The Measurement and Characterisation of Aerosol in the Urban Atmosphere (PM 10) and an Evaluation of the Sources of these Particles by Number Andrew Lindsay Dye Abstract The link between human health and the mass of fine particulate matter below 10 tm (PM10) in air is well documented. Current research suggests that the number, size and shape of particles may be of most concern and that in the urban atmosphere combustion sources of PM10, especially diesel engine sources, dominate the fine (< 1µm) and ultra-fine (<0.1 µm) particles. Despite this, the number, size and shape of particles in urban air has not been reported to any great extent or detail, and the percentage contribution to the numbers of particles from different sources is largely unknown. The objectives of this research were to characterise fine particles with respect to their morphology and thus apportion the sources of particles by number. Urban aerosol above 1 µm was initially examined to study the fluctuations in PM10 number and make retrospective analysis of periods of elevated PM10 for source identification in Plymouth, UK. Aerosol was collected via a Burkard spore trap and examined using light microscopy with image analysis between 16 March 1995 and 31 August 1996, at a background site in Plymouth, UK. Two periods, 19 Januamy-4 February and 10-25 March 1996, identified as UK wide PM 10 episodes, were retrospectively studied and compared with PM10 mass measurements. The mean number count for the whole period was 10.5 x 104 ± 7.9 x 104 particles m-3 . The two PM10 episodes had elevated average number concentrations of 13.5 x 104 ± 7.6 x 104 particles m-3 for 19 January - 4 February 1996, and 13.0 x 104 ± 9.7 x 104 particles n13 for 10-25 March 1996. During the periods of elevated PM10 the tapered element oscillating microbalance (TEOM) mass of particles had a low correlation with the particles less than 5 µm and an increased correlation to the particles greater than 5 µm in size. Outside of these peak periods the PM10 TEOM mass was most closely correlated with the number of particles less than 5 µm in size. This work shows the difference in urban aerosol during periods of air quality guideline exceedence. These findings agree with literature that an aged continental aerosol source has a key role in the generation of UK wide PM10 mass exceedances. Further analysis of the fine urban aerosol (< 1 µm) was made using direct sampling of urban aerosol on to porous carbon films (PCF) developed in this research. The efficiency of collection was low (ca 5%) but the samples were representative and enabled transmission electron microscopy (TEM) for sub-micron particle analysis. Measurement was made of the fractal dimensions and diameter of particles. This was used to identif' any ageing and ultimately the sources of aerosol. PCF were used in the simultaneous collection of urban roadside and background aerosol, on seven dates between December 1996 and August 1997 in Plymouth, UK. The average perimeter fractal dimension (PFD) of aerosol was consistently significantly greater at the roadside than the background (+ 0.02), indicative of a smoother, aged aerosol at the background site. The sampling of a variety of combustion engines was made for source identification purposes. The particle morphology produced from the diesel engines showed great uniformity of particle morphology with varying speed and load; no consistent significant differences were found. The morphology results were comparable to other density fractal dimensions and penmneter fractal dimension values found in other studies for diesel. A natural log relationship between the median particle size and the median PFD was found for the diesel engine sources but not in petrol samples. This natural log trend was considered as a tentative 'fingerprint' of diesel engine combustion and was in harmony with literature values of PFD for diesel engine particles. Using the fractal measures, size and particle classification the bulk of aerosol was identified as from hydrocarbon combustion sources; ca. 88-92% of the roadside and ca. 77-86% of background. A component of carbon ceno-spheres were identified contributing ca. 6-12% of both the roadside and background aerosol. Non-combustion particles increased from ca. 1-4% of the roadside to ca. 7-9% of the background, as did the proportion of aged combustion particles, from 0-1% of roadside to 2-3% of the background aerosol. A strong correlation for the median size vs. PFD morphology curve between, the roadside and diesel sources (0.93 - 0.95) and the background and petrol sources was found (0.95). The roadside aerosol was significantly different to the petrol source in the 120-220nm size range (p=O.007) and there was a low correlation of the petrol and the roadside size vs. morphology curve (0.66). This suggests the domination of roadside aerosol by diesel engine particles. The background aerosol was similar to both diesel and petrol engine sources, especially from a dilution tunnel, thus indicative of a mixture of sources and an aged combustion aerosol. Roadside sources thus dominate the fine and ultra fine urban aerosol by number as compared to most other studies which have only apportioned the sources of particles in the air by mass.

La maîtrise de la contamination générée par temps de pluie en milieu urbain constitue un enjeu environnemental important pour limiter la dégradation des milieux aquatiques superficiels. Les outils de modélisation traditionnelle utilisés pour estimer les flux de polluants dans les eaux de ruissellement sont jugés insuffisants dans leur capacité à reproduire les dynamiques des polluants à l’exutoire. Cela est souvent lié au manque de connaissances précises sur les processus en jeu d’une part, et d’autre part aux difficultés d’acquérir des bases de données représentatives et en continu sur des sites réels. Cette thèse a donc pour objectif d’améliorer l’état de la modélisation de la qualité. Elle vise en particulier le développement d’un outil de modélisation conceptuelle de la qualité des eaux de ruissellement à l’échelle du quartier, à partir d’une compréhension approfondie des processus d'accumulation et de lessivage. La simulation des pollutogrammes de matières en suspension (MES) à l’avaloir du bassin versant routier avec les modèles conceptuels d’accumulation-lessivage montre la faible performance des modèles pour estimer les dynamiques d’émissions de MES pour des longues périodes ; la variabilité du processus d’accumulation est le responsable principal de l’inadéquation de ces modèles. L’évaluation de la contribution des retombées atmosphériques sèches à la contamination des eaux de ruissellement en hydrocarbures aromatiques polycycliques (HAPs) et métaux montrent que l’atmosphère ne joue qu’un rôle très mineur dans la contamination des eaux de ruissellement par ces substances. Ainsi le couplage des modèles atmosphériques, qui ne tiennent pas compte des émissions directes liées au trafic, avec les modèles de qualité de l’eau, ne semble pas très pertinent dans l’objectif d’améliorer la prédiction de la contamination des eaux pluviales à l’exutoire. L’investigation à la micro-échelle du mécanisme de lessivage montre que les particules fines sont les plus susceptibles d’être mobilisées par le ruissellement. Cette étude a été menée en utilisant un simulateur de pluie innovant qui présente les avantages d’être mobile et léger, et la possibilité d’avoir des enregistrements en ligne du débit et de la turbidité. Les nouvelles connaissances acquises sur les processus soulignent une grande variabilité qui remet en cause l'intérêt de leur modélisation avec des approches déterministes. Ces connaissances sont intégrées à l’échelle du quartier pour développer un outil de modélisation conceptuelle basé sur une approche stochastique d'estimation de la concentration moyenne de MES et des paramètres de qualité. Le modèle développé est intégré dans le modèle hydrologique URBS. L’application de ce modèle permet d’intégrer la variabilité spatiale et temporelle des émissions en distinguant les contributions de chaque occupation du sol. Les résultats sont prometteurs en termes d’estimation des niveaux de concentration de MES à l’exutoire du bassin versant et de réplication du comportement général de la dynamique de MES, cependant des améliorations peuvent être envisagés pour consolider l’approche et améliorer ses prédictions. La comparaison de ce modèle avec des approches de modélisation empirique globale, conceptuelle semi-distribuée et physique distribuée, montre qu’en termes de pouvoir prédictif et de fiabilité, l’approche URBS-stochastique en parallèle avec l’approche de modélisation physique distribuée sont les plus performantes. En termes de simplicité d’implémentation et d’ajustement entre les observations et les simulations, les approches de modélisation empirique globale et conceptuelle semi-distribuée sont les plus puissantes. A l’issue de cette comparaison, il est clair qu’il n’existe pas un modèle parfait qui couvre toutes les caractéristiques de la modélisation de la qualité des eaux de ruissellement. Le choix de l’approche de modélisation la plus appropriée doit se faire en fonction des objectifs attendus par le modélisateur / Urban runoff contamination is recognized as a major source of the deterioration of the quality of surface water. Commonly used stormwater quality models have poor performance in predicting the pollutant dynamics at the surface outlet, mainly due to the lack of precise knowledge on the governing processes and the difficulties of acquiring representative and continuous databases on real sites. The main purpose of this Ph.D. thesis is to improve the state of stormwater quality modeling. It aims in particular to develop a conceptual modeling tool for stormwater quality prediction at the scale of a city district catchment, based on a deep understanding of the build-up and the wash-off. The application of commonly used stormwater build-up/wash-off models to simulate the dynamics of total suspended solids (TSS) at the outlet of the road catchment suggests that the models poorly replicate the temporal variability of the TSS concentrations unless short periods are considered. The unpredictable nature of the accumulation is largely responsible for the model failure. The evaluation of the contribution of atmospheric dry deposition to stormwater loads for polycyclic aromatic hydrocarbons (PAHs) and metals shows that atmospheric deposition is not a major source of contaminants in stormwater runoff. Thus, linking the air and water compartment in a modeling chain to have more accurate estimates of pollutant loads in stormwater runoff may not be relevant unless the direct traffic emissions are accounted for. The investigation of the wash-off process on elementary surfaces shows that the fine particles are the most likely to be mobilized and transported during a rainfall event. Stormwater samples were collected for this study using an innovative rainfall simulator that allows continuous, on-site monitoring of instantaneous flow and turbidity measurements and that can be easily transported and used on real sites. The new knowledge acquired on the build-up and wash-off processes underlines the great variability of these processes and calls into question their modeling with deterministic approaches. Hence, this knowledge is incorporated into developing a new conceptual stormwater quality model based on the stochastic drawing of event mean concentrations (EMC) of TSS and water quality parameters. The model is integrated within the hydrological model URBS. The application of this approach accounts for the spatial and temporal variability of pollutant emissions by distinguishing the contributions of each land use separately. The obtained results are promising in terms of estimating the concentration levels of TSS at the outlet of the city district catchment and replicating the general behavior of the TSS dynamics. However, improvements can be envisaged to consolidate the approach and improve its predictions. Comparison of this model with global empirical, semi-distributed conceptual and distributed physical modeling approaches shows that in terms of predictive power and stability, the stochastic-URBS and the physically distributed approaches are the most efficient. However, in terms of ease of implementation and best fit between observations and simulations, the global empirical and semi-distributed conceptual modeling approaches are the most powerful. This comparison shows that the perfect model that covers all aspects of stormwater quality modeling does not exist. The choice of the most appropriate modeling approach should mainly be driven by modeling objectives

Au cours des dix dernières années, les gouvernements de l'Union Européenne ont été encouragés à collecter des données sur le volume et la qualité de tous les effluents d'eaux urbaines ayant un impact environnemental significatif sur les milieux aquatiques récepteurs. Les méthodes de surveillance de ces flux nécessitent des améliorations, en particulier pour les déversoirs d’orage, structures complexes responsables en grande partie de la dégradation de la qualité des milieux récepteurs. Le DSM-flux (Dispositif pour la surveillance et maîtrise des flux d'eaux et polluants des réseaux d'eaux pluviales et unitaires) est un nouveau dispositif préfabriqué et pré-étalonné qui garantit les conditions hydrauliques appropriées permettant de mesurer les débits et volumes déversés ainsi que les concentrations et masses de polluants qui y sont transportés. Dans cette thèse, une relation permettant de mesurer le débit au passage du DSM-flux a été construite grâce à une étude expérimentale sur modèle physique réduit, puis validée pour plusieurs configurations d'écoulement à l'amont du dispositif. Quelles que soient les conditions hydrauliques en amont, les incertitudes relatives sont inférieures à 15% et 2% pour les débits et les volumes étudiés, respectivement, ce qui reste équivalent, voire mieux, par rapport aux incertitudes des méthodes actuelles les plus fiables. La méthode de mesure a été validée in situ sur un dispositif à grande échelle construit sur le terrain et fonctionnant en conditions réelles, ce qui montre la robustesse de la méthode. De plus, grâce à sa conception originale, le DSM-flux favorise l'interception d'une fraction des polluants particulaires. L’hydrodynamique de ce dispositif de mesure a été analysée ainsi que les conditions qui engendrent la décantation des polluants particulaires. En fonction des conditions d'écoulement, ce dispositif peut retenir 50% de la masse totale des matières solides fines en suspension transitant par le dispositif, mais pour des écoulements à débits élevés, cette efficacité est significativement réduite. Sa capacité de rétention a été aussi observée sur le terrain et une méthodologie a été élaborée pour quantifier son efficacité de rétention lors d'études futures. Mise à part sa performance hydraulique, du point de vue opérationnel, le dispositif présente d’autres avantages par rapport à d’autres dispositifs existants : (i) il est pré-étalonné et peut être installé à l’aval de déversoirs d’orage déjà existants, (ii) il peut s’insérer directement au sein du canal de décharge (installation d’un regard de visite équipé d’un DSM), (iii) sa performance hydraulique est indépendante des conditions de l’écoulement à l’amont et (iv) il s’agit d’un dispositif intégré de mesure de débits et de leur qualité simultanément, en plus d’intercepter une partie de polluants particulaires. / Over the past decade, European Union governments have encouraged to collect data on the volume and quality of all urban water effluents with a significant environmental impact on receiving aquatic environments. Methods for monitoring these flows require improvements, particularly for combined sewer overflows, which are complex flows that contribute in significant proportion to the degradation of the quality of the receiving waters. The DSM-flux (Device for Stormwater and combined sewer flows Monitoring and the control of pollutant fluxes) is a new pre-calibrated and pre-designed device that guarantees the appropriate hydraulic conditions for measuring discharged flows and volumes as well as the concentrations and mass loads of pollutants carried in suspension by the flow. In this PhD work, a relationship allowing to measure the flow rates conveying through the DSM-flux was determined thanks to an experimental study on a small-scale physical model, and then validated for several flow configurations upstream of the device. Whatever the upstream hydraulic conditions are, the relative uncertainties are less than 15% and 2% for the flow rates and volumes studied, respectively, which is equivalent to the uncertainties of the most reliable current methods. The monitoring methodology was validated in situ in a large-scale device installed at the field and operating in real conditions, which shows the robustness of the method. Moreover, thanks to its original design, the DSM-flux allows the interception of a fraction of particulate pollutants. The hydrodynamics of this monitoring device were analysed as well as the conditions that cause the settling of particulate pollutants. Depending on the flow conditions, this device can retain 50% of the total mass of fine suspended solid matter transiting through the device, but for flows at high discharge rates, this efficiency is significantly reduced. Its retention capacity has also been observed in the field and a methodology has been developed to quantify its retention efficiency in future studies. Apart from its performance, from an operational point of view, the device has other advantages compared to other current devices: (i) it is pre-calibrated and can be installed downstream from existing combined sewer overflows, (ii) it can be directly installed through a manhole in the discharge channel, (iii) its hydraulic performance is independent from the flow conditions upstream, and (iv) it is an integrated monitoring device, measuring flow rates and their quality simultaneously, in addition to intercepting a part of the particulate pollutants.

In this retrospective cohort from 2002 through 2007, 104,003 singleton live births in Hillsborough County, Florida were analyzed to elucidate the relationship between feto-infant morbidity outcomes and prenatal exposure to six criteria air pollutants. This study is based on three linked databases: The Florida Hospital Discharge database; The vital statistics records of singleton live births; Air Pollution meteorological data from the Environmental Protection Agency. There are six common air pollutants, particulate matter 2.5 (PM2.5), particulate matter 10 (PM10), ground-level ozone (O3), carbon monoxide (CO), nitrogen (NOx), and lead (Pb). These pollutants are harmful to human health and the environment. The primary outcomes of interest were low birth weight (LBW), preterm births, and small for gestational age (SGA). The intent of this project is to address these issues of air pollution effects and the methodology surrounding the study of air pollution. Using modeling, exposure values of the six criteria air pollutants were assigned to mothers over their period of pregnancy. To address these methodological concerns, this study utilizes the structural equation modeling, quartile groupings with dose response, and trimester groupings to evaluate the relationship between air pollution and birth outcomes of pregnant residents. Using structural equation modeling a significant B value of 0.35 indicated that exposure to the six criteria pollutant in pregnancy may have a significant relationship to all five birth outcomes if they are broken down into latent variables. Quartile data demonstrated that NOx seemed to have most significant associations with all outcomes with a dose response for SGA. PM10 and PM2.5 had some association to LBW and VLBW at high levels. PM10 demonstrated significance in the higher doses for SGA. However, the only dose response relationship that was demonstrated for PM10 and PM2.5 was in VLBW. PM10 also demonstrated a dose response with very preterm. If sub-divided into trimester data, PM10 demonstrated a significant relationship between exposures in all trimesters and LBW, VLBW, and SGA. PM2.5 demonstrated a significant relationship between exposures in all trimesters and VLBW. CO demonstrated a significant relationship in the 2nd trimester for LBW as well as for SGA. Mothers and their babies are a vulnerable population who are more susceptible to lower levels of pollution. These air pollutants can possibly have long-term effect on their children. Implantation of laws and regulations, warning system, or more strict EPA standards may be needed to adequately control the cost to our society.