Despite the documented sensitivity of polar environments, long-term monitoring data are especially sparse in these regions. Diatom-based paleolimnology has contributed significantly to understanding the response of Arctic lakes to climate change, but most studies have been conducted in regions with relatively high lakewater buffering capacity. As such, Pim Island (Nunavut, Canada) is a region of limnological interest because, due to the local geology, its surface waters are of relatively lower pH and previous research suggests that such softwater lakes may be especially responsive to climate fluctuations and therefore provide the best paleoclimate records. This thesis has two separate but related chapters, as well as an exploratory study included in appendix. First, a novel approach using visible-near-infrared spectroscopy (VNIRS) was used to infer lakewater dissolved organic carbon (DOC), from a 160-lake calibration set from the Canadian Arctic. Historically sound and similar trends were reconstructed when compared against a Canadian diatom-based DOC and Swedish VNIRS-based total organic carbon (TOC) model on Arctic Holocene sediment records. Second, a diatom and spectroscopically-based multi-proxy approach was utilized on Holocene sedimentary records from two lakes on Pim Island to assess long-term environmental change from this region. Benthic and epiphytic diatom taxa dominated the pre-19th century assemblages, although marked shifts in dominant species were recorded during the mid-Holocene. The mid-Holocene diatom assemblages underwent an abrupt ecological shift from alkaliphilous Fragilaria sensu lato to slightly acidophilous Achnanthes and Navicula. The post-19th century was characterized by an increase in the planktonic species (Cyclotella radiosa), indicating marked lakeice reductions. Third, the limnological properties and modern diatom assemblages of ponds and lakes surveyed from 1979 to 2009 on Pim Island were examined as part of an exploratory study. The ponds and lakes displayed typical characteristics observed in high Arctic lacustrine environments (i.e. oligotrophic, very dilute) but with overall relatively low alkalinity. Poorly-buffered sites had diatom assemblages that were distinct from well-buffered lakes elsewhere in the High Arctic. Our findings contribute to an improved understanding of the interactions between local environments and limnological changes, and also provide insight on the biological responses of lakes to Holocene environmental change and allow us to compare responses to those in more alkaline sites. / Thesis (Master, Biology) -- Queen's University, 2010-12-22 19:53:45.03

L'UMR ITAP d'IRSTEA à Montpellier et la société Pellenc SA souhaitent développer un système de mesure par spectrométrie visible - proche infrarouge permettant d'évaluer la qualité des olives et d'en suivre la maturité. La mesure doit être effectuée sur une seule olive et de manière non destructive. Les critères de maturité retenus pour une première phase d'étude sont les teneurs en eau et en huile. L'objectif de ces travaux est d'optimiser la mesure des critères de maturité par spectrométrie portable, en s'adaptant aux contraintes induites par l'objet d'étude et en levant des verrous imposés par la technologie retenue. En lien avec les objectifs industriels, trois questions scientifiques ont été soulevées :QS1 : Comment obtenir les valeurs de référence des critères de maturité à partir d'une seule olive ?QS2 : Comment mesurer le spectre d'une olive ? Quelle configuration optique est la plus adaptée à l'objet mesuré ? Quel volume de l'olive est interrogé lors de la mesure spectrale ? Le noyau intervient-il dans cette mesure ?QS3 : Comment étalonner la mesure spectrale ? Les modèles de prédiction sont-ils robustes au regard d'une variété non incluse dans leur étalonnage ? Comment inclure la masse du noyau dans les valeurs prédites ?Afin de répondre à ces questions, des études expérimentales et comparatives ont été menées. Pour la détermination de la teneur en huile (QS1) deux méthodes ont été évaluée, la résonance magnétique nucléaire (RMN) et l'extraction à l'hexane, lorsqu'elles sont appliquées à la pulpe d'une olive unique. L'étude sur les différentes configurations optiques (QS2) a permis de mettre en évidence l'impact de chacune sur la mesure spectrale et ainsi déterminer si l'ensemble de ces configurations proposées (transmission, réflexion diffuse avec propagation guidée de la lumière au moyen d'une sphère, réflexion diffuse avec propagation libre de la lumière et rétrodiffusion) sont envisageables pour la mesure sur une seule olive. De plus, ces travaux se sont intéressés au volume de peau et de pulpe réellement interrogé lors de la mesure spectrale par une étude de la perte de lumière transmise à travers la peau et la pulpe. Le questionnement de l'étalonnage des mesures spectrales (QS3) a consisté en une analyse fine des modèles construits mais aussi en une étude de la robustesse et des différentes méthodes envisageables pour l'améliorer (sélection de longueurs d'onde, mise à jour des modèles, correction “biais-pente”, méthode DOP). Le dernier point traité par ces travaux de thèse est la prise en compte de la masse du noyau dans les valeurs prédites et l'évaluation des différentes méthodes pour réaliser cette correction.L'ensemble des résultats obtenus au cours de cette thèse ont servi à fournir des éléments pour guider la conception d'un outil portable de mesures par spectrométrie sur olives individuelles. / ITAP Research Unit of IRSTEA and Pellenc SA company want to developa visible - near infrared spectroscopy measurement system in order to assess the quality of olives and monitor their ripeness. The measurement has to be non-destructive and performed on a single olive. The ripeness criteria selected are water and oil content. The main objective of this work is to optimize the measurement of these criteria, recorded by a portable spectrometer, by taking into account the constraints linked to the studied object and by overcoming the obstacles imposed by the technology used. In relation to the industrial objectives, three scientific questions were raised :SQ1 : How to get the reference values of the ripeness criteria from a single olive ?SQ2 : How to measure the spectrum of one olive ? Which optical configuration isbest suited for an olive ? Which volume of the olive is actually analyzed during thespectral measurement ? Does the spectrum contain information about the kernel ?SQ3 : How to calibrate the spectral measurement ? Are the prediction models robustregarding a variety not used for the calibration step ? How to include the kernel mass in the predicted values ?In order to answer those questions, experimental and comparative studies have been led. As the determination of water content is easily transposable to a single olive, only the measurement of oil content is studied (SQ1). Two existing methods nuclear magnetic resonance and hexane extraction have been characterized end evaluated when they are applied to the pulp of a single olive.The comparative study conducted on different optical configurations(SQ2) has high-lighted the impact of each configuration (transmission, diffuse reflectance with guidedpropagation of light through a sphere, diffuse reflectance with free propagation of light and interactance) on the spectral measurement. This study has also determined if all of these configurations are suitable for the whole olive measurements. Furthermore, the real volume analyzed during the spectral measurement has been investigated by studying the loss of transmitted light through the skin and the pulp.In order to answer SQ3, the present work provides optimized models for prediction ofwater content on the one hand and oil content on the other hand. The robustness study leads us to consider different methods (Model Update, Biais and Slope, DOP, wavelength selection) depending on the correction set used and therefore the finality of the future device. Concerning the introduction of kernel mass in predicted values, it has be done using various methods which are more or less destructive. The choice of one of these methods has been be determined by the technical possibilities of the device and the minimum expected accuracy of water and oil content predictions.Therefore, the results of this thesis provide some elements to guide the development of a portable spectrometer for measurements on individual olive fruits.

Avec l'objectif de réduire de la quantité de gaz à effets de serre dans l'atmosphère, les pouvoirs publics encouragent les pratiques ayant vocation à séquestrer du carbone dans les sols (reforestation, changement de pratiques agricoles). Pour en évaluer les réels bénéfices, des outils analytiques rapides, précis et peu coûteux sont nécessaires pour pouvoir comptabiliser précisément les stocks de carbone et leur évolution dans le temps. La Spectroscopie proche infrarouge (SPIR) est une technologie analytique adaptée à ce cahier des charges mais relève encore du domaine de la recherche en science du sol.Cette thèse s'est focalisée sur la première étape de cette méthode analytique: la formation du signal. Les sols étant des milieux très complexes, en termes de composition chimique et de structure physique, le signal spectroscopique est négativement impacté par les phénomènes de diffusion. Les conditions de la loi de Beer-Lambert n'étant plus remplies, les modèles chimiométriques pour prédire la teneur en carbone des sols sont moins précis et robustes. Nous proposons un système optique de mesure spectrale original et adapté aux milieux très diffusants, qui se base sur le principe de polarisation de la lumière. Il permet de sélectionner les photons ayant été moins impactés par le phénomène de diffusion. Ce signal est utilisé pour calculer un signal d'absorbance étant une bonne approximation de l'absorbance de Beer-Lambert.Ce dispositif, appelé PoLiS, a été validée expérimentalement sur des milieux modèles liquides et particulaires. Appliquée des sols pour prédire la teneur en carbone organique, les modèles de prédictions sont meilleurs avec l'absorbance calculée par PoLiS qu'avec l'absorbance calculée classiquement à partir de la mesure de réflectance. / With the goal of reducing the amount of greenhouse gases in the atmosphere, policy makers encourage practices intended to sequester carbon in soils (reforestation, changes in farming practices). New methods are required to rapidly and accurately measure soil C at field- and landscape-scales. Near infrared spectroscopy (NIRS) is an analytical technology adapted to these specifications but remains experimental research in soil science.This thesis has focused on the first step of this analytical method: signal formation. The soils are very complex materials, in terms of chemical composition and physical structure. Hence, the spectroscopic signal is negatively impacted by light scattering. Consequently, the conditions of the Beer-Lambert are no longer fulfilled, and the chemometric models to predict the carbon content of soils are less accurate and robust. We develop an original optical method based on light polarization spectroscopy to measure the absorbance of highly scattering materials. By selecting photons being less scattered, we compute a new absorbance signal which is a good approximation of the Beer-Lambert absorbance.This method, called Polis, was experimentally validated on model materials in liquid and powdered form. Applied on soils to predict Total Organic Content, the model built with the PoLiS absorbance outperform the models built with the classical absorbance computed from the diffuse reflectance signal.

Natural archives such as lake sediments allow us to assess contemporary ecosystem responses to climate and environmental changes in a long-term context beyond the few decades to at most few centuries covered by monitoring or historical data. To achieve a comprehensive view of the changes preserved in sediment records, multi-proxy studies – ideally in high resolution – are necessary. However, this combination of including a range of analyses and high resolution constrains the amount of material available for analyses and increases the analytical costs. Infrared spectroscopic methods are a cost-efficient alternative to conventional methods because they offer a) a simple sample pre-treatment, b) a rapid measurement time, c) the non- or minimal consumption of sample material, and d) the potential to extract quantitative and qualitative information about organic and inorganic sediment components from a single measurement. The main objective of this doctoral thesis was twofold. The first part was to further explore the potential of Fourier transform infrared (FTIR) and visible-near infrared (VNIR) spectroscopy in paleolimnological studies as a) an alternative tool to conventional methods for quantifying biogenic silica (bSi) – a common proxy of paleoproductivity in lakes – in sediments and b) as a tool to infer past lake-water total organic carbon (TOC) levels from sediments. In a methodological study, I developed an independent application of FTIR spectroscopy and PLS modeling for determining bSi in sediments by using synthetic sediment mixtures with known bSi content. In contrast to previous models, this model is independent from conventional wet-chemical techniques, which had thus far been used as the calibration reference, and their inherent measurement uncertainties. The second part of the research was to apply these techniques as part of three multi-proxy studies aiming to a) improve our understanding of long-term element cycling in boreal and arctic landscapes in response to climatic and environmental changes, and b) to assess ongoing changes, particularly in lake-water TOC, on a centennial to millennial time scale. In the first applied study, high-resolution FTIR measurements of the 318-m long sediment record of Lake El’gygytgyn provided a detailed insight into long-term climate variability in the Siberian Arctic over the past 3.6 million years. Highest bSi accumulation occurred during the warm middle Pliocene (3.6-3.3 Ma), followed by a gradual but variable decline, which reflects the first onset of glacial periods and then the finally full establishment of glacial–interglacial cycles during the Quaternary. The second applied study investigated the sediment record of Torneträsk in subarctic northern Sweden also in relation to climate change, but only over the recent post-glacial period (~10 ka). By comparing responses to past climatic and environmental forcings that were recorded in this large-lake system with those recorded in small lakes from its catchment, I determined the significance and magnitude of larger-scale changes across the study region. Three different types of response were identified over the Holocene: i) a gradual response to the early landscape development following deglaciation (~10000-5300 cal yr BP); ii) an abrupt but delayed response following climate cooling during the late Holocene, which occurred c. 1300 cal yr BP – about 1000-2000 years later than in smaller lakes from the area; and iii) an immediate response to the ongoing climate change during the past century. The rapid, recent response in a previously rather insensitive lake-ecosystem emphasizes the unprecedented scale of ongoing climate change in northern Fennoscandia. In the third applied study, VNIR-inferred lake-water TOC concentrations from lakes across central Sweden showed that the ongoing, observed increase in surface water TOC in this region was in fact preceded by a long-term decline beginning already AD 1450-1600. These dynamics coincided with early human land use activities in the form of widespread summer forest grazing and farming that ceased over the past century. The results of this study show the strong impact of past human activities on past as well as ongoing TOC levels in surface waters, which has thus far been underestimated. The research in this thesis demonstrates that infrared spectroscopic methods can be an essential component in high-resolution, multi-proxy studies of past environmental and climate changes.

<p>The natural chemical and physical variations that occur within volcanic rocks (petrology) provide critical insights into mantle and crust conditions on terrestrial bodies. Visible/near-infrared (VNIR; 0.3-2.5 µm) and thermal infrared (TIR; 5-50 µm) spectroscopy are the main tools available to remotely characterize these materials from satellites in orbit. However, the accuracy of petrologic information that can be gained from spectra when rocks exhibit complex variations in mineralogy, crystallinity, microtexture, and oxidation state occurring together in natural settings is not well constrained. Here, we compare the spectra of a suite of volcanic planetary analog rocks from the Three Sisters, OR to their mineralogy, chemistry, and microtexture from X-ray diffraction, X-ray fluorescence, and electron microprobe analysis. Our results indicate that TIR spectroscopy is an effective petrologic tool in such rocks for modeling bulk mineralogy, crystallinity, and mineral chemistry. Given a library with appropriate glass endmembers, TIR modeling can derive glass abundance with similar accuracy as other major mineral groups and provide first-order estimates of glass wt.% SiO2 in glass-rich samples, but cannot effectively detect variations in microtexture and minor oxide minerals. In contrast, VNIR spectra often yield non-unique mineralogic interpretations due to overlapping absorption bands from olivine, glass, and Fe-bearing plagioclase. In addition, we find that sub-micron oxides hosted in transparent matrix material that are common in fine-grained extrusive rocks can lower albedo and partially to fully suppress mafic absorption bands, leading to very different VNIR spectra in rocks with the same mineralogy and chemistry. Mineralogical interpretations from VNIR spectra should not be treated as rigorous petrologic indicators, but can supplement TIR-based petrology by providing unique constraints on oxide minerals, microtexture, and alteration processes.</p>