The Ditrău Alkaline Massif (Romania) is located in the Eastern Carpathians, as an intrusion in the Bukovina nappe system of the Mesozoic crystalline zone. Nepheline syenites are the most abundant rocks occurring in the central and eastern part of the Massif, and represent the youngest intrusion of the complex. Petrographic observations and fluid inclusion studies were performed on nepheline syenites in order to examine the evolution and the effect of the magmatic fluids on the alteration of nepheline to secondary minerals as sodalite, cancrinite and analcime. Fluid inclusion studies in nepheline, aegirine, albite and cancrinite provide evidence for the role of highly saline fluids in incongruent transformation reactions by which sodalite, cancrinite and analcime crystallize mostly on the expense of nepheline. The fluids, in most cases, can be modeled by the H2O-NaCl system with various NaCl contents; however inclusions with more complex fluid (containing also K, Ca, CO3, etc. besides H2O and NaCl) composition are abundant. Raman spectroscopic studies of daughter minerals in inclusions demonstrate the presence of alkali-carbonatic fluids in some of the earliest inclusions of nepheline, aegirine and albite. The alteration process is supported by the presence of H2O-NaCl fluid inclusions in cancrinite, showing lower salinity compared to those in nepheline. During the crystallization period of the nepheline syenites the rock was in equilibrium with a high salinity, carbonate rich solution that evolved to decreased salinity with time. The following observations support this: • paragenesis of mineral phases and their fluid inclusions: the early phases have high salinity inclusions and the late phases have low-salinity inclusions • the partitioning of chlorine depends on the pressure of the system: at about 2.0 kbars, the fluids coexisting with the melt have a high initial salinity and the salinity decreases with time; inclusions in nepheline show the lowest trapping pressure at ~2.5 kbars, hence the system has a high initial salinity and decreases with time • aH2O increases with time, resulting in the formation of H2O-bearing phases in a late stage of the crystallization of nepheline syenites. / Master of Science

The purpose of this study is to understand the geological, petrographical, mineralogical and geochemical characteristics of analcime-bearing tuffs in the Biga Peninsula and to determine formation process of these tuffs. The study area lies between Ayvacik and K&uuml / &ccedil / &uuml / kkuyu. The rock units are pre-Eocene basement rocks, Miocene Behram Volcanics (Arikli Tuff, andesite, andesitic agglomerate), Pliocene volcanics, Miocene lacustrine sediments (K&uuml / &ccedil / &uuml / kkuyu Formation) and Quaternary alluvium. Analcimes which are found in Arikli Tuff are the main objective of this study. Detailed petrographical, mineralogical and geochemical studies were caried out on the Arikli Tuff samples by using petrographical microscope, X-ray diffractometry, scanning electron microscopy, diffrential thermal analyses inductively coupled plasma &amp / #8211 / mass spectrometry and optical emission spectrometry. Fine-grained and coarse-grained analcime crystals in Arikli Tuff were determined by their colorless, isotropic, trapezohedral and low relief. In addition to petrographic study, SEM and XRD methods also confirmed the presence of analcime. Two modes of occurrences were determined by the petrographical and mineralogical studies / coarse-grained euhedral or anhedral crystals in cavities and pumice fragments and single crystals or clusters of fine-grained analcimes embedded in the matrix. It was stated that there are two types of formation of analcime / alteration of volcanic glass and precipitation from alkaline solution based on petrographical and SEM studies. Geochemical methods, moreover, support the formation types.

Les gisements uranifères nigériens sont localisés dans les formations carbonifères et jurassiques du bassin de Tim Mersoï. AREVA est actionnaire de 3 sites miniers de cette région: la SOMAÏR et la COMINAK dans le district d'Arlit, en exploitation depuis 50ans, et IMOURAREN, 80km plus au Sud, dont l'exploitation est programmée pour 2015. La minéralisation du gisement d'Imouraren est comprise dans la formation fluviatile du Tchirézrine 2 (Jurassique), formée de chenaux et de plaines d'inondation. Les faciès de remplissage de chenaux vont des grès grossiers aux grès très fins (cortège détritique : quartz et feldspaths), tandis que les faciès de débordement sont constitués d'analcimolites. La minéralogie secondaire est acquise lors de 2 évènements : 1- la diagenèse, avec formation de minéraux argileux, d'analcime, de quartz et d'albite secondaires, et 2- un épisode de circulations de fluides, qui induit une altération des minéraux détritiques et diagénétiques, la formation de nouvelles phases et le dépôt de l'uranium. Cette altération dessine une zonation minéralogique à l'échelle du gisement.L'hétérogénéité du Tchirézrine 2, tant au niveau des faciès que de la minéralogie, se perçoit lors du traitement du minerai, puisqu'il réagit différemment selon sa provenance, avec parfois des problèmes de récupération de l'U. Des essais de traitement de minerais, ont montré que analcimes et chlorites étaient les deux pénalisants, pour 3 raisons : 1- les piégeages des phases U au sein des analcimes, 2- la dissolution de ces 2 minéraux a tendance à faire sortir des conditions de solubilisation de l'U (pH et Eh) et à former de nombreux sulfates, 3- problèmes de percolation. Une méthode de détection des minerais riches en analcimes, basée sur la spectroscopie infrarouge, a été développée afin d'optimiser les mélanges de minerais et ainsi de réduire les effets néfastes des pénalisants lors du traitement. / Nigerian uraniferous deposits are located in carboniferous and jurassic formations of Tim Mersoï basin. AREVA is shareholder of 3 mine sites in this area: SOMAÏR and COMINAK, both in exploitation since 1960’s and IMOURAREN, 80km further South, whose exploitation is planned for 2015. Mineralization of Imouraren deposit is included in the fluvial formation of Tchirezrine 2 (Jurassic), composed of channels and flood plains. Facies of channel infillings range from coarse sandstones to siltstones, while overflow facies are composed of analcimolites.Secondary mineralogy was acquired during 2 stages: 1- diagenesis, with formation of clay minerals, analcime, secondary quartz and albites, and 2- stage of fluids circulations, which induced alteration of detrital and diagenetic minerals, formation of new phases and uranium deposition. A mineralogical zoning, at the scale of deposit resulted from this alteration. The heterogeneity of Tchirezrine 2, at the level of both facies and mineralogy, is also evidenced during ore treatment, as ore reacts differently depending on its source, with sometimes problems of U recovery. Ore treatment tests showed that analcimes and chlorites were both penalizing minerals, because of 1- the sequestration of U-bearing minerals into analcimes, 2- their dissolution which trends to move away from U solubilization conditions (pH and Eh) and to form numerous sulfates, and 3- problems of percolation. A detection method of analcime-rich ores, based on infrared spectroscopy, was developed in order to optimize ore blending and so to reduce negative effects during ore treatment process.

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal. / Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa.