Predicting the dissolution rates of immiscible contaminants in groundwater is crucial for developing environmental remediation strategies, but quantitative modeling efforts are inherently subject to multiple uncertainties. These include unknown residual amounts of non-aqueous phase liquids (NAPL) and source zone dimensions, inconsistent historical monitoring of contaminant mass discharge, and the mathematical simulation of field-scale mass transfer processes. Effective methods for simulating NAPL dissolution must therefore be able to assimilate a variety of data through physical and scalable mass transfer parameters to quantify and reduce site-specific uncertainties. This investigation coupled upscaled and numerical mass transfer modeling with uncertainty analyses to understand and develop data-assimilation and parameter-scaling methods for characterizing NAPL source zones and predicting depletion timeframes. Parameters of key interest regulating kinetic NAPL persistence and contaminant fluxes are residual mass and saturation, but neither can be measured directly at field sites. However, monitoring and characterization measurements can constrain source zone dimensions, where NAPL mass is distributed. This work evaluated the worth of source zone delineation and dissolution monitoring for estimating NAPL mass and mass transfer coefficients at multiple scales of spatial resolution. Mass transfer processes in controlled laboratory and field experiments were analyzed by simulating monitored dissolved-phase concentrations through the parameterization of explicit and lumped system properties in volume-averaged (VA) and numerical models of NAPL dissolution, respectively. Both methods were coupled with uncertainty analysis tools to investigate the relationship between data availability and model design for accurately constraining system parameters and predictions. The modeling approaches were also combined for reproducing experimental bulk effluent rates in discretized domains, explicitly parameterizing mass transfer coefficients at multiple grid scales. Research findings linked dissolved-phase monitoring signatures to model estimates of NAPL persistence, supported by source zone delineation data. The accurate characterization of source zone properties and kinetic dissolution rates, governing NAPL longevity, was achieved by adjusting model parameterization complexity to data availability. While multistage effluent rates accurately constrained explicit-process parameters in VA models, spatially-varying lumped-process parameters estimated from late dissolution stages also constrained unbiased predictions of NAPL depletion. Advantages of the numerical method included the simultaneous assimilation of bulk and high-resolution monitoring data for characterizing the distribution of residual NAPL mass and dissolution rates, whereas the VA method predicted source dissipation timeframes from delineation data alone. Additionally, comparative modeling analyses resulted in a methodology for scaling VA mass transfer coefficients to simulate NAPL dissolution and longevity at multiple grid resolutions. This research suggests feasibility in empirical constraining of lumped-process parameters by applying VA concepts to numerical mass transfer and transport models, enabling the assimilation of monitoring and source delineation data to reduce site-specific uncertainties. / Doctor of Philosophy / Predicting the dissolution rates of immiscible contaminants in groundwater is crucial for developing environmental restoration strategies, but quantitative modeling efforts are inherently subject to multiple uncertainties. These include unknown mass and dimensions of contaminant source zones, inconsistent groundwater monitoring, and the mathematical simulation of physical processes controlling dissolution rates at field scales. Effective simulation methods must therefore be able to leverage a variety of data through rate-limiting parameters suitable for quantifying and reducing uncertainties at contaminated sites. This investigation integrated mathematical modeling with uncertainty analyses to understand and develop data-driven approaches for characterizing contaminant source zones and predicting dissolution rates at multiple measurement scales. Parameters of key interest regulating the lifespan of source zones are the distribution and amount of residual contaminant mass, which cannot be measured directly at field sites. However, monitoring and site characterization measurements can constrain source zone dimensions, where contaminant mass is distributed. This work evaluated the worth of source zone delineation and groundwater monitoring for estimating contaminant mass and dissolution rates at multiple measurement scales. Rate-limiting processes in controlled laboratory and field experiments were analyzed by simulating monitored groundwater concentrations through the explicit and lumped representation of system properties in volume-averaged (VA) and numerical models of contaminant dissolution, respectively. Both methods were coupled with uncertainty analysis tools to investigate the relationship between data availability and model design for accurately constraining system parameters and predictions. The approaches were also combined for predicting average contaminant concentrations at multiple scales of spatial resolution. Research findings linked groundwater monitoring profiles to model estimates of contaminant persistence, supported by source zone delineation data. The accurate characterization of source zone properties and contaminant dissolution rates was achieved by adjusting model complexity to data availability. While monitoring profiles indicating multi-rate contaminant dissolution accurately constrained explicit-process parameters in VA models, spatially-varying lumped parameters estimated from late dissolution stages also constrained unbiased predictions of source mass depletion. Advantages of the numerical method included the simultaneous utilization of average and spatially-detailed monitoring data for characterizing the distribution of contaminant mass and dissolution rates, whereas the VA method predicted source longevity timeframes from delineation data alone. Additionally, comparative modeling analyses resulted in a methodology for scaling estimable VA parameters to predict contaminant dissolution rates at multiple scales of spatial resolution. This research suggests feasibility in empirical constraining of lumped parameters by applying VA concepts to numerical models, enabling a comprehensive data-driven methodology to quantify environmental risk and support groundwater cleanup designs.

With increasing global population comes an increase in the need to safe and clean drinking water. Contaminants can arise in drinking water either naturally, or by the interaction of disinfection chemicals with naturally occurring materials, or simply due to by-products of the disinfection mechanism itself. Due to the oxidative nature of our disinfection treatments, these species are in highly oxidized states, and in some cases require chemical reduction to become less harmful. The present work demonstrates the capabilities of aqueous phase corona plasma in reductive treatment of oxidized contaminants found in drinking water. This study focuses on the treatment of the nitrate ion, bromate ion, chlorate ion and monobromoacetic acid, all of which can be found in typical drinking water systems. The second and third chapters within this thesis establish the optimal water matrix conditions for the treatment of bromate, chlorate and nitrate. These experiments investigate the influence of pH, temperature, presence and types of oxidative scavengers, dissolved gases and by-products that are made by this treatment process with these compounds. The main conclusion of these works is that aqueous phase corona discharge is capable of producing chemical compounds with sufficient energy to chemically reduce the nitrate, bromate and chlorate anions. Acidic conditions, under low dissolved oxygen scenarios facilitated the highest amount of reduction of the target contaminants, as well as having the presence of oxidative species scavengers. It was also observed that the anoxic environment could be obtained by introducing alcohols into the contaminated solution which generated sufficient cavitation and bubbling to strip the oxygen from solution. Through a comparison of various carbonaceous compounds as oxidative species scavengers, it was determined that the volatile alcohols provided a better performance than other soluble carbon sources, due to the decrease in dissolved oxygen. The fourth chapter considers different methods of introducing argon, oxygen and nitrogen into the test solution for the effect they would have on the treatment of solutions containing the bromate anion or monobromoacetic acid. The optimal pH for the treatment of monobromoacetic acid was also established, where again the acidic conditions prevailed. Tests were conducted to consider the effect of having the solution pre-saturated with the test gas, continually sparged, or with the gas passing through a hollow discharge electrode. The tests in which gas was blown through the discharge electrode greatly surpassed all other treatment regimes, where nitrogen provided the best removal for both contaminants under acidic conditions for bromate and under acidic and basic conditions for monobromoacetic acid. The fifth chapter provides conclusions for the overall thesis and recommendations for future work. / Thesis / Doctor of Philosophy (PhD)

One of the most significant challenges faced when modeling mass transfer from contaminant source zones is uncertainty regarding parameter estimates. These rate parameters are of particular importance because they control the connectivity between a simulated contaminant source zone and the aqueous phase. Where direct observation has fallen short, this study attempts to interpret field data using an inverse modeling technique for the purpose of constraining mass transfer processes which are poorly understood at the field scale. Inverse modeling was applied to evaluate parameters in rate-limited models for mass transfer. Two processes were analyzed: (i) desorption of hydrophobic contaminants and (ii) multicomponent Non-Aqueous Phase Liquid (NAPL) dissolution. Desorption was investigated using data obtained from elution experiments conducted with weathered sediment contaminated with 2,4,6 trinitrotoluene (TNT) (Sellm and Iskandar, 1994). Transport modeling was performed with four alternative source models, but predictive error was minimized by two first-order models which represented sorption/desorption using a Freundlich isotherm. The results suggest that first-order/Freundlich models can reproduce dynamic desorption attributed to high-and-low relative energy sorption sites. However, additional experimentation with the inversion method suggests that mass constraints are required in order to appropriately determine mass transfer coefficients and sorption parameters. The final portion of this research focused on rate-limited mass transfer from multicomponent NAPLs to the aqueous phase. Previous work has been limited to bench and intermediate scale findings which have been shown to inadequately translate to field conditions. Two studies were conducted in which numerical modeling was used to reproduce dissolution from multicomponent NAPL sources. In the first study, a model was generated to reproduce dissolution of chloroform (TCM), trichloroethylene (TCE) and tetrachloroethylene (PCE) observed during an emplaced-source field experiment conducted within a flow cell (Broholm et al., 1999). In the second study, a methodology was developed for analyzing benzene, toluene, ethylbenzene and xylene (BTEX) data during a field-scale mass transfer test conducted within a vertically-smeared source zone (Kavanaugh, 2010). The findings suggest that the inversion technique, when provided appropriate characterization of site and source parameters and when given appropriate dataset resolution, represents a viable method for parameter determination. Furthermore, the findings of this research suggest that inversion-based modeling provides an innovative predictive method for determining mass transfer parameters for multicomponent mixtures at the field scale. / Ph. D.

La transformation de la biomasse lignocellulosique requiert des conditions opératoires différentes de celles employées dans les procédés du raffinage et de la pétrochimie. Ainsi, certaines transformations de produits bio-sourcés sont opérées en phase aqueuse et en température (« conditions hydrothermales (HT) » : T > 200°C, eau liquide). Les catalyseurs hétérogènes industriels constitués de supports poreux oxydes comme l’alumine se révèlent alors inadaptés. Des modifications structurales et texturales sont observées induisant des performances catalytiques instables et incompatibles avec une viabilité industrielle d’éventuels procédés. La thèse propose de développer des matériaux catalytiques présentant des propriétés de stabilité hydrothermale adaptées au traitement des nouvelles matières premières que sont la biomasse et ses réactifs dérivés. La stratégie consiste à modifier la surface d’alumine afin de la rendre stable en conditions HT. Cette modification de surface est effectuée avec l’aide d’additifs organiques (carbone, polyols) ou inorganiques (silicium).Il est montré que l’alumine devient stable lors de la saturation de certains hydroxyles de sa surface localisés spécifiquement sur les faces basales des cristallites élémentaires. Des stratégies sont développées pour de déposer sélectivement du carbone ou du silicium sur ces sites en question. Une très bonne stabilité HT est ainsi obtenue avec un taux de recouvrement de la surface proche de 20% seulement. Une phase métallique est ensuite déposée sur les matériaux stabilisés et leurs performances catalytiques sont évaluées pour l’hydrogénolyse du glycérol / Biomass transformation reactions are carried under very different conditions from those used in petroleum industry. Some bio-products are transformed in aqueous phase underhigh temperatures (hydrothermal conditions). Heterogeneous catalysts are most likely made with a porous oxide like alumina witch is not suited for such conditions. Its textural and structural properties are modified during the treatment making the material incompatible with any process. The aim of the thesis is to develop new catalytic materials with hydrothermal stability properties adapted to the treatment of biomass products. The strategy is to modify alumina surface in order to make it insensitive to water during a hydrothermal treatment. The surface modification is done with inorganic (silicon) and organic (carbon, polyols) additives.We show here that alumina is stable only if some specific hydroxyls located in basal surfaces of crystallites are saturated. We develop strategy to selectively cover those sites with carbon or silica. A very good hydrothermal stability is obtained with a surface coverage close to 20% only. Then, a metal phase is deposited on the stabilized supports and catalytic performances of the materials are evaluated through the glycerol hydrogenolysis reaction

Multiphase flow and transport in fractured rock is of importance to many practical and engineering applications. In the field of groundwater hydrology an issue of significant environmental concern is the release of dense non-aqueous phase liquids (DNAPLs) which can cause long-term groundwater contamination in fractured aquifers. This study deals with two fundamental processes – fluid displacement and interphase mass transfer – concerning the behavior of the multiphase contaminants in fractured media. The focus of this work has been placed on improving the current understanding of small-scale (single fracture) physics by a combined effort of numerical modeling analysis, laboratory experiments and model development. This thesis contributes to the improved understanding through several aspects. Firstly, the effect of aperture variability, as characterized by geostatistical parameters such as standard deviation and correlation length, on the DNAPL entrapment, dissolution and source-depletion behaviors in single fractures was revealed. Secondly, a novel, generalized approach (adaptive circle fitting approach) to account for the effect of in-plane curvature of fluid-fluid interfaces on immiscible fluid displacement was developed; the new approach has demonstrated good performance when applied to simulate previously published experimental data. Thirdly, the performance of a continuum-based two-phase flow model and an invasion percolation model was compared for modeling fluid displacement in a variable-aperture fracture and the dependence of fracture-scale capillary pressure – saturation relationships on aperture variability was studied. Lastly, through experimental studies and mechanistic numerical modeling of DNAPL dissolution, kinetic mass transfer characteristics of two different entrapment configurations (residual blobs and dead-end pools) were investigated. The obtained understanding from this thesis will be useful for predictive modeling of multiphase contaminant behavior at a larger (fracture network) scale. / Flerfasflöde och ämnestransport i sprickigt berg är av betydelse för många praktiska och tekniska problem. Tunga, svårlösliga organiska vätskor (engelska: dense non-aqueous phase liquids: DNAPLs; t.ex. klorerade lösningsmedel) kan orsaka långvarig förorening av vattenresurser, inklusive akviferer i sprickigt berg, och utgör ett viktigt miljöproblem inom grundvattenhydrologin. Denna studie behandlar två fundamentala processer för spridning av flerfasföroreningar i sprickiga medier – utbredning av den organiska vätskan och massöverföring mellan organisk vätska och vatten. Arbetet har fokuserat på att förbättra nuvarande kunskap om de fysikaliska processerna på liten skala (enskilda sprickor) genom en kombination av numerisk modellering, laboratorieexperiment och modellutveckling. Avhandlingen har bidragit till utökad processförståelse i flera avseenden. För det första har arbetet belyst effekterna av sprickaperturens variabilitet, uttryckt med geostatistiska parametrar som standardavvikelse och rumslig korrelationslängd, på fastläggning och lösning av organiska vätskor i enskilda sprickor, samt utmattningsbeteendet hos dessa källor till grundvattenförorening. För det andra har en ny, generell metod (adaptiva cirkelpassningsmetoden) för att ta hänsyn till effekten av krökningen av gränsytan mellan organisk vätska och vatten i sprickplanet utvecklats; denna metod har visats fungera väl i simuleringar av tidigare publicerade experimentella data. För det tredje, har en jämförelse gjorts mellan en kontinuumbaserad tvåfasflödesmodell och en invasions-perkolationsmodell med avseende på hur väl de kan simulera tvåfasflöde i en spricka med varierande apertur. Här studerades även hur relationen mellan kapillärtryck och mättnadsgrad på sprickplansskala beror av variabiliteten i sprickapertur. Till sist undersöktes lösning av den organiska vätskan i grundvatten för två fastläggningsscenarier (fastläggning i immobila droppar och ansamling i fällor – ”återvändssprickor”) både genom experiment och mekanistisk numerisk modellering. Kunskapen som tagits fram i denna avhandling bedöms vara användbar även för att modellera spridningen av flerfasföroreningar på större (spricknätverks-) skalor.

The aqueous phase photo-oxidation of water soluble organic compounds (WSOC) extracted from α-pinene ozonolysis secondary organic aerosol (SOA) was investigated using high resolution time-of-flight chemical ionization mass spectrometry (CI-ToFMS). The results have shown that WSOC get more functionalized and fragmented as the reaction proceeds. The capabilities of three reagent ions, were assessed; specifically, (H2O)nH+ ionizes organic compounds with carbon oxidation state (OSC) ≤ 1.3, whereas CH3C(O)O- and I(H2O)n- ionize highly oxygenated organics with OSC up to 4, with I(H2O)n- showing more selectivity. The aqueous phase OH oxidation of cis-pinonic acid and tricarballylic acid (a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), recognized as a tracer of α-pinene SOA) were also studied. The respective rate constants at 301 K were measured to be 3.4(±0.5)×10^9 M^-1s^-1 at pH=2 and 3.1(±0.3)×10^8 M^-1s^-1 at pH=4.6. This work also illustrates possible aqueous phase mechanism for MBTCA formation from cis-pinonic oxidation.

The aqueous phase photo-oxidation of water soluble organic compounds (WSOC) extracted from α-pinene ozonolysis secondary organic aerosol (SOA) was investigated using high resolution time-of-flight chemical ionization mass spectrometry (CI-ToFMS). The results have shown that WSOC get more functionalized and fragmented as the reaction proceeds. The capabilities of three reagent ions, were assessed; specifically, (H2O)nH+ ionizes organic compounds with carbon oxidation state (OSC) ≤ 1.3, whereas CH3C(O)O- and I(H2O)n- ionize highly oxygenated organics with OSC up to 4, with I(H2O)n- showing more selectivity. The aqueous phase OH oxidation of cis-pinonic acid and tricarballylic acid (a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), recognized as a tracer of α-pinene SOA) were also studied. The respective rate constants at 301 K were measured to be 3.4(±0.5)×10^9 M^-1s^-1 at pH=2 and 3.1(±0.3)×10^8 M^-1s^-1 at pH=4.6. This work also illustrates possible aqueous phase mechanism for MBTCA formation from cis-pinonic oxidation.

No description available.

Die chemische Zusammensetzung und die physikalischen Eigenschaften von troposphärischen Gasen, Partikeln und Wolken hängen aufgrund zahlreicher Prozesse stark voneinander ab. Insbesondere chemische Multiphasenprozesse in Wolken können die physiko-chemischen Eigenschaften der Luft und troposphärischer Partikel klein- und großräumig verändern. Diese chemische Prozessierung des troposphärischen Aerosols innerhalb von Wolken beeinflusst die chemischen Umwandlungen in der Atmosphäre, die Bildung von Wolken, deren Ausdehnung und Lebensdauer, sowie die Transmissivität von einfallender und ausgehender Strahlung durch die Atmosphäre. Damit sind wolken-chemische Prozesse relevant für das Klima auf der Erde und für verschiedene Umweltaspekte. Daher ist ein umfassendes Verständnis dieser Prozesse wichtig. Die explizite Behandlung chemischer Reaktionen in der Flüssigphase stellt allerdings eine Herausforderung für atmosphärische Computermodelle dar. Detaillierte Beschreibungen der Flüssigphasenchemie werden deshalb häufig nur für Boxmodelle verwendet. Regionale Chemie-Transport-Modelle und Klimamodelle berücksichtigen diese Prozesse meist nur mit vereinfachten chemischen Mechanismen oder Parametrisierungen. Die vorliegende Arbeit hat zum Ziel, den Einfluss der chemischer Mehrphasenprozesse innerhalb von Wolken auf den Verbleib relevanter Spurengase und Partikelbestandteile mit Hilfe des state‑of‑the‑art 3D-Chemie-Transport-Modells COSMO-MUSCAT zu untersuchen. Zu diesem Zweck wurde das Model um eine detaillierte Beschreibung chemischer Prozesse in der Flüssigphase erweitert. Zusätzlich wurde das bestehende Depositionsschema verbessert, um auch die Deposition von Nebeltropfen zu berücksichtigen. Die durchgeführten Modellerweiterungen ermöglichen eine bessere Beschreibung des troposphärischen Multiphasensystems. Das erweiterte Modellsystem wurde sowohl für künstliche 2D-Bergüberströmungsszenarien als auch für reale 3D-Simulationen angewendet. Mittels Prozess- und Sensitivitätsstudien wurde der Einfluss (i) des Detailgrades der verwendeten Mechanismen zur Beschreibung der Flüssigphasenchemie, (ii) der Größenauflösung des Tropfenspektrums und (iii) der Tropfenanzahl auf die chemischen Modellergebnisse untersucht. Die Studien belegen, dass die Auswirkungen der Wolkenchemie aufgrund ihres signifikanten Einflusses auf die Oxidationskapazität in der Gas- und Flüssigphase, die Bildung von organischer und anorganischer Partikelmasse sowie die Azidität der Wolkentropfen und Partikel in regionalen Chemie-Transport-Modellen berücksichtigt werden sollten. Im Vergleich zu einer vereinfachten Beschreibung der Wolkenchemie führt die Verwendung des detaillierten chemischen Flüssigphasenmechanismus C3.0RED zu verringerten Konzentrationen wichtiger Oxidantien in der Gasphase, einer höheren Nitratmasse in der Nacht, geringeren nächtlichen pH-Werten und einer veränderten Sulfatbildung. Darüber hinaus ermöglicht eine detaillierte Wolkenchemie erst Untersuchungen zur Bildung sekundärer organischer Partikelmasse in der Flüssigphase. Die größenaufgelöste Behandlung der Flüssigphasenchemie hatte nur geringen Einfluss auf die chemischen Modellergebnisse. Schließlich wurde das erweiterte Modell für Fallstudien zur Feldmesskampagne HCCT‑2010 genutzt. Zum ersten Mal wurde dabei ein chemischer Mechanismus mit der Komplexität von C3.0RED verwendet. Die räumlichen Effekte realer Wolken z. B. auf troposphärische Oxidantien oder die Bildung anorganischer Masse wurden untersucht. Der Vergleich der Modellergebnisse mit verfügbaren Messungen hat viele Übereinstimmungen aber auch interessante Unterschiede aufgezeigt, die weiter untersucht werden müssen. / In the troposphere, a vast number of interactions between gases, particles, and clouds affect their physico-chemical properties, which, therefore, highly depend on each other. Particularly, multiphase chemical processes within clouds can alter the physico-chemical properties of the gas and the particle phase from the local to the global scale. This cloud processing of the tropospheric aerosol may, therefore, affect chemical conversions in the atmosphere, the formation, extent, and lifetime of clouds, as well as the interaction of particles and clouds with incoming and outgoing radiation. Considering the relevance of these processes for Earth\'s climate and many environmental issues, a detailed understanding of the chemical processes within clouds is important. However, the treatment of aqueous phase chemical reactions in numerical models in a comprehensive and explicit manner is challenging. Therefore, detailed descriptions of aqueous chemistry are only available in box models, whereas regional chemistry transport and climate models usually treat cloud chemical processes by means of rather simplified chemical mechanisms or parameterizations. The present work aims at characterizing the influence of chemical cloud processing of the tropospheric aerosol on the fate of relevant gaseous and particulate aerosol constituents using the state-of-the-art 3‑D chemistry transport model (CTM) COSMO‑MUSCAT. For this purpose, the model was enhanced by a detailed description of aqueous phase chemical processes. In addition, the deposition schemes were improved in order to account for the deposition of cloud droplets of ground layer clouds and fogs. The conducted model enhancements provide a better insight in the tropospheric multiphase system. The extended model system was applied for an artificial mountain streaming scenario as well as for real 3‑D case studies. Process and sensitivity studies were conducted investigating the influence of (i) the detail of the used aqueous phase chemical representation, (ii) the size-resolution of the cloud droplets, and (iii) the total droplet number on the chemical model output. The studies indicated the requirement to consider chemical cloud effects in regional CTMs because of their key impacts on e.g., oxidation capacity in the gas and aqueous phase, formation of organic and inorganic particulate mass, and droplet acidity. In comparison to rather simplified aqueous phase chemical mechanisms focusing on sulfate formation, the use of the detailed aqueous phase chemistry mechanism C3.0RED leads to decreased gas phase oxidant concentrations, increased nighttime nitrate mass, decreased nighttime pH, and differences in sulfate mass. Moreover, the treatment of detailed aqueous phase chemistry enables the investigation of the formation of aqueous secondary organic aerosol mass. The consideration of size-resolved aqueous phase chemistry shows only slight effects on the chemical model output. Finally, the enhanced model was applied for case studies connected to the field experiment HCCT-2010. For the first time, an aqueous phase mechanism with the complexity of C3.0RED was applied in 3‑D chemistry transport simulations. Interesting spatial effects of real clouds on e.g., tropospheric oxidants and inorganic mass have been studied. The comparison of the model output with available measurements revealed many agreements and also interesting disagreements, which need further investigations.

Biomass is one of the most promising replacements for fossil fuels as a feedstock for chemical and transportation fuel production. The combination of low vapor pressure and high polarity of most biomass derived molecules makes water the ideal solvent for biomass upgrading reaction schemes. Metal oxide and metal oxide supported catalysts are heavily used in oil refining and petrochemical production, and are capable of upgrading biomass molecules as well. However, the surface chemistries that dictate the behavior of aqueous phase biomass upgrading reactions over metal oxide catalysts are not nearly as well understood as in the case of gas phase hydrocarbon refining systems. This dissertation aims to investigate the surface chemistries of biomass derived oxygenate molecules on metal oxide and metal oxide supported metal catalysts. There are three main objectives in this dissertation: to understand how two and three carbon polyols interact with metal oxide surfaces, to elucidate the role of various surface sites on polyol-metal oxide interactions, and to discover the surface species of kinetic importance in aqueous phase reforming reactions of biomass molecules. Transmission infrared spectroscopy and density functional theory modeling were the major techniques used to demonstrate that polyols with alcohol groups on the first and third carbons, 1,3-propanediol and glycerol, form a multidentate surface species with a bridging alkoxide bond and an acid/base interaction through their two primary alcohol groups with Lewis acid sites of g-Al₂O₃. These interactions occur in the presence of bulk water. Polyols with alcohol groups only on the first and second carbons, ethylene glycol and 1,2-propanediol, only formed alkoxy bonds with the g-Al₂O₃ surface when bulk water was not coadsorbed, and these bonds were removed by re-adsorbing water. Glycerol also forms the same surface species on other metal oxides with strong Lewis acidic character: TiO₂ anatase, ZrO₂, and CeO₂. Glycerol only forms hydrogen bonds with MgO, which lacks strongly Lewis acidic sites. Basic surface hydroxyls and surface oxygen atoms of the metal oxides only played a minor role in interacting with the adsorbed glycerol. In-situ attenuated total reflectance infrared spectroscopy demonstrated that the aqueous phase reforming of glycerol over a 5 wt% Pt on g-Al₂O₃ catalyst is hindered by residual platinum bound hydrogen or oxygen atoms from commonly utilized catalyst reduction or cleaning procedures, respectively. A pretreatment consisting of multiple iterations of dissolved oxygen, dissolved hydrogen, and dissolved helium in water flow periods provides the cleanest Pt surface for monitoring carbon monoxide formation dynamics, and allows for observing the rate limiting step of the aqueous phase reforming reactions water-gas shift removal of Pt bound carbon monoxide. The bridging bound carbon monoxide is preferentially removed over the linearly bound species via water gas shift reactions even at room temperature.