Gotowa bibliografia na temat „Dykes – Teneur en lithium”

Lithium (Li) has grown to be a strategic key metal due to the enormous demand for the development of new energy industries over the world. As one of the most significant sources of Li resources, pegmatite-type Li deposits hold a large share of the mining market. In recent years, several large and super-large spodumene (Spd)-rich pegmatite deposits have been discovered successively in the Hoh-Xil–Songpan-Garzê (HXSG) orogenic belt of the northern Tibetan Plateau, indicative of the great Li prospecting potential of this belt. Hyperspectral remote sensing (HRS), as a rapidly developing exploration technology, is especially sensitive to the identification of alteration minerals, and has made important breakthroughs in porphyry copper deposit exploration. However, due to the small width of the pegmatite dykes and the lack of typical alteration zones, the ability of HRS in the exploration of Li-rich pegmatite deposits remains to be explored. In this study, Li-rich pegmatite anomalies were directly extracted from ZY1-02D hyperspectral imagery in the Zhawulong (ZWL) area of western Sichuan, China, using target detection techniques including Adaptive Cosine Estimator (ACE), Constrained Energy Minimization (CEM), Spectral Angle Mapper (SAM), and SAM with BandMax (SAMBM). Further, the Li-rich anomalies were superimposed with the distribution of pegmatite dykes delineated based on GF-2 high-resolution imagery. Our final results accurately identified the known range of Spd pegmatite dykes and further predicted two new exploration target areas. The approaches used in this study could be easily extended to other potential mineralization areas to discover new rare metal pegmatite deposits on the Tibetan Plateau.

AbstractThe rare Li-mica taeniolite is described from the Dicker Willem carbonatite complex, Namibia, and from the Alpine carbonatitic lamprophyre dyke swarm at Haast River, New Zealand. At Haast River, taeniolite occurs in sodic and ultrasodic fenites derived from quartzo-feldspathic schists and rarely in metabasites, adjacent to dykes of tinguaite, trachyte and a spectrum of carbonatites ranging from Ca- to Fe- rich types. In Namibia, taeniolite is present in potassic fenites derived from quartz-feldspathic gneisses and granitoids at the margin of an early sövite phase of the complex and in a radial sövite dyke emanating from this centre.The occurrence of taeniolite in these totally disparate carbonatite complexes, together with examples of lithian mica from other carbonatite complexes worldwide, raises the question of the status of Li as a ‘carbonatitic element’. We argue that lithium is not a consequence of crustal assimilation or interaction, but reflects the geochemical character of the magmatic source. Li, an overlooked and little-analysed element, may be an integral part of metasomatic enrichment in the mantle, and of magmas derived by partial melting of such a source.

<p style="text-align: justify;">Lors d'une enquête lancée par la Direction Générale de la Concurrence, de la Consommation et de la Répression des Fraudes en 1991, pour une meilleure connaissance de la teneur en plomb des vins français, la section « éléments minéraux » du Laboratoire de Bordeaux a effectué, sur les soixante-dix échantillons reçus, la détermination de onze éléments minéraux : le fer, le cuivre, le manganèse, le zinc, le plomb, le cadmium, le mercure, le lithium, le rubidium, le fluor et l'arsenic. Ces vins provenaient des régions viticoles du SudOuest et du Val de Loire et comprenaient 38 vins blancs et 32 vins rouges et rosés; pour la grande majorité d'entre eux, il s'agissait de vins d'Appellation d'Origine Contrôlée.</p>

<p style="text-align: justify;">Les profondes différences qui existent entre les trois régions de l'Appellation d'Origine Rioja quant au climat, au sol, au cépage cultivé, et/ou au système d'élaboration, sont la cause d'importantes différences analytiques que l'on retrouve dans les divers genres de vins rouges produits. Ces différences s'expriment non seulement dans les paramètres oenologiques classiques comme le degré alcoolique, l'acidité totale ou le pH, mais aussi dans les composantes minoritaires comme les ions métalliques, et plus particulièrement le potassium. L'étude des oligo-éléments comme le lithium, le rubidium et le manganèse a mis en évidence une fois de plus les différences existantes et a permis la différenciation géographique des vins de la Rioja Alavesa de la Rioja Alta et Baja sur la base de leur teneur en lithium et en manganèse.</p><p style="text-align: justify;">+++</p><p style="text-align: justify;">The basic differences existing between the three regions of the Denomination of Origin « Rioja » in terms of climate, soil and grapewine cultivar variety and/or the wine making process are the causes of the important analytical differences which we find between the different types of red wine obtained not only in the oenological variables like alcoholic grade, total acidity or pH, but in minor components such as metalic ions, and most particulary potassium. The study of oligo-elements like lithium, rubidium and manganese has once again shown the existing differences and has enabled to geographically differenciate the wines allowed the geographie differences or the wines form Rioja Alavesa, Rioja Alta and Rioja Baja on the basis of their contents in lithium and manganese.</p>

Near the Segura pluton, hyper-differentiated magmas enriched in F, P, and Li migrated through shallowly dipping fractures, which were sub-perpendicular to the schistosity of the host Neoproterozoic to Lower Cambrian metasedimentary series, to form two swarms of low-plunging aplite–pegmatite dykes. The high enrichment factors for the fluxing elements (F, P, and Li) compared with peraluminous granites are of the order of 1.5 to 5 and are a consequence of the extraction of low-viscosity magma from the crystallising melt. With magmatic differentiation, increased P and Li activity yielded the crystallisation of the primary amblygonite–montebrasite series and Fe-Mn phosphates. The high activity of sodium during the formation of the albite–topaz assemblage in pegmatites led to the replacement of the primary phosphates by lacroixite. The influx of external, post-magmatic, and Ca-Sr-rich hydrothermal fluids replaced the initial Li-Na phosphates with phosphates of the goyazite–crandallite series and was followed by apatite formation. Dyke emplacement in metasediments took place nearby the main injection site of the muscovite granite, which plausibly occurred during a late major compression event.

The mineralogical studies of rare-element (REL) pegmatites are important for unraveling the ore-forming process and evaluating REL mineralization potential. The Chinese Altai orogenic belt hosting more than 100,000 pegmatite dykes is famous for rare-metal resources worldwide and diverse REL mineralization types. In this paper, we present the results of EMPA and LA-ICP-MS for muscovite from the typical REL pegmatite dykes of the Chinese Altai. The studied pegmatites are Li-Be-Nb-Ta, Li-Nb-Ta, Nb-Ta, Be-Nb-Ta, Be and barren pegmatites. The Li+ accompanied with Fe, Mg and Mn substitute for Al3+ at the octahedral site in muscovite from the REL pegmatites, and the substitution of Rb by Cs at the interlayer space is identified in muscovite from the Be pegmatites. The P and B contents increase with evolution degree and the lenses from the Nb-Ta pegmatite are produced at late fluid-rich stage with high fluxes (P and B). The enrichment of HFSE in muscovite indicates a Nb-Ta-Sn-W rich pegmatite magma for the Be-Nb-Ta pegmatite. From barren pegmatite, beryl-bearing zone, to spodumene-bearing zone, the evolution degrees of pegmatite-forming magmas progressively increase. In the Chinese Altai, the possible indicators of muscovite for REL mineralization types include Rb (ca. 400–600 ppm, barren pegmatite; ca. 1200–4000 ppm, Be pegmatite; >4500 ppm, Li pegmatite), Cs (ca. 5–50 ppm, barren pegmatite; ca. 100–500 ppm, Be pegmatite; >300 ppm, Li pegmatite) and Ge (<3 ppm, barren pegmatite; ca. 4–6 ppm, Be pegmatite; ca. 6–12 ppm, Li pegmatite) coupled with Ta, Be (both <10 ppm, barren pegmatite) and FeO (ca. 3–4 wt%, Be pegmatite; ca. 1–2.5 wt%, Li pegmatite). The plots of Nb/Ta vs. Cs and K/Rb vs. Ge are proposed to discriminate barren, Be- and Nb-Ta-(Li-Be-Rb-Cs) pegmatites. The Li, Be, Rb, Cs and F concentrations of forming liquid are evaluated based on the trace element compositions of muscovite. The high Rb and Cs contents of liquid and lower Be contents than beryl saturation value indicate that both highly evolved pegmatite magma and low temperature at emplacement contribute to beryl formation. The liquids saturated with spodumene have large variations of Li, possibly related to metastable state at Li unsaturation–supersaturation or heterogeneous distribution of lithium in the system.

In this paper we present textural and compositional data for columbite group minerals (CGMs) and associated Nb-Ta-Sn oxides from lithium-beryllium-tantalum pegmatite deposits of the Kolmozero–Voronja belt, NW Russia, with the aim of deciphering these characteristics for minerals from deposits with different mineral signatures and lithium ore grade. Minerals from four deposits, including two of world-class (Kolmozero and Polmostundra), are examined. The main controlling factors for CGM compositional ranges are the diversity and rate of magmatic fractionation, hydrothermal overprint and mineral paragenesis, following the specific geochemical signature of the different pegmatite deposits. CGM from Kolmozero include several mineral species (columbite-(Fe), columbite-(Mn), tantalite-(Fe), and tantalite-(Mn)), showing large compositional variations, mainly controlled by Nb-Ta fractionation (Ta/(Ta + Nb) = 0.16–0.70; Mn/(Mn + Fe) = 0.45–0.63). Textural patterns are various (oscillatory, homogeneous, and patchy); spongy domains and overgrowing Ta-rich rims are also observed somewhere. This indicates the involvement of numerous magmatic and hydrothermal processes. The Polmostundra CGMs are represented by columbite-(Fe) with Ta/(Ta + Nb), ranging from 0.05 to 0.39; some crystals are homogenous, and others present normal, oscillatory, mottled and reverse-zoning patterns. The Okhmylk CGMs are irregular normal, patchy and homogeneous columbite-(Fe) and columbite-(Mn), with Ta/(Ta + Nb) = 0.09–0.24 and Mn/(Mn + Fe) = 0.29–0.92, indicating the suppressed magmatic fractionation and iron drop due to precipitation of Fe minerals. Columbite-(Fe) and columbite-(Mn) from the Be-Ta Shongui deposit are less evolved, with Ta/(Ta + Nb) = 0.07–0.23 and Mn/(Mn + Fe) = 0.31–0.55. The minerals are characterized by progressive normal, oscillatory, homogeneous and irregular reverse patterns. Associated pyrochlore minerals occur both as early magmatic (Kolmozero) and late hydrothermal (Polmostundra, Okhmylk). Cassiterite is found only in the Okhmylk dykes, and is apparently of hydrothermal origin. CGM from Li pegmatites have impurities of Ti (0.01–0.05 apfu) and W (up to 0.02 apfu), whereas CGM from Be pegmatites contains elevated Ti (up to 0.09 apfu). The mineral system analysis presented here is relevant for exploration.

AbstractLithium mineralization is common in the Central Iberian Zone and, to a lesser extent, in the Galizia-Trás-OsMontes Zone of Spain and Portugal, occurring along a ∼500 km-long NNW-SSE striking belt. There are different styles of Li mineralization along this belt; they are mainly associated with aplite-pegmatite bodies and, to a much lesser extent, with veins of quartz and phosphate. Lithium mineralization in the Central Iberian Zone may be classified into four types: aplite-pegmatite dykes occurring in pegmatitic fields, Li mineralization associated with leucogranitic cupolas, beryl-phosphate pegmatites and quartz-montebrasite veins. The main Li minerals of these bodies include Li-mica, spodumene and/or petalite in the pegmatitic fields and leucogranitic cupolas; triphylite–lithiophilite in the beryl-phosphate pegmatites, and amblygonite–montebrasite in the quartz-montebrasite veins. The origin of these different styles of mineralization is considered to be related to differentiation of peraluminous melts, which were generated by partial melting of metasedimentary rocks during the Variscan orogeny. On the basis of paragenesis and chemical composition, the pegmatitic fields and Li mineralization associated with granitic cupolas record the highest fractionation levels, whereas the beryl-phosphate pegmatites and quartz-montebrasite veins show lower degrees of fractionation. There are a number of textural and mineralogical indicators for Li exploration in the Central Iberian Zone and in the Galizia-Trás-Os-Montes Zone, with the highest economic potential for Li being in the pegmatite fields.

The role of the environment in the survivability of an animal is paramount and blood profiles are part of the indices for measuring the health status. Therefore, a study was carried out to determine the blood profile of prominent indigenous breed of sheep (Ram) viz: West African Dwarf, Yankasa, Balami and Ouda breeds reared in Ikorodu Local Government. A total of 20 rams were used comprising of five rams per breed, with average age of 2½ years weighing 31.13±4.8 kg. Blood samples were carefully collected from the rams into labeled sterile bottles containing EDTA for haematological examination and another set of bottles containing Lithium Heparin was used to collect blood for the serum biochemical analysis. Haematological parameter assessed were Packed Cell Volume (PCV), White Blood Cell (WBC), Red Blood Cell (RBC), while the biochemical parameters investigated were Total protein (Tp), Albumin, Glucose, Creatine Cholesterol, and Alkaline phosphatase (ALP). PCV was significantly (p<0.05) highest (32.25%) in Yankassa and lowest (26.25%) in Ouda. Yankasa had statistically (p<0.05) the higher 11.66g/dL Hb, followed by WAD (10.00), Ouda (9.60) and lower (9.20) in Balami. RBC (x10/ml) was significantly (p<0.05) higher in WAD (3.72) than other breeds and lowest in Ouda (3.11). MCV (fl) value was significantly lower in Yankasa (75.83) than other breeds and higher in Ouda (83.60). MCH (pg) was statistically (p<0.05) highest (30.89) in Yankasa and lower (26.93) in Balami. Yankasa had significantly(p<0.05) the higher (8673.00) Total WBC (mm3), followed by WAD (8453.25), Balami (6814.25) and least in Ouda (6718.75). Total protein was significantly (p<0.05) the higher (53.76) in WAD ram and lower (43.76) in Ouda. Yankasa ram recorded significantly (p<0.05) the higher Albumin content (5.45), glucose level (48.87), ALP (129.71) and significantly the least creatine (0.63) while significantly (p<0.05) the least values for Glucose were in Ouda (44.83), Albumin content and Alkaline phosphatase in Balami (4.33, 104.87 respectively). Cholesterol value was significantly the higher (93.22) in WAD and lower (79.70) in Balami. Results revealed significant differences in haematological and serological indices tested though all values obtained were within the normal range for sheep. Le rôle de l'environnement dans la survie d'un animal est primordial et les profils sanguins font partie des indices de mesure de l'état de santé. Par conséquent, une étude a été menée pour déterminer le profil sanguin de la race indigène de moutons (bélier), à savoir: les moutons nains d'Afrique de l'Ouest (WAD), Yankasa, Balami et Ouda élevés dans la collectivité locale d'Ikorodu. Au total, 20 béliers ont été utilisés comprenant cinq béliers par race, avec un âge moyen de 2 ans et demi pesant 31,13 ± 4,8 kg. Des échantillons de sang ont été soigneusement prélevés sur les béliers dans des flacons stériles étiquetés contenant de l'EDTA pour un examen hématologique et un autre ensemble de flacons contenant de l'héparine de lithium a été utilisé pour collecter du sang pour l'analyse biochimique du sérum. Les paramètres hématologiques évalués étaient le volume de cellules emballées (PCV), les globules blancs (WBC), les globules rouges (RBC), tandis que les paramètres biochimiques étudiés étaient la protéine totale (Tp), l'albumine, le glucose, la créatine cholestérol et la phosphatase alcaline (ALP). Le PCV était significativement (p <0,05) le plus élevé (32,25%) à Yankassa et le plus bas (26,25%) à Ouda. Yankasa avait statistiquement (p <0,05) le taux d'Hb le plus élevé de 11,66 g / dL, suivi de WAD (10,00), Ouda (9,60) et moins (9,20) à Balami. Les globules rouges (x10 / ml) étaient significativement (p <0,05) plus élevés chez WAD (3,72) que chez les autres races et plus faibles chez Ouda (3,11). La valeur MCV (fl) était significativement plus faible à Yankasa (75,83) que dans les autres races et plus élevée à Ouda (83,60). MCH (pg) était statistiquement (p <0,05) la plus élevée (30,89) à Yankasa et inférieure (26,93) à Balami. Yankasa avait significativement (p <0,05) le plus élevé (8673,00) WBC total (mm3), suivi des moutons nains d'Afrique de l'Ouest, (8453,25), Balami (6814,25) et inférieur à Ouda (6718,75). La protéine totale était significativement (p <0,05) la plus élevée (53,76) chez les moutons nains d'Afrique de l'Ouest, et la plus faible (43,76) chez Ouda. Le bélier Yankasa a enregistré de manière significative (p <0,05) la plus haute teneur en albumine (5,45), le niveau de glucose (48,87), l'ALP (129,71) et significativement le moins de créatine (0,63) tandis que de manière significative (p <0,05) les valeurs les plus faibles pour le glucose étaient à Ouda (44,83), teneur en albumine et phosphatase alcaline chez Balami (4,33, 104,87 respectivement). La valeur du cholestérol était significativement la plus élevée (93,22) chez les moutons nains d'Afrique de l'Ouest et la plus basse (79,70) chez Balami. Les résultats ont révélé des différences significatives dans les indices hématologiques et sérologiques testés bien que toutes les valeurs obtenues se situent dans la plage normale pour les moutons.

Abstract Ophiolites and high-pressure/low-temperature (HP–LT) terranes are important sites for the study of geochemical cycling in ancient oceanic lithosphere. We have analysed Li abundances and isotope composition in a series of ultrabasic and basic rocks from the Variscan Limousin ophiolite, as well as in basic and pelitic rocks from the Ile de Groix HP–LT terrane. Both bulk and in situ analyses are employed to evaluate Li mobility and isotope fractionation in the oceanic lithosphere during fluid–rock interactions related to seafloor and sub-seafloor hydrothermal alteration, subduction and exhumation processes. In the Limousin ophiolite, early stages of high-temperature (high-T) hydrothermal alteration of oceanic ultrabasic rocks produced serpentine with low Li abundances (0·9–4·6 ppm) and low δ7Li (–8·9‰). The δ7Li increase from –2·2 to +4·2‰ in the following generations of serpentine during late-stage hydrothermal alteration results from changes in the fluid composition and temperature conditions. Therefore, even if dehydrating subducted serpentinites generate high amounts of fluids during subduction, abyssal serpentinites do not constitute an important source of Li for Li-rich metabasic rocks. In the associated amphibolites, hornblende displays typical Li contents (3·1–8·2 ppm) and isotopic compositions (+3·5 to +12·5‰) similar to hydrothermally altered sheeted dykes and gabbros. In contrast, the low Li abundances and extremely high δ7Li values recorded by omphacite and pargasitic amphibole in the ultrahigh-pressure (UHP) zoisite-eclogite from the Limousin probably reflect interaction with a heavy-Li sediment-derived fluid. The HP–LT metabasites of the Ile de Groix record different Li behaviour, with high Li abundances and low δ7Li. They contain Li abundances significantly higher than fresh mid-ocean ridge basalts (MORB) (16–124 ppm), indicating a metasomatic overprint by fluids derived from the neighbouring Li-rich mica-schist (15–52 ppm) in addition to seawater during the early stages of subduction. Lithium is mainly hosted by (1) glaucophane and omphacite in blueschists and eclogites, (2) chlorite and albite in retrograde greenschists, and (3) phengite and chlorite in mica-schists. The metabasites have δ7Li values of –4·8 to +3·2‰ that are generally lower than those of fresh and altered MORB. The intercalated mica-schists display δ7Li values ranging from –1·7 to +0·2‰ that are typical of subducted sediments. The δ7Li decrease from blueschists to eclogites from +1·8 to –4·8‰, as well as the rimward δ7Li decrease in glaucophane from MORB-like δ7Li values to negative values in blueschists (core: –2·4 to +8·8‰; rims: –7·1 to +2·2‰), reveals that significant fluid-induced Li isotope fractionation occurred at the transition from the lawsonite-blueschist facies to the epidote-blueschist facies, and may be triggered by prograde lawsonite breakdown. In eclogites, the low δ7Li measured in whole-rocks (–4·8 to –2·5‰), omphacite (–22·4 to +3·3‰) and glaucophane (–6·9 to +1·4‰) indicates that Li isotope kinetic fractionation had stronger effects under eclogite-facies conditions. The δ7Li increase toward positive values in the most retrogressed greenschist samples suggests Li mineral–fluid isotopic exchange during rehydration reactions and interaction with a Li-heavy fluid that is probably derived from the dehydrating metabasites. Thus, lithium isotope fractionation in the HP–LT rocks of the Ile de Groix highlights migration of heavy-Li fluids along the oceanic crust–mantle interface in the subduction zone.

La région de Bougouni a pour spécificité la présence de pegmatites et d'aplites porteuses de lithium. Le lithium est actuellement un élément stratégique au regard des besoins croissants en cette matière première. Les pegmatites lithinifères font ainsi partie des gisements les plus recherchés pour le lithium.La zone d'étude, située au SE de Bamako (Mali), appartient à la partie sud du craton ouest africain. Les différentes roches de cette zone se sont formées au cours des événements de croissance crustale du Birimien, lors de l'orogenèse éburnéenne, entre ca. 2200 et 1800 Ma. Les formations rencontrées sont des roches métavolcanosédimentaires et plutoniques majoritairement de nature granitoïdique (tonalite à monzogranite à deux micas), structurées dans une direction NNE-SSW par l'existence de grandes zones de cisaillement. Les dykes sont intrusifs dans ces roches encaissantes sous forme de filons d'épaisseur décimétrique à décamétrique depuis des faciès aplitiques à des faciès pegmatitiques. La mise ne place dans un domaine cassant couplé au bas grade métamorphique des métasédiments encaissants indiquent une mise en place des dykes au niveau de la croûte continentale supérieure.La province de Bougouni compte une centaine de dykes riches en lithium (Li2O > 1.00 wt% de la roche totale). Le spodumène, principal phase minérale porteuse de lithium (Li2O = 8 wt%), représente entre 5 et 30 vol.% de la roche, accompagné de feldspath alcalin, plagioclase, quartz et d'une faible quantité de muscovite et de biotite. Sont également présents une centaine de dykes pauvres en lithium (Li2O < 0.05 wt%) caractérisés par le même assemblage minéralogique que les dykes riches en lithium à l'exception du spodumène remplacé par le grenat.Concernant la géochronologie, les âges U-Pb sur zircons pour l'ensemble des granitoïdes (faciès granodioritiques à granitiques à deux micas) s'étendent entre 2100 ± 14 et 2136 ± 19 Ma. Ces âges sont en accord avec les âges d'autres formations plutoniques s'étalant entre 2080 et 2120 Ma à l'échelle du Birimien. Les âges U-Pb sur apatites magmatiques des dykes sont compris entre 2070 - 2000 Ma. La comparaison des données géochronologique à d'autres pegmatites du Birimien permettent de définir la période ca. 2070 - 2000 Ma comme la période de mise en place des dykes pegmatitiques (notamment les pegmatites de la famille LCT) du Birimien. Cette période tardi- à post orogénique représenterait l'étape finale du magmatisme paléoprotérozoïque dans le domaine du Baoulé-Mossi.Concernant la géochimie en éléments majeurs et traces, l'absence d'une évolution géochimique continue depuis les granitoïdes aux dykes ne permettent pas d'expliquer les liquides pegmatitiques comme étant les termes les plus évolués des granitoïdes. Cette conclusion est en accord avec les données géochronologiques qui témoignent d'une différence d'âge beaucoup trop importantes entre ces formations pour qu'elles puissent avoir un lien génétique. Concernant les dykes, bien qu'ils soient contemporains, les différences en termes de signature géochimique ne permettent pas d'expliquer qu'ils puissent avoir évolués depuis un seul et même liquide parent. Cependant, il est fort probable que les liquides à l'origine des deux types de dykes puissent provenir de la fusion du même type de protolithe de nature métapélitique.En somme, les données de terrain, pétrographiques, géochronologiques et géochimiques ne donnent pas de lien génétique entre les dykes et les granitoïdes de Bougouni. Les deux faciès de dykes sont formés à partir de deux liquides distincts issus d'un seul et même protolithe. La différence de composition minéralogique et géochimique, notamment en Li, entre les dykes riches en lithium et ceux pauvres en lithium pourrait être expliquée par le rôle de fluides d'origine sédimentaire ayant pu percoler et interagir avec les roches mères et/ou les liquides pegmatitiques permettant d'enrichir certains liquides en éléments mobiles, tel que le lithium
The Bougouni region in southern Mali is well known for the ore body lithium-bearing pegmatites and aplites. Lithium is currently a strategic element in view of the growing need for this raw material. The lithiniferous pegmatites are thus among the most sought-after deposits for lithium.The study area, located SE of Bamako (Mali), belongs to the southern part of the West African Craton. The various rocks in this area were formed during the Birimian crustal growth events, during the Eburnean oOrogeny, between ca. 2200 and 1800 Ma. The formations encountered are metavolcano sedimentary and plutonic rocks, mostly granitoid (tonalite to two-mica monzogranite), structured in a NNE-SSW direction by the existence of large shear zones. The dykes are intrusive in these host rocks, which occur in the form of decimeter to decameter thick dykes ranging from aplitic to pegmatitic facies. The emplacement in a brittle domain coupled with the low metamorphic grade of the enclosing metasediments indicate a dyke emplacement in the upper continental crust.The Bougouni province has about 100 Li-rich dykes (Li2O > 1.00 wt% of total rock). Spodumene, the main lithium-bearing mineral phase (Li2O = 8 wt%), represents between 5 and 30 vol.% of the rock, accompanied by alkali feldspar, plagioclase, quartz and a small quantity of muscovite and biotite. In addition to, 100 Li-poor dykes (Li2O < 0.05 wt%) that are characterized by the same mineralogical assemblage as the lithium-rich dykes except for spodumene, which is replaced by garnet.Concerning geochronology, U-Pb ages on zircons for all granitoids (granodioritic to granitic facies with two micas) range between 2100 ± 14 and 2136 ± 19 Ma. These ages are in agreement with the ages of other plutonic formations ranging between 2080 and 2120 Ma on the Birimian scale. The U-Pb ages on magmatic apatites of the dykes are between 2070 - 2000 Ma. Comparison of the geochronological data with other pegmatites of the Birimian allow us to define the period ca. 2070 - 2000 Ma as the period of establishment of the pegmatitic dykes (notably the LCT family pegmatites) of the Birimian. This late- to post-Orogenic period would represent the final stage of paleoproterozoic magmatism in the Boulé-Mossi domain.Concerning major and trace elements geochemistry, the absence of a continuous geochemical evolution from granitoids to dykes does not allow to explain the pegmatitic fluids as the most evolved terms of the granitoids. This conclusion is in agreement with the geochronological data that show a much too large age difference between these formations to be genetically related. Concerning the dykes, although they are contemporaneous, the differences in geochemical signature do not allow to explain that they could have evolved from a single parent melt. However, it is very likely that the melts that gave rise to both types of dykes may have been derived from the melting of the same type of metapelitic protolith.In sum, the field, petrographic, geochronological and geochemical data do not provide a genetic link between the Bougouni dykes and granitoids. The two dyke facies are formed from two distinct melts derived from a single protolith. The difference in mineralogical and geochemical composition, particularly in Li, between the Li-rich and Li-poor dykes could be explained by the role of fluids of sedimentary origin that may have percolated and interacted with the source? host rocks and/or the pegmatitic melts, allowing the enrichment of certain fluids in mobile elements such as lithium

La transition énergétique est associée à l'utilisation croissante d'un large éventail de métaux, en particulier ceux nécessaires à la fabrication de batteries lithium-ion (ex : lithium, cobalt), tandis que des besoins constants en métaux de base perdurent (ex : cuivre, zinc). Le développement de ressources alternatives en métaux telles que les « minerais liquides », notamment les eaux de formation des aquifères des bassins sédimentaires, pourrait contribuer à répondre à la demande mondiale. Cependant, les processus géochimiques impliqués dans l'enrichissement en métaux dans ces eaux demeurent mal connus et la démarche suivante a été en conséquence poursuivie dans ce travail : • Établissement d'une base de données des températures et compositions chimiques et isotopiques pour des eaux de formation (3700 analyses) et des inclusions fluides ayant préservé des eaux de formation anciennes (1700 analyses) de 90 bassins sédimentaires du monde entier, à partir de sources publiées. L'objectif est de mettre en évidence les gammes de concentrations caractéristiques de métaux dissous dans les eaux de formation, ainsi que les paramètres qui contrôlent leur concentration. • Application au cas d'étude du graben du Rhin, sur l'exemple du système géothermique de Soultz-sous-Forêts, à travers l'analyse des métaux dans des inclusions fluides et les minéraux du bassin et du socle cristallin. Le but est d'établir un bilan des transferts en métaux liés aux interactions fluide-roche de l'Oligocène à l'Actuel. Les résultats indiquent que les eaux de formation acquièrent généralement leur charge en métaux les plus abondants (Li, Mn, Pb, Zn, Fe, Ba, Cu) principalement suite à des interactions fluide-roche, l'augmentation de la température et de la salinité facilitant leur solubilisation. Dans le cas particulier du lithium, les eaux de formation les plus riches sont le plus souvent des saumures dérivées de l'eau de mer et enrichies en sels et partiellement en lithium par évaporation en surface, et par la suite expulsées des formations évaporitiques dans lesquelles elles sont piégées initialement, lors d'évènements tectoniques. La préservation de toute dilution par des fluides de recharge, et l'interaction avec des lithologies enrichies en lithium (roches silicoclastiques, niveaux volcaniques, socle cristallin) sont deux paramètres clés de l'atteinte des plus fortes concentrations. Les ressources en lithium estimées dans certains réservoirs sont du même ordre que celles des salars et des mines de roches dures (granites, pegmatites) actuellement exploités. Dans le cas d'étude du graben du Rhin, les saumures issues des formations du Trias se mélangent avec des eaux plus diluées infiltrées depuis les reliefs vosgiens, et transportent des quantités significatives de lithium (jusqu'à 200 mg.l⁻¹ dans les eaux de formations actuelles) ainsi que d'autres métaux (e.g. Pb, Zn, Cu, As, Sb). Les inclusions fluides montrent que des concentrations de 3-800 ppm en lithium, ont été atteintes entre l'Oligocène et l'Actuel. L'analyse des minéraux indique que la biotite, l'amphibole et la chlorite du socle cristallin ont probablement été des sources significatives pour ces métaux
The energy transition is associated with the increasing use of a wide range of metals, particularly those needed for lithium-ion batteries (e.g. lithium, cobalt), while there is a continuing need for base metals (e.g. copper, zinc). The development of alternative metal resources such as "liquid ores", notably the formation waters of sedimentary basin aquifers, could potentially contribute to meeting global demand. However, the geochemical processes involved in metal enrichment in formation waters remain poorly understood and the following approach was therefore pursued in this work: • Establishment of a database of temperatures and chemical and isotopic compositions of formation waters (3700 analyses) and fluid inclusions that preserved ancient formation waters (1700 analyses) from 90 sedimentary basins worldwide, based on published sources. The objective is to highlight the characteristic concentration ranges of dissolved metals in formation waters and the parameters that control their concentration. • Application to the case study of the Rhine Graben, on the example of the Soultz-sous-Forêts geothermal system, through the analysis of metals in fluid inclusions and minerals of the basin and the crystalline basement. The aim is to provide an overview of metal transfers related to fluid-rock interactions from the Oligocene to Present. The results indicate that formation waters generally acquire their metal load (Li, Mn, Pb, Zn, Fe, Ba, Cu) mainly through fluid-rock interactions, the increase in temperature and salinity facilitating their dissolution. In the peculiar case of lithium, the richest formation waters are most often brines derived from seawater and enriched in salts and partially in lithium by surface evaporation, and subsequently expelled from the evaporitic formations in which they are initially trapped, during tectonic events. The preservation from dilution by recharge fluids, and the interaction with lithologies enriched in lithium (siliciclastic rocks, volcanic levels, crystalline basement) are two key parameters to reach the highest concentrations. The lithium resources estimated in some reservoirs are of the same order of magnitude as those of the salars and hard-rock mines (granites, pegmatites) currently exploited. In the case of the Rhine Graben, brines from the Triassic formations mix with more diluted waters infiltrated from the Vosges mountains, and carry significant amounts of lithium (up to 200 mg.l⁻¹ in the present-day formation waters) as well as other metals (e.g. Pb, Zn, Cu, As, Sb). Fluid inclusions show that lithium concentrations from 3 to 800 ppm of lithium were reached between the Oligocene and Present. Mineral analysis indicates that the main Li carriers (Fe, Mn, Zn) in the crystalline basement are biotite, amphibole and chlorite, which were probably significant sources for these metals

Pour mieux comprendre le processus géodynamique qui a permis la destruction du craton Nord Chinois (NCC), le rôle des fluides mantelliques a été examiné. Pour cela, les distributions des teneurs en eau et des compositions isotopiques du Lithium dans le manteau lithosphérique NCC ont été déterminées à partir des xénolites de péridotite entrainés par les basaltes mésozoïques et cénozoïques. Une variation temporelle des teneurs en eau est observée. Le manteau lithosphérique cénozoïque est appauvri en eau, sans doute suite à l'amincissement crustal et au réchauffement du manteau résiduel par un flux ascendant asthénosphérique. Le manteau lithosphérique mésozoïque montre des teneurs en eau intermédiaire entre les teneurs élevées du Crétacé et les teneurs basses cénozoïques, indiquant une déshydratation du manteau commençant dès le début de sa destruction. Cette déshydratation, facilitée par la destruction du manteau lithosphérique profond, permet de renforcer la rigidité de la lithosphère et lui permet de résister à la convection mantellique. Les distributions élémentaire et isotopique du Li montrent une grande hétérogénéité, aux échelles intra et inter-cristallines. Par simulation numérique, nous démontrons que deux enrichissements successifs ont affecté le manteau, un enrichissement limité (<5ppm) avec une signature pauvre en 7Li ([delta]7Li ~ -20 [pour mille]), suivi d'un enrichissement important (> 100 ppm) avec une signature riche ([delta]7Li ~ +20 [pour mille]), précédent de peu l'exhumation des xénolites. La formation des liquides métasomatiques responsables de ces enrichissements nécessite une distribution hétérogène dans le manteau NCC d'éléments recyclés lors de la subduction à l'est du NCC
In order to investigate the geodynamic cause for destruction of the North China Craton (NCC), the role of mantle fluids is examined. The aim of the PHD work is to clarify H2O contents and lithium isotopic compositions of the NCC lithospheric mantle by studying peridotite xenoliths hosted by Mesozoic-Cenozoic basalts across eastern NCC. A temporal variation of H2O content has been revealed, and it has deep implications for processes of craton destruction. The Cenozoic lithospheric mantle was featured by low H2O content, interpreted to be the relict mantle that survived the lithospheric thinning and has been dewatered by reheating from upwelling asthenospheric flow. The late-Mesozoic lithospheric mantle showed relatively high H2O content, a hydrous status intermediate between the Cretaceous hydration and the Cenozoic dryness, indicating the dehydration of the NCC mantle with time during NCC destruction. The dehydration, facilitated by thinning of weak mantle pieces at bottom, is one way by which the lithosphere strengthens itself to survive in the convecting mantle. Extreme Li and isotopic disequilibria were observed intra- and inter-mineral in the peridotites. With numerical simulations, we demonstrate two superimposed Li enrichment events occurring at the mantle: a limited Li enrichment (< 5 ppm) and large delta7Li depletion (-20~-10[per 1000]) of the mantle domain, followed by a recent and transient infiltration of high Li and delta7Li (up to +20 [per 1000]) melts/fluids. The anomalous Li isotopic compositions of mantle metasomatic agents call upon the same of their mantle sources, and we assume recycled components, both Li isotopically heavy and light, in the mantle beneath the eastern NCC

L’accroissement des performances des accumulateurs Li-ion sur les 25 dernières années découle principalement de l’optimisation de leurs composants inactifs. Aujourd’hui, l’urgence environnementale impose de développer de nouveaux matériaux actifs d’électrode pour proposer la prochaine génération d’accumulateur qui participera à la transition énergétique. A cet effet, le silicium pourrait avantageusement remplacer le graphite des électrodes négatives à moyen terme. Cependant la rétention de capacité des électrodes de silicium est mise à mal par l’expansion volumique que le matériau subit lors sa réaction d’alliage avec le lithium, qui mène à la déconnexion des particules de Si et à une réduction continue de l’électrolyte. Une compréhension de ces phénomènes de vieillissement à l’échelle de la nanoparticule est nécessaire à la conception d’électrodes de silicium viables. Pour ce faire, la technique STEM-EELS a été optimisée de manière à s’affranchir des problèmes d’irradiation qui empêchent l’analyse des matériaux légers d’électrode négative et de la Solid electrolyte interface (SEI), grâce à l’analyse des pertes faibles EELS. Un puissant outil de cartographie de phase est obtenu et utilisé pour mettre en lumière la lithiation cœur-coquille initiale des nanoparticules de silicium cristallin, la morphologie hétérogène et la composition de la SEI, ainsi que la dégradation du silicium à l’issue de cyclages prolongés. Enfin, un modèle de vieillissement original est proposé, en s’appuyant notamment sur un effort de quantification des mesures STEM-EELS sur un grand nombre de nanoparticules
Over the last 25 years, the performance increase of lithium-ion batteries has been largely driven by the optimization of inactive components. With today’s environmental concerns, the pressure for more cost-effective and energy-dense batteries is enormous and new active materials should be developed to meet those challenges. Silicon’s great theoretical capacity makes it a promising candidate to replace graphite in negative electrodes in the mid-term. So far, Si-based electrodes have however suffered from the colossal volume changes silicon undergoes through its alloying reaction with Li. Si particles will be disconnected from the electrode’s percolating network and the solid electrolyte interface (SEI) continuously grows, causing poor capacity retention. A thorough understanding of both these phenomena, down to the scale of a single silicon nanoparticle (SiNP), is critical to the rational engineering of efficient Si-based electrodes. To this effect, we have developed STEM-EELS into a powerful and versatile toolbox for the study of sensitive materials and heterogeneous systems. Using the low-loss part of the EEL spectrum allows us to overcome the classical limitations of the technique.This is put to use to elucidate the first lithiation mechanism of crystalline SiNPs, revealing Li1.5Si @ Si core-shells which greatly differs from that of microparticles, and propose a comprehensive model to explain this size effect. The implications of that model regarding the stress that develops in the crystalline core of SiNPs are then challenged via stress measurements at the particle scale (nanobeam precession electron diffraction) for the first time, and reveal enormous compressions in excess of 4±2 GPa. Regarding the SEI, the phase-mapping capabilities of STEM-EELS are leveraged to outline the morphology of inorganic and organic components. We show that the latter contracts during electrode discharge in what is referred to as SEI breathing. As electrodes age, disconnection causes a diminishing number of SiNPs to bear the full capacity of the electrode. Overlithiated particles will in turn suffer from larger volumes changes and cause further disconnection in a self-reinforcing detrimental effect. Under extreme conditions, we show that SiNPs even spontaneously turn into a network of thin silicon filaments. Thus an increased active surface will compound the reduction of the electrolyte and the accumulation of the SEI. This can be quantified by summing and averaging STEM-EELS data on 1104 particles. In half-cells, the SEI volume is shown to increase 4-fold after 100 cycles without significant changes in its composition, whereas in full cells the limited lithiation performance understandably leads to a mere 2-fold growth. In addition, as the operating potential of the silicon electrodes increases in full cells – potential slippage – organic products in the SEI switch from being carbonate-rich to oligomer-rich. Finally, we regroup these findings into an extensive aging model of our own, based on both local STEM-EELS analyses and the macro-scale gradients we derived from them as a whole

Les accumulateurs commerciaux à base de lithium-ion (LIB) utilisent des matériaux à base de carbone (graphite) comme électrode négative; cependant, la technologie atteint sa limite en raison de la faible capacité spécifique théorique. L'objectif de cette thèse est d'étudier le comportement électrochimique de trois nouvelles anodes à haute capacité (SnSb microsturé, Ti3SiC2 anodisé et nanotubes de Si poreux) comme alternatives au graphite, d'identifier les principaux paramètres responsables de la perte de capacité et de proposer une solution commune pour améliorer leurs performances électrochimiques. Ces matériaux d'électrode présentent une bonne performance électrochimique qui les rend prometteurs pour remplacer le carbone en tant qu'électrode négative pour batteries au Li-ion. Cependant, ils présentent une perte de capacité initiale importante qui doit être résolue avant la commercialisation. Les limitations observées sont attribuées à de nombreux facteurs, et en particulier à la formation et la croissance d’une SEI à la surface des matériaux. En raison de la forte perte de la capacité et du manque d’études détaillées sur les matériaux à base d’étain, en particulier le SnSb, nous avons concentré la suite du travail à la formation et la croissance de la SEI sur cette électrode négative. L'évolution des propriétés électriques, de la composition chimique et de la morphologie du SnSb microstructuré a été étudiée en détail pour comprendre son comportement électrochimique. Pour limiter l’effet de la SEI, nous avons proposé d’appliquer un film protecteur à la surface de l'électrode
Currently, commercial lithium ion batteries (LIBs) use carbon based materials as negative electrode; however the technology is reaching its limit because of the low theoretical specific capacity. The objective of this thesis is to study the electrochemical behaviour of three different new high capacity anodes (SnSb alloy, anodized Ti3SiC2, and Si nanotubes) as alternative to graphite, identify the main parameters responsible for the capacity fading, and propose a versatile solution to improve their electrochemical performance. These electrode materials exhibit good electrochemical performance which makes them promising candidates to replace carbon as a negative electrode for LIBs. However, their limitation due to capacity fading and the large initial irreversible capacity loss must be resolved before commercialization. The observed limitations are attributed to many factors, and particularly, to the formation and growth of SEI layer which is the common factor for all the three electrode materials. Because of the strong capacity fade and lack of many detailed studies on the Sn-based materials, specifically SnSb, we focus our study to investigate the formation and growth of SEI layer on SnSb electrode. The evolution of the electrical, compositional, and morphological properties have been investigated in detail to understand the electrochemical behavior of micron-sized SnSb. To limit the capacity fade, we propose the use of a protective film on the electrode surface. The electrochemical performance of micron-sized SnSb electrode coated with thermoplastic elastomer protective film, namely poly(styrene-b-2-hydroxyethyl acrylate) PS-b-PHEA has been achieved

La premier thématique a pour objectifs :1) de tracer l’origine de la salinité des eaux des aquifères karstiques en milieu côtier méditerranéen,2) de quantifier les proportions de mélange entre les eaux salées et les eaux karstiques,3) de discriminer les traceurs géochimiques pour identifier et modéliser les processus de salinisation d’aquifères karstiques côtiers. La seconde thématique a pour objectifs:1) d’établir les [As] d’origine naturelle des eaux de surface et des eaux souterraines, 2) de quantifier le niveau de contamination en arsenic de ces eaux et sa variabilité spatio-temporelle 3) de tracer l’origine naturelle ou anthropique de la pollution en As à l’aide d’outils isotopiques adaptés. les origines de la salinité identifié inclue i) des venues d’eaux profondes salées ii) des venues profondes d’eau salées remontant vers la surface par une faille majeure normale. Le 36Cl/Cl a permis d’identifier l’origine profonde des eaux salées et une recharge d’eau météorique infiltrée lors de la période des essais thermonucléaires. La modélisation PHREEQC permet de différentier le mélange avec une eau profonde salée de celui avec une eau de mer actuelle. Le 87Sr/86Sr montre un comportement conservatif pour tracer l’origine des eaux salées dans les aquifères karstiques. Les traceurs Cs, Rb, Li et B permettent de différentier les trois origines identifiées de la salinité. Les données acquises sur la contamination en As soulignent une augmentation nette et pérenne des [As] à partir des anciens sites de traitement minier réhabilités. Les rapports 87Sr/86Sr et δ18O et δ2H se révèlent dans ce cas un traceur très discriminant de l’origine naturelle ou anthropique de l’arsenic
The first theme has for objectives: 1) to trace the origin of the salinity of the waters of the karst aquifers in coastal environment mediterraneen,2) to quantify the mixing proportions between salt waters and the waters karstiques,3) to discriminate the geochemical tracers to identify and model the process of salinization of aquifers coastal karst. The second theme has for objectives:1) to establish the [hast] of natural origin of surface waters and groundwater, 2) to quantify the level of contamination by arsenic in these waters and its spatial and temporal variability 3) to trace the natural or anthropogenic origin of pollution in hast to the aid of isotopic tools adapted. the origins of the salinity identified include i) of came from deep waters salted ii) of come deep water salted dating back toward the surface by a major flaw normal. The 36Cl/Cl has allowed us to identify the origin of deep saline waters and a recharge of meteoric water infiltrated during the period of thermonuclear tests. The PHREEQC modeling used to differentiate between the mixture with a deep water of salt that one with a sea water current. The 87SR/ 86Sr shows a conservative behavior for tracing the origin of saline waters in karst aquifers. The plotters Cs, Rb, Li and B allows to differentiate the three origins identified of salinity. The data acquired on the contamination in hast underline a net increase and perennial of [hast] from the ancient sites of mining processing rehabilitated. The reports 87SR/ 86Sr and δ18O and δ2H will reveal in this case a chartplotter very discriminant of natural or anthropogenic origin of arsenic