Mafic and felsic plutonism in the Elvas region (SW Iberia, Portugal): two distinct Nd isotope sources and geodynamics

The occurrence of mafic (mainly gabbros and diorites) and felsic (syenites and granites) rocks, in close spatial association, in the Elvas region, at the northern part of the Ossa-Morena Zone, could be interpreted as a single bimodal (alkaline) plutonic complex. However, in spite of scarce isotopic (Sm-Nd) data, the co-magmatic origin of both rock groups (mafic and felsic) has already been questioned [1]. Based on the mineral chemistry of primary clinopyroxenes (Di–Hd, %En: 45.5 – 27.2) and representative whole-rock analyses, gabbros and diorites of the Elvas massif show a transitional character between alkaline and non-alkaline fields and wide compositions: SiO2 (42.47 – 58.00 wt%); TiO2 (0.24 – 1.68 wt%); Y/Nb (4.0 – 10.7); Th (0.1 – 6.8 ppm); Zr (18.6 – 576.9 ppm). The felsic group is composed by highly differentiated rocks which correspond to distinct levels of silica saturation and alkalinity. Peralkaline syenites usually present sodic (riebeckite) and sodic-calcic (aegirine-augite, ferrowinchite) inosilicates and reveal quite variable compositions: SiO2 (57.50 – 72.07 wt%); TiO2 (0.10 – 1.45 wt%); Th (1.7 – 67.0 ppm); Zr (133.0 – 4800.0 ppm). The alkaline granites show hedenbergite as the characteristic inosilicate, presenting relatively common compositions: SiO2 (61.85 – 78.06 wt%); TiO2 (0.21 – 0.58 wt%); Th (11.8 – 38.4 ppm); Zr (317.3 – 1234.6 ppm) [2]. Recent Sm-Nd isotopic results, on a total of 18 whole-rock samples (6 mafites and 12 felsites), allow new and more consistent interpretation concerning the petrogenesis of these plutonic rocks. Assuming an age of 490 Ma [3], the felsic rocks provide (0.6 < Nd490 < 4.3), similar to other contemporary (per)alkaline rocks of this region [4], reflecting magmatic extractions from time-integrated depleted mantle sources followed by variable and incomplete mixing (and/or AFC-type) processes with enriched, probably crustal sources. This alkaline/peralkaline magmatism is thought to represent the main regional record of the rifting event which presumably led to the opening of the Rheic Ocean. On the other hand, the mafic plutonic rocks of the Elvas massif cannot represent the magmatic precursors of these syenites and granites as they show completely distinct Nd isotopic ratios (3.7 < Nd490 < 1.2) indicating important contribution of long-term enriched (crustal) sources. Instead, considering the age and the Nd isotopic signature of other mafic plutonic unit emplaced nearby (the Campo Maior massif: ca. 370 Ma; 6.0 < Nd370 < 5.2) [5], and recalculating the isotopic ratios of the Elvas massif for the same age (4.3 < Nd370 < 1.6), it is plausible to consider that these plutons (Campo Maior and Elvas) can be coeval and representative of the Variscan magmatism in this region. In such hypothesis, the differences between these isotopic values could be explained, on a time-integrated basis, either by magmatic sources for the Elvas massif less enriched in LREE than the sources involved in the Campo Maior massif, or, if both plutonites share similar depleted mantle sources, by magmatic differentiation paths considerably affected by crustal contamination processes, which reached higher degrees in the Campo Maior massif.

Preparação, caracterização e modificação de adsorventes para remoção de pesticidas de águas

O objectivo principal deste trabalho de mestrado consistiu em avaliar a potencial utilização de materiais adsorventes, nomeadamente, de carvões activados (AC) preparados por activação química com KOH, a partir de PET reciclado, e de materiais com estrutura mesoporosa ordenada, do tipo MCM-41 e SBA-15, na remoção de ácido 4 - cloro - 2 - metilfenoxiacético (MCPA) e de azul de metileno (MB), presentes nas águas. Nesta tese apresentam-se estudos de preparação e caracterização de materiais micro e mesoporosos e também estudos de avaliação da capacidade adsortiva em fase líquida. Prepararam-se três materiais microporosos, nomeadamente, PET-2-700, PET-2-700ox (AC oxidado) e PET-2-700red (AC reduzido), dois materiais constituídos exclusivamente por mesoporos, Si-MCM-41 e Ti-MCM-41-50 e dois materiais contendo maioritariamente mesoporos, mas que também possuem alguma microporosidade, tais corno, Si-SBA-15 e Ti-SBA-15-50. A caracterização textural dos adsorventes foi inferida por adsorção de azoto a 77K e por de difracção de raios X. Recorreu-se a três métodos de análise das isotérmicas, nomeadamente, Dubinin-Radushkevich, Brunauer-Ernrnett-Teller e alfa-s (as). A caracterização química dos AC foi realizada recorrendo-se a técnicas de análise elementar (AE) e espectroscopia de infravermelho com transformadas de Fourier (FTIR) e à determinação do ponto de carga zero. Os três carvões activados possuem valores de área superficial externa idênticos, o PET-2-700 possui o maior volume microporoso e o PET-2-700ox exibe o maior diâmetro de poros. Por outro lado, o PET-2-700ox possui um carácter fortemente ácido, o PET-2-700 exibe carácter ligeiramente ácido e o PET-2-700red apresenta propriedades ligeiramente alcalinas. Com base na AE, todas as amostras possuem percentagens de carbono elevadas, sendo que o PET-2-700red apresenta o valor mais elevado. Os resultados obtidos para a caracterização estrutural dos revelaram a obtenção de materiais mesoporosos de alta qualidade, definida pela elevada regularidade e uniformidade da estrutura porosa. A análise dos parâmetros de caracterização textura! permitiu inferir que os quatro materiais mesoporosos possuem valores de área superficial elevados, e que os materiais SBA-15 apresentam valores de volume poroso total e de tamanho de poros superiores aos manifestados pelos MCM-41. A incorporação de titânio não conduziu a uma perda significativa de qualidade dos materiais substituídos em relação às correspondentes amostras de sílica. Efectuaram-se estudos de adsorção em fase líquida de forma a avaliar a possível aplicação dos vários adsorventes na remoção de MCPA e de MB de efluentes líquidos. concluiu-se que o tempo de equilíbrio de 72 horas seria adequado e que a capacidade de adsorção dos vários AC era superior em meio ácido. Com base nas isotérmicas de adsorção do MCPA e do MB e na aplicação da representação de Langmuir e de Freundlich, foi possível concluir que o PET-2-700 possui a maior capacidade de adsorção do MCPA, 1.42 mmol/g, enquanto que o PET-2-700ox revelou a maior capacidade de adsorção do MB, 1.43 mmol/g. Na realidade, os materiais microporosos estudados apresentaram percentagens de remoção elevadas, tanto do MCPA como do MB. Relativamente aos materiais mesoporosos ordenados preparados neste trabalho, a percentagem de remoção de para os poluentes em estudo foi relativamente baixa, constatando-se que nesta fase dos estudos não constituem uma alternativa viável à utilização dos AC. No entanto, uma funcionalização criteriosa dos mesmos pode eventualmente proporcionar um aumento da capacidade adsortiva. ABSTRACT: The work presented in this master thesis, consisted of evaluating the potential use of different adsorbents materials, like activated carbon (AC) prepared by chemical activation with KOH, from recycled poly (ethylene terephthalate) (PET) and materials with ordered mesoporous structure such as MCM-41 and SBA-15, for removing acid 4-chlorine-2-metilfenoxiacétic and methylene blue from aqueous phase. We had prepared three microporous materials, PET-200-700, PET-2-700ox (AC oxidized) and PET-2-700red (reduced AC), two materials consisting exclusively of mesopores, Si-MCM-41 and Ti-MCM-41-50 and two materials containing mainly mesopores, but also having some microporosity, such as Si-SBA-15 and Ti-SBA-15-50. The textural characterization of the adsorbents was inferred by nitrogen adsorption at 77K and X-ray diffraction. Three methods were used to analyse the isotherms, namely, Dubinin-Radushkevich, Brunauer-Emmett-Teller and alpha-s (as). The chemical characterization of AC was performed using the elementary analysis, Fourier transform infrared spectroscopy (FTIR) and determination of the point of zero charge. Concerning the AC, the three present almost the same externa! surface area, PET-2-700 has a high micropore volume and PET-2-700ox shows the largest pore size diameter. On the other hand, PET-2-700ox had a strong acid character, PET-2-700 exhibits just a slightly acid character and PET-2-700red presents alkaline properties. The AE analysis allows confirming the high carbon content of theses AC, with PET-2-700red exhibiting the highest carbon proportion. The results from the structural characterization of the mesoporous materials, had disclosed the attainment of materials with high quality, defined by the raised regularity and uniformity of the porous structure. The analysis of the textural parameters allowed inferring that the four studied mesoporous materials possess high superficial area. The SBA-15 type materials present higher values of total porous volume and pores size diameter as the MCM-41. Also, the titanium incorporation did not lead to a significant loss of quality of the materials substituted in relation to the corresponding silica samples. The adsorption studies in liquid phase allow evaluating the possibility of using the different adsorbents for the MCPA and the MB removal. The kinetic studies had allowed to state the equilibrium time as 72 hours and a higher adsorption capacity was achieved in an acid medium. The influence of the pH of the medium, on the MCPA adsorption was evaluated. The MCPA and MB isotherms were analysed based on the Langmuir and Freundlich equation, the representations presented an excellent linearity, indicating the applicability of these equations to these systems. Also, it allows concluded that PET-2-700 had a higher adsorption capacity for MCPA, 1.42 mmol/g, and PET-2-700ox had a higher adsorption capacity for MB, 1.43 mmol/g. The AC used presented high removal percentages for MCPA and MB. Concerning the mesoporous materials prepared in this work, the percentage removal for the pollutants in study was relatively low, and evidencing that at the moment these mesoporous materials do not constitute a viable alternative to the AC. However, an astute funcionalisation of the same ones can, eventually provide an increase of the adsorption capacity.

Tracing the Cambro-Ordovician ferrosilicic to calc-alkaline magmatic

U–Pb geochronological study of zircons from nodular granites and Qtz-diorites comprising part of Variscan high- grade metamorphic complexes in Gredos massif (Spanish Central System batholith) points out the significant presence of Cambro-Ordovician protoliths among the Variscan migmatitic rocks that host the Late Carboniferous intrusive granitoids. Indeed, the studied zone was affected by two contrasted tectono-magmatic episodes, Car- boniferous (Variscan) and Cambro-Ordovician. Three main characteristics denote a close relation between the Cambro-Ordovician protholiths of the Prado de las Pozas high-grade metamorphic complex, strongly reworked during the Variscan Orogeny, and other Cambro-Ordovician igneous domains in the Central Iberian Zone of the Iberian Massif: (1) geochemical features show the ferrosilicic signature of nodular granites. They plot very close to the average analysis of themetavolcanic rocks of the Ollo de Sapo formation (Iberia). Qtz-diorites present typical calc-alkaline signatures and are geochemically similar to intermediate cordilleran granitoids. (2) Both Qtz-diorite and nodular granite samples yield a significant population of Cambro-Ordovician ages, ranging between 483 and 473 Ma and between 487 and 457 Ma, respectively. Besides, (3) the abundance of zircon inher- itance observed on nodular granites matches the significant component of inheritance reported on Cambro- Ordovician metagranites and metavolcanic rocks of central and NW Iberia. The spatial and temporal coincidence of both peraluminous and intermediate granitoids, and specifically in nodular granites and Qtz-diorite enclaves of the Prado de las Pozas high-grade complex, is conducive to a common petrogenetic context for the formation of both magmatic types. Tectonic and geochemical characteristics describe the activity of a Cambro-Ordovician arc-back-arc tectonic set- ting associated with the subduction of the Iapetus–Tornquist Ocean and the birth of the Rheic Ocean. The exten- sional setting is favorable for the generation, emplacement, and fast rise of subduction-related cold diapirs, supported by the presence of typical calc-alkaline cordilleran granitoids contemporary with ferrosilicic volcanism.