Este estudo se propôs a avaliar a influência da cristalinidade e da deformação do quartzo na ocorrência da reação álcali-agregado. A influência da cristalinidade do quartzo foi analisada através da mesóstase, material intersticial que constitui as rochas vulcânicas, que é um material composto por grãos sub-microscópicos de quartzo e feldspatos. Para tanto foram selecionadas duas rochas vulcânicas, constituídas por quartzo em diferentes quantidades e com diferentes graus de cristalinidade: um basalto, com pouca quantidade de sílica, sem quartzo livre e cuja mesóstase apresenta grãos pobremente cristalizados; e um riolito, com grande quantidade de sílica e de quartzo livre, além de uma mesóstase com grãos melhor cristalizados. A caracterização da cristalinidade do quartzo mostrou que a mesóstase, que tem aparência de material amorfo em microscopia ótica, apresenta diferentes feições quando observada através de microscopia eletrônica de varredura: mesóstase com grãos criptocristalinos de quartzo e K-feldspatos (Mm); mesóstase com grãos de quartzo e feldspato microcristalinos (Mq); mesóstase constituída predominantemente por argilominerais (Ma). Relacionando-se essas características com a reatividade das rochas verificou-se que o quartzo presente nas mesóstases Mm e Mq reage rápida e intensamente, sobressaindo-se à dissolução da mesóstase Mm, enquanto os grãos da mesóstase Ma são preservados. Através da compração dessas constatações, obtidas com o basalto e o riolito, com as características do material intersticial de um basalto inócuo, em ensaios acelerados e em campo, verificou-se que seu material intersticial da rocha inócua possui pouca quantidade de sílica livre (quartzo). Isso evidencia que a reatividade das rochas vulcânicas está relacionada à quantidade de sílica livre presente (quartzo) e a velocidade de ocorrência da reação com a cristalinidade do quartzo constituinte da mesóstase (Mm). A influência da deformação do quartzo no desencadeamento da reação álcali-agregado foi avaliada através do estudo de rochas graníticas com diferentes graus de deformação: uma rocha pouco deformada (granito), uma rocha com deformação intermediária (proto-milonito) e uma rocha muito deformada (orto-milonito). Os graus de deformação do quartzo foram caracterizados, através de microscopia ótica, como: grau 0= ausência de deformação; grau 1= grãos pouco deformados, com extinção ondulante leve; grau 2= quartzo muito deformado, com forte extinção ondulante, chegando a formar bandas de deformação; grau 3= forte deformação, com formação de subgrãos; grau 4= grãos recristalizados. O estudo mostrou que a presença preponderante de quartzo com grau 2 nas rochas denota uma maior velocidade de desencadeamento da reação álcali-agregado. A partir dessa constatação efetuou-se a avaliação das características texturais dos grãos de quartzo de rochas reativas em campo, verificando-se que quanto maior a quantidade de grãos com grau 2 mais rápida a ocorrência da reação em campo. / This research aims to study the influence of crystallinity and deformation of quartz to the occurrence of alkali-aggregate reaction. The influence of the cristallinitiy of quartz was analyzed through the interstitial material (volcanic glass/mesostase) into volcanic rocks. This material is composing by sub-microscopic grains of quartz and feldspars, thus it was selected a basaltic rock, with poor crystallized interstitial material and low silica content; and a rhyolitic rock, with better crystallized interstitial material and high silica content. The characterization of the crystallinity of the quartz showed that interstitial mesostase has appearance of amorphous material on the optical microscopy, but, at scanning electron microscopy it was observe the following features: mesostase with microcrystalline grains of quartz and K-feldspar (Mm); mesostase with better crystallized grains of quartz and K-feldspar (Mq); mesostase with clay predominantly (Ma). Reactivity potential tests showed that quartz in Mm and Mq react quickly and intensely, especially Mm, while quartz in Ma was preserved. Comparing these evidences, obtained with basalt and rhyolite, with interstitial material into innocuous basalt, it was found that interstitial material in innocuous rock has smaller amount of free silica (quartz). It proof that reactivity of volcanic rocks is related to the amount of free silica present into the rocks and poor cristalinity of quartz into mesostase make alkali-aggregate reaction quickness (Mm). The influence of the deformation of quartz on alkali-aggregate reaction was analyzed through granitic rocks with different degrees of deformation: a rock with very little deformation (granite), a medium deformed rock (proto-mylonite), a very deformed rock (orto-mylonite). Deformation degree of quartz was characterized through optical microscopy as follows: order 0= absence of the deformation; order 1= slightly deformed grain (weak ondulatory extinction); order 2= very deformed quartz, with strong ondulatory extinction and forming deformation bands; order 3= very deformed quartz, with formation of sub-grains, order 4= recrystallized quartz. The study showed that rocks with most quartz „order 2‟ denotes the development of alkali-aggregate reaction faster than rocks with other „orders‟ deformation of the quartz. From this conclusion it was obseve the textural characteristics of quartz grains in reative rocks on the field, confirming that quartz with deformation bands cause alkali-aggregate reaction quickly.

Made available in DSpace on 2015-03-13T17:08:23Z (GMT). No. of bitstreams: 1 LindaraySC.pdf: 4257838 bytes, checksum: 9412fe333ae2e7c2ddef65c89e08a35e (MD5) Previous issue date: 2009-06-19 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The study area is located at the eastern-central portion of the Serid? Belt, on the interface between the Serid? Group Metasediments and the crystalline basement rocks of the Caic? Complex (RN). Petrographic and geochemical data allow us to define aspects related to the genesis and evolution of the Serra Verde Pluton magmas, which composes the goal of this dissertation The Serra Verde Pluton is a stock with outcropping area of about 25 km?, which is intrusive into metasedimentary sequence and the basement gneisses. The pluton intrusion is sintectonic to the Brasiliano event, elongated along the NE direction, developing a cornue geometry. The rock is a monzogranite mainly composed by K-feldspar, plagioclase and quartz, which usually compose more than 85% of the modal analisys. The main mafic mineral is the biotite, while amphibole, sphene, epidote, opaque minerals, allanite, zircon and apatite occur as accessory minerals. It features still a latemagmatic paragenesis composed by chlorite, granular epidote, carbonates and muscovite, developed through the percolation of late CO2 and H2O rich fluids. Chemically, the Serra Verde Pluton rocks may be classified as metaluminous, of calc-alkaline affiliation, sometimes showing trondhjem?tic characteristics, with high Na2O (>4,5%), Sr (>400ppm) and Ba (>800ppm) and low K2O (&#8804;3,0%), MgO (<1,0%), TiO2 (<0,5%), Rb (<90ppm), Y (&#8804;16ppm) and Zr (&#8804;13ppm). Micropetrographic evidences (mineral assembly and microtextures) indicate that the magma evolution occurred in moderated to high fO2 conditions, above the FMQ buffer. Thermo-barometric data obtained by minor elements geochemistry and the CIPW data, suggest a final/minimal pressure crystallization for the Serra Verde Pluton samples of about 3 to 5 kbar, liquidus temperature around 800o C, solidus temperature between 680o and 660o C. This data is compatible with those observed by many authors for the Neoproterozoic granites of the Serid? Belt. The group of analyzed data (Petrographic, microtextural and geochemical), suggests that the dominant process of the generation and evolution of the Serra Verde Granite magma was the fractional crystallization, probably from basement quartz-dioritic and tonalitic orthogneisses source / A ?rea estudada situa-se na por??o centro-leste da Faixa Serid?, na interface dos metassedimentos do Grupo Serid? e as rochas do embasamento cristalino do Complexo Caic? (RN). Dados petrogr?ficos e qeoqu?micos permitem definir os aspectos relativos ? g?nese e evolu??o do(s) magma(s) do Pl?ton Serra Verde, que constitui o alvo desta Disserta??o de Mestrado. O Pl?ton Serra Verde constitui um stock com ?rea aflorante de aproximadamente 25 Km2, intrusivo na seq??ncia metassedimentar e nos gnaisses do embasamento. Este pl?ton corresponde a uma intrus?o sintect?nica ao evento brasiliano, alongada na dire??o NE, com geometria en cornue. Trata-se de um monzogranito cuja assembl?ia mineral ominante ? composta por K-feldspato, plagiocl?sio e quartzo, que usualmente somam mais de 85% modal. Tem como m?fico principal a biotita, enquanto que anfib?lio itanita, ep?doto, opacos, allanita, zirc?o e apatita s?o os acess?rios. Apresenta ainda uma parag?nese tardi-magm?tica constiut?da de clorita, ep?doto granular, carbonato e muscovita, desenvolvida a partir da atua??o de flu?dos tardios ricos em CO2 e H2O. Quimicamente, as rochas do Pl?ton Serra Verde podem ser classificadas como metaluminosas, de filia??o c?lcio-alcalina, por vezes com caracter?sticas de associa??es trondhjem?ticas, com altos teores de Na2O (>4,5%), Sr (>400ppm) e Ba (>800ppm), e baixos teores de K2O (&#8804;3,0%), MgO (<1,0%), TiO2 (<0,5%), Rb (<90ppm), Y (&#8804;16ppm) e Zr (&#8804;13ppm). Evid?ncias micropetrogr?ficas (assembl?ias minerais e microtexturais) indicam que a evolu??o do magma ocorreu em condi??es de fO2 moderadas a elevadas, acima do tamp?o FMQ. Dados termobarom?tricos obtidos atrav?s da geoqu?mica de elementos menores, tra?os e dados normativos CIPW sugerem uma press?o final/m?nima de cristaliza??o para as amostras do Pl?ton Serra Verde em torno de 3 a 5 kbar, temperatura do l?quidus em torno de 800?C, e temperatura do solidus em torno 680 a 660?C. Estes dados s?o compat?veis com os observados por diversos autores em granit?ides neoproteroz?icos do Dom?nio Serid?. O conjunto de dados analisados (petrogr?ficos microtexturais e geoqu?micos), sugerem ainda que o processo dominante na gera??o e evolu??o do magma do granito Serra Verde se deu por cristaliza??o fracionada, sendo ortognaisses quartzo dior?ticos a tonal?ticos do complexo do embasamento, prov?veis candidatos para sua fonte

>Magister Scientiae - MSc / The thesis provides a study into the main structural features of the Namaqua Region and their relation to the intrusion of the Keimoes Suite. This was achieved by producing a digitized map of the Namaqua Region structural framework using a LandSAT image and MOVE software for remote sensing. The structural framework showed an array of shear zones and fault systems which trend in a NW-SE direction. The validation of the sense of movement, location and orientation of the shear zones was done by field mapping. The general orientation of all shear zones was NW-SE. The sense of movement along the Neusspruit, Boven Rugzeer and Trooilapspan shear zones was found to be dextral strike slip movement and the Cnydas shear zone had a sinistral strike slip movement. The location of the shear zones were determined by analyzing the deviation in general foliation trend which was visualized using Rose Diagrams. The field data and the remote sensing were found to agree with the transpressive environment of the Namaqua Region. The oblique collision of the Namaqua-Natal crustal block with the Kaapvaal Craton during the orogenic event at ~1.2 Ga created a compressionalgeotectonic setting which allowed for the intrusion of the early to late syn-tectonic Keimoes Suite granites. The lateral escape of the Namaqua-Natal crustal block took place along the western margin of the Kaapvaal Craton. This was brought on by prolonged compression which resulted in the formation of a releasing bend in the Namaqua Region. This releasing bend produced the negative flower structure with dextral shear zones which facilitated the intrusion of the post-tectonic Keimoes Suite granites.

Os Plutons Palermo (ca. 250 km2) e Rio Negro (ca. 130 km2) afloram na região Alto Rio Negro (PR) e fazem parte da Província Graciosa, uma província Neoproterozóica (ca. 580 Ma) constituída por granitos e sienitos na região S-SE do Brasil. Em ambos os plutons afloram variedades de rochas graníticas, predominantes, e gabro-dioríticas, bem como rochas híbridas, principalmente granodioritos. Estes plutons apresentam zonamento em geral bem marcado, que é tipicamente inverso caso do Pluton Rio Negro. As rochas graníticas principais correspondem a sieno- e monzogranitos predominantes e álcali-feldspato granitos e quartzo monzonitos subordinados de natureza metaluminosa a levemente peraluminosa. São rochas com estruturas maciças e texturas variadas que apresentam como associação mineral máfica típica hb + bi ± all + zr + ap ± ti + mt + ilm); as rochas gabro-dioríticas incluem gabro-dioritos e quartzo monzogabro-dioritos metaluminosos com estruturas maciças e granulações fina a média, caracterizadas pela associação cpx ± opx + hb + bt ± ti ± ap ± zr. A composição dos plagioclásios nestas rochas varia no intervalo de labradorita a andesina. As rochas híbridas são principalmente granodioritos que se caracterizam por uma variedade de estruturas e texturas indicativas de desequilíbrio, compatíveis com processos de coexistência e mistura parcial entre líquidos ácidos e básico-intermediários que formaram os granitos principais e os gabro-dioritos. Estas rochas são mais comuns no Pluton Rio Negro. A associação mineral máfica é similar, mas com abundâncias distintas de fases, à observada para os granitos principais. Nas rochas graníticas os anfibólios são Fe-hornblenda e Fe-edenita, com valores 0,65 < fe# < 0,95, os valores mais elevados ocorrendo nos álcali-feldspato granitos, as biotitas apresentam 0,71 < fe# < 0,99, observando-se que o componente annítico é também maior nestas últimas rochas. No caso das rochas gabro-dioríticas, os valores fe# variam entre 0,48 e 0,59, 0,41 e 0,56, 0,47 e 0,53 e 0,54 a 0,57 para ortopiroxênio, clinopiroxênio, anfibólio e biotita, respectivamente. As composições médias de orto- e clinopiroxênio coexistentes são \'Wo IND.46\'\' En IND.30\'\' Fe IND.24\' e \'Wo IND.3\'\' En IND.42\'\'Fe IND.55\' e a sugerem uma possível afinidade toleítica, ou cálcio-alcalina, para magma original. Os padrões de elementos terras raras revelam fatores de enriquecimento entre 1-10, 50-70, 100-300 em relação à composição condrítica para ortopiroxênio, clinopiroxênio e anfibólio nas rochas estudadas, com fracionamento bem marcado dos elementos leves em relação aos pesados no ortopiroxênio, não observado no caso de clinopiroxênio e anfibólio. Todos os padrões são caracterizados por anomalia negativa bem marcada de Eu. As pressões de cristalização dos magmas foram estimadas entre 1-3,5 kbar, mas os valores acima de ca. 2 kbar possivelmente não tenham significado real, dadas as composições mais ferroanas dos anfibólios. Temperaturas de saturação de zircão e/ou apatita e de equilíbrio entre orto- e clinopiroxênio, anfibólio-plagioclásio indicam intervalos de cristalização entre ca. 1000 e 750° C para as rochas gabro-dioríticas e entre ca. 900 e 670° C para os granitos principais. As paragêneses minerais e os valores obtidos para o número fe# em biotita em equilíbrio com feldspato alcalino e magnetita apontam para condições de cristalização relativamente oxidantes para as rochas félsicas, exceto os álcali-feldspato granitos, e máfico-intermediárias, superiores ao tampão QFM. / The Palermo (ca. 250 km2) and Rio Negro (ca. 130 km2) Plutons crop out in the so called Alto Rio Negro region , Parana state, making part of the Graciosa Province, a NeoProterozoic province (ca. 580 Ma) constituted by granites and syenites in S-SE Brazil. The plutons are made predominant granitic rocks, gabbro-diorites, as well as hybrid rocks constituted mainly by granodiorites. Both plutons show compositional a zoning pattern, which is inversed in the case of the Rio Negro Pluton. The main granitid rocks are mainly metaluminous to slightly peraluminous syeno- and monzogranites with subordinate quartz monzonites and alkcali-feldspar granites. They show a massive structure and a variety of textures, with hb + bi ± all + zr + ap ± ti + mt + ilm as the typical mafic mineral association. Gabbro-dioritic rocks include fine- to medium-grained metaluminous gabro-diorites and quartz monzogabrros and diorites with massive strucure characterized by the mafic mineral associations with cpx ± opx + hb + bt ± ti ± ap ± zr. In these rocks, the plagioclase compositions vary between labradorite and andesine. Hybrid rocks are mainly granodiorites characterized by several strucures and textures indicative of desiquilibrium and mingling/partial mixing between the silicic and basic-intermediate melts that formed the mainn granites and the gabbro-diorites. Such rocks are more abundant in the Rio Negro Pluton. The mafic mineral association is similar, but in contrasted relative abundance, to the ones found in the main granites. In the main granites the amphiboles are Fe-horblende and Fe-edenite, with 0.65 < fe# < 0.95, the higher among these values appearing in the alkali-feldspar granites. Biotite present 0.70 < fe# < 0.99 and the annitic component are also higher in the later rocks. In the case of the gabbro-dioritic rocks, the fe# numbers range between 0.48 and 0.59, 0.41 and 0.56, 0.47 and 0.53 and 0.54 and 0.57 in ortopyroxene, clinopyroxene, amphibole and biotite, respectively. The averaged compositions of coexisting orto- and clinopyroxene are \'Wo IND.46\'\'En IND.30\'\'Fe IND.24\' and \'Wo IND.3\'\'En IND.42\'\'Fe IND.55\' and suggest a tholeiitic or calk-alkaline nature of the original melts. Rare earth element patterns reveal enrichment factors up to 1-10, 50-70, 100-300 relative to the chondritic composition in ortopyroxene, clinopyroxene and amphibole, respectively, with a well marked fractionation of the heavy over the light rare earths in the case of the ortopyroxene, a feature not observed in clinopyroxene and amphibole. All patterns show a notable Eu negative anomaly. Melts crystallization pressures were estimated to be between 1 and 3.5 kbar; however values higher than ca. 2 kbar seems to be unrealistic given the ferroan compositions of some amphiboles. Zircon and apatite saturation temperatures coupled with ortopyroxene-clinopyroxene and amphibole-plagioclase equilibrium temperatures suggest crystallization intervals between ca. 1000 - 750° C in the case of the gabbro-diorites and ca. 900 - 670° C in the case of the main granites. Mineral paragenesis and fe# values in biotite in equilibrium with alkali-feldspar and magnetite suggests relative oxidizing crystallization conditions for the acid and basic-intermediate melts, higher than the QFM buffer, the alkali-feldspat granites being a possible exeption.

In Sweden the encapsulated nuclear waste will be surrounded by compacted bentonite in the granitic host rock. In contact with water-bearing fractures the bentonite barrier may release montmorillonite colloids that may be further transported in groundwater. If large amounts of material are eroded from the barrier, the buffer functionality can be compromised. Furthermore, in the scenario of a leaking canister, strongly sorbing radionuclides, can be transported by montmorillonite colloids towards the biosphere. This thesis addresses the effects of groundwater chemistry on the generation, stability, sorption and transport of montmorillonite colloids in water bearing rock fractures. To be able to predict quantities of montmorillonite colloids released from the bentonite barrier in contact with groundwater of varying salinity, generation and sedimentation test were performed. The aim is first to gain understanding on the processes involved in colloid generation from the bentonite barrier. Secondly it is to test if concentration gradients of montmorillonite colloids outside the barrier determined by simple sedimentation experiments are comparable to generation tests. Identical final concentrations and colloid size distributions were achieved in both types of tests. Colloid stability is strongly correlated to the groundwater chemistry. The impact of pH, ionic strength and temperature was studied. Aggregation kinetics experiments revealed that for colloid aggregation rate increased with increasing ionic strength. The aggregation rate decreased with increasing pH. The temperature effect on montmorillonite colloid stability is pH-dependent. At pH≤4, the rate constant for colloid aggregation increased with increasing temperature, regardless of ionic strength. At pH≥10, the aggregation rate constant decreased with increasing temperature. In the intermediate pH interval, the aggregation rate constant decreased with increasing temperature except at the highest ionic strength, where it increased. The relationship between the rate constant and the ionic strength allowed the critical coagulation concentration (CCC) for Na- and Ca-montmorillonite to be determined. In order to distinguish the contribution of physical filtration and sorption to colloid retention in transport, the different retention mechanisms were quantified. Sorption on different representative minerals in granite fractures was measured for latex colloids (50, 100, 200 nm) and montmorillonite colloids as a function of ionic strength and pH. Despite of the negative charge in mineral surfaces and colloids, sorption was detected. The sorption is correlated to the mineral point of zero charge and the zeta potential of the colloids, and increases with increasing ionic strength and decreasing pH. In transport experiments with latex colloids in columns packed with fracture filling material, the retention by sorption could clearly be seen. In particular at low flow rates, when the contact time for colloids with the mineral surfaces were the longest, sorption contributed to retention of the transport significantly. The retention of latex colloids appeared to be irreversible in contrary to the reversible montmorillonite colloid retention. Generation, stability and sorption of the montmorillonite colloids are controlled by electrostatic forces; hence, the results were in qualitative agreement with DLVO.

Arsenic and antimony are important trace elements in magmatic-hydrothermal systems, geothermal systems and epithermal deposits, but their partitioning behavior between melt and aqueous fluid is not well understood. The partitioning of arsenic and antimony between aqueous fluid and granitic melt has been studied in the system SiO2-Al2O3-Na2O-K2O-H2O at 800 degree C and 200 MPa. The partition coefficients of As and Sb between aqueous fluid and melt, are 1.4 +- 0.5 and 0.8 +- 0.5, respectively. The partitioning of As is not affected by aluminum saturation index (ASI) or SiO2 content of the melt, or by oxygen fugacity under oxidized conditions (log fO2 > the nickel-nickel oxide buffer, NNO). The partitioning of Sb is independent of and SiO2 content of the melt. However, aluminum saturation index (ASI) does affect Sb partitioning and Sb partition coefficient for peralkaline melt (0.1 +- 0.01) is much smaller than that for metaluminous melts (0.8 +- 0.4) and that for peraluminous melts (1.3 +- 0.7). Thermodynamic calculations show that As(III) is dominant in aqueous fluid at 800 degree C and 200 MPa and XPS analysis of run product glass indicate that only As(III) exists in melt, which confirms the finding that does not affect As partitioning between fluid and melt. XPS analysis of run product glass show that Sb(V) is dominant in melt at oxidized conditions (log fO2 > -10). The peralkaline effect only exhibits on Sb partitioning, not on As partitioning at oxidized conditions, which is consistent with the x-ray photoelectron spectroscopy (XPS) measurements that As(III) and Sb(V) are dominant oxidation states in melt under oxidized conditions, because the peralkaline effect is stronger for pentavalent than trivalent cations. Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon (OC) column showed an initial sulfate reduction rate of 0.4 μmol g(oc)-1 d-1 and exhausted its capacity to promote sulfate reduction after 30 pore volumes (PVs), or 9 months of flow. The Fe0-bearing organic carbon (FeOC) column sustained a relative constant sulfate reduction rate of 0.9 μmol g(oc)-1 d-1 for at least 65 PVs (17 months). The microbial enumerations and isotopic measurements indicate that the sulfate reduction was mediated by sulfate reducing bacteria (SRB). The cathodic production of H2 by anaerobic corrosion of Fe probably is the cause of the difference in sulfate reduction rates between the two reactive mixtures. Zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs and Fe0-bearing organic carbon reactive mixture has a potential to improve the performance of organic carbon PRBs. The δ34S values can be used to determine the extent of sulfate reduction, but the fractionation is not consistent between reactive materials. The δ13C values indicate that methanogenesis is occurring in the front part of both columns. Arsenic and antimony in groundwater are great threats to human health. The PRB technology potentially is an efficient and cost-effective approach to remediate organic and inorganic contamination in groundwater. Two column experiments were conducted to assess the rates and capacities of organic carbon (OC) PRB and Fe-bearing organic carbon (FeOC) PRB to remove As and Sb under controlled groundwater flow conditions. The average As removal rate for the OC column was 13 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity was 11 μmole g-1 (dry weight of organic carbon). The remove rate of the FeOC material was 165 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity was 105 mole g-1 (dry weight of organic carbon). Antimony removal rate of the OC material decreases from 8.2 to 1.4 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity is 2.4 μmole g-1 (dry weight of organic carbon). The minimum removal rate of FeOC material is 13 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity is 8.4 μmole g-1 (dry weight of organic carbon). The As(III) : [As(III)+As(V)] ratio increased from 1% in the influent to 50% at 5.5 cm from the influent end, and to 80% at 15.5 cm from the influent end of the OC column. X-ray absorption near edge spectroscopy (XANES) shows As(III)-sulfide species on solid samples. These results suggest that As(V) is reduced to As(III) both in pore water and precipitate as As sulfides or coprecipitate with iron sulfides. The arsenic reduction rate suggests that As(V) reduction is mediated by bacterial activity in the OC column and that both abiotic reduction and bacterial reduction could be important in FeOC.

Arsenic and antimony are important trace elements in magmatic-hydrothermal systems, geothermal systems and epithermal deposits, but their partitioning behavior between melt and aqueous fluid is not well understood. The partitioning of arsenic and antimony between aqueous fluid and granitic melt has been studied in the system SiO2-Al2O3-Na2O-K2O-H2O at 800 degree C and 200 MPa. The partition coefficients of As and Sb between aqueous fluid and melt, are 1.4 +- 0.5 and 0.8 +- 0.5, respectively. The partitioning of As is not affected by aluminum saturation index (ASI) or SiO2 content of the melt, or by oxygen fugacity under oxidized conditions (log fO2 > the nickel-nickel oxide buffer, NNO). The partitioning of Sb is independent of and SiO2 content of the melt. However, aluminum saturation index (ASI) does affect Sb partitioning and Sb partition coefficient for peralkaline melt (0.1 +- 0.01) is much smaller than that for metaluminous melts (0.8 +- 0.4) and that for peraluminous melts (1.3 +- 0.7). Thermodynamic calculations show that As(III) is dominant in aqueous fluid at 800 degree C and 200 MPa and XPS analysis of run product glass indicate that only As(III) exists in melt, which confirms the finding that does not affect As partitioning between fluid and melt. XPS analysis of run product glass show that Sb(V) is dominant in melt at oxidized conditions (log fO2 > -10). The peralkaline effect only exhibits on Sb partitioning, not on As partitioning at oxidized conditions, which is consistent with the x-ray photoelectron spectroscopy (XPS) measurements that As(III) and Sb(V) are dominant oxidation states in melt under oxidized conditions, because the peralkaline effect is stronger for pentavalent than trivalent cations. Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon (OC) column showed an initial sulfate reduction rate of 0.4 μmol g(oc)-1 d-1 and exhausted its capacity to promote sulfate reduction after 30 pore volumes (PVs), or 9 months of flow. The Fe0-bearing organic carbon (FeOC) column sustained a relative constant sulfate reduction rate of 0.9 μmol g(oc)-1 d-1 for at least 65 PVs (17 months). The microbial enumerations and isotopic measurements indicate that the sulfate reduction was mediated by sulfate reducing bacteria (SRB). The cathodic production of H2 by anaerobic corrosion of Fe probably is the cause of the difference in sulfate reduction rates between the two reactive mixtures. Zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs and Fe0-bearing organic carbon reactive mixture has a potential to improve the performance of organic carbon PRBs. The δ34S values can be used to determine the extent of sulfate reduction, but the fractionation is not consistent between reactive materials. The δ13C values indicate that methanogenesis is occurring in the front part of both columns. Arsenic and antimony in groundwater are great threats to human health. The PRB technology potentially is an efficient and cost-effective approach to remediate organic and inorganic contamination in groundwater. Two column experiments were conducted to assess the rates and capacities of organic carbon (OC) PRB and Fe-bearing organic carbon (FeOC) PRB to remove As and Sb under controlled groundwater flow conditions. The average As removal rate for the OC column was 13 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity was 11 μmole g-1 (dry weight of organic carbon). The remove rate of the FeOC material was 165 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity was 105 mole g-1 (dry weight of organic carbon). Antimony removal rate of the OC material decreases from 8.2 to 1.4 nmole day-1 g-1 (dry weight of organic carbon) and its removal capacity is 2.4 μmole g-1 (dry weight of organic carbon). The minimum removal rate of FeOC material is 13 nmole day-1 g-1 (dry weight of organic carbon) and its minimum removal capacity is 8.4 μmole g-1 (dry weight of organic carbon). The As(III) : [As(III)+As(V)] ratio increased from 1% in the influent to 50% at 5.5 cm from the influent end, and to 80% at 15.5 cm from the influent end of the OC column. X-ray absorption near edge spectroscopy (XANES) shows As(III)-sulfide species on solid samples. These results suggest that As(V) is reduced to As(III) both in pore water and precipitate as As sulfides or coprecipitate with iron sulfides. The arsenic reduction rate suggests that As(V) reduction is mediated by bacterial activity in the OC column and that both abiotic reduction and bacterial reduction could be important in FeOC.

Deformation and partial melting have long been recognized to occur together, but differentiating which actually occurred first has remained enigmatic. Prevailing theories suggest that partial melting typically occurs first, and deformation is localized into melt-rich areas because they are rheologically weak. However, evidence from three different areas, suggests the role of strain has been underestimated in localizing partial melting. The Wet Mountains of central Colorado provide evidence for synchronous partial melting and deformation, with each process enhancing the other. Throughout the Wet Mountains, deformation is concentrated in areas where melt producing reactions occurred, and melt appears to be localized along deformation-related features. Melt microstructures present within the Wet Mountains correlate well with crustal-scale plutons and magmatic bodies and provide a proxy for crustal-scale melt flow. Granitic gneisses from the Llano Uplift, central Texas, provide evidence for partial melting occurring within small-scale shear zones and surrounding country rocks, synchronously. In the field, shear zones appear to contain former melt, whereas the country rock does not provide macroscopic evidence for partial melting. However, detailed microstructural investigation of shear zones and country rocks indicates the same density of melt microstructures, in both rock types. Melt microstructures are important for understanding the full melting history of a rock and without detailed structural and petrographic analysis, erroneous conclusions may be reached. Granulite-facies migmatites of the Albany-Fraser Orogen, southwestern Australia, have undergone partial melting, synchronous with three phases of bidirectional extension. Four major groups of leucosomes, including: foliation-parallel, cross-cutting, boudin neck and jumbled channelway leucosomes and late pegmatites were analyzed via whole-rock geochemistry, and there is evidence for fluid-saturated and -undersaturated biotite- and amphibole-dehydration melting. Migmatites from these three locations contain pseudomorphs of melt along subgrain and grain boundaries, areas of high dislocation density, in quartz and plagioclase. For these rocks that involve multicomponent systems, the primary cause for preferential melting in high strain locations is enhanced diffusion rates along the subgrain boundary because of pipe diffusion or water associated with dislocations. / text

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In Sergipana range exists a large volume of granitic rocks, with expression in the Macururé Domain. In this field the granitic bodies are classified as Type Gloria. The Stock Granitic Gloria Sul intruded into the Macururé Domain has an area of approximately 41 km2, with slightly rounded geometry, with rocks showing a large compositional and textural homogeneity, and consist of leucocratic granites whitish mostly stock, showing types of staining gray, equigranular texture. The presence of mafic microgranular enclaves and sometimes it is noticed that the rocks exhibit anisotropic behavior marked by the orientation of mica crystals is evident. Modally rocks of the stock are classified as granites and their enclaves as alkali-feldspar quartz syenite. The rocks have an essential mineralogy consists of quartz, alkali feldspar, plagioclase (albite-oligoclase), muscovite, biotite, diopside and hornblende and magmatic epidote as accessory minerals, sphene, zircon, apatite, carbonate. The chemistry of major elements is characterized by SiO2 contents between 56,38 to 73,19%, Al2O3 from 13,82 to 15,86%, TiO2 from 0,07 to 0,98%, K2O from 1,57 to 7,05%, Na2O between 2,48 to 4,67%, CaO from 0,69 to 5,46%, Fe2O3 from 0,64 to 5,76%, MgO from 0,10 to 4,5%, MnO between 0,01 to 0,12% of P2O5, and 0,02 to 0,58%. The values of the traces show up well differentiated, showing microgranular mafic enclaves that have higher values compared to granite, with levels of Ba variation between 319-1179 ppm, Rb ranging from 55,3 to 351 ppm, Sr ranging from 183,6 to 693,5 ppm, Zr ranging from 54,2 to 224,2 ppm, Nb ranging from 3,4 to 20,8 ppm and Y ranging from 1,6 to 16,7 ppm. These rocks show ETR (ΣETR 38,58 to 299,21 ppm), Lan/Ybn ranging from 12,57 to 137,22 ppm and Eu/Eu* ranging from 0,72 to 1,94 ppm. For a classification of tectonic setting diagram using the parameters Y+Nb versus Rb, studied rocks are positioning themselves in the field of syn-collisional granitoids with the exception of granite with garnet. / Na Faixa Sergipana existe um grande volume de rochas graniticas, com expressividade no Dominio Macurure. Nesse dominio os corpos graniticos sao classificados como Tipo Gloria. O Stock Granitico Gloria Sul intrudido no Dominio Macurure apresenta uma area de aproximadamente 41 km2, com geometria levemente arredondada, com rochas exibindo uma grande homogeneidade composicional e textural, sendo constituidas por granitos leucocraticos de coloracao esbranquicada na maior parte do stock, exibindo tipos de coloracao acinzentada, textura equigranular. E evidente a presenca de enclaves maficos microgranulares e por vezes percebe-se que as rochas exibem anisotropismo marcado pela orientacao dos cristais de micas. Modalmente as rochas do stock sao classificadas como granitos e seus enclaves como alcali-feldspato quartzo sienito. As rochas apresentam como mineralogia essencial constituida por quartzo, feldspato alcalino, plagioclasio (albita.oligoclasio), muscovita, biotita, diopsidio e hornblenda, e como minerais acessorios epidoto magmatico, titanita, zircao, apatita, carbonato. A quimica de elementos maiores e caracterizada por teores de SiO2 entre 56,38.73,19%, Al2O3 entre 13,82.15,86%, TiO2 entre 0,07.0,98%, K2O entre 1,57.7,05%, Na2O entre 2,48.4,67%, CaO entre 0,69.5,46%, Fe2O3 entre 0,64.5,76%, MgO entre 0,10.4,5%, MnO entre 0,01.0,12% e P2O5 entre 0,02.0,58%. Os valores dos elementos tracos mostram-se bem diferenciados, evidenciando que os enclaves maficos microgranulares apresentam valores mais elevados em comparacao aos granitos, com teores de Ba variacao entre 319.1179 ppm, Rb variando entre 55,3.351 ppm, Sr variando entre 183,6.693,5 ppm, Zr variando entre 54,2.224,2 ppm, Nb variando entre 3,4.20,8 ppm e Y variando entre 1,6.16,7 ppm. Estas rochas mostram valores de ETR ( °ETR 38,58. 299,21 ppm), Lan/Ybn variando entre 12,57.137,22 ppm e Eu/Eu* variando entre 0,72. 1,94 ppm. Para uma classificacao do ambiente geotectonico o diagrama utilizando os parametros de Y+Nb versus Rb, as rochas estudadas posicionam-se no campo dos granitoides sin-colisionais com excecao dos granitos com granada.

Os Plutons Palermo (ca. 250 km2) e Rio Negro (ca. 130 km2) afloram na região Alto Rio Negro (PR) e fazem parte da Província Graciosa, uma província Neoproterozóica (ca. 580 Ma) constituída por granitos e sienitos na região S-SE do Brasil. Em ambos os plutons afloram variedades de rochas graníticas, predominantes, e gabro-dioríticas, bem como rochas híbridas, principalmente granodioritos. Estes plutons apresentam zonamento em geral bem marcado, que é tipicamente inverso caso do Pluton Rio Negro. As rochas graníticas principais correspondem a sieno- e monzogranitos predominantes e álcali-feldspato granitos e quartzo monzonitos subordinados de natureza metaluminosa a levemente peraluminosa. São rochas com estruturas maciças e texturas variadas que apresentam como associação mineral máfica típica hb + bi ± all + zr + ap ± ti + mt + ilm); as rochas gabro-dioríticas incluem gabro-dioritos e quartzo monzogabro-dioritos metaluminosos com estruturas maciças e granulações fina a média, caracterizadas pela associação cpx ± opx + hb + bt ± ti ± ap ± zr. A composição dos plagioclásios nestas rochas varia no intervalo de labradorita a andesina. As rochas híbridas são principalmente granodioritos que se caracterizam por uma variedade de estruturas e texturas indicativas de desequilíbrio, compatíveis com processos de coexistência e mistura parcial entre líquidos ácidos e básico-intermediários que formaram os granitos principais e os gabro-dioritos. Estas rochas são mais comuns no Pluton Rio Negro. A associação mineral máfica é similar, mas com abundâncias distintas de fases, à observada para os granitos principais. Nas rochas graníticas os anfibólios são Fe-hornblenda e Fe-edenita, com valores 0,65 < fe# < 0,95, os valores mais elevados ocorrendo nos álcali-feldspato granitos, as biotitas apresentam 0,71 < fe# < 0,99, observando-se que o componente annítico é também maior nestas últimas rochas. No caso das rochas gabro-dioríticas, os valores fe# variam entre 0,48 e 0,59, 0,41 e 0,56, 0,47 e 0,53 e 0,54 a 0,57 para ortopiroxênio, clinopiroxênio, anfibólio e biotita, respectivamente. As composições médias de orto- e clinopiroxênio coexistentes são \'Wo IND.46\'\' En IND.30\'\' Fe IND.24\' e \'Wo IND.3\'\' En IND.42\'\'Fe IND.55\' e a sugerem uma possível afinidade toleítica, ou cálcio-alcalina, para magma original. Os padrões de elementos terras raras revelam fatores de enriquecimento entre 1-10, 50-70, 100-300 em relação à composição condrítica para ortopiroxênio, clinopiroxênio e anfibólio nas rochas estudadas, com fracionamento bem marcado dos elementos leves em relação aos pesados no ortopiroxênio, não observado no caso de clinopiroxênio e anfibólio. Todos os padrões são caracterizados por anomalia negativa bem marcada de Eu. As pressões de cristalização dos magmas foram estimadas entre 1-3,5 kbar, mas os valores acima de ca. 2 kbar possivelmente não tenham significado real, dadas as composições mais ferroanas dos anfibólios. Temperaturas de saturação de zircão e/ou apatita e de equilíbrio entre orto- e clinopiroxênio, anfibólio-plagioclásio indicam intervalos de cristalização entre ca. 1000 e 750° C para as rochas gabro-dioríticas e entre ca. 900 e 670° C para os granitos principais. As paragêneses minerais e os valores obtidos para o número fe# em biotita em equilíbrio com feldspato alcalino e magnetita apontam para condições de cristalização relativamente oxidantes para as rochas félsicas, exceto os álcali-feldspato granitos, e máfico-intermediárias, superiores ao tampão QFM. / The Palermo (ca. 250 km2) and Rio Negro (ca. 130 km2) Plutons crop out in the so called Alto Rio Negro region , Parana state, making part of the Graciosa Province, a NeoProterozoic province (ca. 580 Ma) constituted by granites and syenites in S-SE Brazil. The plutons are made predominant granitic rocks, gabbro-diorites, as well as hybrid rocks constituted mainly by granodiorites. Both plutons show compositional a zoning pattern, which is inversed in the case of the Rio Negro Pluton. The main granitid rocks are mainly metaluminous to slightly peraluminous syeno- and monzogranites with subordinate quartz monzonites and alkcali-feldspar granites. They show a massive structure and a variety of textures, with hb + bi ± all + zr + ap ± ti + mt + ilm as the typical mafic mineral association. Gabbro-dioritic rocks include fine- to medium-grained metaluminous gabro-diorites and quartz monzogabrros and diorites with massive strucure characterized by the mafic mineral associations with cpx ± opx + hb + bt ± ti ± ap ± zr. In these rocks, the plagioclase compositions vary between labradorite and andesine. Hybrid rocks are mainly granodiorites characterized by several strucures and textures indicative of desiquilibrium and mingling/partial mixing between the silicic and basic-intermediate melts that formed the mainn granites and the gabbro-diorites. Such rocks are more abundant in the Rio Negro Pluton. The mafic mineral association is similar, but in contrasted relative abundance, to the ones found in the main granites. In the main granites the amphiboles are Fe-horblende and Fe-edenite, with 0.65 < fe# < 0.95, the higher among these values appearing in the alkali-feldspar granites. Biotite present 0.70 < fe# < 0.99 and the annitic component are also higher in the later rocks. In the case of the gabbro-dioritic rocks, the fe# numbers range between 0.48 and 0.59, 0.41 and 0.56, 0.47 and 0.53 and 0.54 and 0.57 in ortopyroxene, clinopyroxene, amphibole and biotite, respectively. The averaged compositions of coexisting orto- and clinopyroxene are \'Wo IND.46\'\'En IND.30\'\'Fe IND.24\' and \'Wo IND.3\'\'En IND.42\'\'Fe IND.55\' and suggest a tholeiitic or calk-alkaline nature of the original melts. Rare earth element patterns reveal enrichment factors up to 1-10, 50-70, 100-300 relative to the chondritic composition in ortopyroxene, clinopyroxene and amphibole, respectively, with a well marked fractionation of the heavy over the light rare earths in the case of the ortopyroxene, a feature not observed in clinopyroxene and amphibole. All patterns show a notable Eu negative anomaly. Melts crystallization pressures were estimated to be between 1 and 3.5 kbar; however values higher than ca. 2 kbar seems to be unrealistic given the ferroan compositions of some amphiboles. Zircon and apatite saturation temperatures coupled with ortopyroxene-clinopyroxene and amphibole-plagioclase equilibrium temperatures suggest crystallization intervals between ca. 1000 - 750° C in the case of the gabbro-diorites and ca. 900 - 670° C in the case of the main granites. Mineral paragenesis and fe# values in biotite in equilibrium with alkali-feldspar and magnetite suggests relative oxidizing crystallization conditions for the acid and basic-intermediate melts, higher than the QFM buffer, the alkali-feldspat granites being a possible exeption.