Pinguino In-bearing polymetallic vein deposit, Deseado Massif, Patagonia, Argentina: characteristics of mineralization and ore-forming fluids

The Pinguino deposit, located in the low sulfidation epithermal metallogenetical province of the Deseado Massif, Patagonia, Argentina, represents a distinct deposit type in the region. It evolved through two different mineralization events: an early In-bearing polymetallic event that introduced In, Zn, Pb, Ag, Cd, Au, As, Cu, Sn, W and Bi represented by complex sulfide mineralogy, and a late Ag-Au quartz-rich vein type that crosscut and overprints the early polymetallic mineralization. The indium-bearing polymetallic mineralization developed in three stages: an early Cu-Au-In-As-Sn-W-Bi stage (Ps(1)), a Zn-Pb-Ag-In-Cd-Sb stage (Ps(2)) and a late Zn-In-Cd (Ps(3)). Indium concentrations in the polymetallic veins show a wide range (3.4 to 1,184 ppm In). The highest indium values (up to 1,184 ppm) relate to the Ps(2) mineralization stage, and are associated with Fe-rich sphalerites, although significant In enrichment (up to 159 ppm) is also present in the Ps(1) paragenesis associated with Sn-minerals (ferrokesterite and cassiterite). The hydrothermal alteration associated with the polymetallic mineralization is characterized by advanced argillic alteration within the immediate vein zone, and sericitic alteration enveloping the vein zone. Fluid inclusion studies indicate homogenisation temperatures of 308.2-327A degrees C for Ps(1) and 255-312.4A degrees C for Ps(2), and low to moderate salinities (2 to 5 eq.wt.% NaCl and 4 to 9 eq.wt.% NaCl, respectively). delta(34)S values of sulfide minerals (+0.76aEuro degrees to +3.61aEuro degrees) indicate a possible magmatic source for the sulfur in the polymetallic mineralization while Pb isotope ratios for the sulfides and magmatic rocks ((206)Pb/(204)Pb, (207)Pb/(204)Pb and (208)Pb/(204)Pb ratios of 17.379 to 18.502; 15.588 to 15.730 and 38.234 to 38.756, respectively) are consistent with the possibility that the Pb reservoirs for both had the same crustal source. Spatial relationships, hydrothermal alteration styles, S and Pb isotopic data suggest a probable genetic relation between the polymetallic mineralization and dioritic intrusions that could have been the source of metals and hydrothermal fluids. Mineralization paragenesis, alteration mineralogy, geochemical signatures, fluid inclusion data and isotopic data, confirm that the In-bearing polymetallic mineralization from Pinguino deposit is a distinct type, in comparison with the well-known epithermal low sulfidation mineralization from the Deseado Massif.

Correlation between thermoluminescence sensitivity and crystallization temperatures of quartz: Potential application in geothermometry

The thermoluminescence (TL) characteristics of quartz are highly dependent of its thermal history. Based on the enhancement of quartz luminescence occurred after heating, some authors proposed to use quartz TL to recover thermal events that affected quartz crystals. However, little is know about the influence of the temperature of quartz crystallization on its TL characteristics. In the present study, we evaluate the TL sensitivity and dose response curves of hydrothermal and metamorphic quartz with crystallization temperatures from 209 +/- 15 to 633 +/- 27 degrees C determined through fluid inclusion and mineral chemistry analysis. The studied crystals present a cooling thermal history, which allow the acquiring of their natural TL without influence of heating after crystallization. The TL curves of the studied samples present two main components formed by different peaks overlapped around 110 C and 200-400 degrees C. The TL sensitivity in the 200-400 degrees C region increases linearly with the temperature of quartz crystallization. No relationship was observed between temperatures of quartz crystallization and saturation doses (<100 Gy). The elevated TL sensitivity of the high temperature quartz is attributed to the control exerted by the temperature of crystallization on the substitution of Si(4+) by ions such as Al(3+) and Ti(4+), which produce defects responsible for luminescence phenomena. The linear relationship observed between TL in the 200-400 degrees C region and crystallization temperature has potential use as a quartz geothermometer. The relative abundance of quartz in the earth crust and the easiness to measure TL are advantageous in relation to geothermometry methods based on chemistry of other minerals. (C) 2010 Elsevier Ltd. All rights reserved.

Petrotrama de quartzo e feldspato ao longo da Zona de Cisalhamento de Jundiuvira, Cabreuva (SP)

Fluid inclusions, petrofabric and microstructures studies of mylonites and cataclasites were used to establish the Itu-Jundiuvira Shear Zone (IJSZ) tectonic and metamorphic evolution. The quartz fabric indicates that prism {1000} slip was important during the deformation. This studies have showed that IJSZ changed from deeper crustal levels (12-15km) and ductile conditions to upper levels of about 4 to 6km and brittle strain conditions. -English summary

Estudos de inclusões fluidas e de isótopos estáveis no depósito Moreira Gomes do campo mineralizado do Cuiú-Cuiú, Província Aurífera do Tapajós, Estado do Pará

Moreira Gomes é um dos depósitos do campo mineralizado do Cuiú-Cuiú, província Aurífera do Tapajós, com recursos de 21,7 t de ouro. A zona mineralizada, com 1200 metros de comprimento, 30-50 metros de largura e, pelo menos, 400 metros de profundidade é controlada por uma estrutura subvertical de orientação E-W, associada a um sistema de falhas transcorrentes sinistrais. As rochas hospedeiras nesse depósito são predominantemente tonalitos de 1997 ± 2 Ma (Suite Intrusiva Creporizão). O estilo da alteração hidrotermal relacionado à mineralização é predominantemente fissural e localmente pervasivo. Os tipos de alteração hidrotermal são sericitização, carbonatação, cloritização, sulfetação, silicificação e epidotização, além da formação de veios de quartzo de espessuras variadas. Pirita é principal sulfeto e contém inclusões de galena, esfalerita, calcopirita e, em menor quantidade, de hessita e bismutinita. O ouro ocorre mais comumente como inclusão em cristais de pirita e, secundariamente, na forma livre em veios de quartzo. Ag, Pb e Bi foram detectados por análise semi-quantitativa como componentes das partículas de ouro. Estudo de inclusões fluidas identificou fluidos compostos por CO₂ (Tipo 1), H₂O-C O₂-sal (Tipo 2) e H₂O-sal (Tipo 3). O volátil CO₂ é predominante na fase carbônica. O fluido do Tipo 2 apresenta densidade baixa a moderada, salinidade entre 1,6 e 11,8 % em peso equivalente de NaCl e foi aprisionado principalmente entre 280° e 350°C. No fluido do Tipo 3 o sistema químico pode conter aCl₂ e, talvez, MgCl₂, e a salinidade varia de zero a 10,1% em peso equivalente de NaCl. Apenas localmente a salinidade atingiu 25% em peso equivalente de NaCl. Esse fluido foi aprisionado principalmente entre 120° e 220°C e foi interpretado como resultado de mistura de fluido aquoso mais quente e levemente mais salino, com fluido mais frio e diluído. Globalmente, o estudo das inclusões fluidas indica estado heterogêneo durante o aprisionamento e ocorrência de separação de fases, mistura, flutuação de pressão e reequilíbrio das inclusões durante aprisionamento. A composição isotópica do fluido em equilíbrio com minerais hidrotermais (quartzo, clorita e calcita e pirita) e de inclusões fluidas apresenta valores de δ¹⁸O e δD entre +0,5 e +9,8 ‰, e -49 a -8 ‰, respectivamente. Os valores de ³⁴S de pirita (-0,29 ‰ a 3,95 ‰) são provavelmente indicativos da presença de enxofre magmático. Pares minerais forneceram temperaturas de equilíbrio isotópico em geral concordante com as temperaturas de homogeneização de inclusões fluidas e compatíveis com as relações texturais. Os resultados isotópicos, combinados com os dados mineralógicos e de inclusões fluidas são interpretados como produto da evolução de um sistema magmático hidrotermal em três estágios. (1) Exsolução de fluido magmático aquoso e portador de CO₂ entre 400°C e 320-350°C, seguido de separação de fases e precipitação principal da assembleia clorita-sericita-pirita-quartzo-ouro sob pressões menores que 2,1 kb e a 6-7 km de profundidade. (2) Resfriamento e continuação da exsolução do CO₂ do fluido magmático geraram fluido aquoso, mais pobre a desprovido de CO₂ e levemente mais salino, com aprisionamento dominantemente a 250°-280°C. A assembleia hidrotermal principal ainda precipitou, mas epidoto foi a principal fase nesse estágio. (3) Mistura do fluido aquoso do estágio 2, mais quente e mais salino, com um fluido aquoso mais frio e menos salino, de origem meteórica. Carbonatação está associada com esse estágio. A assembleia hidrotermal e os valores isotópicos indicam que fluido foi neutro a levemente alcalino e relativamente reduzido, que H₂S (ou HS-) pode ter sido a espécie de enxofre predominante, e que Au(HS) ^-2 deve ter sido o complexo transportador de ouro. A deposição do ouro em Moreira Gomes ocorreu em resposta a diversos mecanismos, envolvendo a separação de fases, mistura e reações fluido-rocha. O depósito Moreira Gomes é interpretado como o produto de um sistema magmático-hidrotermal, mas não possui feições clássicas de depósitos relacionados a intrusões graníticas, tanto oxidadas como reduzidas. A idade de deposição do minério (1,86 Ga) sugere que o sistema magmático-hidrotermal pode estar relacionado com a fase final do extenso magmatismo cálcio-alcalino da Suíte Intrusiva Parauari, embora o magmatismo transicional a alcalino da Suíte Intrusiva Maloquinha não possa ser descartado.

Estudos isotópicos e de inclusões fluidas no depósito central do campo mineralizado do Cuiú-Cuiú, província aurífera do Tapajós, estado do Pará

Central é um depósito aurífero do campo mineralizado do Cuiú-Cuiú, Província Aurífera do Tapajós, Cráton Amazônico. A zona mineralizada está hospedada em falha e compreende 800m de comprimento na direção NW-SE, seguindo o trend regional da província Tapajós, com largura entre 50 e 70m e profundidade vertical de pelo menos 450m. A mineralização está hospedada em monzogranito datado em 1984±3 Ma e atribuído à Suíte Intrusiva Parauari. Os recursos auríferos preliminarmente definidos são de 18,6t de ouro. A alteração hidrotermal é predominantemente fissural. Sericitização, cloritização, silicificação, carbonatação e sulfetação foram os tipos de alteração identificados. Pirita é o sulfeto principal e os demais sulfetos (calcopirita, esfalerita e galena) estão em fraturas ou nas bordas da pirita. O ouro preenche fraturas da pirita e análises semi-quantitativas detectaram Ag associada ao ouro. Foram identificados três tipos de inclusões fluidas hospedados em veios e vênulas de quartzo. O tipo 1 é o menos abundante e consiste em inclusões fluidas compostas por uma (CO_2vapor) ou duas fases (CO_2liq-CO_2vapor), o tipo 2 tem abundância intermediária e é formado por inclusões fluidas compostas por duas (H₂O_liq-CO_2liq) ou três fases (H₂O_liq-CO_2liq-CO_2vapor) e o tipo 3 é o mais abundante e consiste em inclusões fluidas compostas por duas fases (H₂O_liq- H₂Ovapor). O CO₂ representa o volátil nas inclusões com CO₂ e essas (tipo 1 e 2) foram geradas pelo processo de separação de fases oriundo de um fluido aquo-carbônico. A densidade global (0,33 - 0,80 g/cm³) e a salinidade (11,15 - 2,42 % em peso equivalente de NaCl) desse fluido são baixas a moderadas e a temperatura de homogeneização mostra um máximo em 340ºC. Quanto ao tipo 3, o NaCl é o principal sal, a densidade global está no intervalo de 0,65 a 1,11 g/cm³, a salinidade compreendida entre 1,16 e 13,3 % em peso equivalente de NaCl e a temperatura de homogeneização é bimodal, com picos em 120-140ºC e 180ºC. A composição isotópica das inclusões fluidas presentes no quartzo e do quartzo, calcita e clorita mostram valores de δ¹⁸O e δD de +7,8 a +13,6 ‰ e -15 a -35 ‰, respectivamente. Os valores de δ³⁴S na pirita são de +0,5 a +4,0 ‰ e δ¹³C na calcita e CO₂ de inclusões fluidas de -18 a -3,7 ‰. Os valores de δ¹⁸O_H2O e de δD_H2O no quartzo e inclusões fluidas, respectivamente, plotam no campo das águas metamórficas, com um desvio em direção à linha da água meteórica. Considerando a inexistência de evento metamórfico na região do Tapajós à época da mineralização, o sistema hidrotermal responsável pela mineralização no Central, inicialmente, deu-se a partir de fluidos aquo-carbônicos magmático-hidrotermais, exsolvidos por magma félsico relacionado com a fase mais tardia de evolução da Suíte Intrusiva Parauari. As inclusões aquo-carbônicas e carbônicas formaram-se nessa etapa, predominantemente em torno de 340°C. A contínua exsolução de fluido pelo magma levou ao empobrecimento em CO₂ nas fases mais tardias e, com o resfriamento do fluido, as inclusões aquosas passaram a predominar. A partir daí o sistema pode ter interagido com água meteórica, responsável pelo aprisionamento da maior parte das inclusões aquosas de mais baixa temperatura. É possível que parte das inclusões aquosas (as de maior temperatura) represente a mistura local dos fluidos de origens distintas. Essas observações e interpretações permitem classificar Central como um depósito de ouro magmático-hidrotermal relacionado à fase final da formação da Suíte Intrusiva Parauari.

Evolução dos fluidos mineralizantes e modelo genético dos veios de quartzo auríferos em zona de cisalhamento do depósito Ouro Roxo, Província Tapajós, Jacareacanga (PA), Brasil

O depósito aurífero Ouro Roxo, localizado no município de Jacareacanga, Província Aurífera do Tapajós, sudoeste do Pará, formou-se em um sistema hidrotermal que gerou veios de quartzo sulfetados, em zona de cisalhamento N-S, dúctil-rúptil, oblíqua, denominada Ouro Roxo-Canta Galo, cortando granitoides calcioalcalinos da Suíte Intrusiva Tropas, de idade paleoproterozoica e hospedeira da mineralização, em rochas localmente milonitizadas. Três tipos de fluidos foram caracterizados como geradores do depósito: 1) fluido aquoso H₂O-NaCl-MgCl₂-FeCl₂ de salinidade baixa a moderada, com temperatura de homogeneização total (Th) = 180-280°C; 2) salmoura H₂O-NaCl-CaCl₂ com Th = 270-400°C, provavelmente portadoras de Cu e Bi, relacionadas geneticamente a um evento magmático contemporâneo ao cisalhamento que sofreu diluição pela mistura com água meteórica, baixando sua salinidade e temperatura (Th = 120-380°C); 3) fluido aquocarbônico de média salinidade, com Th = 230-430°C, que foi interpretado como o fluido mineralizante mais primitivo, provavelmente aurífero, relacionado com o cisalhamento. As condições de temperatura e pressão (T-P) de formação do minério, estimadas conjuntamente pelo geotermômetro da clorita e as isócoras das inclusões fluidas, situam-se entre 315 e 388°C e 2 a 4,1kb. Dois mecanismos simultâneos provocaram a deposição do minério em sítios de transtensão da zona de cisalhamento: 1) mistura de fluido aquocarbônico com salmoura magmática com aumento de fO2 e redução de pH; 2) interação entre os fluidos e os feldspatos e minerais ferromagnesianos do granitoide hospedeiro, com reações de hidrólise e sulfetação, provocaram redução de fO2 e fS2, com precipitação de sulfetos de Fe juntamente com ouro. O ambiente orogênico, o estilo filoneano do depósito, o controle estrutural pela zona de cisalhamento, a alteração hidrotermal (propilítica + fílica + carbonatação), a associação metálica (Au + Cu + Bi), o fluido mineralizante aquocarbônico associado com salmoura magmática na deposição do minério são compatíveis com um modelo orogênico com participação magmática para a gênese do depósito Ouro Roxo.

Contexto geológico, estudos isotópicos (C, O e Pb) e associação metálica do depósito aurífero Tocantinzinho, domínio Tapajós, Província Tapajós-Parima

O depósito Tocantinzinho, localizado em um lineamento de direção NW–SE, a SW de Itaituba (PA), é atualmente o maior depósito aurífero conhecido na Província Tapajós. Está hospedado no granito homônimo, essencialmente isótropo, no qual dominam rochas sieno e monzograníticas, que foram fraca a moderadamente alteradas por fluidos hidrotermais. Microclinização (mais precoce), cloritização, sericitização, silicificação e carbonatação (mais tardia) são os mais importantes tipos de alteração. O principal estágio de mineralização é contemporâneo à sericitização/silicificação e é representado por vênulas com sulfetos (pirita ± calcopirita ± galena ± esfalerita) e ouro associado, as quais mostram localmente trama stockwork. Além de teores expressivos de Cu, Pb e Zn, são anômalos, em algumas amostras, os de As, Bi e Mo. A relação dos teores do Au com os dos metais-base é aleatória e as razões Au/Ag variam de 0,05 a 5,0. O Au é mais enriquecido nas porções com maior abundância de sulfetos de metais-base, embora ocorra principalmente incluso na pirita. Monocristais de zircão, extraídos do granito Tocantinzinho, forneceram idade Pb-Pb média de 1982 ± 8 Ma, permitindo interpretá-lo como uma manifestação magmática precoce do arco Creporizão. Valores de δ¹³C_PDB em calcita do estágio de carbonatação, dominantemente entre -3,45 e -2,29‰, são compatíveis com fonte crustal profunda, quiçá carbonatítica, enquanto os de δ¹⁸O_SMOW (+5,97 a +14,10‰) indicam forte contribuição magmática, ainda que mascarada por influxo de águas provavelmente superficiais. Estudos de inclusões fluidas em andamento revelam a presença de fluidos aquocarbônicos, cujo CO₂ poderia ter estado dissolvido no magma granítico em vez de ser relacionado à zona de cisalhamento. Os dados até aqui disponíveis permitem classificar o depósito aurífero Tocantinzinho como do tipo relacionado à intrusão.

Petrology and geochemistry of Lipari Island (Aeolian archipelago): constraints on magma genesis and evolution

A full set of geochemical and Sr, Nd and Pb isotope data both on bulk-rock and mineral samples is provided for volcanic rocks representative of the whole stratigraphic succession of Lipari Island in the Aeolian archipelago. These data, together with petrographic observations and melt/fluid inclusion investigations from the literature, give outlines on the petrogenesis and evolution of magmas through the magmatic and eruptive history of Lipari. This is the result of nine successive Eruptive Epochs developing between 271 ka and historical times, as derived from recentmost volcanological and stratigraphic studies, combined with available radiometric ages and correlation of tephra layers and marine terrace deposits. These Eruptive Epochs are characterized by distinctive vents partly overlapping in space and time, mostly under control of the main regional tectonic trends (NNW-SSE, N-S and minor E-W). A large variety of lava flows, scoriaceous deposits, lava domes, coulees and pyroclastics are emplaced, ranging in composition through time from calcalkaline (CA) and high-K (HKCA) basaltic andesites to rhyolites. CA and HKCA basaltic andesitic to dacitic magmas were erupted between 271 and 81 ka (Eruptive Epochs 1-6) from volcanic edifices located along the western coast of the island (and subordinately the eastern Monterosa) and the M.Chirica and M.S.Angelo stratocones. These mafic to intermediate magmas mainly evolved through AFC and RAFC processes, involving fractionation of mafic phases, assimilation of wall rocks and mixing with newly injected mafic magmas. Following a 40 ka-long period of volcanic quiescence, the rhyolitic magmas were lately erupted from eruptive vents located in the southern and north-eastern sectors of Lipari between 40 ka and historical times (Eruptive Epochs 7-9). They are suggested to derive from the previous mafic to intermediate melts through AFC processes. During the early phases of rhyolitic magmatism (Eruptive Epochs 7-8), enclaves-rich rocks and banded pumices, ranging in composition from HKCA dacites to low-SiO2 rhyolites were erupted, representing the products of magma mixing between fresh mafic magmas and the fractionated rhyolitic melts. The interaction of mantle-derived magmas with the crust represents an essential process during the whole magmatic hystory of Lipari, and is responsible for the wide range of observed geochemical and isotopic variations. The crustal contribution was particularly important during the intermediate phases of activity of Lipari when the cordierite-bearing lavas were erupted from the M. S.Angelo volcano (Eruptive Epoch 5, 105 ka). These lavas are interpreted as the result of mixing and subsequent hybridization of mantle-derived magmas, akin to the ones characterizing the older phases of activity of Lipari (Eruptive Epochs 1-4), and crustal anatectic melts derived from dehydration-melting reactions of metapelites in the lower crust. A comparison between the adjacent islands of Lipari and Vulcano outlines that their mafic to intermediate magmas seem to be genetically connected and derive from a similar mantle source affected by different degrees of partial melting (and variable extent of crustal assimilation) producing either the CA magmas of Lipari (higher degrees) or the HKCA to SHO magmas of Vulcano (lower degrees). On a regional scale, the most primitive rocks (SiO2<56%, MgO>3.5%) of Lipari, Vulcano, Salina and Filicudi are suggested to derive from a similar MORB-like source, variably metasomatized by aqueous fluids coming from the slab and subordinately by the additions of sediments.

Partial melting within the lower crust – Constraints from bulk rock geochemical data and trace element mineral analyses of granulites and migmatites from Central Finland

This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

Diagenesis of a light, tight-oil chert reservoir at the Ediacaran/Cambrian boundary, Sultanate of Oman

The Al Shomou Silicilyte Member (Athel Formation) in the South Oman Salt Basin shares many of the characteristics of a light, tight-oil (LTO) reservoir: it is a prolifi c source rock mature for light oil, it produces light oil from a very tight matrix and reservoir, and hydraulic fracking technology is required to produce the oil. What is intriguing about the Al Shomou Silicilyte, and different from other LTO reservoirs, is its position related to the Precambrian/Cambrian Boundary (PCB) and the fact that it is a ‘laminated chert‘ rather than a shale. In an integrated diagenetic study we applied microstructural analyses (SEM, BSE) combined with state-of-the-art stable isotope and trace element analysis of the silicilyte matrix and fractures. Fluid inclusion microthermometry was applied to record the salinity and minimum trapping temperatures. The microstructural investigations reveal a fi ne lamination of the silicilyte matrix with a mean lamina thickness of ca. 20 μm consisting of predominantly organic matter-rich and fi nely crystalline quartz-rich layers, respectively. Authigenic, micron-sized idiomorphic quartz crystals are the main matrix components of the silicilyte. Other diagenetic phases are pyrite, apatite, dolomite, magnesite and barite cements. Porosity values based on neutron density logs and core plug data indicate porosity in the silicilyte ranges from less than 2% to almost to 40%. The majority of the pore space in the silicilyte is related to (primary) inter-crystalline pores, with locally important oversized secondary pores. Pore casts of the silica matrix show that pores are extremely irregular in three dimensions, and are generally interconnected by a complex web or meshwork of fi ne elongate pore throats. Mercury injection capillary data are in line with the microstructural observations suggesting two populations of pore throats, with an effective average modal diameter of 0.4 μm. The acquired geochemical data support the interpretation that the primary source of the silica is the ambient seawater rather than hydrothermal or biogenic. A maximum temperature of ca. 45°C for the formation of microcrystalline quartz in the silicilyte is good evidence that the lithifi cation and crystallization of quartz occurred in the fi rst 5 Ma after deposition. Several phases of brittle fracturing and mineralization occurred in response to salt tectonics during burial. The sequences of fracture-fi lling mineral phases (dolomite - layered chalcedony – quartz – apatite - magnesite I+II - barite – halite) indicates a complex fl uid evolution after silicilyte lithifi cation. Primary, all-liquid fl uid inclusions in the fracturefi lling quartz are good evidence of growth beginning at low temperatures, i.e. ≤ 50ºC. Continuous precipitation during increasing temperature and burial is documented by primary two-phase fl uid inclusions in quartz cements that show brines at 50°C and fi rst hydrocarbons at ca. 70°C. The absolute timing of each mineral phase can be constrained based on U-Pb geochronometry, and basin modelling. Secondary fl uid inclusions in quartz, magnesite and barite indicate reactivation of the fracture system after peak burial temperature during the major cooling event, i.e. uplift, between 450 and 310 Ma. A number of fi rst-order trends in porosity and reservoir-quality distribution are observed which are strongly related to the diagenetic and fl uid history of the reservoir: the early in-situ generation of hydrocarbons and overpressure development arrests diagenesis and preserves matrix porosity. Chemical compaction by pressure dissolution in the fl ank areas could be a valid hypothesis to explain the porosity variations in the silicilitye slabs resulting in lower porosity and poorer connectivity on the fl anks of the reservoir. Most of the hydrocarbon storage and production comes from intervals characterized by Amthor et al. 114488 preserved micropores, not hydrocarbon storage in a fracture system. The absence of oil expulsion results in present-day high oil saturations. The main diagenetic modifi cations of the silicilyte occurred and were completed relatively early in its history, i.e. before 300 Ma. An instrumental factor for preserving matrix porosity is the diffi culty for a given slab to evacuate all the fl uids (water and hydrocarbons), or in other words, the very good sealing capacity of the salt embedding the slab.

Glacial–interglacial temperature change in the tropical West Pacific: A comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquide vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O(‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glaciale interglacial cycles (Marine Isotope Stages (MIS) 12 e 9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquide vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion d18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion d18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glaciale interglacial temperature change, indicating temperature shifts of 4-5 C°. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

Geochemical composition and crystallization temperatures of ODP Hole 176-735B gabbroic rocks

The transition from magmatic crystallization to high-temperature metamorphism in deep magma chambers (or lenses) beneath spreading ridges has not been fully described. High-temperature microscopic veins found in olivine gabbros, recovered from Ocean Drilling Program Hole 735B on the Southwest Indian Ridge during Leg 176, yield information on the magmatic-hydrothermal transition beneath spreading ridges. The microscopic veins are composed of high-temperature minerals, (i.e., clinopyroxene, orthopyroxene, brown amphibole, and plagioclase). An important feature of these veins is the 'along-vein variation' in mineralogy, which is correlated with the magmatic minerals that they penetrate. Within grains of magmatic plagioclase, the veins are composed of less calcic plagioclase. In grains of olivine, the veins are composed of orthopyroxene + brown amphibole + plagioclase. In clinopyroxene grains, the veins consist of plagioclase + brown amphibole and are accompanied by an intergrowth of brown amphibole + orthopyroxene. The mode of occurrence of the veins cannot be explained if these veins were crystallized from silicate melts. Consequently, these veins and nearby intergrowths were most likely formed by the reaction of magmatic minerals with fluid phases under the conditions of low fluid/rock ratios. Very similar intergrowths of brown amphibole + orthopyroxene are observed in clinopyroxene grains with 'interfingering' textures. It is believed, in general, that the penetration of seawater does not predate the ductile deformation within Layer 3 gabbros of the slow-spreading ridges. If this is the case, the fluid responsible for the veins did not originate from seawater because the formation of the veins and the interfingering textures preceded ductile deformation and, perhaps, complete solidification of the gabbroic crystal mush. It has been proposed, based on fluid inclusion data, that the exsolution of fluid from the latest-stage magma took place at temperatures >700°C in the slow-spreading Mid-Atlantic Ridge at the Kane Fracture Zone (MARK) area. No obvious mineralogical evidence, however, has been found for these magmatic fluids. The calculated temperatures for the veins and nearby intergrowths found in Hole 735B gabbros are up to 1000°C, and these veins are the most plausible candidate for the mineralogical expression of the migrating magmatic fluids.

Characterization of diagenetic fluids at ODP Site 103-639

Site 639, drilled during Leg 103 of the Ocean Drilling Program, penetrated an Upper Jurassic to Lower Cretaceous carbonate platform on a tilted fault block along the Galicia margin off the northwest Iberian Peninsula. The carbonate platform is composed primarily of a sequence of dolomite overlying limestone. Samples were analyzed for mineral chemistry, stable isotope geochemistry, fluid inclusion microthermometry, and volatile contents and by dolomite pyrolysis mass spectrometry for trace sulfate minerals. The dolomite recovered from the Galicia margin at Site 639 formed during shallow burial from sulfate-bearing, hypersaline brines at slightly elevated temperatures. The light oxygen isotopic signatures of the dolomite are interpreted as the result of the evaporative loop and slightly elevated temperatures during dolomite formation or from reequilibration at higher temperatures during deeper burial. The hypersalinity is interpreted to be associated with a nearby, shallow restricted basin that formed during rifting of the Iberian margin from Newfoundland. The dolomitization of the platform is therefore a by-product of the rifting.