Diet and movements in fishes are often logistically challenging to study. Trace element and stable isotope analyses have advanced these fields considerably, but are still constrained by methodological impediments, such as the tendency towards lethal sampling. Studying endangered fishes is particularly challenging as representative samples are difficult to obtain. However, the information gained from such studies is often critical to the recovery of endangered fishes as knowledge of life history attributes has the potential to greatly influence the success of management strategies. I tested the viability of using fin rays in fishes as a non-lethal approach to study diet and movement patterns over time. I then applied the methods I developed to study the life history of the critically endangered Goliath Grouper, Epinephelus itajara. Fin ray analyses have traditionally been used in age and growth studies, as well as in a limited number of projects that study the chemical constituents of the ray itself. Therefore, I first tested whether fin rays could be used as chronological recorders of chemical properties over time using a pseudo-experimental design. By using samples from various aquaria, I had documentation of the time of capture of every animal used. Based on the assumption that the otolith in fishes represents a conserved, chronological matrix, I compared trace element concentrations between the otolith and the fin ray of each individual. In addition I tested whether stable isotope values of δ13C and δ15N differed between the wild and captive life phases of each individual. Divalent ions and positively-charged transition metals (e.g., Fe, Co) in particular showed strong associations between the two structures, suggesting conservation of material. Stable isotope values of δ13C and δ15N differed between the wild and captive life phases in most of the fishes sampled, also suggestive of conserved matrices. I then tested and modeled the differences in δ15N values over time between the populations of Goliath Groupers on the west and east coasts of Florida. In general, individuals on the west coast had lower overall values and a larger difference between juvenile and adult values. The mechanism that caused the differences between coastal populations may have been an artifact of the environment, rather than different feeding behaviors. Last, I investigated different nursery habitats for Goliath Groupers in southwestern Florida. I characterized juvenile nurseries based on the chemical fingerprints of trace elements within the inorganic matrix of the fin rays. Groupings based on these fingerprints were surprisingly accurate and can be used to identify essential nursery habitat for the species in years to come. This research demonstrated the efficacy of novel techniques that were used to gather information on the life history of a critically endangered fish in the state of Florida. The results can be used to influence management strategies in the future, particularly with regard to nursery habitat use.

Incineration is a mainstream strategy for solid waste management in Sweden and all over the world. Improved knowledge and understanding about the distribution of trace elements (in ashes) during incineration, and how trace element partitioning respond to the changes in waste composition, are important in terms of combustion process optimization and plant efficiency. Moreover, determination of chemical association of trace elements in ashes are vital for avoiding environmental concerns and to promote possible reuse. In this study, partitioning of trace elements in ashes during incineration as function of input waste fuel and incineration technology was investigated. Further, chemical association of trace elements in resulting ashes was studied. An evaluation was also performed about feasibility of metal extraction from sulfidic mining waste and flotation tailings. Moreover, green liquor dreg (GLD) was tested with respect to stabilization of metals within the sulfidic mining waste. Findings showed that the total input of trace elements and chlorine affects the partitioning and increasing chlorine in the input waste caused increase in transfer of trace elements to fly ash especially for lead and zinc. Vaporization, condensation on fly ash particles and adsorption mechanisms play an important role for metal distribution. Firing mixed waste, especially biofuel mix, in grate or fluidized (CFB) boilers caused increased transfer into fly ash for almost all trace elements particularly lead and zinc. Possible reasons might be either an increased input concentration of respective element in the waste fuel, or a change in volatilization behavior due to the addition of certain waste fractions. Chemical association study for fly ashes indicated that overall, Cd, Pb, Zn, Cu and Sb are presenting major risk in most of the fly ashes, while in bottom ashes, most of elements are associated with stable fraction. Further, fuel type affects the association of elements in ashes. Chemical leaching of mining waste materials showed that sulfuric acid (under different conditions) is the best reagent to recover zinc and copper from sulfidic mining waste and also copper from flotation tailings. GLD indicates potential for metal stabilization in mining waste by reducing the metal mobility. Extraction methods could be applied to treat mining waste in order to meet the regulatory level at a specific mining site.Similarly stabilization/solidification  methods might be applied after leaching for recovery of metals.

L’objectif principal de cette thèse est de mieux comprendre les différents facteurs contrôlant la pompe biologique de carbone en Atlantique Nord et dans l’Océan Austral, à proximité des îles Kerguelen, en utilisant notamment deux approches: le Thorium-234 (234Th) et le baryum biogénique (Baxs).En Atlantique Nord, les flux d’export de carbone organique particulaire (POC) augmentent lorsqu’ils sont associés à des minéraux biogéniques (silice biogénique et carbonate de calcium) et lithogènes, capable de lester les particules. L’efficacité d’export, généralement plus faible que précédemment supposé (< 10%), est inversement corrélée à la production, soulignant un décalage temporel entre production et export. La plus forte efficacité de transfert, i.e. la fraction de POC atteignant 400m, est reliée à des particules lestées par du carbonate de calcium ou des minéraux lithogènes.Les flux de reminéralisation mésopélagique sont similaires ou parfois supérieurs aux flux d’exports et dépendent de l’intensité du développement phytoplanctonique, de la structure en taille, des communautés phytoplanctoniques et des processus physiques (advection verticale).Comme observé pour le POC, l’export des éléments traces est influencé par les particules lithogènes provenant des marges océaniques, mais aussi des différentes espèces phytoplanctoniques.Dans l’Océan Austral, la zone à proximité de l’île de Kerguelen est naturellement fertilisée en fer, augmentant les flux d’export de fer, d’azote et de silice biogénique. Il a été démontré que la variabilité des flux dépendait des communautés phytoplanctoniques dans la zone fertilisée. / The main objective of this thesis is to improve our understanding of the different controls that affect the oceanic biological carbon pump. Particulate export and remineralization fluxes were investigated using the thorium-234 (234Th) and biogenic barium (Baxs) proxies.In the North Atlantic, the highest particulate organic carbon (POC) export fluxes were associated to biogenic (biogenic silica or calcium carbonate) and lithogenic minerals, ballasting the particles.Export efficiency was generally low (< 10%) and inversely related to primary production, highlighting a phase lag between production and export. The highest transfer efficiencies, i.e. the fraction of POC that reached 400m, were driven by sinking particles ballasted by calcite or lithogenic minerals.The regional variation of mesopelagic remineralization was attributed to changes in bloom intensity, phytoplankton cell size, community structure and physical forcing (downwelling). Carbon remineralization balanced, or even exceeded, POC export, highlighting the impact of mesopelagic remineralization on the biological pump with a near-zero, deep carbon sequestration for spring 2014.Export of trace metals appeared strongly influenced by lithogenic material advected from the margins. However, at open ocean stations not influenced by lithogenic matter, trace metal export rather depended on phytoplankton activity and biomass.A last part of this work focused on export of biogenic silica, particulate nitrogen and iron near the Kerguelen Island. This area is characterized by a natural iron-fertilization that increases export fluxes. Inside the fertilized area, flux variability is related to phytoplankton community composition.

L’exploitation minière de l’uranium et les processus de traitement du minerai sont à l’origine d’un marquage potentiel de l’environnement par les descendants des chaînes de désintégration U-Th et des éléments traces métalliques (ETM) associés. Ces contaminants s’accumulent ensuite préférentiellement dans des zones de sédimentation continentales (étangs ou lacs) ou des zones humides (tourbières, berges de rivière) situées à l’aval hydraulique des mines. Les zones humides en particulier sont des milieux sensibles aux changements globaux et à la pression anthropique, situés en général en tête de bassin versant. Cela pose donc un risque en cas relargage des contaminants depuis ces milieux. L’objectif de cette étude est de mettre en place une méthodologie aisément reproductible, y compris aux sites miniers orphelins, et permettant l’identification et la caractérisation des contaminations et la compréhension des mécanismes d’accumulation et des risques de relargage. Cette étude a été réalisée dans l’environnement de l’ancienne mine de Bertholène (Aveyron, 12, France). Les zones d’accumulations préférentielles ont été identifiées par spectrométrie gamma in situ mobile et fixe. Des échantillons de sols, sédiments, végétaux, eaux et tourbes ont été prélevés autour du site, afin (a) de caractériser l’activité des différents descendants des chaînes de l’U et du Th et les contaminations en ETM associées à différentes échelles d’observation, (b) de comprendre les mécanismes d’accumulation et de relargage potentiel et (c) de tracer les sources des contaminants. Les résultats obtenus montrent que l’essentiel de la contamination est localisée dans une zone inondable de l’environnement proximal aval de la mine. Les activités en uranium élevées (U-238 > 20000 Bq.kg-1) et le fort enrichissement des radionucléides du début de chaîne par rapport à la fin de chaîne de l’U-238 traduisent un apport préférentiel d’U-238 et de Th-230, par rapport au Ra-226, lors d’inondations. Les contaminations en ETM associées sont relativement faibles, excepté en Mn, en Ba et en S. Les accumulations en radionucléides et en ETM sont expliquées à la fois par les caractéristiques géochimiques du minerai d’uranium et par les processus de traitement du minerai et des eaux d’exhaure. Les lessivages chimiques réalisés révèlent que les fractions acido-solubles et oxydes amorphes des sols constituent des pièges prépondérants des contaminants et que des variations du pH ou du potentiel d’oxydoréduction pourraient générer des relargages important d’uranium et de radium dans l’environnement. Finalement les déséquilibres radiologiques et les isotopes du plomb sont des traceurs fiables de la contamination associée à l’exploitation d’une mine d’uranium. / Uranium mining and uranium ore processing increase the environmental activity of U and Th decay products and trace elements, in particular in case of releases to the adjacent rivers. Contaminants accumulate then preferentially in sedimentation areas (such as ponds or lakes) or in wetlands (peatlands, marshes or riverbanks) located downstream to the mine. Wetlands – generally located at the head of watershed – are particularly sensitive to environmental changes and anthropogenic pressure. This poses a risk of release of contaminants from these accumulation areas. The objective of the present study is to propose an easily reproducible methodology – in particular for the orphan mining sites – to identify and characterize accumulation areas. This study also aims to improve our understanding of the mechanisms of accumulation and release, in these areas. This study was performed around the former mining site of Bertholène (France). Standing and mobile in situ gamma spectrometry is used to accurately locate the accumulation areas. Soils, sediments, vegetation, water and peat are also sampled upstream and downstream of the mine, in order to (a) characterize the activities and the disequilibria of the U-Th decay chains and the associated trace elements according to the scale of observation, (b) understand the mechanisms of accumulation and release and (c) identify the potential sources using geochemical proxies and isotopic analyses. The results obtained show that radionuclides are mainly accumulated in a flooding area located downstream the mine. Strong U-238 activities (> 20000 Bq.kg-1) and strong Ra-226/U-238 and Th-230/Ra-226 activity ratios are recorded, involving preferential inputs of U-238 and Th-230 during flooding events. Trace element contamination is low, except for Mn, Ba and S. Such contaminations are potentially explained by the geochemical composition of the uranium ore and by the past and current processes of ore and water mine. Sequential extractions highlight the importance of the acido-soluble and the amorphous oxides in the trapping of contaminants. Thus, pH or Eh potential changes could induce major releases of uranium to the environment. The large differences in Pb isotope composition between natural soils and uranium ores, as well the activity ratios of the U-238 and decay chain products, make these indicators helpful to identify the soils and the sediments impacted by uranium mining.

>Magister Scientiae - MSc / Millions of tonnes of fly ash are generated worldwide every year to satisfy the large demand for energy. Management of this fly ash has been a concern and various approaches for its beneficial use have been investigated. Over the last two decades, there has been intensive research internationally that has focused on the use of different sources of fly ash for zeolite synthesis.However, most of the studies have concentrated on class C fly ash and very few have reported the use of South African class F fly ash as feedstock for zeolite synthesis.Class F fly ash from South Africa has been confirmed to be a good substrate for zeolite synthesis due to its compositional dominance of aluminosilicate and silicate phases. However, because differences in quartz-mullite/glass proportions of fly ash from different sources produces impure phases or different zeolite mineral phases under the same activation conditions, the present study focused on optimization of synthesis conditions to obtain pure phase zeolite Na-P1 from class F South African coal fly ash. Synthesis variables evaluated in this study were; hydrothermal treatment time (12 - 48 hours), temperature (100 – 160 oC) and addition of varying molar quantities of water during the hydrothermal treatment step (H2O:SiO2 molar ratio ranged between 0 - 0.49).Once the most suitable conditions for the synthesis of pure phase zeolite Na-P1 from fly ash were identified, a statistical approach was adopted to refine the experiments, that was designed to evaluate the interactive effects of some of the most important synthesis variables. In this case, the four synthesis variables; NaOH concentration (NaOH: SiO2 molar ratio ranged between 0.35– 0.71), ageing temperature (35 oC – 55 oC), hydrothermal treatment time (36 - 60 hours) and temperature (130 oC – 150 oC) were studied. The response was determined by evaluating the improvement in the cation exchange capacity of the product zeolite.The starting materials (fly ashes from Arnot, Hendrina and Duvha power stations) and the synthesized zeolite product were characterized chemically, mineralogically and morphologically by X-Ray fluorescence spectrometry, X-ray powder diffraction, scanning electron microscopy, and transmission electron microscopy. Other characterization technique used in the study were Fourier transform infrared spectroscopy to provide structural information and also monitor evolution of crystallinity during synthesis, as well as cation exchange capacity to determine the amount of exchangeable positively charged ions. Nitrogen adsorption was used to determine the surface area and porosity, and inductively coupled mass spectrometry for multi-elemental analysis of the post-synthesis supernatants.The results from the X-ray diffraction spectroscopy showed that the most pure zeolite Na-P1 phase was achieved when the molar regime was 1 SiO2 : 0.36 Al2O3 : 0.59 NaOH : 0.49 H2O and at synthesis conditions such that ageing was done at 47 oC for 48 hours while the hydrothermal treatment time and temperature was held at 48 hours and 140 oC, respectively. Results from statistically designed experiments show that there was a distinct variation of phase purity with synthesis conditions. From the analysis of linear and non linear interactions, it was found that the main effects were ageing temperature and hydrothermal treatment time and temperature, which also showed some interactions. This experimental approach enabled a clearer understanding of the relationship between the synthesis conditions and the purity of the zeolite Na-P1 obtained.The quality of zeolites is a major determinant in the efficiency of toxic element removal from waste water. Preliminary experiments conducted using optimised zeolite Na-P1 obtained in this study with a cation exchange capacity of 4.11 meq/g showed a high percentage removal of Pb,Cd, Ni, Mn, V, As, B, Fe, Se, Mo Sr, Ba and Zn from process brine obtained from Emalahleni water reclamation plant.In summary, a pure phase of zeolite Na-P1 was obtained from South African class F fly ash feedstock at relatively mild temperature. The systematic approach, incorporating statistical design of experiments, developed in this study resulted in a better understanding regarding the relationships of synthesis parameters in the formation of zeolites from fly ash. The zeolite Na-P1 synthesized with a high cation exchange capacity was effective for removal of toxic elements from brine.

L’émergence des bactéries photosynthétiques oxygéniques (BPO), ou cyanobactéries, est probablement l’évènement le plus important de l’histoire de la Terre, depuis l’apparition de la vie elle-même. Par la libération d’O2 dans l’environnement, les BPO ont conduit à l’oxygénation de notre planète, jusqu’alors anoxique, et au développement de la vie complexe. Cependant, cette évolution n’est toujours pas datée. Dans cette étude, j’ai cherché à identifier des signatures chimiques spécifiques aux BPO, in situ à l’échelle du μm, dans des tapis microbien fossiles datant de 3,45 à 1,88 Ga, recouvrant ainsi une période allant de la Terre anoxique à la Terre oxygénée après le « Great Oxidation Event » (GOE). Nous avons utilisé la microscopie optique, la spectroscopie Raman, le MEB/EDX, l’EPMA, la μ-XRF à rayonnement synchrotron (SR-XRF), et des analyses isotopiques. Une nouvelle méthode de quantification élémentaire pour SR-XRF, ainsi qu’une nouvelle méthodologie de préparation d’échantillons ont été developpés. Les résultats obtenus par EPMA et μ-XRF montrent que, dans certains contextes de déposition, un enrichissement en lanthanides (par exemple La, Sm, Gd) de cellules fossiles, et un enrichissement en Cu de pyrites diagénétiques formées en association avec des BPO, pourraient représenter des signatures chimiques spécifiques aux BPO. Suite à ces résultats, je propose que les BPO ont évolué entre 3,33 et 2,98 Ga. Je propose que les techniques élémentaires telles que l’EPMA et la μ-XRF sont les techniques les plus appropriées pour trouver des signatures chimiques spécifiques aux BPO et contraindre leur émergence dans le temps. / The evolution of oxygenic photosynthetic bacteria (OPB) is probably the most important biological event of Earth’s history since the emergence of life itself. The release of their by-product O2 in the environment, which was globally anoxic, fundamentally changed the face of the Earth and led to the development of complex life. However, the specific timing of this evolutionary step remains unclear. This study is based on the search for in situ chemical signatures of OPB at the microbial (μm) scale, within fossilized microbial photosynthetic mats in Archean and Paleoproterozoic sediments dated between 3.45 Ga and 1.88 Ga, i.e. spanning the anoxic Earth to the aftermath of the GOE. We used optical microscopy, Raman spectroscopy, SEM/EDS, EPMA, synchrotron radiation μ-XRF, and isotope analytical techniques. The μXRF results were improved by the use of a new sample preparation method and a new quantification method, both developed during this study.Results obtained by EPMA and μXRF show that, under certain depositional contexts, enrichment in lanthanides (such as Sm, La and Gd) in individual OPB cells, as well as a Cu enrichment in diagenetic pyrites formed in association with OPB, may represent chemical signatures of OPB. I propose that OPB evolved sometime between 3.33 Ga and 2.98 Ga. Also, I argue that elemental techniques such as EPMA and μ-XRF are the most suitable techniques to find chemical signatures of OPB and constrain the timing of their emergence.

Dans les zones portuaires un dragage régulier des sédiments est indispensable afin de maintenir une profondeur satisfaisante des voies de navigation. Dans ce travail, nous avons cherché à étudier la faisabilité d'un traitement de stabilisation en mélangeant 5% et 20% les résidus de bauxite (Bauxaline®, Bauxsol et Bauxaline® neutralisé) avec les sédiments marins de dragage pollués. L'efficacité de cette méthode de traitement a été évaluée en mesurant la concentration en éléments traces lixiviés et la toxicité des lixiviats des sédiments. L’application d’amendements de 20% résidus de bauxite a permis une réduction significative la concentration des éléments traces cationiques de 40 à 80%, et la toxicité des lixiviats. Quel que soit l’amendement, une faible efficacité de la stabilisation a été observée pour les éléments anioniques (As, Mo) / Marine sediments concentrate various pollutants and subsequent sedimentation of harbors and ports require periodic dredging to maintain satisfactory depth of waterways. Direct land deposition of contaminated marine dredged sediments pose risk to the environment due to possible leaching of trace elements. In this context, we aimed to study the feasibility of trace elements stabilization by mixing 5% and 20% of bauxite residues (bauxaline®, bauxsol and neutralized bauxaline®) with composted dredged marine sediment. The treatment efficiency was evaluated by monitoring the leached trace elements concentration and toxicity of sediment leachates. 20% amendment application successfully stabilized cationic pollutants (Cu, Cd, Zn) up to 40-80%, and decreased the toxicity of sediment leachates. Whereas, anionic pollutants (As, Mo) were less immobilized require further investigation

The hallmark of oceanic anoxic event 1a (OAE1a) (early Aptian ~125 Ma) corresponds to worldwide deposition of black shales with total organic carbon (TOC) content > 2% and a d13C positive excursion up to ~5‰. OAE1a has been related to large igneous province volcanism and dissociation of methane hydrates during the Lower Cretaceous. However, the occurrence of atypical, coeval and diachronous organic-rich deposits associated with OAE1a, which are also characterized by positive spikes of the d13C in epicontinental to restricted marine environments of the Tethys Ocean, indicates localized responses decoupled from complex global forcing factors. The present research is a high-resolution, multiproxy approach to assess the paleoenvironmental conditions that led to enhanced carbon sequestration from the late Barremian to the middle Aptian in a restricted, Tethyan marginal basin prior to and during OAE1a. I studied the lower 240 m of the El Pui section, Organyà Basin, Spanish Pyrenees. The basin developed as the result of extensional tectonism linked to the opening of the Atlantic Ocean. At the field scale the section consists of a sequence of alternating beds of cm – m-scale, medium-gray to grayish-black limestones and marlstones with TOC up to ~4%. The results indicate that the lowest 85 m of the section, from latest Barremian –earliest Aptian, characterize a deepening phase of the basin concomitant with sustained riverine flux and intensified primary productivity. These changes induced a shift in the sedimentation pattern and decreased the oxygen levels in the water column through organic matter respiration and limited ventilation of the basin. The upper 155 m comprising the earliest – late-early Aptian document the occurrence of OAE1a and its associated geochemical signatures (TOC up to 3% and a positive shift in d13C of ~5‰). However, a low enrichment of redox-sensitive trace elements indicates that the basin did not achieve anoxic conditions. The results also suggest that a shallower-phase of the basin, coeval with platform progradation, may have increased ventilation of the basin at the same time that heightened sedimentation rates and additional input of organic matter from terrestrial sources increased the burial and preservation rate of TOC in the sediment.

Incineration is an attractive solution to the problems of disposing of municipal solid wastes and supplying energy. Because up to 25 percent of the waste in refuse-derived-fuel systems is ash, the physical and chemical characteristics of ash become more and more important for its potential impacts and methods suitable for their disposal. Trace elements concentration in ash is of great interest because of its relationship to regulatory criteria under the Resource Conservation and Recovery Act (RCRA) regarding toxicity and hazards. The applications of a microwave oven sample dissolution method has been tested on a variety of standard reference materials, with reproducible and accurate results. Fourteen trace elements, As, Ba, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Se, Tl, V, and Zn, from the dissolved ash samples were determined by inductively coupled plasma atomic emission spectrometry.

This work involves the study of the effects of land use on the chemical composition of urban stormwater runoff, and its subsequent acute toxicity to the aquatic invertebrate Daphnia pulex. Samples were obtained from the Brunette drainage basin of Burnaby, British Columbia, from a variety of sites in the land use classifications commercial (C), industrial (I), residential (R) and open/greenspace (0). Results indicate that the toxicity to D. pulex and the chemical composition of the stormwater (measured by such parameters as COD, alkalinity, hardness, hydrocarbons and trace metals) were influenced by land use and the interval between rainfall events. The industrial and commercial land use sites were the major source of those trace metals most often considered toxic to aquatic organisms, with runoff from the commercial sites proving most toxic to the test organism (toxicity followed the sequence C>I>R»0). Bioassays with synthetic stormwater (Cu, Fe, Pb and Zn, at concentrations observed from field samples) demonstrated that pH and suspended solids helped to regulate the toxicity of the trace metals, and implicated the importance of these elements in natural stormwater toxicity. Statistical comparison between synthetic and natural stormwater runoff toxicity yielded poor correlation; however, this was expected due to the inherent differences between the laboratory and field environments. A detailed study of a single storm event indicated that while the "first-flush" of the storm may be contributing to toxicity through the physical scouring of insoluble pollutants, the soluble pollutants proved to be more toxic and were washed out of the area over the entire duration of the event. This prompted the author to propose the complete treatment of all stormwater runoff, and not simply the slug load of the first hour. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate