Dissertations / Theses on the topic 'Organic compound content'

The sorption of five chlorinated benzenes and sixteen other organic solutes was investigated by determining the extent of sorption and the sorption rates in a series of 40 batch and 139 column experiments using surface-modified silica of known chemical composition. These surfaces were used to represent important functional groups in soil, and consisted of porous silica with patchy surface coatings of aliphatic chains (C₁, C₈, and C₁₈), and other substituent groups (phenyl, amine, alcoholic, and carboxylic). Three possible rate-limiting steps were examined: diffusion through immobile pore fluid, diffusion through bound organic matter, and the chemical binding and release rate. First-order desorption rate coefficients were observed to be 10⁻¹ to 10⁻² s⁻¹ on unbonded, and C₈, C₁₈, amine, and alcoholic modified surfaces, and 10⁻³ to 10⁻⁵ s⁻¹ on C₁ and phenyl-polymer modified surfaces. Diffusion through immobile pore fluid had only a minor effect on the sorption rate, as evidenced by similar rates on organic-bound porous and solid particles. The diffusion rate through the bound organic layer is not rate limiting due to the small organic layer thickness. The observed slow desorption on the phenyl-polymer surface is consistent with the rate limiting step being the chemical binding and release rate. The changes in the rate with temperature and within a series of chlorinated benzenes support this conclusion. The free energies for sorption onto the phenyl-polymer surface ranged from -4.0 kcal mol⁻¹ for chlorobenzene to -6.9 kcal mol⁻¹ for pentachlorobenzene, which are within the range expected for van der Waals interactions. The observed sorption energies are slightly stronger than predicted for hydrophobic surfaces, possibly reflecting strong binding due to multiple pi-pi electron interactions on the phenyl-polymer surface. Hydrophobic solute partitioning onto natural soils, as observed by others, is less than that observed on aliphatic and phenyl hydrophobic surfaces in this study, but greater than on amine or alcoholic modified surfaces. The sorption of di-, tri-, and tetra-chlorobenzenes onto the phenyl-polymer surface is apparently driven by the overall sorption enthalpy (ΔH° = -3.9 to -4.9 kcal mo1⁻¹) and to a lesser extent by the entropy (TΔS° = 0.5 to 1.5 kcal mol⁻¹). As equilibrium of the reactions observed in this study are reached within hours, these reactions are important at small field scales where residence times are hundreds of hours or less.

Dissolved organic matter (DOM) is the most dynamic and least understood part of the global oceanic carbon cycle. Furthermore the molecular composition of DOM is largely unknown. This study focused on the distribution pattern, removal processes and molecular characterisation of DOM in a range of estuaries and coastal zones in New Zealand. Doubtful Sound, the longest fjord in Fiordland National Park, South Island, New Zealand was of particular interest, because of the combination of extreme rainfall, enhanced production of DOM within the temperate rainforest which largely appears in the relatively deep ([greater than or equal to] 5 m) low salinity layer (LSL) at the fjord surface. A typical river estuary (Freshwater River) located in Stewart Island, New Zealand was also investigated. Optical water properties such as the UV/Vis absorption coefficient at 355 nm (a[CDOM](355)) and excitation-emission matrix fluorescence (EEM) were determined for samples from freshwater, across the LSL into open ocean water. These optical properties showed a marked decrease with salinity and highest levels of EEM fluorescence and a[CDOM] (355) in the brackish surface water. In addition to the observed changes in the optical properties, ultrahigh resolution Electrospray Ionisation Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS) determination of molecular formulae revealed that in the fjord about 20 % of these formulae changed along a vertical salinity gradient across the LSL between the brackish surface water and the saline water at 5 m depth. This trend was even more pronounced along the salinity gradient of the Fresh Water River Estuary in Stewart Island, where 60 % of all assigned molecular masses changed from freshwater over the mixing zone to ocean water. Associated with these changes was a marked increase in aromaticity with increasing salinity. Comparable behaviour with increasing salinity was also observed in estuarine samples from the Cape Fear River system, North Carolina, USA. In contrast, only minor changes were determined in molecular formulae for surface water samples collected along a transect off the Otago Coast and across the Subtropical Convergence (STC) into Subantarctic Water (SAW). However, a comparison of the molecular formulae assigned to the DOM pool for the STC water and a freshwater stream in Doubtful Sound, revealed that 75 % of all the assigned formulae for the open ocean sample were common to these two markedly different types of natural waters. This seemingly refractory DOM contained nearly 600 assigned molecular formulae, which were all very similar (only spaced by two hydrogen and CH₂ groups) and could be explained with only 9 general molecular formulae. However, the comparison of all assigned formulae for the freshwater sample suggested that about 90 % of the assigned molecular formulae for the terrestrially-derived DOM changed as it moved from rivers to the open ocean and that only 10 % remained the same. Singlet oxygen showed a very close relationship with the optical properties such as the absorption coefficients (a[CDOM](355)) and the EEM fluorescence intensities and these results suggested that singlet oxygen steady state concentrations are linked to CDOM. Photodegradation processes were confirmed to be responsible for a significant destruction of CDOM. Samples collected from different salinity waters showed major differences in wavelength-dependent photo-decay of CDOM suggesting that the rate of photodegradation in the UV range decreased with increase in salinity whereas it was enhanced for longer wavelength radiation ([greater than or equal to]400 nm). Additionally, the predominantly unsaturated compounds produced during estuarine mixing were found to be highly photolabile and were either destroyed or new unsaturated compounds were produced within 21 h of solar irradiation.

The Microwave-Assisted Process (MAP$ sp{ rm TM}$) is an enhanced extraction technology patented by Environment Canada. MAP uses microwaves to rapidly transfer target compounds from one phase to another by selectively heating the phase containing the target compounds. This thesis presents the results of research performed to determine whether the MAP technique can be further developed into a large-scale soil treatment process that overcomes the limitations of conventional remediation technologies.
The dielectric properties of several mixtures of acetone and hexane over a temperature range from 25$ sp circ$C to 50$ sp circ$C were measured. The dielectric constants of these mixtures were found not to vary significantly with temperature.
A study of microwave absorption by heterogeneous mixtures showed that adding a solid material to a low dielectric constant solvent resulted in energy being preferentially absorbed by the solid.
The results of laboratory extraction tests showed that the ability of the MAP technique to extract contaminants was affected by the organic matter content of soil, particularly in the presence of water.
Use of a closed-vessel system yielded a 60% to 175% increase in the extraction of PAHs from a low organic-content soil relative to that achieved in an open-vessel system. (Abstract shortened by UMI.)

Note:
The soil-solution partitioning of dissolved organic carbon (DOC) withinmineral soil horizons is primarily controlled by processes of adsorption and desorption. These abiotic processes largely occur within a short equilibration time of seconds to minutes, which generally occur faster than microbial processes. To characterise the adsorption of DOC to mineral soils, I used the Langmuir adsorption isotherm, which holds several advantages to the commonly used linear initial mass (IM) isotherm. One advantage to using the Langmuir isotherm is anestimation of the maximum DOC adsorption capacity (Qmax). The Qmax estimates the number of remaining DOC binding sites available on the mineral soil particle surfaces. I modified the traditional Langmuir isotherm in order to estimate the DOC desorption potential of native soil organic matter (SOC).[...]
Le partitionnement entre les solutions de sols du carbone organiquedissous (COD) dans les horizons des sols minéraux est essentiellement contrôle par les processus d'adsorption et de désorption. Ces processus abiotiques se déroulent normalement dans un bref temps d'équilibration variant de quelques secondes a quelques minutes, ce qui est en général plus rapide que les processus microbiens. Pour caractériser Fadsorption de COD aux sols minéraux, nous avons utilise l'isotherme d'adsorption de Langmuir. Cette isotherme présente plusieurs avantages par rapport a Fisotherme de masses initiales (IM) linéaires couramment utilisée, en particulier F estimation de la capacité d'adsorption maximale du COD (Qmax). Le Qmax estime le nombre de sites de liaison de COD restants a la surface du sol minéral. Nous avons aussi modifie Fisotherme de Langmuir traditionnelle afin d'évaluer le potentiel de désorption de COD de la matière organique du sol indigène (MOS).[...]

The soil-solution partitioning of dissolved organic carbon (DOC) within mineral soil horizons is primarily controlled by processes of adsorption and desorption. These abiotic processes largely occur within a short equilibration time of seconds to minutes, which generally occur faster than microbial processes. To characterise the adsorption of DOC to mineral soils, I used the Langmuir adsorption isotherm, which holds several advantages to the commonly used linear initial mass (IM) isotherm. One advantage to using the Langmuir isotherm is an estimation of the maximum DOC adsorption capacity (Qmax). The Qmax estimates the number of remaining DOC binding sites available on the mineral soil particle surfaces. I modified the traditional Langmuir isotherm in order to estimate the DOC desorption potential of native soil organic matter (SOC).
Sorption characteristics were derived for a broad range of52 mineral soils collected from 17 soil profiles spanning across Canada from British Columbia to Quebec. Mineral horizons with the greatest Qmax included the Fe-enriched B horizons of acidic Podzols and Volcanic soils, followed by B horizons not enriched in Fe, followed by A and C horizons. Podzol B horizons were distinct from all other horizons due to significantly higher desorption potential. Soil properties predicting the adsorption characteristics of DOC also predicted the adsorption characteristics of dissolved organic nitrogen (DON). Adsorption of DOC and DON was tightly coupled (R 2 = 0.86), however the ratio of DOC:DON in the final equilibrium solution lowered for 48 out of 52 minerals horizons. These results suggest that DON may be slightly more mobile than DOC.
A short-term (32 day) incubation was perform to establish the fate of indigenous soil C, relative to newly adsorbed soil C to four mineral soils with different adsorption characteristics. Soil columns were leached periodically and sampled for DOC and CO2 production. Two Fe-enriched mineral horizons with high adsorption capacity released low amounts of old SOC, yet released almost all of the newly adsorbed SOC. In contrast, two B horizons without Fe-enrichment released greater amounts of old SOC, and retained a greater fraction of the newly adsorbed SOC than the Fe-enriched horizons. These results identify a contrast between the fate of indigenous and newly adsorbed SOC on mineral soils with differing Qmax.
The final component of this study examined changes to the molecular structure of DOC after equilibration with mineral soils. Multiple techniques were used to assess changes in the molecular composition of DOC, including the analysis of aromatic content by specific UV absorbance (SUVA) and fluorescence spectroscopy, analysis of molecular weight distribution (MWD) with high performance size exclusion chromatography (HPSEC) and functional group analysis with Fourier transform infra-red spectroscopy (FTIR). The solution phase DOC generally showed a reduced aromatic content, along with the removal of organic compounds with carboxyl groups. The MWD of DOC was reduced after equilibration to mineral soils, and the reduction in average molecular weight was related to the Qmax of mineral soils.
The various components of this thesis have contributed to the overall understanding of controls on the adsorption of DOC and DON species to mineral soils of the Canadian temperate and boreal forest.

Celem pracy jest określenie wpływu stresu powstałego w wyniku żerowania Aelia acuminata L. i działania syntetycznego dihydrojasmonu na wydzielanie LZO przez rośliny pszenicy jarej oraz określenie wpływu syntetycznych mieszanin LZO wydzielanych przez pszenicę na imagines A. acuminata L.

Soil properties and their spatial variability was measured to provide a strong database to assess the modification in soil properties associated with future changes in land use. Surface (0--10 cm) soil samples were collected from a 9 ha, 46-year-old pasture being converted to a native tree plantation and a neighboring control pasture near Sardinilla, Panama. A small-scale nested grid of surface soil samples was replicated in the future plantation and a primary forest in the region to evaluate the spatial variability of soil properties. Seven 1 m profiles were sampled in the future plantation and litter samples were collected at the forest and the future plantation.
Assuming the three sites were identical before the conversion to pasture, the difference in surface soil organic carbon (SOC) was 0.75 kg m-2 or equivalent to a loss of 0.017 kg m-2 yr -1 since the original land-use change. The control pasture is higher in bulk density but lower in percent SOC than the future plantation, which is critical to future comparisons.
The pasture soils showed signs of soil compaction and of the homogenization of soil properties. For the 7 profiles in the future plantation, total SOC mass ranged from 13.45 to 23.80 kg m-2, and stable isotopes revealed that 82% of the SOC in the top 10 cm is derived from the pasture vegetation, down to 23% at 1 m depth.
Spatially, the full scale of spatial variability was not determined from the nested grids alone. In addition, the 15 x 15 m grid in the future plantation generally over-estimated the semivariance at the scales below 3 m. The nested grids assessed the minimum measurable semivariance below 5 m.
The precision of surface estimations from point observations can be improved by adding a 5 x 5 m grid to any large-scale sampling scheme.

Thesis (MTech (Chemical Engineering))--Peninsula Technikon, 2001
Certain fungi have been shown to excrete extracellular enzymes, including peroxidases, laccases, etc. These enzymes are useful for bioremediation of aromatic pollutants present in industrial effluents (Leukes, 1999; Navotny et aI, 1999). Leukes (1999) made recent significant development in the form of a capillary membrane gradostat (fungal) bioreactor that offers optimal conditions for the production of these enzymes in high concentrations. This system also offers the possibility for the polluted effluent to be treated directly in the bioreactor. Some operating problems relating to continuous production of the enzymes and scale-up of the capillary modules, were, however, indentified. In an attempt to solve the above-mentioned identified problems the research group at Peninsula Technikon considered a number of alternative bioreactor configurations. A pulsed packed bed bioreactor concept suggested by Moreira et at. (1997) was selected for further study. Their reactor used polyurethane pellets as the support medium for the fungal biofilm and relied upon pulsing of the oxygen supply and recycle of nutrient solution in order to control biomass accumulation. These authors reported accumulation due to the recycle of proteases that were believed to destroy the desired ligninases. We experimented with a similar concept without recycle to avoid backrnixing and thereby overcome protease accumulation. In our work, a maximum enzyme productivity of 456 Units.L1day·1 was attained. Since this was significantly greater than the maximum reported by Moreira et aI, 1997 (202 Units.L-1day-I) it appeared that the elimination of recycle had significant benefits. In addition to eliminating recycle we also used a length / diameter (L / D) ratio of 14: 1 (compared with 2.5: 1 used by Moreira et aI, 1997) in order to further reduce backrnixing. Residence time distributions were investigated to gain insight into mechanisms of dispersion in the reactor. It was found that the pulsed packed bed concept presented problems with regard to blockage by excess biomass. This led us to consider the advantages of a fluidized bed using resin beads. Accordingly, growth of fungi on resin beads in shake flasks was investigated with favorable results. An experimental program is proposed to further investigate the fluidized bed concept with a view to extending the operation time of the bioreactor. From our literature survey to date, packed bed fungal bioreactors are still the best reactor configuration for continuous production ofligninolytic enzymes. An interesting study of the application of laccases to the degradation of naphthalene and MTBE is described in an addendum to this thesis.

Helium tracer experiments were conducted to characterize conservative tracer behavior in a wedge-shaped lysimeter containing alternating layers of unsaturated silty sand, and clay loam. Experiments were conducted with trichloroethylene and 1,1,1-trichloroethane to determine if air stripping in unsaturated soil could be characterized by mass transfer from the sorbed to the liquid to the vapor phase. Batch experiments were conducted to measure liquid--vapor mass transfer. Solid-liquid-vapor mass transfer was characterized by measuring the vapor phase re-equilibration after the air stripping experiment. The Discrete State Compartment model was used to simulate a conservative gas tracer. The results were compared to the helium tracer. Liquid-vapor, and solid-liquid-vapor mass transfer were modeled by fitting simulated data to experimental data. The conservative tracer, and mass transfer models were combined to simulate air stripping in unsaturated soil.

Dissolved organic matter (DOM) is operationally defined as soluble/colloidal material passing through a 0.45~m filter paper. The importance of DOM in soils relies on its role in soil formation and weathering processes, plant and microbial assimilation and soil and water acidification. However, the scientific community studying DOM still disagrees on whether fresh or humified material is the major source of DOM within the forest floor.[...]
La matière organique dissoute (DOM) est composée de particules dissoutes et colloïdales passant au travers un filtre de 0.45 Ilm. L'importance de DOM dans les sols est liée à son rôle dans la pédogenèse, les processus d'altération des minéraux, l'assimilation par les plantes et microbes, ainsi que l'acidification des plans d'eau et des sols.[...]

Dissolved organic matter (DOM) is operationally defined as soluble/colloidal material passing through a 0.45mum filter paper. The importance of DOM in soils relies on its role in soil formation and weathering processes, plant and microbial assimilation and soil and water acidification. However, the scientific community studying DOM still disagrees on whether fresh or humified material is the major source of DOM within the forest floor. One of the factors that could influence the overall importance of DOM production by organic horizons is its potential for biodegradability. In addition, the interaction occurring between the nutrients (i.e. nitrogen (N) and phosphorus (P)) and carbon (C) substrate is believed to be of major importance.
To acquire more knowledge on the production and biodegradation of dissolved C, N and P during decomposition of organic matter (OM), I performed laboratory incubations to evaluate rates of production and transformation, the influence of the degree of OM decomposition and stand type on these rates, and the stoichiometric relationships of the different quotients during the incubations. First, I performed a 30-day incubation of coniferous and deciduous OM from 10 Canadian forest floors representing various degrees of OM decomposition and subsequently measured the amount of: dissolved organic carbon (DOC), total dissolved nitrogen (TDN), nitrate (NO3-N), ammonium (NH4-N), dissolved organic nitrogen (DON), total dissolved phosphorus (TOP) and carbon dioxide (CO2-C). I performed water extractions with the same set of samples to evaluate the biodegradability of DOC and DON and the transformations of TDN, NO3-N and NH4-N.
Fresh material produces more DOM than humified material; material in the midpoint of decomposition (F horizon) produced the largest amount of DIN. Coniferous and deciduous samples did not display different rates of DOM production, most likely because of the overshadowing effect of OM degree of decomposition. I found strong links between the organic matter and dissolved phase C and N content and C:N quotient. The biodegradation, measured as DOC disappearance and mineralization of CO2-C, showed a discrepancy, reflecting the importance of increasing microbial biomass at the beginning of the incubation in response to priming effect. The sharp decrease of TDN and DON observed in the first few days of the incubation, in addition to increasing amount of dissolved inorganic N as waste products during decomposition of DON, supports this hypothesis. A better understanding of the dynamics of dissolved C, N and P in soil is essential to further understand their role in global elemental cycles, including climate change, forest management and pollution.

Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Civil and Environmental Engineering; and the Woods Hole Oceanographic Institution), 2015.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Microorganisms play a central role mediating biogeochemical cycles in the ocean. Marine dissolved organic matter (DOM) - a reservoir of organic solutes and colloids derived from plankton is a major source of carbon, nutrients, and energy to microbial communities. The biological transformation and remineralization of DOM sustains marine productivity by linking the microbial food web to higher trophic levels (the microbial loop) and exerts important controls over the cycles of carbon and bioessential elements, such as nitrogen and phosphorus, in the sea. Yet insight into the underlying metabolism and reactions driving the degradation of DOM is limited partly because its exact molecular composition is difficult to constrain and appropriate microbial model systems known to decompose marine DOM are lacking. This thesis identifies marine microorganisms that can serve as model systems to study the metabolic pathways and biochemical reactions that control an important ecosystem function, DOM turnover. To accomplish this goal, bacterial isolates were obtained by enriching seawater in dilution-to-extinction culturing experiments with a natural source of DOM, specifically, the high molecular weight (HMW) fraction (>1 kDa nominal molecular weight) obtained by ultrafiltration. Because it is relatively easy to concentrate and it is fairly uniform in its chemical composition across the global ocean and other aquatic environments, HMW DOM has the potential to serve as a model growth substrate to study the biological breakdown of DOM. The phylogeny, genomes, and growth characteristics of the organisms identified through this work indicate that HMW DOM contains bioavailable substrates that may support widespread microbial populations in coastal and open-ocean environments. The availability of ecologically relevant isolates in culture can now serve to test hypothesis emerging from cultivation-independent studies pertaining the potential role of microbial groups in the decomposition of organic matter in the sea. Detailed studies of the biochemical changes exerted on DOM by selected bacterial strains will provide new insight into the processes driving the aerobic microbial food chain in the upper ocean.
by Oscar Abraham Sosa.
Ph. D.

Upland peat catchments are usually assumed to function as carbon sinks, however, there have been extensive studies witnessing increasing trends in concentrations and fluxes of organic carbon in UK rivers over the last few decades. A number of controls on dissolved organic carbon (DOC) release from peatlands, such as climatic changes and landuse management, have been proposed. This study examines the effects of land use and management on organic carbon exports in the Dyke catchment of the River Halladale (northern Scotland) with a nested catchment approach. This study provides insight into the processes controlling the DOC dynamics in the Dyke catchment, and the impact of disturbance caused by landuse changes such as afforestation and tree felling for restoration. The results from factor analysis, end-member mixing, absorbance (E4/E6), and hysteresis analyses on stream water chemistry from individual sub-catchments identified the major hydrological pathways during storm events, and based on these results, conceptual models were developed to explain DOC evolution during storm events. At all the sites studied, nearsurface soil water was identified as the major controlling end-member for stream DOC concentrations. The calculated annual flux of DOC from the Dyke catchment, up-scaled from the results of the individual sub-catchments, is 521.6 kg C ha-1 yr-1, which is significantly (~5 times) higher than the previously published value (103.4 kg C ha-1 yr-1) for the River Halladale catchment (Hope et al., 1997). In this study, it is shown that about 57 - 95% of the DOC export occur during 5 - 10% of the high flows, therefore, it is crucial that quantitative records of DOC export are developed using high frequency storm event measurements, as well as lower frequency low flow sampling. Climatic changes related to precipitation, temperature, coupled with water yield capacity of the sub-catchments, are identified as significant controls on DOC fluxes, rather than landuse change, as the intact site releases more organic carbon per unit area compared to the disturbed and re-wetted site undergoing restoration. In addition, the results from this study provide landowners, policy makers and organisations with the evidence they require for initiating future peatland restoration works, as felling of forestry coupled with drain-blocking is shown to be an effective restoration technique that may help a catchment to eventually return to a near-pristine state.

The California Air Resources Board (CARB) plans to reduce the volatile organic compound (VOC) limit of specialty primers, sealers, and undercoaters (SPSU), also referred to as stain blocking primers, from 350 g/L to 100 g/L in January of 2012. These coatings are primarily used as stain blocking primers over a variety of substrates, such as wood and drywall. Currently the stain blocking primers that are considered most effective are solvent based primers that contain VOC levels much higher than 100 g/L. The goal of this study is to determine if primers on the market today with a VOC content of 100 g/L or less can provide acceptable performance in comparison to primers with a VOC content greater than 100 g/L. This project had four milestones: 1) survey currently available SPSU coatings and related literature, 2) substrate and stain characterization, 3) benchmark testing of existing formulated commercial products, and 4) prepare a final report. This report: 1) describes the preliminary work performed in preparation of a more systematic and comprehensive study to evaluate the performance of paints sold for the SPSU market, 2) describes the final results of selected test methods for all primers, and 3) discusses the future steps required for the completion of this project. In preliminary testing, six primers, both waterborne and solvent based, were selected for testing and comparison. Basic primer characterization was completed, including sag, leveling, contrast ratio, and density, as was preliminary stain blocking testing, including stains by various common markers and tannin staining from dark wood. From the tests conducted during this portion of the project, and through input from an industrial advisory panel, a total of 15 commercially available primers, 7 solvent based and 8 water based, were tested. Acceptable test methods representing both the physical properties and the stain blocking capabilities of the SPSU primers were also selected from the preliminary testing and industry counsel. As a result of the data obtained from stain blocking testing, conclusions were drawn regarding the stain blocking capabilities of both categories of primer and also about each primer individually. Although it cannot be said that all stain blocking primers, both waterborne and solvent based, perform equally, it can be said that there are waterborne primers that perform as well or nearly as well as solvent based primers in several of the stain blocking tests. Part B of this report addresses the characterization of a water reducible coating for polypropylene. The solvent retention of the paint with varying drying times and film thicknesses is analyzed using thermogravimetric analysis (TGA). Solvent retention affects the production and shipment of coated polypropylene siding. When solvent is retained within the coating, adhesion can be reduced, and stacking or movement of the product may result in adhesion failure. Corona treatment of polypropylene was used to increase the surface tension of the substrate and improve adhesion. It was hoped that the surface tension would rise to 60 dynes/cm, however this could not be accomplished. An increase in surface tension to 38 dynes/cm was achieved and proved to be effective at significantly increasing the adhesion of the coating to the substrate.

Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Biology; and the Woods Hole Oceanographic Institution), 2013.
Cataloged from PDF version of thesis.
Includes bibliographical references.
The sinking flux of particles is an important removal mechanism of carbon from the surface ocean as part of the biological pump and can play a role in cycling of other chemical species. This work dealt with improving methods of measuring particle export and measuring export on different scales to assess its spatial variability. First, the assumption of ²³⁸U linearity with salinity, used in the ²³⁸U-²³⁴Th method, was reevaluated using a large sample set over a wide salinity range. Next, neutrally buoyant and surface-tethered sediment traps were compared during a three-year time series in the subtropical Atlantic. This study suggested that previously observed imbalances between carbon stocks and fluxes in this region are not due to undersampling by traps. To assess regional variability of particle export, surface and water-column measurements of ²³⁴Th were combined for the first time to measure fluxes on ~20 km scales. Attempts to relate surface properties to particle export were complicated by the temporal decoupling of production and export. Finally, particle export from ²³⁴Th was measured on transects of the Atlantic Ocean to evaluate basin-scale export variability. High-resolution sampling through the water-column allowed for the identification of unique ²³⁴Th features in the intermediate water column.
by Stephanie Anne Owens.
Ph.D.

Thesis (Ph. D.)--University of Oregon, 2007.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 158-183). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

Phosphorous fertilizer has an efficiency of about 10 percent, and this efficiency must be improved, in order to avoid excessive loss of a non-renewable resource. Ammonium lignosulphonate (ALS), a by-product of the pulp and paper industry, is expected to improve efficiency of fertilizer phosphate (P) for corn (Zea mays L.) production. Field experiments were conducted to investigate effects of added ALS and P on soil organic matter and P fractions, as well as corn yields and nutrient uptake in a Ste. Rosalie clay soil and an Ormstown silty clay loam soil in 1990 and 1991. Incubation studies showed that added ALS increased organic matter but added P as diammonium phosphate (DAP) decreased organic matter in the fertilizer band location in both soils. Applied ALS with P increased Mehlich-III (M$ sb3$P) extractable P and bicarbonate extractable P in the fertilizer band location in both soils during early incubation periods. Soil Ca-P was decreased with increased ALS. However, soil Al-P and Fe-P compounds were increased with increased ALS. Applied P increased corn shoot P concentration at the six leaf stage, and increased grain yields, total dry matter (TDM) and N and P uptake in both soils. Applied ALS at up to 608 kg ha$ sp{-1}$ with P increased corn shoot P concentration at the six leaf stage in the Ste. Rosalie soil in 1991. Applied ALS at up to 304 kg ha$ sp{-1}$ with P increased grain yield, N and P uptake. However, applied ALS without P decreased stover N concentration. Thus, ALS may improve efficiency of fertilizer P for corn production depending on soil and application methods.

Os Processos Oxidativos Avançados (POAs) têm sido largamente empregados para o tratamento de efluentes contendo compostos orgânicos altamente tóxicos, que por sua vez, são dificilmente degradados pelos sistemas de tratamento biológico convencional. Além disso, os tratamentos físico-químicos, como filtração, adsorção e floculação, não destroem o composto tóxico, e sim, apenas transferem-no para outra fase, causando um subseqüente problema de descarte. A principal barreira para a aplicação do POA em escala industrial é o alto custo relacionado à utilização da radiação ultravioleta (UV). Desta maneira, torna-se interessante desenvolver um reator com uma fonte artificial de radiação UV de custo reduzido. Neste trabalho, foi projetado um reator tubular fotoquímico de aço inox 304 que apresenta um conjunto de 12 lâmpadas fluorescentes como fonte de radiação UV (40W/lâmpada), posicionadas verticalmente na superfície interna do mesmo. O processo estudado foi o processo foto-Fenton, que consiste em uma combinação de íons ferrosos, peróxido de hidrogênio e radiação UV, aplicado na degradação de um efluente aquoso contendo fenol como poluente modelo (100–500 mgC.L-1). Os resultados experimentais indicaram que a taxa de degradação aumenta com a radiação UV, até atingir a saturação de fótons da luz UV . Com o objetivo de verificar a influência das variáveis de processo, foi realizado um planejamento experimental, no qual possibilitou-se obter um modelo para o processo e a respectiva superfície de resposta. Neste processo foi utilizada uma combinação de Fe2+ (0,27–30 mM), H2O2 (0,2–6 moles) e radiação UV, chegando-se a uma mineralização de 82% para 100 mgC.L-1 de fenol e 81% para 500 mgC.L-1 de fenol. Devido à complexidade apresentada pelo processo foto-Fenton, foi aplicado outro tipo de modelagem matemática, baseado na técnica de redes neurais artificiais (RNA), chegando-se a um coeficiente de determinação de 99% entre os valores experimentais e os valores calculados pelo modelo.
Advanced Oxidation Processes (AOPs) have been largely used for the treatment of wastewaters containing highly toxic organic compounds, which are hardly degraded by the conventional biological systems. Besides, the physicalchemical treatments, such as filtration, adsorption and flocculation, do not destroy the target compounds, which are simply transferred to another phase, causing a subsequent problem of disposal. The main barrier for the application of the POA in industrial scale is the high cost related to the use of ultraviolet radiation (UV) sources. Therefore, it has been proposed a development of a reduced cost reactor with an artificial source of UV radiation. In the present work, a tubular photochemical reactor was developed, which is made in stainless steel and presents a row of 12 fluorescent lamps as the UV radiation source (40W/lamp), attached vertically onto the inner surface of the reactor. It has been studied the photo-Fenton process, that consists in a combination of ferrous ions, hydrogen peroxide and UV radiation, applied in the degradation of an aqueous solution containing phenol as pollutant model (100–500 mgC.L-1). The experimental results indicated that the degradation rate increases as the UV irradiance increases. In order to verify the influence of the process variables in phenol degradation, an experimental design was carried out by the response surface method and the corresponding polynomial model was determined. In this process, it was used a combination of Fe2+ (0,27–30 mM), H2O2 (0,2–6 moles) and UV radiation. The mineralisation efficiency was 82% for phenol 100 mgC.L-1 and 81% for phenol 500 mgC.L-1. Due to the complexity presented by the photo-Fenton process, another type of mathematical modelling was applied, based on the artificial neural network (ANN), obtaining 99% of coefficient of determination between the experimental values and the values calculated by the model.

Since the 1970s, the study of molecular organics preserved in archaeological ceramics, commonly referred to as organic residue analysis, has been used to infer vessel use and study dietary, economic, and ritual activities in the past. The purpose of this project is to analyse organic residues from a variety of ancient vessels and attempt to understand further the relationship between molecular organic preservation and vessel characteristics. It has been previously assumed that the absorption of these organics in the ceramic matrix is predominantly responsible for their preservation. The clarification of this or other preservative mechanisms and the further understanding of the relationships of vessels with their contents has a direct impact on the interpretation of organic residues and vessel use. The first section addresses the preservation of molecular organics in pottery vessels from Tel Kabri, Israel; Tel Megiddo, Israel; and Lefkandi, Greece. The one hundred and thirty-three samples from these three sites represent vessels used in domestic, burial, ritual, and elite contexts from the Early Bronze Age through the Iron Age Eastern Mediterranean. The focus of the study is the quantification of residue yields and identification of potential links with vessel properties and characteristics of the ceramic samples. Sequential extractions using two methods, conventional chloroform/methanol solvent extraction and direct FAME extraction/derivatisation, were applied to the sherds to test the absorption and adsorption of organics into ceramic materials. The majority of samples were tested non-destructively, enabling the comparison of residue yields to certain vessel properties and characteristics displayed in the same sherds. Where available, data concerning vessel form, sampling location on the vessel profile, thickness measurements were recorded, and XRF measurements were taken, with this in mind. The second section investigates the question of whether bronze and copper alloy vessels have the capability to preserve molecular organics within their corrosion products. Twenty-two samples of corrosion and associated material from five Early Roman bronze vessels found in cremation burials during the A2 Pepperhill to Cobham project in County Kent, United Kingdom were studied for organic material. These samples provide some of the first evidence that the residues of original content are preserved in copper alloy vessels either through entrapment in or reactions with copper corrosion.

This project focus on investigating the dissolution of low water-soluble intermediate organic compounds called active pharmaceutical ingredients (API) and organic substances that are manufactured by a pharmaceutical company, Cambrex Karlskoga in Sweden. Several dissolution methods were used and evaluated using methods including total organic carbon (TOC), chemical oxygen demand (COD), biochemical oxygen demand (BOD) and Microtox toxicity test. The selection of solvents were based on previous studies and specifications from the Swedish Institute of Standards, SIS.The performance of eight solvents for different organic substances were evaluated using the above mentioned methods. Solvents that are highly volatile and have low solubility in water were excluded. Therefore, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and Pluronic F-68, that had highest water solubility, low acute toxicity and not degradable by microorganisms, were further used to dissolve four organic substances. Furthermore, DMSO and DMF were then also used to dissolve four censored chemicals with addition of physical treatment and solvent mixtures (DMF:DMSO with ratio 1:2).Results from each method were discussed and statistical tests were also performed in order to compare different dissolution methods. In addition, quality control and quality assurance were made in order to ensure the quality of measured values from analytical methods. Four organic substances were dissolve in DMSO, DMF and Pluronic F-68 with dissolution ≥79% using six ratios of DMSO and DMF and five ratios of Pluronic F-68 which were analyzed using TOC. Physical treatment increased dissolution of two APIs with 40%. Using BOD, para-aminobenzonic acid (PABA) and 5-nitroisophthalic acid (5-NIPA) had values higher than the guideline values, which indicate high biodegradability of these organic substances. PABA, 5-NIPA and bupivacaine base were acute toxic where PABA showed EC50 values of 27.9 mg/L using DMSO and 36.0 mg/L using DMF, and EC50 values of 5-NIPA were 102 mg/L using DMSO and 84.0 mg/L using DMF, and bupivacaine base had EC50 value of 174 mg/L using solvent mixture (DMF:DMSO with ratio 1:2). With increasing amount of Pluronic F-68, 5-NIPA had increased values of EC50, thereby Pluronic F-68 was not appropriate to use.In conclusion, DMSO and DMF were most appropriate solvents to use in order to dissolve APIs and organic substances with analyte: DMSO ratio of 1:0.5 and analyte: DMF ratio of 1:0.25. In addition, physical treatment could be used in order to increase dissolution of the APIs.

L'emballage alimentaire est l'un des principaux acteurs de la préservation de la sécurité alimentaire et de la qualité au cours du stockage. Toutefois, de transferts de masse se produisent entre le l'emballage polymère et les denrées alimentaires. Polylactide (PLA) est un nouveau polymère biosourcé utilisé dans les applications d'emballage. Pour cela son interaction avec des denrées alimentaires a été étudiée dans des conditions réelles d'utilisation. Une méthodologie originale basée sur l'extraction multiple de l'espace de tête (MHE) et l'extraction multiple de l'espace de tête couplée à la microextraction sur phase solide (MHS-SPME) pour la mesure de sorption de composés organiques volatils (COVs) dans le PLA a été développé à des activités faibles et dans le domaine vitreux du polymère. Les COVs ayant une structure chimique modérément hydrophobe et des similarités de structure avec le PLA montrent une forte affinité pour le polymère. Plus surprenant, la forte sorption de composés aromatiques, notamment du benzaldéhyde, a été montrée. En mélange avec d'autres COVs le benzaldéhyde favorise leur sorption par un effet synergique. De plus, même à des activités faibles (0,01) et en présence de benzaldéhyde, la sorption de COVs induit une cristallisation du PLA. En contact avec un aliment aqueux, le PLA se montre résistant à l'hydrolyse et la sorption des matières grasses est faible, même en utilisant des conditions de stockage proches de sa transition vitreuse. L'apparition de COVs pendant le procédé de transformation a été étudiée par MHS-SPME. Des lactides, l'acétaldéhyde et le 2,3-pentanedione étaient détectés après extrusion et thermoformage. Les quantités des deux derniers composés diminuaient cependant pendant le procédé de thermoformage.

Carrier mediated nutrient import is vital for cell and tissue homeostasis. Structural insights of carrier mediated transport, particularly the human glucose transporter GLUT1, are essential for understanding the mechanisms of human metabolic disease, and provide model systems for cellular processes as a whole. GLUT1 function and expression is characterized by a complexity unexplained by the current hypotheses for carrier-mediated sugar transport (9). It is possible that the operational properties of GLUT1 are determined by host cell environment. A glucose transport-null strain of Saccharomyces cerevisiae(RE700A) was transfected with the p426 GPD yeast expression vector containing DNA encoding the wild-type human glucose transport protein (GLUT1) to characterize its functional properties. Identical protein sequences generated different kinetic parameters when expressed in RE700A yeast, erythrocytes, and HEK293 cells. These findings support the hypothesis that red cell sugar transport complexity is host cell-specific. Cytochalasin B (CB) and forskolin (FSK) inhibit GLUT1-mediated sugar transport in red cells by binding at or close to the GLUT1 sugar export site. Paradoxically, very low concentrations of these inhibitors produce a modest stimulation of sugar transport (16). This result is consistent with the hypothesis that the glucose transporter contains multiple, interacting, intracellular binding sites for e1 ligands CB and FSK. The present study tests this hypothesis directly and, by screening a library of cytochalasin and forskolin analogs, asks what structural features of exit site ligands determine binding site affinity and cooperativity. Our findings are explained by a carrier that presents at least two interacting endofacial binding sites for CB or FSK. We discuss this result within the context of GLUT1 quaternary structure and evaluate the major determinants of ligand binding affinity and cooperativity. Cytochalasin B (CB) inhibits GLUT1 substrate transport at or near the endofacial sugar binding site. N-bromosuccinamide analysis combined with 3H-CB photolabeling implicates the region between Trp388 and Trp412 in ligand binding. Although its structure has been modeled(5), the specific residues comprising the sugar binding site are unknown. A series of alanine point mutants were made, and mutant protein 2-deoxy glucose transport was tested in the presence of increasing [CB]. Arg126Ala and Cys421Ala GLUT1 mutations altered CB affinity but were determined not to be in the e1 site. The Arg400Ala mutation decreased binding affinity for CB, and may comprise part of the e1 binding site. Because point mutations were individually insufficient to abrogate CB binding, Trp388 to Trp412 chimeras were made. GLUT1/GLUT4388-412/GLUT1 and GLUT1/GLUT5388-412/GLUT1 chimeras showed moderately less sensitivity to CB inhibition of transport; these amino acids likely comprise regions determinant of CB binding affinity. Furthermore GLUT1/GLUT5388-412/GLUT1 shows enhancement of 2-DG uptake at 50nM CB, but an overall dose response indistinguishable from WT GLUT1. A multisite fit of the data suggested GLUT1/GLUT5388-412/GLUT1 chimera possesses strong first site affinity for CB but slight negative second-site cooperativity. We conclude that point mutants were insufficient to abrogate CB binding and that the Trp388 to Trp412 sequence is necessary for CB binding affinity but is not the sole determinant of inhibition of 2 deoxyglucose uptake by CB. We discuss these results with their implications for structure-function sequence localization of the CB binding site, and by extension, the e1 sugar binding site.

Thesis: Ph. D., Joint Program in Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2014.
122
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 149-158).
Understanding the fate of primary production in the ocean is a challenging task because once produced, organic material is oxidized over timescales which range from minutes, to millions of years. This timescale diversity is matched by an equal heterogeneity in both the local physical and chemical environment. In this thesis we explore the relationship between the distinct reservoirs of organic carbon in the ocean and their underlying complexity. First, we show how the heterogeneity of portions of the carbon cycle can be packaged in terms of age structured models and their accompanying age and rate distributions. We further relate the moments of the rate distributions to bulk reservoir properties like average age and flux. Explicit relationships are then derived for the specific case of a single turnover time and a lognormal distribution. We apply these ideas to the problem of dissolved organic carbon (DOC) cycling in the ocean. Current models of bulk concentration and isotope data suggest a microbially sourced DOC reservoir consisting of two components. A nearly homogeneous background component with a long turnover time (> 6000 years) is joined by a component of fast turnover time (~ 1 year) and equal concentration in the surface ocean. We confirm the presence of isotopically enriched, modern DOC co-cycling with an isotopically depleted older fraction in the upper ocean. However, our results show that up to 30% of the deep DOC reservoir is modern and supported by a 1 Pg per year carbon flux, ten times higher than inferred from bulk isotope measurements. Isotopically depleted material turns over at an apparent time scale of 30, 000 years, far slower than indicated by bulk isotope measurements. These results are consistent with global DOC measurements and explain both the fluctuations in deep DOC concentration and the anomalous radiocarbon values of DOC in the Southern Ocean. Finally, the thesis explores methods for determining the validity of diffusion limitation as the mechanism behind the power-law slowdown in organic remineralization in sediment. We find that diffusion limitation connects the decay behavior of organic material to the correlations found between mineral surface area and organic matter content in sediments.
by Christopher L. Follett.
Ph. D.

O estudo de compostos organolantanídeos consiste em um dos campos de maior interesse dentro da química organometálica, principalmente devido ao uso potencial como precursores ou catalisadores em reações de hidrogenação, hidroformilação, carbonilação, oxidação e principalmente polimerização de olefinas. Este interesse tem levado diversos grupos de pesquisa a sintetizarem compostos utilizando o ânion ciclopentadienil e seus derivados ligados a íons lantanídeos (III). O presente trabalho tem como objetivo contribuir para a aplicação desses compostos organolantanídeos como catalisadores em reações de polimerização de olefinas. O trabalho envolveu uma etapa de síntese e caracterização de duas classes de compostos organolantanídeos Ln(MS)2Cp*(Ln = Tb e Yb), e Ln(MS)2Cp*PzA (Ln = Sm, Tb e Yb) e uma etapa de estudo da atividade catalítica desses compostos frente a reações de polimerização de etileno, propileno e estireno, utilizando metilaluminoxano como co-catalisador e a caracterização dos polímeros formados. Os compostos sintetizados apresentaram atividade catalítica apenas para polimerização de estireno. O polímero formado, independente do composto organolantanídeo utilizado, foi caracterizado como poliestireno principalmente atático, indicando que a polimerização não é estereoespecífica e apresentou massa molar da ordem de 104 g/mol.
The study of organolanthanide compounds consists in a most interesting area in organometalic chemistry, mainly because their potential use as precursors and catalysts in hydrogenation, hydroformilation, carbonilation, oxidation and mainly olefin polymerization reactions. This interest has taken many research groups to synthesize compounds using the cyclopentadienil anion and its derivatives coordinated to lanthanides (III) ions. The present work aims to contribute to the application of these organolanthanide compounds as catalysts in olefin polymerization reactions. The work involves a step of syntheses and characterization of two kinds of organolanthanide compounds Ln(MS)2Cp* and Ln(MS)2Cp*PzA (Ln = Sm, Tb and Yb) and a step of catalytic activity study of these compounds in ethylene, propylene and styrene polymerization reactions, usmg methylaluminoxane as co-catalyst and characterization ofthe obtained polymers. Synthesized compounds have showed catalytic activity only to styrene polymerization., Independent of the organolanthanide compound used as catalyst, the produced polymer was characterized as mainly atatic polystyrene indicating that polymerization is not stereo specific and presented molar mass in the order of 104 g/mol.

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior
The groundwater pollution arising due to fuel leaks gas stations has presented a problem aggravating. Increasingly studies related to environmental problems such accidents and seek to propose some solutions for the treatment of groundwater and soils that are contaminated by gasoline. This study evaluated the use of molecular sieve TiSBA-15 as a catalyst for the reaction of removing of volatile organic compounds, particularly benzene, toluene, ethylbenzene and xylenes, known as BTEX, one of the main pollutants found in groundwater. The catalyst was synthesized by the method post-synthesis techniques and characterized by XSD, TG/DTG, adsorption/desorption of N2, XRF-EDX, for checking the incorporation of titanium and formation of the structure of the catalyst. The reaction occurred with the presence of hydrogen peroxide, H2O2, in aqueous medium to form hydroxyl radicals, which are needed in the process of removal of BTEX compounds. The catalytic reaction was carried out for 5 hours at 60 ?C, pH to 3.0, and analyzes of the compounds were made in a gas chromatograph with a flame detection means photoionization static headspace (HS-GC-PID). The catalytic tests have shown the efficacy of using this type of catalyst for the removal of these volatile organic compounds, having a removal rate of 90.60% in the range where the catalyst was studied TiSBA-15(5,0)
A polui??o das ?guas subterr?neas devido a decorrentes vazamentos de combust?vel por postos de gasolina tem se apresentado um problema agravante. Cada vez mais estudos relacionam problemas ambientais com tais acidentes e procuram propor algumas solu??es para o tratamento das ?guas subterr?neas e solos que s?o contaminados pela gasolina. Este trabalho avalia o uso da peneira molecular TiSBA-15 como catalisador da rea??o de remo??o de compostos org?nicos vol?teis, especificamente benzeno, tolueno, etilbenzeno e xilenos, conhecidos como BTEX, um dos principais poluentes encontrados em ?guas subterr?neas. O catalisador foi sintetizado pelo m?todo p?s-s?ntese e caracterizado pelas t?cnicas de DRX, TG/DTG, adsor??o/dessor??o de N2, e FRX-EDX. O estudo da atividade catal?tica da TiSBA- 15 ocorreu com a presen?a de per?xido de hidrog?nio, H2O2, em meio aquoso, para a forma??o de radicais hidroxilas, os quais ser?o necess?rios no processo de remo??o dos compostos BTEX. A rea??o catal?tica foi realizada durante 5h a 60 ?C, pH igual a 5,0, e as an?lises dos compostos foram feitas em um cromat?grafo a g?s com detec??o por fotoioniza??o de chama via headspace est?tico (HS-GC-PID). Os testes catal?ticos mostraram a efic?cia no uso deste tipo de catalisador para a remo??o desses compostos org?nicos vol?teis, apresentando uma taxa de remo??o na faixa de 90,60%, onde o catalisador em estudo foi o TiSBA-15(5,0)

O Fenol e compostos fenolicos foram classificados como poluentes primarios pela Environmental Protection Agency (EPA USA). Eles sao geralmente encontrados em efluentes industriais como: poupa e papel; madeireiras; plasticos e polimeros sinteticos; farmaceuticos, pesticidas, oleo e petroquimicas. Os tratamentos de agua convencionais tem mostrado ineficiencia em altas concentracoes de fenol. Este trabalho visa o tratamento de solucao aquosa de fenol via Processos Oxidativos Avancados (POAs) com o objetivo de aumentar a biodegradabilidade possibilitando a aplicacao de um processo convencional (lodos ativados) como pos-tratamento. O pre-tratamento e usado para modificar a estrutura do fenol levando-o a seus subprodutos como substancias aromaticas e acidos carboxilicos. Os experimentos mostraram a eficiencia do pre-tratamento atraves do parametro de biodegradabilidade (DBO5/DQO) apresentando 0,19 em 30 min de reacao foto- Fenton, com concentracao inicial de fenol de 1000 mg.L-1 de Carbono Organico Total (TOC), 1 mmol.L-1 de FeSO4 e 100 mmol.L-1 de H2O2, dosado durante 2 horas de reacao. Apos pre-tratada fotoquimicamente, esta mesma solucao foi utilizada como fonte de carbono em um sistema continuo de lodos ativados para remocao da materia organica residual, apresentando reducao de 92% do TOC inicial. Estes resultados evidenciam a eficiencia da integracao entre os processos foto-Fenton e lodo ativado no tratamento de efluentes contendo compostos recalcitrantes.
Phenol and phenolic compounds have been listed as priority-pollutants by the Environmental Protection Agency (EPA USA). They are often found in industrial effluents such as from pulp and paper, timber, plastics and synthetic polymer, pharmaceutical, pesticide, oil and petrochemical industries. Most of the traditional wastewater treatments have shown inefficiency against high phenol concentrations. This work aims to treat phenol solution via Advanced Oxidation Processes (AOP´s) to enhance medium biodegradability and using it as an effluent in a continuous activated sludge process. The purpose of the pre treatment is to modify the phenol structure leading it to its byproducts such as aromatics compounds and carboxylic acids. The experiments have shown the effectiveness of the pre-treatment by the biodegradability parameter BOD5/COD which was achieved 0,19 at 30 min of photo- Fenton reaction with a initial phenol concentration of 1000 mg.L-1 of TOC, 1 mmol.L-1 of FeSO4 and 100 mmol.L-1 of H2O2, added with a peristaltic pump along 2 hours of reaction. After the photochemical pre treatment, the same solution was used as a carbon source in a continuous activated sludge system for removing residual organic matter, with a reduction of 92% of the TOC initial. Those results have shown the efficiency when integrating photo-Fenton and activated sludge processes on the treatment of effluents containing recalcitrant organic compounds.

[ES] La citricultura se enfrenta a escenarios ambientales cambiantes que provocan diferentes estreses bióticos y abióticos que pueden dificultar la producción o afectar a la calidad de la fruta. El patrón sobre el cual se injerta una variedad específica es una importante herramienta para mejorar su adaptabilidad a cada área de cultivo. En la presente Tesis se realiza el estudio del efecto del patrón sobre la calidad físico-química y nutricional de la fruta en variedades de gran interés comercial en la actualidad, mandarinas 'Clemenules' y 'Tango' y naranjas sanguinas 'Tarocco Rosso' y 'Moro'. En 'Clemenules' se llevó a cabo la evaluación de la calidad de la fruta de árboles injertados sobre ocho patrones en tres momentos de cosecha durante dos campañas. Los patrones Forner-Alcaide 13 y C-35 destacaron por adelantar el cambio de color, lo que es de gran interés comercial. Por otra parte, Forner-Alcaide V17 destacó por mantener niveles óptimos de acidez hasta el final de la campaña y presentar el mayor contenido en vitamina C, flavonoides, glucosa y fructosa. Carrizo Citrange también indujo altas concentraciones de sacarosa y vitamina C. 'Tango' es una mandarina de reciente introducción en el área mediterránea de gran interés por su periodo de recolección tardío. En esta Tesis se abordó el estudio de los cambios en la calidad fisicoquímica, nutricional y sensorial de la mandarina 'Tango' injertada sobre dos patrones (Carrizo Citrange y Forner-Alcaide 5) en las dos áreas principales de producción de Andalucía. Los resultados revelaron que la calidad de la fruta se vio influenciada por la localización de las parcelas, lo que se relacionó con la composición de la textura del suelo. En ambas localizaciones, Forner-Alcaide 5 indujo mayor contenido en acidez, sólidos solubles totales, sacarosa, vitamina C y ácido cítrico en la fruta. Las determinaciones físico-químicas, junto con la evaluación sensorial permitieron establecer el momento óptimo de recolección dependiendo de las diferentes condiciones estudiadas. También se ha incluido un estudio del comportamiento postcosecha de esta variedad, ya que no existían datos en nuestras condiciones de cultivo. La mandarina 'Tango' presentó síntomas externos de daños por frío a partir de los 20 días almacenada a 1°C y 5°C. Se realizó un estudio micro-estructural para caracterizar la alteración. Los frutos del patrón Forner-Alcaide 5 presentaron una menor incidencia de los daños por frío. El almacenamiento a 9°C no comprometió la calidad externa o interna. Dentro del grupo de naranjas, en los últimos años existe una creciente demanda por las naranjas sanguinas para su consumo en fresco. Para evaluar el efecto del patrón se tomaron las variedades 'Moro' y 'Tarocco Rosso' injertadas sobre ocho patrones. La calidad interna se vio afectada por el momento de cosecha, siendo más evidente en 'Moro'. En ambas variedades el patrón afectó a los parámetros de calidad durante la maduración. En 'Moro', se observó una reducción en el color del zumo debido a la degradación de los antocianos, siendo los patrones C-35, Macrophylla y Volkameriana los que mostraron un mayor descenso. Esta degradación se relacionó con los cambio de la temperatura durante el periodo de recolección. En 'Tarocco Rosso' no se evidenció ninguna degradación, lo que sugiere que esta variedad es menos sensible a los cambios de temperatura. En esta variedad Forner-Alcaide 5 y Forner-Alcaide 13 produjeron fruta con mayor contenido en antocianos y azúcares. Además se llevó a cabo el estudio de la aptitud a la frigoconservación de las variedades de sanguinas 'Tarocco Rosso' y 'Sanguinelli'. Mientras que la calidad interna no se vio afectada por el almacenamiento (1°C, 5°C y 9°C) durante 45 días, la fruta presentó síntomas de daños por frío a 1°C. 'Sanguinelli' presentó mayor incidencia que 'Tarocco Rosso'. Estas sanguinas se pueden almacenar entre 5 y 9°C
[CA] La citricultura s'enfronta constantment a escenaris ambientals canviants que provoquen diferents estressos biòtics i abiòtics. El patró sobre el qual s'empelta una varietat específica és una important eina per a millorar la seua adaptabilitat agronòmica en cada àrea de cultiu. En la present Tesi s'ha dut a terme l'estudi de l'efecte del patró sobre la qualitat físic-química i nutricional de la fruita en varietats de gran interés comercial, mandarines 'Clemenules' i 'Tango' i, taronges sanguines 'Tarocco Rosso' i 'Moro'. En 'Clemenules' es va dur a terme l'avaluació de la qualitat de la fruita d'arbres empeltats sobre huit patrons en tres moments de collita, en dues campanyes. Entre els patrons avaluats, Forner-Alcaide 13 i C-35 van destacar per avançar el canvi de color. D'altra banda Forner-Alcaide V17 va destacar per mantindre nivells òptims d'acidesa fins al final de la campanya i va presentar el major contingut en vitamina C, flavonoides, glucosa i fructosa. Carrizo Citrange també va induir altes concentracions de sacarosa i vitamina C en la fruita. 'Tango' és una mandarina de recent introducció en l'àrea mediterrània amb gran interés pel seu període de recol·lecció que comença quan finalitza el de les clementines. En la present Tesi es van estudiar els canvis en la qualitat físic-química, nutricional i sensorial de la mandarina Tango empeltada sobre dos patrons (Carrizo Citrange i Forner-Alcaide 5) durant el període de collita en les dues àrees principals de producció d'Andalusia. La qualitat de la fruita es va veure influenciada per la localització, la qual cosa es va relacionar amb la composició de la textura del sòl. En totes dues localitzacions, Forner-Alcaide 5 va ser el patró que va induir major contingut en acidesa, sòlids solubles totals, sacarosa, vitamina C i àcid cítric en la fruita. Les determinacions físic-químiques i l'avaluació sensorial van permetre establir el moment òptim de recol·lecció depenent de les diferents condicions estudiades. També s'ha inclòs un estudi del comportament postcollita d'aquesta varietat, ja que no existien dades en les nostres condicions de cultiu. La mandarina 'Tango' va presentar símptomes externs de danys per fred a partir dels 20 dies emmagatzemada a 1°C i 5°C. Es va realitzar un estudi micro-estructural per a caracteritzar l'alteració provocada per les baixes temperatures. Els fruits del patró Forner-Alcaide 5 van presentar una menor incidència dels danys per fred. L'emmagatzematge a 9°C no va comprometre la qualitat externa o interna d'aquesta varietat. Dins del grup de taronges, en els últims anys existeix una creixent demanda per les taronges sanguines pel seu consum en fresc. Per a avaluar l'efecte del patró sobre sanguines es van prendre dues varietats, 'Moro' i 'Tarocco Rosso' empeltades sobre huit patrons. La qualitat interna es va veure influenciada pel moment de collita, la qual cosa va ser més evident en la varietat 'Moro'. En totes dues varietats el patró va afectar els canvis en els paràmetres de qualitat estudiats. En 'Moro', es va observar una reducció en el color del suc degut a la degradació del antocians. Aquesta degradació es va relacionar amb el canvi de la temperatura experimentada durant el període de recol·lecció. 'Tarocco Rosso' és menys sensible als canvis de temperatura. En aquesta varietat els patrons Forner-Alcaide 5 i Forner-Alcaide 13 van produir la fruita amb major contingut en antocianos i sucres. A mes s'aporta l'estudi de l'aptitud a la frigoconservació en les sanguines 'Tarocco Rosso' i 'Sanguinelli'. Mentre que la qualitat interna no es va veure afectada per l'emmagatzematge a cap de les temperatures assajades (1°C, 5°C i 9°C) durant 45 dies, la fruita va presentar símptomes de danys per fred a 1°C. `Sanguinelli' va presentar major incidència que 'Tarocco Rosso'. La fruita es pot emmagatzemar entre 5°C i 9°C durant 30 dies en el cas de 'Sanguinelli' i fins a 45 en e
[EN] Citriculture faces changing environmental scenarios that cause biotic and abiotic stress. The rootstock onto which a specific variety is grafted is an important tool to help to improve its agronomic adaptability to each crop area. The present Thesis was carried out to study the effect of rootstock on physico-chemical and nutritional fruit quality in some varieties of commercial interest today: 'Clemenules' and 'Tango' mandarins, and 'Tarocco Rosso' and 'Moro' blood oranges. In 'Clemenules', the fruit of the trees grafted into eight rootstocks at three harvest times was evaluated by performing studies during two seasons. Forner-Alcaide 13 and C-35 Citrange stood out for their earlier color change, which is very interesting for this variety, in which early harvesting is a relevant aspect from the commercial point of view. Forner-Alcaide V17 stood out for maintaining optimum acidity levels until the season ended and presented the highest contents in vitamin C, flavonoids, glucose and fructose. Carrizo Citrange brought about high concentrations of sucrose and vitamin C in fruit. 'Tango' is a mandarin variety that has been recently introduced into the Mediterranean Region. Its harvest time is very interesting because it starts when that of clementines ends. The present Thesis studies changes in the physico-chemical, nutritional and sensorial quality of 'Tango' fruit grafted onto two rootstocks (Carrizo Citrange and Forner-Alcaide 5) during the harvest period in the two main production areas in Andalusia. The results revealed that fruit quality during harvest was influenced by the location, which was particularly related to soil texture composition. In both areas, Forner-Alcaide 5 was the rootstock that induced higher acidity content, and more total soluble solids, sucrose, vitamin C and citric acid in fruit. The physico-chemical determinations, along with the sensorial evaluation, allowed the optimum harvest time to be established depending on the different studied conditions. This Thesis also includes a study about this variety's postharvest behavior as no data are available for our crop conditions. The 'Tango' mandarin presented outer chilling injury symptoms after being stored for 20 days at 1°C and 5°C. A microstructural study was done to characterize the alteration caused by low temperatures. The Forner-Alcaide 5 rootstock fruit showed a lower chilling injury incidence. Storage at 9°C did not compromise quality fruit. Among oranges, demand for blood oranges to be eaten fresh has grown in recent years, basically due to their high content in anthocyanins and their positive effect for human health. To assess the effect that rootstock had on blood oranges, two varieties were taken, 'Moro' and 'Tarocco Rosso', grafted onto eight rootstocks. Internal quality was strongly influenced by harvest time, which was more evident for 'Moro'. In both varieties, rootstock affected changes in the quality parameter studied. In 'Moro', juice color faded as anthocyanins degraded, and rootstocks C-35 Citrange, Macrophylla and Volkameriana showed the most marked reduction. Such anthocyanin degradation was related to the change in temperature that took place during the harvest period. In 'Tarocco Rosso', anthocyanins did not undergo degradation, which suggests that this variety is less sensitive to changes in temperature. In this variety, rootstocks Forner-Alcaide 5 and Forner-Alcaide 13 gave fruit with a higher content of anthocyanins and sugars. This Thesis also includes a study of the suitability of cold storage of two blood orange varieties: 'Tarocco Rosso' and 'Sanguinelli'. Although storage at any tested temperature (1°C, 5°C and 9°C) did not affect internal quality for 45 days, fruit displayed chilling injury symptoms at 1°C, with a higher incidence for 'Sanguinelli' than for 'Tarocco Rosso'. Fruit can be stored between 5°C and 9°C for 30 days for 'Sanguinelli' and for up to 45 days with 'Tarocco Rosso'.
This study has been supported by Instituto Valenciano de Investigaciones Agrarias and co-financed by FEDER and European Social Fund. The authors thank Anecoop S. Coop. and Frutaria Agricultura, S.L for supplying the fruit herein used and its technical support.
Morales Alfaro, J. (2021). Effect of Rootstock on the Fruit Quality of Mandarins "Clemenules" and "Tango", and Blood Oranges "Tarocco Rosso" and "Moro" [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/165858
TESIS

The purpose of this thesis work was to develop a headspace solid phase microextraction gas chromatography mass spectrometry (HS-SPME-GC-MS) method to detect volatile organic compounds (VOCs) in board samples and to statistically investigate potential correlation between chromatographic data and flavor data obtained from a trained panel. The developed method would hopefully serve as a complement to the already established routine analyses at Stora Enso and gain an increased understanding of which VOCs in the board influence its flavor properties. The impact of incubation time and adsorption time on the area under curve (AUC) was studied with a Design of Experiment screening using the software MODDE. The screening data showed a correlation between large AUC and low repeatability measured as relative standard deviation (RSD). The data was hard to fit to a model due to the large RSD values for the replicates, AUC for identified compounds as response gave an acceptable fit. The regression coefficients for the model showed that a longer adsorption time gave larger AUC, while incubation time had no significant impact on the response.  Instead of following up the screening with an optimization, the focus was shifted to improving the repeatability of the method, i.e. lowering the RSD. The high RSD was believed to mainly be the result of leakage of analytes and unstable temperature during adsorption, preventing the system from reaching equilibrium. Different heating options and capping options for the vial was tested. Septum in crimp cap ensured a gas tight seal for the vial, giving lower RSD values and larger AUC compared to the other alternatives, showing that there was indeed a leakage. Using oil bath ensured stable temperature during the adsorption and detection of a larger number of VOCs but created a temperature gradient in the vial due to it not being fully submerged in the oil. Oil bath gave larger AUC, but still high RSD due to the temperature gradient making the method sensitive to variance in fiber depth in the vial. The final method was performed with 2 g of board sample in a 20 ml headspace vial sealed with a crimp cap with septa. The incubation and adsorption were performed with the vial immersed in a 90-degree oil bath. 20 min incubation time was chosen based on the time it took to get a stable temperature gradient in the vial, and 20 minutes adsorption time was chosen as a good compromise between large AUC and low RSD. Compared to Stora Ensos routine analysis, the developed SPME method gave chromatograms with an improved signal-to-noise ratio for the base line and several more peaks with larger AUC. For the board sample used during method development, the SPME-method identified 34 VOCs, while the routine analysis only identified 12. The developed method was applied on 11 archived board samples of the same quality that were selected based on their original flavor properties, to get a large diversity of samples. Flavor analysis was performed by letting a trained flavor panel describe the flavor based on intensity and character of the water that had individually been in indirect contact with one of the 11 board sample for 24 h. Potential correlation between chromatographic data obtained with the developed method and the flavor experience described by the flavor panelists was statistically investigated with the multivariate analysis software SIMCA. The correlation study showed that a combination of 12 VOCs with short retention time are most likely the main source of off-flavor which of 5 could only be identified with the developed SPME method. VOCs with long retention time did not contribute to an off-flavor and might have a masking effect on flavor given by other VOCS, however not confirmed in this study. Furthermore, the age of the board samples proved to be a good indicator for prediction of the flavor intensity, whereas the total AUC of the samples was not. Possible correlation between detected VOCs in the samples and flavor character given by the flavor panel were seen, however the variation in the data and the sample set were too small, preventing from making conclusions on individual VOCs impact on the flavor experience. The developed HS-SPME-GC-MS method would serve as a complement to the already established routine analyses at Stora Enso and has slightly increased the understanding of which VOCs in the board influence the flavor properties

Povrchy inorganických materiálov, zvlášť kovov alebo kovových oxidov, ktoré sú často charakteristické vysokou povrchovou energiou, sú zvyčajne kontaminované adsorbovanými organickými molekulami. Tieto molekuly majú na povrchy zväčša nepriaznivý vplyv, do značnej miery napríklad ovplyvňujú funkcionalitu a výkonnosť polovodičov a znemožňujú, prípadne sťažujú prevedenie povrchových úprav na povrchoch kovov aj keramík. Taktiež majú nepriaznivý vplyv na priľnavosť. Adsorbované častice spôsobujú znižovanie hydrofilicity povrchu. Hydrofilicita, adhezivita a zmáčavosť povrchu sa veľmi dobre posudzujú prostredníctvom merania kontaktného uhlu. V tejto práci je značná pozornosť venovaná práve meraniu statického kontaktného uhlu. [10] Samotné meranie kontaktného uhlu je možné vykonať rôznymi spôsobmi, v tejto práci bol však použitý najvhodnejší prístup, a to metódou „sessile-drop“, teda pokladanej alebo depozitovanej kvapky na meraný povrch. K meraniu bol využitý klasický „sessile-drop goniometer“, teda aparatúra, ktorá pozostávala z nastaviteľného stojanu na vzorky, nad ktorým bol umiestnený zdroj svetla, a objektívu fotoaparátu, ktorý bol prepojený s kamerou zabudovaného smartfónu. Meranie prebiehalo tak, že kvapka s objemom 3L destilovanej superčistej vody bola depozitovaná na povrch substrátu pomocou mikroinjekčnej striekačky. Cieľom tejto práce bolo nielen stanoviť kontaktné uhly a porovnať ich hodnoty medzi rôznymi typmi materiálov navzájom a po upravách tepelného a/lebo chemického charakteru. Vyhodnotené údaje zachycovali zmeny, ku ktorým došlo na povrchoch daných keramických materiálov pri adsorpcii organických molekúl. Proces tepelnej úpravy (kalcinácia na teplote 800°C, následne pokles na teplotu 600°C, po celkovú dobu 16 hodín) bol aplikovaný na všetkých typoch vzoriek, kde niektoré sa medzi sebou líšili teplotou slinovania. Ihneď po kalcinácii boli vzorky podrobené meraniu kontaktných uhlov, z ktorého jasne vyplynulo, že hydrofilicita a zmáčavosť povrchu sa zvýšila. Tento jav bol pozorovaný na všetkých vzorkách, a na všetkých vzorkách sa hodnoty kontaktného uhlu líšili veľmi významne od hodnoty, ktorá bola získaná v tzv. primárnom meraní. Všetky detailné hodnoty a vyhodnotené výsledky sú posudzované v časti diskusia. Ďalšou úpravou povrchu, ktorá bola vykonaná na vybraných vzorkách, bolo čistenie povrchu etanolom. Proces bol opäť realizovaný na všetkých vzorkách. Potom, ako boli zrealizované všetky merania na kalcinovaných vzorkách, boli všetky tieto vzorky ponorené do etanolu na približne 2 hodiny. Po vybratí vzoriek a ich osušení na vzduchu boli uskutočnené ďalšie merania kontaktných uhlov. Výsledky priniesli opäť rozdielne hodnoty v porovnaní s predchádzajúcimi meraniami a sú rozvinuté v časti diskusia.

O presente trabalho teve por objetivo apresentar e discutir um caso de identificação e remediação emergencial de compostos orgânicos voláteis, oclusos em camada arenosa do Terciário da Formação São Paulo, em decorrência do vazamento de tanques de combustíveis de um posto de serviços. A técnica de remediação adotada para o caso consistiu na extração in situ dos vapores do solo e no tratamento dos mesmos por adsorção em filtros de carvão ativado (SVE - soil vapor extraction). Os processos de seleção, projeto, implantação, operação e descomissionamento da tecnologia SVE seguiram as metodologias indicadas pela literatura, adaptadas às condições locais. O acompanhamento da eficiência da remediação foi baseado na quantificação inicial dos hidrocarbonetos totais de petróleo leves presentes no subsolo, através das técnicas de cromatografia gasosa e espectrometria de massa, e na medição em campo das concentrações de voláteis e dos respectivos teores de explosividade. O resultado da campanha laboratorial apresentou fortes indícios de que a contaminação local fosse proveniente do combustível gasolina e indicou a ocorrência do composto benzeno em concentrações superiores aos limites adotados como referência. As leituras realizadas em campo mostraram rápido declínio das concentrações de voláteis e dos teores de explosividade com a operação da tecnologia SVE, indicando baixa ocorrência de fatores limitantes do transporte de massa no local. Corroborou com tal hipótese, o fato das metas de remediação terem sido atingidas com poucas trocas de ar, parâmetro retro-analisado a partir de dados de ensaios geológico-geotécnicos. Assim, concluiu-se que, para áreas com características semelhantes à estudada, a tecnologia SVE pode ser eficiente como medida de remediação de voláteis e redução dos riscos de explosividade.
This work aims to present and to discuss a case study of identification and emergency remediation of volatile organic compounds, occluded in a sand layer of the São Paulo Tertiary Formation, as a result of the leakage of fuel tanks of a service station. The adopted remediation technique was in situ soil vapor extraction (SVE) and offgas treatment for adsorption in activated carbon filters. Selection, design, commissioning, operation and shutdown processes of SVE technology followed literature methodologies, which were adapted to local conditions. Remediation efficiency monitoring was based on the initial quantification of light total petroleum hydrocarbons in the subsoil, through gas chromatography and mass spectrometry techniques, and on measurement of the volatile concentrations and respective explosive contents in the field. The result of the laboratorial campaign presented strong indications that the local contamination proceeded from combustible gasoline and it indicated the occurrence of benzene in concentrations higher than the adopted reference. Field measurements showed fast decline of the volatile concentrations and explosive contents with the SVE technology operation, fact that indicated low occurrence of mass transfer limitations in the place. The fact that remediation goals were achieved with few air exchanges, parameter back-analyzed from geologicgeotechnical tests, contributed to reinforce such hypothesis. Thus, SVE technique can be considered efficient for volatile remediation and explosive risks reduction, for areas with characteristics similar to the studied one.

La combustion de la biomasse et en particulier du bois constitue une alternative intéressante à l'utilisation des combustibles fossiles pour l'approvisionnement en énergie. Elle présente l'avantage de pouvoir être renouvelable sans contribuer à une émission supplémentaire de CO₂. Cependant, il est connu que les appareils de chauffage utilisant la biomasse comme combustible peuvent générer certains polluants gazeux dont notamment les Composés Organiques Volatils (COV) et le monoxyde de carbone (CO). Le post-traitement catalytique se révèle comme une des technologies les plus prometteuses pour limiter ces émissions de polluants. Ce projet vise donc à développer des matériaux catalytiques actifs, sélectifs en dioxyde de carbone et stables, assurant une décomposition complète du mélange de COV et de CO. Les catalyseurs à base de métaux nobles, étant reconnus pour leur bonne activité pour ce type de réaction d'oxydation, engendrent cependant un coût important pour le développement d'un tel procédé. L'objectif de nos travaux sera donc basé sur la synthèse et le développement de nouveaux matériaux catalytiques peu onéreux à base d'oxydes de métaux de transition qui seront utilisés comme alternatifs aux catalyseurs à base de métaux nobles. Afin d'obtenir des oxydes performants, la synthèse des matériaux en utilisant la voie hydrotalcite a été choisie. Nous avons montré l'effet bénéfique de l'ajout du cérium dans les oxydes MgAl-O et CuAl-O vis-à-vis de l'oxydation du toluène et/ou du CO. Une relation entre la réductibilité et l'activité de ces solides pour ces réactions a été observée. Pour les catalyseurs MgAlCe-O, aucun effet sur la conversion du toluène n'a été observé, cependant un effet significatif sur la conversion du CO en présence de toluène a été mis en évidence. Ainsi, un oxyde du type CuAlCe-O s'est avéré actif et stable pour la destruction de mélanges de COV et de CO. De plus, l'intérêt d'utiliser la voie hydrotalcite pour synthétiser ces oxydes CuAlCe-O a été vérifié par comparaison avec d'autres voies de synthèses. L'activité supérieure du catalyseur CuAlCe-O peut être corrélée à un effet de synergie entre les éléments cuivre et cérium
Biomass burning, in particular wood, is an attractive alternative to the utilization of fossil fuels for energy supply, as it is renewable and does contribute to any additional CO₂ emission into atmospher. However, it is known that heating appliances using biomass generate large amounts of Volatile Organic Compounds (VOCs) and carbon monoxide (CO) during the combustion cycle. A catalytic post-treatment is one of the most promising technologies to limit the emissions of these pollutants. This project aims to develop active and selective catalytic materials with enhanced redox properties in order to achieve the total oxidation of VOCs and CO at low temperature. Noble metals based catalysts are considered as good candidates for such types of reactions. However, these catalysts are very expensive for adaptation to domestic heating device. The objective of our work is focused on the synthesis and development of innovative and cheaper catalytic materials composed of transition metal oxides that could be used as alternatives to noble metal catalysts. In order to obtain efficient oxides, the hydrotelcite route was chosen for the synthesis of the catalysts. The beneficial effect of adding cerium to MgAl-O and CuAl-O oxides towards the oxidation of toluene and/or CO was demonstrated. A relationship between the reducibility and activity of these solids for these reactions has been also identified. For MgAlCe-O catalysts, a beneficial effect on the conversion of toluene in presence of CO was observed. Indeed, the temperature of toluene oxidation was shifted at lower temperatures in presence of CO. In contrary, no effect on toluene conversion was observed for the CuAlCe-O materials. However, a significant effect on the conversion of CO in presence of toluene was revealed. Briefly, a CuAlCe-O type oxide with high activity and stability has been synthesized for the destruction of VOCs and CO mixtures. In addition, the advantage of using the hydrotalcite route to synthesize these CuAlCe-O oxides has been verified by comparison with other synthetic routes. The high activity of the CuAlCe-O catalyst can be attributed to the synergic effect between copper and cerium elements

Le toluène est un solvant fréquemment utilisé par l’industrie manufacturière. Il appartient à la catégorie des composés organiques volatils (COV), dont nombre d’entre eux présentent des impacts néfastes sur la santé humaine et sont aujourd’hui classés cancérogènes, mutagènes et/ou reprotoxiques. Afin de diminuer la présence dans l’air de composés nocifs comme le toluène, il apparait essentiel d’envisager leur substitution dans les procédés industriels par des composés moins toxiques et/ou de réduire au maximum leurs émissions à la source. Dans ce contexte, le premier objectif du travail de recherche est d’étudier la toxicité aiguë et répétée du toluène, de ses homologues supérieurs, pouvant être utilisés comme composés de substitution, ainsi que de son homologue inférieur sur des cellules épithéliales bronchiques humaines à l’aide d’un dispositif d’exposition en interface air/liquide. Le deuxième objectif vise à évaluer le caractère toxique d’effluents gazeux issus de la dégradation du toluène par oxydation catalytique. Pour cela, les cellules BEAS-2B ont été exposées 1 heure par jour pendant 1, 3 et 5 jours au benzène, au toluène, au xylène ou au mésitylène, ainsi qu’aux effluents gazeux obtenus après traitement catalytique du toluène. Les effets toxiques ont été évalués au travers des paramètres de cytotoxicité, de réponse inflammatoire et d’expression génique des enzymes de métabolisation des xénobiotiques (EMX). L’exposition des cellules BEAS-2B au toluène et à ses homologues a révélé l’implication de voies métaboliques spécifiques à chaque composé. Une augmentation significative des marqueurs de l’inflammation a également été observée, avec une concentration plus importante pour le benzène et le xylène par rapport aux autres molécules. Concernant l’exposition aux effluents gazeux issus de l’oxydation catalytique du toluène, l’expression tardive de gènes impliqués dans le métabolisme des xénobiotiques organiques aromatiques, est compatible avec la présence de sous-produits, tels que le benzène ou les hydrocarbures aromatiques polycycliques. En conclusion, les résultats obtenus dans ce projet montrent l’intérêt de mener des expositions in vitro en condition répétée permettant de déceler de potentiels effets tardifs et la pertinence de la validation toxicologique des systèmes catalytiques avant leur formulation en pilote industriel
Toluene is a solvent widely used in manufacturing industries. It belongs to a family of volatile organic compounds (VOCs), many of which have adverse impacts on human health and are classified as carcinogenic, mutagenic or toxic for reproduction. Different measures have been implemented to reduce the emissions of toxic compounds, such as their replacement in the industry by less harmful compounds and/or reducing gas emissions at the source. In this context, the first objective of the research was to investigate the acute toxicity and the one after repeated exposure to toluene and its superior homologous solvents, which can be used as its substitution compounds, as well as its lower homologous on human bronchial epithelial cells using an air/liquid interface exposure device. The second objective was to assess the toxicity of gaseous effluents from the degradation of toluene by catalytic oxidation. For this purpose, BEAS-2B cells were exposed during 1 hour for 1, 3 or 5 days to benzene, toluene, xylene or mesitylene, and to the exhausts of catalytic oxidation of toluene. Toxic effects were evaluated through cytotoxicity, inflammatory response and gene expression of xenobiotic metabolism enzymes (XME). Exposure of BEAS-2B cells to toluene and its homologous compounds revealed the involvement of metabolic pathways specific to each compound. A significant increase in inflammatory marker response was also observed, with a higher concentration after cell exposure to benzene and to xylene compared to the other molecules. With regard to exposure to gaseous effluents from the catalytic oxidation of toluene, the late expression of genes involved in the metabolism of aromatic organic xenobiotics has made possible to highlight the presence of by-products, such as benzene or polycyclic aromatic hydrocarbons. In conclusion, the results obtained in this project show the interest of conducting repeated in vitro exposures to detect potential late effects, and the importance of toxicological validation of catalytic systems before scaling-up in industrial pilots

Nous rapportons dans ce travail l'utilisation de couches minces de polymères contenant des porphyrines pour la détection de composes organiques volatils. Deux types de polluants ont été étudiés la pyridine et le benzène. Pour réaliser des couches sensibles à des vapeurs de pyridine, des porphyrines de zinc ont été immobilisées dans des couches minces de polymères. Les modifications des propriétés spectroscopiques (absorption, fluorescence) dues à la complexation du zinc par la pyridine ont été utilisées pour étudier la diffusion de la pyridine. Dans le cas de films de polystyrène et de polyméthylméthacrylate, cet équilibre est atteint au bout de quelques minutes et la réaction est réversible. Le seuil de détection de ces couches sensibles a pu être déterminé, il est de 2 g/l dans le cas de couches minces de polystyrène. Pour les films de polyvinylpyrrolidone, la réaction de complexation provoque la formation irréversible d'agrégats. De tels agrégats ont été caractérisés par microscopie et par spectroscopie (absorption, fluorescence stationnaire et fluorescence résolue dans le temps). Les porphyrines hydrosolubles sont susceptibles de former des complexes de types Van der Waals avec les dérivés aromatiques. Cette propriété a été mise à profit pour détecter le benzène. Deux molécules ont été envisagées la tétraméthylpyridiniumporphyrine (tmpyp) et la dmabp, une nouvelle porphyrine dicationique possédant deux groupements triméthylbenzylammoniums en position méso de la porphyrine. Les stabilités des complexes porphyrine-benzène ont été déterminées par modélisation moléculaire: la dmabp forme un complexe plus stable avec le benzène que la tmpyp. Pour confirmer ce résultat théorique, la dmabp a été synthétisée et les constantes de stabilité des complexes porphyrine-benzène ont été déterminées expérimentalement par dosage spectrophotométrique. Nous retrouvons alors l'ordre de stabilité établi par mécanique moléculaire. En dernier lieu la diffusion du benzène a été étudiée dans des films de polymères contenant les porphyrines mentionnées ci-dessus. Nous avons montre que ces couches minces sont capables de détecter le benzène a des concentrations de 150 g/l

Ce travail se place a la convergence de deux grands themes etudies au laboratoire: le marquage de molecules par un atome de fluor et l'etude de la complexation de cations metalliques par des ligands. La premiere partie concerne la preparation de deux series de ligands contenant du fluor: des biphenols et des composes contenant des groupements 2-fluoropyridines. Les biphenols substitues par deux ou quatre atomes de fluor (en position 4,4' ; 5,5' ; 4,4 ;,5,5') ont ete obtenus a partir de bromophenols par une reaction de type ullman. Leurs derives sulfones ont egalement ete prepares pour augmenter la solubilite dans l'eau. Les ligands de la seconde serie, tel la n,n,n',n' tetrakis(6-fluoro-2-pyridylmethyl)ethylenediamine, ont ete obtenus par alkylation de differentes amines avec la 2-fluoro-6-bromomethylpyridine, dans des conditions de transfert de phase. Ces ligands ont ete caracterises par rmn du #1h, #1#9f et #1#3c et des resultats interessants, concernant les constantes de couplage, ont ete observes. Ces deux familles de ligands ont ete prepares afin de permettre, par la suite, une etude de leur complexation par rmn du #1#9f, analogue a celle entreprise dans la partie suivante. La seconde partie concerne l'etude de la complexation de la 5-fluoro-8-hydroxyquinoline (fox) avec des cations metalliques (le gallium et le fer) par rmn du #1#9f et par spectroscopie uv-visible. Concernant l'etude de la complexation de ga par la fox utilisant la rmn du fluor nous avons constate que les trois complexes gafox, gafox#2 et gafox#3 ont des deplacements chimiques du fluor differents, obtenu les diagrammes de repartition des especes en fonction du ph pour differents rapports molaires c#m/c#f#o#x (c#m et c#f#o#x sont les concentrations en metal et ligand) et calcule les trois constantes de formation des complexes gafox, gafox#2 et gafox#3. Le complexe gafox#3 a egalement ete etudie seul en solvant organique (dmf-d7). Nous avons mis en evidence que dans ce complexe, qui existe presque uniquement sous la forme de l'isomere mer, les trois ligands subissent une interconversion intramoleculaire rapide

Marine microorganisms play a significant role in the cycling of nutrients in the open ocean through production, consumption, and degradation of organic matter (OM). Carbon (C), nitrogen (N), and phosphorus (P) are essential ingredients in every known recipe for life. However, the cycling of each of these elements proceeds at different rates such that the ratio of C:N:P can vary widely between particulate, dissolved, organic, and inorganic pools. To better understand the mechanisms controlling these transformations, this study investigated the bacterial remineralization of photosynthetically-derived organic matter derived from cultures of Trichodesmium IMS101, Thalassiosira weissflogii, Prochlorococcus MED4, and particulate material collected from the surface waters of an upwelling regime. Experiments were conducted at sea for a short duration (<6d) and in the laboratory for longer periods (<150 days). In all treatments, across experiments, we observed rapid and selective P remineralization independent of the type of organic material added. Full solubilization and remineralization of P typically occurred within a week. Conversely, N remineralization was slower, with only 39-45% of particulate N (PN) remineralized in shorter (6d) experiments and 55-75% of PN remineralized in <150d experiments. Nitrification was observed after 70-98 days depending on the remineralizing bacteria (isolated from either the Oregon coastal upwelling regime or the North Pacific Subtropical Gyre (NPSG). Notably, these events did not transform the full complement of ammonium to nitrate. This differential lability between N and P led to rapid changes in the N:P ratio of inorganic pools as organic matter was depolymerized by varying bacterial populations. The variable input of potentially limiting elements could have consequences for primary productivity and particle export. Finally, we observed that in short-term experiments with heterotrophic bacteria collected from the NPSG, the N:P ratio of remineralization (11 ± 2.2) was independent of the N:P of added organic material (5-23). This uniformity of inorganic ratios implies differential lability and N:P composition of residual semi-labile and refractory organic matter. Formation of refractory C and N rich organic matter, often termed the microbial pump, is a significant pathway for the transport and sequestration of elements in the aphotic zone of the ocean interior. The experimental results reported here suggest that differential supply of POM leads to rapid and preferential P remineralization, N:P remineralization independent of the N:P of added substrates, and variable N:P of residual organic matter. These findings help constrain our knowledge of elemental cycling in the marine environment.
Graduation date: 2013

Globally, the forestry sector is the second largest contributor of greenhouse gases, and sustainable forest management is a major target of international environmental policy. However, there is the assumption underlying many policy recommendations that an increase in above-ground carbon stocks correspond to long term increases in ecosystem carbon stocks, the majority of which is stored in soils. We analyzed soil carbon and nitrogen dynamics in forest soils that had undergone twenty years of organic inputs manipulations as part of the Detritus Input and Removal Treatment (DIRT) network. There was no statistically significant effect of the rate of litter or root inputs on the carbon or nitrogen in bulk soil, on respiration rates of soil in laboratory incubations, on the non-hydrolyzed fraction of soil organic matter, or on any organic matter associated with any density. However, there is evidence for positive priming due to increased litter inputs; doubling the rate of litter inputs decreased C and N contents of bulk soil and decreased respiration rates of soil. Furthermore, there is evidence that roots influence soil organic matter dynamics more strongly than above-ground inputs. Both of these results trends match data from other DIRT sites, and are supported by the literature.
Graduation date: 2012

A study of the interactions of the specifically interacting organic compound pyridine with a model soil organic matter sorbent (Pahokee peat) was carried out from different nonaqueous organic liquid media, including neat n-hexadecane, acetonitrile, acetone and nhexadecane mixtures with either acetone or acetonitrile. Kinetic and equilibrium studies using an activity-based comparison of the organic compounds in solution was used to study the interactions of soil organic matter (SOM) and pyridine sorption capability in the various non-aqueous organic liquid media. Quantification and qualification of pyridine and the other co-solvents were done using Gas Chromatography (GC). Sorption of pyridine from neat organic solvents was not masked by sorption of the organic solvent. The apparent sorbed amount calculated from the change in solute concentration and reported on a dry weight basis was considered to represent the true sorbed concentration of pyridine in the sorbent phase. Pyridine sorption was found to be non-linear and distribution coefficients decreased with solute concentration, by approximately three times in n-hexadecane, more than five times in acetonitrile, and by ten times in acetone over the experimental concentration range. Pyridine sorption from nhexadecane was also found to be comparable with sorbed amounts from acetone, but much lower in comparison to sorption from acetonitrile. Sorption of pyridine from n-hexadecane mixtures with acetonitrile or acetone demonstrated the solvent assisted effect of pyridine sorption. Sorption uptake of pyridine increased as initial acetonitrile concentration increased, this acetonitrile assisted trend for pyridine sorption was found in the presence of a large excess of n-hexadecane. Sorbed concentrations of pyridine measured in the presence of high concentrations of acetonitrile (close to it's solubility limit) were found to be very similar to pyridine sorption from neat acetonitrile. Sorption behaviour of pyridine in n-hexadecane-acetone mixtures showed that increasing acetone concentrations had no effect on pyridine sorption. Pyridine sorbed from n-hexadecane, n-hexadecane-acetonitrile, and n-hexadecaneacetone mixtures showed a hysteretic desorption to n-hexadecane. After a series of repeated solvent extractions with solvents of increasing solvating power(1,4-dioxane, ethanol, dimethylsulfoxide), a fraction of pyridine remained bound to the peat. This nonrecoverable fraction was approximately the same for the different organic media (OA5± 0.09 in n-hexadecane suspensions, 0.57±O.12 in n-hexadecane-acetonitrile mixtures, and OA6±0.07 in n-hexadecane-acetone mixtures). Acetonitrile sorption by peat from nhexadecane was found to be very non-linear and hysteretic. The acetonitrile sorbed was almost fully recoverable, around 90%, for the initial acetonitrile concentration range varying from 0.14-0.7% by volume. However in the presence of pyridine a significant portion of acetonitrile was not recovered even after multiple extractions of polar organic solvents. Pyridine irreversible binding was not induced by acetonitrile additions and was found to occur to the same extent in both neat n-hexadecane and n-hexadecane-acetone mixtures. The solubilities of acetonitrile and acetone were determined by the flask method at 25°C using GC analysis. Solubility in volume percent for acetonitrile in n-hexadecane, 0.9±0.07, 0.57±0.02 for n-hexadecane in acetonitrile, 24.0±OA for acetone in nhexadecane, and 13 A±O.2 for n-hexadecane in acetone, were found. Log Ostwald coefficient (1.63±O.02) for acetonitrile in n-hexadecane was measured at 25°C using head space analysis and was found to be constant in the acetonitrile concentration range 0.10.8% by volume. Log Ostwald coefficient for pyridine in hexadecane used was 3.02, for the pyridine concentration range 50 mgIL-500 mg/L, this value was constant even with 0.5% by volume additions of acetonitrile. Analyses of sorption isotherms were reported on an activity basis to eliminate the effect of differential solute interactions in the solvent, calculated using the solute equilibrium concentration, the concentration of saturated vapour, and the Ostwald coefficient. Dissolution of peat components into n-hexadecane are known to be negligible. Peat components extracted after 12 hours and 3,5 months acetonitrile and acetone treatment (solid liquid ratio 1: 10) Showed 15 to 20 times less visible absorbance respectively (A. 465, 620, and 665, E4:E6 ratios using DV-Visible Spectroscopy), than the 12 hours aqueous peat extract. Quantification of the dissolved humic materials in the aqueous extract was followed using a Total Organic Carbon analyser. The study found the degree of humification to be much lower in non-aqueous organic solvent extracts (2.5 for acetone extracts, and 3 for acetonitrile extracts) than in aqueous solution extracts (8.2).
Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 2002.
The Moshe Greidinger Scholarship Fund.