A sampler has been fabricated to facilitate the in-situ speciation of Cr. Teflon® was selected as the material for the samplers because of its inert chemical nature. The design of the sampler is based on the Supported Liquid Membrane (SLM) extraction technique, which utilizes charged organic carrier molecules loaded onto a polymeric (Teflon®) support membrane and the principles of electrostatics to selectively transport Cr ions through an ion-pairing mechanism. Cr ions in the feed solution that have an opposite charge from the carrier molecule form an ion-pair with the carrier and are transported through the membrane and deposited into a second aqueous phase referred to as the acceptor phase. A counter-ion from the acceptor phase is exchanged for the Cr ion to complete the extraction process. Since the acceptor phase is contained in a Teflon® bottle, the SLM sampler is capable of speciation and storage of Cr ions, which is a major advantage over current speciation techniques. A food coloring test was used to check the samplers for leaks. A plastic barrier was used in place of the polymeric membrane and the acceptor phase bottle was filled with DI water. The sampler was submerged in a beaker containing food coloring and DI water. The bottle contents were checked for the presence of food coloring using UV-vis spectroscopy. The sampler was determined to be leak-free if the bottle did not contain food coloring. All systems prepared were validated upon the initial test and required no further manipulation to ensure structural soundness. The SLM extraction technique involves two liquid-liquid extractions (LLEs). Before the samplers could be evaluated for their performance and stability in Cr speciation applications, liquid-liquid extraction studies were conducted on both systems (Cr (III) and Cr (VI)) to determine the optimal operating parameters (carrier concentration, decanol concentration, and acceptor phase concentration) of the SLM system. The selectivity of each system was also evaluated to validate proper SLM function. The performance of the samplers was evaluated in a series of tank studies that focused on the uptake of Cr into the acceptor phase as well as the depletion of Cr ion from this phase. The goal of the performance studies was to determine the mechanical and chemical stability of the SLM samplers. As part of the validation process, selectivity studies and studies without the carrier molecule were conducted to ensure that the systems were functioning according to SLM theory. Tank studies that simulated natural sampling condition were also conducted. The results of the tests conducted in the laboratory indicate that the SLM samplers are a stable, reliable, and viable method for Cr speciation. Future directions of this project will include the incorporation of the SLM sampler into the existing Multi-layer Sampler (MLS) technology as well as the analysis of the stability and performance of the incorporated systems in the ""in-situ speciation application. / Ph. D.

In-situ geotechnical testing of surficial sediment layers in areas of active sediment dynamics can provide essential information about physical and geotechnical variations of sediment properties with regards to active sediment remobilization processes. For example, portable free fall penetrometers (PFFPs) can assist with the detection of mobile sediment layers. They are easy to deploy, and can provide a large spatial coverage in a time- and cost-effective manner. However, they often struggle to provide more detailed information about the properties of mobile sediment layers due to a lack of calibration and validation in existing data sets. Currently, existing sediment samplers often disturb, or ignore the uppermost sediment layers. Simultaneous sediment sampling and geotechnical profiling is needed to fill this gap, and to drive data interpretation forward. A field investigation of surficial sediments was conducted in the wetland waterways of coastal Louisiana in 2014. In-situ tests were conducted using PFFP, and disturbed sediment samples were collected in selected locations. The results allowed us to map changes in sediment strength and stratification, and correlate the geotechnical results to local site characteristics. However, the need for high quality sediment samples for calibration and validation was emphasized by the results. Three different sediment sampler add-on units targeting mobile layers were designed and manufactured based on lessons-learned from the literature. The designs were tested in the laboratory and in the field (Yakutat, Alaska and York River, Virginia) in 2017. The samples were analyzed to understand the influence of different sampler characteristics on collected sample quality, and, to define mobile layer sampler characteristics that enable simultaneous geotechnical testing and the collection of high quality samples. Following field survey campaigns in the York River, Virginia in 2016 allowed to assess surficial sediment layer characteristics and behavior based on a coupled analysis of geotechnical data from in-situ PFFP tests and the sedimentological data collected using box cores and the novel sediment sampler. In summary, novel strategies and instrumentation to carry out simultaneous sediment sampling and geotechnical profiling of seabed surface layers were tested, and new pathways for geotechnical data analysis for the investigation of mobile seabed layers were presented. / PHD

Les méthodes de Monte Carlo par chaînes de Markov (MCCM) sont des méthodes servant à échantillonner à partir de distributions de probabilité. Ces techniques se basent sur le parcours de chaînes de Markov ayant pour lois stationnaires les distributions à échantillonner. Étant donné leur facilité d’application, elles constituent une des approches les plus utilisées dans la communauté statistique, et tout particulièrement en analyse bayésienne. Ce sont des outils très populaires pour l’échantillonnage de lois de probabilité complexes et/ou en grandes dimensions. Depuis l’apparition de la première méthode MCCM en 1953 (la méthode de Metropolis, voir [10]), l’intérêt pour ces méthodes, ainsi que l’éventail d’algorithmes disponibles ne cessent de s’accroître d’une année à l’autre. Bien que l’algorithme Metropolis-Hastings (voir [8]) puisse être considéré comme l’un des algorithmes de Monte Carlo par chaînes de Markov les plus généraux, il est aussi l’un des plus simples à comprendre et à expliquer, ce qui en fait un algorithme idéal pour débuter. Il a été sujet de développement par plusieurs chercheurs. L’algorithme Metropolis à essais multiples (MTM), introduit dans la littérature statistique par [9], est considéré comme un développement intéressant dans ce domaine, mais malheureusement son implémentation est très coûteuse (en termes de temps). Récemment, un nouvel algorithme a été développé par [1]. Il s’agit de l’algorithme Metropolis à essais multiples revisité (MTM revisité), qui définit la méthode MTM standard mentionnée précédemment dans le cadre de l’algorithme Metropolis-Hastings sur un espace étendu. L’objectif de ce travail est, en premier lieu, de présenter les méthodes MCCM, et par la suite d’étudier et d’analyser les algorithmes Metropolis-Hastings ainsi que le MTM standard afin de permettre aux lecteurs une meilleure compréhension de l’implémentation de ces méthodes. Un deuxième objectif est d’étudier les perspectives ainsi que les inconvénients de l’algorithme MTM revisité afin de voir s’il répond aux attentes de la communauté statistique. Enfin, nous tentons de combattre le problème de sédentarité de l’algorithme MTM revisité, ce qui donne lieu à un tout nouvel algorithme. Ce nouvel algorithme performe bien lorsque le nombre de candidats générés à chaque itérations est petit, mais sa performance se dégrade à mesure que ce nombre de candidats croît. / Markov Chain Monte Carlo (MCMC) algorithms are methods that are used for sampling from probability distributions. These tools are based on the path of a Markov chain whose stationary distribution is the distribution to be sampled. Given their relative ease of application, they are one of the most popular approaches in the statistical community, especially in Bayesian analysis. These methods are very popular for sampling from complex and/or high dimensional probability distributions. Since the appearance of the first MCMC method in 1953 (the Metropolis algorithm, see [10]), the interest for these methods, as well as the range of algorithms available, continue to increase from one year to another. Although the Metropolis-Hastings algorithm (see [8]) can be considered as one of the most general Markov chain Monte Carlo algorithms, it is also one of the easiest to understand and explain, making it an ideal algorithm for beginners. As such, it has been studied by several researchers. The multiple-try Metropolis (MTM) algorithm , proposed by [9], is considered as one interesting development in this field, but unfortunately its implementation is quite expensive (in terms of time). Recently, a new algorithm was developed by [1]. This method is named the revisited multiple-try Metropolis algorithm (MTM revisited), which is obtained by expressing the MTM method as a Metropolis-Hastings algorithm on an extended space. The objective of this work is to first present MCMC methods, and subsequently study and analyze the Metropolis-Hastings and standard MTM algorithms to allow readers a better perspective on the implementation of these methods. A second objective is to explore the opportunities and disadvantages of the revisited MTM algorithm to see if it meets the expectations of the statistical community. We finally attempt to fight the sedentarity of the revisited MTM algorithm, which leads to a new algorithm. The latter performs efficiently when the number of generated candidates in a given iteration is small, but the performance of this new algorithm then deteriorates as the number of candidates in a given iteration increases.

Perfluoroalkyl substances (PFASs) are global environmental contaminants and a need for monitoring levels has arisen due to their persistency and their ability to bioaccumulate. One relatively novel method of monitoring for both long and short time intervals and generating time-weighted average (TWA) concentrations is passive sampling for which no power, maintenance and supervision is required. The polar organic compound integrative sampler (POCIS) with a weak anion exchange (WAX) sorbent and the POCIS with a hydrophilic-lipophilic balance (HLB) adsorbent were calibrated for PFASs in a laboratory uptake experiment, and applied at a drinking water treatment plant (DWTP) in Stockholm, Sweden.   In the calibration study, all of the 14 studied PFASs were taken up by both passive samplers. Two and three out of the 14 studied PFASs had reached equilibrium after 28 days using POCIS WAX (PFBA and PFTeDA) and POCIS HLB (PFBA, PFPeA and PFTeDA), respectively. The sampling rate (Rs), which is the extracted water in liters per day, ranged between 0.003 and 0.10 L day-1 for the POCIS WAX and between 0.00052 and 0.13 L day-1 for the POCIS HLB. In general, Rs increased with increasing perfluorocarbon chain-length (C4 to C8) and for a perfluorocarbon chain-length longer than C8, Rs decreased with increasing perfluorocarbon chain-length (C8 to C13) for both passive samplers. FOSA had the highest Rs-value (0.10 and 0.13 L day-1) for both POCIS WAX and POCIS HLB, respectively. The POCIS WAX had a higher uptake for the short-chained PFASs PFBA (134 ng after 28 days), PFPeA (410 ng) and PFHxA (834 ng), compared to the POCIS HLB (0.5 ng, 58 ng, and 373 ng, respectively). For all other compounds, the accumulated amounts in the POCIS HLB were in the same range as in the POCIS WAX.   The application of the passive samplers at the DWTP showed that both passive samplers could detect ultra-trace (pg to ng L-1) levels of PFASs. A comparison of the TWA concentration showed that the two passive samplers had a good linear correlation (R2 = 0.63), but the TWA concentrations derived by POCIS WAX was approximately 40% higher compared to POCIS HLB. A comparison between the passive samplers and the grab samples did not show a correlation (R2 = 0.24 for POCIS WAX and R2 = 0.10 for POCIS HLB). The application also included a comparison of the removal efficiency in the conventional DWTP and a pilot plant with additional treatments steps of granulated activated carbon (GAC) and nanofiltration (NF). For the full-scale DWTP the average removal efficiency was 32% and high removal efficiency was observed for PFBA (81%). For the pilot plant, the removal efficiency was 100% for all the detected PFASs in the raw water. / Perfluoroalkylsubstanser (PFAS) har blivit uppmärksammade som globala miljöföroreningar, och ett behov av att övervaka dessa ämnens förekomst i miljön har uppkommit på grund av hög persistens i kombination med hög förmåga att bioackumulera. En relativt ny metod för tidsintegrerad provtagning är så kallad passiv provtagning. En adsorbent placeras i fält och ackumulerar PFAS från vattnet. Tillgång till elektricitet behövs inte, och behov av övervakning och underhåll är minimalt. I denna studie kalibrerades en så kallad ’polar organic compound integrative sampler’ (POCIS) för mätning av PFAS genom upptagsexperiment med två olika adsorbenter: en svag anjons adsorbent (WAX) och en hydrofil-lipofil balanserad adsorbent (HLB). Metodiken tillämpades sedan på vatten från ett dricksvattenverk i Stockholm, Sverige.   Upptagsexperimenten utfördes med 14 PFAS och samtliga togs upp av båda adsorbenterna. Två respektive tre av de studerade PFAS uppnådde jämvikt efter 28 dagar för WAX (PFBS och PFTeDA) samt HLB (PFBA, PFPeA och PFTeDA). Upptagshastigheten (Rs), det vill säga den volym som extraheras per dag, varierade mellan 0,003 och 0,1 L dag-1 för WAX och mellan 0,00052 och 0,13 L dag-1 för HLB. Generellt ökade Rs med en ökande längd på kedjan av perfluorerade kol upp till C8, för att sedan avta med ökande kedjelängd. FOSA hade det högsta Rs-värdet (0,10 och 0,13 L dag-1) för både WAX och HLB. WAX hade ett högre upptag (upp till 134, 410 och 834 ng) för PFAS med kort perfluorerad kolkedja (PFBA, PFPeA respektive PFHxA) jämfört med HLB (upp till 0,5, 58, och 373 ng). Den ackumulerade mängden för alla andra PFAS överensstämde väl mellan de båda provtagarna.   Mätning av PFAS halter i dricksvattenverket med hjälp av POCIS WAX och POCIS HLB visade att även PFAS kunde detekteras även vid miljörelevanta halter. En jämförelse mellan de båda passiva provtagarna visade på ett linjärt samband (R2 = 0,63), men där POCIS WAX hade en tendens att överskatta koncentrationen med ca 40%. En jämförelse mellan de passiva provtagarna och traditionell uppsamlingsprovtagning visade på låg överrensstämmelse (R2 = 0.24 för POCIS WAX och 0.10 för POCIS HLB). Vid tillämpningen gjordes även en beräkning för reningseffektiviteten av PFAS i dricksvattenverket och i en pilotanläggning där ytterligare rening med granulerat aktivt kol (GAC) och nanofiltration (NF) används. I dricksvattenverket var den genomsnittliga reningen 32%, med den högsta reningseffektiviteten för PFBA (81%). I pilotanläggningen var reningen 100% för alla upptäckta PFAS i råvattnet.

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La pollution atmosphérique est une problématique urbaine majeure, avec des concentrations de polluants dépassant fréquemment les seuils de recommandations pour la santé. Les véhicules participent fortement à la pollution atmosphérique malgré l’intégration de systèmes de dépollution dans leur ligne d’échappement. L’objectif de ce travail de recherche était de caractériser les émissions primaires à l’échappement des véhicules ainsi que leur évolution physique en champ proche pour mieux comprendre la contribution des émissions primaires liées au trafic à la pollution atmosphérique urbaine. L’évolution des émissions a été étudiée dans une chambre de simulation atmosphérique qui a permis de simuler des conditions atmosphériques contrôlées.La première partie de ce travail était centrée sur les mesures d’émissions à l’échappement des véhicules récents qui sont ou seront majoritaires dans le parc automobile français dans les prochaines années. Pour cela, un échantillon de véhicules regroupant les principales technologies de dépollution commercialisées a été testé. Les gaz d’échappement émis par les véhicules ont été analysés lors de tests sur un banc à rouleau suivant différentes conditions de conduites. Les polluants soumis aux réglementations Européennes ont été mesurés, ainsi que certains composés non-réglementés par les normes Européennes mais dont la dangerosité a été mise en évidence par la communauté scientifique.La deuxième partie de ce travail se concentre sur l’évolution en champ proche des polluants particulaires dans les heures qui suivent leur rejet dans l’atmosphère. L’effet de la dilution soudaine des gaz en sortie de pot d’échappement a été étudié en utilisant une méthodologie innovante de prélèvement directement à l’échappement. Ensuite l’évolution des particules dans les premières heures après leur rejet a été étudiée dans une chambre de simulation atmosphérique de 8 m3, construite spécifiquement dans le cadre de cette thèse pour être couplé au banc à rouleau. / Air pollution is a major urban issue, with pollutant concentrations frequently exceeding health recommendations. Vehicles are highly involved in air pollution despite the integration of pollution control systems. The objective of this research is to characterise the primary exhaust emissions of vehicles and their physical evolution in the near field to better understand the impact of primary emissions related to traffic on urban air pollution. Emissions evolution was studied in an atmospheric simulation chamber with controlled atmospheric conditions. The first part of this work aims to determine the exhaust emissions of recent vehicles that are or will be major in the French car fleet in the coming years. A sample of vehicles grouping the main commercialised depollution technologies was tested on a chassis dynamometer according to different driving conditions and the emissions from their exhaust gas were analysed. The pollutants subject to European regulations were taken into account, as well as compounds not regulated by European standards but whose toxicity has been highlighted by the scientific community.The second part of this work focuses on the near-field evolution of particulate pollutants in the hours following their release into the atmosphere. The effect of the abrupt gas dilution at the end of the exhaust has been studied using an innovative sampling methodology directly at the exhaust of the vehicles. Then the evolution of the particles in the first hours after their rejection was studied in an atmospheric simulation chamber of 8 m3, built specifically within the framework of this thesis to be coupled with the dynamometer.

The investigation of the atmospheric fate and transport of semi-volatile organic compounds (SOCs) often requires the sampling of large volumes of air (>100 m3) in a relatively short period of time. Conventionally high-volume pumps are not suitable for remote areas without access to reliable network power. We have developed a flow through sampler for such situations. It consists of a horizontally-oriented flow-tube, that can collect gaseous and particle-bound SOCs from large volumes of air by turning into the wind and having the wind blow through a porous sampling medium such as polyurethane foam. Through both indoor and outdoor experiments, we quantified its air sampling rate (through battery operated anemometers inside and outside of the flow tube), its sampling efficiency (by theoretical plate number analysis of the break-though curves for PCBs, PAHs, OCPs and PBDEs), and its accuracy (by comparison of concentrations, time trends, temperature dependences and isomer ratios with those obtained by conventional high-volume sampling) under conditions of constant and variable meteorological conditions (wind speed, temperature). The flow-through sampler was deployed to monitor SOC concentrations at a remote Chinese research station located close to Nam Co Lake, Tibet. During the campaign, fifteen 1 month-long samples were taken, corresponding to sample volumes between 5,000 and 20,000 m3. Despite those large sample volumes, only HCB and HCHs experienced break-through, but application of frontal chromatograph theory allows the estimation of breakthrough-corrected air concentrations even for those relatively volatile SOCs. The pesticide levels at Nam Co are generally very low. Most pesticides had higher levels during summer, resulting in a strong temperature dependence. This is correlated with air mass origin across the Himalayas in the Gangetic plains of India and Bangladesh. The flow through sampler constitutes a feasible method for reliably and quantitatively collecting SOCs from large air volumes.

The purpose of this study was to use the Global Water Stormwater Sampler SS201 to characterize the urban runoff in Pecan Creek. Location of the samplers was influenced by land use and ease of installation. Determination of the constituents for analysis was modeled after those used in the NPDES permit for seven cities within the Dallas/Ft.Worth metroplex. Some metals, notably cadmium and arsenic, exceeded the U.S. EPA's MCL's. Statistical analysis revealed first flush samples to be significantly more concentrated than composite samples. Minimum discharge loadings were found to be significantly lower than maximum discharge loadings. Additionally there were significant differences of specific constituents between station locations and storm events.

A presente pesquisa foi desenvolvida com o intuito de agregar alguns procedimentos ao Ensaio SPT, para se obter um maior número de parâmetros para o dimensionamento de fundações, visto que este ensaio é o tipo de investigação de subsolo mais utilizado no Brasil para este fim. Os procedimentos adicionados foram: medida de eficiência do equipamento e ensaio de arrancamento do amostrador em cada camada distinta de solo atravessado. Foram realizados nove ensaios de arrancamento do amostrador, em três furos de sondagem, nas profundidades de dois, cinco e dez metros (três camadas de solos distintas). Em um quarto furo foram realizadas duas provas de carga à compressão no amostrador (nas profundidades de dois e cinco metros) para determinação da eficiência do equipamento. Por meio destes ensaios foi possível obter: a resistência de ponta do ensaio SPT, a resistência por atrito lateral na face externa do amostrador, e a razão de atrito do ensaio SPT, que pode ser usada para a classificação de solo de modo similar ao utilizado para o ensaio de cone. Além destes resultados, neste trabalho foi também analisada a relação entre a resistência por atrito interna e externa no amostrador durante o ensaio, conhecida por a. Esta relação mostrou-se maior para a camada de solo com grande porcentagem de pedregulho e menor para a camada que apresentava maior porcentagem de argila. Foi observado também que o valor de a cresce linearmente com a razão entre o valor de NSPT e a tensão vertical efetiva na profundidade do ensaio. Os resultados deste trabalho também mostraram que o valor da razão entre a resistência de ponta do ensaio SPT (qSPT) e o valor de NSPT é único para o mesmo tipo de solo. Além disso, os valores encontrados nesta pesquisa da razão qSPT/ NSPT são próximos aos valores da razão entre a resistência de ponta do ensaio de cone e o NSPT encontrados na literatura. / This research was developed in order to add some procedures to the SPT test, to obtain new parameters for the design of foundations, since this test is the most used in Brazil for this purpose. The additional measurements are: the energy delivered to the rod during a hammer impact, and the sampler\'s shaft resistance known from static uplift. For this investigation, nine uplift tests were conducted on the SPT sampler, in three boreholes, at three different depths (two, five and ten meters) to the determination of the SPT side friction resistance. Additionally, two compressive static load tests were carried out on the sampler in a fourth borehole to the determination of the efficiency of the SPT equipment. The results showed that the SPT test could provide measurements of end bearing and side friction resistances. Also, a SPT normalized friction ratio was determined for the classification of soil in a similar way used based on CPT data. In addition, the ratio between the internal and the external skin friction in the sampler during the test, known as \"a\" was analyzed. The values of this ratio were higher for the soil with higher percentage of gravel, and smaller for the soil with higher percentage of fines. Additionally, the \"a\" value increases linearly with the ratio between the NSPT value and the effective vertical stress at the tested depth. The results of the ratio between the SPT end bearing resistance and the NSPT found in this research are of similar magnitude to the ratios between CPT end bearing resistance and the NSPT found in the literature.

Over the past decade of accounting and finance research, the Ohlson (1995) model has been widely adopted as a framework for stock price prediction. While using the accounting data of 391 companies from SP500 in this paper, Bayesian statistical techniques are adopted to enhance both the estimative and predictive qualities of the Ohlson model comparing to the classical approaches. Specifically, the classical methods are used for the exploratory data analysis and then the Bayesian strategies are applied using Markov chain Monte Carlo method in three stages: individual analysis for each company, grouping analysis for each group and adaptive analysis by pooling information across companies. The base data, which consist of 20 quarters' observations starting from the first quarter of 1998, are used to make inferences for the regression coefficients (or parameters), evaluate the model adequacy and predict the stock price for the first quarter of 2004, when the real observations are set as the test data to evaluate the predictive ability of the Ohlson model. The results are averaged within each specified group categorized via the general industrial classification (GIC). The empirical results show that classical models result in larger stock price prediction errors, more positively-biased predictions and have much smaller explanatory powers than Bayesian models. A few transformations of both classical and Bayesian models are also performed in this paper, however, transformations of the classical models do not outweigh the usefulness of applying Bayesian statistics.