This thesis examined the use of two-phase partitioning bioreactors (TPPBs) for the biodegradation of poorly water-soluble compounds. TPPBs are stirred tank bioreactors composed of a biocatalyst-containing aqueous phase and an immiscible second phase containing large amounts of poorly water-soluble or toxic substrates. Degradation of the bioavailable substrate in the aqueous phase will result in equilibrium-driven partitioning of additional substrate from the immiscible phase into the aqueous phase, theoretically allowing for complete substrate degradation. Fundamental work was undertaken with the PCB-degrading organisms Burkholderia xenovorans LB400 in liquid-liquid and solid-liquid TPPBs. Initially biphenyl was used as the sole carbon source due to its hydrophobic nature and structural similarity to the environmentally relevant PCBs. The critical LogKO/W (octanol/water partitioning coefficient) of the organism was determined to be 5.5 and its growth kinetics on biphenyl were determined in a liquid-liquid TPPB. A polymer selection strategy for solid-liquid TPPBs was developed in the next chapter, and it was shown in the following chapter that biphenyl degradation in solid-liquid TPPBs was mass transfer limited, as described mathematically utilising the previously estimated microbial kinetics. The fundamental knowledge gained in the early chapters was then applied to the degradation of PCBs by the same organism. It was shown that the aqueous phase availability of PCBs is the rate-limiting step in biphasic bioreactors, and not the mass transfer rate. The low specific microbial degradation rates, resulting from substrate-limited growth were addressed with increased biomass concentrations; however, it was also found that an additional carbon source was required to maintain microbial activity over an extended period of time. Pyruvic acid was selected as a carbon source which, once added to actively PCB-degrading cells, maintained the cells’ activity towards PCBs and up to 85 % of 100 mg l-1 was degraded in 15 h. It was shown as the final contribution in this thesis that TPPBs can be combined with a PCB soil extraction step as a potential remediation scheme for PCB contaminated soil. PCBs were extracted from soil with polymer beads (up to 75 % removal), followed by biodegradation of the PCBs in a solid-liquid TPPB in which PCBs were delivered to the degrading organism from the same polymer. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2007-08-07 16:11:00.494

Knowledge of effective reef restoration techniques are necessary in this age of worldwide coral reef decline. Coral transplantation is a restoration technique employed after natural (i.e. hurricanes) and anthropogenic (i.e. vessel groundings) physical disturbance events. The study was conducted to compare the efficacy of propagating small colony fragments in laboratory and field conditions in terms of survival and growth. Fragment growth and survival were assessed for six scleractinian boulder corals common to Florida and Caribbean reefs: Montastraea annularis, M. cavernosa, Diploria clivosa, Siderastrea siderea, S. radians and Dichocoenia stokesii. Broken coral colonies were salvaged from vessel grounding sites and marine debris, fragmented into pucks and secured to travertine tiles. One hundred and fifty-three coral colony fragments were cultivated in an ex situ laboratory nursery and 133 coral colony fragments were cultivated in an in situ field nursery and monitored for 13 months. Survival of all colonies was 94%, with 98% survival in the laboratory treatment and 89% survival in the field treatment. Complete colony mortality was documented in three S. radians colonies, all in the laboratory treatment. All colony loss in the field treatment was due to colony pucks being detached from the tiles. Overall mean percent change in colony tissue area from initial to final monitoring events was calculated to determine growth. Across species, growth was greater in the laboratory treatment (76 ± 4 % SEM) in comparison to the field treatment (27 ± 5 % SEM). Positive growth was observed in D. clivosa, D. stokesii, M. annularis, M. cavernosa and S. siderea in the laboratory treatment. In the field treatment, D. clivosa, M. annularis and M. cavernosa were the only species that exhibited positive growth. Negative growth was observed in both the laboratory and field treatments for S. radians. In conclusion, colonies propagated in the ex situ nursery (laboratory treatment) had higher growth and survival than colonies propagated in the in situ nursery (field treatment). A critical acclimation period accomplished through the use of stable laboratory conditions will produce healthier, more secure coral colonies that may be used to repopulate disturbed reef sites.

The demand for today's material resources for energy storage is rapidly increasing and can result in both environmental and political conflicts that can affect the development of electronic devices due to high prices and limitations of raw materials for batteries. In this study, potential future composite electrodes were synthesised with an ex-situ approach by compositing redox-active 2,6-Diaminoanthraquinone and 1,3,5-Triformylphloroglucinol covalent organic framework (DAAQ-TFP COF) with conductive delaminated Ti3C2Tx MXene to maximise the number of redox-active moieties during cycling. In addition, solvothermal synthesis with the implementation of mechanical grinding as an exfoliation method was used to try to obtain DAAQ-TFP nanosheets to increase both the contact area between the two materials and the number of charge carriers. The sample was analysed with PXRD and BET surface analysis to characterise the crystallinity meanwhile SEM was utilised to study the morphology of the COF and the composite material. The specific capacitance of each electrode was estimated by cyclic voltammetry. The study showed a decrease in reduced specific capacitance with lower MXene content. Hence, this concludes pure Ti3C2Tx sheets have the highest capacitance contribution with a value of 48.79 Fg-1 meanwhile the composite electrode with a ratio of 1:1 was estimated to 32.26 Fg-1 with 0.0928 % of its moieties undergoing a redox reaction. A reduced capacitance with an increased COF-MXene ratio indicates that MXene contributes with more capacity relative to the COF, in combination with a non-successful exfoliation of DAAQ-TFP to single-layered nanosheets, reducing the interactions between the two materials.

L'objectif de cette thèse est l'étude de la déformation, à l'échelle microscopique, de la phase MAX Ti2AlN, synthétisée par métallurgie des poudres. Ce travail se divise en trois parties : une première dans laquelle l'accent a été mis sur l'hystérèse mécanique des phases MAX via des essais cyclés, en nanoindentation sphérique et compression ex-situ de micro-piliers, sur des grains d'orientations différentes déterminées par l'EBSD. Dans la deuxième nous nous sommes intéressés à la déformation de micropiliers via des essais de compression cyclés in-situ couplés à la micro-diffraction Laue. L'objectif a été d'analyser les taches diffraction au cours de la déformation du pilier afin de mettre en évidence les mécanismes de déformation élémentaires mis en jeu et d'observer les structures finales via des images MEB post-mortem des piliers. Enfin, une dernière dans laquelle l'objectif a été l'étude des mécanismes de déformation en température à l'échelle microscopique via des essais de nano-indentation allant jusqu'à 800°C. La caractérisation des lignes de glissement en surface et des configurations microstructurales sous l'empreinte a été réalisée par AFM et MET respectivement. Toutes les données recueillies par ces divers essais aux petites échelles, ont permis d'affiner notre compréhension des mécanismes de déformation du monocristal de phase MAX, notamment vis à vis des modèles usuellement proposés dans la littérature. / The thesis's goal is to study the deformation, at microscopic scale, of the MAX phase Ti2AlN synthesized by powder metallurgy. This work is divided into three parts: in the first part, the interest has been put on the hysteretic behavior of the MAX phases via cyclic mechanical solicitations, during spherical indentation tests and ex-situ compression of micro-pillars, on differently orientated grains beforehand determined by EBSD. In the second part, we were interested into the micro-pillar's deformation via insitu cyclic compression tests coupled with Laue micro-diffraction. The goal was to analyse the evolution diffraction lines during the pillar's deformation in order to highlight the elementary deformation mechanisms and to observe the finale structures via the post-mortem SEM imaging of the pillars. Finally, a last part was devoted to study the deformation mechanisms in temperature at microscopic scale via nano-indentation tests up to 800°C. The characterization of the slip lines on the surface has been revealed by AFM and that of t he microstructural configurations (dislocations) under the indent has been done by TEM. All data collected by these various tests at the small scales have refined our understanding of the deformation mechanisms of crystal MAX phase, particularly with respect to the models usually proposed in the literature.

Present organic carbon fluxes from an upland peat catchment were quantified through measurement of in-situ direct and indirect greenhouse gas fluxes. To predict future greenhouse gas (GHG) fluxes, peat from eroded (E) and uneroded (U) site of an upland peat catchment was characterized.Composition of peat from E and U sites at the Crowden Great Brook catchment, Peak District Nation Park, UK that was characterized by Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS) at 700 oC. Pyrolysis products of the peat were then classified using the Vancampenhout classification into 6 compound classes - viz. aromatic and polyaromatic (Ar), phenols (Ph), lignin compounds (Lg), soil lipids (Lp), polysaccharide compounds (Ps) and N-compounds (N). There was no significant difference in the composition between the eroded and uneroded sites within the study area or between peats from different depths within each site. Nevertheless, there was a significant difference between sites in the proportions of Sphagnum that had contributed to the peat. Pyrolysis products of the peat were also classified into pedogenic (Pd) and aquagenic (Aq) OC – the mean percentage of Pd in both eroded and uneroded peats was 43.93 ± 4.30 % with the balance of the OC classified as Aq.Greenhouse gas (GHG) fluxes were quantified directly by in-situ continuous measurement of GHG was carried out at the E and U sites of the catchment using a GasClam: mean in-situ gas concentrations of CH4 (1.30 ± 0.04 % v/v (E), 0.59 ± 0.05 % v/v (U) and CO2 (8.83 ± 0.22 % v/v (E), 1.77 ± 0.03 % v/v (U)) were observed, with both the CH4 and CO2 concentrations apparently unrelated to atmospheric pressure and temperature changes. Laboratory measurements of ex-situ gas production - for both CH4 and CO2 this was higher for U site soils than for E site soils. At the U site, maximum production rates of both CH4 (46.11±1.47 mMol t-1 day-1) and CO2 (45.56 ± 10.19 mMol t-1 day-1) were observed for 0-50 cm depth in soils. Increased temperature did not affect gas production, whilst increased oxygen increased gas production. The CH4/CO2 ratios observed in-situ are not similar to those observed in the ex-situ laboratory experiments; suggest that some caution is advised in interpreting the latter. However, the maximum OC loss of 2.3 wt. % observed after 20 weeks of ex-situ incubation is nevertheless consistent with the long-term degradation noted by Bellamy et al (1985) from organic-rich UK soils. Indirect greenhouse gas (GHG) fluxes were quantified through the mass flux of suspended organic carbon (SsOC) drained from studied catchments. The SsOC was quantified by interpolating and rating methods. Unfiltered (UF) organic carbon (OC) fluxes in 2010 were calculated to be 8.86 t/km2/yr for the eroded sub-catchment and 6.74 t/km2/yr for the uneroded sub-catchment. All the rating relationships have a large amount of scatter. Both UF OC and <0.2 µm fraction OC are positively correlated with discharge at the eroded site, whilst there is no discernable relationship with discharge at the uneroded site. SsOC is dominated by Pd type OC (95.23 ± 10.20 % from E; 92.84 ± 5.38 % from U) far more so than in sources of the peats, suggesting slower oxidation of Pd (cf. Aq) OC.

No description available.

Vid utvidgning av befintliga hamnar kan den relativt nya metoden stabiliserade/solidifierade (S/S) förorenade muddermassor användas i anslutning till spont. S/S metoden används för att binda föroreningarna fysikaliskt eller stänga in dem samt för att förbättra massornas hållfasthets- och deformationsegenskaper. Istället för att deponera dessa, ofta förorenade, muddermassor till ett högt pris kan det återanvändas i hamnkonstruktionen som ett byggmaterial. Det finns få rapporter som behandlar stabiliserade massor i anslutning till spont och hur de samverkar, vilket gör att det inte finns tydliga riktlinjer för hur metoden ska användas. Dessutom finns det stora osäkerheter kring hur utvecklingen av den odränerade skjuvhållfastheten ökar över tid och hur den kan tas hänsyn till vid projekteringen och därför kan metoden inte utnyttjas på ett effektivt sätt. Den odränerade skjuvhållfastheten utvärderas som halva tryckhållfastheten. Syftet med studien är att kunna prognostisera hur jordtrycket mot en spont beror på de S/S -behandlade muddermassornas egenskaper. Vidare har en projekteringsmetodik till S/S massor i anslutning till spont föreslagits. För att svara på detta har en litteraturstudie gjorts för att samla bakgrundsinformation och skapa en djupare förståelse för ämnet. Därefter gjordes en parameterstudie i FEM-programmet PLAXIS. Resultatet från parameterstudien kunde sedan jämföras med tidigare fält- och laboratorieförsök där egenskapernas förändringar över tid har studerats. Med detta som bakgrund kunde en projekteringsmetodik föreslås. Muddermassorna kan initialt liknas vid en vätska som orsakar ett hydrostatiskt tryck mot sponten. Med tiden kommer massorna härda och därigenom ökar hållfastheten, detta gör så att det horisontella jordtrycket minskar samtidigt som en vertikal pålastning sker vilket ökar det horisontella jordtrycket. Från litteraturstudien kunde det även ses att muddermassornas slutgiltiga hållfasthet och tillväxt beror på bindemedelsmängd och kombination som i sin tur måste anpassas efter muddermassornas vattenkvot och organisk halt. Från parameterstudien kan slutsatsen dras att en av faktorerna som har en större påverkan är hur hög skjuvhållfastheten är efter första härdningen när alla muddermassor har pumpats på plats samt förhållandet mellan skjuvhållfastheten och elasticitetsmodulen och hur de utvecklas. I den föreslagna projekteringsmetoden rekommenderas att dräneringstyp odränerad A och materialmodell Mohr-Coulomb ska användas vid simuleringar. Då det finns så stora osäkerheter kring S/S muddermassor anses materialmodell Mohr-Coulomb vara fullt tillräcklig jämfört med andra mer avancerade modeller då det finns stora osäkerheter kring indatan. Dräneringstyp odränerad A är den mer avancerade dräneringstypen av de tre och tar hänsyn till fler parametrar. Eftersom det kommer ske en utveckling av friktionsvinkel kommer modellen ge en bättre representation. / When expanding existing ports, the relatively new method ofvstabilized/solidified (S/S) contaminated dredged material can be used in connection with a sheet pile wall. The S/S method is used to physically bind the contaminants or trap them and to improve the strength and deformation properties of the masses. Instead of depositing these, often polluted, dredged materials at a high price, it can be reused in the port construction as a buildingmaterial. There are few reports that deal with stabilized masses in connection with a sheet pile wall and how they interact, which means that there are no clear guidelines for how the method should be used. In addition, there are great uncertainties about how the development of the undrained shear strength increases over time and how it can be taken into account in the design and therefore the method cannot be used in an efficient manner. The undrained shear strength is evaluated as half of the compressive strength. The purpose of the study is to be able to forecast how the earth pressure against a sheet pile wall depends on the properties of the S/S-treated dredged material. Furthermore, a design methodology for S/S material in connection with sheet pile wall has been proposed. To answer this, a literature study has been done to gather background information and create a deeper understanding of the subject. A parameter study was also done in the FEM-program PLAXIS. The results from the parameter study could then be compared with previous field and laboratory experiments where the changes in properties over time have been studied. With this as a background, a design methodology could be proposed. The dredged masses can initially be likened to a liquid which causes a hydrostatic pressure against the sheet pile wall. Over time, the masses will harden and thereby increase the shear strength, this means that the horizontal earth pressure decreases at the same time as a vertical loading takes place, which increases the horizontal earth pressure. From the literature study, it could also be seen that the final shear strength and growth of the dredged material depends on the amount of binder and combination, which in turn must be adapted to the water content and the organic content. From the parameter study, it can be concluded that one of the factors that has a greater impact is how high the shear strength is after the first hardening when all dredged materials have been pumped in place and the relationship between the shear strength and modulus of elasticity and the development. In the proposed design method, it is recommended that drainage type undrained A and material model Mohr-Coulomb should be used in simulations. As there are such large uncertainties regarding S/S dredged materials, the Mohr-Coulomb material model is considered to be fully sufficient compared with other more advanced models as there are large uncertainties regarding the input data. Drainage type undrained A is the more advanced drainage type of the three tested and takes the materials friction angle into account. Which will give a better representation.