sdu.stu
Rodrigo Winck Lopes 
  
Rodrigo Winck 
email: rodrigo.winck@ufrgs.br
  
/ Thèse 
  
A S Mexias 
email: andre.mexias@ufrgs.br
  
R P Philipp 
email: ruy.philipp@ufrgs.br
  
E M Bongiolo 
email: ebongiolo@geologia.ufrj.br
  
C Renac 
  
M M Bicca 
  
E Fontana 
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
  
UNIVERSIDADE FEDERAL DO RIO

Keywords: Altération hydrothermale, Minéralisations de Cu-Ag, Géologie structurale, Bassin de Camaquã Hydrothermal alteration, Cu-Ag mineralizations, Structural geology, Camaquã Basin. UNIVERSIDADE

Les roches volcanogéniques de la Mine de Seival appartiennent à la Formation Hilário du Bassin de Camaquã, d'âge Néoprotérozoique. Cette zone contient six mines inactives avec diverses zones de prospection du cuivre et de l'argent. Les minéralisations semblent associées à un contrôle structural en régime cassant. La compréhension des transformations chimiques liées à l'hydrothermalisme et associées aux paléo-contraintes est assez méconnue dans la région. L'étude présentée fut basée sur l'obtention de mesures structurales pour comprendre les contraintes et leur cinématique dans la région, associée aux transformations chimiques des minéraux des phases magmatiques et hydrothermales de haute et basse températures. Fractures et les minéralisations montrent une direction principale N40-60°E/70-88°NW souvent associées à des veines de calcite. Les structures profondes de direction NW-SE et NE-SW étaient liées aux filons volcaniques, aux circulations de fluides hydrothermaux et aux minéralisations associées. Une modélisation thermodynamique utilisant les différentes phases minérales (magmatiques et hydrothermales) a permis d'estimer les températures de haute (tardi-magmatique) et basse (altération hydrothermale). L'albitisation (650 à 250°C) s'est produite en association avec une chloritisation (312 à 120°C). La déstabilisation des sulfures primaires (pyrite et chalcopyrite) dans les sulfures riches en cuivre (bornite-chalcocite) était associée à des interstratifiés de chlorite/smectite à des températures d'environ 250 à 50°C. Ces mêmes interstratifiés chlorite/smectite indiquent des zones riches en cuivre. Les événements plus tardifs (<150°C) souvent associés à la précipitation de barytine ont été étudiés par la chimie et les concentrations en Éléments Terres Rares de cette dernière. Cette étude montre que la source du baryum est liée au processus d'albitisation puis à l'oxydation des sulfures lors de circulation l'eau météoriques.

RESUMO

As rochas vulcanogênicas da Mina do Seival pertencem à Formação Hilário da Bacia do Camaquã, de idade Neoproterozoica. Esta área possui seis minas inativas e diversas zonas com prospectos de cobre e prata. As mineralizações foram associadas ao controle estrutural em regime rúptil. O entendimento das transformações químicas relacionadas ao hidrotermalismo e associadas ao paleostresse é pouco conhecida na região. O estudo apresentado foi baseado na obtenção de medidas estruturais para entender os esforços e sua cinemática na região, associadas às transformações químicas dos minerais das fases magmática e hidrotermal de alta e baixa temperaturas. Fraturas e mineralizações tem uma direção principal N40-60°E/70-88°NW associadas a veios de calcita. As estruturas profundas de direção NW-SE e NE-SW foram relacionadas aos filões vulcânicos, a circulação de fluidos e as mineralizações associadas. Uma modelagem termodinâmica utilizando diferentes fases minerais (magmática e hidrotermal) permitiu estimar as altas (tardi-magmática) e baixas (alteração hidrotermal) temperaturas. A albitização (650 a 250°C) ocorreu associada à cloritização (312 a 120°C). A desestabilização dos sulfetos primários (pirita e calcopirita) em sulfetos ricos em cobre (bornita-calcocita) foi associada aos interestratificados de clorita/esmectita com temperaturas em torno de ~250 a 50°C. Esses interestratificados de clorita/esmectita indicam zonas ricas em cobre. Os eventos posteriores (<150°C) frequentemente associados à precipitação de barita foram estudados através da química mineral e concentrações de Elementos Terras Raras.

Este estudo mostrou que a fonte de bário está relacionada ao processo de albitização e posterior desestabilização de sulfetos durante a circulação de água meteórica.

LISTA DE FIGURAS

Figura 1. Localização da área de estudo e vias de acesso sobre uma imagem Landsat TM 147 (adaptado de Toniolo et al., 2007) Figura 3. Modelo evolutivo do Escudo Sul-rio-grandense (600-580 Ma) com representação da colisão entre os crátons Rio de la Plata e Kalahari (sem escala; mod. de Chemale Jr., 2000;Bongiolo et al., 2011;Gastal et al., 2015) As principais estruturas e falhas estão marcadas sobre uma imagem Hillshade ASTER (mod. de Wildner et al., 2002;Toniolo et al., 2007). Zonas Figura 8. Perfil estratigráfico simplificado das sequências vulcano-sedimentar da Bacia do Camaquã (mod. de Wildner et al., 2002;Almeida et al., 2012). ........ Figura 9. Ilustração sintética dos dados geocronológicos da Bacia do Camaquã e Granitos associados. Chaves: (1) Borba et al., 2008; (2) Almeida et al., 2012; (3) Janikian et al., 2008;(4) Janikian et al., 2012; (5) Liz et al., 2009b;(6) [START_REF] Sommer | Potassic and Low-and High-Ti Mildly Alkaline Volcanism in the Neoproterozoic Ramada Plateau, Southernmost Brazil[END_REF](7) Matté et al 2016;(8) Bicca et al., 2013;(9) Oliveira et al., 2014;(10) Remus et al., 1999;(11) Gastal et al., 2006;(12) Chemale Jr., 2000. ................................................................................................ Figura 10. Mapa geológico do centro-oeste da Bacia do Camaquã com indicação da área da Associação Shoshonítica de Lavras do Sul (mod. de Toniolo et al., 2007;Gastal et al., 2015) Figura 11. Mapa geológico do Distrito Mineiro de Lavras do Sul e localização das mineralizações (mod. de Bongiolo, 2002). Depósitos e ocorrências: 1 = Bloco do Butiá; 2 = Galvão; 3 = Zeca Souza; 4 = Caneleira; 5 = Taruman Figura 13. Mapa Geológico da Mina Seival (mod. de Reischl, 1978;Lopes et al., 2014) Figura 15. A) FM07 -Amostra de testemunho de sondagem de lava andesítica amigdalóide de fluxo preenchida por calcita; B) WL13 -Amostra de mão de lava andesítica porfirítica de fluxo com minerais máficos alterados para clorita; C) WL19 -Amostra de mão de lava andesítica porfirítica de fluxo a base de plagioclásio e piroxênio alterados para clorita; D) RFM32 -Fotomicrografia em luz polarizada de lava andesítica amigdalóide de fluxo preenchida por clorita, calcita, quartzo e minerais opacos; E) WL19 -Fotomicrografia em luz natural de lava andesítica porfirítica de fluxo com fenocristal de plagioclásio alterado para calcita; F) WL19 -Fotomicrografia em luz polarizada de lava andesítica porfirítica de fluxo com fenocristal de plagioclásio e piroxênio alterados para calcita. Chaves: Cal = calcita, Clo = clorita, Pl = plagioclásio, Qtz = quartzo, Px = piroxênio......................................... 53 Figura 16. A) FM 52 -Fotografia macroscópica de testemunho de sondagem de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo; B) FM65 -Amostra de testemunho de sondagem de lapili tufo com matriz fina a base de plagioclásio e quartzo; C) RFM48 -Fotomicrografia em luz polarizada de lapili tufo com matriz fina a base de plagioclásio e quartzo; D) FM44 -Fotomicrografia em luz polarizada de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo com variação de piroclastos e diferentes cores; E, F e G) FM60, FM60 e FM62 -Fotomicrografia em luz polarizada de lapili tufo com matriz média a base de plagioclásio, piroxênio e quartzo. Figura 18. A) FM30 -Fotografia de testemunho de sondagem de dique de andesito com fenocristais de plagioclásio e piroxênio e com oxidação da matriz (cor marrom mais claro); B) RFM51 -Fotografia de amostra de mão de dique de traquiandesito com fenocristais de plagioclásio, piroxênio e biotita com intensa oxidação da matriz (cor avermelhada) e alteração dos máficos para calcita; C) DD62 -Fotomicrografia em luz polarizada de dique de andesito com zonação do plagioclásio; D) RFM66 -Fotomicrografia em luz polarizada de dique de andesito com fenocristais de plagioclásio e textura traquítica da matriz com micrólitos de plagioclásio; E) DD62 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com alteração do plagioclásio para ilita; F) RFM66 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com plagioclásio intensamente alterado para calcita; G) DD62 -Fotomicrografia em luz polarizada de dique de andesito com fenocristal preservado de piroxênio; H) RFM51 -Fotomicrografia em luz polarizada de dique de traquiandesito com fenocristal de biotita associado com titanita, apatita e minerais opacos. Figura 19. Fotomicrografia em luz polarizada dos argilominerais da Mina do Seival. A) SV77 -Lava andesítica amigdalóide de fluxo com esmectita (mod. de Fontana et al., 2017); B) FM25 -Lava andesítica amigdalóide de fluxo com interestratificado clorita/esmectita; C) FM13 -Dique de andesito com corrensita e calcita; D) RFM48 -Matriz de lapili tufo com clorita, calcita, quartzo, sulfeto, titanita e minerais opacos (mod. de Fontana et al., 2017). Figura 22. A) WL11 -Amostra de mão de lapili tufo mineralizado da Mina do Meio com bolsões de diferentes cores e associação de veios de calcocita; B) WL11 -Foto de lupa evidenciando calcocita associada a veio de calcita; C) RFM48N -Foto de lupa evidenciando bornita associada a veio de calcita; D) WL07 -Associação de malaquita e azurita como alteração de sulfetos de cobre; E) WL07 -Silicificação de matriz marcado pela textura vuggy; F) FM83 -Micrografia em luz refletida da reação de calcocita e bornita,; G) FM07 -Micrografia em luz refletida da reação de calcocita e calcopirita coronítica (mod. de Fontana et al., 2017); H) FM81 -Micrografia em luz refletida da calcopirita associada com clorita e quartzo na matriz. Chaves: Cc = calcocita, Bn = bornita, Az = azurita, Mlc = malaquita, Cpi = calcopirita. .............................. 61

Figura 23. Geoquímica de solo com anomalias de cobre, localização das minas inativas e furos de sondagem (mod. de Reischl, 1978). ............................. 63

Figura 24. Perfil A-B da figura 20 ilustrando a projeção da mineralização na Mina João Dahne (mod. de Reischl, 1978) Chaves: Cc = calcocita, Mlc = malaquita, Hem = hematita, Brt = barita, Ca = calcita. Figuras B, C e D mod. de Reischl (1978). Fonte: Google Earth. ............... 65

Figura 26. Perfil litológico e de amostragem de 6 furos de sondagem da Mina do Seival (mod. de Reischl, 1978) -Les références de ce résumé se trouvent dans le Chapitre 6 de cette thèse.

INTRODUCTION

Le Bassin Camaquã contient d'importants dépôts d'or, de cuivre et d'argent (Remus et al., 2000;Bongiolo et al., 2011;Renac et al., 2014). Dans la section du centre-ouest de ce bassin, les roches volcanogeniques (Lopes et al., 2014;Fontana et al., 2017) et plutoniques (Mexias et al., 2005) montrent une altération décrite comme altération hydrothermale tardi-magmatique (Mexias et al., 1990c(Mexias et al., et 2005;;Bongiolo et al., 2011;Fontana et al., 2017).

La zone d'étude est située à 308 km de Porto Alegre, RS -Brésil. La localité se situe entre les limites municipales de Caçapava do Sul et de Lavras do Sul, insérée dans les cartes géologiques et topographiques, Folha Arroio América (SH.22-Y-A-IV-1, 1975), échelle 1/50.000 entre coordonnées géographiques 30°41' à 30°45' S et 53°45' à 53°48' W.

La séquence volcanogénique de la 'Mina do Seival' contient six mines d'argent cuivre inactives (Reischl, 1978;Lopes et al., 2014). Des différentes mines ont ~ 0,20 Mt, avec un contenu de ~ 1,40 % de cuivre (Reischl, 1978). Les sulfures de cuivre disséminés dans des tufs à lapilli, des andésites et agglomérés volcaniques, ainsi que sur des plans de failles ou fractures. La chlorite, les interstratifiés chlorite/smectite, la malachite, l'azurite, l'hématite, la calcite, la barytine et le quartz sont associés aux sulfures de cuivre.

La chimie des minéraux magmatiques, des altérations hydrothermales et des minéralisations ainsi que le contrôle structural des dépôts minéraux ne sont pas bien caractérisées dans cette région. Cette thèse se propose de mieux les caractériser dans le but de mieux comprendre ces minéralisations.

GÉOLOGIE RÈGIONAL

La région de Lavras do Sul est constituée d'un socle composé de roches ultramafiques, de métagranitoïdes et de schistes (Cambaí Complexes). Ce socle est partiellement recouvert des roches sédimentaires de la Formation Maricá (Borba et al., 2006). Ces roches plutoniques et volcano-sédimentaires furent intrudées par les roches du complexe de Lavras do Sul (Mexias et al., 2005;Bongiolo et al., 2011), Morcego; iv: Meio; v: Cruzeta; vi: Alcides) sur six sites miniers, désormais inactifs (Reischl, 1978) ont été exploités dans la Formation Hilário. Ces carrières à ciel ouvert et galeries semblent associés à une structuration régionale d'orientation NE-SW et parfois NW-SE.

UNIVERSIDADE

METHODES

Les observations pétrographiques, la diffraction de rayons X, les mesures structurales, la géochimie et la chimie minérale collaborent à cette compréhension de l'hydrotermalisme dans la région. Le travail sur le terrain et la pétrographie ont rendu possible la classification de la roche, la description de la minéralogie et des aspects texturaux, mettant l'accent sur les phases secondaires dites d'altération.

Grâce à la diffraction de rayons X, à la chimie minérale et à la géochimie des Éléments Terres Rares, il a été possible d'établir une corrélation entre les éléments liés à la minéralisation de cuivre. Sont présentées ci-dessous les principales méthodes utilisées et leurs applications dans cette thèse :

-Description pétrographique d'échantillons de surface et de 7 forages

(ayant jusqu'à 130 m de profondeur) pour la compréhension de la lithologie;

-Analyse structurale avec mesures cinématiques et direction des failles/fractures pour la détermination des paléo-contraintes de la région; -Chimie minérale des phases magmatiques (andésine -labradorite, augite et biotite) et hydrothermales (albite, titanite, chlorite, smectite et minéraux interstratifiés chlorite/smectite) mesurés par microsonde électronique.

-Géochimie des éléments traces, mesurés par ICPMS, extraits de concentrés de plagioclase, de barytine et de calcite. 

INTRODUÇÃO

A Bacia do Camaquã e as rochas graníticas associadas de idade Neoproterozoica contêm significativos depósitos de ouro, cobre, prata, chumbo e zinco (Remus et al., 2000;Bongiolo et al., 2011;Renac et al., 2014). Dentre estes, o maior depósito de cobre-ouro e chumbo-zinco desta bacia é a Mina do Camaquã, hospedada em uma sequência de rochas sedimentares (Ronchi et al., 2000;Remus et al., 2000;Laux et al., 2005;Renac et al., 2014). Este depósito possui uma reserva de minério de ~30,8 Mt, com teor médio de ~1,06 % de cobre, ocorrendo como calcopirita, pirita, bornita, calcocita, ouro, prata e hematita na forma de veios maciços, stockwork ou disseminados na rocha.

Na seção centro-oeste desta bacia, as rochas vulcanogênicas (Lopes et al., 2014;Fontana, 2017;Fontana et al., 2017) e plutônicas (Mexias et al., 2005) são caracterizadas por uma alteração pervasiva descrita como alteração hidrotermal tardi-magmática (Mexias et al., 1990c(Mexias et al., e 2005;;Bongiolo et al., 2011;Fontana et al., 2017). Neste contexto, as áreas estudadas de Lavras do Sul e Seival hospedam ouro-cobre nas rochas graníticas e cobre-prata nas unidades vulcanogênicas.

As rochas do Distrito Mineiro de Lavras do Sul compreendem dezenove depósitos ou ocorrências (Mexias et al., 2007;Bongiolo et al., 2011). Dentro desses depósitos as zonas de minério consistem em veios de quartzo ricos em sulfetos (Mexias et al., 2005) associados à alteração hidrotermal de "sericita", clorita, pirita, calcopirita e minério de ouro e cobre (Bongiolo et al., 2011).

A sequência vulcanogênica da Mina do Seival possui seis minas inativas de cobre-prata (Reischl, 1978;Lopes et al., 2014). A reserva foi cubada em ~0,20 Mt de rocha mineralizada com um teor de ~1,40 % de cobre (Reischl, 1978). Os sulfetos ricos em cobre ocorrem associados com interestratificado clorita/esmectita. Esses sulfetos estão disseminados na porosidade de rochas como o lapili tufo e do aglomerado vulcânico, assim como formam uma rede de stockwork e veios ao longo de planos de falha ou fratura.

A relação da química do hidrotermalismo e das mineralizações com o paleostresse e controle estrutural não é bem caracterizada na região. Além disso, apenas algumas análises de geoquímica em baritas foram realizadas na Bacia do Camaquã. Minha proposta nesta tese é a caracterização da química mineral das fases hidrotermais tardi-magmáticas de alta a baixa temperatura, assim como a determinação dos esforços estruturais responsáveis pela circulação do fluido hidrotermal e pelas mineralizações.

Objetivos

O objetivo principal desta tese é caracterizar os esforços envolvidos, as estruturas que controlam a migração de fluidos mineralizantes e as assembleias minerais da Mina do Seival, para com isso determinar uma relação mineralógica entre as fases magmática e de alteração hidrotermal e as mineralizações de cobreprata. A contribuição desse estudo, para a área de trabalho, é a caracterização da alteração hidrotermal e, para a grande área de conhecimento, uma contribuição na exploração de depósitos similares da Bacia do Camaquã ou ambientes similares.

Com a obtenção de testemunhos de sondagens e coleta de amostras nos trabalhos de campo, foi possível levantar algumas questões importantes ainda não conhecidas, como:

-Quais são os esforços e as estruturas que controlam o fluxo hidrotermal e as mineralizações?

-Quais são as modificações químio-mineralógicas associadas à alteração hidrotermal e as mineralizações?

-Quais são as temperaturas dos processos hidrotermais envolvidos? 

Localização e vias de acesso

A área de estudo está situada a cerca de 308 km de Porto Alegre, percorrese 240 km pela rodovia BR-290, 17 km pela BR-392 e 51 km pela RS-357, sentido SW, até o limite entre os municípios de Caçapava do Sul e Lavras do Sul (Fig. 1).

O acesso a área da Mina do Seival se dá por estrada não pavimentada. A localidade está inserida na carta topográfica do Serviço Geológico do Exército, Folha Arroio América (SH.22-Y-A-IV-1, 1975), em escala de 1:50.000, entre as coordenadas geográficas 30°41' a 30°45' S e 53°45' a 53°48' W.

Figura 1. Localização da área de estudo e vias de acesso sobre uma imagem Landsat TM 147 (adaptado de Toniolo et al., 2007).

Amostragem

A amostragem realizada em trabalhos de campo teve como objetivo comparar e caracterizar as diferentes litologias e texturas. A amostragem também foi realizada em testemunhos de sondagem, com a vantagem de poder observar variações destas em profundidade e em sequência e também compará-las com as feições encontradas nos afloramentos. Foram amostrados sete testemunhos de sondagem na área da Mina do Seival. A partir do objetivo traçado, a utilização das técnicas foi uma etapa importante para obter os resultados esperados. Para facilitar, a descrição das técnicas utilizadas foi dividida em oito partes.

Para isso, foram realizadas análises químicas em amostras de campo e em testemunhos de sondagens de diversas fases minerais, assim como medidas estruturais em falhas e fraturas. Dessa maneira, com o auxílio da petrografia, química mineral, difratometria de raios X e geologia estrutural foi possível avançar no conhecimento da alteração hidrotermal, das temperaturas envolvidas nos processos de cristalização e dos esforços responsáveis pela circulação de fluidos e mineralizações.

Revisão bibliográfica

A revisão bibliográfica reuniu um conjunto de publicações referentes às áreas de estudo e a assuntos relacionados ao tema, como química mineral, alteração hidrotermal, mineralizações de cobre, e sobre a Bacia do Camaquã, sistematizando assim um coleção de referências dos métodos e de comparação geológica a serem utilizados neste trabalho.

Campo e descrição de testemunhos de sondagem

Essa etapa consistiu na realização de trabalhos de campo para a coleta de amostras, descrições das ocorrências e mineralizações. O mapeamento geológico contribuiu para a representação da distribuição das rochas na área. A descrição de 

Imagens utilizadas no mapeamento geológico

Os materiais utilizados no mapeamento geológico foram a Folha do Exército -Arroio América (SH.22-Y-A-IV-1, 1975) na escala 1:50.000 e um mapa geológico da região desenvolvido por Reischl (1978) com poucos detalhes litoestatigráficos.

Também se utilizou imagem TM Landsat banda 4 e imagens de satélite obtidas pelo software Google Earth, além de fotointerpretação através de fotografias aéreas, que foram utilizadas para traçar os contatos dos litotipos, as estruturas e as falhas, auxiliando a compreensão da estruturação das minas, assim como sua relação com falhas e estruturas locais/regionais.

Pós campo

A reformulação do mapa geológico anterior (Reischl, 1978;[START_REF] Lopes | Alteração hidrotermal e mineralização de cobre na Mina do Seival, Bacia do Camaquã, RS. Porto Alegre[END_REF]Lopes et al., 2014) foi realizada com a ferramenta GIS com a geração de um novo mapa geológico apresentado na parte 3 desta tese. O ANEXO C contém o número do ponto, localização com a UTM em Datum Córrego Alegre, unidade litológica e tipo de rocha, bem como profundidade nas amostras de testemunho de sondagem.

Geologia estrutural

A análise de imagens de satélite consistiu na visualização e no traçado dos lineamentos que ocorrem na região e na escala regional. 

Caracterização petrográfica

A mineralogia, as texturas e as relações entre os minerais foram identificadas com o uso de diversos microscópios em diferentes instituições de ensino e foram fotografadas sempre que possível ou necessário. A análise petrográfica foi realizada em amostras coletadas nos trabalhos de campo e de testemunhos de sondagem.

Um total de 91 lâminas petrográficas foram confeccionadas no Instituto de Geociências -UFRGS amostradas nos trabalhos de campo (37 lâminas) e testemunhos de sondagem SV 78-11 (19 lâminas), SV 78-01 (9 lâminas), SV 78-15 (11 lâminas), SV 78-16 (6 lâminas), SV 78-18 (4 lâminas) e SV 78-09 (5 lâminas), relativos também à monografia de conclusão de curso e à dissertação de mestrado.

Caracterização mineralógica

A caracterização mineralógica primária e secundária foi realizada através das técnicas de difratometria de raios X (DRX), microscopia eletrônica de varredura (MEV) e microssonda eletrônica (MSE). A seguir, é apresentada cada uma dessas técnicas.

Difratometria de raios X

As análises de DRX tiveram como objetivo a caracterização dos minerais de alteração e do controle de pureza em minerais separados, como no caso da barita.

Foram confeccionados cerca de 50 difratogramas pelo método do pó e 41 difratogramas pelo método das amostras orientadas, estando presentes esses últimos no ANEXO G.

Os fragmentos de amostras foram moídos em grau de ágata até a porção pó.

Foram separados cerca de 8 ml (medida do frasco) de pó de cada amostra. Após moagem e ultrassom, as amostras passaram pelo agitador por no mínimo 24 horas, tempo determinado para obter a fração desejada de < 0,4 μm. calculados através do programa NEWMOD [START_REF] Reynolds | NEWMOD, a Computer Program for the Calculation of Onedimensional Diffraction Patterns of Mixed-layered Clays[END_REF] em colaboração com a tese publicada por Fontana (2017). 

Microssonda eletrônica

Os minerais ígneos e hidrotermais foram analisados para química mineral.

Os minerais ígneos analisados foram piroxênio, plagioclásio e biotita, enquanto os minerais hidrotermais analisados foram albita, titanita, clorita, esmectita e interestratificado clorita/esmectita. 

CONTEXTUALIZAÇÃO -BACIA DO CAMAQUÃ

Nesta parte do trabalho é descrito o estado da arte da geologia regional com descrição da Bacia do Camaquã, Associação Shoshonítica de Lavras do Sul e mineralizações associadas.

Bacia do Camaquã

A orogenia que promoveu a colagem de terrenos Neoproterozoicos deu origem ao Paleocontinente Gondwana Ocidental (Fig. 2). A Província Mantiqueira Associado ao Escudo Sul-rio-grandense, ocorre a Bacia do Camaquã, uma bacia plutono-vulcano-sedimentar com idades Neoproterozoica-Cambriana (Fig. 3), de elongação NE-SW, onde situa-se a área de estudo. Essa bacia pode ser correlacionada com a Bacia do Itajaí no estado de Santa Catarina [START_REF] Guadagnin | Depositional age and provenance of the Itajaí Basin, Santa Catarina State, Brazil: Implications for SW Gondwana correlation[END_REF][START_REF] Basei | The Itajaí foreland basin: a tectono-sedimentary record of the Ediacaran period, Southern Brazil[END_REF][START_REF] Font | Paleomagnetism and rock magnetism of the Neoproterozoic Itajaí Basin of the Rio de la Plata craton (Brazil): Cambrian to Cretaceous widespread remagnetizations of South America[END_REF][START_REF] Lopes | Alteração hidrotermal e mineralização de cobre na Mina do Seival, Bacia do Camaquã, RS. Porto Alegre[END_REF], com a Bacia de Castro no estado do

Paraná, e com as bacias de Barriga Negra, Piriápolis, San Carlos e Cerros de Aguirre no Uruguai [START_REF] Sánchez-Bettucci | Neoproterozoic subaqueous extrusive-intrusive rocks in the Playa Hermosa Formation in Uruguay: regional and stratigraphic significance[END_REF] e com a Bacia do Nama na Namíbia [START_REF] Meert | The Nama Group, Namibia revisited[END_REF] (Fig. 4).

Figura 3. Modelo evolutivo do Escudo Sul-rio-grandense (600-580 Ma) com representação da colisão entre os crátons Rio de la Plata e Kalahari (sem escala; mod. de Chemale Jr., 2000;Bongiolo et al., 2011;Gastal et al., 2015). O Escudo Sul-rio-grandense consiste em Terreno Taquarembó, Terreno São Gabriel, Terreno Tijucas e Batólito Pelotas [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Hartmann et al., 2007). Esses terrenos tectônicos possuem três zonas de cisalhamento principais:

Ibaré; Caçapava do Sul; Dorsal do Canguçu. O Terreno São Gabriel está separado do Terreno Taquarembó pela Zona de Cisalhamento Ibaré (NW-SE), localizado a sudoeste e separado do Terreno Tijucas pela Zona de Cisalhamento Caçapava do Sul (NE-SW), localizada a leste (Saalmann et al., 2005;Hartmann et al., 2007). O Terreno São Gabriel possui estruturas principais de direção NE-SW representada pelas falhas Cabritos-Perau e Segredo (Fig. 5).

Figura 5. Mapa esquemático da geologia do Escudo Sul-rio-grandense com os 4 blocos tectônicos e localização da Bacia do Camaquã (mod. de Hartmann et al., 2007).

O embasamento da Bacia do Camaquã compreende gnaisse, paragnaisse e rochas meta-vulcano-sedimentar, com movimento NW-SE, deformadas entre 750-680 Ma [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Saalmann et al., 2011). A Bacia de Camaquã é dividida em quatro grupos e várias formações depositadas em quatro eventos diferentes: i) o Grupo Maricá é depositado como parte de uma bacia de retro-arco ou foreland [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Borba et al., 2008); ii) as unidades do Grupo Bom Jardim são depositadas em uma bacia do tipo transpresional strike-slip (Lima et al., 2007;Janikian et al., 2008); iii) as unidades dos grupos Santa Bárbara são formadas em um evento transtensional strike-slip (Paim et al., 2000;Bicca et al., 2013); iv) O Grupo Guaritas é formado durante um evento de subsidência transtensional (Bicca et al., 2013;Oliveira et al., 2014) (Fig. 6).

Figura 6. Mapa Geológico da Bacia de Camaquã com transparência de 50%. As principais estruturas e falhas estão marcadas sobre uma imagem Hillshade ASTER (mod. de Wildner et al., 2002;Toniolo et al., 2007). Zonas de Cisalhamento: ZCI = Ibaré; ZCCS = Caçapava do Sul; ZCDC = Dorsal do Canguçu.

Na Bacia de Camaquã, as jazidas mais significativas são as Minas do Camaquã, que possuem o maior volume de minério (Remus et al., 2000;Laux et al., 2005;Renac et al., 2014) Grupo Bom Jardim (Remus et al., 2000;Toniolo et al., 2004), localizado na região de Caçapava do Sul. As minas Crespos e Silveira ocorrem associadas ao magmatismo Acampamento Velho, ao norte da Mina do Seival. A localização das principais minas associadas à Bacia do Camaquã é apresentada na Figura 7.

Figura 7. Localização das principais minas de Cu, Au-Cu e Pb-Zn na Bacia do Camaquã (mod. de Toniolo et al., 2007).

Estratigrafia da Bacia do Camaquã

O Grupo Maricá é representado pela Formação Maricá, interpretada como uma sequência sedimentar de rochas com clastos vulcânico (Borba et al., 2008) com aproximadamente 4.000 metros de espessura (Paim et al., 2000) dividida em três pacotes sedimentares (Borba et al., 2006).

Neste trabalho, consideramos o Complexo Intrusivo de Lavras do Sul correlato ao Grupo Bom Jardim, e ambos pertencem à Associação Shoshonítica de Lavras do Sul (Lima e Nardi, 1998). O Grupo Bom Jardim é uma sequência de 2.000 metros de espessura (Janikian et al., 2003) de rochas vulcano-sedimentares da Formação Hilário, representadas por lava andesítica de fluxo (Nardi e Lima, 1985) e rochas piroclásticas (Lopes et al., 2014) associadas a rochas lamprofíricas (Lima e Nardi, 1998) e sedimentares na porção oeste e central da bacia. O Complexo Intrusivo de Lavras do Sul corta a Formação Hilário e é composto de um núcleo de fase plutônica (Nardi, 1984;Raposo e Gastal, 2009;Gastal et al., 2015) e intrusões superficiais de rochas monzoníticas concentradas principalmente na margem nordeste (Nardi, 1984;Gastal et al., 2006).

O Grupo Santa Bárbara é composto por rochas vulcano-sedimentares da Formação Santa Fé, rochas sedimentares da Formação Santa Bárbara (Bicca et al., 2013;Oliveira et al., 2014) e rochas vulcânicas bimodais da Formação Acampamento Velho [START_REF] Sommer | Reoignimbritos e ignimbritos de alto grau do vulcanismo Acampamento Velho, RS: origem e temperatura de formação[END_REF]Almeida et al., 2012).

O Grupo Guaritas hospeda rochas vulcânicas da Formação Rodeio Velho e pacotes sedimentares da Formação Pedra Pintada e Guaritas (Almeida et al., 2012;Oliveira et al., 2014). A Figura 8 representa um perfil estratigráfico simplificado da Bacia do Camaquã com uma breve descrição dos grupos associados. Figura 8. Perfil estratigráfico simplificado das sequências vulcano-sedimentar da Bacia do Camaquã (mod. de Wildner et al., 2002;Almeida et al., 2012).

Dados geocronológicos

Os dados geocronológicos disponíveis são ainda restritos. Existe um questionamento em relação às rochas da Formação Hilário com idades referentes às lavas andesíticas de fluxo que ocorrem próximo à área.

A Formação Maricá foi datada pelo método 238 Pb/ 206 U com 630 ± 3,4 Ma, (Borba et al., 2008) em zircão de um clasto riolítico do conglomerado localizado no planalto Ramada, sul da cidade de Vila Nova do Sul, interpretado como uma idade de proveniência ou idade máxima. O zircão detrítico de arenito localizado a oeste e próximo a Lavras do Sul tem a base deposicional máxima no topo desta unidade, com idade de 601 ± 13 Ma (Almeida et al., 2012), datada pelo mesmo método.

As primeiras idades determinadas em plagioclásios de rochas andesíticas na Formação Hilário pelo método K-Ar estão entre 510-535 Ma (Ribeiro e Teixeira, 1970). As idades preliminares obtidas pelo método Rb/Sr têm idades de 510 e 535 (Almeida et al., 2012), sendo interpretadas como pertencentes à Formação Hilário. O Cerro da Angélica, localizado cerca de 30 km a leste da área de estudo, foi datado em grãos de zircão pelo método de 238 Pb/ 206 U com idades de 600,5 ± 2,4 Ma para dique granítico, interpretada como a idade de cristalização do granito (Janikian et al., 2012).

A Formação Santa Bárbara foi datada pelo método 238 Pb/ 206 U em zircão com idades de 573 ± 18 Ma [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF], 574 ± 7 e 572 ± 6,5 Ma (Janikian et al., 2012) na região central da bacia. Na região das Minas de Camaquã, no leste da bacia, as análises de proveniência de zircão pelo método 238 Pb/ 206 U obtiveram idades de 566 ± 6,9 Ma, interpretadas como idade de deposição máxima (Bicca et al., 2013). As idades deposicionais máximas das três sequências deposicionais primárias da Formação Santa Bárbara, em sucessão ascendente, são 567,9 ± 5,9

Ma, 562,5 ± 5,5 e 553 ± 22 Ma (Oliveira et al., 2014).

A Formação Acampamento Velho foi datada pelo método 238 Pb/ 206 U apresentando idades de 549,3 ± 5 Ma em grãos de zircão das rochas hipo-abissais riolíticas do Planalto Ramada [START_REF] Sommer | Potassic and Low-and High-Ti Mildly Alkaline Volcanism in the Neoproterozoic Ramada Plateau, Southernmost Brazil[END_REF]. As rochas vulcânicas ácidas da região de Caçapava do Sul foram datadas com 574 ± 7 Ma (Janikian et al., 2008) e 553 ± 5,4 Ma (Almeida et al., 2012) [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF][START_REF] Almeida | The Acampamento Velho Formation, a Lower Cambrian bimodal volcanic package: geochemical and stratigraphics studies from the Cerro do Bugio, Perau and Serra de Santa Bárbara (Caçapava do Sul, Rio Grande do Sul, RS-Brazil)[END_REF] 

Associação Shoshonítica de Lavras do Sul

A Associação Shoshonítica de Lavras do Sul apresenta características de um magmatismo pós-colisional relacionado aos estágios finais da orogenia Brasiliana, conforme discutido em Lima e Nardi (1998), Sommer et al. (2006) e Liz et al. (2009).

Localizada no Terreno São Gabriel, possui estratigraficamente na base traquibasaltos potássicos, sucedidos por quatro ciclos efusivos shoshoníticos, além de depósitos piroclástico de queda e fluxo [START_REF] Lima | Petrologia das Rochas Vulcânicas e Hipabissais da Associação Shoshonítica de Lavras do Sul -ASLS, RS. Porto Alegre, Tese de Doutorado[END_REF]. Ocorrem intrusões monzonítica rasa, dique traquiandesítico a riolítico e lamprófiro espessartítico (Müller et al., 2012). A fração plutônica da Associação Shoshonítica de Lavras do Sul é representada pelo Complexo Intrusivo de Lavras do Sul (Gastal et al., 2015) e a porção vulcanogênica é representada pela Formação Hilário. A Figura 10 representa a parte centro-oeste da Bacia do Camaquã e delimita a área da Associação Shoshonítica de Lavras do Sul. Figura 10. Mapa geológico do centro-oeste da Bacia do Camaquã com indicação da área da Associação Shoshonítica de Lavras do Sul (mod. de Toniolo et al., 2007;Gastal et al., 2015).

As rochas vulcanogênicas básicas da Associação Shoshonítica de Lavras do Sul possuem composições traquibasáltica a traquiandesítica pelo diagrama TAS e mostram que o potássio é superior ao valor de sódio, sendo classificadas como traquibasaltos potássicos e shoshonitos (Lima e Nardi, 1998). Ocorrem expressivos depósitos efusivos aliados a uma fração piroclástica de fluxo de natureza traquiandesítica a riolítica [START_REF] Lima | Petrologia das Rochas Vulcânicas e Hipabissais da Associação Shoshonítica de Lavras do Sul -ASLS, RS. Porto Alegre, Tese de Doutorado[END_REF], especialmente na porção sudeste do Complexo Intrusivo de Lavras do Sul, o que permite sugerir uma extração gradativa do magma responsável pela geração de um sistema de caldeira (Gastal et al., 2015).

As [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Paim et al., 2000;Hartmann et al., 2007).

Este conjunto foi posteriormente sobreposto e intrudido por rochas do Complexo Intrusivo de Lavras do Sul (Nardi, 1984;Bongiolo et al., 2011;Gastal et al., 2015).

Vulcanitos ácidos e básicos, de afinidade alcalina sódica saturada em sílica, e rochas sedimentares do Grupo Santa Bárbara sucedem esta associação (Paim et al., 2000;Toniolo et al., 2007).

Na Mina do Seival, a Formação Hilário é representada por lava andesítica de fluxo, lapili tufo, aglomerado vulcânico e corpos hipo-abissais de composição andesítica a traquiandesítica, principalmente diques de orientação NE-SW. As rochas piroclásticas são lapili tufo com mineralogia a base de plagioclásio e piroxênio, variando conforme a profundidade. As lavas andesíticas de fluxo podem ser amigdalóides com matriz fina ou porfiríticas. Em algumas porções, essas rochas vulcanogênicas encontram-se intensamente fraturadas. O aglomerado vulcânico é composto de piroclastos arredondados em uma matriz afanítica de coloração escura. Todo este conjunto é coberto pelas rochas conglomerática e vulcânica vesiculada da Formação Santa Fé (Toniolo et al., 2007). Esse conglomerado polimítico de clasto-suportado varia de centimétrico a decamétrico, enquanto que a vulcânica vesiculada possui matriz a base de plagioclásio e vesículas de 0,2 a 0,5 cm, o que difere da lava andesítica de fluxo da Formação Hilário. Os depósitos aluvionares são sedimentos fluviais dominantemente arenosos e localizam-se na porção oeste da área de estudo ao longo do Arroio Teixeira. As projeções fenocristal de piroxênio geralmente é zonado, e o de plagioclásio é alterado para albita. A textura traquítica é marcada pela orientação dos micrólitos de plagioclásio.

A Figura 15 apresenta as principais características das amostras de lavas andesíticas de fluxo.

Figura 15. A) FM07 -Amostra de testemunho de sondagem de lava andesítica amigdalóide de fluxo preenchida por calcita; B) WL13 -Amostra de mão de lava andesítica porfirítica de fluxo com minerais máficos alterados para clorita; C) WL19 -Amostra de mão de lava andesítica porfirítica de fluxo a base de plagioclásio e piroxênio alterados para clorita; D) RFM32 -Fotomicrografia em luz polarizada de lava andesítica amigdalóide de fluxo preenchida por clorita, calcita, quartzo e minerais opacos; E) WL19 -Fotomicrografia em luz natural de lava andesítica porfirítica de fluxo com fenocristal de plagioclásio alterado para calcita; F) WL19 -Fotomicrografia em luz polarizada de lava andesítica porfirítica de fluxo com fenocristal de plagioclásio e piroxênio alterados para calcita. Chaves: Cal = calcita, Clo = clorita, Pl = plagioclásio, Qtz = quartzo, Px = piroxênio.

As rochas piroclásticas foram classificadas com base na granulometria em lapili tufo e aglomerados vulcânicos. São compostas por piroclastos de diferentes composições (lava andesítica porfirítica, lava andesítica amigdalóide, lava andesítica avermelhada e rochas piroclásticas) e possuem diversas formas, desde arredondadas a angulosas, geralmente com bordas curvilíneas. A matriz da rocha piroclástica é um tufo grosso (0,05 a 0,12 mm) a fino (<0,05 mm) composto por cristaloclastos de plagioclásio, ± piroxênio, quartzo, matriz vítrea microcristalina e material opaco. As rochas piroclásticas foram separadas, de acordo com a composição da matriz, em ricas em plagioclásio e ricas em plagioclásio e piroxênio. Na rocha piroclástica rica em plagioclásio, a matriz é composta por material fino, amorfo, descrito como cinza ou pó vulcânico, ou até mesmo porção vítrea com muitos cristaloclastos e partes de cristaloclastos de plagioclásio e quartzo. As rochas piroclásticas são predominantemente de lava andesítica de fluxo ricas em plagioclásio. Na rocha piroclástica rica em plagioclásio e piroxênio, a matriz é composta por material grosso a muito fino com muitos cristaloclastos e partes de cristaloclastos de plagioclásio, piroxênio e quartzo. Nessas últimas, os piroclastos são predominantemente de lava andesítica de fluxo ricas em plagioclásio e piroxênio. Em geral, o lapili tufo possui uma grande variação na composição dos piroclastos, sendo distinguíveis pela mineralogia e cor de alteração. A Figura 16 apresenta as principais características das amostras de lapili tufo.

Figura 16. A) FM 52 -Fotografia macroscópica de testemunho de sondagem de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo; B) FM65 -Amostra de testemunho de sondagem de lapili tufo com matriz fina a base de plagioclásio e quartzo; C) RFM48 -Fotomicrografia em luz polarizada de lapili tufo com matriz fina a base de plagioclásio e quartzo; D) FM44 -Fotomicrografia em luz polarizada de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo com variação de piroclastos e diferentes Figura 18. A) FM30 -Fotografia de testemunho de sondagem de dique de andesito com fenocristais de plagioclásio e piroxênio e com oxidação da matriz (cor marrom mais claro); B) RFM51 -Fotografia de amostra de mão de dique de traquiandesito com fenocristais de plagioclásio, piroxênio e biotita com intensa oxidação da matriz (cor avermelhada) e alteração dos máficos para calcita; C) DD62 -Fotomicrografia em luz polarizada de dique de andesito com zonação do plagioclásio; D) RFM66 -Fotomicrografia em luz polarizada de dique de andesito com fenocristais de plagioclásio e textura traquítica da matriz com micrólitos de plagioclásio; E) DD62 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com alteração do plagioclásio para ilita; F) RFM66 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com plagioclásio intensamente alterado para calcita; G) DD62 -Fotomicrografia em luz polarizada de dique de andesito com fenocristal preservado de piroxênio; H) RFM51 -Fotomicrografia em luz polarizada de dique de traquiandesito com fenocristal de biotita associado com titanita, apatita e minerais opacos. A alteração pervasiva transforma a grande maioria dos minerais máficos e subordinadamente os feldspatos que ocorrem na matriz e piroclastos. O piroxênio aparece totalmente substituído para clorita, carbonato e hematita. A alteração supergênica é representada pela malaquita e azurita e ocorre nas zonas mineralizadas (Fig. 22D). A silicificação ocorre sempre em falhas e fraturas substituindo parcial ou totalmente a rocha, descrita como textura Vuggy (Fig. 22E).

Os sulfetos ricos em cobre (calcocita e bornita) estão corroídos (Fig. 22F e G). Os sulfetos de ferro e cobre-ferro são pirita e calcopirita (Fig. 22H). A barita ocorre preenchendo fraturas de espessuras centimétricas e sob a forma de cristais tabulares geminados, localmente alterados.

A Figura 22 ilustra os sulfetos da Mina do Seival e a alteração supergênica.

Figura 22. A) WL11 -Amostra de mão de lapili tufo mineralizado da Mina do Meio com bolsões de diferentes cores e associação de veios de calcocita; B) WL11 -Foto de lupa evidenciando calcocita associada a veio de calcita; C) RFM48N -Foto de lupa evidenciando bornita associada a veio de calcita; D) WL07 -Associação de malaquita e azurita como alteração de sulfetos de cobre; E) WL07 -Silicificação de matriz marcado pela textura vuggy; F) FM83 -Micrografia em luz refletida da reação de calcocita e bornita,; G) FM07 -Micrografia em luz refletida da reação de calcocita e calcopirita coronítica (mod. de Fontana et al., 2017); H) FM81 -Micrografia em luz refletida da calcopirita associada com clorita e quartzo na matriz. Chaves: Cc = calcocita, Bn = bornita, Az = azurita, Mlc = malaquita, Cpi = calcopirita.

Mineralizações

As mineralizações na Mina do Seival estão descritas em Reischl (1978), A geoquímica de solo mostra as anomalias de cobre (Reischl, 1978) e evidencia o padrão alinhado das mineralizações (Fig. 23).

UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES

MINA DO SEIVAL | 63

Rodrigo Winck LOPES

-2018-Tese de doutorado / THÈSE Figura 23. Geoquímica de solo com anomalias de cobre, localização das minas inativas e furos de sondagem (mod. de Reischl, 1978).

A Figura 24 ilustra três perfis litológicos do mapa geológico simplificado da Figura 12.

Figura 24. Perfil A-B da figura 20 ilustrando a projeção da mineralização na Mina João Dahne (mod. de Reischl, 1978).

A Tabela 4 apresenta uma compilação descritiva de cada uma das seis minas que compreende o depósito da Mina do Seival com tonelagem e teores de Cu e Ag para as minas desativadas. (Reischl, 1978). Ton. = tonelagem.

A Figura 25 ilustra as mineralizações em planta. As localizações das mineralizações podem ser encontradas nas seguintes coordenadas geográficas: 1) Falha de direção 40° NE (100 m de extensão) e filão imbricado em várias direções a partir desta principal. Filão de 2 m de espessura com "pockets" de cores avermelhado e amarelado. Muitos veios de barita com direção N-S.

João Dahne

Lapili tufo / lava andesítica de fluxo Mina desativada com 3 trincheiras. A mais ao norte tem difícil acesso e muita vegetação. A mais ao sul está inundada e com acesso muito difícil. A cava ao centro é de fácil acesso e com menor dimensão. Pilhas de rejeito.

20.000* -

3 trincheiras/cavas principais com minério disseminado. Contato entre piroclástica e lava andesítica porfirítica de fluxo. As dimensões da cava variam de 20 a 40 m.

Morcego

Lava andesítica de fluxo

Filão e pequena galeria de 4x4 m. Acesso pela mata ciliar. 15.000 2,5% Cu Filão de 2 m com mergulho subvertical e minério disseminado.

Cava com 10 m de extensão.

Meio

Lapili tufo

Trincheira não inundada com 60 m de extensão e poço. Fácil acesso.

18.000 0,6% Cu e 15 ppm Ag Trincheira de 2 m de espessura de direção N-S com "pockets" de cores avermelhado e amarelado e minério disseminado.

Cruzeta

Lava andesítica de fluxo

Acesso difícil pela pilha de rejeito até o interior da cava/trincheira. 2 filões sendo o de direção NW inundado.

15.000* -Minério disseminado ao longo dos planos de falha/fratura com 30 m de extensão.

Alcides

Lapili tufo

Fácil acesso as cavas e pilhas de rejeito. 3 cavas principais parcialmente inundadas. 

Introduction

Structurally controlled mineralization is well documented in Au-Cu-Ag deposits of orogenic belts. These deposits tend to be formed by reactivation of shear zones, allowing the development of intense fracturing, leading to fluid percolation and ore deposits. This sort of mineralizations is characteristic of porphyry-epithermal models (Seedorff et al., 2005;[START_REF] Sillitoe | Porphyry copper systems[END_REF], as occurs in Potrerill Cu-Mo porphyry deposits and El Hueso Au epithermal deposits [START_REF] Sillitoe | Gold metallogeny of Chilean introduction[END_REF], Nevada porphyry (Carten, 1986;Barton and Johnson, 2000), and as well as in iron oxide copper-gold deposits (IOCG, Dilles and Einaudi, 1992;[START_REF] Sillitoe | Iron oxide-copper-gold deposits: An Andean view[END_REF]Mark et al., 2006).

In the Sul-rio-grandense Shield, the ore deposits are associated with development of NE-SW and NW-SE oriented shear zones that cross cut the Camaquã Basin and associated granitoid rocks of Late Neoproterozoic age. Along these faults, a series of Au, Cu, Ag, Pb and Zn-rich ores occur within volcanogenic and granitoid rocks associated with the Camaquã Basin, a post-collisional basin related to the final evolution of the Neoproterozoic Dom Feliciano Belt (Paim et al., 2000 and[START_REF] Barton | Iron oxide(-Cu-Au-REE-P-Ag-U-Co) systems[END_REF]Remus et al., 2000;Laux et al., 2005;Bongiolo et al., 2011;Renac et al., 2014). The Camaquã Basin presents NE-SW elongated structure bounded by steeply dipping brittle faults and filled with immature terrigenous sedimentary successions with volcanic and volcanoclastic intercalations. The basin is aligned parallel to the major structures of the underlying Dom Feliciano Belt, which was formed during the main collisional event of the Brasiliano-Pan African Orogeny in the region. The Camaquã Basin comprises more than 10.000 meters of sedimentary and volcanogenic successions that record the paleogeographic evolution of the region between ca. 610 Ma and 530 Ma. This basin is ideal for paleostress analysis since they are affected by very low-grade metamorphism and low rates of brittleductile deformation. In addition it is possible to recognize the depositional paleoenvironments and stratigraphic elements to obtain the age of the volcanic units through the geochronological analysis and to delimit the distinct subsidence events through the recognition of nonconformities (Almeida et al., 2012b;Philipp et al., 2016a). The integration of this set of information allows to determe an absolute chronology for the tectonic events occurred during the evolution of the basin.

We present structural data on brittle faults as fault slip planes, slickenlines striations and fractures systems of sedimentary and volcanic rocks of Bom Jardim Group of the Camaquã Basin, as well as some younger units, in order to establish the chronology of the deformational events and the relationships with the Cu-Pb-Au mineralization, and to distinguish the directions of paleostress axes related to basin formation from those that were responsible for its later deformation.

This paper analyzes the relationships between the main regional structures and the structural features observed in mineralized areas using remote sensing structural data, including measurements of faults, lineations and fractures from nonmineralized and mineralized areas. When possible, we determined the stress orientation at the time of mineralization by kinematic indicators associated with dextral and sinistral transcurrent or normal faults. The interpretation of tectonic structures allowed the reconstruction of a relative chronology and paleostress field associated with ore deposition.

Geological setting

2.1 Regional geology and tectonic structures eastern Minas Gerais and southern Bahia states; e.g., [START_REF] Heilbron | Timing of Terrane Accretion in the Neoproterozoic -Eopaleozoic Ribeira Belt (SE Brazil)[END_REF]. Its African counterpart includes the Saldania-Gariep, Damara, Kaoko and West Congo belts. Several models have been presented to explain the tectonic evolution of this orogen and its role in the assembly of West Gondwana (e.g., [START_REF] Cordani | From Rodinia to Gondwana: A review of the Available Evidence from South America[END_REF][START_REF] Basei | West Gondwana amalgamation based on detrital zircon ages from Neoproterozoic Ribeira and Dom Feliciano belts of South America and comparison with coeval sequences from SW Africa[END_REF]. The southern portion of the Mantiqueira Province represents a zone of collision between the Rio de La Plata (Brazil) and the Kalahari (Africa) cratons (Almeida and Hasui, 1984;[START_REF] Silva | The neoproterozoic Mantiqueira Province and its African connections: a zircon based U-Pb geochronologic subdivision for the Brasiliano/Pan-African systems of orogens[END_REF]. The southern Brazilian and Uruguay shields are subdivided in two geotectonic units: the Rio de La Plata Craton and Dom Feliciano Belt (Fig. 1) [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Hartmann et al., 2007;Philipp et al., 2016a). In southern Brazil, the Rio de La Plata Craton is represented by the Taquarembó Terrane, composed by Paleoproterozoic (2.45 to 1.8 Ga) ortho-and paragneisses of amphibolite to granulite facies [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Philipp et al., 2016a). The Dom Feliciano Belt is constituted by the São Gabriel Terrane, the Tijucas Terrane and the Pelotas Batholith, units composed by petrotectonic associations generated between Tonian and Ediacaran periods (930-540 Ma). The evolution of the Dom Feliciano Belt units is related to Brasiliano Orogenic Cycle and involves three main orogenic episodes denominated Passinho (890-850 Ma), São Gabriel (770-680 Ma) and Dom Feliciano (650-540 Ma) [START_REF] Saalmann | Tectonic evolution of the Neoproterozoic juvenile São Gabriel Belt, southern Brazilconstraints on Brasiliano orogenic evolution of the La Plata cratonic margin[END_REF][START_REF] Sillitoe | Porphyry copper systems[END_REF]Philipp et al., 2016a;[START_REF] Hueck | The Dom Feliciano Belt in Southern Brazil and Uruguay. Geology of the SW Gondwana[END_REF].

The São Gabriel Terrane take place in the northwest portion of the Dom Feliciano Belt and is represented by ophiolitic complexes [START_REF] Leite | SHRIMP U/Pb zircon geochronology of Neoproterozoic juvenile and crustal reworked terranes in southernmost Brazil[END_REF][START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF] and arc-related rocks, including ortho-and paragneisses, low-grade metavolcano-sedimentary associations and late-orogenic granitic to dioritic magmatism, covered by late-orogenic basin (930-680 Ma) (Remus et al., 1999;

UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES

MANUSCRITO I | 72

Rodrigo Winck LOPES

-2018-Tese de doutorado / THÈSE [START_REF] Saalmann | Tectonic evolution of the Neoproterozoic juvenile São Gabriel Belt, southern Brazilconstraints on Brasiliano orogenic evolution of the La Plata cratonic margin[END_REF][START_REF] Hartmann | Time frame of 753-680 Ma juvenile accretion during the São Gabriel orogeny, southern Brazil[END_REF][START_REF] Lena | The evolution of the Neoproterozoic São Gabriel juvenile terrane, southern Brazil based on high spatial resolution U-Pb ages and δ 18 O data from detrital zircons[END_REF][START_REF] Gubert | U-Pb geochronology and tectonic implications for the Neoproterozoic São Gabriel Arc, southernmost Brazil[END_REF]Vedana et al., 2017). In this terrane, the development of rocks association was related to the closure of the Charrua Ocean through the formation of two magmatic arcs accretionary systems generated during Passinho (890-850 Ma) and São

Gabriel (770-680 Ma) orogenies [START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a and2018). The Sul-rio-grandense Shield shows three major regional-scale lineaments: (i)

The Ibaré Shear Zone [START_REF] Luzardo | Análise estrutural do Lineamento de Ibaré, Parte Ifilitos de Ibaré: greenstone belt ou cobertura cratônica deformada?[END_REF]Philipp et al., 2016a) with NW-SE (N40-50°W) direction, defining the contact between Taquarembó and São Gabriel terranes, (ii) the Caçapava do Sul Shear Zone [START_REF] Costa | Teste e modelagem geofísica das associações litotectônicas précambrianas no Escudo Sul-rio-grandense[END_REF] do Canguçu Shear Zone [START_REF] Mesquita | Petrografia dos granitóides deformados na Zona de Cisalhamento Dorsal de Canguçu (Região de Quitéria-Capivarita)[END_REF][START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF][START_REF] Philipp | Reconhecimento estrutural e geoquímico dos granitóides Brasilianos na região de Pelotas, RS[END_REF] with NE-SW (N40-50°E) direction, delimiting the Tijucas Terrane and the Pelotas Batholith.

The Ediacaran to Cambrian basins of the southeastern portion of the Mantiqueira Province, like Itajaí (SC), Camaquã (RS), Barriga Negra, Piriápolis, San Carlos and Cerros de Aguirre (Uruguay), were formed over Paleoproterozoic rocks of the Rio de La Plata Craton and over the Neoproterozoic units of the Dom Feliciano Belt (Almeida et al., 2012b). These basement units were affected by Brasiliano orogenic deformation associated with collisional metamorphism, dated by the U-Pb zircon method (SHRIMP and LA-ICPMS) between 650 to 620 Ma, and with the postcollisional metamorphism associated to transcurrent shear zones between 600 to 560 Ma [START_REF] Leite | SHRIMP U/Pb zircon geochronology of Neoproterozoic juvenile and crustal reworked terranes in southernmost Brazil[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF][START_REF] Philipp | Lu-Hf and U-Pb age determination of the Capivarita Anorthosite, Dom Feliciano belt, Brazil[END_REF]Camozatto et al., 2013a,b;Philipp et al., 2016a,b).

The Camaquã Basin is the largest and best known of the post-collisional strike slip basins of the south portion of Mantiqueira Province, with an area of 3.000 km 2 divided into four sub-basins. The geology and stratigraphy of the Camaquã Basin was investigated by many authors, and the evolution of its units was recognized and related to the events of subsidence and deformation during the post-collisional stage of Dom Feliciano orogenesis (ca. 620 to 530 Ma), characterizing the final evolution of the SW Gondwana supercontinent [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Hartmann et al., 2007;[START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a). Detailed stratigraphic descriptions and available geochronological data from volcanogenic units of the basin can be found in Lima and Nardi (1998), Paim et al. (2000), Wildner et al. (2002), Janikian et al. (2003[START_REF] Janikian | Evolução paleoambiental e sequências deposicionais do Grupo Bom Jardim e Formação Acampamento Velho (Supergrupo Camaquã) na porção norte da Sub-Bacia Camaquã Ocidental[END_REF]Janikian et al. ( and 2012)), [START_REF] Fambrini | O Grupo Santa Bárbara (Neoproterozóico III) na sub-bacia Camaquã Central, RS: sistemas deposicionais, paleogeografia e implicações tectônicas[END_REF]2007), Borba et al. (2006 and2008), [START_REF] Paim | High-resolution stratigraphy and depositional model of wind-and waterlaid deposits in the ordovician Guaritas rift (Southernmost Brazil)[END_REF] and Almeida et al. (2009[START_REF] Almeida | The Ediacaran to Cambrian rift system of Southeastern South America: tectonic implications[END_REF]Almeida et al. ( and 2012b)). Guaritas Group, frequently occurring as shallow intrusive sills (Almeida et al., 2012a). The studied area is located in the south portion of the São Gabriel Terrane, on the western rim of the Camaquã Basin, in a major structure of NE-SW direction denominated Santa Bárbara Rift (Fig. 2) [START_REF] Robertson | Revision of the stratigraphy and nomenclature of the rock units in Caçapava e Lavras Region, State of Rio Grande do Sul, Brazil[END_REF]. Santa Bárbara allogroups were characterized as two successions formed during transtensional events. Finally, the Guaritas Allogroup was featured by a transtensional subsidence event that filled a half-graben generated by the reactivation of NE-SW oriented regional fault systems.

The tectonic setting of the Ediacaran to Cambrian basins is controversial, and a series of different models have been proposed. The currently accepted conceptions can be grouped into three main types: (i) syn-orogenic settings, mainly of peripheral foreland basins (e.g., [START_REF] Fragoso-Cesar | Tectônica de Placas no Ciclo Brasiliano: as orogenias dos Cinturões Dom Feliciano e Ribeira no Rio Grande do Sul[END_REF][START_REF] Gresse | Late-to post-orogenic basins of the Pan-African-Brasiliano collision orogen in southern Africa and southern Brazil[END_REF]Paim et al., 2000),

(ii) post-collisional settings, with strike-slip or pull-apart basins (e.g., Oliveira and[START_REF] Oliveira | Estágios finais da evolução do Cinturão Dom Feliciano: Tectônica e sedimentação da Formação Arroio dos Nobres[END_REF]1992;[START_REF] Machado | Aplicação da análise geométrica e cinemática nos falhamentos que condicionaram a bacia molássica do Arroio Boici, RS[END_REF]Paim et al., 2000) and (iii) anorogenic settings, with extensional origin [START_REF] Fragoso-Cesar | The Camaquã extensional basin: Neoproterozoic to early Cambrian sequences in southernmost Brazil[END_REF]2001;Almeida et al., 2012b;Janikian et al., 2012). The existence of different models is the result of the increment of the studies on the structural and tectonic record preserved within the basins and of the recent U-Pb geochronology zircon data. Most of the hypotheses are based on models generated from the tectonic significance of the metamorphic and granitic rocks of the basement of the basin. Indeed, very few papers with paleostress tensor data and kinematic analysis of the Camaquã Basin have been published (Almeida et al., 2012b).

Despite the importance of the Camaquã Basin to elucidate some important issues, such as the mineralization episodes and the origin of the basin, or to evaluate the tectonic conditions of the final stage of the Brasiliano Orogenic Cycle, very few studies have focused on structural analysis. As highlighted by Almeida et al. (2012b), the majority of the published tectonic interpretations are based on hypotheses of the supposed role of the Camaquã Basin in regional tectonic models. [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF][START_REF] Silva | The neoproterozoic Mantiqueira Province and its African connections: a zircon based U-Pb geochronologic subdivision for the Brasiliano/Pan-African systems of orogens[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a). These processes are associated with the collision between the Rio de La Plata and Kalahari cratons during the construction of the SW portion of the Gondwana paleocontinent [START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a;[START_REF] Hueck | The Dom Feliciano Belt in Southern Brazil and Uruguay. Geology of the SW Gondwana[END_REF]. The evolution of this collisional system originated the processes of tectonic escape that distributed the deformation through the alternation between bands with transpressional (domes) and transtensional regimes (elongated basins) [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF]Philipp et al., 2016a). These basement highs are limited by steeply dipping NE-SW oriented fault zones, referred as Irapuá Fault System by Ribeiro et al. (1966). The same authors also highlighted the occurrence of steeply dipping NW-SE oriented fault zones, denominated Cerro da Vigia Fault System.

Based on stratigraphic analysis of individual sedimentary and volcanic groups of the Camaquã Basin, recent researchers [START_REF] Fragoso-Cesar | The Camaquã extensional basin: Neoproterozoic to early Cambrian sequences in southernmost Brazil[END_REF], Paim et al., 2000, Janikian et al., 2003and 2005;[START_REF] Fambrini | O Grupo Santa Bárbara (Neoproterozóico III) na sub-bacia Camaquã Central, RS: sistemas deposicionais, paleogeografia e implicações tectônicas[END_REF]2007;Borba et al., 2006;Lima et al., 2007;[START_REF] Almeida | The Ediacaran to Cambrian rift system of Southeastern South America: tectonic implications[END_REF]2012b) Ma (Lima and Nardi, 1998;Wildner et al., 2002;Sommer et al., 2006;Lima et al., 2007). The importance of extensional and strike-slip kinematic is described during the post-collisional stage of the Dom Feliciano Orogeny associated to the latest escape movements of the main shear zones that affected the Dom Feliciano Belt and generated the Camaquã Basin [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF][START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Paim et al., 2000 and[START_REF] Barton | Iron oxide(-Cu-Au-REE-P-Ag-U-Co) systems[END_REF]Philipp et al., 2016a).

Geology of the Lavras do Sul Mining District and Seival Mine

The rocks of the Lavras do Sul Mining District and Seival Mine area are limited by the Caçapava do Sul and Ibaré shear zones and Cabritos-Perau, Segredo and Palma-Jacques as subsidiary faults (Fig. 3). The basement rocks occur west and south of the mineralized areas and are represented by tectonic interleave of mafic to ultramafic rocks of the Cerro Mantiqueira Ophiolite, tonalitic to dioritic gneisses of the Imbicuí Complex (890-850 Ma) (Philipp et al., 2016a), tonalitic to dioritic and metagranites of the Cambaí Complex (740-700 Ma) [START_REF] Leite | SHRIMP U/Pb zircon geochronology of Neoproterozoic juvenile and crustal reworked terranes in southernmost Brazil[END_REF][START_REF] Hartmann | Time frame of 753-680 Ma juvenile accretion during the São Gabriel orogeny, southern Brazil[END_REF] and by the low-grade metavolcano-sedimentary rocks of the Marmeleiro Complex. These petrotectonic units constitute E-W oriented belts interpreted as arc-related associations generated during the Passinho and São Gabriel orogenies (890-850 and 760-680 Ma) [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Hartmann et al., 2007;[START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF][START_REF] Philipp | Tectonic evolution of the São Gabriel Terrane, Dom Feliciano Belt, southern Brazil: the closure of the Charrua Ocean. Geology of the SW Gondwana[END_REF]. These units recorded an orogenic metamorphism generated under low-to medium-grade and low-pressure conditions. The contacts between the units of the São Gabriel Terrane are tectonic and are related to the processes of deformation and collisional metamorphism generated during the final evolution of this terrane. These relationships are associated with a main regional compression with sigma 1 positioned in the NW-SE direction [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF][START_REF] Philipp | Tectonic evolution of the São Gabriel Terrane, Dom Feliciano Belt, southern Brazil: the closure of the Charrua Ocean. Geology of the SW Gondwana[END_REF].

The Camaquã Basin is represented by the sedimentary and volcanic rocks associated with the Maricá, Bom Jardim, Santa Bárbara and Guaritas groups. The Maricá Group is composed of an approximately 4000 m total thick sedimentary sequence with volcanic clast (Paim et al., 2000;Almeida et al., 2009 and[START_REF] Sillitoe | Porphyry copper systems[END_REF]Borba et al., 2008) and has been subdivided into three sedimentary packages (Borba et al., 2006).

In the Seival Mine, the Bom Jardim Group is represented by the effusive successions of Hilário Formation, including lapilli tuff, volcanic agglomerate, andesite lava flows and andesitic to trachyandesite dikes (Fig. 4) (Reischl, 1978;Lopes et al., 2014). The alteration minerals occur in halos related to fractures and faults with chlorite, chlorite/smectite mixed-layers and smectite associated with titanite and calcite (Fontana et al., 2017). On the east side of granitoids, the Hilário Lavras do Sul Intrusive Complex is represented by plutonic granitic and shallow intrusions concentrated mainly in the northeastern margin (Nardi, 1984;Gastal et al., 2006;Bongiolo et al., 2011). The granitoids are represented by a ring structure composed by Lavras do Sul Granite, Arroio dos Jaques Monzonite and Tapera Granite (Gastal et al., 2006). Lavras do Sul Granite is represented by porphyritic quartz-monzonite, granodiorite and syenogranite to monzogranite rocks (Gastal et al., 2006;Liz et al., 2009b). The granite intrusion caused contact metamorphism in the older volcanogenic rocks of the Hilário Formation. Nardi, 1998;Liz et al., 2009b) with mixing and mingling textures (Müller et al., 2012).

The Au and Cu-Ag mineralizations are hosted in granitoids of Lavras do Sul Mining District and in Bom Jardim Group sedimentation of Seival Mine area (Fig. 4), respectively. Reischl, 1978;[START_REF] Gastal | Gênese e evolução dos granitóides metaluminosos de afinidade alcalina da porção oeste do Escudo Sul-riograndense: geoquímica e isótopos de Rb-Sr e Pb-Pb[END_REF]Bongiolo, 2002;Toniolo et al., 2007). Shear zones: ISZ= Ibaré; CSSZ= Caçapava do Sul; DCSZ= Dorsal do Canguçu. Faults: CPF= Cabritos-Perau; SF= Segredo; PJF= Palma-Jacques.

Description of the copper-bearing bodies of the Lavras do Sul Mining

District and Seival Mine

The Au-Cu prospects of the Lavras do Sul Mining District host nineteen inactive mines or deposits located in the granitoid rocks of Lavras do Sul Intrusive Complex and volcanogenic rocks of Hilário Formation (Fig. 4) (Mexias et al., 2007;Bongiolo et al., 2011). The multi-intrusive activity generated pervasive and vein-type fractures represented by ore-zones, quartz and sulfide-rich veins (Mexias et al., 1990a,b and2005;Bongiolo et al., 2011). The alteration assemblages consist of clays, quartz and sulfides (Bongiolo et al., 2011). The estimated temperatures were determined by chlorite geothermometry and mineral characteristics, and the alteration assemblages were classified as: potassic (> 350 °C) with ± alkali feldspar, biotite, tourmaline, chalcopyrite and alunita; propylitic (250 to 350 °C) with ± alkali feldspar, biotite, tourmaline, chalcopyrite and alunita; phyllic (> 300 °C) with quartz, ± chlorite, ± phengite, ± illite, sulfide (pyrite>chalcopyrite) and ore (Au>Cu);

intermediate argillic alterations (160 to 230 °C) with illite-smectite, carbonate, ± chlorite, hematite and ± corrensite [START_REF] Bongiolo | Spatial and temporal evolution of hydrothermal alteration at Lavras do Sul, Brazil: evidence from dioctahedral clay minerals[END_REF]. The pyrite, chalcopyrite, arsenopyrite and Au are associated to propylitic-potassic alteration [START_REF] Bongiolo | Spatial and temporal evolution of hydrothermal alteration at Lavras do Sul, Brazil: evidence from dioctahedral clay minerals[END_REF][START_REF] Lopes | Alteração hidrotermal e mineralização de cobre na Mina do Seival, Bacia do Camaquã, RS. Porto Alegre[END_REF]Liz et al., 2009a) with assemblage of phengite, chlorite and illite/smectite mixed-layers (Mexias et al., 1990c;[START_REF] Bongiolo | Spatial and temporal evolution of hydrothermal alteration at Lavras do Sul, Brazil: evidence from dioctahedral clay minerals[END_REF][START_REF] Lopes | Alteração hidrotermal e mineralização de cobre na Mina do Seival, Bacia do Camaquã, RS. Porto Alegre[END_REF].

These mineralized structures formed a NW-SE direction trend parallel to Palma-Jacques Fault. (Fig. 5) (Reischl, 1978;Lopes et al., 2014). Fractures and faults contain Cu-rich sulfides as chalcopyrite, bornite, chalcocite and covellite (Fontana et al., 2017). This

Cu-enrichment is related to propylitic alteration with formation of albite (600 to 350 °C), Mg-chamosite to Fe-clinochlore (251 to 180 °C) and smectite (< 250 °C). The lower temperature of alteration are associated to an increasing proportion of meteoric water in the host rock with precipitation of barite, calcite and quartz (150 to 80 °C; Fontana et al., 2017). In preserved parts of these inactive mines, a stockwork of veins (Fig. 6A), volcanic agglomerate (Fig. 6B) and porosity of volcaniclastics rocks (Fig. 6C) host Cu-rich sulfides (Fontana et al., 2017). The open pit and prospects (ca. ~N-S to N40-60°E oriented) seem to form a trend of mineralized structures, fracture and dikes (Reischl, 1978). These alteration process can be related to these andesitic intrusions and local hydrothermal cells. 

Methods

In order to evaluate the structural framework of the granitic and volcanosedimentary units of the Lavras do Sul Mining District and the Seival Mine area, data were collected on a regional scale and on an outcrop scale. Regional data were obtained from delineation of the lineaments in the satellite imagery. The lineaments were defined from negative and positive linear features, delimited only in their visible portion. Regional lineaments (n= 2114) were extracted through GIS tool on Hill shade ASTER (VNIR 15 meters; Toniolo et al., 2007) and TM Landsat (band #4) satellite images. Structures were recorded as (i) fractures or (ii) faults based on discontinuity surfaces or slickenlines, respectively, within 1:10.000 scale density, and the whole regional dataset was integrated with published data on the same area [START_REF] Kaul | Distrito aurífero de Lavras do Sul (RS) histórico dos trabalhos de pesquisa e exploração[END_REF]1976;Gastal et al., 2015). In this study, the longer lineaments were interpreted as deep and ancient crustal structures. We also used as indicators of relative chronology: (i) the cut-off relationships between the structures; (ii) the orientation of dikes; (iii) extensions and influences of structures on rocks adjacent to the studied region. The length distribution was divided into long (5 to 40 km) and short (0.1 to 4 km) lineaments and was described as main and secondary structures, respectively. The division of the regional structures was based on [START_REF] Picada | Ensaio sobre a tectônica do Escudo Sul-Riograndense. Caracterização dos sistemas de falhas[END_REF], with three main directions: NE-SW (0-30°), NNE-SSW (31-90°) and NW-SE (271-359°). These main and secondary structures may be associated with timing or competency of rocks.

For the reconstitution of the paleostress fields, more than 162 measurements were collected on faults with striations distributed in 12 outcrops of the volcanic and sedimentary successions of the Bom Jardim Group in the Camaquã Basin and of the granitoids in the Lavras do Sul Intrusive Complex. The successive tectonic events were classified using relative chronology criteria based on stratigraphic data from the Camaquã Basin and superimposition of slickenlines fibers and striations. The stratigraphy of this basin was based on the available geochronological data (Almeida et al., 2012a;Janikian et al., 2012).

Structural measurements on faults and fractures were carried out in the field. We have also collected data along slickensides, including groove lineation and kinematic analysis (Supplementary Table ). The Win-Tensor software (Delvaux and Sperner, 2003) was used to produce stereograms and to reconstruct paleostress directions of principal stress axes [START_REF] Twiss | Structural Geology[END_REF]Angelier, 1994;Hatcher, 1995).

The paleostress was determined by three main stress axes σ1, σ2 and σ3 (σ1 ≥ σ2

≥ σ3), stress ratio R (R= [σ2-σ3]/[σ1-σ3]
) and a stress regime index R' (see Delvaux and Sperner, 2003). In the Win-Tensor software, paleostress values were adjusted to optimize and refine the paleostress inversion results (for more details, see Delvaux and Sperner, 2003). A relative chronology of paleostress was then integrated into the geological maps of the Lavras do Sul Mining District and Seival

Mine with available data from the mineralized locations (i.e., Reischl, 1978;Bongiolo et al., 2011). The interpretation of the paleostress tensor analyses of this paper were compared with the analysis of the structural data from other mineralized areas of the Camaquã Basin (e.g., Almeida et al., 2012b;[START_REF] Santos | Paleostress analysis in brittle structures of the Camaquã copper mines[END_REF]Bicca et al., 2013).

The macroscopic classification of fractures was used according to [START_REF] Twiss | Structural Geology[END_REF].

Results

Regional structures

In a regional perspective, the topographic lineament directions are potential We recognized two scarce generations of slickenlines in the Seival area (Fig. 11A), similar to slickenlines on fault planes. These slickenlines contain deformed calcite and oriented hematite (Fig. 11B) for both slickenlines generation. The mineral lineation exhibits different structural events marked by kinematic indicators.

Subvertical slickenlines (e.g., N05°W/30°NE oriented) cutting the subhorizontal ones (Fig. 11C) (e.g., N66°E/62°NE oriented) show an early transcurrent and late normal displacement marked by NE-SW and NE-SW directions, respectively. 

Fractures and veins

The Vertical-to subvertical fractures were measured in Lavras do Sul Mining District.

The barren and ore-bearing fractures are mostly N70-80°W/>60°NE oriented and subordinately N10°W/>60°NE oriented (Fig. 12A). These ore-bearing fractures are filled with quartz. The Seival rocks host mainly subvertical and subordinated subhorizontal fractures. These fractures are N10°E/>60°NW oriented and N70-80°E/>60°NW oriented (Fig. 12B). In addition, the faults are associated with the orientation of copper soil metallic anomalies (Reischl, 1978) and mineralized structures, whereas the NW/SE oriented structures have no metal concentration indicators. These orebearing fractures are filled with calcite, hematite and barite.

Discussion

Tectonic Context

Most of the current tectonic models for southern portion of Brazil consider that the evolution of the Dom Feliciano Belt between 950 Ma and 530 Ma records the closing of the Charrua and Adamastor oceans and the collisional episodes of the Brasiliano Orogeny, evolving the Rio de La Plata and Kalahari cratons (e.g., Ribeiro and Fantinel, 1978;[START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF][START_REF] Basei | West Gondwana amalgamation based on detrital zircon ages from Neoproterozoic Ribeira and Dom Feliciano belts of South America and comparison with coeval sequences from SW Africa[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF], Philipp et al., 2016aand 2018[START_REF] Hueck | The Dom Feliciano Belt in Southern Brazil and Uruguay. Geology of the SW Gondwana[END_REF]. In this context, the Ediacaran to Cambrian Camaquã Basin has been considered as post-collisional, with its origin related to late-orogenic strike-slip deformation. The stratigraphic record of the deformational events of the basin reveals the recurrence of strike-slip and extensional episodes with no major thrusting (Almeida et al., 2012b). In the Camaquã Basin, the occurrence of three distinct volcanic successions suggests that they were formed associated to movement of deep high-angle shear zones and during a period of enhanced thermal gradient. This hypothesis is confirmed by the presence of several voluminous granitic intrusions coeval to the basins, as the Lavras do Sul Intrusive Complex, Caçapava do Sul and São Sepé granites. Almeida et al. (2012b) considered that the generation of the Camaquã Basin is not related to extensional collapse of thickened crust caused by the collisional processes that had taken place between 650-620 Ma. For these researchers, the paleostress fields do not support a syn-collisional peripheral foreland basin model for this basin and the evidences suggest that the extensional events responsible for the subsidence cycles and that the strike-slip faulting activities are related to younger and anorogenic deformation (Almeida et al., 2012b).

In our vision, the Camaquã Basin was generated shortly after a major event of collisional orogenic metamorphism. The period of generation of the basin is associated with an intense volcanic activity, being contemporaneous to the development of the Pelotas Batholith, located to the east of the main depocenter of the basin. The generation of these two large tectonic units of the Dom Feliciano Belt was associated with the activity of the large NE-SW high-angle transcurrent shear zones [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF]1995a;[START_REF] Philipp | The Neoproterozoic to Cambrian granitic magmatism of Pelotas Batholith, Southern Brazil[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a). These shear zones were active at high depths up to 560 Ma and were associated with events of compressive deformation and postcollisional orogenic metamorphism as described in the metavolcano-sedimentary associations of the São Gabriel and Tijucas terranes (Cambaizinho, Passo Feio and Porongos complexes) [START_REF] Saalmann | Tectonic evolution of the Neoproterozoic juvenile São Gabriel Belt, southern Brazilconstraints on Brasiliano orogenic evolution of the La Plata cratonic margin[END_REF][START_REF] Sillitoe | Porphyry copper systems[END_REF]Camozzato et al., 2013a,b;[START_REF] Pertille | Origin of the Ediacaran Porongos Group, Dom Feliciano Belt, southern Brazilian Shield, with UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE[END_REF]Philipp et al., 2016a;Zvirtes et al., 2017).

The recurrence of strike-slip events is related with the third deformational event and Candiotinha Metagranite (Camozzato et al., 2013a, b) show that the metamorphism associated to high-angle ductile shear zones occurred after 580 Ma.

These events of deformation and metamorphism are recorded in the basement nuclei (Caçacapa do Sul and Lavras do Sul highlands, Santana da Boa Vista and Vigia domes and Capané Antiform) that separate the sedimentary sub-basin with the successions of the Maricá, Bom Jardim, Santa Bárbara and Guaritas groups.

The simultaneous occurrence of the contractional deformation and the metamorphism, associated with the shear zones in deeper portions of the basement and the opening of space with the deposition of the sedimentary rocks of the Camaquã Basin in pull-apart basins, is suggestive of the performance of oblique deformation processes (Philipp et al., 2016a;Zvirtes et al., 2017). Several researchers have suggested that the deposition of the Camaquã Basin occurred under compressive conditions and characterizes the final stage of formation of the Dom Feliciano Belt [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF]1995a;Paim et al., 2000;Philipp et al., 2016a). 

Structures of the Lavras do Sul Mining District and Seival Mine

The Camaquã Basin is a structure generated during the post-collisional stage of the Dom Feliciano orogeny (610-540 Ma) (Paim et al., 2000;Janikian et al., 2012;Philipp et al., 2016a). The basin structuring occurred in four main episodes (Paim et al., 2000) controlled by the activation of ductile to brittle-ductile transcurrent shear zones of N40-60°E direction and vertical to subvertical dip (e.g., [START_REF] Ramsay | Shear zone geometry: a review[END_REF][START_REF] Hodgson | The structure of shear-related, vein-type gold deposits: a review[END_REF][START_REF] Fossen | Shear zones -A review[END_REF]. These shear zones mark the tectonic contact between the different units of Dom Feliciano Belt and represent deep crustal structures [START_REF] Picada | Ensaio sobre a tectônica do Escudo Sul-Riograndense. Caracterização dos sistemas de falhas[END_REF]Almeida et al., 2012b;Janikian et al., 2012).

The deposition cycles associated to each groups of the Camaquã Basin were delimited by regional sinistral transcurrent faults of N40-60°E direction and vertical to subvertical dip. These faults were also responsible for the ascent and control of volcanogenic magmatism related to the development of the Bom Jardim, Santa

Bárbara and Guaritas groups and by emplacement of the associated post-collisional granitic magmatism (Philipp et al., 2016a). [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF] assigns the transcurrent movements to a escape tectonic model.

The main tectonic structures that control magmatism and sedimentation during the evolution of the Dom Feliciano Belt show NE-SW direction (Fernandes et al., 1995a;[START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF][START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a;[START_REF] Hueck | The Dom Feliciano Belt in Southern Brazil and Uruguay. Geology of the SW Gondwana[END_REF]. The compressional direction with N40-60°W dominant stress occurred during the Dom Feliciano orogeny. The Lavras do Sul Mining District area is located in the southern portion of the São Gabriel Terrane, which is delimited from the adjacent terranes by Ibaré Shear Zone [START_REF] Luzardo | Análise estrutural do Lineamento de Ibaré, Parte Ifilitos de Ibaré: greenstone belt ou cobertura cratônica deformada?[END_REF]Philipp et al., 2016a and2018) and Caçapava do Sul Shear Zone (Fernandes et al., 1995b). Regionally, Seival Mine areas (Table 1).

Table 1: Detailed information of main paleostress field orientation related to each deformation event in Lavras do Sul Mining District and Seival Mine.

Faults at regional scale and paleostress-fields

The lineaments analyzed are associated with a large number of N50°E/80- Mine rocks are older than Lavras do Sul granitoids (Gastal et al., 2015). The ages obtained by the U-Pb method in zircon also confirm this stratigraphic relation (Remus et al., 2009;Janikian et al., 2012). The evaluation of the rheological behavior of the different rock types in relation to the main compressional stress indicates that the volcanogenic rocks of Seival Mine were more deformed and have a higher fracture density. Reciprocally, the dominant occurrences of N70°W/70-88°NE direction structures in Lavras do Sul compared to Seival Mine suggest that the granitoids did not accommodate the strain of NE-SW direction. On the other hand, the NE-SW strain is well marked in these volcanogenic rocks. The emplacement of the Lavras do Sul Intrusive Complex units is related to the opening of space generated by the movement of Cabritos-Perau Fault (N50°E/80-88°SE) and

Segredo Fault (N40°E/80-88°NW) as suggested by [START_REF] Picada | Ensaio sobre a tectônica do Escudo Sul-Riograndense. Caracterização dos sistemas de falhas[END_REF]. The main regional structures and Cu-Au-Ag deposits of the Dom Feliciano Belt are formed by the regional NW-SE compression associated with collisional processes related to the formation of the SW portion of Gondwana [START_REF] Saalmann | A multiple accretion at the eastern margin of the Rio de la Plata craton: the prolonged Brasiliano orogeny in southernmost Brazil[END_REF]Philipp et al., 2016a;[START_REF] Hueck | The Dom Feliciano Belt in Southern Brazil and Uruguay. Geology of the SW Gondwana[END_REF]. The stress orientation in the mineralized areas was obtained from the integration of orientation and kinematic indicators determined in the transcurrent and normal faults that control the mineralizations. The paleostresses calculated are associated with regional movement related to 

Mineralizations associated with faults and fractures

The 600 to 580 Ma ago (Gastal et al., 2006;Janikian et al., 2008;Almeida et al., 2012a) and indicated a period of intense tectonic activity.

The results allowed us to associate the same regional stress with both shear zones and mineralized areas. Au and Cu-Ag mineralizations in Lavras do Sul Mining District and Seival, respectively, are located immediately adjacent to Cabritos-Perau and Palma-Jacques faults. The mineralized structures are associated with dikes and hydrothermal fluids percolation and were probably responsible for the ascent and emplacement of the Lavras do Sul Intrusive Complex (Bongiolo et al., 2011;Gastal et al., 2015), as well as the volcanogenic rocks of the Hilário Formation (Lopes et al., 2014;Fontana et al., 2017). At least two other copper occurrences are associated to these structures (Teixeira, 1937;Toniolo et al., 2007) indicating a fertile structure in the region. A significant regional stress relationship with NW-SE oriented faults and Au-Cu mineralizations has been reported also for Camaquã Mine (e.g., [START_REF] Santos | Paleostress analysis in brittle structures of the Camaquã copper mines[END_REF]Bicca et al., 2013).

The mineralized fractures were formed by opening cracks in the rocks. Euhedral or drusiform quartz fill the fractures (Fontana et al., 2017) evidencing the Mode 1 fractures. These fractures and faults allowed hydrothermal fluid percolation in these rocks. The regular to irregular veins are characteristic of porphyry-epithermal (Seedorff et al., 2005;[START_REF] Sillitoe | Porphyry copper systems[END_REF] or iron oxide copper-gold deposits (IOCG; Dilles and Einaudi, 1992;[START_REF] Sillitoe | Iron oxide-copper-gold deposits: An Andean view[END_REF] indicating possible models for mineralizations in Lavras do Sul Mining District and Seival Mine. We correlated Lavras do Sul Intrusive Complex and volcanogenic rocks of Seival Mine suggesting a porphyry-epithermal system to the Au-Cu-Ag mineralizations.

In Lavras do Sul Mining District, the maximum compressional stress of NW-SE direction was responsible for vein type-fractures of N70°W/70-88°NE direction, which provided a drain for the circulation of hydrothermal fluids and the Au-Cu deposition. In volcanogenic rocks of Lavras do Sul Mining District Au-quartz veins occur in monzonites (Liz et al., 2009a;Müller et al., 2012). Lamprophyre intrusions of ~590 Ma (Almeida et al., 2012a) occur in the volcanogenic rocks, which indicates influence in regional mineralization [START_REF] Nardi | Hidrotermalismo no Complexo Granítico Lavras e vulcânicas associadas[END_REF]Mexias et al., 1990a, b andc). In Seival Mine area the enrichment of Cu and Ag in whole-rock analysis of monzonitic and andesitic to trachyandesitic dikes suggests, probably, those mineralization elements are associated with dike magmatism (Lopes et al., 2014;Fontana et al., 2017).

The relative chronology of regional structures and the influence of the regional maximum compressive stress in the ore location are associated to regional tectonic events. The similar stress of mineralized fractures in the region are related with the evolution and emplacement of Tapera Granite, Lavras do Sul Granite and the volcanogenic rocks of the Hilário Formation of Bom Jardim Group. The probable origin of hydrothermal fluids is associated with monzonitic and andesitic to trachyandesite dikes. The magmatism of Bom Jardim Group is so characterized: (i) high content of water and, consequently, volatiles favoring the hydrotermalism [START_REF] Nardi | Hidrotermalismo no Complexo Granítico Lavras e vulcânicas associadas[END_REF]; (ii) the granitic magmatism structure is characterized by a caldera limited by NE-SW oriented structures (Caçapava do Sul Shear Zone and Cabritos-Perau Fault) and with centered in Lavras do Sul granitoids (Gastal et al., 2015). The similar compressive stress in Lavras do Sul Mining District and Seival Mine suggested this pattern affected regionally the Dom Feliciano Belt. We related the same compressional stress with the generation and emplacement of monzonitic and andesitic to trachyandesitic dikes in Lavras do Sul Mining District and Seival Mine, respectively, suggesting those structures are deeper in the crust and allowed hydrothermal percolation and Au-Cu-Ag mineralization.

Conclusion

The The Neoproterozoic Camaquã Basin and its associated igneous rocks contain significant Au, Cu and Ag ore deposits, such as the Uruguay-São Luiz mines and the Lavras do Sul Mining District (Remus et al., 2000;Bongiolo et al., 2011;Renac et al., 2014). In the central-western section of this basin, volcanogenic (Lopes et al., 2014;Fontana et al., 2017) and plutonic rocks (Mexias et al., 2005) show pervasive alteration described as late-magmatic albitization and hydrothermal alteration with the influx of meteoric fluids (Mexias et al., 1990a(Mexias et al., , 2005;;Bongiolo et al., 2011;Fontana et al., 2017). The largest Cu deposit in this basin is the Camaquã Mine, which is hosted in a Neoproterozoic sedimentary sequence and was exploited from the 18 th century until 1996 (Remus et al., 2000;Laux et al., 2005;Renac et al., 2014).

This exploited deposit has an ore reserve of ~30.8 Mt with an average Cu grade of ~1.06%, which is manifested as massive veins, stockworks and disseminated chalcopyrite, pyrite, bornite, chalcocite, gold, silver and hematite. The extrusive and intrusive rocks from the Lavras do Sul Mining District (Mexias et al., 2007), which are located on the central-western rim of the Camaquã Basin, host nineteen Au and Au-Cu deposits that were exploited during the same time frame (Bongiolo et al., 2011). The ore zones consist of quartz and sulfide-rich quartz veins (Mexias et al., 2005) associated with wall-rock alteration characterized by 'sericite', chlorite, pyrite and chalcopyrite (Bongiolo et al., 2011). In the vicinity of the Lavras do Sul area, the volcanogenic sequence in the Seival area hosts Cu-Ag deposits (Reischl, 1978;Lopes et al., 2014). The different mines yielded ca. 0.20 Mt of Cu-ore with an average grade of ~1.40%. The chalcopyrite, pyrite, chalcocite, bornite and covellite sulfides occurred in association with chlorite, hematite, calcite, barite and quartz disseminated in andesitic lapilli tuff and volcanic agglomerates or along fault planes cutting the volcanic sequence. A recent study on the Seival Mine (Fontana et al., 2017) improved current knowledge about the clay minerals in these ore deposits. Both albitization and chloritization processes were observed in the granite-related epithermal systems of the Lavras do Sul area (Mexias et al., 2007;Bongiolo et al., 2011) and the Camaquã Mine (Laux et al., 2005;Renac et al., 2014). A similar alteration mineralogy in the vicinity of the Lavras do Sul Intrusive Complex, located 10 km west of the Seival area, suggests that the Lavras do Sul porphyry-epithermal system contributes to the alteration of the andesitic rocks and ore deposition in the Seival area, as also occurs in the Potrerill Cu-Mo porphyry deposits and El Hueso Au epithermal deposits [START_REF] Sillitoe | Gold metallogeny of Chilean introduction[END_REF][START_REF] Marsh | 40 Ar/ 39 Ar geochronolgy of Cu-Au and Au-Ag mineralization in the Potrerillos district, Chile[END_REF].

Consequently, this study focused on the chemical signatures of albite and chlorite to smectite in the hydrothermal alteration products. The petrographic and chemical analyses of the minerals were used to estimate the temperatures and bracket temperatures of late-magmatic to hydrothermal alteration. Petrographic observations and temperatures estimated by chlorite geothermometers were introduced into a thermodynamic model. This model was used to reconstruct the chemical conditions favorable to ore deposition in the process of base-metal migration in the Seival area.

Geological Setting

Regional geology

The Mantiqueira Province extends from the southeast of Brazil to Uruguay (Almeida and Hasui, 1984;[START_REF] Silva | The neoproterozoic Mantiqueira Province and its African connections: a zircon based U-Pb geochronologic subdivision for the Brasiliano/Pan-African systems of orogens[END_REF]. In the Gondwana supercontinent, the southern portion of collision between the Rio de La Plata (Brazil) and the Kalahari (Africa) cratons is characterized by the Sul-rio-grandense Shield (Fig. 1A) with Neoproterozoic ages. This collision is represented by the Braziliano Orogeny and the opening of the Camaquã Basin related to the post-collisional stage (Lima and Nardi, 1998;Gastal et al., 2005a, b). The Sul-rio-grandense Shield comprises four geotectonic units: the Taquarembó Terrane, São Gabriel Terrene, Tijucas Terrene, and Pelotas Batholith. Recovering these units, the Camaquã Basin was considered (Paim et al., 2000;Almeida et al., 2012). These effusive rocks have basic to intermediate sodic compositions with mildly alkaline to high-K tholeiitic affinities (Almeida et al., 2012). The volcano-sedimentary units that occur in the Seival area (Fig. 2) have dominant intermediate compositions with basic and acidic end-members. The Bom Jardim Group, as previously described, consists of the effusive units of the Hilário Formation in the study area (Ribeiro and Fantinel, 1978). The deformation of the Hilário Formation along the Lavras do Sul contact suggests that the Hilário Formation is older than the Lavras do Sul Intrusive Complex (Gastal et al., 2015).

The Hilário Formation consists of dominantly andesitic rocks represented by andesitic lava flows, lapilli tuff, volcanic agglomerates, and dikes with a shoshonitic geochemical affinity (Lopes et al., 2014;Fontana et al., 2017). The Ar-Ar radiogenic dating of plagioclase suggests an age of 600 to 590 Ma (Janikian et al., 2008) that might be thermally influenced by intrusive magmas such as dikes or the Lavras do Sul granitoids. The other vesicular lava flows and volcanic clastic materials are represented by the polymictic conglomerates of the Santa Fé Formation. The Acampamento Velho Formation occurs as rhyolite dikes that cross-cut the Hilário Formation.

The granitoids of the Lavras do Sul Intrusive Complex with U-Pb ages varying from 601 to 587 Ma (SHRIMP in zircon, Remus et al., 1999Remus et al., , 2000;;Gastal et al., 2006;Liz et al., 2009), comprise a ring structure composed of porphyritic quartzmonzonite granodiorite and syenogranite to monzogranite with monzonitic intrusions in its northeastern margin (Gastal et al., 2006;Liz et al., 2009). In the contact zone between the Lavras do Sul granitoids and the Hilário Formation is a hectometer-thick metamorphic halo (Mexias et al., 1990a, b;Bongiolo et al., 2011) attesting to the thermal influence of granitoids on the volcano-sedimentary pile. 

Ore geology

The Seival hosts six inactive Cu-bearing deposits and several prospects. This reserve was estimated at ~0.20 Mt of ore with an average grade of ~1.40% of Cu and 10-70 ppm of Ag (Fig. 3A; Reischl, 1978;Lopes et al., 2014). The ore deposits in the Seival area were associated with the development of NE-SW-oriented shear zones that cross-cut the Camaquã Basin [START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF]Philipp et al., 2016). The emplacement of metallic mineralizations are bracketed between 600 and 580 Ma ago based on the ages of lava flows (Janikian et al., 2008), tectonic activity (Gastal et al., 2015) and the Lavras do Sul magmatism (Gastal et al., 2006;Almeida et al., 2012).

The sulfides are represented by chalcopyrite, bornite, chalcocite and covellite (Fontana et al., 2017) and are part of the main Cu-bearing veins that fill fractures and faults. The alteration halos are related to the distances of mineralized structures (Lopes et al., 2014;Fontana et al., 2017). The mineral association of chlorite, epidote and calcite formed at temperature of ~300 °C (Mexias et al., 1990b;Mexias et al., 2007;Bongiolo et al., 2011) in the volcanogenic rocks of the Hilário Formation close to the Lavras do Sul granitoids.

The mineral assemblages allow for the characterization of hydrothermal zones (Seedorff et al., 2005;[START_REF] Sillitoe | Porphyry copper systems[END_REF]. Propylitic alteration was related to chlorite, C/S mixed-layer, hematite, titanite, calcite, barite and quartz associated with pyritechalcopyrite and chalcocite-bornite, while argillic alteration was related to smectite and quartz (Fig. 3B; Lopes et al., 2014;Fontana et al., 2017). Cu enrichment was associated with propylitic alteration and the formation of albite (600 to 250 °C; Fontana et al., 2019) and Mg-chamosite to Fe-clinochlore (251 to 180 °C). The latehydrothermal veins are composed of barite, calcite and minor proportion of veins with calcite-quartz assemblage . These late precipitations represent the lowest temperatures of hydrothermal alteration (150 to 80 °C; Fontana et al., 2017). In the preserved parts of these inactive mines, mineralization occurs as a stockwork of veins or disseminated in volcaniclastic rocks and andesitic lava flows (Fontana et al., 2017). The faults, mineralized structures and dikes are considered contemporaneous based on the mineralogy and alteration type. Thus, the hydrothermal processes can be associated with the intrusion of NE-SW-oriented andesite (Lopes et al., 2018) and local hydrothermal cells. 

Analytical methods

Field work consisted of sample collection and logging of drill cores. The samples collected were representative of lapilli tuff, amygdaloidal to porphyritic andesitic lava flows and dikes. Petrographic observations of thin sections allowed the description of magmatic and hydrothermally altered crystals. The minerals, after of crushing and sieving, were separated using a magnetic separator, heavy liquids and hand-picking under a binocular microscope. Products of alteration were either collected under a binocular microscope in the altered phenocrysts or identified in the clay-size fraction.

These petrographic observations, mineral separation and clay-size fraction were characterized by scanning electron microscopy combined with energy-dispersive spectrometry (SEM-EDS, Zeiss EVO LS15, 20 kV, 2.5 nA with X-Max Oxford EDS The different mineralogical and chemical data of magmatic minerals were used with the petrogenetic model (MELTS software modeling; Ghiorso and Sack, 1995) to reconstruct magmatic conditions. The magmatic and hydrothermal minerals were combined in a thermodynamic model (PHREEQC interactive; [START_REF] Parkhurst | User's guide to PHREEQC-A computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations[END_REF] to estimate the favorable conditions for precipitation of hydrothermal phases and sulfides.

Results

Textures and petrographic observations

The host rocks of the Cu deposits in the Seival area are predominantly andesitic lava flows and lapilli tuff (Fig. 4A) to volcanic agglomerates with rounded andesitic pyroclasts. Their aphyric matrixes are dark to glassy and green with disseminated microlites of plagioclase and fragments of pyroxene. Amygdaloidal and porphyritic andesitic lava flows are predominant in the southern and northeastern parts of the Seival area and are in contact with the Santa Fé Formation (Fig. 2). Subvolcanic rocks have andesitic (Fig. 4B) to trachyandesitic compositions with feldspar phenocrysts, dominant pyroxene and scarce biotite phenocrysts.

Most of the rocks are intensively fractured and brecciated, particularly those spaces filled by clay minerals, quartz, calcite, titanite, pyrite, chalcopyrite, and minor hematite (Fig. 4C).

Porphyritic andesitic lava flows have phenocrysts of plagioclase and clinopyroxene in a trachytic matrix with oriented plagioclase. Andesitic dikes host subhedral grains of feldspars further identified as plagioclase with rims of K-feldspar (Fig. 4D) and phenocrysts of pyroxene. Some trachyandesitic dikes have subhedral phenocrysts of plagioclase, pyroxene and biotite. Some plagioclase and biotite phenocrysts have inclusions of apatite, zircon (50 to 200 µm) and titanite, while the oxidized matrix contains hematite. The titanite grains occur as euhedral grains associated with biotite and pyroxene and as anhedral grains of smaller granular agglomerates in the altered matrix.

As previously described (Lopes et al., 2014;Fontana et al., 2017), the Hilário volcanic sequence in the studied area is pervasively altered to clay minerals, calcite, barite and quartz. The original igneous mafic minerals and different matrixes have a light green material recognized as chlorite/smectite mixed-layer (Fig. 4E). Albite, chlorite and sulfide occur in the more altered rocks with traces of calcite and specular hematite, and euhedral or agglomerates of titanite occur with albite and microscopic euhedral quartz (Fig. 4F). 

Less

Major element compositions of magmatic to late-magmatic minerals and REE compositions of feldspars

Phenocrysts and microlites or crystalloclasts of pyroxene in porphyritic andesitic lava flows and andesitic dikes are augite (Wo 0.40-0.47 En 0.32-0.41 Fs 0.12-0.28; Fig. 5A; Supplementary Table A). According to the structural formula of augite (Table 1), the atomic ratios of [Mg/(Mg+Fetot)= 0.67-0.85] are high and those of [Na/(Ca+Na)= 0.02-0.05)] are low.

Prismatic biotite phenocrysts recognized in trachyandesitic dikes are classified as Mg-biotite with the structural formula expressed in Supplementary Table B. The less pristine Mg-biotites show slightly different compositions (Table 1), with increases in Al VI (Fig. 5B) and lower contents of Fe, Mg and Mn (Table 1). The euhedral to agglomerate titanite grains (Fig. 5C; Table 1 and Supplementary Table C) are associated with albite and biotite phenocrysts, and the anhedral grains in the matrix have similar chemical compositions.

The chemical compositions of feldspars were analyzed in thin section. The plagioclase phenocrysts have compositions of andesine-labradorite (An 0.43-0.53 Ab 0.43-0.54 Or 0.03-0.05) (Table 1). Moreover, some of the andesine-labradorite phenocrysts have a thin rim of K-feldspar (An 0-0.01 Ab 0-0.33 Or 0.66-1; Fig. 4B and Fig. 5D; Table 1), further described as Group I. In contrast, the microlites and phenocrysts of plagioclase (Supplementary Table D) from altered lapilli tuff, porphyritic andesitic lava flows and andesitic dikes consist of dominant albite (An 0- 0.06 Ab 0.89-1 Or 0-0.10; 

Mineralogy and major elemental compositions of clay minerals

Petrographic observations show "green clays" replacing pyroxene, biotite or feldspars that fill vesicles and intergranular porosity. Similar to Fontana et al. (2017), using X-ray diffraction techniques on clay-size fractions allowed for the identification of dominant trioctahedral smectite and smectite-rich (C/S) in less altered andesitic lava flows, as well as chlorite-rich chlorite/smectite mixed-layer and chlorite in more altered andesitic lava flows and lapilli tuff. The occurrence of different clay minerals for similar andesitic lithotypes suggests that hydrothermal alteration is not completely related to the primary magmatic mineralogy but to the influx of external fluid. The insitu electron microprobe analyses allowed for the identification of the composition of the large chlorite flakes (Fig. 6) in the cleavage of andesine-labradorite and albite and the replacement of augite phenocrysts or micrometer vugs in the andesitic dikes with a light green color (Table 1). Based on the Fe 2+ /(Fe 2+ +Mg) ratio, these chlorites have compositions of Fe-clinochlore to Mg-chamosite (Supplementary Table E).

The observed Fe 2+ /(Fe 2+ +Mg) atomic ratios between 0.47 and 0.64 suggest that values < 0.5 are Fe-clinochlore and those of > 0.5 are Mg-chamosite. These two types of chlorite were also recognized in a regional epithermal system (Fig. 7; Mexias et al., 1990b;Bongiolo et al., 2011) and distal-epithermal halo from the Camaquã Mine (Fig. 7; [START_REF] Troian | Cloritização na Mina Uruguai, Minas do Camaquã, RS, Brasil[END_REF]Renac et al., 2014). Low Fe 2+ /(Fe 2+ +Mg) proportions are structurally compensated by tetrahedral and octahedral aluminum (Al IV = 1.7 to 3.4; Al VI = 2.7 to 3.11). The Fe-clinochlore to Mg-chamosite in andesitic lava flows and lapilli tuff have lower Fe 2+ +Mg atomic proportions (7.5 to 8.5; atomic ratios of Fe 3+/ Fetot= 0.01 to 0.06) than in andesitic dikes (Fe 2+ +Mg= 9 to 10.1; atomic ratio of Fe 3+ /Fetot= 0.05). However, the chloritization of augite and filling of vugs reflect increasing contents of Fe+Al and Fe+Mg total contents in lapilli tuff and andesitic dikes, respectively. In addition, the Fe-clinochlore to Mg-chamosite compositions are very similar (Fig. 8A; Table 1) and were described using the same structural formula. [START_REF] Velde | Clay minerals: a physico-chemical explanation of their occurrence[END_REF]adapted from Inoue et al., 1984) with detail showing the smectite, chlorite-rich C/S mixedlayer (C/S) and chlorite compositions from Seival Mine, as well as comparison between chlorites analyzes from epithermal Lavras do Sul (Mexias et al., 1990b,c;Bongiolo et al., 2011) and Camaquã Mine (Renac et al., 2014). comparison with epithermal system from Lavras do Sul (Mexias et al., 1990b;Bongiolo et al., 2011) and Camaquã Mine (Renac et al., 2014). The occurrence of dominant chlorite/smectite, trioctahedral smectite and corrensite recognized by their dark green color and identified using X-ray diffraction (Fig. 8) was confirmed by electron microprobe measurements. The smectite-rich chlorite/smectite, smectite (Supplementary Table F) and corrensite (Fig. 8B and Figs. 9A-B) represent the dominant hydrothermal phase of andesitic lava flows and andesitic dikes. The dominant trioctahedral smectite (Fig. 8C) has a Mg-saponite composition (Table 1). The dominant chlorite-rich chlorite-smectite (Fig. ,8D;

Supplementary Table G) with micrometer-scale fan-shaped particles (Fig. 4C) occurs in altered porphyritic and amygdaloidal andesitic lava flows. The chlorite-rich chlorite-smectite have Al VI and IV contents (Altot 2.21+ 1.25 to 2.46+ 1.48 a.p.f.u.) that are higher in the porphyritic andesitic lava flows than the chlorite-rich chloritesmectite (Altot= 1.59+ 0.77 to 1.93+ 1.47) in the amygdaloidal andesitic lava flows.

The proportion of Fe and its valency balance are represented by changes in tetrahedral and octahedral Al. The chlorite-rich chlorite-smectite structural formulas vary between porphyritic and amygdaloidal andesitic lava flows (Table 1). These mineral associations suggest a sequence of crystallization and hydrothermal alteration over time.

Discussion

Chemistry of magmatic and late-magmatic minerals

The volcanogenic rocks in the Seival area are interpreted as part of the Lavras do Sul Shoshonitic Association (Lima and Nardi, 1998), which are related to the Lavras do Sul granitoids and lamprophyres. The occurrence of lamprophyres (Lima and Nardi, 1998;Almeida et al., 2012), andesitic dikes and various volcanic events in the region suggests long and intense episodes of magmatism in the Seival area constrained by the dating of zircon (Almeida et al., 2012;Janikian et al., 2012) between 600 ± 2 to 590 ± 6 Ma. The mineralogy of andesitic rocks with andesinelabradorite, augite and Mg-biotite phenocrysts and their whole-rock compositions (Lima and Nardi, 1998;Sommer et al., 2006;Lopes et al., 2014) suggest a petrogenetic link with the Lavras do Sul Shoshonitic Association.

Petrogenetic modeling (MELTS Software: Ghiorso and Sack, 1995) used with whole-rock compositions (Lopes et al., 2014) estimates a liquidus temperature of ca. 1080 °C. The modeling shows a sequence of crystallization initiated by calcic plagioclase followed by low-Ca-pyroxene, late orthoclase and high-Ca pyroxene or biotite (ca. 800 °C). The stages below 800 °C include late-magmatic minerals formed by volatile-rich melt (c.f. [START_REF] Dixon | An experimental study of water and carbon dioxide solubilities in mid-ocean ridge basaltic liquids. Part 1: Calibration and solubility models[END_REF]. In this context, the biotites observed with the higher Al IV contents of less pristine biotite compared with the biotite phenocrysts might represent two stages of biotite crystallization or slightly altered crystals. The late-magmatic stage initiated at solidus temperatures (800 to 500 °C) with volatile oversaturation and the degassing of the melt (c.f. [START_REF] Dixon | An experimental study of water and carbon dioxide solubilities in mid-ocean ridge basaltic liquids. Part 1: Calibration and solubility models[END_REF]. This interpretation is reinforced by the oxygen isotopic values of andesinelabradorite (δ 18 O andesine-labradorite: 6.6 to 8.2 ‰; Fontana et al., 2019) showing the magmatic signature of fluids in equilibrium with feldspars [START_REF] Taylor | Stable isotope geochemistry of low temperature processes[END_REF] evolving toward the mixing of meteoric and magmatic fluids for albite (δ 18 O albite: 14.2 to 16.2 ‰; Fontana et al., 2019). Consequently, presume that observed Mg-biotite formation, euhedral F-rich titanite grains and albite are related to late-magmatic crystallization and albitization processes of andesine-labradorite. According to thermodynamic modelling and the literrature (c.f. Higgins and Ribb, 1976;Franz and Spear, 1985;[START_REF] Enami | Al-Fe 3+ and F-OH substitution in titanite and constraints on their P-T-dependence[END_REF][START_REF] Tropper | The substitution of Al and F in titanite at high pressure and temperature: experimental constraints on phase relations and solid solution properties[END_REF]Harlov et al., 2006;[START_REF] Hövelmann | The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments[END_REF]Kaur et al., 2012) this albitization process occurs at temperatures below 800 °C, presumably from ca. 600 to 250 °C. The widely observed albite suggests a magmatic to high-temperature hydrothermal system (epithermal-porphyry: [START_REF] Richards | Tectono-magmatic precursors for porphyry Cu-(Mo-Au) deposit formation[END_REF]Sillitoe, 2010 or Iron Oxide-Copper-Gold;[START_REF] Sillitoe | Iron oxide-copper-gold deposits: An Andean view[END_REF]Williams et al., 2005;Groves et al., 2010). The alkaline and acidic fluids in these systems are related to the albitization process and K-rich alteration [START_REF] Perez | An empirically derived kinetic model for albitization of detrital plagioclase[END_REF][START_REF] Boulvais | Cretaceous albitization and dequartzification of Hercynian peraluminous granite in the Salvezines Massif (French Pyrénées)[END_REF] that, to some degree, participated or started the leaching of base metals from the lava [START_REF] Moody | An experimental investigation of the albitization of plagioclase[END_REF][START_REF] Perez | An empirically derived kinetic model for albitization of detrital plagioclase[END_REF][START_REF] Hövelmann | The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments[END_REF]Kontonikas-Charos et al., 2014). Non-magmatic basinal brine has also reported in the albitization process [START_REF] Barton | Iron oxide(-Cu-Au-REE-P-Ag-U-Co) systems[END_REF][START_REF] Barton | Evaporitic source model for igneousrelated Fe oxide-(REE-Cu-Au-U) mineralization[END_REF]2000), such as in the Nevada porphyry, IOCG deposits (Carten, 1986;Dilles and Einaudi, 1992;[START_REF] Dilles | Overview of the Yerington porphyry copper district: magmatic to nonmagmatic sources of hydrothermal fluids, their flow paths, alteration affects on rocks, and Cu-Mo-Fe-Au ores[END_REF][START_REF] Sillitoe | Iron oxide-copper-gold deposits: An Andean view[END_REF]Mark et al., 2006;Kendrick et al., 2007) or Chilean "Manto-type" deposits, such as Michilla, with the mixing of magmatic and basinal brine [START_REF] Barton | Iron oxide(-Cu-Au-REE-P-Ag-U-Co) systems[END_REF]. In the Seival area, the change of andesine-labradorite (An 0.43- 0.53 Ab 0.43-0.54 Or 0.03-0.05) to albite (An 0-0.06 Ab 0.89-1 Or 0-0.10) with rare K-feldspar rims on andesine-labradorite or rare illite attest to the circulation of alkaline fluid.

Moreover, the sizes of the quartz and calcite crystals with liquid inclusions did not allow fluid inclusion microthermometry to recognize high-density fluid, as in IOCGtype deposits [START_REF] Reeve | Olympic Dam copper-uranium-gold-silver deposit[END_REF][START_REF] Davidson | Proterozoic copper-gold deposits[END_REF]. Nevertheless, the REE patterns of the plagioclase separates (Groups I and II) are not similar to the whole-rock patterns (Fig. 10; Lopes et al., 2014) with positive Eu positive anomalies (Eu/Eu*= >1; Table 2) that are higher in the andesine-labradorite-rich grains (group I) than albite (group II; Fig. 10A-B). These changes can be related to apatite inclusions in plagioclase, as mentioned in the petrography section, since these samples were acid-leached to remove traces of carbonates, Ca-phosphates and Fe and HREE variations from albites and andesine-labradorite suggest a similar source Therefore, the albitization process in the Hilário Formation was related to the neutral to mildly acidic water circulation of Na-rich magmatic fluid, such as late-magmatic glass interactions with outgassing magmatic fluids (CO2 and H2O), but these data cannot decipher between a magmatic to late-magmatic crystallization with the mixing of magmatic fluids and brine (e.g. IOCG: [START_REF] Barton | Iron oxide(-Cu-Au-REE-P-Ag-U-Co) systems[END_REF][START_REF] Barton | Evaporitic source model for igneousrelated Fe oxide-(REE-Cu-Au-U) mineralization[END_REF]2000). The aligned Cu-Ag ore bodies and disseminated mineralizations (see Figure 3) with similar mineral assemblages (albite, chlorite, chlorite/smectite mixed-layers, chalcocite-bornite, barite, and minor calcite, hematite and quartz) could be typical of epithermal deposits [START_REF] Sillitoe | Porphyry copper systems[END_REF] associated with the geothermal influence of andesitic dikes or the Lavras do Sul granitoids. These observations and interpretations suggest that Seival would be a superficial part of the Lavras do Sul porphyry (Mexias et al., 2007;Bongiolo et al., 2011). We assumed that low-hematite contents in the Seival area associated with calcite in small veins and ore deposits without an iron-oxide caprock are clues discarding the hypotheses of an IOCG type deposit or a metallic enrichment related to weathering profile such as Gossan genetic model of ore deposits.

Clay minerals and chlorite during hydrothermal stages

The hydrothermal stages associated with saponite, chlorite/smectite and chlorite precipitations surrounding albite suggest hydrothermal fluids of below 350 °C. Previous studies (Lopes et al., 2014;Fontana et al., 2017) characterized the occurrence of Fe-Cu-rich sulfides associated with chlorite/smectite. The association of Cu-rich sulfides with Fe -Al -Mg rich chlorite/smectite suggests that the Fe 2+ , Mg and Al contents of the clay minerals are related to ore deposition (Wilkinson et al., 2015;Yoneda et al., 2016). Nevertheless, the origin, chemistry and temperature of the fluids are not well characterized.

In the Seival area, crystallography realized by X-ray diffraction and mineral chemistry obtained by electron electron microprobe analyses identified Mg-saponite (smectite), chlorite/smectite mixed-layer and corrensite infilling the porosity or intergranular spaces. The occurrence of dominant clay minerals with Mg-saponite, chlorite/smectite and corrensite in different lithotypes was interpreted as a lithological control of alteration rather than being derived from local equilibrium (Fontana et al., 2017). The comparison of the major element compositions of magmatic minerals (Part 4.2), clay mineral (part 4.3) and whole-rock samples (Lopes et al., 2014) provided information to support this hypothesis. The predominant Fe-Mg-rich clay minerals and their Fetot/Fetot+Mg atomic ratios compared to augite (0.14 to 0.27) and biotite (0.37 to 0.44) indicate that Mg-saponite (0.22 to 0.27) and chlorite/smectite mixed-layers may be derived from the alteration of magmatic minerals and glass. In contrast, the high Fe-clinochlore to Mg-chamosite ratio (0.47 to 0.63;

Supplementary Table E) suggests the addition of Fe and Mg during the chloritization process. This interpretation as confirmed by mass-balance calculations performed by Fontana et al. (2019).

We estimated the temperatures of chlorites using chemical thermometers (Inoue et al., 2009;[START_REF] Bourdelle | Low-temperature chlorite geothermometry: a graphical representation based on a T-R 2+ diagram[END_REF]. These thermometers are the only available temperature constraint considering the small sizes of the fluid inclusions (Fontana et al., 2017). We discarded the chemical thermometer of chlorite related to metamorphic conditions and selected one determined in similar lithotypes and pressure conditions. The chosen chemical thermometers use a structural formula with an uncertainty dominantly controlled by the Fe valency and different octahedral layers. Assuming an error of 20% in the Fe distribution, the uncertainty is in the Seival area compared to those in the Lavras do Sul area (Mexias et al., 1990b;Bongiolo et al., 2011) or the Camaquã Mine (Renac et al., 2014) yield comparable temperatures. These different uncertainties (± 50 °C) and calculated temperatures reflect chloritization below of the minimum temperature of albitization. The higher temperature of chlorite associated with andesitic dikes suggests a temperature related to intrusive bodies or different thermal gradients between lapilli tuff and andesitic dikes.

Hydrothermal evolution and thermodynamic modeling

The chlorite and chlorite/smectite mixed-layers associated with sulfides are typical mineralogical assemblages of hydrothermal deposits [START_REF] Barnes | Geochemistry of Hydrothermal Ore Deposits[END_REF][START_REF] Pirajno | Hydrothermal processes and mineral systems[END_REF][START_REF] Sillitoe | Porphyry copper systems[END_REF]. In the Seival area, different Fe-Cu -rich sulfide assemblages occur in the intergranular space or are mixed with clay minerals (Fontana et al., 2017).

Hydrothermal alteration minerals are associated with a sequence of precipitations rather than a paragenetic assemblage, as occurs in metamorphic reactions. Therefore, thermodynamic modeling can be erroneous when based on the assumption of an output represented by all of the hydrothermal phases observed. reacting with initial fluid (low-concentration water similar to rainfall, [START_REF] Salve | Chemical composition of major ions in rainwater[END_REF], and carbonic fluids (CO2 as recognized in fluid inclusions (Fontana et al., 2017). The temperature domain of these calculations was bracketed by the albitization process (< 350 °C) and the calculations of the chlorite thermometer (120 to 320 °C). Each calculation considers a molar proportion of water a hundred times higher than those of minerals and fluids for varying pH values and temperatures below 350 °C. Consequently, the thermodynamic changes in calculated fluids and the dissolution or precipitation of primary and secondary minerals equilibrated at 350, 300, 250, 200 and 150 °C with pH and Eh were adjusted for charge balance and redox conditions. These preliminary calculations indicate multiple solutions with more products than were identified in the altered rocks. Therefore, we forced the software to uniquely consider results with chlorite, calcite, quartz and Fe-Cu rich sulfide or barite, which are here assumed to be products of hydrothermal reactions, without any constraints related to their precipitation or dissolution.

These thermodynamic calculations were obtained for neutral (pH: 7) and acidic (pH: 4) initial water conditions. Regardless of the considered temperature, all final waters remained neutral for an initial fluid with a neutral pH (pH: 7 to 7.3), whereas acidic waters changed to a neutral pH (pH 4 to 7.3).

The high-temperature (350 °C) calculations indicate the coprecipitation of albite and titanite with the total consumption of the Ca-rich feldspars and pyroxene, but no minor chlorite or smectite. The conservation of some pyroxene and andesinelabradorite observed in the petrography and the lack of clay minerals suggests unrealistic solutions for hydrothermal alteration forming albite with titanite and chlorite. Consequently, we forced the precipitation of chlorites in a second data set.

-For temperatures between 350 and 250 °C, the chlorite, quartz and calcite associated with pyrite and chalcopyrite can be formed, whereas silica-rich glass, titanite and Ti-magnetite are consumed anorthite, albite and pyroxene are partially dissolved.

-For temperatures between 250 and 150 °C, neutral or acid water dissolved magmatic minerals with predicted precipitations of chlorite, barite, calcite, quartz and -Below 150 °C, the lower activities of Fe 2+ with decreasing HS -/(HS -+SO4) molar ratios increased the saturation with respect to chalcocite and sulfate and Fe oxides, such as barite and hematite. These calculations confirm that pyrite and chalcopyrite were probably precipitated from a dominant magmatic fluid at temperatures between 350 to 250 °C. The further mixing of the magmatic fluid with meteoric water or basinal brine at temperatures varying from 250 to 150 °C promoted chalcocite-bornite deposition. Considering the domain of barite saturation and the lack of supergene alteration or gossan profiles in this region, the lower temperature of the Cu enrichment of sulfide ranged from 150 to 50 °C.

Conclusions

The Seival area contains hydrothermal Cu-sulfide deposits hosted in volcanic rocks with a shoshonitic affinity. Interpretations based on mineralogical and chemical data suggest that volatile-rich magma produced Mg-biotite, followed by late- 

RESUMO

Barita, calcita e hematita são associadas a depósitos de minério na Bacia do Camaquã e relacionadas ao estágio tardi-magmático a hidrotermal de baixatemperatura. As análises de Microssonda Eletrônica e Elementos Terras Raras (ETR) nos cristais de barita foram medidas para reconstruir as condições hidrotermais de baixa temperatura. Albitização do plagioclásio (andesinalabradorita) foi associada com parte ou porção de bário e a desestabilização do sulfeto deve ter fornecido enxofre para o fluido responsável pela precipitação de barita (<150°C). A precipitação tardia de barita e seus conteúdos de elementos maiores, traços e ETR sugerem uma fonte de metal relacionada a albitização e retransmitido por cloritização associada com uma crescente proporção de água meteórica. O influxo de fluido meteórico (conteúdo de ETR) tem providenciado mudanças nas condições de Eh-pH e oxidação de fluido dominante H2S-rico (calcocita, covelita) para fluido com SO4-rico dominante associado com precipitação de barita. Baseado na diferença do conteúdo de bário de andesina-labradorita magmática e albita, um volume de 1 m 3 de andesito alterado é necessário para produzir 1,6 kg de barita. O volume de andesito alterado através do processo hidrotermal (albitização, cloritização e desestabilização de sulfetos) corresponde a 0,06 % e ocorre nos últimos veios na área do Seival. PALAVRAS-CHAVES: Baritas; Geoquímica de ETR; Alteração hidrotermal; Mineralizações na Bacia do Camaquã.

INTRODUCTION

In hydrothermal and supergene contexts, the precipitation of barite is associated with low-temperature fluids (<150 °C; [START_REF] Hanor | Barite-celestine geochemistry and environments of formation[END_REF]. The extremely lowsolubility of barite [START_REF] Deer | An Introduction to the Rock Forming Minerals[END_REF][START_REF] Jamieson | Precipitation and growth of barite within hydrothermal vent deposits from the Endeavour Segment, Juan de Fuca Ridge[END_REF] makes this mineral resistant to weathering and reconstruction of low-temperature conditions. Therefore, the crystallization of barite promoted by barium and SO4 2-fluids records alteration of Ba-rich feldspar and pyroxene [START_REF] Sorrell | Solid state formation of barium, strontium and lead feldspars in clay-sulfate mixtures[END_REF][START_REF] Green | Island arc and continent building magmatism -A review of petrogenic models based on experimental petrology and geochemistry[END_REF][START_REF] Mehnert | The Ba content of K feldspar megacrysts in granites, a criterion for their formation[END_REF][START_REF] Deer | An Introduction to the Rock Forming Minerals[END_REF][START_REF] Chang | Rock-Forming Minerals. Non-Silicates: Sulfates, Carbonates, Phosphates, Halides[END_REF] and sulfate from seawater [START_REF] Goldberg | Differences between barites of marine and continental origins[END_REF][START_REF] Piper | Rare-Earth Elements in the Sedi Cycle: A Summary[END_REF][START_REF] Michard | Chemistry of solutions from 13°N East Pacific Rise hydrothermal site[END_REF][START_REF] Elderfield | The oceanic chemistry of the rare earth elements[END_REF][START_REF] Martin | Strontium and neodymium isotopic analysis of marine barite separates[END_REF] or oxidation of sulfides [START_REF] Brimhall | Thermodynamic modeling of geological materials: minerals, fluids and melts[END_REF]Vaugham and Craig, 1997).

Barite precipitation in the Camaquã Basin is associated with vein-type or disseminated Cu-Pb-Zn-rich sulfide forming ore deposits [START_REF] Bettencourt | Mineralogia, inclusões fluídas e isótopos estáveis de oxigênio e enxofre da Mina de Cobre de Camaquã RS[END_REF]Remus et al., 2000;Toniolo et al., 2004;Renac et al., 2014). In this case, the precipitation of sulfides and gangue minerals as barite and calcite were related to late-magmatic to low-temperature hydrothermal stage. In the Seival area, metallic Fontana et al., 2017) and chloritization of pyroxene (312 to 120 °C). Barite, calcite and minor hematite fill fractures and residual porosity of andesite lavas (Lopes et al., 2014;Fontana et al., 2017) and represent the latest aqueous-fluid circulation interpreted as low-temperature meteoric fluids (Fontana et al., 2017). In the literature, hydrothermal-volcanic systems with barite and calcite may have different trace element concentrations and Rare Earth Element (REE) patterns from continental-hydrothermal barite to seawater [START_REF] Michard | Rare earth element systematics in hydrothermal fluids[END_REF]. Few studies concern barite origin and its formation conditions [START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF][START_REF] Michard | Rare earth element systematics in hydrothermal fluids[END_REF][START_REF] Barrett | Rare earth element geochemistry of massive sulfides sulfates and gossans on the Southern Explorer Ridge[END_REF][START_REF] Martin | Strontium and neodymium isotopic analysis of marine barite separates[END_REF]. Major, trace and REE contents may contribute to the understanding of metal source related to alteration of surrounding volcanogenic rocks or external fluids (eg., [START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF][START_REF] Morgan | Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control[END_REF][START_REF] Jurkovic | Geochemical characteristics of barite occurrences in the Palaeozoic complex of south-eastern Bosnia and their relationship to the barite deposits of the mid-BosnianSchist Mountain[END_REF][START_REF] Zarasvandi | Geochemistry and fluid-inclusion microthermometry of the Farsesh barite deposit[END_REF]. We studied major elements and REE contents of barite to propose an origin of low-temperature fluid in the Seival area.

GEOLOGICAL SETTINGS

REGIONAL GEOLOGY

The Mantiqueira Province extends from northeast Brazil to Uruguay as a Gondwanian-orogenic system with Neoproterozoic age, formed during collision between La Plata and Kalahari cratons (Almeida and Hasui, 1984;Saalmann et al., 2005) (Fig. 1A). Its southernmost portion in Brazil receives the denomination of Sulrio-grandense Shield. This shield was subdivided in two geotectonic units: (i) Rio de La Plata Craton and Dom Feliciano Belt [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Hartmann et al., 2007;Philipp et al., 2016) (Fig. 1B). The Seival area is a zone of volcanogenic rocks associated with the Bom Jardim Group (600-590 Ma; Lima et al., 2007;Janikian et al., 2008 and[START_REF] Ehya | Rare earth element and stable isotope (O, S) geochemistry of barite from the Bijgan deposit, Markazi Province, Iran[END_REF] from the Camaquã Basin (630-540 Ga;[START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Paim et al., 2000) (Fig. 2) related to the final evolution of the Dom Feliciano Belt [START_REF] Chemale | Evolução Geológica do Escudo Sul-rio-grandense[END_REF]Paim et al., 2000;Philipp et al 2016;Lopes et al., 2018). The Hilário Formation (600-590 Ma; Janikian et al., 2008) deposition (Paim et al., 2000). These volcanogenic rocks were associated with the Lavras do Sul Intrusive Complex (601 to 598 Ma; Nardi, 1984;Lima and Nardi, 1998;Remus et al., 1999;Remus et al. 2000;Gastal et al., 2006;Liz et al. 2009;Fontana et al., 2017;Lopes et al., 2018).

The fractures and dikes in the Seival area are associated with tectonic reworking related to shear zones and deformation episodes that allowed the 

TEXTURE AND MINERALOGY

Volcanogenic rocks and andesitic to trachyandesitic dikes (Lopes et al., 2014;Fontana et al., 2017) of the Seival area (Fig. 3) host Cu-Ag mineralizations surrounded by extensive hydrothermal halos, ca. 0.20 Mt of Cu with an average grade of ~1.40 % (Reischl, 1978;Lopes et al., 2018). This sequence is represented by lapilli tuff supported in a matrix of vesicular fine ash with crystals of plagioclase, pyroxene, quartz, opaque minerals and porosity with clasts of several volcanic materials, generally vesicular andesite rocks (Lopes et al., 2014;Fontana et al., 2017). Andesite lava flows have phenocrysts of plagioclase and clinopyroxene dispersed in a trachytic matrix with oriented plagioclase and pyroxene (Lopes et al., 2014). Volcanic agglomerates contain rounded volcanic clast and occur associated with faults and fractures. Andesitic and trachyandesitic dikes have subhedral phenocrysts of plagioclase and pyroxene in a trachytic matrix with oriented plagioclase. Relicts of pyroxene phenocrysts are scarce and most were partially or totally replaced by clay minerals and calcite, sometimes keeping its original shape.

The andesitic dikes have albitized plagioclase phenocrysts, while some of them preserved a magmatic chemistry in the center or some preserved part of crystals.

The andesitic to trachyandesitic dikes are also associated with NE-SW oriented structures (Lopes et al., 2014;Fontana et al., 2017;Lopes et al., 2018). 

METHODOLOGY

The samples of field and drill-core consist of volcanogenic rocks with hydrothermal alteration. The selected veins of barite are hosted in the lapilli tuff and andesite lava flows from one and five locations, respectively. We prepared grain mounts and thin sections of barite for petrography and Electron Microprobe (EMPA)

analysis. Further on, the mono-mineral content of separates were checked by X- The REE contents were determined in concentrates of veins of barite and calcite. The calcite (< 100 mg) was digested with 10 % HNO3 (ultra-pure). Barite was digested (500 to 250 mg) using ten times more NaCO3-ultrapure (Merck 99.999% pure) through the flux-based fusing method, as described by [START_REF] Barbieri | Strontium geochemistry in the epithermal barite deposits from the Apuan Alps (Northern Tuscany, Italy)[END_REF] and [START_REF] Breit | Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate[END_REF]. Barite -NaCO3 mixture was loaded in a Pt-crucible (20 mL crucibles) with an addition of 1 mL Lithium-Iodide (LiI), enhancing the recovery of the fused material from the Pt-crucibles. This LiI was removed by evaporation during the fusing process. The mixture was heated for 10 hours in a muffle furnace (1100 °C). The cooled material was grounded into a very fine powder using an agate grinder. This powder was dissolved in a cleaned Teflon beaker with distilled water (UHQ). The residues (Na2CO3 and BaCO3) and sulfate-free solution were heated in 10 mL of HCl and then evaporated to dryness and dissolved in HNO3

(1 M). The dissolved material went through C18 Sep-Pak cartridges [START_REF] Shabani | Preconcentration of trace Rare Earth Elements in sea water by complexation with bis (2-ethylhexyl) hydrogen phosphate and 2-ethylhexyl dihydrogen phosphate adsorbed on a C18 cartridge and determination by inductively coupled plasma mass spectrometry[END_REF] to reduce barium and strontium amount. In this resin, we expected that all barium would be transported through the column without being bonded to the bis (2ethylhexyl) orthophosphoric acid. The cartridge was rinsed (10 mL of 0.01 M HCl)

then its content was eluated with HCl (30 mL, 6 M).

The digested solutions were analyzed by ICP-MS (Elan DRCII, Perkin Elmer)

at GEOAZUR (Université Côte d'Azur). Quantification limits were below 50 ng/L. The REEs were determined by ICP-MS measurements of a digested sulfate-sulfide mineral, thereby correcting for the interference of 135 Ba 16 O on 153 Eu using the 'doubly charged' technique [START_REF] Barrett | Rare earth element geochemistry of massive sulfides sulfates and gossans on the Southern Explorer Ridge[END_REF][START_REF] Jarvis | Avoidance of spectral interference on Europium in Inductively Coupled Plasma Mass Spectrometry by sensitive measurement of the doubly charged ion[END_REF]. The use of a Ba-REEspiked solution (1.5 mg L -1 ) allowed the determination of an optimal elution time for a REE recovering rate of 87 %. The elements concentrations were expressed as ppm (mg kg -1 ) and normalized by chondrite values (McDonough and Sun, 1995).

RESULTS

STRUCTURAL GEOLOGY AND CRYSTALLIZATION SEQUENCE

Barite and calcite veins occur located in the same geological context of faults and fractures hosted in the volcanogenic rocks associated with Cu-Ag 

TEXTURES AND PETROGRAPHIC OBSERVATIONS

The veins and veinlets of barite and calcite take place in fractured and hydrothermal altered zone with rims or halos with hematite (Hem-2), chlorite and chlorite/smectite mixed-layers and remains of Cu-Ag ore represented by disseminated crystals of Fe-and Cu-rich sulfides (Fontana et al., 2017). In veins and veinlets, macroscopic observations show white to pinkish barite occur as aggregates of tabular and prismatic crystals with subhedral to euhedral forms (Fig. 5A). A special attention has been paid to barite crystals and mineral inclusion in barite. These mineral inclusions in larger barite are calcite with oxidized sulfides and hematite. In calcite-rich veins the petrography confirmed the association of dominant calcite-filled (Cal-3) fractures (Fig. 5B) with quartz (Fig. 5C), a smaller proportion of barite or malachite particularly in the mineralized zones (Fig. 5D) with

Cu-sulfides such as chalcocite (Fig. 5E) and bornite (Fig. 5F).

The petrographic observations show barite crystals with calcite inclusions and indicate the predominance of clay minerals associated with sulfides. The associations of barite and Cal-3 do not represent mineral assemblages since no grain intergrowth of these minerals was observed. Barite is cutted by Cal-3 veins (Fig. 6A), which also occur in the contact between barite veins and host rock (Fig. 6B). Cal-3 also occurs within joints of barite crystals. This Cal-3 is associated with sulfides grains, hematite and white mica. The sulfides were identified as chalcocite.

These sulfides are filling vesicles and the intergranular porosity of the volcanogenic rock (Fig. 6C). The chalcocite grains are concentrated in the Cal-3 veins and in a few millimeters of contact between barite and Cal-3 veins (Fig. 6D). The malachite and azurite were observed in the different Cu occurrences and were considered as a product of the recent weathering of Cu-sulfides. 

BARITE AND BARIUM COMPOSITIONS IN PLAGIOCLASE

The EMPA analysis tested barium variation in the plagioclase. The content of Na (0.02 to 0.16 atomic weight %), S (13.08 to 14.05 atomic weight %), Ba (56.87 to 59.10 atomic weight %), Sr (0.02 to 1.01 atomic weight %) and O (26.42 to 27.94 atomic weight %) is showed in Table 1. The contents of Si, Mg, Al, K, Ca, Ti, Cu, Mn and Fe are low-content or trace (< 0.2 atomic weight %) in the analyzes. Low concentration of Sr marked barite end-member of barite-celestine solid solution series. 1.

We measured the barium compositions in the plagioclases with slight albitization and strong albitization to verify the barium variation (Fig. 8A). The andesine-labradorite and albite compositions (Fig. 8B) showed different content of barium. The andesine-labradorite has 0.11 to 0.14 atomic weight % (Table 2) of barium and the albite has < 0.02 atomic weight % (Table 2). 

REE OF BARITE, CALCITE AND WHOLE-ROCK

The concentrations of REE in barite, calcite (Cal-3) and whole-rock (Lopes et al., 2014) samples are showed in 3). The very high Eu estimated concentration was probably due to the interference effect of barium despite resin separation, using "doubly charged"

technique to interference corrections [START_REF] Jarvis | Avoidance of spectral interference on Europium in Inductively Coupled Plasma Mass Spectrometry by sensitive measurement of the doubly charged ion[END_REF]. The REE content in the barite showed two distinct patterns (Fig. 9A). The first pattern (Brt2 and Brt3) is similar in LREE and HREE. The second pattern (Brt1) is depleted in LREE (Ce, Pr and Nd) and HREE (Dy and Er) compared to the first group. The analyzes with Ce/La= ~1.7 (not normalized calculi) are similar to those formed in continental barite [START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF][START_REF] Barrett | Rare earth element geochemistry of massive sulfides sulfates and gossans on the Southern Explorer Ridge[END_REF][START_REF] Martin | Strontium and neodymium isotopic analysis of marine barite separates[END_REF], higher than negative Ce anomalies in the barites of the seawater (Ce/La= ~0.5) [START_REF] Goldberg | Differences between barites of marine and continental origins[END_REF][START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF]. The calcite REE contents showed patterns similar to whole-rocks analyzes. The depleted REE contents in calcite are associated with samples located in the mineralized areas. The wide variation of La/LuN ratios in calcite indicates a progressive enrichment of LREE (Fig. 9B). The whole-rock REE patterns are similar to those in albitization and chloritization alteration (Lopes et al., 2014;Fontana et al., 2017) (Fig. 9C). The comparison between the REE patterns in the barite and albitized rocks evidenced enrichment in the barite (Fig. 9D), probably related to pyroxene chloritization, providing REE to hydrothermal fluid. These REE patterns are similar to those found by [START_REF] Michard | Rare earth element systematics in hydrothermal fluids[END_REF], which showed barites of high-temperature acidic waters origin (pH < 6; T > 230 °C) from submarine hydrothermal vents on the East Pacific Rise. 

DISCUSSION

EVOLUTION OF HYDROTHERMAL ALTERATION

The Andesitic volcano-sedimentary rocks from Seival area comprise andesine-labradorite and augite phenocrysts (Lopes et al., 2014;Fontana et al., 2017) indicating magma chamber crystallization. From magma ascent to lava flow emplacement, outgassing through melting has precipitated microlithic plagioclase and magmatic sulfide. The thermodynamic modeling and stable isotopes analysis (Fontana Ph.D.) of less to more altered lavas indicate late-magmatic and incursion of meteoric fluids associated with albitization process (650 to 250 °C; [START_REF] Hövelmann | The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments[END_REF][START_REF] Huang | Chemical and isotopic fractionation of wet andesite in a temperature gradient: Experiments and models suggesting a new mechanism of magma differentiation[END_REF] followed by chloritization (310 to 120 °C; Lopes et al., 2014;Fontana et al., 2017).

The fractures and veins filled with barite, calcite (Cal-3) and quartz do not represent a paragenetic assemblage but a sequential precipitation, most probably proportion and oxygen fugacity. The precipitation of a large amount of barite is related to high-Ba-SO4 activities and very negative Gibbs-free enthalpy of barite compared to calcite (Cal-3) and minor hematite (Hem-2) (Lawrence Livermore National Laboratory, thermodynamic database). However, the source of barium and sulfur can be associated with either volcanic rocks or seawater. The barium content in andesine-labradorite (0.12 atomic wt %) is higher than in albite (below detection limit), which indicates that albitization process leached barium. The main peak (3.43 Å) in barites shows strontium content in the barite structure, rather than a mixture of barite and celestine (SrSO4). We compared these values to found by Abidi et al.

(2012), while possible < 0.5 % of Sr in the barite structure.

We used the Ba-molar content in andesine-labradorite [0.061 molar %= 0.12 % Ba in andesine-labradorite x 137.3 g mol -1 Ba / 268.62 g mol ). Consequently, the albitization of 1m 3 with formation of pure albite would produce 9.5 x10 -4 m 3 of barite (5.5x10 -5 /0.058 m 3 ).

We also used the same formula of Ba-molar content in seawater [0.006 to 0.023 molar %= 0.0008 to 0.0031 % Ba in seawater x 137.3 g mol -1 Ba / 18.01 g mol 

SOURCE OF BARIUM, SULFUR AND RARE EARTH ELEMENTS IN BARITE

This chapter features a characterization of alteration mineral assemblages generated in different temperatures of hydrothermal fluids that occur in the Seival area. An order of crystallization was defined, as well as mineral associations of each thermal step of the alteration process, with the purpose of understanding the physical-chemical evolution of the hydrothermal system and Cu-enriched phases.

Volcanogenic rocks from the Seival area are characterized by a magmatic phase including pyroxene (augite) and plagioclase (andesine-labradorite) (Lopes et al., 2014;Fontana et al., 2017). Deposition of primary sulfide (pyrite and chalcopyrite) was considered as a late-magmatic hydrothermal alteration precipitated in temperatures around ~350°C (Fig. 10A). Moreover, Cal-II (Fontana et al., 2017), Hem-I and quartz are associated with relicts or pseudomorphic of pyroxene and plagioclase.

The albitization of plagioclase, chloritization of pyroxene and destabilization of primary sulfides occur associated with the same hydrothermal fluids (Lopes et al., 2014;Fontana et al., 2017) with temperatures of ~250 °C. The barium is not detected in albitized portions of andesine-labradorite (see part 4.3) and, therefore, part or portion of barium in barite crystallization is linked to the albitization of plagioclase (andesine-labradorite).

Crystallization of barite (1 mole) might be produced by the albitization of 483 moles of andesine-labradorite (0.12 weight % of Ba). The albitization of 1m 3 of andesite lava flows (density of 2.6 g/cm³) with 30 % of andesine-labradorite would allow precipitation of 360 cm³ of barite, equivalent to 1.6 kg of barite (d= 4.48 g/cm 3 ).

Hence, an estimated reserve of ~0.20 Mt of andesitic albitized rock can produce 123 ton of barite, representing 0.06 % in the altered rock. This low volume of barite generated through the albitization probably does not represent the whole barium source but indicates a certain amount which contributes to the formation of barite.

However, barite crystallization occurring after albite and chlorite [START_REF] Hövelmann | The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments[END_REF]Fontana et al., 2017) indicates a late and low-temperature precipitation.

Moreover, the previous calculation is valid for the source of barium but do not present the source of sulfate. The origin and evolution of fluids through fluid-rock interaction has been bracketed by oxygen isotopic analysis in plagioclases and sulfur isotopic analysis in chalcocite-bornite and barite (Fontana, 2017). These oxygen isotopes in plagioclase calculated with temperatures of 600 to 350 °C (Fontana, 2017) suggest an albitization dominantly related to a Na-rich magmatic-fluid (CO2 and H2O), whereas sulfur isotopes combined with chlorite thermometer indicate lowtemperature alteration ca. ~250 °C [START_REF] Hövelmann | The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments[END_REF][START_REF] Huang | Chemical and isotopic fractionation of wet andesite in a temperature gradient: Experiments and models suggesting a new mechanism of magma differentiation[END_REF]Bongiolo et al., 2011;Renac et al., 2014).

The chloritization of pyroxene occurs associated with the presence of Cal-II (Fontana et al., 2017), titanite and quartz with temperatures between 280 to 130 °C (Lopes et al., 2014;Fontana et al., 2017). The chloritization of augite can furnish REE [START_REF] Green | Island arc and continent building magmatism -A review of petrogenic models based on experimental petrology and geochemistry[END_REF] mainly to barite (Fig. 9A). In the Seival area, copper-sulfides crystallization were associated with chlorite and chlorite/smectite mixed-layers (~250 °C) [START_REF] Kameda | Smectite to chlorite conversion by frictional heating along a subduction-zone thrust[END_REF][START_REF] Schleicher | Chlorite-smectite clay minerals and fault behavior: New evidence from the San Andreas Fault Observatory at Depth (SAFOD) core[END_REF]. The alteration with chlorite/smectite mixed-layers precipitation was related to destabilization of primary sulfides with increasing activity of Cu and S compared to Fe (Pyrite + Chalcopyrite  Bornite) and an increasing content of dissolved CO2 in fluids for the precipitation of calcite associated with chalcocite. The association of barite and hematite attests oxidation of iron (II to III) and the change from H2S and HS -dominant fluid to a SO4 2- rich fluid [START_REF] Brimhall | Thermodynamic modeling of geological materials: minerals, fluids and melts[END_REF]Vaugham and Craig, 1997;[START_REF] Dill | Supergene Alteration of Ore Deposits: From Nature to Humans[END_REF][START_REF] Vaughan | Mineralogy of sulfides[END_REF]. Similar to [START_REF] Church | Marine barite saturation[END_REF] and [START_REF] Hanor | Barite-celestine geochemistry and environments of formation[END_REF] works these changes are related to increase of oxygen activity and pH changes [START_REF] Chiba | Oxygen isotope exchange between dissolved sulfate and water at hydrothermal temperatures[END_REF]Renac et al.. 2014) most probably associated with meteoric water and weathering (Fontana et al., 2017).

Barite is spatially associated with Cu-Ag mineralizations, but it did not crystallize at the same time (Fig. 10B). Barite and Cal-III crystallization was interpreted as a low-temperature mineral association [START_REF] Hogarth | Rare-earth element minerals in four carbonatites near Gatineau, Quebec[END_REF]. The relation of barite and mineralized fractures suggests barite crystallization temperatures < 157 °C (ca. chlorite temperature; Lopes et al., 2014;Fontana et al., 2017). In this case, barite precipitation may have been generated by hydrothermal [START_REF] Hanor | Barite-celestine geochemistry and environments of formation[END_REF]. In other deposits in the Camaquã Basin, similar barite occurrences were observed with estimated temperatures in oxygen isotopes and fluid inclusions between 125 to 115 °C (e.g., Cerro dos Martins; Toniolo et al., 2004) and 180 to 80 °C (e.g., the Camaquã Mine; [START_REF] Bettencourt | Mineralogia, inclusões fluídas e isótopos estáveis de oxigênio e enxofre da Mina de Cobre de Camaquã RS[END_REF]Ronchi et al., 2000;Renac et al., 2014). Hem-II in the last stages of hydrothermal alteration and with REE enrichment in barite. We related these change to the low-temperature stage represented by barite, Cal-III (Fontana et al., 2017) and Hem-II, indicating high oxygen fugacity.

Seival mineralizations (Cu-Ag) occur mainly in subvertical fractures. These fractures are also filled by barite with ~N-S orientation (Lopes et al., 2018).

Therefore, the deeper structures allowed reactivation and reinjection of hydrothermal fluid and consequent precipitation of barite in the last veins of Seival area.

REE PATTERNS

The studies on barite for REE geochemistry have been applied for the understanding of barite origin, hydrothermal process and source of fluids (e.g., [START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF][START_REF] Barrett | Rare earth element geochemistry of massive sulfides sulfates and gossans on the Southern Explorer Ridge[END_REF][START_REF] Martin | Strontium and neodymium isotopic analysis of marine barite separates[END_REF]. These barites with different patterns suggest variation of the REE contents associated with hydrothermal alteration. Moreover, in Brt1 samples the negative anomalies of Ce can be associated with marine barite [START_REF] Hogdahl | Neutron activation analysis of lanthanide elements in sea water[END_REF][START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF] or hydrothermal activities in seawater [START_REF] Ehya | Rare earth element and stable isotope (O, S) geochemistry of barite from the Bijgan deposit, Markazi Province, Iran[END_REF]. These Ce negative anomalies suggest neutral pH rather than more basic like in seawater. The samples Brt1 and Brt2 have no Ce anomalies and confirm meteoric water. Barite analyzes have a large positive Eu anomaly (Fig. 9A). The hydrothermal fluid keeps Eu anomalies positive once Eu is stable under reduced and high-temperature conditions (Sveijensky, 1984;[START_REF] Barrett | Rare earth element geochemistry of massive sulfides sulfates and gossans on the Southern Explorer Ridge[END_REF], as in the continental barite [START_REF] Guichard | Rare earths in barites: distribution and effects on aqueous partitioning[END_REF]. [START_REF] Morgan | Rare earth element distribution in some hydrothermal minerals: evidence for crystallographic control[END_REF] indicate Eu with similar size of barium or strontium accommodates in the barite structure.

In a previous study of the Seival area, the REE chemistry characterization in the andesine-labradorite and the albite-rich separates showed two groups with different REE contents (Lopes et al., 2014;Fontana et al., 2017). The Group I was characterized by andesine-labradorite partially replaced by albite (weak albitization; Fig. 9C)) and the Group II includes plagioclases totally replaced by albite (Fig. 9C).

Moreover, the REE patterns of andesine-labradorite (ΣREE andesine-labradorite= ~20 ppm) and albite (ΣREE albite= ~40 ppm) have similar aspects in comparison to the [START_REF] Green | Island arc and continent building magmatism -A review of petrogenic models based on experimental petrology and geochemistry[END_REF] or external fluid, and the source of barium is the albitization of primary plagioclase (andesite-labradorite).

CONCLUSIONS

The low-temperature hydrothermal alteration was characterized by barite, A química mineral de estágios magmáticos e hidrotermais tardi-magmáticos na área da Mina do Seival é apresentada no manuscrito II (parte 4.2). Este estudo Point FM 13 FM 13 WL 19 WL 19 WL 19WL 19WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 .83 20.22 20.48 20.10 20.26 20.47 21.79 20.58 20.26 20.64 20.27 20.40 20.38 20.29 20.19 20.56 20.04 20.40 20.07 20.31 20.23 20.45 20.40 5.67 10.24 11.94 12.04 11.74 11.77 10.71 11.62 11.90 11.83 11.90 11.58 11.85 11.77 11.80 11.62 11.79 12.01 11.70 11.65 11.92 11.83 11.74 34 11.90 11.91 11.86 11.97 11.94 11.70 11.92 11.94 11.93 11.95 11.97 11.98 11.97 11.95 11.92 11.96 11.92 11.95 11.94 11.90 11.90 11.95 

Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: G) Interestratificados clorita/esmectita

Tabela suplementar do manuscrito II. Tabela G: Análises por microssonda eletrônica de interestratificados clorita/esmectita. FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 Point 1_cla 3_cla 4_cla 5_cla 6_cla 9_cla 11_cla 12_cla 14_cla 15_cla 16_cla 17_cla 19_cla 20_cla 22_cla SiO 2 34.70 33.78 32.22 33.17 33.68 33.33 30.25 33.49 35.06 34.55 30.14 31.72 31.85 

Sample

  Figura 1. Localização da área de estudo e vias de acesso sobre uma imagem Landsat TM 147 (adaptadode Toniolo et al., 2007). ............................................. Figura 2. Mapa da área do Gondwana Ocidental com a indicação dos crátons (área em azul) e das faixas móveis (em itálico na figura) (adaptado de Almeida e Hasui, 1984). ........................................................................................

Figura 6 .

 6 Figura 3. Modelo evolutivo do Escudo Sul-rio-grandense (600-580 Ma) com representação da colisão entre os crátons Rio de la Plata e Kalahari (sem escala; mod.de Chemale Jr., 2000; Bongiolo et al., 2011; Gastal et al., 2015). ..............................................................................................................................Figura 4. Mapa das rochas Neoproterozoicas do Sul do Brasil e Uruguai (à esquerda) e oeste da Namíbia e África do Sul (à direita), com indicação dos crátons, cinturões e bacias associadas (adaptado de Guadagnin et al., 2010 e referências contidas). Chaves: Co = Cráton do Congo; Ka = Cráton Kalahari; LP = Cráton Rio de la Plata; LA = Cráton Luis Alves; F = Cinturão Dom Feliciano; G = Cinturão Gariep; S = Cinturão Saldania; D = Cinturão Damara.................................................................................................................. Figura 5. Mapa esquemático da geologia do Escudo Sul-rio-grandense com os 4 blocos tectônicos e localização da Bacia do Camaquã (mod. de Hartmann et al., 2007). .......................................................................................... Figura 6. Mapa Geológico da Bacia de Camaquã com transparência de 50%.As principais estruturas e falhas estão marcadas sobre uma imagem Hillshade ASTER (mod.de Wildner et al., 2002; Toniolo et al., 2007). Zonas de Cisalhamento: ZCI = Ibaré; ZCCS = Caçapava do Sul; ZCDC = Dorsal do Canguçu. ...............................................................................................................

  Figura 6. Mapa Geológico da Bacia de Camaquã com transparência de 50%. As principais estruturas e falhas estão marcadas sobre uma imagem Hillshade ASTER (mod.de Wildner et al., 2002; Toniolo et al., 2007). Zonas de Cisalhamento: ZCI = Ibaré; ZCCS = Caçapava do Sul; ZCDC = Dorsal do Canguçu. ............................................................................................................... Figura 7. Localização das principais minas de Cu, Au-Cu e Pb-Zn na Bacia do Camaquã (mod. de Toniolo et al., 2007). .........................................................

  Figura 10. Mapa geológico do centro-oeste da Bacia do Camaquã com indicação da área da Associação Shoshonítica de Lavras do Sul (mod.de Toniolo et al., 2007; Gastal et al., 2015). ...............................................................

; 6 =

 6 Figura 11. Mapa geológico do Distrito Mineiro de Lavras do Sul e localização das mineralizações (mod.de Bongiolo, 2002). Depósitos e ocorrências: 1 = Bloco do Butiá; 2 = Galvão; 3 = Zeca Souza; 4 = Caneleira; 5 = Taruman; 6 = Olaria; 7 = Pitangueira; 8 = Santo Expedito; 9 = Paredão; 10 = São José; 11 = Virgínia; 12 = Cerritos (Pires e Resende); 13 = Dourada; 14 = Aurora; 15 = Mato Feio; 16 = Valdo Teixeira; 17 = Cerro Rico; 18 = Volta Grande; 19 = Saraiva. .............................................................................................................. 46 Figura 12. Mapa com localização das linhas e dos furos de sondagem, bem como indicação do nome e direção de cada furo de sondagem. Também são ilustrados os diques de andesito a traquiandesito e o contato litológico entre as formações Hilário e Santa Fé. .......................................................................... 48

  Figura 13. Mapa Geológico da Mina Seival (mod.de Reischl, 1978; Lopes et al., 2014) contendo localização das antigas minas, falhas, mineralizações, caimento das rochas, rio e estradas. ..................................................................... 49 Figura 14. Mapa de pontos da área do Distrito Mineiro de Lavras do Sul (exceto PT 18) e mapa dos pontos/minas da área da Mina do Seival. Chaves: 1 = Mina da Barita, 2 = Mina João Dahne, 3 = Mina do Morcego, 4 = Mina do Meio, 5 = Mina Cruzeta, 6 = Mina Alcides. ............................................................ 50

  Figura 16. A) FM 52 -Fotografia macroscópica de testemunho de sondagem de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo; B) FM65 -Amostra de testemunho de sondagem de lapili tufo com matriz fina a base de plagioclásio e quartzo; C) RFM48 -Fotomicrografia em luz polarizada de lapili tufo com matriz fina a base de plagioclásio e quartzo; D) FM44 -Fotomicrografia em luz polarizada de lapili tufo com matriz grossa a base de plagioclásio, piroxênio e quartzo com variação de piroclastos e diferentes cores; E, F e G) FM60, FM60 e FM62 -Fotomicrografia em luz polarizada de lapili tufo com matriz média a base de plagioclásio, piroxênio e quartzo. Chaves: Cal = calcita, Pl = plagioclásio, Px = piroxênio, Qtz = quartzo. ................................................................................................................. 54

  Figura 18. A) FM30 -Fotografia de testemunho de sondagem de dique de andesito com fenocristais de plagioclásio e piroxênio e com oxidação da matriz (cor marrom mais claro); B) RFM51 -Fotografia de amostra de mão de dique de traquiandesito com fenocristais de plagioclásio, piroxênio e biotita com intensa oxidação da matriz (cor avermelhada) e alteração dos máficos para calcita; C) DD62 -Fotomicrografia em luz polarizada de dique de andesito com zonação do plagioclásio; D) RFM66 -Fotomicrografia em luz polarizada de dique de andesito com fenocristais de plagioclásio e textura traquítica da matriz com micrólitos de plagioclásio; E) DD62 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com alteração do plagioclásio para ilita; F) RFM66 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com plagioclásio intensamente alterado para calcita; G) DD62 -Fotomicrografia em luz polarizada de dique de andesito com fenocristal preservado de piroxênio; H) RFM51 -Fotomicrografia em luz polarizada de dique de traquiandesito com fenocristal de biotita associado com titanita, apatita e minerais opacos. Chaves: Pl = plagioclásio, Px = piroxênio, Cal = calcita, Il = ilita, Bt = biotita, Tit = titanita, Opc = minerais opacos, Apt = apatita. ............................................................................................ 56

  Figura 19. Fotomicrografia em luz polarizada dos argilominerais da Mina do Seival. A) SV77 -Lava andesítica amigdalóide de fluxo com esmectita (mod.de Fontana et al., 2017); B) FM25 -Lava andesítica amigdalóide de fluxo com interestratificado clorita/esmectita; C) FM13 -Dique de andesito com corrensita e calcita; D) RFM48 -Matriz de lapili tufo com clorita, calcita, quartzo, sulfeto, titanita e minerais opacos (mod.de Fontana et al., 2017). Chaves: Esmec = esmectita, C/S = interestratificado clorita/esmectita,Cor = corrensite, Cal = calcita, Clo = clorita, Qtz = quartzo. ........................................... 58 Figura 20. Perfil esquemático com a distribuição espacial dos argilominerais com clorita, interestratificado clorita/esmectita (C/S) e corrensita (Cor) próximo às fraturas/falhas e esmectita mais distante (mod. de Fontana et al., 2017). .................................................................................................................... 58 Figura 21. Difratogramas de raios X da Mina do Seival. A) Esmectita em lava andesítica amigdalóide de fluxo; B) Interestratificado clorita/esmectita em lava andesítica amigdalóide de fluxo; C) Corrensita em diques de andesito; D) Clorita em lava andesítica porfirítica de fluxo da Mina do Morcego. ................. 59

::

  Figura 26. Perfil litológico e de amostragem de 6 furos de sondagem da Mina do Seival (mod.de Reischl, 1978). A) Linha 700: furos SV 78-16 e SV 78-15; B) Linha 800: furos SV 78-01 e SV 78-11; C) Mina do Meio: SV 78-09; D) Mina do Meio: SV 78-18. Chaves: Cc = calcocita; Cov = covelita; Bo = bornita; Ca = calcita; Mlc = malaquita; Pl = plagioclásio; Px = Piroxênio. .......................... 66

  Les minerais, et les assemblages minéraux, les caractéristiques structurales varient entre chacunes des zones minières de 'Mina do Seival' et le district Minier de Lavras do Sul. La principale différence est liée à l'influence de roches magmatiques granitiques de Lavras do Sul et les roches volcanogeniques de 'Mina do Seival'. La presence d'un métamorphisme de contact entre les deux zones et la présence de nombreuses intrusions et filons andésitiques ainsi que les structures faillée et filonienne différent semblent être responsables d'une partie des minéralisations (Cu -Au : Lavras ; Cu-Ag : Seival) entre les deux zones. Dans la Mina do Seival, les minéralisations suivent l'alignement des filons andesitiques d'orientation NE-SW, tandis que dans le District Minier de Lavras do Sul, les minéralisations suivent une direction principale NW-SE. Les études minéralogies des roches volcano-sédimentaires de Seival et la prédominance des argiles traduisent une altération hydrothermale intense. Ces minéraux majoritairement argileux remplacent les minéraux magmatiques primaires (phénocristaux de plagioclase et de pyroxène), la matrice microcristalline feldspathique, ou remplissent le bord d'amygdales et de cavités. Ces argiles sont généralement associées à du quartz, de la calcite, de l'hématite et des minéraux opaques. Ces argiles sont des smectites, interstratifiés de chlorite/ smectite, corrensite et des chlorites. Les filons de trachyandésite à biotite sont d'ailleur plus altérés que ceux d'andésite et les minéraux ferromagnésiens remplacés par des chlorites et oxydes de fer. Tese de doutorado / THÈSE Les mesures des structures cassantes (linéaments et failles) à la Mina do Seival et Lavras do Sul font l'objet d'un travail de reconstitution des contraintes présentées dans le manuscrit I. Les principales contraintes obtenues présentent les orientations compression NW-SE, compression NE-SW et distension ENE-WSW. Des arguments de chronologie relative permettent d'identifier que les failles NE-SW sont antérieures à NW-SE. Cette chronologie relative suggéré une compression NW-SE antérieure à la compression NE-SW. Cette paléo-contrainte (NW-SW) a également été associée au contrôle des structures minéralisées. Les failles et les fractures de direction NE-SW sont associées à la faille majeure Cabritos-Perau et celles de direction NW-SE sont associées à la faille de Palma-Jacques. Grâce à cela, nous avons relié le NW-SE compression à l'évolution tectonique au cours de la phase de transtension (600-580 Ma) associée à l'agglutination des blocs dans le Bouclier Sul-rio-grandense. Cette paléo-contrainte fut responsable du magmatisme des dykes et des structures minéralisées. La chimie minérale de stades magmatiques et hydrothermaux tardimagmatiques est présentée dans le manuscrit II. Cette étude caractérise la signature chimique des minéraux magmatiques préservés, les effets de l'albitisation et les produits d'altération hydrothermale comme le chlorite, la smectite et les minéraux interstratifiés associés à la précipitation de sulfures de cuivre. Cet manuscrit présente la chimie minérale de l'augite, de la biotite, titanite et de l'andésine-labradorite transformée en albite formées par des processus magmatiques et tardi-magmatiques (600-250 °C). Cette altération de haute température correspond aux fluides magmatiques tardifs, comme en témoigne la géochimie des Éléments Terres Rares de plagioclases primaires et secondaires. La chimie de minéraux d'altération comme les Mg-smectites, interstratifiés chlorite/smectite et Mg-chamosite reflète la métastabilité des minéraux tardimagmatiques avec un apport d'eau non-magmatique, la diminution de température et une mobilité des éléments métalliques. Enfin, les données de composition et géochimiques d'Éléments Terres Rares des barytes sont présentée dans le manuscrit III. Ces barytes précipitent dans les Tese de doutorado / THÈSE failles associées au oxyde de fer et la calcite. Cette minéralogie indique la circulation de fluide oxydant. Les conditions thermiques des fluides sont contraintes la minéralogie des argiles (<150 °C) et barite. Les analyses des concentrés de baryte et de calcite montrent des concentrations en Éléments Terres Rares différentes. Ces différences des origines météoriques différentes pour ces 2 minéraux. Il pourrait s'agir de précipitation diachrones avec des sources distinctes de Ba, S et Ca, C. Pour les barytes, la source de baryum est probablement magmatique. L'analyse sur roche totale a montré qu'albitisation du plagioclase est liée à l'enrichissement d'ETR en barytes et a indiqué un fluide oxydant météorique riche en SO4 -2 comme source de sulfate, étant donné que la source de chaleur et les fluides chauds peuvent être reliés aux intrusions andésitiques. Ainsi, nous interprétons l'altération hydrothermale était responsable de l'enrichissement des valeurs en Éeléments Terres Rares des barytes.

  Essas amostras foram analisadas em lâmina orientada na forma natural, saturada com etileno-glicol e serem aquecidas a 550ºC durante duas horas (calcinadas). O equipamento utilizado foi o difratômetro SIEMENS BRUKER AXS Modelo D5000 com goniômetro θ-θ do Laboratório de Difratometria de Raios X (CPGq-IG-UFRGS). A radiação é Kα em tubo de Cu nas condições analíticas de 40 kV e 25 mA. Assembleias minerais de alteração hidrotermal foram identificadas nos difratogramas confeccionados, tais como: clorita, esmectita, interestratificado de clorita/esmectita e carbonatos presentes nas rochas. Os argilominerais foram identificados por comparação com padrões do banco de dados do computador (JCPDS), sendo indicado e referenciado o pico mais importante do mineral. Para interpretação das análises utilizou-se o software DiffractPlus e Match 3. O método de DRX dificilmente identifica estruturas cristalinas que ocorram em quantidades inferiores a 3 a 5% na amostra analisada. Um cálculo estimativo classificou os difratogramas de raios X que indicaram interestratificados de clorita/esmectita, segundo os critérios adotados por Beaufort e Meunier (1994),

  Para um estudo preliminar de química mineral e identificação mineralógica, foi utilizado um microscópio eletrônico de varredura (MEV). Com isso, foi possível realizar um mapeamento da distribuição de elementos químicos nos minerais, principalmente de plagioclásio e alguns argilominerais. Para este estudo utilizou-se o microscópio eletrônico Jeol JSM-5800 com detectores de elétrons secundários (SEM), elétrons primários retroespalhados (BSE) e detector de energia dispersada (EDS), Noran pertencente ao Centro de Microscopia Eletrônica da UFRGS. Também se utilizou o microscópio eletrônico Zeiss EVO LS15, 20 kV, 2.5 nA com o detector X-Max Oxford EDS, pertencente ao IAEA (UNESCO), do Principado de Mônaco, durante o período de doutorado sanduíche.

(

  Figura 2. Mapa da área do Gondwana Ocidental com a indicação dos crátons (área em azul) e das faixas móveis (em itálico na figura) (adaptadode Almeida e Hasui, 1984).

Figura 4 .

 4 Figura 4. Mapa das rochas Neoproterozoicas do Sul do Brasil e Uruguai (à esquerda) e oeste da Namíbia e África do Sul (à direita), com indicação dos crátons, cinturões e bacias associadas (adaptado de Guadagnin et al., 2010 e referências contidas). Chaves: Co = Cráton do Congo; Ka = Cráton Kalahari; LP = Cráton Rio de la Plata; LA = Cráton Luis Alves; F = Cinturão Dom Feliciano; G = Cinturão Gariep; S = Cinturão Saldania; D = Cinturão Damara.

Figura 11 .

 11 Figura 11. Mapa geológico do Distrito Mineiro de Lavras do Sul e localização das mineralizações (mod. de Bongiolo, 2002). Depósitos e ocorrências: 1 = Bloco do Butiá; 2 = Galvão; 3 = Zeca Souza; 4 = Caneleira; 5 = Taruman; 6 = Olaria; 7 = Pitangueira; 8 = Santo Expedito; 9 = Paredão; 10 = São José; 11 = Virgínia; 12 = Cerritos (Pires e Resende); 13 = Dourada; 14 = Aurora; 15 = Mato Feio; 16 = Valdo Teixeira; 17 = Cerro Rico; 18 = Volta Grande; 19 = Saraiva.

Figura 14 .

 14 Figura 14. Mapa de pontos da área do Distrito Mineiro de Lavras do Sul (exceto PT 18) e mapa dos pontos/minas da área da Mina do Seival. Chaves: 1 = Mina da Barita, 2 = Mina João Dahne, 3 = Mina do Morcego, 4 = Mina do Meio, 5 = Mina Cruzeta, 6 = Mina Alcides.

  Figura 17. Fotografia macroscópica de amostras de mão. RFM48 -Aglomerado vulcânico alterado (A) e preenchido por malaquita (B). Chave: Mlc = malaquita.As rochas subvulcânicas são representadas pelos diques de andesito e traquiandesito. Os diques de andesito possuem textura traquítica com fenocristais abundantes de plagioclásio e ±K-feldspato com intensa sericitização e substituição para ilita. Os plagioclásios possuem bordas e planos de maclas corroídas e preenchidas por clorita, calcita e titanita. Pseudomorfos de piroxênio são geralmente substituídos por clorita, calcita, titanita e opacos dispersos em matriz composta por micrólitos de plagioclásios e piroxênios. Algumas amostras dos diques de traquiandesito possuem cor avermelhada devido à oxidação de minerais contendo ferro. A alteração da matriz é predominantemente hematita e por vezes clorita, quartzo, titanita, calcita e esmectita. Os diques de traquiandesito possuem cor amarronzada com fenocristais de plagioclásio e biotita lamelar numa matriz oxidada, composta por plagioclásio, quartzo, ±K-feldspato e hematita. Associados à biotita observam-se cristais euédricos de apatitas e amorfos de óxido de ferro. A Figura 18 apresenta as amostras dos diques de andesito e traquiandesito.

Figura 19 .

 19 Figura 18. A) FM30 -Fotografia de testemunho de sondagem de dique de andesito com fenocristais de plagioclásio e piroxênio e com oxidação da matriz (cor marrom mais claro); B) RFM51 -Fotografia de amostra de mão de dique de traquiandesito com fenocristais de plagioclásio, piroxênio e biotita com intensa oxidação da matriz (cor avermelhada) e alteração dos máficos para calcita; C) DD62 -Fotomicrografia em luz polarizada de dique de andesito com zonação do plagioclásio; D) RFM66 -Fotomicrografia em luz polarizada de dique de andesito com fenocristais de plagioclásio e textura traquítica da matriz com micrólitos de plagioclásio; E) DD62 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com alteração do plagioclásio para ilita; F) RFM66 -Detalhe de fotomicrografia em luz polarizada de dique de andesito com plagioclásio intensamente alterado para calcita; G) DD62 -Fotomicrografia em luz polarizada de dique de andesito com fenocristal preservado de piroxênio; H) RFM51 -Fotomicrografia em luz polarizada de dique de traquiandesito com fenocristal de biotita associado com titanita, apatita e minerais opacos. Chaves: Pl = plagioclásio, Px = piroxênio, Cal = calcita, Il = ilita, Bt = biotita, Tit = titanita, Opc = minerais opacos, Apt = apatita.

  sendo elas: (1) Mina Barita; (2) Mina João Dahne; (3) Mina Morcego; (4) Mina do Meio; (5) Mina Cruzeta); (6) Mina Alcides. As mineralizações ocorrem na intersecção dos planos de falhas. Uma descrição detalhada dessas minas e ocorrências é apresentada nos trabalhos de Reischl (1978) e em Lopes (2013).

  Figura 25. Imagens de satélite com detalhamento em planta das mineralizações (linhas brancas). A) Mina da Barita; B) Mina João Dahne; C) Mina do Morcego; D) Mina do Meio; E) Mina Cruzeta; F) Mina Alcides. Chaves: Cc = calcocita, Mlc = malaquita, Hem = hematita, Brt = barita, Ca = calcita. Figuras B, C e D mod.de Reischl (1978). Fonte: Google Earth.

Figure 1 .

 1 Figure 1. A) Southern part of the Mantiqueira Province localization in South America. B) Geotectonic units of the southern Brazilian and Uruguay shields and localization of the studied area (from Hartmann et al., 2007; Oyhantçabal et al., 2011; Philipp et al., 2016a). Shear zones: 1= Itajaí-Perimbó; 2= Major Gercino; 3= Santana da Boa Vista; 4= Dorsal do Canguçu; 5= Passo do Marinheiro; 6= Ibaré; 7= Sarandi Del Yí; 8= Sierra Ballena; 9= Cerro Amaro; 10= Arroio Grande.

The

  Camaquã Basin is composed of four sedimentary successions accompanied by three volcanic associations deposited between ~600 to 530 Ma ago in different depocenters and resulted from the activation of distinct syn-depositional faults. The lithostratigraphic units of the basin base belong to Maricá Group (630-601 Ma), composed by the intercalation of fluvial and pebbly sandstones, marine fine-grained Tese de doutorado / THÈSE sandstones and siltstones. The Bom Jardim Group (600-590 Ma) occurs above and is constituted by deep to shallow lacustrine sandstone, conglomerate, rhythmite and mudstone with expressive occurrence of intermediate to basic volcanic and pyroclastic rocks. These units are covered by the acid volcanic and volcanoclastic rocks of the Acampamento Velho Formation (574-550 Ma) and by the alluvial sandstone, conglomerate and rhythmites of the Santa Bárbara Group. The basin top is composed of the alluvial sandstone and conglomerate, aeolian sandstone and mudstones of the Guaritas Group (540-530 Ma). Basic and intermediate subvolcanic rocks of the Rodeio Velho Suite cut across the other units of the

Figure 2 .

 2 Figure 2. Geological map of the São Gabriel Terrane. Cities: SS= São Sepé; CS= Caçapava do Sul; VN= Vila Nova do Sul; LS= Lavras do Sul; DP= Dom Pedrito; B=

  demonstrated the influence of the syn-sedimentary faults at the border of Camaquã Basin and its importance to the facies architecture evolution. Most researchers highlighted the occurrence of large transcurrent faults within the boundaries of each major depositional cycle. The facies architecture of most stratigraphic groups indicated deposition in alluvial-fan and braided fluvial systems running toward the center of the basin. These UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES MANUSCRITO I | 77 Rodrigo Winck LOPES -2018-Tese de doutorado / THÈSE characteristics suggested that the kinematics of failure were associated with simultaneous transcurrent and extension movements. The occurrence of volcanic successions in Bom Jardim, Santa Bárbara and Guaritas groups of the Camaquã Basin and associated granites, indicate a relationship between the high thermal gradient of the crust and the main transcurrent fault systems. The isotope and geochemical composition of the volcanic associations suggests magmatism related to the mantle upwelling, occurred during around of 50

Formation

  is represented by tuff, lapilli tuff, volcanic agglomerate and andesite lava flows with chloritic alteration represented by chlorite, epidote and calcite in a temperature of ~300 °C and east bedding direction. The NE-SW to NW-SE oriented andesitic and lamprophyric dikes have subvertical disposition. The shoshonitic affinity of the rocks from Hilário Formation and Lavras do Sul Intrusive Complex form the Lavras do Sul Shoshonitic Association, defined byLima and Nardi (1998).

Figure 3 .

 3 Figure 3. Geological map of the Camaquã Basin with the regional and local structures (modified fromWildner et al., 2003; Toniolo et al., 2007) in an ASTER digital image (elevation models;Toniolo et al., 2007). The black rectangle comprises the area of the geologic map showed in Figure4. Shear zones: ISZ= Ibaré; CSSZ=

Figure 5 .

 5 Figure 5. Seival Mine geological map. Sequence of lapilli tuff, volcanic agglomerate and andesite lava flows with andesitic to trachyandesitic dikes (NE direction) of the

Figure 6 .

 6 Figure 6. The different mineralogical assemblages associated with the mineralizations in the Seival Mine. A) Mineralized stockwork structure with subvertical and irregular form influenced by high permeability of lapilli tuff in Barita Mine; B) Malachite deposition in cavities and matrix of volcanic agglomerate in Barite

Figure 8 .

 8 Figure 7. A) Lineaments map marked in 1:10.000 scale on an ASTER digital elevation model (Toniolo et al., 2007) from the Sul-rio-grandense Shield. Rose diagram with the statistical analysis of the lineaments and their length (B) and frequency (C). Shear zones: ISZ= Ibaré; CSSZ= Caçapava do Sul; DCSZ= Dorsal do Canguçu. Faults: CPF= Cabritos-Perau; SF= Segredo; PJF= Palma-Jacques.

Figure 9 :

 9 Figure 9: Photography of the measured kinematic indicators. A) Slickenside of footwall block in normal fault; B) Subhorizontal dextral sense of movement in

Figure 11 .

 11 Figure 11. Photography of slickensides from Seival Mine area. A) Two generations of slickenlines with sinistral transcurrent and normal sense of movement filled by hematite-rich in lapilli tuff, Meio Mine; B) Slickenlines with hematite and calcite in lapilli tuff, Meio Mine; C) Two generations of slickenlines with dextral transcurrent and normal sense of movement filled by calcite-hematite in andesite porphyritic lava flows, Morcego Mine. Keys: Hem= Hematite; Cal= Calcite.

  fractures and veins occur along extensional cracks classified as Mode 1 fractures. These fractures are barren and ore-bearing. The extensional barren fractures are similar in Lavras do Sul Mining District and Seival area. The orebearing fractures are uniform veins with massive texture. These veins have a thickness with 0.1 to 1 cm of straight to irregular morphology forming a stockwork connectivity with the same orientation as the faults in both areas. The ore-bearing Tese de doutorado / THÈSE fractures are mineralized structures with Au-Cu in quartz veins and Cu-Ag in calcite veins in Lavras do Sul Mining District and Seival Mine, respectively.

Figure 12 .

 12 Figure 12. Lower hemisphere stereoplots showing the fractures data of mineralized and non-mineralized. A) Lavras do Sul Mining District: fractures barren with indistinct main direction and ore-bearing with N10°W and N70-80°W directions; B) Seival Mine: fractures barren and ore-bearing with N10°E and N70-80°E directions.

  of regional scale and associated to formation of NE-SW normal F3 folds in Passo Feio and Porongos complexes as described by Fernandes et al. (1992), Saalmann et al. (2010), Philipp et al. (2016a), Zvirtes et al. (2017) and others researchers. This event was associated with the escape tectonics by[START_REF] Fernandes | Deformation patterns in the Southern Brazilian branch of the Dom Feliciano Belt: a reappraisal[END_REF], and the U-Pb ages of the intrusive syn-tectonic Capané Metagranite(Zvirtes et al., 2015) 

the

  Lavras do Sul Mining District area is delimited by vertical to subvertical N50°E oriented shear zones delimited in its northwest portion by the Cabritos-Perau Fault and in its southeast portion by the Caçapava do Sul Shear Zone and Segredo Fault. These fault systems were active during the deposition of the Bom Jardim and Santa Bárbara groups. The structural control of the Camaquã Basin suggests that NE-SW Tese de doutorado / THÈSE trending transcurrent fault systems are responsible for the ascent and emplacement of the volcanogenic rocks. In the Sul-rio-grandense Shield, most of the mineralized areas are controlled mainly by Neoproterozoic tectonic events related to development of the Neoproterozoic Dom Feliciano Belt. Bongiolo et al. (2011) and Gastal et al. (2015) associated brittle structural control to mineralization of Lavras do Sul Mining District. Santos et al. (2012) and Bicca et al. (2013) associated the influence of main compressional stress of NW-SE direction with the Cu and Au mineralization in the Camaquã Mine. Similar control is characterized by predominance of structures with direction of NW-SE and NE-SW in Lavras do Sul Mining District and Seival Mine, respectively. Most of the stereograms with kinematic analysis shows that the maximum principal stress is oriented NW-SE in the Lavras do Sul granitoids and

Figure 13 .

 13 Figure 13. Deformations events, disposition of the main structures and paleostress fields from Lavras do Sul Mining District and Seival Mine. A) Event 1= Subhorizontal NW-SE compressional paleostress associated to sinistral NE-SW movement of the Cabritos-Perau and Segredo faults and to dextral NW-SE movement related to Palma-Jacques Fault; B) Event 2= Subhorizontal compressional NE-SW paleostress and NW-SE distension associated to sinistral N50°E/80-88°SE oriented Cabritos-Perau and N20°E/80-88°NW oriented Segredo faults and to sinistral N70°W/80-88°NE oriented Palma-Jacques Fault; C) Event 3= Subvertical distention NE-SW and NW-SE in Seival area. Keys: CPF= Cabritos-Perau Fault; SF= Segredo Fault; PJF= Palma-Jacques Fault; R= Riedel; R´= anti-Riedel; X= normal.

  mineralized structures with variable orientations are considered contemporaneous based on mineralogy and alteration type. The main maximum compressional stress of NW-SE direction is associated with the development of Caçapava do Sul Shear Zone and generation of Cabritos-Perau Fault, Segredo Fault and Palma-Jacques Fault. It is difficult to define a structural model for mineralized structures. These mineralized structures were formed probably between

  analysis of the brittle tectonic activity in the Lavras do Sul Mining District and Seival Mine shows that the Au-Cu mineralizations are associated with the NE-SW and NW-SE transcurrent and normal faults and with extensional vein-type fractures. The fault systems associated with the Caçapava do Sul Shear Zone as well as Cabritos-Perau and Segredo faults formed in a stress field with a subhorizontal NW-SE oriented maximum principal stress direction. The mineralized areas are Tese de doutorado / THÈSE associated with the ascent and emplacement of the monzonitic and andesitic to trachyandesitic dikes and with Lavras do Sul Intrusive Complex. The two studied areas were subjected to the main NW-SE compression stress system; however, the volcanogenic rocks of the Seival Mine region also recorded structures generated under a NE-SW direction stress system. The Palma-Jacques Fault (N70°W) is the main structure related to the Lavras do Sul Mining District, while the Cabritos-Perau Fault (N50°E) and the Segredo Fault (N20°E) are related to the Seival Mine area. These faults systems are associated respectively with the activation of the the Ibaré and Caçapava do Sul shear zones. The relative chronology indicates that NW-SE compression and consequent mineralized fractures are associated with transcurrent movements related to post-collisional period of the Dom Feliciano Belt evolution. The development of these high-angle shear zones suggests escape tectonic activity during the Middle-to Late-Ediacaran period, including the magmatism in the Bom Jardim Group, with intense fluid circulation and ore precipitation associated to andesite dikes emplacement.

Fontana

  et al. (2017) described the zoning and lithotypes with the predominant occurrence of smectite, chlorite/smectite mixed-layers, chlorite and corrensite, and suggested that the base-metal deposition was related to the late-magmatic process Tese de doutorado / THÈSE of albitization and high-temperature hydrothermal alteration. Later low-temperature hydrothermal alteration represented the mixing of magmatic and meteoric fluids.

Figure 1 .

 1 Figure 1. Geological setting of the study area. A) Schematic Sul-rio-grandense Shield map (modified from Hartmann et al., 2007); B) Central-western Camaquã Basin geological map with Seival Mine area and Cu occurrences localization (modified fromToniolo et al., 2007; Gastal et al., 2015). Keys: 1= Seival Mine (Cu and Ag); 2= Silveira Mine (Cu); 3= Crespos Mine (Cu); 4= Volta Grande and Merita Mine (Cu and Au).

Figure 2 .

 2 Figure 2. Geological map of the Seival Mine. Sequence of lapilli tuff, andesitic lava flows and volcanic agglomerate with andesitic and trachyandesitic dike (NE direction) from Hilário Formation (HF), polymictic conglomerate and vesicular lava flows from Santa Fé Formation (SFF), rhyolite dikes of Acampamento Velho Formation (AVF), faults, mineralization projections, inactive open pit mines and bore-hole localization (modified from Reischl, 1978; Lopes et al., 2014). Keys: 1= Barita Mine; 2= João Dahne Mine; 3= Morcego Mine; 4= Meio Mine; 5= Cruzeta Mine; 6= Alcides Mine.

Figure 3 .

 3 Figure 3. Mineralization in the Seival Mine area. A) Cu soil anomaly (modified from Reischl, 1978) and inactive open pit mines, faults and Cu-mineralization; B) Schematic section of alteration zones in Hilário Formation. Keys: Chl= Chlorite; C/S= Chlorite/smectite mixed-layer; Hem= Hematite; Tit= Titanite; Cal= Calcite; Qtz= Quartz; Cc= Chalcocite; Bn= Bornite; Smec= Smectite.

  with higher Cu sulfide contents. The andesitic pyroclasts in the lapilli tuff show vesicles or amygdaloids. The amygdaloidal matrix in the lapilli tuff consists of fragments of igneous plagioclase and pyroxene. The petrographic observations of pyroxene revealed the replacement by clay minerals and calcite or intergranular

Figure 4 .

 4 Figure 4. Macroscopic photograph (A and B), photomicrograph in natural (C and F) and polarized light (D, E, G and H). A) Hand sample containing altered pyroclasts of

Figure 5 .

 5 Figure 5. Plots of mineral compositions. A) Ca-Mg-Fe clinopyroxenes showing augite compositions in andesitic lava flows and andesitic dike; B) Biotite (white point) and less pristine biotite (gray point) in the Altot vs Al VI diagram; C) Al+Fe 3+ vs Ti and Al vs Fe binary diagram of the hydrothermal titanite compositions (diagram extracted from Cao et al., 2015); D) An-Ab-Or ternary feldspar diagram showing albitization in andesine-labradorite and rims with K-feldspar in some zoned plagioclase (An= Anorthite; Ab= Albite; Or= Orthoclase).

Figure 6 .

 6 Figure 6. Chemical compositions of a series of saponite, chlorite and chlorite/smectite mixed-layers in projection M + , 4Si and 3R 2+[START_REF] Velde | Clay minerals: a physico-chemical explanation of their occurrence[END_REF] adapted from Inoue et al., 1984) with detail showing the smectite, chlorite-rich C/S mixedlayer (C/S) and chlorite compositions from Seival Mine, as well as comparison between chlorites analyzes from epithermal Lavras do Sul(Mexias et al., 1990b,c; Bongiolo et al., 2011) and Camaquã Mine(Renac et al., 2014).

Figure 7 .

 7 Figure 7. Atomic proportions of chlorites in vein and matrix of andesitic dikes presented in Wiewiora and Weiss diagram (1990), of Si and divalent transition metals normalized to chlorite atom per formula (28 oxygen total anions atoms) in

Figure 8 .

 8 Figure 8. X-ray diffraction patters of < 0.4 μm clay-size fraction of chlorite (A), corrensite (B), smectite (C) and chlorite/smectite mixed-layer (D). Keys: Air dried (black line); EG= Ethylene glycol solvation (gray line); Heating treatment (light gray line).

Figure 9 .

 9 Figure 9. S.E.M. images obtained from drill hole fresh rock sample fragment of amygdaloidal andesitic lava flows described by Fontana et al. (2017). A) Albite fragment associated with corrensite clay minerals of the andesitic lava flows matrix; B) Detail of corrensite morphology of the altered andesitic lava flows matrix. Keys: Ab= Albite; Cor= Corrensite.

Figure 10 .

 10 Figure 10. REE normalized patterns by the chondrite values (McDonough and Sun, 1995). A) Andesine-labradorite with slight albitization of group I; B) Albite-rich plagioclases of group II.

  Consequently, we tested the different equilibrium conditions of the hydrothermal stage (below 350 °C) with thermodynamic modeling (PHREEQC interactive;Parkhurst, 1995, rather than SUPCRIT or the equivalent CHONZ Rpackage). The PHREEQC thermodynamic models primarily use minerals with an initial water content and propose secondary minerals as outputs with the new composition of the final fluid. In our case, reactions involved observed magmatic minerals observed (feldspars: andesine-labradorite and albite and Ca-pyroxene: augite) and latemagmatic minerals (biotite, titanite, Fe-titanium oxides and silica-rich glass)

  magmatic alteration with titanite and the albitization of andesine-labradorite (650 to 250 °C), as suggested by the REE contents of albite. Thermodynamic modeling indicates that late albitization (ca. < 350 °C) was associated with the formation of primary pyrite-chalcopyrite, or that high-temperature chloritization (350 to 250 °C) was associated with bornite-chalcocite. Moreover, the Fetot/Fetot+Mg atomic ratios of Fe-clinochlore to Mg-chamosite suggest that fluids altered the pyroxene or residual material with the addition of external Fe compared to smectite precipitation.The high Fetot/Fetot+Mg atomic ratios and high Fe 2+ /Fe 3+ atomic ratios of these chlorites suggest an Fe-rich and reduced fluid in agreement with the migration of Fe, Cu and S species producing sulfides. However, the origin of fluid, whether the mixing of magmatic and meteoric fluids or basinal brines (IOCG, Chilean 'Manto type'), was not identified. Nevertheless, the chloritization process occurred from 312 to 120 °C. Despite the errors related to chlorite thermometers, the ranges of temperatures in the lapilli tuff (275 to 129 °C; median= 183 ± 39 °C) and andesitic 172 °C, median= 251 ± 56 °C) suggest the existence of changing thermal gradients related to the cooling of the lava pile or intrusive dike and fluids with different temperatures at different times.The lowest-temperature stage was related to the widespread formation of Mg-saponite and smectite-rich C/S (200 to 50 °C). The formations of chlorites, chlorite/smectite mixed-layers and Mg-saponite were related to the influx of fluids (meteoric water or basinal brine) at lower thermal fluxes associated with the sulfide assemblage of bornite-chalcocite, chalcocite, and barite with the increasing concentration of sulfate. Consequently, the petrographic association of albite and chlorite with pyrite and chalcopyrite suggests that the albitization to chloritization stage and structural control may be prospective guides for Cu fertile magmatic systems. The chlorite/smectite mixed-layers emphasized favorable Cu-enriched zones, such as fluid circulation in faults or along dikes and percolation in the porosity of the lapilli tuff.

  development of intense fracturing and, consequently, fluid percolation. Lopes et al. (2018) indicated the ore deposition associated with the development of these shear zones with NE-SW and NW-SE directions in the Sul-rio-grandense Shield. The mineralization structures have NE-SW direction and barite veins occur mainly in fractures of N-S direction.

Figure 1 .

 1 Figure1. A) Sul-rio-grandense and Uruguay shields location in South America; B) Geotectonic units of the Sul-rio-grandense and Uruguay shields (fromHartmann et al., 2007;[START_REF] Oyhantçabal | The Rio de la Plata Craton: a review of units, boundaries, ages and isotopic signature[END_REF] Philipp et al., 2016a).

Figure 2 .

 2 Figure 2. Geological map of the Camaquã Basin and associated granites (modified from Wildner et al., 2002; Toniolo et al., 2007). Granitoids: LG = Lavras do Sul Intrusive Complex; CG = Caçapava do Sul granite; Shear zones: ISZ = Ibaré; CSSZ = Caçapava do Sul; DCSZ = Dorsal do Canguçu.

Figure 3 .

 3 Figure 3. Seival Mine geological map. Sequence of lapilli tuff, volcanic agglomerate and andesite lava flows with andesitic and trachyandesitic dikes (NE direction) of the Hilário Formation (modified from Reischl, 1978; Lopes et al., 2014). Keys: 1= Barite; 2= João Dahne; 3= Morcego; 4= Meio; 5= Cruzeta; 6= Alcides.

  Tese de doutorado / THÈSE ray diffraction (Siemens D5000, KαCu, 40 kV and 25 mA;Lopes et al., 2014) at the Geoscience Institute (CPGq IGEO-UFRGS).The X-ray diffraction of powdered samples and EMPA analysis identified their crystallography and mineral compositions. The major and trace element compositions of the plagioclase and barite were examined on a CAMECA, SXFive Electron Probe Micro Analyzer (EPMA) equipped with 5 wavelength dispersive spectrometers with TAP, PET and LIF crystal detector at the Geoscience Institute (CPGq IGEO-UFRGS). The analytical procedure used standard conditions optimized to silicate (plagioclase) analysis, using a 5 μm defocused beam, with an acceleration voltage of 15 kV and beam current of 10 nA with peak counting time of 10 sec and two background measurements with counting times of 5 sec. Analytical procedure measurements for barite used LPET detector with a 5 μm defocused beam (beam 15 kV, 100 nA, peak and background counting times of 30 and 10 s, respectively). First, the Na content was measured to minimize its loss by volatilization with increasing time of analysis. Standards were calibrated with synthetic and standard minerals with various diffracting crystals, as follows: albite to Na on TAP, diopside to Mg on TAP, CaSiO3 to Si and Ca on TAP and LPET respectively, sanidine to Al and K on TAP and LPET respectively, rutile to Ti on LPET, hematite to Fe on LLIF and rhodonite to Mn on LLIF. We also used barite to S and Ba on LPET, celestite to Sr on LPET, anhydrite to Ca on LPET in the barite analysis. Measured X-ray intensities were ZAF-corrected. Procedures used to Ba detection on plagioclase were: a backscatter-electron image to detect Ba in plagioclase grain, the procedure to measure Ba contents used first a measurement of background intensity on each side of Ba peak and Ba measurement in the selected area. Traces of Ba in plagioclase standard and samples were calibrated using a Ba-poor feldspar (orthoclase, Ba: 0.12 %). The TiO2 and Al2O3 contents were simultaneously measured to reduce the interference of overlapping peaks (TiKα-BaLα1 and AlKα-BaLα3) on Ba measurements. Limits of detection varied from 206 to 2019 ppm (n= 33); equivalent to standard error of 0.02 % (2σ).

  Tese de doutorado / THÈSE mineralizations. The Barita Mine (the main barite location) is the main occurrence of barite in the area, where subvertical fault plans (N10°E/70-88°NW oriented, N10°W/70-88°NE oriented and N40-60°E/70-88°NW oriented) (Fig. 4) host series of 0.1 to 0.5 cm veinlets filled by barite and Cal-3. Outside the Barita Mine, the veinlets are smaller with a filling of Cal-3 and quartz.

Figure 4 .

 4 Figure 4. Photography of the Barita Mine (the main barite location) with mineralized structure and NE-SW and N-S oriented faults in the Seival area.

Figure 5 .Figure 6 .Figure 7

 567 Figure 5. Barite and calcite (Cal-3; Fontana et al., 2017) in Seival area. (A) White to pinkish barite and aggregates of tabular and prismatic crystals; (B) Calcite (Cal-3) veins in mineralized structures; (C) Two generations of calcite (Cal-3) and calcitequartz veins; (D) Association of malachite, calcite (Cal-3) and hematite (Hem-2); (E) Hand sample of lapilli tuff with calcite (Cal-3) vein and remobilized chalcocite; (F) Hand sample of andesite lava flow with calcite (Cal-3) vein and bornite. Keys: Brt= Barite; Qtz= Quartz; Cal= Calcite; Hem= Hematite; Mlc= Malachite; Cc= Chalcocite; Bn= Bornite.

Figure 8 .

 8 Figure 8. (A) Thin section natural photography of sample from andesitic dikes with phenocrysts of original plagioclase in the center and altered in boundaries; (B) Scanning electron microscope (SEM) backscattered image showing detail of central part andesine-labradorite crystal altered to albite. Keys: And-lab= Andesinelabradorite.

Figure 9 .

 9 Figure 9. REE patterns normalized by the chondrite values (McDonough and Sun, 1995). (A) Two patterns of barite with REE enrichment; (B) Calcite (Cal-3) veins with variable patterns; (C) Andesine-labradorite, albite and whole-rock patterns (Lopes et al., 2014; Fontana et al., 2017); (D) Comparison of barite and calcite patterns evidencing REE enrichment in barite. Keys: And-lab= Andesine-labradorite.

Figure 10 :

 10 Figure 10: Evolution of hydrothermal alteration in the Seival area. (A) Late-magmatic alteration characterized by Cal-2+Qtz+Hem-1 and Py+Cpy (350 to 250 °C); (B) Low-temperature hydrothermal alteration characterized by association of Ab+Chl+C/S and Cc+Bn ou Cc+Cv (250 to 50 °C) and association of Brt+Cal-3+Hem-2 (150 to 50 °C). Keys: And-lab= Andesine-labradorite; Aug= Augite; Cal= Calcite; Qtz= Quartz; Hem= Hematite; Py= Pyrite; Cpy= Chalcopyrite; Ab= Albite; Chl= Chlorite; C/S= Chlorite/smectite mixed-layers; Cc= Chalcocite; Bn= Bornite; Cv= Covellite; Brt= Barite.

  calcite and minor hematite located in the same geological context of Cu-Ag mineralizations hosted in volcanogenic rocks from Seival Mine. Barite occurs with NE-SE and NNE-SSW directions in faults and fractures. The EMPA analysis in altered (albite) and not altered (andesine-labradorite) portions of plagioclase showed albite without barium content. The change of H2S -dominant fluid to SO4 2-rich fluid probably occurs with influence of meteoric and oxidant fluid and represents sulfur source promoted by destabilization of primary sulfides (pyrite and chalcopyrite), with formation of chalcocite-bornite or chalcocite-covellite and barite, calcite and hematite. Consequently, barite, calcite and minor hematite were formed in low temperature (< 157 °C) and in more oxidant conditions than albite, chloritesmectite and Cu-rich sulfides. The REE geochemistry in concentrates of barite, calcite and whole-rock shows very high values of ΣREE in barites, evidencing that REE released from chloritization of pyroxene may be concentrated in the barites related to the affinity of SO4 group to accommodate REE in BaSO4 structure. The two patterns of barite were related to LREE depleted, negative anomalies of Ce, Pr and Nd and strong depletion of HREE (Dy), indicating association with hydrothermal alteration. These REE patterns are compatible with low-temperature hydrothermal barites. desenvolvida na forma de manuscritos científicos submetidos a periódicos, conforme exigência do Programa de Pós-Graduação em Geociências da Universidade Federal do Rio Grande do Sul, estando um deles já publicado. As medidas de geologia estrutural na Mina do Seival e no Distrito Mineiro de Lavras do Sul são apresentadas no manuscrito I (parte 4.1). Em ambas as áreas ocorre um intenso fraturamento e falhas em regime rúptil. As mineralizações são associadas com falhas transcorrentes e fraturas extensionais de direções NE-SE e NW-SE. A determinação dos principais campos de tensões possibilitou a interpretação do controle estrutural das mineralizações e dos diques. Os principais estresses obtidos foram: compressão NW-SE; compressão NE-SW; distenção ENE-WSW. A reconstrução do paleostresse indicou o controle da circulação de fluidos e, consequentemente, da deposição de minério. A compressão NW-SE foi considerada anterior em relação à compressão NE-SW. Este paleostresse de direção NW-SE também foi associado ao controle das estruturas mineralizadas. A fragilidade das rochas vulcanogênicas da Mina do Seival evidencia outros paleostresses como a compressão NE-SW e a distensão ENE-WSW, sendo esta última relacionada aos movimentos tectônicos finais na área. As mineralizações possuem direção NW-SE para o Distrito Mineiro de Lavras do Sul, enquanto que as mineralizações na Mina do Seival possuem direção NE-SW. A mesma orientação é encontrada nos diques de monzonito, andesito e traquiandesito para ambas as áreas. As falhas e fraturas com direções NW-SE são associadas à falha de Palma-Jacques e à Zona de Cisalhamento de Ibaré. As falhas e fraturas com direção NE-SW são associadas à falha principal Cabritos-Perau e à Zona de Cisalhamento de Caçapava do Sul. Com isso, foi possível relacionar a compressão NW-SE com a evolução tectônica durante o estágio de transtensão (600-580 Ma) associados com as zonas de cisalhamento e a aglutinação dos blocos no Escudo Sul-rio-grandense, e consequentemente a circulação de fluidos e mineralizações.

  manuscrito II. Tabela D: Análises por microssonda eletrônica de albita.

  manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita.

  manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita. Sample 60pln_3 5clay1 1pl1 2pl1 3pl1 4pl1c 5pl1 6pl1 7pl1 8pl1 9pl1 10pl1c 11pl1c 12pl2b 13pl2b 14pl2b 15pl2b 16pl2b 17pl2b 18pl2b 19pl2c 20pl2c 21pl2c 22pl2c

  manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita.

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  . .......................................................... 63 Figura 25. Imagens de satélite com detalhamento em planta das mineralizações (linhas brancas).

A) Mina da Barita; B) Mina João Dahne; C) Mina do Morcego; D) Mina do Meio; E) Mina Cruzeta; F) Mina Alcides.

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  Tese de doutorado / THÈSE granitoïdes, vulcanites acides et basiques d'affinité shoshonitique. La zone de la 'Mina do Seival' se situe à proximité de ces corps plutoniques et volcaniques dans des dépôts volcano-sédimentaires de la Formation Hilário antérieure à l'activité magmatique de Lavras do Sul. Les roches volcano-sédimentaires de la 'Mina do Seival' sont des tufs à lapilli, andésites, agglomérés volcaniques et filons andésitiques et trachyandésitiques. Une plus grande proportion de conglomérats polymictique et des andésites vésiculaires forment la partie Est où ce sont déposés la plus récente Formation Santa Fé du groupe Santa Bárbara.

		| 14
	Rodrigo Winck LOPES	-2018-

Dans la zone fut l'objet d'une extraction minière (i: Barite; ii: João Dahne, iii:

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-Minéralogie et cristallographie des phases d'altération, dont les minéraux argileux, ont été obtenues par la diffraction des rayons X.

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			INTRODUÇÃO | 19
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			INTRODUÇÃO | 21
	1.4 Métodos utilizados		
	O trabalho teve como metodologia revisão bibliográfica, trabalhos de campo,
	análises petrográficas, análises estruturais, difratometria de raios X e química
	mineral. A partir dos trabalhos de campo e petrografia, as rochas da Mina do Seival
	foram classificadas, e foram descritas sua mineralogia e seus aspectos texturais
	com ênfase nas fases secundárias que ocorrem como minerais de alteração. Com
	a difratometria de raios X e química mineral em diversas fases, foi possível
	estabelecer uma correlação dos elementos ligados às mineralizações e a sua
	relação com o controle estrutural.		
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			INTRODUÇÃO | 22
	testemunhos de sondagens possibilitou analisar a rocha em profundidade de uma
	maneira menos alterada por processos de intemperismo e superficiais. Para isso,
	foram utilizados equipamentos tradicionais como GPS (Datum Córrego Alegre),
	marretas, martelos, bússolas, lupa de mão, máquina fotográfica, caderneta de
	campo e equipamentos de proteção individual.	
	Os trabalhos de campo foram realizados em cinco dias de maio de 2013,
	onde foram coletadas amostras para química mineral, e quatro dias em agosto de
	2016, para realização de medidas estruturais. Em 2017 foi realizado um campo de
	dois dias para coleta de amostras específicas na Mina da Barita. Também foram
	incorporados dados e amostras de trabalhos de campo anteriores (2011 e 2012),
	Rodrigo Winck LOPES	-2018-	Tese de doutorado / THÈSE

relativos à monografia de conclusão de curso e dissertação de mestrado. Com isso, foram amostrados 120 pontos, subdivididos quando necessário.

Os testemunhos de sondagem foram descritos, além de coletadas amostras de mão de sete testemunhos de sondagem na área da Mina do Seival. Seis desses furos de sondagem foram realizados pela Companhia Brasileira de Cobre (CBC), em ~1978, hoje pertencentes à Votorantim Metais, que realizou o sétimo furo de sondagem em 2010 e gentilmente possibilitou a coleta das amostras. Os testemunhos de sondagem descritos e coletados foram: 31 amostras do SV 78-11 -Ocorrência Vila do Torrão, Linha 800 -(30°43'21" S e 53°46'56" W) e 28 amostras do SV 78-01 (30°43'22" S e 53°47'0" W); 13 amostras do SV 78-15 -Ocorrência Lagoa do Jacaré, Linha 700 -(30°43'14" S e 53°47'18" W) e 10 amostras do SV 78-16 (30°43'12" S e 53°47'20" W); 8 amostras do SV 78-18 -Mina do Meio, Linha 900 -(30°42'26" S e 53°46'41" W) e 11 amostras do SV 78-09 (30°42'27" S e 53°46'44" W); 10 amostras do SV 001 -Mina Alcides -(30°43'45" S e 53°47'08" W). Nessa amostragem foram coletadas um total de 111 amostras.

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8 Geoquímica de concentrados de plagioclásio, barita e calcita

  Tese de doutorado / THÈSE interestratificado clorita/esmectita (28). As proporções de Fe 2+ e Fe 3+ foram ajustadas para obter um melhor balanço de cargas em cada análise. No ANEXO F são apresentados os dados de microssonda eletrônica do manuscrito II.

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			INTRODUÇÃO | 27
	1.4.As microanálises para elementos traços em concentrados de plagioclásio,
	barita e calcita foram realizadas com um Perkin Elmer modelo 320 Laser ASC em
	um espectrômetro de massa PE Sciex. O laser é um Nd YAG operado em 1064 nm,
	com repetição de 1-10 Hz, com tamanho de pulso de 8 ns e um pulso de energia de
	120 mJ. Essa etapa foi realizada no Laboratoire de Chimie da Université Côte
	Os elementos maiores utilizados (SiO2, TiO2, Al2O3, FeOtotal, MnO, MgO,
	CaO, Na2O e K2O) foram recalculados para sua fórmula estrutural (atom per formula
	Rodrigo Winck LOPES	-2018-

Todas as análises foram realizadas no Laboratório de Microssonda Eletrônica do IG-UFRGS, nos anos de 2013, 2015 e 2017. As análises de química mineral quantitativas foram obtidas por microssonda eletrônica marca CAMECA, modelo SXFive (15 kV, 15 nA 10s counting time equipado com coletores TAP, PET e LIF). Os padrões utilizados foram: albita para Na; jadeita para Si; diopsídeo para Mg, Ca; sanidina para Al, K; rutilo para Ti; rodonita para Mn; hematita para Fe. O teor de bário no plagioclásio foi determinado com padrão de bário-feldspato (ortoclásio) e com feixe de 5 µm com 10 seg para cada elemento e 5 seg para o ruído de fundo (background). As análises de barita foram determinadas com feixe de 5 μm (15 kV, 100 nA) com 30 seg para o pico e 10 para o ruído de fundo. unit: a.p.f.u.) assumindo o oxigênio estrutural para cada fase mineral: feldspatos (32), piroxênio (12), titanita (5), biotita (22), esmectita (22), clorita (28) e D´Azur, França. Os Elementos Terras Raras foram escolhidos a partir dos padrões, tendo em vista a similaridade e a possibilidade satisfatória de bons resultados para as rochas da Mina do Seival. O software utilizado pelo equipamento para exposição e interpretação de análises foi ELAN Instrumental Control Session.

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  Ma[START_REF] Cordani | Comentários sobre as determinações geocronológicas da Folha de Porto Alegre[END_REF] e 580 Ma em zircão 238 Pb/ 206 U(Remus et al., 1999) para as rochas intermediárias. Chemale Jr. (2000) mencionou idade de 592 Ma para a Formação Hilário. A sequência vulcânica tem idades, pelo método 40 Ar/ 39 Ar em

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			BACIA DO CAMAQUÃ | 36
	plagioclásio, de 590 ± 6 Ma para a base do ciclo vulcânico e idades de 586 ± 8 Ma
	para o ciclo efusivo superior (Janikian et al., 2008; Janikian et al., 2012), onde o
	platô de idades das amostras de lava andesítica de fluxo mostrou porcentagem
	cumulativa de 39 Ar liberado. O método 238 Pb/ 206 U analisado em zircão obteve idades
	de 590,5 ± 5,7 Ma a partir do depósito de tufo. As rochas lamprofíricas da
	Associação Shoshonítica de Lavras do Sul, localizadas a 2 km em sentido sul da
	Mina do Seival, foram datadas pelo método 238 Pb/ 206 U em zircão com idades de
	591,8 ± 3,0 Ma		
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  e consideradas como base da sequência. A

			BACIA DO CAMAQUÃ | 37
	Formação Acampamento Velho foi datada pelo método 238 Pb/ 206 U em zircão de
	riolitos subalcalinos, na região Passo do Salsinho com idades de 573 ± 18 Ma
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	, e na associação intrusiva da região do planalto Taquarembó (Gastal e Lafon, 2001) com idades de 572 ± 3 Ma. A nova datação na Formação Acampamento Velho em zircão pelo método 238 Pb/ 206 U Tabela 1. Dados geocronológicos da Bacia do Camaquã e granitos associados. Chaves: (1) Borba et al., 2008; (2) Almeida et al., 2012; (3) Janikian et al., 2008; (4) Janikian et al., 2012; (5) Liz et al., 2009b; (6) Sommer et al., 2005; (7) Matté et al 2016; (8) Bicca et al., 2013; (9) Oliveira et al., 2014; (10) Remus et al., 1999; (11) Gastal et al., 2006; (12) Chemale Jr., 2000. indicou uma idade de cristalização de 560 ± 2 Ma para o ignibrito densamente Groupo Unidade Idade e autor Mineral Método
	soldado, 560 ± 14 Ma para o traquito máfico e 562 ± 2 Ma para o riolito subvulcânico Guaritas Guaritas 535 ± 10 Ma (9) zircão SHRIMP
	Guaritas (Matté et al., 2016). Guaritas Guaritas Rodeio Velho As idades centrais de granodiorito em zircão pelo método 238 Pb/ 206 U (Remus 547 ± 6 Ma (9) zircão SHRIMP 547 ± 6.3 Ma (2) zircão LA-ICP-MS Santa Bárbara Acamp.Velho 560 ± 2; 560 ± 14 Ma; 562 ± 2 Ma (7) zircão SHRIMP
	et al., 2000) foram revistas por Gastal et al. (2006) e apresentam idades de 601 ± 2 Santa Bárbara Acamp.Velho 579,9 ± 13; 569,8 ± 4,6 Ma (4) zircão SHRIMP
	Santa Bárbara Ma. Novas análises pelo método 207 Pb/ 206 Pb em zircão do sienogranito da borda Acamp.Velho 544,2 ± 5,5 Ma (4) zircão TIMS Santa Bárbara Acamp.Velho 553 ± 5,4 Ma (2) zircão LA-ICP-MS apresentam idades de 598 ± 3 Ma, rochas monzonítica-dioríticas (Monzonito Santa Bárbara Acamp.Velho 574 ± 7 Ma (3) zircão SHRIMP
	Tapera) de 601 ± 5 Ma, e monzonito (Arroio dos Jaques) de 599 ± 7 Ma. Gastal et Santa Bárbara Acamp.Velho 549,3 ± 5 Ma (6) zircão SHRIMP
	al. (2006) descreveu algumas idades mais jovens com 580 ± 1,8 Ma em granito com Santa Bárbara Santa Bárbara 567,9 ± 5,9 Ma; 562,5 ± 5,5 Ma (9) zircão SHRIMP
	Santa Bárbara alteração hidrotermal associada à mineralização aurífera. O Granito Jaguari foi Santa Bárbara 566 ± 6,9 Ma (8) zircão SHRIMP Santa Bárbara Santa Bárbara 553 ± 22 Ma (9) zircão SHRIMP
	datado pelo método 207 Pb/ 206 Pb com idades de 567 ± 4 Ma, representando um Santa Bárbara Santa Bárbara 573 ± 18 Ma(12) zircão SHRIMP
	evento distinto do magmatismo Lavras do Sul (Gastal et al., 2006). Bom Jardim Lavras do Sul 587 ± 4 Ma (5) zircão	SHRIMP
	Bom Jardim As análises de isótopos de Pb em calcopirita, pirita e bornita da região das Lavras do Sul 599 ± 2; 586 ± 3 Ma (11) zircão SHRIMP Bom Jardim Lavras do Sul 580 ± 1,8 Ma (10) zircão SHRIMP
	Minas do Camaquã, em arenitos e rochas de minérios, apresentam idades de 592 Bom Jardim Arroio dos Jaques 599 ± 7 Ma (11) zircão evaporação
	Bom Jardim ± 5 Ma (Remus et al., 1997), podendo ser temporalmente correlacionadas ao granito Arroio dos Jaques 601 ± 5 Ma (11) zircão evaporação Bom Jardim Lavras do Sul 598 ± 3 Ma (11) zircão evaporação de Lavras e à lava andesítica de fluxo da Formação Hilário. A borda alcalina ácida Bom Jardim Tapera 601 ± 2 Ma (11) zircão evaporação
	do Complexo Intrusivo de Lavras do Sul foi datada em zircão apresentando idades Bom Jardim Hilário 600,5 ± 2,4 Ma (3) zircão SHRIMP
	Bom Jardim de 580 ± 11 Ma pelo método 238 Pb/ 206 U (Leite, 1995). O Complexo de Granito de Hilário 591,8 ± 3,0 Ma (2) zircão LA-ICP-MS Bom Jardim Hilário 590,5 ± 5,7 Ma (3) zircão SHRIMP
	Caçapava do Sul tem idades de ~550 Ma pelo método 238 Pb/ 206 U (Nardi e Bitencourt Bom Jardim Hilário 587 ± 8 Ma (3) plagioclásio Ar-Ar
	Bom Jardim 1989; Remus et al., 1997). A Tabela 1 e a Figura 9 ilustram os dados Hilário 590 ± 6 Ma (3) plagioclásio Ar-Ar Maricá Maricá 601 ± 13 Ma (2) zircão LA-ICP-MS geocronológicos da Bacia do Camaquã e granitos associados. Maricá Maricá 630 ± 3,4 Ma (1) zircão SHRIMP
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	Figura 9. Ilustração sintética dos dados geocronológicos da Bacia do Camaquã e Granitos associados. Chaves: (1) Borba et al., 2008; (2) Almeida et al., 2012; (3) Janikian et al., 2008; (4) Janikian et al., 2012; (5) Liz et al., 2009b; (6) Sommer et al., 2005; (7) Matté et al 2016;
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(8)

Bicca et al., 2013; (9) 

Oliveira et al., 2014; (10) 

Remus et al., 1999; (11) 

Gastal et al., 2006; (12) Chemale Jr., 2000

.

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5 Histórico das mineralizações da Mina do Seival

  

	intrusões monzoníticas rasas concentram-se principalmente na borda
	nordeste do Complexo Intrusivo de Lavras do Sul, definindo um padrão geométrico
	semicircular, semelhante ao encontrado em terrenos vulcânicos associados a
	caldeiras, como sugerido por Lima (1995) e Gastal et al. (2015). Estes foram
	posicionados em condições epizonais, tendo incorporado grande quantidade de
	xenólitos do pacote de vulcanoclástica basculada durante o evento de subsidência
	de caldeira. Temporalmente vinculados aos monzonitos hipabissais ocorrem os
	diques riolíticos e as últimas manifestações efusivas intermediárias. Rochas latíticas
	estão representadas por diques com direção NW-SE na porção nordeste de Lavras
	do Sul. As rochas graníticas são caracterizadas pela zonação inversa de fácies.
	2.Devido à descoberta de mineralizações de ouro no sul do Brasil, também
	foram descobertas as ocorrências de cobre. Na primeira metade do século XX, em
	torno do ano de 1930, a maior exploração de cobre no sul do Brasil ocorreu na
	região conhecida como Mina do Seival.
	Em 1901, as ocorrências foram descritas e pesquisadas por companhias
	particulares e estatais, até o ano de 1931. Após, a Cia E.F. e Minas de São Jerônimo
	realizaram uma série de escavações rasas. Em 1937, a mina foi explorada por uma
	companhia de Porto Alegre e teve seu teor avaliado em 4,7% de Cu. A Cia Indústria
	Eletro-Químicas S/A explorou entre os anos de 1939-42. No período de 1935-62, a
	mina foi lavrada intermitentemente com produção de cobre eletrolítico e sulfato de
	cobre. Nos anos de 1955-62, a mina chegou a produzir cerca de 1.000 toneladas
	de minério por mês, com teor médio de 1,6% de Cu total (1,0% Cu sulfetado). Entre
	os anos de 1942-64, a Mina da Barita foi cubada em torno de 64.000 toneladas, com
	1,71% de cobre e 70 ppm de prata. Em 1957, a Mina João Dahne foi explorada

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			BACIA DO CAMAQUÃ | 43
	através de uma trincheira de dezena de metros, lavrando minério de baixo teor.
	Após isso, a Mina Alcides teve sua produção ligada à extração de sulfatos para
	correção de solos agrícolas.		
	A Companhia Brasileira do Cobre (CBC), nos anos de 1977 e 1978, realizou
	uma série de pesquisas na região, incluindo campanhas de sondagem que foram
	incorporadas nesse trabalho. Reischl (1978) classificou e nomeou as
	mineralizações na área, sendo elas: (i) Mina da Barita: corpo de minério lenticular
	de direção NE-SW, mergulhando 50º para NW, na forma de calcocita em bolsões
	irregulares junto às falhas, com uma reserva em torno de 64.000 toneladas e teor
	de 1,7% de Cu (sulfetado e oxidado), com alta Ag associada (70 ppm) e barita como
	o principal mineral de ganga; (ii) Mina João Dahne: explorada em 1957 por uma
	trincheira de dezenas de metros, com baixo teor, e direção NE-SW com mergulho
	acentuado; (iii) Mina do Morcego: lavrada e considerada antieconômica devido à
	elevada presença de oxidados (70% do minério) com calcocita e malaquita
	finamente disseminada em superfície, próximo a zonas de fraturas da lava
	andesítica de fluxo, com direção N-S a NE-SW; (iv) Mina do Meio: malaquita na
	forma de concentrações irregulares controladas pelo fraturamento do tufo
	andesítico com direção N-S a NE-SW; (v) Mina da Cruzeta: calcocita na forma de
	veios ao longo de fraturas e raramente disseminada com direção NE-SW e NW-SE
	subvertical em lava andesítica de fluxo porfirítica; (vi) Mina Alcides: bolsões de
	calcocita finamente disseminados em lapili tufo com ganga a base de barita e
	preenchendo falhas de direção N-S; (vii) Ocorrências Lagoa do Jacaré e Vila do
	Torrão são caracterizadas por malaquita em superfície e calcocita disseminada,
	controladas pelo fraturamento da rocha em concentrações irregulares, numa ganga
	de barita e calcita. Portanto, é notável um forte controle estrutural, associado ao
	fraturamento e falhas da rocha estando ligadas as mineralizações. A partir de 2000,
	a Mina do Seival despertou interesse de várias empresas multinacionais.
	Entretanto, o investimento foi baixo e não ocorreram muitas pesquisas. Ainda é
	gerada uma grande expectativa para a exploração desses depósitos.
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			BACIA DO CAMAQUÃ | 44
	2		
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.6 Histórico das mineralizações do Distrito Mineiro de Lavras do Sul

  

	O Distrito Mineiro de Lavras do Sul contém diversas minas e prospectos com
	ouro e cobre associado, sendo elas as minas Aurora, Bloco do Butiá, Caneleira,
	Cerritos (Pires e Resende), Dourada, Galvão, Mato Feio, Olaria, Paredão,
	Pitangueira, Taruman, Valdo Teixeira, Virgínia, São José, Santo Expedito e Zeca
	Souza, associadas ao Complexo Intrusivo de Lavras do Sul, e as minas de Volta
	Grande, Cerro Rico, Saraiva e Merita, associadas à Formação Hilário (Bongiolo et
	al., 2011).
	Goñi (1961) apresentou um trabalho com base nos aspectos metalográficos,
	a partir da primeira análise detalhada ao microscópio óptico das rochas
	mineralizadas de Lavras do Sul. Ele destacou que o cobre não ocorre apenas nas
	rochas vulcanogênicas da Formação Hilário, mas também é encontrado nas rochas
	do Complexo Intrusivo de Lavras do Sul. Barbosa e Constantino (1961), estudando
	o minério de cobre na área de Volta Grande, determinaram a "influência positiva" do
	granito na lava andesítica de fluxo mineralizada, discutindo a influência do
	magmatismo granítico versus andesítico na formação das jazidas do Seival e
	Camaquã. Ribeiro et al. (1966), ao estudarem as mineralizações na quadrícula de
	Caçapava do Sul, salientaram que as mineralizações cupríferas nas áreas de Volta
	Grande e Vista Alegre estariam relacionadas às rochas andesíticas, alojadas em
	filões e em falhas secundárias. Na década de 70, a Companhia de Pesquisa e
	Recursos Minerais (CPRM) fez um grande levantamento e amostragem de todas as
	ocorrências. Kaul e Zir Filho (1974) apresentaram a tipologia, o controle tectônico e
	aspectos genéticos para as mineralizações auríferas de Lavras do Sul. Os autores
	descreveram as principais ocorrências e as classificaram quanto ao tipo (filoneano
	ou disseminado) tanto nas rochas graníticas (disseminado do Bloco do Butiá) como
	na sequência vulcânica encaixante. Apresentaram um detalhado estudo
	estrutural/tectônico para o Distrito Mineiro de Lavras do Sul, assim denominado pela
	primeira vez, demonstrando que os esforços compressivos de direção próxima a E-
	W atuaram sobre os granitos e as rochas vulcanogênicas, gerando falhas de tensão
	onde preferencialmente estariam encaixadas as estruturas e filões mineralizados.

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			BACIA DO CAMAQUÃ | 45
	Mostraram que as quantidades de cobre nos granitos são insignificantes, ao
	contrário das rochas vulcanogênicas, onde as concentrações atingiram valores
	economicamente interessantes para a época. Neste caso, a ligação genética do
	cobre com a lava andesítica de fluxo foi defendida pelos autores. Nas décadas de
	1980-90, a Companhia Rio-grandense de Mineração (CRM) explorou ouro na região
	de Lavras do Sul. Nardi (1984) atribuiu a geração das soluções hidrotermais à
	intrusão dos pertita granitos e outras intrusões alcalinas, tendo estas sido
	responsáveis pelas mineralizações no Granito Lavras do Sul, bem como nas
	sequências vulcanogênicas e sedimentares. Por fim, Mexias et al. (1990b) propôs
	que a intrusão granítica teria atuado como fonte de calor na geração e manutenção
	de um sistema hidrotermal cujas características, bem como os padrões de zonação
	dos produtos de alteração muito se assemelham ao que se observa nos depósitos
	do tipo pórfiro (Mexias et al., 1990a).		
	A Figura 11 ilustra as mineralizações do Distrito Mineiro de Lavras do Sul. As
	mineralizações na Mina do Seival são apresentadas em detalhe no Capítulo 3.
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			MINA DO SEIVAL | 47
	3		
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. ESTADO DA ARTE -MINA DO SEIVAL

  

	Nessa parte do trabalho é apresentado o mapeamento geológico, geologia
	estrutural, petrografia e descrição das mineralizações, como base para a
	compreensão dos manuscritos científicos apresentados no Capítulo 4.
	3.1 Mapeamento geológico
	A região da Mina do Seival é constituída por um embasamento (parte 2.1)
	composto por metaultramafito, metagranitoide e xisto (Complexo Cambaí),
	parcialmente coberto por rochas sedimentar da Formação Maricá e vulcanogênica
	da Formação Hilário

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			MINA DO SEIVAL | 48
	estereográficas mostram diferentes padrões para o acamamento entre as
	formações Hilário e Santa Fé.		
	Na área da Mina Seival, a Formação Hilário tem caimento para NW e ângulo
	de inclinação de ~30°, enquanto que próximo ao granito Lavras do Sul e na
	Formação Santa Fé ela possui caimento para ~E-W e ângulos de ~10 a 20°. Um
	mapa de pontos é apresentado no ANEXO C. Na Figura 12 são apresentados a
	localização dos testemunhos de sondagem e perfis da parte 3.3. A Figura 13 ilustra
	o mapa geológico de detalhe da área. Uma tabela de pontos com nome das
	amostras coletadas, unidade a que pertencem, localização e litologia associada é
	apresentada no ANEXO D.		
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Figura 12. Mapa com localização das linhas e dos furos de sondagem, bem como indicação do nome e direção de cada furo de sondagem. Também são ilustrados os diques de andesito a traquiandesito e o contato litológico entre as formações Hilário e Santa Fé.

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Winck LOPES -2018- 

Tese de doutorado / THÈSE Figura 13. Mapa Geológico da Mina Seival (mod.

de Reischl, 1978; Lopes et al., 2014) 

contendo localização das antigas minas, falhas, mineralizações, caimento das rochas, rio e estradas.

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  Formação Hilário. Esses dados foram levantados durante seu estudo de mestrado e doutorado com o acompanhamento do prof. Ruy Paulo Philipp, da Universidade Federal do Rio Grande do Sul, entre os anos de 2002 e 2006. Os pontos marcados da geologia estrutural estão simplificados na Figura 14, e os dados medidos e calculados estão compilados na tabela do ANEXO E.

			MINA DO SEIVAL | 50
	3.2 Geologia estrutural		
	A geologia estrutural descrita no manuscrito I foi realizada em duas áreas.
	Iniciou-se com o levantamento estrutural das mineralizações da Mina do Seival,
	tendo em vista que nesses locais ocorrem estrias de falhas, possibilitando medições
	de cinemática. Também foram adicionados dados do perfil na estrada RS-357,
	cedidos pelo prof. Everton Marques Bongiolo, da Universidade Federal do Rio de
	Janeiro, em algumas mineralizações do Distrito Mineiro de Lavras do Sul e
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			MINA DO SEIVAL | 51
	Como mencionado anteriormente, a Mina do Seival e o Distrito Mineiro de
	Lavras do Sul estão localizados no Terreno São Gabriel do Escudo Sul-rio-
	grandense. As duas falhas principais com mergulho vertical a subvertical dentro
	deste terreno são Cabritos-Perau e Segredo, ambas com direção NE-SW sinistral
	(ver Figuras 5 e 6). Neste trabalho, a Falha de Cerro Alegre é considerada como a
	continuação ao sul da Falha do Segredo. No norte do Complexo Intrusivo de Lavras
	do Sul, a Falha Palma-Jacques é um lineamento que controla a posição dos
	granitóides e das rochas vulcanogênicas separando a Formação Hilário em
	andesitos de fluxo na porção central e sequência piroclástica-andesito na porção
	norte (Lopes et al., 2014). A Falha Palma-Jacques tem direção NW-SE com uma
	última cinemática sinistral (Gastal et al. 2015). No sul do complexo granítico de
	Lavras do Sul, a Falha Volta Grande é o lineamento que controla a porção sul das
	rochas vulcanogênicas e granitoides.		
	As rochas vulcanogênicas da Mina do Seival estão muito fraturadas,
	evidenciando uma tectônica rúptil em que predominam fraturas subverticais de
	direção NE-SW e NW-SE. As estruturas rúpteis são em grande parte resultantes de
	reativações das zonas de cisalhamento de direção NE-SW. A reativação das falhas
	é função direta da orientação dos campos tensionais principais durante os eventos
	tectônicos que afetaram o Escudo Sul-rio-grandense. O sistema de falhas com
	direção NW-SE é correlacionável ao Lineamento de Ibaré, localizada a oeste da
	área de estudo. Portanto, a unidade não apresenta feições deformacionais dúcteis,
	sendo afetada somente por falhas e fraturas subverticais de direção
	dominantemente NE-SW e subordinadamente NW-SE.	
	As medidas de falhas obtidas para a Mina do Seival e para o Distrito Mineiro
	de Lavras do Sul tiveram a correção através do software Win-Tensor (Delvaux and
	Sperner, 2003). No manuscrito I, também são interpretadas as medidas de fraturas
	e veios de ambas as áreas estudadas.		
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					MINA DO SEIVAL | 52
	3.3 Petrografia		
	Como mencionado anteriormente, as rochas vulcanogênicas da Mina do
	Seival são lava andesítica de fluxo, lapili tufos, aglomerados vulcânicos e corpos
	hipoabissais de composições andesíticas a traquiandesíticas (Tab. 2). Nessa parte
	do trabalho são descritas as rochas vulcanogênicas que ocorrem na área.
	Tabela 2. Tabela mineralógica das rochas vulcanogênicas da Mina do Seival com descrição da textura, mineralogia e localização.
	Rocha	Textura	Mineralogia		Localização
			Micrólitos de plagioclásio,	
	Lava andesítica amigdalóide de fluxo	Traquítica com micrólitos de plagioclásios orientados.	calcita ou clorita-quartzo. piroxênio e quartzo. Amigdalas preenchidas principalmente por clorita-calcita, clorita-esmectita-	Principalmente no sul da área.
	Lava andesítica porfirítica de fluxo	Traquítica com matriz grossa a fina rica em micrólitos de piroxênio e plagioclásio.	Fenocristais de plagioclásio e piroxênio em uma matriz a base de micrólitos de plagioclásio.	Principalmente no nordeste da área proximo ao contato com a Formação Santa Fé.
	Lapili tufo	Matriz é um tufo grosso (0,05 a 0,12 mm) composto por cristaloclastos de plagioclásio, quartzo, matriz vítrea microcristalina e material opaco. bordas curvilíneas. angulosas, geralmente com diversas, desde arredondadas a Piroclastos possuem formas	Matriz rica em plagioclásio ou plagioclásio e piroxênio; Piroclastos com diversas piroclásticas). avermelhado e rochas lava andesítica de fluxo composições (lava andesítica porfirítica e amigdaloidal de fluxo,	Toda a área.
	Aglomerado vulcânico	Matriz afanítica com piroclastos arredondados.	Matriz porosa; piroclastos de principalmente andesitíca. composição vulcânica,	Em zonas de falha.
	Dique de andesito	Traquítica marcada pelos fenocristais de plagioclásio.	Plagioclásio, ± K-feldspato, quartzo e piroxênio.		Orientação NE-SW
	Dique de traquiandesito	Traquítica marcada pelos fenocristais de plagioclásio.	Plagioclásio, quartzo, biotita e piroxênio.	Orientação NE-SW
	As lavas andesíticas de fluxo podem ser separadas em amigdalóides e
	porfiríticos. As lavas andesíticas amigdalóides de fluxo possuem matriz fina a base
	de micrólitos de plagioclásios orientados com textura traquítica e os pseudomorfos
	de minerais máficos, como piroxênio e possivelmente anfibólio. As amígdalas têm
	cerca de 0,5 a 1,0 mm e aparentam orientação por fluxo, e por vezes coalescência,
	com formas achatadas ou arredondadas. São preenchidas por diversos minerais,
	principalmente calcita, clorita e/ou quartzo. As lavas andesíticas porfiríticas de fluxo
	possuem matriz grossa a fina rica em micrólitos de piroxênio e plagioclásio. O
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			MINA DO SEIVAL | 54
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MINA DO SEIVAL | 64 Rodrigo Winck LOPES -2018-Tese de doutorado / THÈSE Tabela 4. Descrição simplificada das mineralizações na Mina do Seival com principais características, tonelagem (*= inferido) e teores de Cu e Ag

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  The Mantiqueira Province is a NE-SW mobile belt running parallel to the southern and eastern coast of Brazil extending for more than 3,000 km from Bahia State (NE of Brazil) to Uruguay. The Mantiqueira orogenic system is of one of the main Neoproterozoic orogens formed during the assembly of West Gondwana. It comprises the Dom Feliciano (Uruguay and southern Brazil), Ribeira (Paraná, São Paulo, Minas Gerais and Rio de Janeiro states) and Araçuaí belts (Espírito Santo,

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with NE-SW (N20°E) direction, separating São Gabriel and Tijucas terranes, and (iii) the Dorsal UNIVERSIDADE FEDERAL DO MANUSCRITO I | 73 Rodrigo Winck LOPES -2018-Tese de doutorado / THÈSE

  The distribution of the Camaquã Basin fill is delimited by NE-SW oriented elongated depressions, separated by the basement highs, represented by the Santana da Boa Vista and Vigia domes, Capané Antiform, Caçapava do Sul and Lavras do Sul highlands. The alternation between domes and elongated basins (pull-apart type) associated with transcurrent and oblique high-angle shear zones have been interpreted as the result of compressive deformational processes, which dominated the final evolution of the Dom Feliciano Belt

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	2.2 Camaquã Basin structures		
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	Caçapava do Sul; DCSZ= Dorsal do Canguçu. Faults: CPF= Cabritos-Perau; SF= Segredo; PJF= Palma-Jacques.
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  Geological map of the Lavras do Sul Mining District and Seival Mine (square) (modified from

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	Figure 4.		
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Rodrigo Winck LOPES

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  Hilário Formation, polymictic conglomerate and vesicular andesite lava flows of the Santa Fé Formation and rhyolite dikes of the Acampamento Velho Formation (modified fromReischl, 1978; Lopes et al., 2014) with inactive open pit mines, faults and mineralization localization.

	Meio; 5= Cruzeta; 6= Alcides.	Keys: 1= Barita; 2 = João Dahne; 3= Morcego; 4=
	The Seival Mine area hosted six inactive Cu-bearing mines and several
	prospects ca. 0.20 Mt of mineralized rocks with an average grade of ~1.40 % Cu

MANUSCRITO I | 85

Rodrigo Winck LOPES

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Table )

 ) 

	In Seival Mine area the volcanogenic rocks of the Hilário Formation have main
	structures represented by transcurrent and normal faults (stereogram 7 to 12 of the
	Fig. 10A; Supplementary Table). These faults are oriented NE-SW/70-88°NW
	(48%) and NW-SE/70-88°NE (48%). Few subhorizontal transcurrent fault (< 30°N-
	S) with slickenlines were observed (4%) with ~E-W orientation. The structural
	analysis indicates that most of the lineations are associated with transcurrent faults
	and show subhorizontal orientation with dextral (44%) and sinistral (30%)
	kinematics. Only 26% of the slickenlines are subvertical and associated with normal

. Minor normal kinematics were observed (0-5%). The direction of kinematic indicators is mainly NW-SE/10-40°NE (70%) and NE-SW/10-40°SE (30%) oriented. However, in the Hilário Formation of the Lavras do Sul Mining District, the kinematic analysis of volcanogenic rocks are mainly ENE-WSW/10-30°SE oriented (stereogram 6 of the Fig.

10A;

(Supplementary Table

)

. The orientation of the mineralized structures was associated with the main N70°W direction. The intermediate to basic volcanogenic rocks of the Hilário Formation is delimited by N50°E/80-88°SE oriented Cabritos-Perau and N20°E/80-88°NW oriented Segredo faults. The ~E and NW bedding variation in volcanogenic rocks is found in Hilário Formation close to granitoids and Seival Mine, respectively. These changes are related to the original volcano-sedimentary deposition. faults. The mineralized fractures and faults show NE-SW and NNE-SSW directions and vertical to subvertical disposition.

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  Structural analysis from Lavras do Sul Mining District and Seival Mine. A) Stereographic projections of faults with slickenside and kinematic indicators: 1 to 5= Lavras do Sul Intrusive Complex; 6= Hilário Formation; 7 to 12: Seival Mine (stress values see Table 1); B) Measured points localization, main structures and simplified geological map of the studied areas.

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	Figure 10.		
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  SE σ1; stereograms 1-5 and 7-8 of the Fig.10A; Supplementary Table) comparedto Seival (NE-SW σ1; stereograms 6 and 9-11 of the Fig.10A; Supplementary Table), suggests that NE-SW stress was more expressive in the volcanogenic rocks.A second factor would be that subhorizontal thin pyroclastic layers of the lapilli tuff of the Seival Mine have a lower resistance to stress than massive granitoids of Lavras do Sul Mining District, and for this reason recorded more deformation.

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The large number of NE-SW normal faults and fracture systems in Seival compared to Lavras do Sul Mining District area suggest a superposition of two distinct deformational events with main subhorizontal NW-SE and NE-SW oriented compressive maximum stress, respectively. A first interpretation of these stress directions, based on a dominant occurrence in Lavras do Sul Mining District (NW-

  Zvirtes, G.,Philipp, R.P., Camozzato, E., Chemale Jr., F., 2015. Metagranito alcalino Capané: evidências de rifteamento e metamorfismo regional orogênico neoproterozóico nos estágios finais de evolução do Cinturão Dom Feliciano. In: IX SIMPÓSIO SUL-BRASILEIRO DE GEOLOGIA, 9, Anais, SBG, Florianópolis, v. 1.

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			MANUSCRITO I | 119 MANUSCRITO I | 120 MANUSCRITO II | 121
	origin of hypogene features. Society of Economic Geologists, Economic Geology 4.2 Manuscrito II
	100th Anniversary Volume, 251-298. O manuscrito II foi primeiramente submetido ao Journal of Geochemical Sillitoe, R.H., 1991. Gold metallogeny of Chile -an introduction. Economic Exploration em 11/01/2017 e recusado com possível resubmissão em 24/06/2017. Geology, 86, 1187-1205. Sillitoe, R.H., 2003. Iron oxide-copper-gold deposits: An Andean view. Zvirtes, G., Philipp, R.P., Camozzato, E., Guadagnin, F., 2017. Análise estrutural O manuscrito foi reescrito e resubmetido em 01/11/2017 para a mesma revista
	Mineralium Deposita, 38, 787-812. do Metagranito Capané, Antiforme Capané, Complexo Porongos, Cachoeira do Sul,
	Sillitoe, R.H., 2010, Porphyry copper systems. Economic Geology, 105, 3-41. RS. Revista Pesquisas em Geociências, 44, 05-23.
	Silva, L.C., McNaughton, N.J., Armstrong, R., Hartmann, L.A., Fletcher, I.R.,
	2005. The neoproterozoic Mantiqueira Province and its African connections: a
	zircon-based U-Pb geochronologic subdivision for the Brasiliano/Pan-African
	systems of orogens. Precambrian Research, 136, 203-240.
	Vedana, L.A., Philipp, R.P., Basei, M.A.S., 2018. Tonian to early Cryogenian
	synorogenic basin of the São Gabriel Terrane, Dom Feliciano Belt, southernmost
	Brazil. International Geology Review, 60, 109-133.
	Wildner, W., Lima, E.F., Nardi, L.V.S., Sommer, C.A., 2002. Volcanic cycles and
	setting in the Neoproterozoic III to Ordovician Camaquã Basin succession in
	southern Brazil: characteristics of post-collisional magmatism. Journal of
	Volcanology and Geothermal Research, 118, 261-283.
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Sommer, C.A., Lima, E.F., Nardi, L.V.S., Figueiredo, A.M.G., Pierosan, R., 2006. Potassic and low-and high-Ti mildly alkaline volcanism in the Neoproterozoic Ramada Plateau, southermost Brazil. Journal of South American Earth Sciences, 18, 237-254. Teixeira, E., 1937. Cobre no Rio Grande do Sul. DNPM, Divisão de Fomento da Produção Mineral, 22, 29 p. Toniolo, J.A., Gil, C.A.A., Sander, A., 2007. Projeto BANEO-Metalogenia das Bacias Neoproterozóico-Eopaleozóicas do Sul do Brasil -Bacia do Camaquã. CPRM -Serviço Geológico do Brasil, CD Rom. Twiss, R.J., Moores, E.M, 1992. Structural geology. University of California, 532 p. científica. Esta segunda versão passou por uma primeira revisão e foi resubmetida seguindo as correções e sugestões em 23/02/2018. Uma nova revisão foi solicitada e o manuscrito foi resubmetido em 30/08/2018. Após revisão, uma nova versão ainda não submetida foi inserida na presente tese. A tabela suplementar com os dados de microssonda eletrônica é apresentada no ANEXO F. 1. Introduction

Table 1 .

 1 Summary of mineral, host rock and structural formula of magmatic, magmatic to late-magmatic and hydrothermal phases. Nomenclature of chlorites after[START_REF] Bayliss | Nomenclature of the trioctahedral chlorites[END_REF].

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Fe 3+ 0.46-0.61 Fe 2+ 2.19-2.74 Mg 5.59-5.86 Mn 0.06-0.07 ) VI (Si 6.52-6.75 Al 1.25-1.48 ) IV O 20 (OH) 8 ]

Table 2 .

 2 Measured REE analyzes and normalized values to McDonough and Sun (1995) in separate plagioclase grains of the Seival Mine, andesitic lava flows located outside of the area (black line) and whole-rock analyzes(Lopes et al., 2014). Keys: And= Andesitic lava flows; AD= Andesitic dike; Outs. area= Andesitic lava flows located of outside studied area; Light REE= La to Sm; Heavy REE= Eu to Lu; ΣREE= Sum of total concentration of not normalized rare earth elements; Eu/Eu*= The value of the normalized Eu anomaly calculated by the formula [Eu/Eu*]= [(EuN)/((SmN x GdN) 1/2 )] from[START_REF] Worrall | Water-rock interaction in an acidic mine discharge as indicated by rare earth element patterns[END_REF].

	Sample (mg/kg)	RFM 55 -And	WL 13 -And	WL 19 -And	FM 13 -AD	DD 62 -AD
	Y	9.18	3.15	2.26	0.23	1.61
	La	28.39	7.70	5.47	1.66	6.18
	Ce	55.31	19.25	16.08	2.68	15.41
	Pr	8.15	2.29	2.06	0.32	1.65
	Nd	32.46	8.71	8.07	1.14	6.10
	Sm	5.85	2.12	2.25	0.18	1.77
	Eu	2.28	0.60	0.67	0.17	1.79
	Gd	5.55	1.94	1.92	0.18	1.89
	Tb	0.74	0.26	0.26	0.02	0.21
	Dy	3.07	1.11	1.05	0.07	0.78
	Ho	0.65	0.23	0.21	0.02	0.15
	Er	1.80	0.59	0.56	0.04	0.40
	Tm	0.28	0.09	0.09	0.01	0.06
	Yb	1.46	0.45	0.45	0.03	0.29
	Lu	0.35	0.12	0.12	0.01	0.08
	Normalization standard CI chondrite (McDonough and Sun, 1995)		
	La	119.77	32.50	23.10	6.99	26.07
	Ce	90.23	31.40	26.23	4.37	25.14
	Pr	87.81	24.68	22.19	3.41	17.80
	Nd	71.04	19.06	17.66	2.49	13.35
	Sm	39.55	14.32	15.20	1.20	11.98
	Eu	40.48	10.57	11.87	3.04	31.85
	Gd	27.90	9.74	9.66	0.89	9.50
	Tb	20.44	7.31	7.15	0.55	5.73
	Dy	12.48	4.50	4.26	0.30	3.16
	Ho	11.83	4.12	3.83	0.27	2.71
	Er	11.27	3.69	3.53	0.26	2.51
	Yb	9.09	2.80	2.81	0.20	1.82
	Lu	14.27	4.72	4.88	0.28	3.09
	ΣLREE	130.16	40.07	33.93	5.98	31.11
	ΣHREE	16.18	5.39	5.33	0.55	5.65
	ΣREE	155.52	48.61	41.52	6.76	38.37
	Eu/Eu*	1.22	0.90	0.98	2.94	2.99

Continuation of Table 2

  

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	Sample (mg/kg)	RFM 66 -AD	FM 33 -AD	FM 32 -AD	DD 76 -AD	RFM 68 -Outs. Area
	Y	1.63	0.41	1.36	11.03	1.24
	La	9.95	2.16	4.30	31.66	8.09
	Ce	17.54	5.57	14.19	60.18	13.61
	Pr	1.90	0.66	1.89	7.79	1.46
	Nd	6.54	2.51	7.31	29.43	5.04
	Sm	1.51	0.45	2.61	6.47	0.82
	Eu	2.36	0.17	0.82	3.05	1.75
	Gd	1.62	0.37	2.19	6.50	0.90
	Tb	0.17	0.04	0.28	0.81	0.09
	Dy	0.58	0.16	1.04	3.20	0.30
	Ho	0.11	0.03	0.20	0.63	0.06
	Er	0.31	0.09	0.54	1.64	0.16
	Tm	0.04	0.01	0.08	0.24	0.02
	Yb	0.22	0.07	0.39	1.21	0.11
	Lu	0.05	0.02	0.12	0.29	0.03
	Normalization standard CI chondrite (McDonough and Sun, 1995)		
	La	42.00	9.10	18.16	133.60	34.12
	Ce	28.62	9.09	23.15	98.18	22.21
	Pr	20.48	7.12	20.42	83.91	15.70
	Nd	14.32	5.48	16.01	64.40	11.03
	Sm	10.22	3.02	17.66	43.73	5.53
	Eu	41.95	2.98	14.55	54.09	31.07
	Gd	8.14	1.88	10.98	32.67	4.50
	Tb	4.63	1.22	7.73	22.49	2.41
	Dy	2.35	0.64	4.24	13.02	1.21
	Ho	2.03	0.57	3.70	11.45	1.04
	Er	1.94	0.56	3.39	10.26	0.98
	Yb	1.37	0.43	2.43	7.54	0.69
	Lu	2.15	0.69	4.67	11.91	1.06
	ΣLREE	37.44	11.35	30.30	135.53	29.02
	ΣHREE	5.46	0.96	5.66	17.57	3.42
	ΣREE	44.53	12.72	37.32	164.13	33.68
	Eu/Eu*	4.60	1.25	1.04	1.43	6.23
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			MANUSCRITO II | 143
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  Wilkinson, J.J., Chang, Z., Cooke, D.R., Baker, M.J., Wilkinson, C.C., Inglis, S., Chen, H., Gemmell, J.B., 2015. The chlorite proximitor: A new tool for detecting porphyry ore deposits. Journal of GeochemicalExploration, 152,[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] 

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			MANUSCRITO II | 161 MANUSCRITO III | 164
	Williams, P.J., Barton, M.D., Johnson, D.A., Fontboté, L., de Haller, A., Mark,
	G., Oliver, N.H.S., Marschik, R., 2005. Iron oxide copper-gold deposits: Geology,
	Space-time distribution, and possible modes of origin. Economic Geology, 100th
	Anniversary Volume, 371-405.		
	Worrall, F., Pearson, D.G., 2001. Water-rock interaction in an acidic mine
	discharge as indicated by rare earth element patterns. Geochimica et Cosmochimica
	Acta, 65, 3027-3040.		
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Yoneda, T., Watanabe, T., Sato, T., 2016. Mineralogical aspects of interstratified chlorite-smectite associated with epithermal ore veins: A case study of the Todoroki Au-Ag ore deposit, Japan. Clay Minerals, 51, 653-674.

  belongs to the Bom Jardim Group

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Table 1 .

 1 Representative barite chemical compositions from Seival Mine.

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  Continuation of Table 1.

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	Point	10	11	12	13	14	15	16	17	18
	SiO 2 (wt %)	0	0	0.05	0.02	0	0.03	0.01	0.05	0.02
	TiO 2	0.02	0	0	0.05	0	0.02	0.02	0	0.04
	Al 2 O 3	0	0	0	0.06	0	0	0	0	0
	FeO	0	0	0.05	0.09	0.04	0	0.01	0	0
	MnO	0	0.04	0.03	0	0	0	0	0	0
	MgO	0	0	0	0	0	0	0.02	0	0
	CaO	0	0	0.01	0	0.01	0.03	0.03	0.01	0
	Na 2 O	0.03	0.09	0.17	0.15	0.09	0.15	0.12	0.06	0.05
	K 2 O	0	0.01	0	0	0	0	0	0.01	0.01
	BaO	65.55 64.80 65.05 65.23 65.28 65.28 63.50 65.24 65.71
	SrO	0.03	0.63	0.55	0.12	0.33	0.05	1.14	0.06	0.09
	CuO	0	0.05	0	0.05	0.06	0.13	0	0.06	0
	SO 3	34.43 34.77 34.33 33.72 34.17 34.14 34.78 33.88 34.06
	Sum	100.06 100.39 100.24 99.49 99.98 99.83 99.63 99.37 99.98
	Si (wt %)	0	0	0.02	0.01	0	0.01	0.01	0.02	0.01
	Ti	0.01	0	0	0.03	0	0.01	0.01	0	0.03
	Al	0	0	0	0.03	0	0	0	0	0
	Fe	0	0	0.04	0.07	0.03	0	0.01	0	0
	Mn	0	0.03	0.03	0	0	0	0	0	0
	Mg	0	0	0	0	0	0	0.01	0	0
	Ca	0	0	0.01	0	0.01	0.02	0.02	0.01	0
	Na	0.02	0.07	0.12	0.11	0.06	0.11	0.09	0.05	0.04
	K	0	0.01	0	0	0	0	0	0.01	0.01
	Ba	58.71 58.04 58.26 58.43 58.47 58.47 56.87 58.43 58.85
	Sr	0.02	0.53	0.47	0.10	0.28	0.05	0.96	0.05	0.07
	Cu	0	0.04	0	0.04	0.05	0.10	0	0.04	0
	S	13.79 13.93 13.75 13.50 13.68 13.67 13.93 13.57 13.64
	O	27.51 27.75 27.55 27.17 27.40 27.39 27.72 27.19 27.33
	Sum	100.06 100.40 100.25 99.49 99.98 99.83 99.63 99.37 99.98
	Rodrigo Winck LOPES			-2018-			Tese de doutorado / THÈSE

  Continuation of Table 1.

	UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO	UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES
								MANUSCRITO III | 180
	Point	19	20	21	22	23	24	25	26	27
	SiO 2 (wt %)	0	0.05	0	0.05	0.02	0.04	0	0.02	0
	TiO 2	0.01	0	0.01	0	0	0.04	0	0.01	0
	Al 2 O 3	0	0.01	0	0	0	0	0	0.01	0
	FeO	0.01	0	0.04	0	0	0.04	0.05	0	0
	MnO	0	0	0.03	0	0	0	0	0	0
	MgO	0	0	0	0	0	0	0	0	0
	CaO	0	0	0	0.03	0	0	0	0	0.01
	Na 2 O	0.12	0.04	0.11	0.05	0.13	0.07	0.12	0.13	0.12
	K 2 O	0	0	0	0	0	0	0.01	0	0
	BaO	65.19 65.76 64.71 65.14 65.22 65.24 64.29 65.46	65.18
	SrO	0.33	0.11	0.58	0.31	0.38	0.27	0.57	0.31	0.17
	CuO	0.04	0.09	0	0.06	0	0	0	0.08	0.01
	SO 3	34.38 34.64 34.21 35.08 34.10 34.69 33.89 34.14	33.91
	Sum	100.08 100.7 99.69 100.72 99.85 100.39 98.93 100.16	99.40
	Si (wt %)	0	0.02	0	0.02	0.01	0.02	0	0.01	0
	Ti	0.01	0	0.01	0	0	0.03	0	0.01	0
	Al	0	0.01	0	0	0	0	0	0	0
	Fe	0.01	0	0.03	0	0	0.03	0.04	0	0
	Mn	0	0	0.02	0	0	0	0	0	0
	Mg	0	0	0	0	0	0	0	0	0
	Ca	0	0	0	0.02	0	0	0	0	0
	Na	0.09	0.03	0.08	0.04	0.10	0.05	0.09	0.10	0.09
	K	0	0	0	0	0	0	0.01	0	0
	Ba	58.38 58.90 57.96 58.34 58.42 58.43 57.58 58.63	58.38
	Sr	0.27	0.09	0.49	0.26	0.32	0.23	0.48	0.26	0.14
	Cu	0.04	0.07	0	0.05	0	0	0	0.07	0.01
	S	13.77 13.87 13.70 14.05 13.66 13.89 13.57 13.67	13.58
	O	27.51 27.70 27.40 27.94 27.36 27.72 27.16 27.42	27.20
	Sum	100.08 100.69 99.69 100.72 99.87 100.40 98.93 100.17	99.40
	Rodrigo Winck LOPES			-2018-			Tese de doutorado / THÈSE

Table 2 .

 2 Representative barium compositions with a standard deviation of 0.02 weight % in andesine-labradorite and albite. Keys: DL= detection limits; And-lab= Andesine-labradorite.

	Point	1	2	3	4	5	6	7	8	9
	BaO (wt %)	0.12	0.02	0.13	0.14	0.14	0.15	0.15	0.13	0.13
	Ba (wt %)	0.11	0.02	0.11	0.13	0.13	0.14	0.13	0.11	0.12
	O	0.01	0	0.01	0.01	0.01	0.02	0.02	0.01	0.01
	Sum	0.12	0.02	0.13	0.14	0.14	0.15	0.15	0.13	0.13
	DL (ppm)	217	206	218	216	217	215	218	218	217
	Composition	and-lab albite and-lab and-lab and-lab and-lab and-lab and-lab and-lab
	Point	10	11	12	13	14	15	16	17	18
	BaO (wt %)	0.14	0.13	0.13	0.14	0.13	0.14	0.12	0.12	0.12
	Ba (wt %)	0.13	0.11	0.12	0.13	0.11	0.13	0.11	0.11	0.10
	O	0.02	0.01	0.01	0.01	0.01	0.01	0.01	0.01	0.01
	Sum	0.14	0.13	0.13	0.14	0.13	0.14	0.12	0.12	0.12
	DL (ppm)	219	217	219	216	217	217	217	219	218
	Composition	and-lab and-lab and-lab and-lab and-lab and-lab and-lab and-lab and-lab
	Point	19	20	21	22	23	24	25	26	27
	BaO (wt %)	0	0	0.01	0.01	0.01	0.01	0.14	0.14	0.12
	Ba (wt %)	0	0	0.01	0.01	0.01	0.01	0.12	0.13	0.11
	O	0	0	0	0	0	0	0.01	0.02	0.01
	Sum	0	0	0.01	0.01	0.01	0.01	0.14	0.14	0.12
	DL (ppm)	210	209	206	207	209	209	216	215	218
	Composition	albite	albite albite albite albite albite and-lab and-lab and-lab
	Point	28	29	30	31	32	33			
	BaO (wt %)	0.13	0.11	0.14	0.14	0.12	0.14			
	Ba (wt %)	0.12	0.10	0.12	0.12	0.11	0.13			
	O	0.01	0.01	0.01	0.01	0.01	0.01			
	Sum	0.13	0.11	0.14	0.14	0.12	0.14			
	DL (ppm)	219	217	215	216	217	215			
	Composition	And-lab And-lab And-lab And-lab And-lab And-lab			

UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES

  

			MANUSCRITO III | 182
	Rodrigo Winck LOPES	-2018-	Tese de doutorado / THÈSE

Table 3 .

 3 The total concentrations of REE in

	barite (ΣREE not normalized) vary from 769.76 to 2476.35 ppm; whereas calcites
	range from 1.06 to 14.18 ppm and whole-rock from 10.97 to 16.05 ppm. The La/LuN
	normalized ratio representing Light Rare Earth Elements (LREE) compared to Heavy
	Rare Earth Element (HREE) enrichment varies in barites from 0.04 to 0.11; whereas
	in calcite and whole-rocks they range from 3.61 to 201.15 and 18.43 to 28.25,
	respectively. The elevated REE patterns of the barite compared to the flatten calcite
	and whole-rocks is associated with similar Ce/LaN and Ce/Ce* normalized ratio
	(Table

Table 3 .

 3 Concentrations of Rare Earth Elements and normalization values (McDonough and Sun, 1995) to barite, calcite and whole-rock samples from Seival Mine. Light REE (LREE: La to Sm); Heavy REE (HREE: Eu to Lu); ΣREE= sum of total concentration of Rare Earth Elements; Ratio= ΣLREE/ΣHREE; Eu/Eu*= The

	value of the normalized Eu anomaly calculated by the formula [Eu/Eu*]= [(EuN)/((SmN x GdN) 1/2 )]; Ce/Ce*= Value of Ce anomaly calculated by formula Ce/Ce*= [(CeN)/((LaN x PrN) -1/2 )] (Worrall and Pearson, 2001).

  Continuation of Table3.

	UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO	UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES
						MANUSCRITO III | 185
	Sample	Calcite-1	Calcite-2	Calcite-3	Calcite-4	Calcite-5
	La	4.63	26.89	49.46	9.09	1.15
	Ce	9.59	40.63	140.29	14.79	1.70
	Pr	1.12	3.82	13.69	1.78	0.18
	Nd	5.39	16.60	54.93	10.42	0.91
	Sm	0.89	2.20	11.16	2.68	0.16
	Gd	0.95	2.60	10.86	3.66	0.25
	Tb	-	-	-	-	-
	Dy	0.22	0.42	1.74	2.89	0.23
	Ho	0.03	0.05	0.20	0.52	0.05
	Er	0.10	0.24	0.91	1.71	0.23
	Tm	0.01	0.01	0.04	0.20	0.03
	Yb	0.05	0.11	0.39	1.39	0.24
	Lu	0.01	0.01	0.04	0.19	0.03
	Normalization standard, chondrite (McDonough and Sun, 1995)	
	La N	19.53	113.44	208.67	38.34	4.84
	Ce N	15.65	66.28	228.85	24.12	2.77
	Pr N	12.07	41.13	147.49	19.20	1.95
	Nd N	11.79	36.33	120.19	22.81	1.98
	Sm N	6.00	14.84	75.44	18.11	1.08
	Gd N	4.77	13.06	54.56	18.40	1.27
	Tb N	-	-	-	-	-
	Dy N	0.90	1.70	7.07	11.76	0.95
	Ho N	0.50	0.94	3.59	9.44	1.00
	Er N	0.63	1.47	5.69	10.69	1.45
	Yb N	0.32	0.71	2.42	8.66	1.48
	Lu N	0.25	0.56	1.72	7.73	1.34
	ΣLREE ΣHREE ΣREE	21.62 1.62 23.24	90.13 4.02 94.15	269.52 17.35 286.87	38.76 11.12 49.88	4.09 1.13 5.22
	Ratio	13.31	22.42	15.53	3.49	3.63
	La/Lu N	77.34	201.15	121.48	4.96	3.61
	Ce/La N	0.80	0.58	1.10	0.63	0.57
	Ce/Ce*	1.02	0.97	1.30	0.89	0.90
	Rodrigo Winck LOPES		-2018-	Tese de doutorado / THÈSE

  Continuation of Table3.

	UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO	UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES
					MANUSCRITO III | 186
	Sample	WR	WR	WR	WR
	La	35.40	50.20	62.60	44.40
	Ce	72.80	97.70	102.20	83.70
	Pr	8.37	11.53	11.38	10.89
	Nd	34.60	43.20	39.20	42.60
	Sm	6.07	7.78	6.91	8.40
	Gd	4.29	6.14	5.00	6.53
	Tb	0.52	0.75	0.63	0.79
	Dy	2.86	3.72	3.30	3.92
	Ho	0.45	0.68	0.59	0.73
	Er	1.23	1.69	1.53	1.88
	Tm	0.18	0.23	0.22	0.26
	Yb	1.26	1.58	1.48	1.69
	Lu	0.18	0.23	0.23	0.25
	Normalization standard, chondrite (McDonough and Sun, 1995)
	La N	149.37	211.81	264.14	187.34
	Ce N	118.76	159.38	166.72	136.54
	Pr N	90.19	124.25	122.63	117.35
	Nd N	75.71	94.53	85.78	93.22
	Sm N	41.01	52.57	46.69	56.76
	Gd N	21.56	30.85	25.13	32.81
	Tb N	14.40	20.78	17.45	21.88
	Dy N	11.63	15.12	13.41	15.93
	Ho N	8.24	12.45	10.81	13.37
	Er N	7.69	10.56	9.56	11.75
	Yb N	7.83	9.81	9.19	10.50
	Lu N	7.32	9.35	9.35	10.16
	ΣLREE ΣHREE ΣREE	157.24 12.56 169.80	210.41 16.94 227.35	222.29 14.72 237.01	189.99 18.41 208.40
	Ratio	12.52	12.42	15.10	10.32
	La/Lu N	20.41	22.65	28.25	18.43
	Ce/La N	0.80	0.75	0.63	0.73
	Ce/Ce*	1.02	0.98	0.93	0.92
	Rodrigo Winck LOPES		-2018-		Tese de doutorado / THÈSE

  REE-enriched barite (ΣREE barite= ~1631.01) (Fig.9D). Therefore, the barite high REE values do not derive from albitization. The plagioclase maintains REE values even with the albitization process. The probable source of REE in barites is the chloritization of pyroxene

	UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO	UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES
			MANUSCRITO III | 193
	Rodrigo Winck LOPES	-2018-	Tese de doutorado / THÈSE

SUPLEMENTAR DO MANUSCRITO I: Mina do Seival

  

	UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO caracterizou a assinatura química de minerais magmáticos preservados, os efeitos UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES SÍNTESE INTEGRADORA | 203 da albitização e os produtos de alteração hidrotermal como clorita, esmectita e interestratificados relacionados à precipitação de sulfetos de cobre. A mineralogia sugere magmas ricos em voláteis cristalizando biotita e minerais de alteração tardi-magmática como a titanita e processo de albitização do plagioclásio magmático em temperaturas entre 650 a 250°C. A albitização (<350°C) foi associada com precipitação de pirita e calcopirita. Esta alteração de alta temperatura está relacionada com fluidos magmáticos tardios, como indicado pela geoquímica de Elementos Terras Raras de plagioclásios primários e secundários. A cloritização (312 a 120°C) e formação de clorita, interestratificados de clorita/esmectita e esmectita foram associadas com a formação de bornita-calcocita e barita. A química de minerais de alteração hidrotermal, como esmectita, interestratificado clorita/esmectita, Fe-clinocloro e Mg-chamosita refletem a metaestabilidade dos SV 64,8 64,8 Hilário Lapili tufo FM 60 38 Hilário Lapili tufo NF07 126 Hilário Lava andesítica amigdalóide 045/80 315/09 S 315/09 S 5 326/70 240/18 S 240/18 S 8 252/60 315/40 D 315/40 D 10 091/72 176/45 N 176/45 N Mn 0.01 0.01 0.01 0.01 0.01 0.01 0 0.01 0.01 0.01 0 0 Si 5.02 5.31 5.39 5.57 5.46 5.61 minerais magmáticos com entrada de água meteórica e diminuição de temperatura. UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: C) Titanita SÍNTESE INTEGRADORA | 204 de cobre, e os interestratificados de clorita/esmectita podem ser relacionados com o processo de enriquecimento em cobre. A cristalização de barita, calcita e hematita sugerem uma condição mais oxidante e de mais baixa temperatura (<150°C) do que albita, clorita-esmectita e sulfetos ricos em cobre. FM 06 13,1 Hilário Lava andesítica amigdalóide FM 07 13,7 Hilário Lava andesítica amigdalóide SV 13,3 13,3 Hilário Lava andesítica amigdalóide SV 14,3 14,3 Hilário Lapili tufo SV 16,3 16,3 Hilário Lapili tufo FM 08 15,5 Hilário Lava andesítica amigdalóide FM 09 16,8 Hilário Lapili tufo FM 10 20,5 Hilário Lapili tufo SV 23,4 23,4 Hilário Lapili tufo SV 30,4 30,4 Hilário Lapili tufo FM 11 33 Hilário Lapili tufo FM 12 33,4 Hilário Dique de andesito FM 13 38,5 Hilário Dique de andesito FM 14 41,5 Hilário Dique de andesito SV 40,7 40,7 Hilário Dique de andesito FM 15 43 Hilário Dique de andesito FM 16 50,5 Hilário Lapili tufo FM 17 54 Hilário Lapili tufo SV 55 55 Hilário Lapili tufo FM 18 59 Hilário Lapili tufo FM 19 63,5 Hilário Lapili tufo Continuação da TABELA DE PONTOS FM 42 110 Hilário Lapili tufo FM 43 112 Hilário Lapili tufo FM 44 116 Hilário Lapili tufo FM 45 116,9 Hilário Lapili tufo FM 46 119,5 Hilário Lapili tufo FM 47 120,6 Hilário Lapili tufo FM 48 128,5 Hilário Lapili tufo FM 49 129 Hilário Lapili tufo FM 50 129,6 Hilário Lapili tufo AMOSTRA PROF. (m) LINHA 700 UNIDADE LITOLOGIA FM 51 4,5 Hilário Lapili tufo FM 51A 11,8 Hilário Lapili tufo FM 52 15 Hilário Lapili tufo FM 53 16,8 Hilário Lapili tufo FM 54 23 Hilário Lapili tufo FM 55 23,5 Hilário Lapili tufo FM 56 27,8 Hilário Lapili tufo FM 57 30,9 Hilário Lava andesítica porfirítica FM 58 31,6 Hilário Lava andesítica porfirítica FM 59 36 Hilário Lapili tufo SV 78-15 (30°43'14" S e 53°47'18" O) SV 78-15 (30°43'14" S e 53°47'18" O) Continuação da TABELA DE PONTOS AMOSTRA PROF. (m) MINA DO MEIO UNIDADE SV 78-09 (30°42'27" S e 53°46'44" S) Lavras do Sul Granite Continuação: TABELA SUPLEMENTAR DO MANUSCRITO I: Formação Hilário Hilário Formation Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: B) Biotita Sample DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 Point 1ep1dir 3ep1esq 4ep2 5ep3 6ep4 8epclay2 10epclay2 16clay3epid 17clay3epid 4pln_3 5pln_3 Continuação: TABELA Seival Mine Sample DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 0 0.01 0 0.01 0 0.01 0.01 FM 13 FM 13 FM 13 FM 13 6ep1d 7ep1d 8ep2d 9ep3d More pristine biotite compositions Less pristine biotite compositions SiO 2 (wt.%) 31.22 31 31.02 31.19 31.27 30.49 31 30.60 30.96 31.06 31.32 30.46 30.13 30.05 29.65 LITOLOGIA FM 81 8 Hilário N°Slickenside Slickenline Kin Slickenline* Kin* N°Slickenside Slickenline Kin Slickenline* Kin* N°Slickenside Slickenline Kin Slickenline* Kin* N°Slickenside Slickenline Kin Slickenline* Kin* N°Slickenside Slickenline Kin Slickenline* Kin* N°Slickenside Slickenline Kin Slickenline* Kin* Point 1px_c 2px_c 3px_h 4px_b 5px_b 1px2_b 1px3_b 2px3_b 3px3_b 4px3_b 5px3_c 6px3_c 7px3_c 49_px1 50_px1 51_px1 52_px1 53_px1 54_px1 Sample DD 36 DD 36 DD 36 DD 36 DD 36 DD 36 TiO 2 32.88 32.96 32.95 33.07 32.9 32.38 32.93 32.75 32.78 32.81 30.64 32.61 33.00 34.55 34.49 Lapili tufo FM 82 27,5 Hilário 350/88 070/06 D 070/06 D 3 042/82 120/24 D 120/24 D 6 174/88 086/40 S 086/40 S 6 176/83 060/24 N 089/23 S 7 214/78 314/10 D 302/08 D 9 090/70 013/32 S 013/32 S SiO 2 (wt.%) 53.24 51.81 51.34 53.36 50.34 51.32 53.92 54.01 54.15 52.07 53.25 53.25 54.00 53.01 51.55 52.21 51.76 51.77 51.28 Point 1 / 1 . 3 / 1 . 7 / 1 . 2 / 1 . 4 / 1 . 5 / 1 . Al 2 O 3 2.43 2.47 2.62 2.49 2.3 2.63 2.66 2.65 2.83 2.45 2.77 4.05 3.72 2.47 2.46 Lapili tufo FM 83 49,8 Hilário Lapili tufo FM 84 63,9 Hilário Lapili tufo FM 85 74 Hilário Lapili tufo FM 86 75 Hilário Lapili tufo FM 87 76,9 Hilário Lava andesítica amigdalóide FM 88 77 Hilário Lava andesítica amigdalóide FM 89 78 Hilário Lapili tufo FM 90 93 Hilário Lapili tufo FM 91 80 Hilário Lapili tufo AMOSTRA PROF. (m) MINA ALCIDES UNIDADE LITOLOGIA NF01 13 Hilário Lapili tufo NF02 31 Hilário Lapili tufo NF03 113 Hilário Lava andesítica amigdalóide NF04 122 Hilário SV 001 (30°43'45" S e 53°47'08" O) 202/40 298/08 D 298/08 D 3 020/84 085/08 D 109/11 D 214/55 290/10 S 290/10 S 3 020/84 085/24 D 107/28 D 212/57 295/02 D 295/02 D 3 025/88 320/06 S 295/08 S 248/23 300/14 D 300/14 D 4 002/82 094/08 D 094/08 D 200/42 092/07 S 283/06 D 4 012/78 086/10 D 099/13 D 185/59 062/99 N 183/59 N 4 064/86 168/12 D 153/11 D 187/70 097/06 S 097/06 S 4 026/88 114/22 D 114/22 D 202/76 108/16 S 108/16 S 4 016/87 102/18 D 102/18 D 028/88 124/20 D 124/20 D 4 348/86 264/10 S 264/10 S 030/86 300/21 S 300/21 S 4 358/84 110/18 S 086/17 D 025/88 110/45 D 110/45 D 4 016/80 106/18 D 106/18 D 034/80 116/12 D 116/12 D 4 240/76 140/26 S 156/23 S 035/84 118/34 D 118/34 D 4 354/82 080/12 D 080/12 D Tabela suplementar do manuscrito I. Medidas estruturais dos pontos da Formação Hilário. Chaves: N° = numero do ponto; Kin = cinemática; Linha* = linha calculada; Kin* = cinemática calculada; S = sinistral; D = dextral; N = normal. A localização dos pontos pode ser encontrada na Figura 14 da tese e na Figura 10 do manuscrito I (parte 4.2). 6 148/86 064/24 S 064/24 S 6 160/86 064/20 S 064/20 S 6 182/84 086/18 S 086/18 S 6 346/82 074/20 D 074/20 D 6 174/88 080/22 S 080/22 S 6 182/86 090/22 S 090/22 S 6 008/88 090/22 D 090/22 D 6 214/88 286/40 D 302/42 D 6 190/88 104/18 S 104/18 S 6 292/80 020/36 D 020/36 D 6 342/78 070/18 D 070/18 D 6 172/88 070/16 S 083/16 S 6 184/87 050/52 N 099/60 S 6 278/74 358/40 D 358/40 D 7 085/76* 002/40 S 007/39 S 9 351/87 074/80 N 074/80 N 7 085/76* 001/82 N 054/74 N 9 347/78 259/30 S 259/30 S 7 082/89 004/73 N 355/73 N 9 308/50 010/34 N 010/34 N 7 081/90 350/22 S 350/22 S 9 355/24 047/12 D 047/12 D 7 093/52 010/13 X 012/11 X 9 338/40 002/38 D 002/38 D 7 001/90 075/26 D 091/27 D 9 074/62 353/22 S 353/22 S 7 095/74 015/43 D 020/42 D 10 054/83 180/02 D 180/02 D 7 273/86 001/51 S 358/51 S 10 269/75 350/00 D 350/01 T iO 2 0.34 0.85 0.77 0.24 0.85 0.81 0.31 0.26 0.25 0.46 0.25 0.30 0.29 0.33 0.57 0.53 0.58 0.52 0.77 Al 2 O 3 2.11 2.42 2.41 1.61 3.03 2.47 1.52 1.46 1.39 2.93 1.94 1.65 1.52 1.96 3.41 2.26 3.74 3.50 4.46 FeO 6.54 11.15 11.39 5.67 12.36 9.16 5.68 5.77 5.36 6.21 5.56 5.98 5.53 6.88 6.74 8.64 7.08 6.55 SiO 2 (wt.%) 31.99 33.57 34.05 33.3 32.59 FeO 1.67 1.64 1.64 1.85 2.2 2.68 1.63 1.94 1.62 1.59 3.38 1.02 1.17 1.94 1.71 35.06 TiO 2 3.69 5.27 6.42 4.86 5.94 MnO 0.04 0.04 0.01 0.04 0.03 0.02 -0.02 0.03 0.04 -0.01 0.02 -0.02 -0.01 0.02 0.01 5.50 MgO 0.15 0.10 0.11 0.21 0.17 0.60 0.08 0.22 0.14 0.10 0.26 -0.02 0.01 -0.01 0 7.04 MnO 0.21 0.26 0.31 0.19 0.36 0.22 0.15 0.19 0.18 0.16 0.16 0.14 0.15 0.16 0.15 0.17 0.12 0.16 Al 2 O 3 16.49 14.56 14.00 14.02 13.17 13.95 CaO 26.87 27 26.99 27.09 26.9 25.68 26.82 26.2 26.68 26.92 26.57 28.04 28.16 27.88 27.85 0.20 MgO 16.93 14.64 14.49 17.28 14.12 14.73 17.44 17.52 17.57 16.37 17.31 17.22 17.71 16.46 15.97 15.49 15.94 16.23 FeO 17.55 16.37 14.49 14.43 13.52 13.41 0.06 0 0.02 0.04 0.04 0.03 0.03 0.01 0.01 0.02 0.05 0.02 -0.02 0 -0.01 Na 2 O 15.74 CaO 19.80 18.88 18.38 20.08 17.54 20.4 20.43 20.11 19.97 20.20 20.55 19.95 20.19 19.93 19.85 19.45 19.74 20.13 MnO 0.25 0.18 0.08 0.11 0.08 K 2 O 0.08 0.07 0.04 0.04 0.05 0.04 0.13 0.04 0.04 0.08 0.17 0 -0.02 -0.02 0.01 0.09 19.72 Na 2 O 0.32 0.41 0.42 0.31 0.54 0.37 0.28 0.27 0.28 0.34 0.32 0.29 0.28 0.43 0.45 0.50 0.46 0.42 0.45 K 2 O -0.01 0 0 0 -0.01 -0.01 -0.01 0 -0.01 0 0 0 0 0 -0.01 -0.01 -0.02 0 0 MgO 16.29 13.25 12.5 10.91 11.58 Sum 95.39 95.29 95.4 96.02 95.85 94.72 95.37 94.59 96.14 95.02 95.17 96.59 96.31 97.42 96.81 11.59 CaO 0.15 0.15 0.06 0.11 0.04 Number of ions on the basis 5 0.11 Si 1.06 1.05 1.05 1.05 1.06 1.05 1.05 1.05 1.05 1.06 1.07 1.03 1.02 1.01 1.01 D 7 238/70 330/05 S 327/04 S 10 245/60 071/08 D 270/54 D 7 100/78 011/60 S 029/57 S 10 077/84 295/42 D 014/77 D 8 060/62 060/62 N 060/62 N 10 236/64* 315/10 D 315/10 D 8 005/90 280/00 D 280/01 D 10 236/64* 310/30 D 310/30 D 8 355/75 270/00 D 270/01 D 10 102/75 180/18 D 180/18 D 99.49 100.41 99.53 98.74 99.14 99.46 99.71 99.58 99.14 98.73 99.33 98.78 99.67 99.2 98.92 99.02 99.78 99.18 99.66 Na 2 O 0.31 0.65 0.82 0.63 0.74 0.69 Ti 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.84 0.79 0.83 0.84 0.88 0.88 T otal Number of ions on the basis 12 Si 1.96 1.92 1.93 1.97 1.90 1.91 1.97 1.98 1.99 1.93 1.95 1.97 1.98 1.96 1.91 1.94 1.91 1.91 1.89 Ti 0.01 0.02 0.02 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.02 Al 0.09 0.11 0.11 0.07 0.13 0.11 0.07 0.06 0.06 0.13 0.08 0.07 0.07 0.09 0.15 0.10 0.16 0.15 0.19 3.02 5.94 6.99 5.72 6.95 6.44 Al 0.10 0.10 0.11 0.10 0.09 0.11 0.11 0.11 0.11 0.10 0.11 0.16 0.15 0.10 0.10 K 2 O F 0.08 0.22 0.50 0.28 0.50 Fe 3+ 0.04 0.04 0.04 0.05 0.06 0.07 0.04 0.05 0.04 0.04 0.09 0.03 0.03 0.05 0.04 0.31 *Li 2 O 0 0.08 0.22 0.01 0 Fe 2+ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.51 *H 2 O 3.79 3.69 3.55 3.45 3.34 Mn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3.60 Mg 0.01 0 0.01 0.01 0.01 0.03 0 0.01 0.01 0 0.01 0 0 0 0 Lava andesítica amigdalóide NF05 122 Hilário 052/80 118/08 D 140/13 D 5 190/82 100/18 S 100/18 S 8 057/13 115/08 D 115/08 D 10 260/60 005/03 D 172/04 D Fe 3+ 0 0.03 0.03 0 0.06 0.04 0 0 0 0.01 0.01 0 0 0.01 0.02 0.02 0.02 0.03 0.02 Sum 93.58 93.84 93.46 87.72 88.22 91.13 Ca 0.98 0.98 0.98 0.98 0.98 0.94 0.98 0.96 0.97 0.98 0.97 1.01 1.02 1.01 1.01 Lava andesítica amigdalóide NF06 124 Hilário Lava andesítica amigdalóide 062/68 140/06 D 140/06 D 5 026/64 092/15 D 105/22 D 8 295/84 025/05 S 025/05 S 10 098/83 185/18 D 185/18 D Fe 2+ 0.20 0.32 0.33 0.18 0.33 0.24 0.17 0.18 0.16 0.18 0.16 0.19 0.17 0.21 0.19 0.25 0.20 0.17 0.20 Number of ions on the basis 22 Na
	Por fim, os dados de composição e de Elementos Terras Raras em baritas são apresentados no manuscrito III (parte 4.3). A composição química de barita e plagioclásios foram utilizados para uma melhor compreensão do processo hidrotermal de baixa temperatura na área. Os concentrados de barita mostraram FM 20 70 Hilário Lapili tufo FM 21 72,5 Hilário Lapili tufo FM 22 72,5 Hilário Lapili tufo SV 77 77 Hilário Lapili tufo AMOSTRA PROF. (m) LINHA 800 UNIDADE LITOLOGIA FM 23 4,5 Hilário Lapili tufo SV 78-01 (30°43'22" S e 53°47'0" O) FM 61 38,7 Hilário Lapili tufo FM 62 50,1 Hilário Lapili tufo AMOSTRA PROF. (m) LINHA 700 UNIDADE LITOLOGIA FM 63 5,9 Hilário Lapili tufo FM 64 9,1 Hilário SV 78-16 (30°43'12" S e 53°47'20" O) SV 78-16 (30°43'12" S e 53°47'20" O) NF08 149 Topo do derrame Hilário Lapili tufo e lava amigdalóide NF 09 162 Hilário Lapili tufo NF 10 183 Hilário Lapili tufo 132/72 218/06 D 218/06 D 5 326/70 238/16 S 238/16 S 140/60 230/15 D 230/15 D 5 326/70 230/14 S 240/11 S 302/74 300/54 N 297/74 N 5 332/52 048/26 D 048/26 D 040/65 310/25 S 121/19 D 5 352/56 048/12 D 064/25 D 318/82 148/35 S 252/71 S 5 335/76 060/09 D 060/09 D 8 245/60 323/10 D 323/10 D 10 272/63 110/61 N 251/61 N 8 160/90 075/27 D 075/27 D 11 303/76 224/50 S 224/50 S 8 254/78 327/14 S 327/14 S 11 100/66* 175/30 D 175/30 D 8 328/68 233/00 D 233/01 D 11 100/66* 010/76 N 010/76 Mg 0.93 0.81 0.81 0.95 0.79 0.82 0.95 0.96 0.96 0.90 0.95 0.95 Ca 0.78 0.75 0.74 0.80 0.71 0.82 0.80 0.79 0.79 0.80 0.81 0.79 2.98 2.69 2.61 2.43 2.54 2.39 Al iv 0.02 0.03 0.03 0.02 0.04 0.03 0.02 0.02 0.02 0.02 0.02 0.02 Al vi 0.07 0.02 0 0.33 0.07 0.24 Na K 0 0 0 0 0 0 0 0 0 0 0 0 Ti 0.44 0.63 0.76 0.61 0.75 0.66 N 8 255/76 345/08 S 345/08 S 11 122/90 215/12 S 215/12 S T otal 4 4 4 4 4 4 4 4 4 4 4 4 Fe 2+ 2.30 2.16 1.92 2.02 1.90 1.79 Lapili tufo FM 65 22 Hilário Lapili tufo 310/35 050/08 D 223/02 S 5 340/60 072/12 D 072/12 D 9 316/66* 255/56 S 255/56 S 12 193/68 260/39 D 263/40 D Wo 0.46 0.42 0.42 0.47 0.40 0.46 0.47 0.46 0.47 0.47 0.47 0.46 Mn 0.03 0.02 0.01 0.02 0.01 0.01	0.97 0.79 0.02 0 4 0.46	0.91 0.79 0.03 0 4 0.46	0.88 0.79 0.03 0 4 0.47	0.86 0.78 0.04 0 4 0.45	0.88 0.78 0.03 0 4 0.46	0.89 0.80 0.03 0 4 0.47	0.86 0.78 0.03 0 4 0.46
	enriquecimento em Elementos Terras Raras em comparação às análises de calcita FM 24 6,3 Hilário Lapili tufo FM 66 22,5 Hilário Lapili tufo 310/36 050/08 D 223/02 S 5 340/72 084/28 D 062/23 D 9 316/66* 316/66 N 316/66 N 12 176/70 150/40 D 127/61 D En 0.39 0.33 0.33 0.40 0.32 0.33 0.40 0.40 0.41 0.38 0.40 0.40 Mg 3.81 3.12 2.95 2.72 2.89 2.76	0.41	0.38	0.38	0.36	0.37	0.38	0.37
	FM 25 FM 67 208/55 113/68 e rocha total. As baritas possuem a fonte de bário provavelmente magmática 16 Hilário Lapili tufo 25,4 Hilário Lapili tufo 118/02 S 118/02 S 5 352/78 072/30 D 072/30 D 9 036/26 S 036/26 S 12 193/68 260/35 D 265/37 D Fs 0.15 0.25 0.26 0.13 0.28 0.21 0.13 0.13 0.12 0.15 0.13 0.14 *Li 0 0.05 0.14 0 0 0.33 provenientes da albitização do plagioclásio. A análise de rocha total evidenciou que a albitização do plagioclásio está relacionada com a elevação dos teores de Elementos Terras Raras em baritas e indicou um fluido oxidante meteórico rico em FM 26 16,9 Hilário Lapili tufo FM 27 19 Hilário FM 68 40,3 Hilário Lapili tufo 045/86 132/09 D 132/09 D 5 132/72 070/18 S 051/26 S 0.02 0.02 0.02 0.02 0.03 0.02 0.01 0.01 0.01 0.02 0.02 0.01 Ca 0.03 0.02 0.01 0.02 0.01 0.02 Na 2 O/(CaO+Na 2 O) Lapili tufo FM 28 20,6 Hilário Lapili tufo FM 29 28 Hilário Lava andesítica amigdalóide FM 30 36,8 Hilário Lava andesítica amigdalóide FM 31 37,7 Hilário Lapili tufo FM 69 44,3 Hilário Lapili tufo FM 70 48,3 Hilário 050/82 142/04 D 142/04 D 5 128/88 230/18 D 217/18 D MgO/(MgO+FeO t ) 0.72 0.57 0.56 0.75 0.53 0.62 0.75 0.75 0.77 0.73 0.76 0.74 Na 0.09 0.20 0.25 0.20 0.24 0.21 Lapili tufo FM 71 51,5 Hilário 330/75 050/05 D 050/05 D 5 240/34 304/22 D 304/22 D Charge 0.01 -0.08 -0.09 0.01 -0.18 -0.13 0.01 0.02 0.04 -0.03 -0.04 0.01 K 0.61 1.20 1.41 1.22 1.49 1.31 Lava andesítica porfirítica FM 72 62 Hilário 055/80 145/36 D 145/36 D 5 100/82 010/11 S 010/11 S OH 3.96 3.89 3.75 3.85 3.73 3.84 Lapili tufo SV 78-18 (30°42'26" S e 53°46'41" O) SV 78-18 (30°42'26" S e 53°46'41" O) 045/82 120/09 D 133/11 D 5 232/88 142/30 S 142/30 S F 0.04 0.11 0.25 0.15 0.27 0.16	0.13 0.01 0.76 0.01	0.16 0.02 0.71 -0.02	0.16 0.02 0.70 -0.06	0.20 0.03 0.64 -0.07	0.17 0.02 0.69 -0.05	0.15 0.02 0.71 -0.09	0.17 0.02 0.69 -0.06
	FM 32 AMOSTRA 060/86 Sum SO4 -2 como fonte de sulfato, uma vez que a fonte de calor e fluidos quentes pode 38,5 Hilário Dique de andesito PROF. (m) MINA DO MEIO UNIDADE LITOLOGIA 148/35 D 148/35 D 5 008/70 104/18 D 093/14 N 19.37 19.43 19.45 19.15 19.35 19.34 FM 33 39,5 Hilário Dique de andesito FM 73 7,6 Hilário Lapili tufo 068/80 148/35 D 148/35 D 5 040/64 122/34 D 122/34 D Fe/Fe+Mg 0 0.41 0.39 0.43 0.40 0.39 estar relacionada com intrusões andesíticas. Dessa maneira, foi possível interpretar a alteração hidrotermal que precipitou barita, calcita e hematita como sendo de baixa temperatura (<157°C). Portanto, as estruturas de direção NW-SE e NE-SW controlam o fluxo FM 34 39,8 Hilário Dique de andesito FM 35 70,5 Hilário Lapili tufo FM 36 73,3 Hilário Lapili tufo FM 37 83,6 Hilário Lapili tufo FM 38 86,8 Hilário Lapili tufo FM 39 94,8 Hilário Lapili tufo FM 74 8 Hilário Lapili tufo FM 75 15,3 Hilário 308/86 224/06 S 224/06 S 5 054/72 114/40 D 114/40 D Mg/Mg+Fe 0.62 0.59 0.61 0.57 0.60 0.61 Lapili tufo FM 76 18 Hilário Lava andesítica amigdalóide FM 77 18,7 Hilário Lava andesítica amigdalóide FM 78 24 Hilário FM 79 30,5 Hilário Lapili tufo 054/65 112/25 D 126/33 D Tabela suplementar do manuscrito II. Tabela B: Análises por microssonda eletrônica de biotita. Lapili tufo 050/82 142/04 D 142/04 D 5 038/70 110/38 D 110/38 D 042/80 112/25 D 127/28 D 5 030/74 086/32 D 106/40 0.02 0.01 0 0.12 0.03 0.09 Al vi /Al vi +Al iv D 040/65 112/25 D 115/29 D 5 034/74 110/14 D 110/14 D Charge 1.87 1.54 1.15 1.41 1.15 1.13					
	clorita com pirita e calcopirita sugerem um guia prospectivo para as mineralizações FM 41 108 Hilário Lapili tufo hidrotermal, os diques e as mineralizações. A associação petrográfica de albita e FM 40 95,5 Hilário Lapili tufo FM 80 43 Hilário Lapili tufo					
	Rodrigo Winck LOPES Rodrigo Winck LOPES	-2018--2018-	Tese de doutorado / THÈSE Tese de doutorado / THÈSE					

E) TABELA SUPLEMENTAR DO MANUSCRITO I: Lavras do Sul

Tabela suplementar do manuscrito I. Medidas estruturais dos pontos de Lavras do Sul. Chaves: N° = numero do ponto; Kin = cinemática; Linha* = linha calculada; Kin* = cinemática calculada; S = sinistral; D = dextral; N = normal. A localização dos pontos pode ser encontrada na Figura 14 da tese e na Figura 10 do manuscrito I (parte 4.2).

Tabela suplementar do manuscrito I. Medidas estruturais dos pontos da mina do Seival. Chaves: N° = numero do ponto; Kin = cinemática; Linha* = linha calculada; Kin* = cinemática calculada; S = sinistral; D = dextral; N = normal; X = indefinida. A localização dos pontos pode ser encontrada na Figura 14 da tese e na Figura 10 do manuscrito I (parte 4.2).

F) TABELA SUPLEMENTAR DO MANUSCRITO II: A) Piroxênio

Tabela suplementar do manuscrito II. Tabela A: Análises por microssonda eletrônica de piroxênio.

Tabela suplementar do manuscrito II. Tabela C: Análises por microssonda eletrônica de titanita.

Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: D) Feldspatos -Albita Tabela

  Sample Ponto 1 Ponto 2 Ponto 3 Ponto 6 Ponto 7 Ponto 8 Ponto 1 Ponto 3 Ponto 5 Ponto 7 Ponto 12 Ponto 13 Ponto 16 Ponto 1 Ponto 2 Ponto 3 Ponto 5 Ponto 14Tabela suplementar do manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita. suplementar do manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita.Tabela suplementar do manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de albita.

		Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: D) Feldspatos -Albita Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: D) Feldspatos -Albita
	Sample Sample Sample	Ponto 15 Ponto 14 Ponto 15 Ponto 16 Ponto 17 Ponto 30 Ponto 31 Ponto 32 3pln_1b 4pln_1b 6pln_1 8pln_1 11pln_1 12pln_1 15pln_1 16pln_1 1pln_2 7pln_2 2pln_3 6pln_3 7pln_3 8pln_3 10pln_3 12pln_3 17pln_3 1pln_4 3pln_4 8pln_4 9pln_4 11pln_4 12pln_4 16pln_4 3pln_1 6pln_1 8pln_1 9pln_1 12pln_1 13pln_1 16pln_1 18pln_1 19pln_1 23pln_1 24pln_1 28pln_1 29pln_1 30pln_1 31pln_1 32pln_2 33pln_2 34pln_2 35pln_2 36pln_2 37pln_2 38pln_2 39pln_2 40pln_2 42pln_2 43pln_2
	Point Point Point Point	FM 12 FM 12 DD 40 WL 13 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 12 FM 12 FM 12 FM 12 DD 36 DD 36 DD 36 DD 36 DD 36 DD 36 DD 36 DD 40 DD 40 DD 40 DD 40 DD 40 WL 13 WL 13 WL 13 WL 13 WL 13 WL 13 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13 FM 13
	SiO 2 (wt.%) 66.12 SiO 2 (wt.%) 65.43 SiO 2 (wt.%) 67.44 66.51 65.60 67.65 SiO 2 (wt.%) 68.17 67.5	67.45 67.58 66.66 68.58	66.54 68.01 67.67 68.41	66.07 68.27 68.07 67.19 68.28 67.61 68.06 67.07 67.04 67.87 67.46 66.33 67.41 68.66 68.60 68.00 68.81	68.35 65.8 68.02 67.22 67.71 67.92 67.73 67.4 64.66 67.34 68.11 67.99 68.69	64.78 68.49 68.46 67.16 68.91 68.64 66.93 66.06 67.33 66.88 66.81 65.66 68.21 66.45 66.81 65.45 67.52 65.19 68.19 68.79 67.99 68.43 67.51 69.22 68.35 67.59	66.67 67.5 67.33 68.49
	T iO 2 T iO 2 T iO 2 T iO 2	0.07 0 0 0.02	0.11 0.03 0.01 0.01	0.03 0.02 0.04 0.01	0.02 0.01 0.04 0.01	0.03 0 -0.02 0.01	0.01 0.07 0.01 0.02 0.03 0.01 0.01 0.02 0.01	0.03 0.03 0.04 0	0.01 -0.01 0.01 0.01	0.03 0.01 0.06 0.05 0.02	0.02 0 0.02 0.01	0.02 0.02 0 0.02	0.03 0 0.02 -0.01	0	0.06 0.01 0.01 0.03	0.02 0.04 0 0.04	0.02 0.05 0 0.01	0	0.01 0.02 0.01 0.01	0.02 0 0 -0.01
	Al 2 O 3 Al 2 O 3 Al 2 O 3 Al 2 O 3	19.61 21.06 21.01 21.52 20.20 19.83 19.94 20.08	20.08 20.1 21.94 20.09	20.3 19.67 20.67 19.76	20.98 19.92 20.96 20.97 20.12 20.95 21.11 20.13 20.01 19.88 20.06 20.26 20.25 22.61 19.75 20.35 21.06 19.9 20.02 20.74 20.00 23.34 21.54 19.85 19.99 19.96 19.56 20.21 20.18 19.74	19.63 20.39 20.28 21.16 19.98 20.63 20.23 21.25 21.98 21.09 22.00 21.56 20.07 21.54 21.98 22.19 20.80 20.56 20.12 20.51 19.63 19.83 20.88 20.37 20.01 20.03 19.45 20.26 20.27 19.88
	FeO FeO FeO FeO	0.65 0.78 0.19 0.05	0.56 0 0.08 0.01	0.07 0.10 0.25 0.09	0.04 0.07 0.03 0.11	0.05 0.06 0.02 0	0.03 0.11 0.36 0.02 0.28 0.08 -0.04 0.24 0.01 0.04 0.01 0.04 0.02		0.02 0.26 -0.01 0.04 0.02 0.17 0.06 0.01 -0.04	0.76 0.22 0.08 -0.04	1.91 0.04 0.05 0.06	0.75 0.07 0.08 -0.01 0.05 0.28 0.03 0.01 0.05	0.23 0.15 0 0.05	0.21 0.08 0.01 0.12 0.03	0.12 0.16 0.01 0	0.32 0.09 0.03 -0.01
	MnO MnO MnO MnO	-0.01 0.02 -0.03 0.01	0.03 0.09 0 -0.03	0.01 0.02 0.01 0.01	0.05 0.01 0.01 -0.01	0.01 0.01 0.01 0.01	0.02 0.01 0.02 -0.01 0.02 0.01 -0.01 -0.01	0		0.04 0 -0.01 0	0.03 0.01 0.02 0.02	0.01 0.02 -0.01 0 0	0.01 0.05 -0.02 0	0.05 0.04 0.02 0	0.01 0.03 0 -0.01 -0.02 0.06 -0.03 0.04 0.02 -0.01 0.05 0.02 -0.01 -0.02 0.02 -0.01 -0.04 0	0.01 0.01 -0.02 -0.01	0.03 0.01 0 0
	MgO CaO Na 2 O K 2 O MgO CaO MgO MgO Na 2 O CaO CaO Na 2 O Na 2 O K 2 O Sum K 2 O K 2 O	0.28 0.72 10.25 0.74 0.15 0.24 0.08 -0.01 9.92 0.35 0.17 1.05 10.67 10.92 11.040 0.42 0.01 0.99 0.25 9.84 11.10 0.48 0.09 0.02 0.01 0.05 0.11 0.01 0.01 -0.01 -0.01 11.26 11.4 1.07 0.81 0.69 0.13 0.03 0.03 11.76 11.37 11.6 98.65 98.96 99.35 0.21 0.17 0.52 0.05 0.07 0.05	0.01 0.19 11.25 0.10 0.02 0.04 0.01 0 11.16 0.61 0.21 0.05 11.50 11.78 98.98 0.04 0.04	0.01 0.38 10.82 0.56 0.02 0.04 -0.03 0 11.18 0.39 0.07 0.04 11.67 11.37 11.88 11.28 11.15 -0.01 0 0.02 0.14 0.13 0.10 11.13 10.23 11.10 0.07 0.86 0.03 0.02 0.09 0.07 0.11 0.13 0.07 0.15 0 -0.01 -0.01 -0.01 -0.01 -0.02 10.73 10.39 10.85 10.23 0.01 0.04 11.11 0.03 0.04 0.30 0.01 0 11.18 0.11 0 11.05 0.09 0.01 0.02 0.52 0.28 0.05 0.01 10.95 10.71 0.26 0.14 10.47 0.45 0.05 0.57 0 0 0.36 0.18 0.33 0.60 0.31 1.13 0.61 0.06 0.26 0.19 0.32 0.18 0.06 0.31 0.67 0.26 1.01 0.13 0.04 0.85 11.71 10.03 11.34 11.63 11.90 11.67 11.82 11.72 11.36 11.84 99.52 98.85 98.20 99.18 100.25 100.21 99.33 100.91 100.94 101.43 100.10 0.73 0.38 0.06 0.18 0.10 0.28 9.30 10.79 10.05 1.63 0.52 0.81 0 0.01 0.01 0.27 0.42 0.78 -0.01 0.05 -0.01 0.01 0 -0.02 0 11.65 11.23 11.21 10.89 0.10 0.18 10.17 1.19 0.03 0.52 -0.01 0.01 0.08 0.13 10.88 0.44 0.01 0.61 0.54 0.01 0 0.01 0.17 1.21 0.19 0.15 0.27 0.3 0.15 0.34 0.26 0.03 0.15 10.87 11.22 10.50 11.41 0.02 0.06 0.10 0.17 11.21 10.36 0.14 0.88 0.02 0 1.13 0 0.01 0 -0.01 0.49 0.19 0.9 0.22 0.05 0.05 0.36 0.11 0.31 0.77 0.30 0.50 0.17 11.82 10.96 11.71 11.74 11.63 11.61 11.74 11.2 11.66 11.4 11.66 11.98 11.71 11.67 11.84 100.8 100.43 100.98 99.98 100.47 0.06 0.14 0.03 0.03 0.48 0.01 1.01 0.14 0.05 0.12 0.07 0.08 0.03 0.07 0.06 0.09 0.03 0.04 0.07 0.05 0.12 0.04 0.05 0.09 0.03 0.05 0.04 0.04 0.13 0.05
	Sum Number of ions on the basis 32 98.42 98.24 Sum 99.91 100.30 101.29 100.58 101.11 100.57 100.53 100.17 101.47 100.45 100.45 101.05 100.85 100.75 100.82 101.27 100.21 99.1 98.47 98.88 98.59 98.31 99.03 99.32 98.90 99.52 98.23 99.71 100 100 Sum 100.17 99.69 100.53 100.31 100.27 100.60 100.00 100.42 100.52 99.75 100.35 100.32 100.21 99.58 100.77	100 99.81 100.56	100 100.6 99.89	99.03 100.43 100.30
	Number of ions on the basis 32 Si 11.66 11.93 Number of ions on the basis 32 Number of ions on the basis 32	11.91	11.99	12.04	11.89		11.69	11.88		12.47	12.74			12.87 12.83	12.98	12.76	12.67	12.66	12.59 12.66 12.40 12.79
	Si Ti Si Si	11.81 0 12.78 12.60 11.72 0 11.9 11.85	12.05 0 12.63 11.92	11.89 0 12.82 11.93	11.80 0 12.90 12.73 12.94 12.81 12.89 11.98 11.91 12.06 0.01 0 0 11.95 11.92 11.89 11.97	12.14 0 12.89 11.86	0	12.03 0.01 12.25 11.89	11.98 0 12.76 11.96	11.51 0 11.87 11.69 11.94 11.85 11.89 11.7 0 0 0.01 11.63 11.90 0.01 11.82 11.94 0 11.85 11.92 11.86 12.00 11.88	11.77 0 11.95 11.84	11.8 0 11.74 11.93
	Ti Al Ti Ti	0.01 4.42 0 0	0.02 4.12 0 0	0 4.18 0.01 0	0 4.09 0.01 0	0 4.14 0 0	0 4.17 0 0	0	0.01 4.21 0	0	0 4.21 0.01 0		0 0 5.05	0	4.70	0 0.01 4.47 0	0 4.63 0 0	0 4.55 0 0	0 4.91 0 0	0	0.01 4.71 0	0	0 4.91 0	0	4.81	0 0	0	4.91	0 0	4.96 0	0 4.65 0 0
	Al Fe 2+ Al Al	4.13 0.12 4.69 4.1	4.25 0 4.81 4.15	4.23 0.01 4.90 4.11	4.27 0.01 4.62 4.06	4.42 0.01 4.68 4.07	4.24 0.02 4.68 4.49 0.04 4.19 4.68 4.09 4.12	4.16 0.03 4.72 4.01		4.14 0.04 4.55 4.15	4.17 0.01 5.21 0.01 4.16	4.19 0.03 4.81 4.05	4.11 0.01 4.15 4.19	4.24 0.01 4.34 4.11	4.44 0.01 4.08 4.2 4.15	4.50 0.02 4.13 0.01 4.25 4.05 0.02 3.97 4.15	4.28 0.03 4.06 4.19	4.28 0.01 4.29 4.08
	Fe 2+ Mn Fe 2+ Fe 2+	0.10 0 0.03 0.01	0.08 0.01 0.01 0	0.01 0 0.04 0.01	0.01 -0.01 0 0.02	0	0.01 0 0	0.01 0 0.06 0	0	0.01 0 -0.01 0.01	0 0	0 0.01		0	0 0	0		0	0 0.03 -0.01	0	0.11 0.01 0.01 -0.01	0.28 0.01 0.01 0.01	0.11 0.01 0.01 0	0	0.04 0 0.01	0	0.03 0.01 0 0.01	0.03 0.01 0 0	0	0.02 0 0	0	0.05 0 0 0
	Mn Mg Mn Mn	0.01 0.04 -0.01 0	0.01 0.01 0 0	0	0 0 0	0	0.01 0 0	0.01 0.01 0 0	0	0	0	0	0	0.01 0.02 0	0	0.01 0.02 0 0		0 0 0.01	0		0		0 0	0	0.01	0 0.01 0 0	0.01 0 0 0	0	0 0 0	0	0.01 0 0	0	0 0.01 -0.01 0	0	0 0	0	0	0 0	0	0	0.01 0 0 0
	Mg Ca Mg Mg	0.08 0.04 0.02 0	0.11 0.01 0 0	0 0.02 0 0	0.01 0.01 0 0	0 0.01 -0.01 0	0 0.02 0.04 0	0	0 0.02 0	0	0 0.01 0	0		0.01 0.06 0 0	0.10	0 0.01 0.06 0	0.07 0.12 0 0	0.19 0.05 0 0	0.10 0.08 0.01 0	0	0.01 0.16 0	0	0.03 0.11 0 0	0.02 0.12 0 0	0.11	0.01 0.23 0 0	0.02 0.10 0 0
	Ca Na Ca Ca	0.14 3.43 0.07 0.03	0.19 3.85 0.22 0.13	0.05 3.9 0.16 0.02	0.04 3.81 0.12 0.04	0.07 3.82 0.08 0.01	0.03 3.67 0.07 0.04 3.55 0.02 0.07 0.01 0.05	0.02 3.71 0.12 0.04		0.01 3.76 0.06 0.06	0.02 4.11 0.23 4.02 0.03	0.03 3.93 0.12 0.01	0.04 4.28 0.03 0.03	0.02 4.12 0.23 0.06	0.05 4.12 0.03 0.03 0.05	0.03 4.00 0.05 3.99 0.02 0.06 4.12 0.01 0.03	0.02 3.86 0.04 0.04	0.03 4.19 0.17 0.01
	Na K Na Na	3.55 0.24 3.92 3.98	3.41 0.01 4.01 3.87	3.84 0.01 4.06 3.91	3.90 0.01 4.22 3.98	3.75 0.01 4.29 3.93	3.85 0.07 4.18 4.36 0.15 3.52 4.14 4.01 3.96	3.82 0.06 4.09 3.99		3.83 0.24 4.30 3.96	3.81 0.03 3.68 0.01 3.85	3.61 0.21 4.16 4.00	3.20 0.01 3.98 3.94	3.72 0.09 3.7 3.85	3.45 0.03 3.93 3.93 3.97	3.49 0.07 3.93 0.19 3.70 3.94 0.07 4.03 3.95	3.93 0.12 3.95 3.96	3.56 0.04 3.79 4.00
	K Sum K K	0.17 19.96 0.05 0.01	0.11 19.94 0.04 0.02	0.02 20.03 0.12 0.01	0.02 19.92 0.01 0.01	0.13 20.03 0.01 0.01	0.02 19.85 0.03 0.01 19.70 0.19 0.01 19.93 0.01 0.11 0.01 0.02 0.01	0.01 21.63 0 0.03	0.02 21.7 21.45 21.77 0.10 0.24 0.03 0.01 0.01	0.37 21.89 0.01 0.02	0.12 21.98 0.03 0.01	0.18 21.69 0.01 0.02 0.01	0.27 21.8 0.01 21.73 21.89 0.10 0.02 0.01 0.01	0.03 21.6 0.01 0.03	0.20 21.78 0.02 0.01
	Sum An Sum Sum	19.97 0.01 21.56 20.04	19.89 0 21.7 20.01	20.21 0.01 21.93 19.98	20.13 0 21.81 20.04	20.18 0 21.95 21.80 21.84 21.70 21.95 20.12 19.85 20.08 0.01 0.01 0 19.98 20.04 20.04 20.02	20.13 0.01 21.81 0.02 20.05 0.01 21.67 20.06 19.95	20.09 0.03 21.90 20.02	19.72 0.01 20.05 20.00 20.00 20.02 20.20 19.89 0.02 0.04 0.03 20 20.01 0.03 19.95 0.03 20.01 20.03 19.95 20.05 20.02 20.02	20.06 0.05 20.01 20.06	19.94 0.02 20.02 20.03
	An Al An An	0.04 0.92 0.02 0.01	0.05 1 0.05 0.03	0.01 0.99 0.04 0.01	0.01 0.99 0.03 0.01	0.02 1 0.02 0	0.01 0.98 0.02 0.01 0.95 0.01 0.02 0 0.01	0 0.98 0.03 0.01		0 0.01 0.01 0.92	0.01 0.97 0.06 0.98 0.01	0.01 0.92 0.03 0	0.01 0.98 0.01 0.01	0 0.96 0.06 0.02	0.01 0.96 0.01 0.01 0.01	0.01 0.96 0.01 0.93 0.01 0.01 0.96 0 0.01	0 0.01 0.92 0.01	0.01 0.97 0.04 0
	Al Or Al Al	0.92 0.06 0.97 0.99	0.92 0 0.94 0.96	0.98 0 0.93 0.99	0.99 0 0.97 0.99	0.95 0 0.98 1	0.99 0.02 0.98 0.99 0.04 0.94 0.98 1 0.98	0.99 0.02 0.95 0.99		1 0.99 0.98 0.06	0.99 0.01 0.89 0.99	0	0.97 0.05 0.96 0.99	0.89 0 0.99 0.99	0.96 0.02 0.94 0.98	0.94 0.01 0.99 0.99 0.99	0.92 0.02 0.99 0.04 0.97 0.98 0.02 1 0.99	0.99 0.03 0.99 0.98	0.94 0.01 0.95 0.99
	Or Charge Or	0.04 0 0.01	0.03 0 0.01	0.01 0.17 0.03	0.01 0.09 0	0.03 0.43 0	0 -0.07 0.01	0	0.05 -0.69	0	0 0.08 0.03		5.24	0	0	0.01 5.44 0.06 5.09	0.03 5.71 0.01	0.10 6.00 0	0.03 6.18 0.01	0	0.05 5.29	0	0.07 5.76 0	0.03 5.29 0	5.81	0.01 4.99 0	0.05 5.55 0.01
	Charge Charge	0.02 5.39	-0.01 5.35	0.89 5.84	0.41 5.65	0.54 6.06	5.54	0.58 5.69	0.08 5.55		0.62 6.21			0.88 5.64			0.52 5.14		0.62 5.94	-1 0	0	0.59	0	0	0	0	0	0	0	0	0	0 0

  WL 19 SiO 2 (wt.%) 71.70 69.08 69.83 67.93 70.40 70.43 69.20 70.60 69.99 70.50 70.27 70.64 70.91 70.41 69.74 69.66 69.42 69.85 69.14 69.49 68.89 69.31 70.08 70.45

	T iO 2	0	0.04 0.02 0.02 0.02 0.03 0.13 0.05 0.02 0 0.01 0.03	0.02	0.01	0.01	0.01	0	0.01	0	-0.01	0.02	0.01	0.02	0.02
	Al 2 O 3	20													

  .80102.39 100.07 102.59103.04103.72 103.64 102.25 102.95 102.79 103.06 103.32 102.35 101.89 101.85 101.16 102.46 100.79 101.61 101.33 101.80 102.24 103.17

															11.83
	K 2 O	0.04	1.12 0.04 0.02 0.03 0.03 0.62 0.25 0.03 0.05 0.03 0.04	0.04	0.03	0.02	0.07	0.01	0.02	0.06	0.03	0.05	0.04	0.05	0.03
	Sum 98.35 101Number of ions on the basis 32												
	Si	12.													

  .01 20.11 19.94 19.95 19.93 19.95 19.99 19.96 19.99 19.89 19.94 19.94 19.97 19.94 19.98 20.01 19.97 19.95 20.04 20.00 19.95 19.95 

										01 0.01	0.01	0.01	0.01	0.01	0	0	0.01	0.01	0.01	0.01	0.01	0.02
	Na	1.89	3.42 3.95 4.08 3.87 3.87 3.51 3.81 3.93 3.88 3.92 3.81	3.88	3.88	3.92	3.85	3.94	3.97	3.92	3.88	3.99	3.94	3.88	3.88
	K	0.01	0.25 0.01 0 0.01 0.01 0.13 0.05 0.01 0.01 0.01 0.01	0.01	0.01	0	0.01	0	0	0.01	0.01	0.01	0.01	0.01	0.01
	Sum 19.87 20An 18.49 0.01 0.04	0	0	0	0	0.03 0.01 0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
	Al	0.99	0.90	1 0.99 1	0.99 0.93 0.98 1 0.99 1	0.99	1	1	1	0.99	1	1	0.99	1	1	0.99	0.99	0.99

  Tabela suplementar do manuscrito II. Continuação da Tabela D: Análises por microssonda eletrônica de K-feldspato e andesinalabradorita.Chlorite of filled pores (sulfide bearing rocks)Chlorite as alteration of residual augite (sulfide bearing rocks)Tabela suplementar do manuscrito II. Continuação da Tabela E: Análises por microssonda eletrônica de clorita.

	Sample Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: D) Feldspatos -K-feldspato e andesina-32_px 33_px 34_px 35_px 27_ve 28_ve 29_ve 30_ve 31_ve 5clat1_chl 12clat 20cla Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: E) Clorita Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: F) Esmectita labradorita. Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: E) Clorita Sample 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77	77	77
	Point SiO 2 (wt.%) 68.42 70.18 70.76 70.27 69.23 69.17 66.09 68.39 71.22 WL 19 WL 19 WL 19 WL 19 RFM 48 RFM 48 RFM 48 RFM 48RFM 48 RFM 48 RFM 48RFM 48 72.02 71.34 70.87 T iO 2 0 0 0.02 -0.01 0.01 0.02 0.03 0 0 0.01 0 0.02 13pln_1 21pln_1 3pln_2 5pln_2 16pln_3 Sample 10pln_1 11pln_1 14pln_1 21pln_1 41pln_2 8pln_2 10pln_2 12pln_2 18pln_1 20pln1 10pln4 55pl1 56pl1 57pl1 58pl1 DD 62 DD 62 DD 62 DD 62 DD 62 Point FM 13 FM 13 FM 13 FM 13 FM 13 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 FM 25 FM 25 FM 25 FM 25 SiO 2 (wt.%) 63.38 Sample Point 53.79 55.24 62.48 63.33 SiO 2 56.70 55.14 54.86 54.52 55.46 55.74 54.73 55.45 53.71 54.08 55.48 56.67 56.77 56.52 56.75 Sample RFM 48 RFM 48 RFM 48 RFM 48 RFM 48 RFM 48 RFM 48 RFM 48 WL13 WL13 WL13 WL13 WL13 WL13 WL13 WL13 WL13 WL13 Point 11cl 23_ve 13clat 14clat 15clat 17clat 19clat 21clat 1 / 1 . Ponto 11 Ponto 12 13 / 1 . Ponto 22 Ponto 23 24 / 1 . 25 / 1 . 26 / 1 . 27 / 1 . SiO 2 27.54 26.45 27.88 28.02 28.41 28.08 27.65 27.59 27.83 27.05 27.44 27.85 28.6 26.15 27.50 28.24 27.14 26.72 Point 1cla 2cla 3cla 4cla 5cla 6cla 9cla 10cla 11cla 13cla 14cla 15cla 16cla 17cla 18cla 19cla 23cla Representative chlorite compositions of matrix of andesite dike 42.12 40.31 40.18 43.54 42.48 42.60 42.74 38.87 40.46 42.32 45.29 38.99 43.80 39.63 41.91 40.71 42.79 SiO 2 Sample DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 DD 62 TiO 2 0.01 0.01 0.02 0.03 0.01 0 0.05 0.04 0.02 0.02 0.03 0.05 0.02 0.01 0.02 0.04 0.03
	20.04 20.32 20.26 20.16 20.48 20.45 20.25 20.08 21.01 0.01 T iO 2 0.08 0.05 0.10 0.09 0.09 0.05 0.07 0.01 0.03 0.02 0.04 0.02 0.03 0.05 0.05 0.04 0.09 20.51 0.02 0.07 20.32 20.41 0.06 0.01 3clay1 0.05 5clay1 2clay1 3clay1 4clay2 12clay 14clay 8.62 0.17 0.02 2clay1 8.77 8.42 8.56 6.41 8.38 8.40 8.11 9.29 7.42 8.71 7.75 Al 2 O 3 FeO 0.11 0.03 0.05 0.05 0.26 0.43 2.94 0.24 0.5 0.59 19.46 18.77 18.26 Al 2 O 3 25.81 27.01 27.33 27.57 27.00 27.02 27.77 27.16 28.07 27.86 27.11 27.28 26.91 26.97 26.85 0.09 0.09 0.10 0.10 0.11 0.01 0.06 0.06 0.09 8.62 7.64 7.58 6.95 19.47 19.06 18.73 19.51 21.73 21.53 18.70 19.34 18.56 18.03 18.92 17.70 17.79 16.95 17.71 18.66 30.94 30.06 29.67 29.64 31.01 29.73 28.82 30.36 12.83 12.73 12.33 12.29 9.82 12.10 12.90 11.90 12.33 12.22 12.20 10.96 11.10 10.40 10.35 10.09 0.42 0.19 MnO 0.02 0.03 0.02 0.02 0 -0.04 0.01 -0.01 -0.01 -0.01 0 0.1 0 FeO 0.53 0.54 0.52 0.55 0.47 0.59 0.60 0.59 0.58 0.55 0.52 0.68 0.56 0.54 0.61 29.89 30.46 30.11 29.94 27.84 28.33 29.58 26.11 28.50 30.01 23.39 29.41 24.98 28.62 29.72 28.77 0.01 0.02 0.04 0.05 0.04 0.02 0.03 0.03 0.15 0.13 0.12 0.16 0.12 0.15 0.20 0.11 0.16 0.20 0.18 0.12 0.12 0.13 0.14 0.12 0.01 0.04 MgO -0.01 0.01 -0.01 -0.01 0 0.01 1.42 0.02 0.04 0 0 0.01 -0.01 -0.02 MnO -0.01 0.01 0.02 -0.04 0.03 0.01 0.01 -0.02 0.01 0 0 0 0.03 -0.05 0 0.05 0.06 0.03 0.07 0.03 0.05 0.09 0.19 0.13 0.06 0.21 0.10 0.09 0.11 0.12 0.11 12.40 11.95 11.81 13.90 13.44 12.61 15.01 14.97 19.45 19.97 20.75 20.31 18.44 20.68 18.66 18.70 21.23 20.30 18.50 19.94 18.67 18.93 18.62 18.84 0.01 CaO 0.03 0.03 0.04 0.06 0.07 0.11 0.04 0.05 0.07 0.06 0.07 0.04 Na 2 O 11.91 11.89 11.86 11.83 11.89 11.91 10.60 12.05 11.58 11.94 12.11 12.10 K 2 O 0.04 0.04 0.06 0.02 0.05 0.10 0.16 0.02 0.31 0.09 0.09 0.04 Sum 100.50 102.31 102.95 102.43 102.09 102.19 101.31 100.82 104.63 105.01 104.35 103.59 0.01 -0.01 0.01 MgO 0.06 0.07 0.08 0.07 0.06 0.08 0.08 0.08 0.07 0.09 0.06 0.11 0.11 0.10 0.11 -0.02 -0.02 -0.03 CaO 8.74 9.99 10.49 10.80 9.47 9.71 10.59 9.89 10.69 10.76 9.85 9.71 9.46 9.65 11.10 10.85 10.62 11.15 11.28 10.46 10.20 10.14 10.08 9.52 12.44 9.090 10.80 9.74 9.25 9.29 28.91 30.68 29.79 28.52 27.17 29.57 29.41 25.80 1.14 1.17 1.24 1.28 1.62 1.25 1.36 1.80 1.33 1.74 1.49 1.79 1.69 1.49 1.44 1.56 9.50 0.16 0.32 0.05 Na 2 O 6.10 5.21 4.83 4.88 5.38 5.35 5.10 5.33 4.93 4.78 5.32 5.41 5.50 5.47 5.60 12.96 15.99 16.33 K 2 O 0.64 0.76 0.68 0.63 0.89 0.81 0.67 0.80 0.70 0.66 0.80 0.58 0.60 0.57 0.58 87.99 97.67 97.94 Sum 98.64 98.79 98.91 99.07 98.85 99.36 99.62 99.38 98.82 98.84 99.24 100.54 100.04 99.86 100.10 Number of ions on the basis 32 0.08 0.09 0.13 0.08 0.08 0.05 0.19 0.23 0.20 0.22 0.22 0.22 0.25 0.22 0.23 0.19 0.04 0.05 0.03 0.03 0.02 0.02 0.03 0.03 0.04 0.03 0 0.04 0.01 0.01 0.03 0.19 0.19 0.18 0.28 0.32 0.19 0.44 0.42 0.15 0.05 0.07 0.09 0.14 0.06 0.05 0.08 0.08 0.09 0.10 0.08 0.06 0.09 0.10 0.13 0.03 0.05 0.03 0.21 0.05 0.02 0.18 0.04 0.11 0.10 0.09 0.20 0.03 0.10 0.14 0.07 14.73 14.09 13.93 14.01 15.04 14.14 13.73 15.08 0.18 0.25 0.36 0.26 0.15 0.13 0.16 0.14 0.12 0.11 0.15 0.10 0.32 0.12 0.15 0.14 0.08 88.59 88.64 88.30 88.92 88.69 88.23 86.70 83.26 85.09 85.85 84.01 82.76 81.52 84.09 84.33 0.19 0.11 0.14 0.24 0.28 0.15 0.17 0.54 3.74 3.76 3.95 3.88 3.66 3.90 3.63 3.69 3.95 3.99 3.63 3.88 3.65 3.71 3.63 3.72 83.94 -0.01 0 0.02 0.03 0.02 0.03 0.02 86.58 87.03 90.83 89.33 82.97 89.44 84.26 85.02 90.83 91.39 83.98 88.45 83.86 84.44 82.75 84.35 0.01 Number of ions on the basis 32 Si 11.90 11.95 11.98 11.97 11.88 11.86 11.55 11.88 11.90 11.97 10.47 11.84 12 Si 10.35 10.09 10.02 9.96 10.13 10.56 10.37 10.51 10.18 10.25 10.51 10.16 10.22 10.19 10.21 5.88 5.92 6.01 5.89 5.73 5.76 5.99 5.96 6.00 6.07 6.12 5.95 6.15 6.24 6.04 5.94 0.09 0.04 0.04 0.08 0.09 0.02 0.06 Number of ions on the basis 22 T iO 2 0.09 0.16 T iO 2 0.02 0 Point Al 2 O 3 8.79 Al 2 O 3 18.42 19.44 Al 2 O 3 19.76 21.19 SiO 2 FeO 13.19 FeO 0.19 0 FeO 29.53 30.71 T iO 2 MnO 0.15 MnO 0.07 -0.06 MnO 0.09 0.08 Al 2 O 3 MgO 20.70 MgO 0 -0.02 CaO 0.10 0 MgO 11.10 10.01 FeO CaO 1.09 Na 2 O 0.50 0.23 K 2 O 15.76 12 Sum 98.51 85.54 Number of ions on the basis 32 CaO 0.05 0.02 Na 2 O 0 0.01 MnO Na 2 O 0.07 K 2 O 0 0.01 MgO K 2 O 0.19 Sum 88.09 88.49 CaO H 2 O 3.90 Number of ions on the basis 28 Na 2 O Sum 90.22 Si 12.01 10.19 Si 5.83 5.62 K 2 O 0.09 11.96 11.95 Ti 0 0 0 0 0 0 0 0 0 0 0 Ti 0.01 0.02 0.02 0.01 0 Ti 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Al iv 2.17 2.38 2.12 2.08 1.99 2.11 2.27 2.24 2.01 2.04 2.00 1.93 1.88 2.05 1.85 1.76 1.96 2.06 Sum 87.45 87.14 85.6 86.76 87.41 86.47 87.7 Si 6.47 6.46 6.41 6.61 6.56 6.98 6.58 6.43 6.58 6.43 6.81 6.44 6.77 6.52 6.77 6.73 6.90 87.28 0 Al 4.11 4.08 4.04 4.05 4.14 4.13 4.17 4.11 4.14 4.02 Al 4.11 4.34 4.35 4.19 4.08 Al 5.55 5.83 5.89 5.94 5.81 6.03 6.20 6.07 6.27 6.22 6.05 5.77 5.71 5.73 5.70 Sum iv 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 Al iv 1.53 1.54 1.59 1.39 1.44 1.02 1.42 1.57 1.42 1.57 1.19 1.56 1.23 1.48 1.23 1.27 1.10 Number of ions on the basis 28 4.02 4.06 Fe 2+ 0.02 0 0.01 0.01 0.04 0.06 0.43 0.03 0.07 0.08 Fe 2+ 0.03 0 0 0.02 0 Fe 2+ 0.08 0.08 0.08 0.08 0.07 0.09 0.09 0.09 0.09 0.09 0.08 0.1 0.08 0.08 0.09 Al vi 2.79 2.95 2.75 2.70 2.72 2.75 3.08 3.11 2.77 3.03 2.82 2.75 2.95 2.73 2.89 2.7 2.73 2.87 Si 6.62 6.55 6.56 6.40 6.56 6.49 6.20 Sum iv 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 6.39 0.06 0.03 Mn 0 0 0 0 0 -0.01 0 0 0 0 0 Mn 0.01 -0.01 0 0 0 Mn 0 0 0 -0.01 0.01 0 0 0 0 0 0 0 0 -0.01 0 Ti 0 0 0 0 0 0 0.01 0 0 0.01 0.01 0.01 0 0 0 0.01 0.01 0.01 Al iv 1.38 1.45 1.44 1.60 1.44 1.51 1.80 Al vi 0.07 0.09 0.06 0.11 0.12 0.22 0.10 0.07 0.13 0.09 0.12 0.14 0.18 0.19 0.23 0.20 0.22 1.61 0.01 Mg 0 0 0 0 0 0 0.37 0 0.01 0 0 0 Ca 0 0 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 Na 4.02 3.93 3.89 3.91 3.96 3.96 3.59 4.06 3.75 3.85 3.94 3.95 K 0.01 0.01 0.01 0 0.01 0.02 0.04 0 0.07 0.02 Mg 0 -0.01 0 0 0 Mg 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.03 0.03 0.03 0.03 Ca 0.02 0 0 0 -0.01 Ca 1.71 1.96 2.05 2.11 1.85 1.97 2.15 2.01 2.17 2.18 2.00 1.87 1.82 1.86 1.83 Na 0.18 0.09 0.06 0.12 0.02 Na 2.16 1.85 1.71 1.73 1.91 1.97 1.88 1.96 1.81 1.76 1.95 1.88 1.92 1.91 1.96 K 3.81 2.9 3.13 3.86 3.95 K 0.15 0.18 0.16 0.15 0.21 0.20 0.16 0.19 0.17 0.16 0.19 0.13 0.14 0.13 0.13 Sum 20.19 17.53 18.03 20.03 20.04 Sum 20.02 20.01 19.95 20.00 20.01 20.85 20.89 20.86 20.72 20.69 20.83 19.95 19.94 19.95 19.97 Fe 3+ 0.35 0.31 0.33 0.33 0.38 0.35 0.45 0.46 0.42 0.54 0.44 0.45 0.57 0.37 0.57 0.52 0.42 0.45 Fe 2+ 4.88 5.14 4.94 5.05 4.95 4.90 4.38 4.48 4.91 4.27 4.77 5.02 3.61 5.23 4.11 4.77 5.11 4.90 Mn 0.02 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.04 0.02 0.01 0.04 0.02 0.02 0.02 0.02 0.02 Mg 3.50 3.17 3.49 3.42 3.35 3.49 3.49 3.26 3.27 3.33 3.28 3.09 3.97 3.09 3.60 3.21 3.07 3.08 Ca 0.01 0 0.02 0.02 0.03 0.02 0.02 0.01 0.04 0.06 0.05 0.05 0.05 0.05 0.06 0.05 0.06 0.04 Sum iv 8 8 8 8 8 8 8 Ti 0 0 0 0 0 0 0.01 0 0 0 0 0.01 0 0 0 0 0 8 Al vi 1.76 1.63 1.65 1.95 1.93 1.74 2.01 Fe 2+ 1.70 1.72 1.70 1.56 1.59 1.35 1.56 1.78 1.62 1.57 1.54 1.69 1.42 1.53 1.41 1.43 1.36 2.13 Ti 0 0 0.01 0.01 0.01 0 0 Mn 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0 Mg 4.74 4.65 4.75 4.69 4.68 4.5 4.75 4.6 4.53 4.81 4.55 4.56 4.59 4.58 4.56 4.59 4.53 Fe 3+ 0.20 0.10 0.12 0.19 0.27 0.12 0.11 0.28 Ca 0.18 0.20 0.20 0.20 0.21 0.28 0.21 0.24 0.31 0.22 0.28 0.26 0.30 0.30 0.26 0.26 0.27 0.02 0.01 Sum 20.06 19.98 19.95 19.96 20.03 20.06 20.17 20.10 19.94 19.95 20.01 20.01 An 0.01 0 0 0 0 An 0.43 0.49 0.52 0.53 0.47 0.48 0.51 0.48 0.52 0.53 0.48 0.48 0.47 0.48 0.47 Na 0 0.01 0.04 0.04 0.03 0.02 0.02 0.02 0.03 0.02 0.03 0.02 0 0.04 0.01 0.01 0.02 0.03 Fe 2+ 4.97 5.49 5.39 4.96 4.54 5.27 5.18 4.26 Na 0.02 0.05 0.02 0.02 0.03 0.04 0.02 0.02 0.02 0.02 0.03 0.03 0.02 0.02 0.03 0.03 0.04
	Al K K	0.05 0	Mn	0.03 0 0.04	An 0.03 0.03 0.02 0.03 0.04		0 0.05 0.02 0.04	0	Al 0.11 0.03 0.07	0	0 0.05 0.54 0.02 0.05	0 0.46 0.01 0.06 0.03	0 0.44 0.09 0.04 0.03	0.01 0.43 0.02 0.03 0.08 0.48 0 0.06 0.03	0 0.48 0.06 0.07 0.02 0.45 0	0 0.47 0.05 0.02	0.44 0.11 0.03	0	0.43 0.02 0.02	0	0.47 0.05 0.07	0.48 0.08 0.02	0.49	0.49 0.04 0.03	0.50 0.05 0.03
	Or OH OH Charge R 2+ R 2+ R 3+ R 3+ 4Si 4Si	0.95 16 0.54 8.40 Mg Ca 3.14 Na 1.46 K	0.97 16 4 -7.16 8.33 6.46 3.27 0.07 1.40 1.62	Al 16 0.98 4.70 4 Or 0.97 -5.81 -0.05 8.43 0.04 6.39 Charge 3.08 0 0.09 1.47 0.05 1.62	1 0 0.18 Charge 1 1 Or 16 4.58 16 4.59 4 4 0 8.48 8.30 0.03 0.03 6.47 6.27 0 0 3.04 3.09 0 0.01 0.06 0.11 1.48 1.50 0.02 0.02 1.60 1.65	1 4.51 0.04 16 4 0 0 8.40 0.06 6.29 0 3.10 0.02 0.12 1.47 0.05 1.64	1 0.04 16 4.74 4 0 0 7.87 0.06 5.87 0 3.53 0.01 0.22 1.43 0.05 1.74	0.99 0.04 16 4.60 4 0 0 7.75 0.04 6.32 0 3.58 0.03 0.10 1.44 0.01 1.64	0.99 0.04 16 4 0.01 0 8.20 6.41 4.40 0.99 0.05 16 4 0.01 0 7.64 0.04 6.17 0 0 3.19 3.57 0.01 0.07 0.13 1.50 1.49 0.04 1.61 1.64	1 0.05 4.73 0 2.71 8.07 16 4 0.12 6.40 0.04 0.98 0.02 2.69 0 0 3.26 0 0.09 1.50 0.05 1.61	0.99 0.05 0 2.67 8.13 16 4 7.62 0.04 0.99 16 4 0 2.09 8.33 0.04 16 4 2.19 6.11 6.27 6.03 0 0 3.20 3.52 3.11 0.12 0.14 0.18 1.52 1.53 1.49 1.70 1.61 1.69	1 0 0	0.05 16 4 2.61 7.72 6.12 3.46 0.19 1.54 1.63	0.03 16 4 0 8.00 5.98 3.22 0.23 1.56 1.69	0.04 0	0.03 16 4 0 8.20 6.04 3.15 0.2 1.51 1.68	0.03 16 4 0 8.00 5.91 3.32 0.22 1.49 1.73
	3R 2+ Fe/Fe+Mg 3R 2+ M + M + Charge Charge	2.80 0.58 OH 0.02 R 2+ 0.09 R 3+	2.78 0.62 2.15 0.02 0.42 0.09 -0.04	2.81 0.59 16 2.13 0.10 9.70 0.48 0.07 1.96 -0.04	2.83 0.60 16 2.16 0.10 10.11 0.47 0.08 1.72 -0.05		2.77 0.60 16 2.09 0.20 10.02 0.49 0 1.77 -0.07		2.80 0.58 16 2.10 0.08 9.52 0.50 0.07 2.13 -0.05	2.62 0.56 16 1.96 0.06 9.34 0.64 0.12 2.20 -0.03	2.58 0.58 2.11 16 0.13 9.91 0.46 0.06 1.87 -0.03	2.73 0.60 2.14 0.14 9.66 16 0.53 0.09 2.12 -0.03	2.55 0.56 2.06 0.19 0.68 0.10 -0.03 9.06 16 2.41	2.69 0.59 2.13 0.18 0.48 0.07 -0.02	2.71 0.62 2.04 0.18 0.61 0.07 -0.02	2.54 0.48 2.09 0.21 0.59 0.05 -0.03		2.78 0.63 2.01 0.16 0.64 0.08 -0.02		2.57 0.53 2.04 0.18 0.68 0.10 -0.07	2.67 0.60 1.99 0.19 0.57 0.05 -0.02	2.73 0.62 2.01 0.17 0.57 0.08 -0.03	2.67 1.97 0.61 0.61 0.16 0.08 -0.03
			4Si		1.65		1.64		1.64		1.60	1.64	1.62	1.55		1.60								
			3R 2+	3.23		3.37		3.34		3.17	3.11	3.30	3.22		3.02								
			Fe/Fe+Mg	0.51		0.55		0.54		0.52	0.49	0.53	0.54		0.47								
			M +		0.13		0.08		0.11		0.18	0.19	0.11	0.13		0.30								
			Charge	-0.01		0		0		0	0	0.01	-0.01		0.01								

Tabela suplementar do manuscrito II. Tabela E: Análises por microssonda eletrônica de clorita.

Tabela suplementar do manuscrito II. Tabela F: Análises por microssonda eletrônica de esmectita.

Continuação da TABELA SUPLEMENTAR DO MANUSCRITO II: G) Interestratificados clorita/esmectita

  Tabela suplementar do manuscrito II. Continuação da Tabela G: Análises por microssonda eletrônica de interestratificados clorita/esmectita.FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 FM 25 WL 19 WL 19 WL 19 WL 19 WL 19 WL 19 

	Sample																		
	Point	23_cla 24_cla 25_cla 26_cla 27_cla 28_cla 30_cla 31_cla 24_cla 25_cla 28_cla 29_cla 30_cla 31_cla
	SiO 2	34.01	32.40	32.97	32.92	35.29	32.25	32.35 32.15 31.29	32.41	31.50	31.29		32.53 31.43 31.88 33.58
	TiO 2 TiO 2	0 0	0.02 0.01	0.02 0.01	0.02 0.01	-0.01 0.02	0	0.02	0.03 -0.01	0	0.01	0.05 0.03	0.02 0.02	0.05	0.08	0.03	0.01 0.14	0.01 0.06	0.02 0.03
	Al 2 O 3 Al 2 O 3	12.17 11.96 12.59 11.95 12.56 13.14 8.32 12.69 12.80 13.08 13.37 12.18 12.59 12.59 12.56 15.59 12.56 11.98 12.76 12.82 13.20 12.76 13.16 14.60 15.58 15.89 14.35 15.85 11.38
	FeO FeO	20.17 21.07 21.38 19.91 21.16 22.40 16.01 20.94 20.33 21.22 21.85 21.88 21.76 21.55 21.18 21.77 21.77 21.62 20.9 21.02 21.17 21.87 17.49 16.10 17.4 17.01 18.18 16.93 17.91
	MnO MnO	0.15 0.21	0.21 0.20	0.25 0.19	0.24 0.23	0.17 0.23	0.20 0.21	0.13 0.21	0.28 0.21	0.18 0.35	0.19 0.37	0.18	0.36	0.15	0.21 0.34	0.20 0.32	0.14 0.41
	MgO MgO	20.22 20.05 19.31 18.43 19.55 19.47 17.86 19.60 20.93 20.77 17.99 18.28 18.40 19.24 19.94 19.17 19.43 19.16 20.88 19.23 19.06 18.83 17.90 18.89 18.43 18.30 18.47 18.66 20.45
	CaO CaO	0.49 0.48	0.39 0.39	0.35 0.38	0.44 0.47	0.42 0.49	0.38 0.41	0.63 0.21	0.45 0.25	0.73 0.29	0.60 0.23	0.43	0.25	0.38	0.40 0.28	0.40 0.32	0.56 0.29
	Na 2 O Na 2 O	0.07 0.08	0.05 0.04	0.05 0.06	0.05 0.08	0.07 0.06	0.05 0.06	0.04 0.06	0.08 0.05	0.12 0.07	0.07 0.08	0.06	0.08	0.07	0.03	0	0.05 0.06	0.06 0.08
	K 2 O K 2 O	0.05 0.01	0.02 0.03	0.01 0.04	0.05 0.04	0.05 0.03	0.01 0.03	0.03 0.09	0.03 0.08	0.03 0.03	0.08 0.03	0.03	0.05	0.04	0.01 0.05	0.05 0.03	0.02 0.03
	Sum Sum	88.01 87.55 86.19 84.25 87.65 88.98 73.30 87.42 89.40 90.27 83.55 85.75 85.41 87.18 88.60 86.81 87.92 87.89 90.09 85.82 85.74 86.00 83.04 82.73 83.75 83.33 83.23 84.16 84.12
	Number of ions on the basis 28 Number of ions on the basis 28															
	Si Si	6.95 6.82	6.86 6.69	6.69 6.70	6.95 6.69	6.83 6.93	6.71 6.71	7.23 6.74	6.81 6.71	6.93 6.56	6.80 6.75	6.53	6.55	6.64	6.69 6.52	6.67 6.62	6.98 6.56
	Al iv Al iv Sum iv Sum iv Al vi Al vi Ti Ti	1.05 1.18 8 8 1.84 1.84 0 0	1.14 1.31 8 8 1.75 1.82 0 0	1.31 1.30 8 8 1.79 1.86 0 0	1.05 1.31 8 8 1.93 1.91 0 0	1.17 1.07 8 8 1.85 1.77 0 0	1.29 1.29 8 8 1.84 1.82 0 0	0.77 1.26 8 8 1.59 1.85 0 0	1.19 1.29 8 8 1.84 1.82 0 0	1.07 1.44 8 8 1.74 2.45 0.01 0	1.20 1.25 8 8 1.78 2.37 0 0	1.47 8 1.81 0.01	1.45 8 2.40 0.01	1.36 8 1.91 0	1.31 1.48 8 8 1.87 2.46 0 0.02	1.33 1.38 8 8 1.87 2.21 0 0.01	1.02 1.44 8 8 1.79 2.45 0 0
	Fe 3+ Fe 3+ Fe 2+ Fe 2+ Mn Mn Mg Mg Ca Ca Na Na K K R 2+ R 2+ R 3+ R 3+ 4Si 4Si 3R 2+ 3R 2+ M + M + Charge	0.43 0.36 2.95 3.20 0.03 0.04 6.04 5.96 0.10 0.10 0.05 0.06 0.02 0.01 9.01 9.19 2.27 2.20 1.74 1.70 3.00 3.06 0.29 0.27 0.06	0.34 0.28 3.24 3.48 0.04 0.03 6.07 5.90 0.08 0.09 0.04 0.03 0.01 0.02 9.35 9.41 2.09 2.10 1.72 1.67 3.12 3.14 0.22 0.22 0.04	0.27 0.30 3.45 3.40 0.04 0.03 5.98 5.89 0.08 0.08 0.04 0.05 0.01 0.02 9.47 9.32 2.06 2.16 1.67 1.68 3.16 3.11 0.21 0.23 0.04	0.49 0.32 3.00 3.35 0.04 0.04 5.76 5.80 0.10 0.10 0.04 0.06 0.03 0.02 8.81 9.19 2.42 2.23 1.74 1.67 2.94 3.06 0.27 0.28 0.04	0.37 0.38 3.22 3.05 0.03 0.04 5.91 6.11 0.09 0.10 0.05 0.05 0.03 0.02 9.16 9.20 2.22 2.15 1.71 1.73 3.05 3.07 0.27 0.27 0.05	0.30 0.29 3.47 3.37 0.03 0.04 5.84 5.97 0.08 0.09 0.04 0.05 0.01 0.02 9.35 9.37 2.15 2.11 1.68 1.68 3.12 3.12 0.21 0.24 0.04	0.46 0.31 2.74 3.38 0.03 0.04 6.37 5.92 0.16 0.05 0.04 0.05 0.02 0.05 9.13 9.33 2.06 2.16 1.81 1.68 3.04 3.11 0.38 0.19 0.01	0.35 0.28 3.21 3.54 0.05 0.04 5.94 5.86 0.10 0.06 0.06 0.04 0.01 0.04 9.20 9.43 2.20 2.10 1.70 1.68 3.07 3.14 0.27 0.19 0.01	0.36 0.55 3.00 2.51 0.03 0.06 6.17 5.59 0.16 0.06 0.09 0.06 0.02 0.01 9.19 8.16 2.10 3.00 1.73 1.64 3.06 2.72 0.42 0.20 0.11	0.31 0.61 3.18 2.19 0.03 0.07 6.10 5.86 0.13 0.05 0.06 0.06 0.04 0.02 9.31 8.12 2.09 2.98 1.70 1.69 3.10 2.71 0.35 0.18 0.11	0.18 3.77 0.03 5.81 0.1 0.05 0.02 9.61 2 1.63 3.20 0.27	0.52 2.50 0.06 5.71 0.06 0.06 0.03 8.27 2.92 1.64 2.76 0.21 0.09	0.30 3.53 0.03 5.70 0.09 0.06 0.02 9.26 2.21 1.66 3.09 0.25	0.32 0.56 3.51 2.40 0.04 0.06 5.76 5.68 0.09 0.06 0 0.02 0.01 0.03 9.31 8.15 2.19 3.02 1.67 1.63 3.1 2.72 0.18 0.17 0.10	0.29 0.46 3.40 2.74 0.03 0.06 5.88 5.80 0.09 0.07 0.04 0.05 0.03 0.01 9.32 8.60 2.17 2.68 1.67 1.65 3.11 2.87 0.24 0.21 0.08	0.56 0.43 2.36 2.68 0.07 0.03 5.73 6.34 0.06 0.12 0.06 0.05 0.02 0.01 8.16 9.05 3.01 2.22 1.64 1.75 2.72 3.02 0.21 0.31 0.11
	Charge	0.05	0.05	0.04	0.06	0.04	0.05	0.04	0.05	0.05	0.02	0.02		0.04	0.05	0.03	0.06

Lopes, R.W., 2017. Mineralizações e argilominerais da Mina do Seival (Cu-Ag), Bacia do Camaquã. 1° SISBRAMME. Porto Alegre, Brasil.

Rodrigo W. Lopes, André S. Mexias, Christophe Renac, Eduardo Fontana, Aurélie Barats, Gabriel B. Drago, 2017. Geoquímica de Elementos Terras Raras em veios hidrotermais de barita, Mina do Seival, Bacia do Camaquã, Neoproterozoico. XVI Congresso Brasileiro de Geoquímica. Búzios, RJ.

Acknowledgements

This study is part of the co-tutela doctoral thesis of Rodrigo Winck Lopes at Universidade Federal do Rio Grande do Sul (Brazil) and Université Côte d´Azur (France). R.P. Philipp expresses thanks for the research grant from the Brazilian National Council for Scientific and Technological Development (CNPq). We wish to thank the CNPq, CAPES and Programa Ciências Sem Fronteiras (Process number: 200081/2014-4) for financial support and Votorantim Metais for allowing access to drill-cores. We wish to thank Luiz F. G. Morales and anonymous reviewers for the review and suggestions as well as and Reinhardt A. Fuck for thorough editorial support. We wish to thank Maria José M. de Mesquita for additional review, and Marcelo Lindenberg, Bruno Petracco and Amós Martini for help in sampling and fieldworks.

Acknowledgements

This study is part of the cotutelle doctoral thesis of Rodrigo Winck Lopes at Universidade Federal do Rio Grande do Sul and Université Côte d´Azur. We wish to thank the Conselho Nacional do Desenvolvimento e Pesquisa (CNPq), CAPES and Programa Ciências Sem Fronteiras (Process number: 200081/2014-4) for financial support. We thank Votorantim Metais for allowing access to drill-cores. We thank Robert Ayuso, Karel Breiter, Douglas Kreiner, Bruno Lemiere and anonymous reviewer for their constructive remarks during the reviewing and editing processes.

We wish to thank Everton Bongiolo and Maria José Mesquita for additional revision.

We wish to thank the members of the research group Marcelo Lindenberg, Bruno Petracco and the technician laboratory: Denise Canarim, Susan Drago, Edgar Bercht and Lucas Jantsch.

ACKNOWLEDGMENTS

This study is part of the co-tutela doctoral thesis of Rodrigo Winck Lopes at Universidade Federal do Rio Grande do Sul and Université Côte d´Azur. We wish to

A tese foi realizada na forma de doutorado sanduíche em acordo de cotutela entre a Universidade Federal do Rio Grande do Sul (Brasil) e a Université Côte D´Azur (França). Sul Mining District and Seival Mine deposits, Camaquã Basin, southern Brazil", publicado no Journal of South America Earth Science. O segundo manuscrito é intitulado "Mineral assemblages and temperature associated with Cu-enrichment in the Seival area (Camaquã Basin, Neoproterozoic of Southern Brazil)", submetido ao Journal of Geochemical Exploration. O terceiro manuscrito é intitulado "Composition and REE analysis of barite from Seival Mine Cu-Ag deposits (Camaquã Basin, Neoproterozoic of Southern Brazil)", submetido ao Brazilian Journal of Geology. O capítulo 5 contém as considerações finais da tese na forma de uma síntese integradora das principais conclusões obtidas. No capitulo 6 são listadas as referências bibliográficas citadas nos capítulos que antecedem os manuscritos, permanecendo as referências dos artigos listados nos mesmos. Nos anexos consta a capa do artigo publicado em co-autoria (ANEXO A) e os resumos de trabalhos apresentados durante o período de doutoramento (ANEXO B), com o objetivo de mostrar o avanço no conhecimento sobre o tema. Também são apresentados o mapa de pontos (ANEXO C), a tabela de pontos (ANEXO D), as medidas estruturais (ANEXO E), os dados de microssonda eletrônica (ANEXO F) e os difratogramas de raios X (ANEXO G). A Mina do Seival tem sido investigada pelo presente autor desde a Graduação em Geologia com o projeto temático intitulado "Alteração Hidrotermal e Mineralizações de Cobre na Mina do Seival, Bacia do Camaquã, RS", que caracterizou a alteração hidrotermal na área, bem como forneceu um mapa geológico de detalhe para a continuidade dos estudos. Em continuidade, o projeto de mestrado intitulado "Caracterização petrográfica e geoquímica da Mina do Seival, Bacia do Camaquã, RS" teve como objetivo fornecer informações sobre a UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES Winck LOPES -2018-Tese de doutorado / THÈSE petrografia e geoquímica das rochas da região da Mina do Seival, bem como caracterizar as minas e as ocorrências de cobre. UNIVERSIDADE -2018-Tese de doutorado / THÈSE solicitada e o manuscrito foi aceito para publicação em

MANUSCRITO II | 156 Rodrigo Winck LOPES -2018-Tese de doutorado / THÈSE Janikian, L., Almeida, R.P., Trindade, R.I.F., Fragoso-Cesar, A.R.S., D´Agrella-Filho, M.S., Dantas, E.L., Tohver, E., 2008. The continental record of Ediacaran volcano-sedimentary successions in southern Brazil and their global implications. Terra Nova, 20, 259-266. Janikian, L., Almeida, R.P., Fragoso-Cesar, A.R.S., Martins, V.T.S., Dantas, E.L., Tohver, E., McReath, I., D'Agrella-Filho, M.S., 2012. Ages (U-Pb SHRIMP and LA ICPMS) and stratigraphic evolution of the Neoproterozoic volcano-sedimentary successions from the extensional Camaquã Basin, Southern Brazil. Gondwana Research, 21, 466-482. Kaur, P., Chaudhri, N., Hofmann, A., Raczek, I., Okrusch, M., Skora, S., 2012. Two-Stage, extreme albitization of A-type granites from Rajasthan, NW India. Journal of Petrology, 53, 919-948. Kendrick, M.A., Mark, G., Phillips, D., 2007. Mid-crustal fluid mixing in a Proterozoic Fe oxide-Cu-Au deposit, Ernest Henry, Australia: Evidence from Ar, Kr, Xe, Cl, Br and I. Earth and Planetary Science Letters, 256, 328-343. Kontonikas-Charos, A., Ciobanu, C.L., Cook, N.J., 2014. Albitization and redistribution of REE and Y in IOCG systems: Insights from Moonta-Wallaroo, Yorke Peninsula, South Australia. Lithos, 208-209, 178-201. Laux, J.H., Lindenmayer, Z.G., Teixeira, J.B.G., Neto, A.B., 2005. Ore genesis at the Camaquã copper mine, a neoproterozoic sediment-hosted deposit in Southern Brazil. Ore Geology Review, 26, 71-89. Lima, E.F., Nardi, L.V.S., 1998. The Lavras do Sul Shoshonitic Association: implications for origin and evolution of neoproterozoic shoshonitic magmatism in southernmost Brazil. Journal of South American Earth Science, 11, 67-77. Liz, J.D., Lima, E.F., Nardi, L.V.S., Sommer, C.A., Saldanha, D.L., Pierosan, R., 2009. Petrologia e sucessão estratigráfica das rochas monzoníticas da associação shoshonítica de Lavras do Sul (RS). Revista Brasileira de Geologia (Portuguese -Brazil), 39, 244-255. Lopes, R.W., Fontana, E., Mexias, A.S., Gomes, M.E.B., Nardi, L.V.S., Renac, C., 2014. Caracterização petrográfica e geoquímica da sequência magmática da UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL INSTITUTO DE GEOCIÊNCIAS -PPGGEO UNIVERSITÉ CÔTE D´AZUR SCIENCES FONDAMENTALES ET APPLIQUÉES MANUSCRITO II | 157 Rodrigo Winck LOPES -2018-Tese de doutorado / THÈSE Mina do Seival, Formação Hilário (Bacia do Camaquã -Neoproterozoico), Rio Grande do Sul, Brasil. Pesquisas em Geociências (Portuguese -Brazil), 41, 51-64.