Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

Contribution of SHRIMP U-Pb zircon geochronology to unravelling the evolution of Brazilian Neoproterozoic fold belts

The South-American continent is constituted of three major geologic-geotectonic entities the homonym platform (consolidated at the end of the Cambrian) the Andean chain (essentially Meso-Cenozoic) and the Patagonian terrains affected by tectonism and magmatism through almost all of the Phanerozoic The platform is constituted by a series of cratonic nuclei (pre-Tonian fragments of the Rodinia fission) surrounded by a complex fabric of Neoproterozoic structural provinces Two major groups of orogenic processes (plate interaction cycles) constitute the evolution of these provinces the older occurred in the Tonian (smaller in area) and the younger Brasiliano that is present in all provinces The Tonian cycles (pre-Rodinia fission?) are still being sorted out and many questions still need to be answered The Brasiliano orogenic collage events (post-Rodinia fission?) developed in three main stages in part coeval from a province to another and are 650-600 580-560 and 540-500 Ma respectively (the late event reaching the Ordovician) The first group of orogenies is recorded in practically all provinces The third group is restricted to part of the Mantiqueira Province (southeast of the platform Buzios Orogeny) and present in the Pampean province (SW of the platform) For all these groups of orogenic events there are considerable records of rock assemblages related to processes of convergent plate interaction opening accretion collision and further extrusion There is a good correlation between the geologic and geotectonic data and geochemical and isotopic data The late tectonic processes (post-orogenic magmatism foreland basins etc) of the first two groups compete in time in distinct spaces with the peak of orogenic processes in the third group The introduction of the SHRIMP U-Pb methodology was fundamental to separate the Tonian and post-Tonian orogenic groups and their respective divisions in time and space Thus there are still many open points/problems which lead to expectations of addressing these issues in the near future with the more Intense use of this methodology (C) 2010 Elsevier B V All rights reserved

The Cariris Velhos tectonic event in Northeast Brazil

The Borborema Province in northeastern South America is a typical Brasiliano-Pan-African branching system of Neoproterozoic orogens that forms part of the Western Gondwana assembly. The province is positioned between the Sao Luis-West Africa craton to the north and the Sao Francisco (Congo-Kasai) craton to the south. For this province the main characteristics are (a) its subdivision into five major tectonic domains, bounded mostly by long shear zones, as follows: Medio Coreau, Ceara Central, Rio Grande do Norte, Transversal, and Southern; (b) the alternation of supracrustal belts with reworked basement inliers (Archean nuclei + Paleoproterozoic belts); and (c) the diversity of granitic plutonism, from Neoproterozoic to Early Cambrian ages, that affect supracrustal rocks as well as basement inliers. Recently, orogenic rock assemblages of early Tonian (1000-920 Ma) orogenic evolution have been recognized, which are restricted to the Transversal and Southern domains of the Province. Within the Transversal Zone, the Alto Pajeu terrane locally includes some remnants of oceanic crust along with island arc and continental arc rock assemblages, but the dominant supracrustal rocks are mature and immature pelitic metasedimentary and metavolcaniclastic rocks. Contiguous and parallel to the Alto Pajeu terrane, the Riacho Gravata subterrane consists mainly of low-grade metamorphic successions of metarhythmites, some of which are clearly turbiditic in origin, metaconglomerates, and sporadic marbles, along with interbedded metarhyolitic and metadacitic volcanic or metavolcaniclastic rocks. Both terrane and subterrane are cut by syn-contractional intrusive sheets of dominantly peraluminous high-K calc-alkaline, granititic to granodioritic metaplutonic rocks. The geochemical patterns of both supracrustal and intrusive rocks show similarities with associations of mature continental arc volcano-sedimentary sequences, but some subordinate intra-plate characteristics are also found. In both the Alto Pajeu and Riacho Gravata terranes, TIMS and SHRIMP U-Pb isotopic data from zircons from both metavolcanic and metaplutonic rocks yield ages between 1.0 and 0.92 Ga, which define the time span for an event of orogenic character, the Cariris Velhos event. Less extensive occurrences of rocks of Cariris Velhos age are recognized mainly in the southernmost domains of the Province, as for example in the Polo Redondo-Maranco terrane, where arc-affinity migmatite-granitic and meta-volcano-sedimentary rocks show U-Pb ages (SHRIMP data) around 0.98-0.97 Ga. For all these domains, Sm-Nd data exhibit Tom model ages between 1.9 and 1.1 Ga with corresponding slightly negative to slightly positive epsilon(Nd)(t) values. These domains, along with the Borborema Province as a whole, were significantly affected by tectonic and magmatic events of the Brasiliano Cycle (0.7-0.5 Ga), so that it is possible that there are some other early Tonian rock assemblages which were completely masked and hidden by these later Brasiliano events. Cariris Velhos processes are younger than the majority of orogenic systems at the end of Mesoproterozoic Era and beginning of Neoproterozoic throughout the world, e.g. Irumide belt, Kibaride belt and Namaqua-Natal belt, and considerably younger than those of the youngest orogenic process (Ottawan) in the Grenvillian System. Therefore, they were probably not associated with the proposed assembly of Rodinia. We suggest, instead, that Cariris Velhos magmatism and tectonism could have been related to a continental margin magmatic arc, with possible back-arc associations, and that this margin may have been a short-lived (<100 m.y.) leading edge of the newly assembled Rodinia supercontinent. (C) 2009 Elsevier Ltd. All rights reserved.

Evolução geodinâmica e condicionamento estrutural dos terrenos Piancó-Alto Brígida e Alto Pajeú, domínio da zona transversal, NE do Brasil

This thesis aims to advance in the geological knowledge of the region comprising the Piancó-Alto Brígida (TPAB) and Alto pajeú (TAP) terranes, in the Transversal Zone Domain (Borborema Province, NE Brazil), with the main objective of understanding the geodynamic evolution and the structural framework of these units. To reach this objective, and besides field work and interpretation of traditional aerial photographs, other tools were employed like of remote sensing products (Landsat 7 ETM+, aeroradiometrics, aeromagnetics and topographical images), lithogeochemical (whole rock) analyses and geochronological dating (U-Pb in zircon), besides integration with literature data. In the area, several precambrian geological units outcrop, represented in the TAP by the paleoproterozoic Serra Talhada and Afogados da Ingazeira complexes, Riacho Gravatá Complex (metavolcano-sedimentary sequence of Stenian-Tonian age) and Cariris Velhos orthogneisses (of Tonian age). The TPAB comprises the Santana do Garrote (lower unit) and Serra do Olho d'Água (upper unit) formations of the Cachoeirinha Group (Neoproterozoic III), besides the Piancó orthogneisses and Bom Jesus paragneisses; the latter correspond to an older (basement ?) block and a possible high grade equivalent of the Cachoeirinha Group (or Seridó Group ?), respectively. Several Brasiliano-age plutons occur in both terranes.The aeromagnetic data show the continuity, at depth, of the main shear zones mapped in the region. The Patos, Pernambuco, Boqueirão dos Cochos, Serra do Caboclo, Afogados da Ingazeira/Jabitacá and Congo-Cruzeiro do Nordeste shear zones reach depths greater than to 6-16 km. The aeromagnetic signature of other shear zones, like the Juru one, suggests that these structures correspond to shallower crustal features. The satellite images (Landsat 7 ETM+) and aerogamaspectrometric images discriminate different geological units, contributing to the mapping of the structural framework of the region. The Serra do Caboclo Shear Zone was characterized as the boundary/suture between the TPAB and TAP. This structure is an outstanding, pervasive feature that separates contrasting geological units, such as the Neoproterozoic III Cachoeirinha Group in the TPAB and the Riacho Gravatá Complex and the Cariris Velhos metaplutonics, of Stenian-Tonian age, in the TAP. Occupying different blocks, these units are not found in authoctonous relations, like unconformities and intrusive contacts. Concerning the Cariris Velhos (ca. 1,0 Ga old) event is recorded by radiometric ages of the Riacho Gravatá Complex metavolcanics and intrusive augen and orthogneisses, all of them displaying geochemical affinities of arc or collisional settings. A structural signature of this event was not recorded in the region, possibly due to its low grade/low strain style, obliterated by the overprinting of younger, higher grade/high strain Brasiliano-age fabrics.The first tectonic event (D1) observed in the Cariris Velhos lithotypes presents contractional kinematics with transport to the NW. Neoproterozoic III geochronologic dates, obtained in late-D1 granitoids, imply a Brasiliano age (ca. 610-600 Ma) for this deformation event. The second tectonic event (D2) characterized in the region corresponds to the Brasiliano transcurrent kinematics of the outstanding shear zones and associated granitoid plutons. The geochronological (U-Pb in zircon) data obtained during this thesis also confirms the occurrence of the Cariris Velhos magmatic suite in the TAP, as well as the Neoproterozoic III age to the Cachoeirinha Group in the TPAB. The TAP (Riacho Gravatá Complex, augen and orthogneisses) is interpreted as a continental arc possibly accreted to a microcontinent during the Cariris Velhos (Stenian-Tonian) event. Later on, this terrane collided with the TPAB at the beginning of the Brasiliano orogeny (D1 contractional deformation), and both domins were reworked by the transcurrent shear deformation of the D2 event

Aprimoramento da sistemática U-Pb através do método de traços de fissão e técnicas de caracterização: termocronologia da faixa Brasília e sua correlação com a bacia do Paraná

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Depositional age, provenance and metamorphic age of metasedimentary rocks from southern Madagascar

Southern Madagascar is the core of a >1 million km(2) Gondwanan metasedimentary belt that forms much of the southern East African Orogen of eastern Africa, Madagascar, southern India and Sri Lanka. Here the Vohibory Series yielded U-Pb isotopic data from detrital zircon cores that indicate that it was deposited in the latest Tonian to late Cryogenian (between -900 and 640 Ma). The deposition of the Graphite and Androyen Series protoliths is poorly constrained to between the late Palaeoproterozoic and the Cambrian (similar to 1830-530 Ma). The Vohibory Series protoliths were sourced from very restricted-aged sources with a maximum age range between 910 and 760 Ma. The Androyen and Graphite Series protoliths were sourced from Palaeoproterozoic rocks ranging in age between 2300 and 1800 Ma. The best evidence of the timing of metamorphism in the Vohibory Series is a weighted mean Pb-206/U-238 age of 642 +/- 8 Ma from 3 analyses of zircon from sample M03-01. A considerably younger Pb-206/U-238 metamorphic age of 531 +/- 7 Ma is produced from 10 analyses of zircon from sample M03-28 in the Androyen Series. This similar to 110 Ma difference in age is correlated with the early East African Orogeny affecting the west of Madagascar along with its type area in East Africa, whereas the Cambrian Malagasy Orogeny affected the east of Madagascar and southern India during the final suturing of the Mozambique Ocean. (C) 2011 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Neoproterozoic evolution of the basement of the South-American platform

Neoproterozoic geologic and geotectonic processes were of utmost importance in forming and structuring the basement framework of the South-American platform. Two large domains with distinct evolutionary histories are identified with respect to the Neoproterozoic era: the northwest-west (Amazonian craton and surroundings) and the central-southeast (the extra-Amazonian domain). In the first domain, Neoproterozoic events occurred only locally and were of secondary significance, and the geologic events, processes, and structures of the pre-Neoproterozoic (and syn-Brasiliano) cratonic block were much more influential. In the second, the extra-Amazonian domain, the final evolution, structures and forms are assigned to events related to the development of a complex net of Neoproterozoic mobile belts. These in turn resulted in strong reworking of the older pre-Neoproterozoic basement. In this domain, four distinct structural provinces circumscribe or are separated by relatively small pre- Neoproterozoic cratonic nuclei, namely the Pampean, Tocantins, Borborema and Mantiqueira provinces. These extra-Amazonian provinces were formed by a complex framework of orogenic branching systems following a diversified post-Mesoproterozoic paleogeographic scenario. This scenario included many types of basement inliers as well as a diversified organization of accretionary and collisional orogens. The basement inliers date from the Archean toMesoproterozoic periods and are different in nature. The escape tectonics that operated during the final consolidation stages of the provinces were important to and responsible for the final forms currently observed. These latest events, which occurred from the Late Ediacaran to the Early Ordovician, present serious obstacles to paleogeographic reconstructions. Two groups of orogenic collage systems are identified. The older system from the Tonian (>850 Ma) period is of restricted occurrence and is not fully understood due to strong reworking subsequent to Tonian times. The second group of orogenies is more extensive and more important. Its development began with diachronic taphrogenic processes in the Early Cryogenian period (ca. 850e750 Ma) and preceded a complex scenario of continental, transitional and oceanic basins. Subsequent orogenies (post 800 Ma) were also created by diachronic processes that ended in the Early Ordovician. More than one orogeny (plate interaction) can be identified either in space or in time in every province. The orogenic processes were not necessarily synchronous in different parts of the orogenic system, even within the same province. This particular group of orogenic collage events is known as the “Brasiliano”. All of the structural provinces of the extra-Amazonian domain exhibit final events that are marked by extrusion processes, are represented by long lineaments, and are fundamental to unraveling the structural history of the Phanerozoic sedimentary basins.