgrund ihres weit verbreiteten Vorkommens und der toxischen Risiken für die menschliche Gesundheit und das Ökosystem ist es unerlässlich, durch systematische Forschung wirksame Minderungsstrategien auf verschiedenen Ebenen zu etablieren. In dieser Dissertation wurden Quellenzuordnung, Multimedia-Schicksal, Schlüsselemis-sionssektoren und globale gesundheitliche Auswirkungen von PAK-Belastungen unter-sucht. Diese Forschung wurde durchgeführt, um Daten zur Verfügung zu stellen, die po-tenzielle Minderungsstrategien unterstützen, um PAK-Verschmutzungen und damit ver-bundene gesundheitliche Auswirkungen auf regionaler, nationaler und globaler Ebene zu reduzieren. Zunächst wurde die Quellenzuordnung von Langzeit-PAH in acht Flüssen untersucht. Diese Studie untersuchte systematisch die zeitlichen und saisonalen Trends, die peri-odische Oszillation, die Quellenzuordnung und die Risikobewertung von PAKs für die menschliche Gesundheit in acht Flüssen, die eine quellenorientierte PAK-Minderung in der Region unterstützen können. Zweitens ist das Multimedia-Schicksal von PAKs entscheidend für eine bessere Umwelt-politik. Diese Studie bewertete systematisch die räumlich-zeitliche Verteilung, die Quellenzuordnung, den multimedialen Transport und den Verbleib von PAK, die an Schwebstaub (SPM) in Rhein und Elbe adsorbiert sind, was die Stadtplanung unterstützen kann, um PAK in den Regionen zu lindern. Drittens wurden in dieser Studie die wichtigsten Emissionssektoren von PAK bestimmt, indem die langfristigen verkörperten und ermöglichten PAK-Emissionen in verschiedenen Sektoren abgeschätzt und die Beiträge sozioökonomischer Determinanten quantifiziert wurden. Die Ergebnisse können wirksame Strategien zur Verringerung der PAK-Emissionen in verschiedenen Sektoren aus der Perspektive des Endverbrauchs und des primären Inputverhaltens auf nationaler Ebene unterstützen. Schließlich wurden in dieser Studie die globalen Triebkräfte der gesundheitlichen Auswir-kungen von PAH untersucht, indem ein integrierender Rahmen angewendet wurde, der das globale PAH-Emissionsinventar, das um die Umwelt erweiterte multiregionale Input-Output-Modell, das GEOS-Chem-Chemikalientransportmodell und das lebenslange Lung-enkrebsrisiko verknüpfte Bewertung und Analyse der Strukturzerlegung. Die Ergebnisse können politische Entscheidungen zur Optimierung von Minderungsstrategien aus verschiedenen Perspektiven unterstützen, um PAK-Emissionen und gesundheitliche Aus-wirkungen weltweit effektiv zu reduzieren. / Polycyclic aromatic hydrocarbons (PAHs) are a class of carcinogenic pollutants. Due to their widespread occurrence and toxic risks to human health and ecosystem, it is essen-tial to establish effective mitigation strategies at different scales through systematic re-search. In this dissertation, source apportionment, multimedia fate, key emission sectors and global health impacts of PAH pollutions have been investigated. This research was conducted to provide data to assist potential mitigation strategies to reduce PAH pollu-tions and related health impacts at regional, national, and global scales. Firstly, the source apportionment of long-term PAHs in eight rivers were investigated. This study systematically investigated the temporal and seasonal trends, periodic oscilla-tion, source apportionment, and human health risk assessment of PAHs in eight rivers, which can assist source-oriented PAH mitigation in the region. Secondly, the multimedia fate of PAHs is critical for achieving better environmental poli-cies. This study systematically evaluated the spatiotemporal distribution, source appor-tionment, multimedia transport and fate of PAHs adsorbed on suspended particulate matter (SPM) in Rhine and Elbe Rivers, which can assist urban planning to alleviate PAHs in the regions. Thirdly, the key emission sectors of PAHs were determined in this study through estimat-ing the long-term embodied and enabled PAH emissions in various sectors and quantify-ing the contributions of socioeconomic determinants. The results can assist effective strategies for mitigating PAH emissions in different sectors from the perspectives of final consumption and primary input behaviors at a national scale. Finally, the global driving forces of PAH health impacts were investigated in this study through applying an integrating framework, linking global PAH emission inventory, envi-ronmentally extended multi-regional input-output model, GEOS-Chem chemical transport model, lifetime lung cancer risk assessment, and structure decomposition analysis. The results can assist policy decisions to optimize mitigation strategies from different per-spectives for effectively reducing PAH emissions and health impacts in the world.

Anthropogenic emissions into the troposphere can impact air quality, leading to poorer health outcomes in the affected areas. Volatile organic compounds (VOCs) are a group of chemical compounds, including some which are toxic, that are precursors in the formation of ground-level ozone and secondary organic aerosols. VOCs have a variety of sources, and the distribution of atmospheric VOCs differs significantly over time and space. Historically, the large number of chemical species present at low concentrations (parts-per-trillion to parts-per-billion by volume) have made VOCs difficult to measure in ambient air. However, with improvements in analytical instrumentation, these measurements are becoming more common place. Direct mass spectrometry (MS), such as membrane introduction mass spectrometry (MIMS) and proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) facilitate real-time, continuous measurements of VOCs in air, with full scan mass spectral data capturing changes in chemical composition with high temporal resolution. Operated on-road, mobilized direct MS has been used for quantitative mapping of VOCs at the neighborhood scale, but identifying VOC sources based on the observed mixture of molecules in the full scan MS dataset has yet to be explored. This dissertation describes the use of chemometric techniques to interrogate full scan MS data, and the progression from discriminating VOC samples of known chemical composition based on full scan MIMS data through to the apportionment of VOC sources measured continuously with a PTR-ToF-MS system operating in a moving vehicle. Lab‐constructed VOC samples of known chemical composition and concentration demonstrated the use of principal component analysis (PCA) to discriminate, and k-nearest neighbours to classify, samples based on normalized full scan MIMS data. Furthermore, multivariate curve resolution-alternating least squares (MCR-ALS) was used to resolve mixtures into molecular component contributions. PCA was also used to discriminate ‘real-world’ VOC mixtures (e.g., woodsmoke VOCs, headspace above aqueous hydrocarbon samples) of unknown chemical composition measured by MIMS. Using vehicle mounted MIMS and PTR-ToF-MS systems, full scan MS data of ambient atmospheric VOCs were collected and PCA was applied to the normalized full scan MS data. A supervised analysis performed PCA on samples collected near known VOC sources, while an unsupervised analysis using PCA followed by cluster analysis was used to identify groups in a continuous, time series PTR-ToF-MS dataset measured between Nanaimo and Crofton, British Columbia (BC). In both the supervised and unsupervised analysis, samples impacted by emissions from different sources (e.g., internal combustion engines, sawmills, composting facilities, pulp mills) were discriminated. With PCA, samples were discriminated based on differences in the observed full scan MS data, however real-world samples are often impacted by multiple VOC sources. MCR-weighted ALS (MCR-WALS) was applied to the continuous, time series PTR-ToF-MS data from three field campaigns on Vancouver Island, BC for source apportionment. Variable selection based on signal-to-noise ratios was used to reduce the mass list while retaining the observed m/z that capture changes in the mixture of VOCs measured, improving model results, and reducing computation time. Both point (e.g., anthropogenic hydrocarbon emissions, pulp mill emissions) and diffuse (e.g., VOCs from forest fire smoke) VOC sources were identified in the data, and were apportioned to determine their contributions to the measured samples. The data analyzed captured fine scale changes in the ambient VOCs present in the air, and geospatial maps of each individual source, and of the source apportionment were used to visualize the distribution of VOC sources across the sampling area. This work represents the first use of MCR-WALS to identify and apportion ambient VOC sources based on continuous PTR-ToF-MS data measured from a moving vehicle. The methods described can be applied to larger scale field campaigns for the source apportionment of VOCs across multiple days to capture diurnal and seasonal variations. Identifying spatial and temporal trends in the sources of VOCs at the regional scale can help to identify pollution ‘hot spots’ and inform evidence-based public policy for improving air quality. / Graduate / 2022-08-17