Dissertations / Theses on the topic 'Dissolved and colloidal components'

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013.<br>Cataloged from PDF version of thesis.<br>Includes bibliographical references.<br>Iron is a redox active trace metal micronutrient essential for primary production and nitrogen acquisition in the open ocean. Dissolved iron (dFe) has extremely low concentrations in marine waters that can drive phytoplankton to Fe limitation, effectively linking the Fe and carbon cycles. Understanding the marine biogeochemical cycling and composition of dFe was the focus of this thesis, with an emphasis on the role of the size partitioning of dFe (<0.2 jm) into soluble (sFe<0.02 jm) and colloidal (0.02ptm<cFe<0.2 m) size fractions. This was accomplished through the measurement of the dFe distribution and size partitioning along basin-scale transects experiencing a range of biogeochemical influences. dFe provenance was investigated in the tropical North Atlantic and South Pacific Oceans. In the North Atlantic, elevated dFe (>I nmol/kg) concentrations coincident with the oxygen minimum zone were determined to be caused by remineralization of a high Fe:C organic material (vertical flux), instead of a laterally advected low oxygen-high dFe plume from the African margin. In the South Pacific Ocean, dFe maxima near 2000m were determined by comparison with dissolved manganese and 3He to be caused by hydrothermal venting. The location of these stations hundreds to thousands of kilometers from the nearest vents confirms the "leaky vent" hypothesis that enough dFe escapes precipitation at the vent site to contribute significantly to abyssal dFe inventories. The size partitioning of dFe was also investigated in order to trace the role of dFe composition on its cycling. First, the two most commonly utilized methods of sFe filtration were compared: cross flow filtration (CFF) and Anopore filtration. Both were found to be robust sFe collection methods, and sFe filtrate through CFF (10 kDa) was found to be only 74±21% of the sFe through Anopore (0.02pjm) filters at 28 locations, a function of both pore size differences and the natural variability in distribution of 1 OkDa- 0.02 [m colloids. In the North Atlantic, a colloidal-dominated partitioning was observed in the surface ocean underlying the North African dust plume, in and downstream of the TAG hydrothermal system, and along the western Atlantic margin. However, cFe was depleted or absent at the deep chlorophyll maximum. A summary model of dFe size partitioning in the North Atlantic open ocean is presented in conclusion, hypothesizing that a constant dFe exchange between soluble and colloidal pools modulates the constant partitioning of nearly 50% dFe into the colloidal phase throughout the subsurface North Atlantic Ocean, while sFe and cFe cycle independently in the upper ocean.<br>by Jessica Nicole Fitzsimmons.<br>Ph.D.

Steroidal estrogens in the environment exert toxicological effects at very low concentrations. Furthermore, dissolved and colloidal fractions of soil and manure play an important role in the environmental fate and transport of steroidal estrogens. One objective of this study was to quantify the association of the natural estrogen, 17?-estradiol (E2), with the dissolved fraction and colloidal fraction isolated from liquid swine manure (LSM), soil, and soil+LSM mixtures. The second objective of this study was to evaluate whether the E2 associated with the dissolved fraction/colloidal fraction, dissolved fraction and colloidal fraction of the various media could induce an estrogenic response. Estrogenicity was assessed using an E2 receptor (ER) competitor assay, which provided E2 equivalent concentration (EEQ) of dissolved fraction/colloidal fraction, dissolved fraction and colloidal fraction solutions created from the Soil, Soil+LSM and LSM.

Steroidal estrogens in the environment exert toxicological effects at very low concentrations. Furthermore, dissolved and colloidal fractions of soil and manure play an important role in the environmental fate and transport of steroidal estrogens. One objective of this study was to quantify the association of the natural estrogen, 17β-estradiol (E2), with the dissolved fraction and colloidal fraction isolated from liquid swine manure (LSM), soil, and soil+LSM mixtures. The second objective of this study was to evaluate whether the E2 associated with the dissolved fraction/colloidal fraction, dissolved fraction and colloidal fraction of the various media could induce an estrogenic response. Estrogenicity was assessed using an E2 receptor (ER) competitor assay, which provided E2 equivalent concentration (EEQ) of dissolved fraction/colloidal fraction, dissolved fraction and colloidal fraction solutions created from the Soil, Soil+LSM and LSM.

During kraft cooking a significant part of the wood material, especially lignin and hemicelluloses, is degraded and dissolved in the cooking liquor, rendering a broad range of degradation products with different molecular mass and functional groups. The main part of this thesis has been devoted to clarify the role of these dissolved wood components (DWC) during kraft cooking. The investigations have covered their influence on e.g. the delignification rate, pulp yield, point of defibration, unbleached pulp c olour and pulp bleachability, i.e. the amount of bleaching chemicals consumed per kappa number or lignin unit to reach a certain brightness. Both softwood (Picea Abies) and hardwood (Eucalyptus urograndis) have been studied. During kraft cooking, many reactions occur simultaneously. Therefore emphasis has been put on separating the effects of hydroxide ions, hydrogen sulphide ions, sodium ions and DWC. This has been enabled by the use of a so called constant-composition-cooking technique, which enables the use of almost constant concentrations of the cooking chemicals during the cook and also results in a very low concentration of DWC in the cooking liquor. The presence of DWC has been controlled by the addition of industrial black liquor. To further scrutinise the role of DWC, the effect of different molecular mass fractions were studied and representative model substances were used to clarify the origin of the observed effects. A kinetic study showed that the delignification rate was significantly affected by the presence of DWC in the cooking liquor and resulted in a rate increase in the part of the cook where the bulk phase dominates and a decreased delignification rate when the residual phase dominates. The increase in delignification rate was dependent on the concentration of DWC and was observed in softwood as well as hardwood kraft cooks. The rate increasing effect was investigated further by the use of ultra- and nanofiltra tion. This way the DWC was divided into fractions with different molecular mass distributions. The results showed that the increase in delignification rate related more strongly to the content of free phenolic groups in the DWC than on the total amount of DWC. By cooking in the presence of representative model substances the effect was further clarified. Aromatic structures with free phenolic groups gave a rate increasing effect while no visible effect could be seen from other structures. This supports the finding that the delignification rate relates to the amount of free phenols in the cooking liquor and shows that the phenolic functionality take active part in the delignification reactions. Free phenolic groups in the degraded lignin may explain a large part of the rate increasing effect seen from the presence of DWC. Further, the presence of DWC increased the point of defibration in a eucalyptus kraft cook and made it possible to terminate the cook at a higher kappa number with the same amount of reject. By terminating the cook at a higher kappa number it was possible to noticeably increase the fully bleached pulp yield. The content of hexenuronic acids (HexA) in the eucalyptus pulp depends on the H-factor and increases with delignification, providing that the bulk phase still dominates. Therefore, by increasing the rat e of delignification and terminating the cook at a higher kappa number it was possible to significantly decrease the amount of HexA in the pulp. The presence of DWC causes a darkening of the unbleached pulp. Bleachability in a D(EOP)DD sequence was negatively affected by the presence of DWC during pulping of softwood, while no effect was seen on the bleachability of hardwood<br>QC 20100920

Le phosphore (P) est un nutriment essentiel dans le contrôle de l'eutrophisation des eaux de surface. La majorité du P causant cette eutrophisation dans les pays occidentaux est aujourd'hui issu des sols agricoles, ce qui explique pourquoi les recherches actuelles sur l'eutrophisation se focalisent sur la compréhension des mécanismes par lequel le P est relargué de ces sols. Dans cette thèse, nous étudions ces mécanismes en nous focalisant sur la fraction dissoute (DP) du P, fraction la plus menaçante du point de vue de l'eutrophisation. Une double approche a été utilisée, combinant le suivi de la composition d'eaux du sol et d'eaux de ruisseau dans un petit bassin versant (BV) agricole représentatif (BV de Kervidy-Naizin, France) et des simulations expérimentales au laboratoire. Les suivis de terrain ont révélé que les zones humides ripariennes (RW) étaient les principales zones de relargage de DP dans le BV étudié, via deux mécanismes essentiellement déclenchée par les fluctuations des hauteurs de nappe, i) la réhumectation des sols (DRW) et ii) la dissolution réductrice des oxydes de fer du sol dans de périodes d'anoxie. Ces mêmes suivis ont révélé la présence de fortes variations spatiales de la nature chimique (inorganique et organique/colloïdale) du DP relargué. Les variations saisonnières et interannuelles de l'hydroclimat, combinées aux variations locales de topographie ont été démontrées être les deux facteurs principaux contrôlant i) la fréquence des épisodes DRW, et ii) la durée des périodes anoxiques, entraînant au final de fortes variations saisonnières et interannuelles de la dynamique de relargage du DP. Comme indiqué dans un modèle conceptuel général, la topographie est sans doute le facteur clé de contrôle des variations observées, en raison de son rôle sur i) le transfert de P à partir des parcelles agricoles amont, ii) le taux de minéralisation du P organique du sol P et iii), le déclenchement des deux mécanismes de relargage précités. Les expériences en laboratoire ont confirmé le rôle des événements DRW comme processus clé causant le relargage de DP dans les RWs. Les résultats ont démontré que le DP relargué consistait non seulement de "vrai" DP inorganique et organique, mais aussi de P colloïdal, le P colloïdal et le DP organique étant les plus réactifs aux événements DRW. Les données ont aussi révélées que ces différentes formes de P provenaient de différentes sources dans le sol (méso et macroporosité pour P colloïdal et le DP organique; microporosité pour DP inorganique), et que la quantité de P colloïdal relargué était positivement corrélée avec la teneur en matière organique et la taille de biomasse microbienne du sol. Ces mêmes expériences ont confirmé le rôle des conditions anoxiques comme conditions favorisant la libération de DP dans les RWs. La dissolution réductive de sol Fe-oxyhydroxydes n'est cependant pas le seul processus impliqué, un autre processus étant la hausse du pH causée par des réactions de réduction. Les résultats obtenus démontrent que l'augmentation de pH contrôle la libération de DP dans les sols riches en matière organique, alors que ce relargage est contrôlé principalement par la réduction des oxydes de fer dans les sols pauvres en matière organique. Les données expérimentales démontrent également que l'apport de sédiments issus des sols agricoles amont accroit le relargage de DP dans les RW, probablement en raison de la dissolution des oxydes de fer de ces mêmes sédiments par les bactéries ferroréductrices des Rws. Au final, cette thèse permet de mieux contraindre les mécanismes et facteurs responsables du relargage de DP dans les bassins versants agricoles. Une conséquence très pratique de ce travail est que la conception de stratégies pour limiter les fuites de DP dans ces bassins ne peut se faire sans une prise en compte des rôles de l'hydroclimat, de la topographie locale et des propriétés du sol sur ce relargage<br>Phosphorus (P) is a key nutrient in controlling surface water eutrophication. Because of the decrease of urban and industrial P emissions, most of the P nowadays causing surface water eutrophication in western countries consists of P transferred from agricultural soils, explaining why current eutrophication research focused on understanding the mechanisms by which P is released from soils. In this thesis, we studied these release mechanisms for dissolved P (DP) – i.e. the most bioavailable P component for algae - using an approach combining field monitoring of soil and stream water compositions in a small, headwater catchment typical of western countries agricultural catchments (the Kervidy-Naizn catchment, France), and laboratory experimental simulations. Field monitoring data revealed that riparian wetlands (RW) are the main zones of DP release and DP production in the studied catchment, through essentially two mechanisms triggered by groundwater table fluctuations, namely i) rewetting of dry soils (DRW), and ii) reductive dissolution of soil Fe (hydr)oxides during anaerobic periods. Field monitoring data also revealed the presence of strong spatial variations in the chemical nature (inorganic vs. organic/colloidal) of the released DP, which was in relation to differences in soil properties and local topography. Seasonal and inter-annual hydroclimate variations, combined with variations in local topography were found to control the frequency of soil DRW events and duration of anaerobic periods, resulting in strong seasonal and inter-annual variations of DP release dynamics. As shown in a conceptual model, topography is likely to be the key driver of the observed spatial and temporal variations, because of its combined control on i) the transfer of P from upland fields to RW zones, ii) the mineralization rates of soil organic P and iii) the triggering of the above two release mechanisms. Laboratory leaching experiments on the same soils confirmed the role of DRW events as a major process causing DP release pulses in RWs. The data demonstrated that the released DP consisted not only of true dissolved inorganic and organic P but also of colloidal P, the latter phase being the most reactive to DRW events. The data also revealed that the different P forms came from different P sources in the soil (soil macro/mesopores for colloidal P and organic DP; soil micropores for inorganic DP) and that the amount of released colloidal P correlated positively with the organic matter contents and soil microbial biomass size of the soil. Anaerobic incubation experiments, on their hand, confirmed the role of anoxic conditions as conditions favoring the release of DP in RW. Reductive dissolution of soil Fe-oxyhydroxide was, however, not the sole process involved in that release, another process being the rise in pH caused by reduction reactions. Experimental data showed that the pH rise controlled the DP release in organic-rich soils, this release being on the contrary mainly controlled by soil Fe-oxyhydroxides reductive dissolution in organic-poor soils. Experimental data also showed that the input of soil sediments from upland fields enhanced the release of DP in RW, most likely due to the enhanced dissolution of sediment Fe-oxyhydroxides by RW Fe-reducing bacteria. Overall, this thesis allowed new constraints to be placed on the release mechanisms of DP in headwater agricultural catchments. One very practical output is that great care should be taken of hydroclimate variability, local topography, and soil property when designing and implementing management options to reduce DP release and transfer in agricultural catchments

Knowledge about whether/how natural water chemistry influences the fate, dissolution, and toxicity of silver nanoparticles (AgNPs) should contribute to ecological risk assessment and informed decision making. The effects of three critical water chemistry parameters – dissolved organic carbon (DOC), pH, and hardness – were investigated on the colloidal stability, dissolution dynamics, and antimicrobial activity of citrate-functionalized AgNPs (citrate–AgNPs) against Escherichia coli. Toxicities of citrate–AgNPs and AgNO3 were also determined in the river water samples collected across three seasons (for seven months). Detectable changes in hydrodynamic diameter, surface charge, and plasmonic resonance revealed the modulating effects of the water chemistry parameters on the colloidal stability of citrate–AgNPs. Although, overall Ag release from citrate–AgNPs was low (0.33–3.62%), it increased with increasing DOC concentrations (0–20 mg L−1) but decreased with increasing pH (5–7.5) or hardness (150–280 mg L−1). Citrate–AgNP toxicity was 3–44 fold lower than of AgNO3 (Ag mass basis). Notably, higher DOC or pH conferred protection to E. coli against citrate–AgNPs or AgNO3; increasing solution hardness tended to enhance toxicity, however. Citrate–AgNPs or AgNO3 toxicity in the river water matrix revealed no seasonality. Generalized linear models developed, by parameterizing particle properties, could fairly predict empirically-derived nanotoxicity. Our results show that particle size, surface properties, ion release kinetics, and toxicity of citrate–AgNPs can be modified upon release into aquatic environments, suggesting potential implications to ecosystem health and functions.

The majority of lakes on Earth are shallow, unproductive and located at high latitudes. These lakes are experiencing big changes due to climate change, where two environmental drivers operate simultaneously, browning and warming. How they affect lake ecosystems is not well understood. Here, I addressed this issue by using a theoretical and an experimental approach. In particular, I generated model predictions and compared them with the results of a realistic large-scale experiment, where browning and warming were manipulated in a factorial design. In addition, model outcomes were compared with data from 12 unproductive lakes sampled along a gradient of browning. Another novelty of my thesis is that it integrates benthic and pelagic food web components in the model and experimental approaches. I found that browning affected the resources availability for benthic and pelagic producers in the model and in the experiment. With browning, benthic primary producers became increasingly light limited and declined, while pelagic producers became less nutrient limited and increased. Pelagic nutrient limitation was alleviated by two non-exclusive mechanisms. Browning directly enriched the water with nutrients, and browning indirectly increased the nutrient flowing from the sediment to the pelagic habitat via suppression of benthic producers. To tease apart these two mechanisms I applied structural equation modeling (SEM). The indirect evidence by SEM suggests that both mechanisms contributed equally to the pelagic nutrient concentration in the experiment. Interestingly, a model food web with only primary producers shows similar qualitative behavior as a food web with grazers and carnivores included. This happens because carnivorous fish exert strong top-down control in the more productive habitat, which relaxes grazing pressure on primary producers and increases resource limitation in the adjacent habitat. Biomass of benthic and pelagic consumers followed the same pattern as their resources. The lake data were largely congruent with model expectations and supported the findings of the experiment. Furthermore, the model also predicted a negative relationship between total phosphorus and both primary and fish production, which was observed across the 12 lakes. Warming effects were more complex. The model predicts that warming effects should depend on browning and are expected to be strongest in the more productive of the two (benthic and pelagic) habitats. For example, at low levels of browning the biomasses of benthic algae and fish are expected to decline with warming, which was observed in the experiment. In contrast, observed warming effects at high levels of browning deviated from model expectations. The mechanisms by which browning and warming interactively affect lake food webs are still poorly understood. This thesis offers a conceptual foundation for their further study through the integration of within- and between-habitat interactions.

During the production of paper in paper mills, detrimental wood resin is released into the water circuit of the mill during the pulping process of the wood into fibres. This wood resin, termed pitch, can detrimentally deposit on the paper and on the paper machine equipment. The deposits mark the paper or can lead to a tear of the paper web involving a loss of output and a reduction in paper quality. Furthermore, the wood resinous compounds in paper mill effluents need to be reduced in order to minimise their toxic effects on water organisms. Talc has been the benchmark for many years as a mineral additive in pitch control. Since the papermaking process has changed over the years, the concept of mineral addition needs to be redefined and adopted towards the new circumstances. By understanding the fundamentals behind the adsorption of wood resin compounds from aqueous systems on to talc new mineral additives can be developed. A model for the determination of the aspect ratio of platy and rod-like particles has been developed, based on commonly available characterisations such as particle size, specific surface area and shape. It was found that the adsorption capacity of a mineral is directly proportional to its specific surface area, but only within its mineral family. Including the effect of surface hydrophilicity and hydrophobicity allowed fine tuning of the adsorption capacity of newly developed calcium carbonate grades. Furthermore, size exclusion effects, in porous, high surface area modified calcium carbonate, were seen to hinder complete coverage of the surface area by wood resin. With increasing pH, the adsorption efficiency of talc for colloidal wood resin was found to decrease. Under these alkaline conditions, which are common in modern paper making processes, talc preferentially adsorbed dissolved species. The use of the newly developed surface treated and modified calcium carbonates allowed more efficient adsorption of the colloidal fraction and, therefore, represent an efficient alternative to talc in pitch control. An increase in temperature led to an increased adsorption capacity of talc. This observation indicates the type of interaction tat controls the adsorption of hydrophobic pitch particles onto talc, i.e. the entropically favoured release of water from the hydrophobic talc surface as well as the hydrophobic methylene backbone of the hemicellulose.

[ES] En la presente Tesis Doctoral se investigó la aplicación del proceso de ultrafiltración (UF) y el fenómeno de ensuciamiento de las membranas en la eliminación de sustancias disueltas y coloidales (DCS) de efluentes tratados de la industria papelera (PMTE) para su reutilización en los diferentes procesos de fabricación de papel y cartón reciclado. El objetivo general de esta investigación se dividió en tres partes principales: i) describe cómo encontrar las condiciones óptimas de operación de cuatro parámetros de proceso: presión transmembrana (TMP), velocidad de flujo cruzado (CFV), temperatura y corte de peso molecular (MWCO) para maximizar el flujo promedio de permeado (Jp) y rechazo de la demanda química de oxígeno (COD) y minimizar el descenso del flujo de permeado acumulado (SFD) utilizando el método de Taguchi (Design Robusto) y utility concept aplicado a un proceso de UF a flujo cruzado, para remover DCS de efluentes tratados de la industria papelera, ii) el descenso del flujo de permeado y los mecanismos de ensuciamiento de las membranas de UF ensuciadas con PMTE se examinaron mediante modelos matemáticos semi-empíricos. Los resultados para los diferentes ensayos de UF se expresaron en términos de variación del Jp en función del tiempo para verificar la precisión del ajuste (mayor valor de R2 y menor valor de desviación estándar) de los distintos modelos de Hermia adaptados a flujo tangencial y del modelo de formación de torta en filtración a presión constante ajustados a los datos experimentales, y iii) describe métodos de identificación, caracterización y posibles orígenes de las sustancias contaminantes (foulants) en las membranas de UF. Técnicas como el análisis físico-química, FESEM, SEM-EDS, ATR-FTIR y 3DEEM se llevaron a cabo para comprender qué fracción de los contaminantes son responsables por la formación de incrustaciones en las membranas. Los resultados obtenidos durante la etapa de optimización de parámetros del procesos demostraron que TMP y MWCO tienen la mayor contribución en el Jp y SFD. En el caso de la tasa de rechazo de COD, los resultados mostraron que MWCO tiene la mayor contribución seguida de CFV. Por consiguiente, las condiciones óptimas se encontraron para el segundo nivel de TMP (2.0 bar), el tercer nivel del CFV (1.041 m/s), el segundo nivel de la temperatura (15°C) y el tercer nivel de MWCO (100 kDa). Bajo estas condiciones óptimas de operación Jp, rechazo de COD y SFD alcanzaron respuestas de 81.15 L/m2.h, 43.90% y 6.01 (alrededor de 28.96 % para (FD), respectivamente, valores dentro del rango previsto del intervalo de confianza del 95%. Además, los modelos de Hermia adaptados a UF en flujo tangencial fueron capaces de predecir con gran precisión el descenso del Jp y los mecanismos de ensuciamiento en función del tiempo para todas las membranas seleccionadas (10, 30 y 100 kDa) y bajo diferentes condiciones ensayadas de UF. Por lo tanto, los modelos que presentan un mayor grado de ajuste son el bloqueo completo de poros (coeficiente de determinación R2 >0.97) y bloqueo intermedio (R2 >0.96), seguido por el modelo de formación de torta (R2 >0.94), lo que indica que estés son los principales mecanismos de ensuciamiento de las membranas. Análisis de 3DEEM revelaron que la mayoría de la materia orgánica fluorescentes en las membranas sucias eran proteínas coloidales (componentes similares a proteínas I + II) y proteínas macromoleculares (componentes similares a SMP). Además, polisacáridos (especie celulósica) y sustancias como ácidos grasos y resinosos fueron identificadas en las membranas contaminadas mediante análisis ATR-FTIR. Por fin, análisis SEM-EDS para las membranas ensuciadas con PMTE se detectó concentración de contaminantes inorgánicos (iones metálicos multivalentes) especialmente el Ca2+ que podría acelerar la formación torta en la superficie de la membrana.<br>[CA] En la present Tesi Doctoral es va investigar l'aplicació del procés d'ultrafiltració (UF) i el fenomen d'embrutiment de les membranes en l'eliminació de substàncies dissoltes i col·loïdals (DCS) d'efluents tractats de la indústria paperera (PMTE) per al seu reutilització en els diferents processos de fabricació de paper i cartó reciclatge. L'objectiu general d'aquesta investigació es va dividir en tres parts principals: i) descriu com trobar les condicions òptimes d'operació de quatre paràmetres de procés: pressió transmembrana (TMP), velocitat de flux creuat (CFV), temperatura i tall de pes molecular (MWCO) per a maximitzar el flux mitjà de permeat (Jp) i rebuig de la demanda química d'oxigen (COD) i minimitzar el descens del flux de permeado acumulat (SFD) utilitzant el mètode de Taguchi (Design Robust) i utility concept aplicat a un procés de UF a flux creuat en escala pilot, per a remoure DCS d'efluents tractats de la indústria paperera (PMTE), ii) el descens del flux de permeat i els mecanismes de embrutiment (fouling) de les membranes de UF embrutades amb PMTE es van examinar mitjançant models matemàtics semi-empírics. Els resultats per als diferents assajos de UF es van expressar en termes de variació del flux de permeat (Jp) en funció del temps per a verificar la precisió de l'ajust (major valor de R2 i menor valor de desviació estàndard) dels diferents models de Hermia adaptats a flux tangencial i del model de formació de coca en filtració a pressió constant ajustats a les dades experimentals, i iii) descriu mètodes d'identificació, caracterització i possibles orígens de les substàncies contaminants (foulants) en les membranes de UF. Tècniques com l'anàlisi física-química, FESEM, SEM-EDS, ATR-FTIR i 3DEEM es van dur a terme per a comprendre quina fracció dels contaminants són responsables per la formació d'incrustacions sobre la superfície i adsorció dins dels porus de les membranes. Els resultats obtinguts durant l'etapa d'optimització de paràmetres del processos van demostrar que TMP i MWCO tenen la major contribució en el Jp i SFD. En el cas de la taxa de rebuig de COD, els resultats van mostrar que MWCO té la major contribució seguida de CFV. Per consegüent, les condicions òptimes es van trobar per al segon nivell de TMP (2.0 bar), el tercer nivell del CFV (1.041 m/s), el segon nivell de la temperatura (15°C) i el tercer nivell de MWCO (100 kDa). Sota aquestes condicions òptimes d'operació Jp, rebuig de COD i SFD van aconseguir respostes de 81.15 L/m².h, 43.90% i 6.01 (al voltant de 28.96% per a (FD)), respectivament, valors dins del rang previst de l'interval de confiança del 95%. A més, els models de Hermia adaptats a UF en flux tangencial van ser capaços de predir amb gran precisió el descens del Jp i els mecanismes de embrutiment en funció del temps per a totes les membranes seleccionades (10, 30 i 100 kDa) i baix diferents condicions assajades de UF. Per tant, els models que presenten un major grau d'ajust són el bloqueig complet de porus (coeficient de determinació R2 >0.97) i bloqueig intermedi (R2 >0.96), seguit pel model de formació de coca (R2 >0.94), la qual cosa indica que estigues són els principals mecanismes de embrutiment de les membranes. Anàlisi de 3DEEM van revelar que la majoria de la matèria orgànica fluorescents en les membranes brutes eren proteïnes col·loidals (components similars a proteïnes I + II) i proteïnes macromoleculars (components similars a SMP). A més, polisacàrids (espècie cel·lulòsica) i substàncies com a àcids grassos i resinosos van ser identificades en les membranes contaminades mitjançant anàlisis ATR-FTIR, tals substàncies exerceixen un paper important en el embrutiment de les membranes. Per fi, anàlisi SEM-EDS per a les membranes embrutades amb PMTE es va detectar concentració de contaminants inorgànics (ions metàl·lics multivalents) especialment el Ca2+ que podria accelerar la formació coca en la àrea de la membrana.<br>[EN] In this PhD Thesis, the application of ultrafiltration process (UF) and membrane fouling phenomenon used to remove dissolved and colloidal substances (DCS) from paper mill treated effluent (PMTE) for reuse in different recycled paper and cardboard manufacturing processes was investigated. The overall goal of this research has been divided into three main parts: i) describes how to find optimal operating conditions of four controlling parameters, such as transmembrane pressure (TMP), cross-flow velocity (CFV), temperature and molecular weight cut-off (MWCO) for maximizing the average permeate flux (Jp) and chemical oxygen demand (COD) rejection, and minimizing the cumulative flux decline (SFD) using Taguchi method and utility concept for a cross-flow UF in pilot scale, used to remove DCS from a paper mill treated effluent (PMTE), ii) flux decline and fouling mechanisms of UF membranes fouled with PMTE were examined by theoretical modelling. The results from UF tests were expressed in terms of permeate flux (Jp) as a function of time to check modified Hermia's models adapted to crossflow filtration and cake formation in constant-pressure filtration, and iii) describes the Identification, characterization and possible origins of UF membrane foulants. Techniques such as chemical analysis, FESEM, SEM-EDS, ATR-FTIR and 3DEEM analysis were applied to understand which fraction of the foulants caused the fouling. This research found that the TMP and MWCO have the greatest contribution to the average permeate flux and SFD. In the case of the COD rejection rate, the results showed that MWCO has the highest contribution followed by CFV. The optimum conditions were found to be the second level of TMP (2.0 bar), the third level of the CFV (1.041 m/s), the second level of the temperature (15°C), and the third level of MWCO (100 kDa). Under these optimum conditions Jp, COD rejection and SFD resistance of 81.15 L/m2/h, 43.90% and 6.01 (around 28.96 % of (FD), respectively, were obtained and they were within of the predicted range at the 95% confidence interval. Furthermore, the results showed that the predictions of the modified Hermia's models adapted to cross-flow UF had good agreements with experimental data, under different conditions tested for PMTE. Therefore, it can be concluded that for all cases the best fit (higher accuracy) to the experimental data corresponds to the complete (coefficient of determination R2 >0.97) and intermediate (R2 >0.96) blocking, followed by the cake layer formation (R2 >0.94). Moreover, measurements of particle size distribution and zeta potential near the isoelectric point, showed a substantial reduction in colloidal compounds. The 3DEEM analysis revealed that the majority of the organic foulants with fluorescence characteristics on the fouled membranes were colloidal proteins (protein-like substances I+II) and macromolecular proteins (SMP-like substances). Further, polysaccharide (cellulosic specie), fatty and resin acid substances were identified on the fouled membrane by the ATR-FTIR analysis and they play an important role in membrane fouling. In addition, the membrane SEM-EDS analysis showed accumulate and adsorbed onto the membrane surfaces of inorganic foulants, such as multivalent metal ions and especially Ca2+ (acts as a binding agent) that could accelerate cake layer formation on the membrane.<br>Santos Sousa, MR. (2020). Optimization of Operation Parameters in Ultrafiltration by Experiment Design, Mathematical Modelling and Fouling Characterization of the Membranes Used to Remove Dissolved and Colloidal Substances from a Treated Paper Mill Effluent [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/155975<br>TESIS

Le but principal de cette thèse était d'étudier les caractéristiques de la matière organique dissoute (MOD) dans le bassin versant de la Seine. Ce travail a été réalisé dans le cadre du programme de recherche PIREN-Seine. Les travaux présentés ici visaient plus particulièrement à identifier les sources de MOD et à suivre son évolution dans les zones d’étude. L’analyse des propriétés optiques (UV-Visible, fluorescence) de la MOD, couplée aux traitements PARAFAC et ACP, a permis de discriminer différentes sources de MOD et de mettre en évidence des variations spatio-temporelles de ses propriétés. L’axe Seine, en aval de Paris, a notamment été caractérisé par l'activité biologique la plus forte. La MOD du bassin de l’Oise a montré des caractéristiques plus "humiques", tandis que le bassin de la Marne a été caractérisé par un troisième type spécifique de MOD. Il a d’autre part été mis en évidence la présence de MODs spécifiques dans chaque zone pour les échantillons prélevés en périodes d’étiage, alors qu’une distribution homogène des composants a été obtenue pour l’ensemble des échantillons prélevés en période de crue.Le rôle environnemental des colloïdes naturels étant étroitement lié à leur taille, il a d’autre part été développé une technique analytique/séparative originale pour l’étude de ce matériel complexe, un fractionnement par couplage flux/force avec flux asymétrique (AF4). Le fractionnement par AF4 des échantillons a confirmé la variabilité spatio-temporelle en composition et en taille de la MOD d'un site de prélèvement à un autre et a permis de distinguer différentes sources de MOD colloïdale confirmant les résultats de l’étude de ses propriétés optiques<br>The main goal of this thesis was to investigate the characteristics of dissolvedorganic matter (DOM) within the Seine River catchment in the Northern part of France. ThisPhD thesis was performed within the framework of the PIREN-Seine research program. Theapplication of UV/visible absorbance and EEM fluorescence spectroscopy combined toPARAFAC and PCA analyses allowed us to identify different sources of DOM andhighlighted spatial and temporal variations of DOM properties. The Seine River wascharacterized by the strongest biological activity. DOM from the Oise basin seemed to havemore "humic" characteristics, while the Marne basin was characterized by a third specifictype of DOM. For samples collected during low-water periods, the distributions of the 7components determined by PARAFAC treatment varied between the studied sub-basins,highlighting different organic materials in each zone. A homogeneous distribution of thecomponents was obtained for the samples collected in period of flood.Then, a semi-quantitative asymmetrical flow field-flow fractionation (AF4) methodology wasdeveloped to fractionate DOM. The following optimized parameters were determined: across-flow rate of 2 ml min-1 during the focus step with a focusing time of 2 min and anexponential gradient of cross-flow from 3.5 to 0.2 ml min-1 during the elution step. Thefluorescence properties of various size-based fractions of DOM were evaluated by applyingthe optimized AF4 methodology to fractionate 13 samples, selected from the three sub-basins.The fluorescence properties of these fractions were analysed, allowing us to discriminatebetween the terrestrial or autochthonous origin of DOM

Dans le cadre du projet européen « Optimized Products for Elderly Populations (OPTIFEL) » (ou « produits optimisés pour des gens âgés »), des produits alimentaires sont conçus pour les besoins particuliers des personnes âgées. Puisque cette population est souvent mal-nourrie, l’objectif du projet consistait à produire des aliments riches en nutriments et appétants. Ce but a été mis en œuvre en enrichissant des produits à base de fruits et légumes avec des protéines, des minéraux et vitamines, dont la vitamine C et les folates. Cependant, les deux dernières vitamines sont connues pour être fragiles et pour être rapidement perdues lors du chauffage. Pour atteindre le but de la supplémentation, c’est-à-dire augmenter l’absorption des nutriments, l’étude de leur stabilité est d’une grande importance. Ce travail, en particulier, a été dédié à l’étude de la stabilité de la vitamine C et des folates lors du réchauffage des aliments. Le réchauffage des aliments nécessite de respecter une température minimum de 60°C afin d’éviter la croissance des bactéries sporulées. Une deuxième contrainte, qui se démarque des méthodes de cuisson, est la durée du maintien en température. Selon que le réchauffage se déroule à la maison ou dans un système de restauration collective en liaison chaude, le temps de réchauffage est de courte durée ou peut atteindre quelques heures. La pomme et la carotte ont été choisies en tant qu’exemple d’un fruit et un légume pour le projet OPTIFEL et aussi pour le travail présent. La pomme et la carotte sont des produits qui sont appréciés à travers l’Europe et contiennent des quantités naturelles négligeables en vitamine C et folates. La stabilité de la vitamine C a fait objet de nombreuses études dans la littérature. Cependant, les facteurs qui impactent sa stabilité ont été principalement examinés en solution modèle et leur importance respective dans un vrai aliment manque d’études. Bien que la disponibilité de l’oxygène ait un impact primordial, et qu’il soit connu que l’oxygène est soluble jusqu’à 100°C, sa disponibilité dans le milieu alimentaire est très mal connue pendant le chauffage à des températures intermédiaires. L’acide folique est un vitamère synthétique, qui est habituellement utilisé pour la supplémentation mais qui a l’inconvénient de pouvoir masquer un déficit en vitamine B12. C’est pourquoi le vitamère naturellement abondant, l’acide 5-méthyltétrahydrofolate, a été proposé comme alternative pour l’enrichissement. Son inconvénient majeur, outre le prix, est qu’il est fragile et se dégrade rapidement en l’absence de réducteurs. L’objectif de cette thèse de doctorat consistait à comprendre la stabilité de la vitamine C et de l’acide 5-méthyltétrafolique à des températures intermédiaires. Une attention particulière a été portée à la stabilité dans des matrices alimentaires et à la disponibilité de l’oxygène. Dans un premier temps, la stabilité de la vitamine C et de l’acide 5-méthyltétrahydrofolique a été étudiée à une échelle laboratoire. Ensuite, l’impact des différentes méthodes de réchauffage a été examiné. Le travail a été divisé en quatre chapitres. Le premier chapitre a été consacré à l’étude de la stabilité de la vitamine C. Dans le deuxième chapitre, la disponibilité de l’oxygène a été étudiée. La troisième étude a été dédiée à la stabilité de l’acide 5-méthyltétrahydrofolique. Et dans le quatrième chapitre, trois méthodes de réchauffage ont été comparées<br>The European project « Optimized Products for Elderly Populations (OPTIFEL) » was launched to ameliorate elderlies’ nutritional status. Since this population often suffers from malnutrition, it was envisaged to conceive food products based on fruit and vegetables, with a dense nutritive value. Therefore, products were enriched with important nutrients, among vitamin C and folates. To comply with the intention of supplementations consisting in an increased intake of nutrients, the study of their stability, especially of easy degradable molecules, is of utmost importance. The present work in particular, was dedicated to the stability of vitamin C and 5-methyltetrahydrofolate when food is warmed-up that is heated at an intermediate temperature range (60-80°C). It turned out that the deterioration pace of vitamin C is principally influenced by the filling volume of recipients on a lab-scale. A negligible effect was found for the food matrix meaning that products based on apples and carrots can interchangeably be used for fortifications. Concentration adaptions are easy to control as the degradation loss per time in the concentration range 2-5 mmol/kg, is independent of the initial concentration. Increasing temperature in the range 60-80°C, does not have an impact in a real food matrix either. The latter indicates that another factor, probably oxygen, becomes limiting as enhancing the supply of energy does not increase degradation rates anymore. Thus, by heating products at 80°C, the microbial safety margin can be increased while the nutritional value is kept as if heated at 60°C. From literature it is known that degradation at this temperature range only proceeds via the aerobic degradation pathway. It has been shown in the present work that in food products, the oxygen availability decreases down to anaerobic conditions, also near the surface, during heat treatments at 80°C while oxygen in model solutions stays abundant. Hence, the headspace gains in importance during long warm holding of real food products and dynamics of oxygen and ascorbic acid might determine degradation paces. However, oxygen is not alone responsible for the degradation initiation since ascorbic acid in ultrapure water does not degrade at 80°C during 8 h, even if oxygen is abundant during the whole length of time. An additional trigger, as Fe3+ ions or maybe also other constituents in food matrices, must be present. An interaction between oxygen and the trigger might result in the generation of reactive oxygen species that finally deteriorate the vitamin. For complete stabilization of 5-methyltetrahydrofolate, the amount of ascorbic acid is crucial in contrast to the food matrix that is used for supplementation. The protective effect of ascorbic acid is however time-limited even if it remains in excess. The duration of complete stability can be prolonged by increasing the initial ascorbic acid concentration. Heat treatments under real conditions that is when food products are warmed-up by a microwave, an Actifry ® device or held warm by a water bath, lead to minor to negligible vitamin losses. These are good news for the project since the vitamin amount that is added, is preserved during warming-up of products and must not be controlled. The results indicate the complexity of vitamin degradation since the stability depends crucially on the experimental set-up. It can be concluded that predictive modeling should be performed under real conditions. Vitamin C and 5-methyltetrahydrofolate, which are generally referred to be very susceptible to oxygen and heat, are fairly stable under reheating conditions in real food products

La séparation de nanoparticules (NPs) contenues dans des milieux aqueux est un sérieux challenge pour le traitement des eaux à cause de la grande stabilité et de la nature colloïdale de ces particules. Ce travail concerne le développement de procédés efficaces de flottation pour la séparation de nanoparticules. La première partie du travail est conduite pour obtenir une connaissance plus étroite de la nature et du comportement colloïdal des nanoparticules en suspension. Des tests de modifications de leur surface et des expériences d’adsorption-agrégation sont ensuite menés pour comprendre les mécanismes d’interactions entre les NPs et des réactifs d’aide à la flottation. Deux type des techniques de flottation (la flottation à air dissout (DAF) et la flottation par des aphrons colloïdaux (CGAs)) sont utilisés : le premier type a ici pour objectif de séparer les nanoparticules par des bulles d’air avec l’aide d’acides humiques (HA), alors que le second utilise des microbulles dont la surface est fonctionnalisée par des tensioactifs (CGAs), dans l’objectif d’accroître l’efficacité de séparation. Les résultats montrent que, par mélange avec une solution basique de HA (pH 12.9), la charge de surface de nanoparticules de TiO2 (TNPs) est d’abord neutralisée par des ions OH- et ensuite écrantée par les polyanions de HA. Quand le pH des suspensions TNPs-HA est en dessous de 3 par ajout de solution mère de HA de pH 4.9-9.0, l’attraction électrostatique entre les TNPs et les anions est insuffisante, mais on observe quand même l’agrégation entre TNPs et la part colloïdale de l’HA. Par des essais de DAF en continu, le pH optimal de la solution mère de HA (pH≦ 9) et la concentration optimale en HA (11.1 mg/L COD) permettent d’éliminer plus de 95% des nanoparticules. La concentration résiduelle de HA reste à un très bas niveau même quand l’acide humique est surdosé. Quand le pH des suspensions TNPs-HA est très acide, la plupart des molécules d’acides humiques ne sont pas solubles et ne sont pas chargées. Elles peuvent s’agréger entre-elles et former un précipité colloïdal hydrophobe pour minimiser leur contact avec le milieu aqueux. En ce qui concerne les CGAs, leur caractérisation montre que la vitesse d’agitation est un paramètre crucial pour créer des aphrons de l’ordre de la dizaine de micromètres. Les CGAs peuvent être chargés négativement ou positivement en utilisant des tensioactifs adaptés. Différentes nanoparticules de SiO2 (SNPs) peuvent être efficacement (près de 100%) séparées de suspensions aqueuses par le procédé continu de flottation par CGAs. La comparaison entre flottation par CGAs et DAF montre l’avantage du premier procédé plus efficace avec une moindre quantité de surfactant<br>The removal of nanoparticles (NPs) from waters is a serious challenge in the water treatment field owing to the high stability and colloidal nature of particles. This study is devoted to develop effective flotation processes for NP separation. The investigation is firstly conducted to get a good knowledge of features and colloidal behaviors of NPs in suspension. Surface modification tests and adsorption-aggregation experiments are then carried out to understand the interaction mechanisms between NPs and flotation assisting reagents. Two types of flotation (dissolved air flotation (DAF) and colloidal gas aphrons (CGAs) involved flotation) were specially focused on: the former aims at using air bubbles to remove NP aggregates with the assistance of humic acid (HA), while the later employs the surface functionalized microbubbles, CGAs, to enhance the interaction of NP-bubble for the sake of high treating efficiency. Results show that, on mixing with the highly basic HA solution (pH12.9), the surface charge of TNPs is primarily neutralized by and then screened by polyanions of HA. When the pH of TNP-HA suspension is lower than 3 by adding HA stock solutions at pH4.0~9.0, the electrostatic attraction between TNPs and anions becomes insufficient but the aggregation of TNPs-colloidal HA occurs. In continuous DAF trials, the appropriate pH of HA stock solution (pH ≦ 9) and optimum HA concentration (11.1 mg/L DOC) for high TNP removals (&gt; 95 %) are determined. The residual HA concentration remained in a low level even when HA is overdosed. When the pH of the TNP-HA suspension is highly acidic, most HA molecules are not really soluble and uncharged, and they may aggregate themselves and form hydrophobic colloidal precipitates to minimize the contact with the aqueous environment. As for the study of CGAs, the characterization results denote that introducing air flow during the CGA generation process can slow down the liquid drainage speed and may facilitate the particle separation performance; the stirring speed is a crucial parameter to create micron scale bubbles, and CGAs can be positively or negatively surface charged by using different surfactants. Different SiO2 NP (SNPs) can be efficiently separated from aqueous suspensions by the continuous CGA generation-flotation process with the highest SNP removal close to 100 %. The comparison tests between CGA-flotation and DAF denote that the former take the greater advantage because of its better treating effect and less surfactant demand

Shelf seas represent an important source of iron (Fe) to the open ocean. Additionally, shelf seas are highly productive environments which contribute to atmospheric carbon dioxide drawdown and support large fisheries. The work presented in this thesis describes the seasonal cycle of Fe in the Celtic and Hebridean Shelf Seas, and determines the physico-chemical speciation of Fe supplied from oxic margins. The results from repeated field surveys of the central Celtic Sea showed a nutrient type seasonal cycling of dissolved Fe (< 0.2 µm; dFe), which is surprising in a particle rich shelf system, suggesting a balance of scavenging and remineralisation processes. Coincident drawdown of dFe and nitrate (NO3-) was observed during the phytoplankton spring bloom. During the bloom, preferential drawdown of soluble Fe (< 0.02 µm; sFe) over colloidal Fe (0.02-0.2 µm; cFe) indicated greater bioavailability of the soluble fraction. Throughout summer stratification, it is known that NO3- is drawn down to < 0.02 µM in surface waters. This study revealed that both dFe and labile particulate Fe (LpFe) were also seasonally drawn down to < 0.2 nM. Consequently, it is hypothesised that the availability of Fe seasonally co-limits primary production in this region. At depth both dFe and NO3- concentrations increased from spring to autumn, indicating that remineralisation is an important process governing the seasonal cycling of dFe in the central Celtic Sea. In spring, summer and autumn, distinctive intermediate nepheloid layers (INL) were observed emanating from the Celtic Sea shelf slope. The INLs were associated with elevated concentrations of dFe (up to 3.25 ± 0.16 nM) and particulate Fe (up to 315 ± 1.8 nM) indicating that they are a persistent conduit for the supply of Fe to the open ocean. Typically > 15% of particulate Fe was labile and 60-90% of dFe was in the colloidal fraction. Despite being < 50 km from the 200 m isobath, the concentration of dFe was < 0.1 nM in surface waters at several stations. Broadly, the concentration of nutrients in surface waters described an oligotrophic environment where co-limitation between multiple nutrients, including Fe, appears likely. Over the Hebridean shelf break, residual surface NO3- concentrations (5.27 ± 0.79 µM) and very low concentrations of dFe (0.09 ± 0.04 nM) were observed during autumn, implying seasonal Fe limitation. The dFe:NO3- ratio observed is attributed to sub-optimal vertical supply of Fe relative to NO3- from sub-surface waters. In contrast to the shelf break, surface water in coastal regions contained elevated dFe concentrations (1.73 ± 1.16 nM) alongside low NO3-. Seasonal Fe limitation is known to occur in the Irminger and Iceland Basins; therefore, the Hebridean shelf break likely represents the eastern extent of sub-Arctic Atlantic seasonal Fe limitation, thus indicating that the associated weakening of the biological carbon pump exists over a wider region of the sub-Arctic Atlantic than previously recognised. These key findings demonstrate that the availability of Fe to phytoplankton may seasonally reach limiting levels in temperate shelf waters and that oxic margins persistently supply Fe dominated by colloidal and particulate fractions to the ocean.

L’indisponibilité d’un transformateur de puissance a de fortes répercussions financières aussi bien pour les exploitants de réseaux d’énergie électriques que pour les clients qui y sont connectés. Afin de prévenir les pannes et d’optimiser la performance de ces équipements d’importance stratégique, de nombreuses techniques et outils de diagnostic ont été développés. L’huile contient environ 70 % des informations de diagnostic sur l’état des transformateurs. Le défi consiste à y accéder et à les utiliser efficacement. L’atteinte d’un tel objectif passe nécessairement par des techniques de diagnostic fiables. En plus des techniques traditionnellement utilisées, trois nouvelles techniques de diagnostic issues des normes ASTM sont utilisées : (1) le test de stabilité qui permet de simuler le comportement sous champ électrique d’une huile en fournissant des informations sur la qualité de celle-ci ; (2) la spectrophotométrie UV/Visible qui permet de mesurer la quantité relative de produits de décomposition dissous dans l’huile ; et (3) la turbidité qui mesure la pureté d’une huile neuve ou usagée. Une méthode quantitative permettant de déterminer les paramètres affectant la formation du soufre corrosif sur les conducteurs en cuivre dans les transformateurs de puissance est proposée. Il est montré entre autres que la tendance au gazage des esters naturels est plus faible que celle de tous les autres types d’huile (minérales, esters synthétiques, silicone). La turbidité et la spectrophotométrie UV/Visible permettent de quantifier efficacement les contaminants qui résultent de l’action d’une décharge électrique sur l’huile isolante. Un nombre important de cycles de régénération (au moins 15) est nécessaire pour qu’une huile vieillie en service retrouve les aptitudes d’une huile neuve. Une nouvelle technique de régénération est présentée pour réduire le nombre de cycles de régénération ; celle-ci consiste à utiliser la terre à foulon traitée avec de l’azote. Il est montré également que le temps constitue le paramètre le plus nuisible dans la formation de soufre corrosif. L’action combinée du temps et de l’agressivité de l’oxygène dissous l’accélère fortement<br>A power transformer outage has a dramatic financial consequence not only for electric power systems utilities but also for interconnected customers. In order to prevent any failure and to optimize their maintenance, various diagnostic techniques and tools have been developed. Insulating oil contains about 70% of diagnostic information on the transformer condition. The challenge is to access and use them efficiently. To meet this objective reliable diagnostic techniques are required. In addition to traditional testing methods, three recently developed ASTM testing techniques were used: (1) oil stability testing that simulates the behaviour of oil under electrical stress by providing information on its quality; (2) the UV/Visspectrophotometry that measures the amount of the relative dissolved decay products in insulating oil; and (3) the turbidity that measures the purity of virgin and aged oil. A quantitative laboratory technique capable of determining the parameters affecting the formation of corrosive sulphur deposition on copper conductors in power transformer is proposed. It is shown among other that the gassing tendency of natural esters is lower than that of the other types of insulating fluids (mineral oil, synthetics esters and silicone oil). The turbidity and UV/Vis spectrophotometry allow quantifying effectively, the relative amount of contaminants resulting from electrical discharge in oils. A large number of reclamation cycles (around 15 passes) are required for in-service aged oil to regenerate to the level of new oil. Anew technique enabling reducing the number of reclamation cycles is proposed; this latter consists in the use of Fuller’s Earth previously treated with dry nitrogen. It is also shown that time is the most influential parameter in the formation of corrosive sulfur. The process is accelerated when time and aggressiveness of oxygen are partnered

Ce travail est axé sur l’étude d’un profil de sol et des solutions de sol prélevés sur une parcelle expérimentale couvertes d’épicéas. Tous ces échantillons proviennent du Bassin Versant du Strengbach (Observatoire HydroGéochimique de l’Environnement – OHGE), ont été échantillonnés à différentes profondeurs (5, 10, 30 et 60 cm) et durant la période comprise entre 2009 et 2013.Les caractérisations des extraits des sols par spectroscopie Infra-Rouge ont permis de mettre en évidence les modifications des groupements fonctionnels organiques avec la profondeur et que ces modifications ont une forte incidence sur le comportement des cations (majeurs et traces) dans le sol. Des expérimentations d’ultra-filtration ont permis d’identifier les flux colloïdaux et dissous du carbone organique ainsi que ceux des éléments majeurs et traces présents dans les solutions de sol. L’utilisation conjointe des traceurs isotopiques (87Sr/86Sr et δ44/40Ca) et chimiques (Terres Rares) ont mis en évidence des processus ayant lieu aux interfaces eau-sol-plante, comme le prélèvement racinaire ou l’altération des sols<br>This work is focused on the study of a profile of soil and soil solutions collected on an experimental plot covered with spruce. All these samples come from the watershed of the Strengbach (environment - OHGE Hydrogeochimique Observatory), were sampled at different depths (5, 10, 30 and 60 cm) and during the period between 2009 and 2013. Characterizations of soil extracts by infrared spectroscopy allowed to highlight changes in the organic functional groups with depth and that these changes have a significant impact on the behaviour of the cations (major and trace) in the soil. Ultrafiltration experiments helped to identify flows of colloidal and dissolved organic carbon as well as those of the major and trace-element present in soil solutions. The joint use of isotope tracers (87Sr / 86Sr and δ44 / 40 Ca) and chemical (Rare Earth Elements) have highlighted processes taking place at the water-soil-plant interface, as the uptake by root or soil alteration

博士<br>國立臺灣大學<br>海洋研究所<br>107<br>Arsenic (As) is a metalloid element receiving major concern due to its toxicity. This element in the ocean shows nutrient-like vertical distributions, with a change of the concentrations mostly in the euphotic zone. Earlier studies had found that As(V) is the most dominant species, followed by As(III) and methylated As; the latter two are common in the surface of the P-stressed waters. However, there was no evidence of colloidal arsenic in the ocean, even though colloids are found labile to microbes and influence the partitioning of other bioactive elements in seawater. Here we used cross-flow ultrafiltration and chemical speciation methods to prove and provide the first evidence on the existence of colloidal arsenic and the molecular weight distributions of various dissolved arsenic species in the ocean. Dissolved inorganic arsenic (DIAs) showed typical nutrient-like depth profiles in the western Philippine Sea and the South China Sea. Moreover, 10–20% of the DIAs was composed of HMW-DIAs, which is discovered for the first time. Besides, nearly all the HMW-DIAs was As(V). Dissolved organic arsenic (DOAs) concentrations, in contrast, displayed decreasing trends with depth, with an average concentration of 3.2±1.1 nM in the surface. 56% of the DOAs was in colloidal phase. With molecular weight fractionation and chemical methods, dissolved arsenic species in seawater is redefined. In a short-term study in the western Philippine Sea, we found clear diel variations of the HMW-As in the upper euphotic zone, indicating a rapid turnover of arsenic in colloidal phase. Positive correlations between HMW-As and HMW-DOP in the upper euphotic zone were found in both the western Philippine Sea and the South China Sea, suggesting a close linkage with phosphorus. Overall, the results prove that colloids play a major role in biogeochemical cycle of arsenic in the ocean.

碩士<br>國立臺灣大學<br>海洋研究所<br>107<br>Silver (Ag) is one of the most toxic elements, and it can accumulate in aquatic organisms and cause lethal consequences. Since the Industrial Revolution, silver has been widely used for coins, electronics, metal fabrication, photography, and many other industries. In recent years, silver nanoparticles have been engineered and extensively used for its antimicrobial effects, which causes silver concentration in nature water is getting much higher than before and still rising. As studies showed, silver can be removed to sediments at a fairly rapid rate in estuarine systems. However, little is known about releasing silver due to resuspension. The purpose of this study is to investigate the distribution and transformation of dissolved and colloidal silver during river-sea mixing, and the effects of sediment resuspension. Water samples were collected in fall 2017 from Danshuei river using ultra-clean sampling protocols, and sampling is categorized into two parts sampling at different geographic locations in Danshuei mainstream by a small boat and time series sampling at a fixed station at Guandu pier. Real time in-line filtration was achieved by a 0.45 μm capsule filter, and then the filtered waters were subsequently further processed with cross flow ultrafiltration by a 1 kDa spiral wound membrane. Ag in both filtered (< 0.45 μm) and ultrafiltered (< 1kDa) waters were extracted by Ammonium pyrrolidinedithiocarbamate(APDC)/Sodium diethyldithiocarbamate (DETC) complexed method and then measured by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). Particles collected on 0.45 μm PC filters were digested and measured by graphite furnace atomic absorption spectrometer (GFAAS). Silver in each fractions are defined as total dissolved (< 0.45 μm), colloidal (1 kDa-0.45 μm), truly dissolved (< 1 kDa), and particulate (> 0.45 μm). The results showed that total dissolved fraction ranged from 46 to 298 pM and exhibited a non-conservative estuarine removal mixing pattern as previous study. We also found that 10-90% of dissolved silver fraction was present in the colloidal phase, and the percentage decreased with salinity. Simultaneously, strong correlation between colloidal Ag and colloidal Fe was observed to prove the removal of Ag may be controlled by the generation of hydrous iron oxides. However, truly dissolved fraction increased with salinity because silver chloride complexes were dominant in saline water, which was proved by mixing and thermodynamic speciation model calculation. At Guandu pier station, dynamic changes and remobilizations were found in truly dissolved fractions, which were due to competition reactions of the formation of silver chloride complexes, desorption from re-suspended particulate matter, and colloidal pumping. All these processes may cause failure to access Ag species by the mixing and thermodynamic modeling (MINEQL+ Version 5.0). In conclusion, to accurately predict the fates of Ag in shallow estuary, the effects of sediment resuspension and colloidal pumping should be incorporated.

碩士<br>國立臺灣大學<br>海洋研究所<br>103<br>Colloidal organic phosphorus (COP) plays an important role in marine P cycle; however, studies on COP are still scarce. This study focused on the distribution and variation of dissolved and colloidal organic phosphorus in euphotic zone of the Western Philippine Sea. Seawater samples were separated into total dissolved (≤0.45 μm), truly dissolved (≤1 kDa), and colloidal (1 kDa ~ 0.45 μm) fractions by in-line filtration of 0.45 μm-size capsule filter and then Cross-Flow Ultrafiltration (1kDa). After separation, each fraction were digested by a high temperature oxidation method and analyzed by phosphomolybdate-blue spectrophotometry. Therefore, different fractions of both inorganic and organic phosphorus were determined. Results shown that the DOP concentration ranged 0.06 ~ 0.24 μM, and the COP concentration ranged 0.03 ~ 0.15 μΜ in the euphotic zone. The COP accounted for a significant amount of 61±16% in the DOP. Also, it was found that the depths of COP maximum concentration coincided with the depths of chlorophyll A maximum. In addition, it is also found that COP varies between day time and night hours. All these evidences highlight the strong biological effect on production and assimilation of COP and its vital importance in marine P cycle.

碩士<br>國立屏東科技大學<br>環境工程與科學系<br>90<br>Heavy metal contamination is one of soil pollution problems. The major factors of affecting heavy metal adsorption are the colloid components including silicate clays, organic matter (OM) and Fe oxides. Past studies had discussed the adsorption characteristics of heavy metal in soil, but little was related to the interactions of different soil colloids. Cadmium contamination is popularly found in the arable soils of Taiwan. Therefore, Lungchung (Lt, Plinthic Paleaquult) and Santai (St, Typic Hapludert) series with diverse silicate clay, organic matter (OM) and Free Fe oxide (Fed) contents were selected to study Cd adsorption. Clays of the two soils were separated into coarse (0.2-2.0μm) and fine (<0.2μm) fractions after removal of H2O2 and dithionite-citrate-bicarbonate (DCB) extract to remove OM and Fed, respectively. Results indicate that the determining coefficients (R2) are more than 0.9 in describing the adsorption isotherms of Ca by Langmuir equation. This is related to higher smectite with large specific surface in the St soil. For the two soils, the sequence of adsorption amount of Cd in different clay fractions is fine clay > coarse clay > whole clay, respectively. Higher specific surface and CEC values of finer sized particles cause to increase the adsorption amount of Cd. When OM was removed, the adsorption amount of Cd decreased. But the adsorption amount of Cd increased with the removal of Fed for the H2O2 treated clays, this is resulted from the coating of Fe oxide on the mineral surface to the exposure of adsorption sites. When soil pH increase, the adsorption amount of Cd increased associated with higher variable negative charge on the clay surface.

This study has assessed the effects of using hydrogen peroxide, Fenton's reagent treatment and alum coagulation on the removal of organic dissolved and colloidal substances (DCS) from TMP/Newsprint cloudy white water (MWW), fungal cultural filtrate (FCF) and fungal enzymatic treated white water (FWW). It was shown that employing hydrogen peroxide did not significantly remove the colour, even i f a high dosage (2% by wt/wt) of hydrogen peroxide was employed. Both the Fenton's reagent treatment and alum coagulation were effective in reducing detrimental components present in both the fungal cultural filtrate and the fungal enzymatic treated white water, without the requirement of either pH adjustment or the need for changed temperature. We confirmed that fungal enzymatic treatment played a key role in enhancing these two posttreatments. The presence of chelating agents was shown to be the major inhibitor of successful Fenton's reagent treatment of the MWW and FWW. The percentage removal of colour and of organic DCS components were increased up to 90% and 92% respectively of the Fenton's reagent treatment. When using alum coagulation, the removal rates of lignin, extractives and colour were 95%, 85% and 95% respectively. The zeta potential was shown to be the most dominant factor which affected efficient precipitation. The supernatants obtained after each of the treatments were virtually clear and only slightly coloured when compared to the original MWW and FWW samples.