Estudo diagenético aplicado ao Membro Maruim da Formação Riachuelo , na parte terrestre da sub-bacia de Sergipe, Brasil

O Membro Maruim da Formação Riachuelo (Neoalbiano), na parte terrestre da Sub-bacia de Sergipe, contém fácies de água rasa compostas, principalmente, por rudstone/grainstone oncolítico oolítico, com baixo conteúdo e variedade de bioclastos. A correlação dos afloramentos e análise petrográfica detalhada, envolvendo catodoluminescência, microscopia eletrônica de varredura (MEV) e estudos isotópicos e análise química elementar, permitiram a reconstrução da história diagenética do intervalo estudado. As rochas carbonáticas do Membro Maruim estão completamente afetadas por processos diagenéticos associados aos estágios eogenético, mesogenético e telogenético. A dolomitização foi um dos principais produtos diagenéticos observados no estágio eogenético e encontra-se substituindo total ou parcialmente os calcários do Membro Maruim. A dolomitização concentra-se no topo dos ciclos deposicionais descritos na área de estudo e diminuem gradativamente para a base dos mesmos. As relações entre a porosidade e a dolomitização foram estudadas com base nas comparações da fábrica cristalina da dolomita preservada nos afloramentos estudados. Os resultados isotópicos das dolomitas indicam que o processo de dolomitização ocorreu a partir do refluxo de salmouras em um ambiente ligeiramente hipersalino (penesalino). As áreas mais próximas ao contato com a salmoura, fonte dos fluidos dolomitizantes, exibem menor desenvolvimento de porosidade, uma vez que nessas regiões ocorreriam processos de superdolomitização (Pedreira Carapeba). Nestas áreas a assinatura isotópica do carbono e do oxigênio é muito positiva (o valor do δ13C varia de 2.37 a 4.83 e o valor do δ18O oscila entre 0.61 e 3.92), indicando que os processos diagenéticos tardios não teriam alterado significativamente a assinatura isotópica original. As dolomitas geradas nas áreas afastadas da salmoura (pedreiras Massapé, Inorcal I, Inorcal II, Inhumas e Santo Antônio) exibem um maior desenvolvimento de porosidade e têm uma composição isotópica de carbono e oxigênio mais negativa (o valor do δ13C varia de -5.66 a 2.61 e o valor do δ18O oscila entre -4.25 e 0.38). A assinatura isotópica das dolomitas descritas nestas pedreiras também se encontra alterada por processos de dedolomitização. Os cimentos diagenéticos precipitados durante o estágio mesogenético foram os principais responsáveis pela obliteração da porosidade primária e secundária dos calcários do Membro Maruim. Adicionalmente, estes cimentos diagenéticos tardios calcitizaram as dolomitas, fechando parcialmente a porosidade secundária das mesmas. A porosidade das rochas carbonáticas também se encontra fortemente reduzida pela compactação mecânica e química. A dissolução foi o único processo que levou à geração de porosidade secundária no estágio telogenético, porém em porcentagens muito baixas. As fácies dolomíticas são as que apresentam maior desenvolvimento de porosidade secundária, como consequência dos processos de dissolução no ambiente telogenético. A dissolução compreende um dos últimos eventos diagenéticos identificados no intervalo estudado.

Nova metodologia para caracterização litológica das rochas carbonáticas do pré-sal com base na perfilagem e espectroscopia de poço

O cenário mundial de crescimento está favorecendo uma demanda cada vez maior por petróleo e gás. Para se adequar a esta demanda crescente, as companhias petroleiras têm perfurado em regiões de águas profundas e com caráter geológico particular, como os depósitos carbonáticos recém explorados no Brasil pela Petrobras e que entraram em produção a partir de 2008. Para a produção de hidrocarbonetos é preciso um conhecimento profundo das rochas que os contém. Isto se deve ao fato que os sensores usados para detectar hidrocarbonetos no processo conhecido como perfilagem de poço na indústria petroleira são influenciados em suas medições pelas características das rochas. No caso deste trabalho, carbonatos do pré-sal, aparece uma complicação adicional em termos litológicos que é a presença do mineral Estevensita que não é comumente encontrado em ambientes carbonáticos. Em função de não haver uma forma de detectar sem ambiguidades o mineral Estevensita (rico em magnésio) com a Dolomita (também rica em magnésio), e levando-se em consideração o fato de que a Estevensita fecha os poros da rocha (rocha não reservatório) enquanto a Dolomita normalmente pode ser uma excelente rocha reservatório é de fundamental importância conhecer se o magnésio é proveniente da Estevensita ou do processo de dolomitização do carbonato (substituição de cálcio por magnésio). Não existe hoje em dia uma metodologia de perfilagem de poço que possa indicar a proveniência do magnésio. Estevensita ou Dolomita? Rocha reservatório ou não-reservatório? O objetivo deste trabalho é prover respostas às perguntas acima. Desenvolver uma forma de analisar os minerais presentes no pré-sal através da perfilagem e espectroscopia de poço e fazer a separação entre os diversos constituintes das rochas encontradas no pré-sal. O pré-sal brasileiro é constituído por litologia carbonática complexa, sendo a seção rifte formada por coquinas e a seção sag por microbialitos. Estas rochas foram depositadas antes da deposição da camada de sal no fim do Aptiano. Para atingir o resultado esperado neste trabalho serão utilizadas medições convencionais e não convencionais no laboratório com rochas análogas ao pré-sal e minerais puros tais como a Estevensita a fim de determinar respostas padrão para serem utilizados em programas de análise de registros de perfilagem. O produto final deste trabalho é desenvolver um procedimento para determinação de litologia no pré-sal brasileiro através de registros a cabo (wireline) ou enquanto se perfura (Logging While Drilling - LWD)

重庆老龙洞二叠系-三叠系界线地层微生物岩研究

The largest mass extinction in the Phanerozoic happened at the end of the Permian. The microbialites formed in the extreme environments after the mass extinction has become a hotspot for geologists and paleontologists throughout the world. The dendroid microbialites that were described for the first time in 1999 from the Permian-Triassic boundary section at Laolongdong, Chongqing, have been studied by many geologists from China and overseas. Two important viewpoints about their origin have been proposed. Some researchers believed that they resemble Quaternary travertine shrubs in form, and may belong to microbialites. Some other researchers proposed that the dendroid structure is composed of clots formed by coccoidal cynaobacteria, and is microbialite. Our detailed survey on the section reveals that: (1) there is an interval of speckled “microbialite” in the section, and it underlies the dendroid “microbialite”, (2) the dendroid “microbialite” does not always have dendroid appearance; they are dendroid only in very local places; they are not dendroid in most places; for this reason, they are not comparable to recent tufa; (3) the volume of the dendroid structure greatly increases toward the top of the dendroid microbialite interval: accounting to 70% of the whole rock in the top part. This distribution pattern implies that the formation of this structure may be related to downward migration of the diagenetic fluid. Examination of thin sections reveals that the dendroid structure or point-like structure in the “microbialite” look as lighter areas in the thin sections and are composed of large blocky clear calcites containing scattered yellow dirty small calcite rhombi and irregular “points” of relict lime mudstone or wackestone or packstone. Their formation is by any one of the following two processes: (1) dissolution → filling of large blocky calcite; (2) dolomitization → dedolomitization → dissolution by meteoric fresh water → filling by large blocky calcites. It has been found that there are at least two sea-level falls during the P-T transition. As the sea level fall, the carbonate deposits came into supratidal environment, and suffered dolomitization caused by evaporative fluid or mixing water of sea water and meteoric water. Since the fluid migrated downward from the top of the deposits and in random pathway, the dolomitization formed dendroid or speckled dolomitic areas. As the deposits came into subaerial environments, the meteoric fresh water migrated along the dendroid or speckled dolomitic area with higher porosity, and dissolution happened, which caused the rock became spongy or alveolate. In later time, after the strata came into phreatic zone, large clear blocky calcites grew in and filled the pores in the spongy areas. The dendroid and speckled structure were formed in this way, rather than composed of clots formed by coccoid cyanobecteria. The microbial fossils in Laolongdong section include two types. The first is the tube-like cyanobecteria in middle Bed 3, which are generally less than 1 mm in length, taper toward one end, and are internally filled by microspars. They are straight or sinuous, with micritic wall 0.005~0.01 mm thick. Since this kind of microbial fossils are abundant in middle Bed 3, this rock belongs to microbialite. The second type occurs in Bed 5 and lower and middle Bed 6. They are irregular globular in shape, generally 0.2 ~ 0.5 mm in size, with several outward progresses, and internally filled by one layer of needle-like calcite cements on the wall and the large blocky calcite in the inner space. According to their shape and preservation way, it is inferred that this kind of fossils were formed from some kind of bacterial colony. The bacterial colony may be cuticle in composition, since it has some hardness as it is indicated by its resistance to deposit loading. These organisms discomposed during diagenetic time, and formed good porosity. In later diagenetic time, these pores were firstly cemented by needle-like calcites and later filled by large blocky calcites. So, the bacterial colony promoted the formation of dendroid and speckled structures. However, they did not always form such structures. On the other hand, even though no bacterial colony or other microbes or any kind of fossils were present, dendroid or speckled structures can form. Bed 4 of Laolongdong section contains abundant gastropods but no microbial fossils, and is not microbialite, even though it is speckled. The top of Bed 6 is dendroid, but contain no microbial fossils, and is not micrbialite.

塔里木盆地柯坪-巴楚露头区白云岩成岩作用机理研究

Through field outcrop dolomite observation, laboratory petrography (macroscopy, microscopy, cathodeluminescence and scan electronic microscopy), geochemistry (carbon-oxygen-strontium isotopes and trace elements) and fluid inclusion microthermometry study in Keping-Bachu area of Tarim Basin, it can be inferred that there are existing eight dolomite texture types within four evolution phases in Keping-Bachu area of Tarim Basin. The paragenesis of different dolomite texture types and associated minerals in Keping-Bachu area has been established. The carbon and oxygen isotopes of saddle dolomites and matrix dolomites overlap greatly. The Strontium isotopes results of Keping-Bachu outcrop area show that the strontium isotopes differentiation of the matrix and saddle dolomites is not obvious, the reason of which is that there is thousands of Cambrian-Ordovician dolomite strata below the stratum bearing the saddle dolomite. In the process of the heat flow upward migration, the isotopes of the heat interacts with the host rock, which leads to the similarity betwwen the strontium of the saddle dolomite and matrix dolomite. The strontium isotope of the saddle dolomite is not very radiogenic. the six types samples within four phases in the study area show Eu negatively. Comparing to the other types of samples, the δEu of saddle dolomite is relatively high falling into the range of 0.510-0.874, which shows that the saddle dolomite forms in the hydrothermal setting and is affected by the hydrothermal activity to some extend.The Lan/Ybn of saddle dolomite is high up to 15.726, which means that the HREE is very rich. It belongs to the typical hydrothermal genesis model. The δCe of saddle dolomite is positive anomaly, which is the result of high effect from the land source debris. The homogeneous temperature of the saddle dolomite falls into two ranges 110-120℃ and 125-160℃, after pressure correction, they are 141-152℃，157.5-196℃, the salinity of the saddle dolomite can reach to 20-25%. With the comparing with the burial history, the Th of the saddle dolomite is high than the ambient strata temperature, these data show that the saddle dolomite is of hydrothermal origin. The evolution trend of different dolomite and associated minerals is from matrix dolomite, dolomite cementation, saddle dolomite, quartz to calcite. Alonging with this evolution trend, the temperature of the diagenetic flow initiated from 80-100℃, after rising to 135-160℃, then gradually declined. Finally, a structurally-controlled dolomitization model is established in Keping-Bachu area of Tarim Basin.

塔里木盆地寒武－奥陶系白云岩类型、成因机理及其孔隙性研究

Cambrian-Ordovician dolostones in Tarim Basin are hydrocarbon reservoir rocks of vital importance. Under the guidance of the theories of sedimentology and the sedimentology of carbonate reservoir, based on the first-hand qualitative and quantitative data especially, combined with micro-study, geochemical and reservoir capacity analysis, and precursor research, the origin and reservoir characteristics of the dolostones were discussed. Based on detailed petrographic investigations, four types of dolostone have been recognized, which are, respecitively, mud-silt-sized dolostones, algal laminated dolostones (ALD), prophyritic dolostone, and neomorphic dolostone. Mud-silt-sized dolostones always presents as laminas together with evaporated signatures, its REE patterns and ΣREE are all close to that of the finely crystalline limestone. This kind of dolomite probably experienced relatively low fluid-rock ratio during diagenesis was formed in hypersaline and oxidizing environment and involved fast dolomitization process. It was dolomitized by evaporated seawater in sabkha environment.The main primary fabrics of algal lamination in algal laminated dolomite (ALD) can still be identified and its ΣREE (21.37) is very close to that of algae. This reveals that ALD was dolomitized during early diagenesis and algae possibly played an important role. The ALD was formed under mediation of organic matter and Mg2+ were supplied by magnesium concentrated algal laminites and sea water. Prophyritic dolostones presents mainly as patchy occurrence and yield the lowest δ13C and Z value. Its ΣREE is much less than that of the finely crystalline limestone. These characteristics reveal that the cloudy cores were dolomitized in shallow early diagenetic environments by pore fluids riched in Mg2+. Whereas the clear rims were likely formed in subsequent burial into deeper subsurface environments, and the Mg2+ needed for further dolomitization possibly was supplied by the transformations of clay minerals. Neomorphic dolostones consist of coarse, turbid crystals and exhibits sucrosic and mosaic textures. It has highest Fe2+ contents and average homogeneous temperature (110.2℃). Collectively, these characteristics demonstrate that the neomorphic dolostones was likely formed by recrystallization of pre-existing dolomites during deep burial. The ΣREE of the four types of dolostone distinctly differentiates from each other. However, their REE patterns are all enriched in LREE, depleted in HREE and have Eu negative anomalies. Its ΣREE 13.64 ppm, less than 1/4 of finely crystalline limestone, and ranks the lowest in the 4 types.These characteristics are comparable to those of finely crystalline limestone, and are mainly infuenced by the sea water. These four types of dolostone show similar REE mobility behaviour and no significant fractionation, althouth they have been subjected to evidently different diageneses. Seven main pore types are identified in the dolostones , which are fenestral, moldic, intercrystal, dissolved，breccia, dissolved breccia and stylolite pores. Fenestral pores are primary and the others are secondary. The dissolved pores and intercrystal pores are the most important reservoir spaces and followed by breccias and dissolved breccia pores, and the moldic and fenestral pores are less important. Stylolites can enhance permeability of reservoir rocks in one hand, for the other hand, the capacity of reservoir and permeability are enhanced and then better reservoir rocks can be formed when they are combined with patchy dolostones. The relationship between porosity and the type of dolostones is that the dissolved neomorphic dolostones have the highest porosity of 3.65%, than followed by dissolved Mud-silt-sized dolostones of 3.35%. The mud-silt-sized dolostones without dissolution have the lowest porosity of 0.90%. Moreover, the porosity of prophyritic dolostones and the neomorphic dolostones without dissolution are lower, respectively 1.675% and 1.41%. Although algal laminated dolostones consist of euhedral crystals and riched in intercrystal pores, its porosity just yields 1.20%. The relationship between permeability and the type of dolostones is that that algal laminated dolostones have the highest permeability of 0.462mD and followed by 0.065mD of prophyritic dolostones. Dissolution have no significant influence on the permeability of neomorphic dolostones and this presented by the permeability of dissolved and non-dissolved are very close, respectively 0.043mD and 0.062mD. No matter dissolved or not, mud-silt-sized dolostones are much less permeable. The permeability of non-dissolved and dissolved are 0.051mD and 0.016mD. Collectively, in the study area, neomorphic dolostones can form high quality reservoir.

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

济阳坳陷及其南缘奥陶系碳酸盐岩潜山储集性及控制因素

The main research area of this thesis is Jiyang Depression in the Bohaiwan Basin and its southern margin. The object formation is Ordovician carbonate. The research is based on the outcrop observation and measurement of Ordovician carbonate and the drilling data of the oilfield. The internal reservoir characteristics of carbonate buried hill and its distribution were studied by comprehensive methods of sedimentology, reservoir geology and structural geology and technics of cathodoluminescence(CL)3electron microprobe,casting and C O isotope analysis etc. The influence depth of paleokarst facies formed during the Paleozoic is discriminated as 36-84m. The sollution porosity is well developed in paleokarst facies of Ordovician carbonate and is an important type of internal reservoir of buried hill. It may be infered that the fractures may be formed mainly during the Mesozoic and Cenozoic, they were not developed during the early Paleozoic when only micro-fractures might be created. The carbon and oxigen isotope analysis shows that the calcite cements in the fractures of Ordovician carbonate and secondary solution pores were related with meteoric water and three stages of fractures were divided. The reservoir space of Ordovician carbonate are mainly secondary porosity, cavern and fracture. The development of structural fracture was controlled by the lithology and tectonic background. More fractures exist in dolomite than that in limestone. There are also more fractures near the fault and the axis of fold. The development of porous reservoir is mainly controlled by the lithology and diagenesis, especially dolomitization and dissolution. It also results in the heterogeneity vertically. So the lithology is the basic factor for the forming of internal reservoir of buried hill and the tectogenesis and diagenesis are key factors to improve it. The porosity in carbonate might experienced solution-cementation-resolution or recementation. The porosity evolution history was a kind of historical dynamic equilibrium. The internal reservoir of Ordovician carbonate is the comprehensive result of constructive and/or destructive diagenesis. The worm's eye maps of the early Paleozoic and middle-upper Proterozoic were plotted. It was inferred that the paleostress field evoluted from NNW to NW during the Mesozoic and Cenozoic. Three types of buried hills can be divided: C-P/Pzi, Mz/ Pzi and E/ Pzi. The unconformity of the buried hill of E/ Pzi type, comparatively, was formed and reconstructed latestly, t he p orous r eservoir c ould b e w ell p reseved. T his c ondition w as v ery favorable t o t he migration and accumulation of oil and gas and could form upstanding association of source-reservoir-cap rocks. The buried hills of Mz/ Pzi and C-P/Pz] type were took second place.

Microfacies analysis of the lower paleocene beda formation in Western Concession 59 and Block 59F, Sirte Basin, Libya /

The rock sequence of the Tertiary Beda Formation of S. W. concession 59 and 59F block in Sirte Basin of Libya has been subdivided into twelve platformal carbonate microfacies. These microfacies are dominated by muddy carbonates, such as skeletal mudstones, wackestones, and packstones with dolomites and anhydrite. Rock textures, faunal assemblages and sedimentary structures suggest shallow, clear, warm waters and low to moderate energy conditions within the depositional shelf environment. The Beda Formation represents a shallowing-upward sequence typical of lagoonal and tidal flat environments marked at the top by sabkha and brackish-water sediments. Microfossils include benthonic foraminifera, such as miliolids, Nummulites, - oerculina and other smaller benthonics, in addition to dasycladacean algae, ostracods, molluscs, echinoderms, bryozoans and charophytes. Fecal pellets and pelloids, along with the biotic allochems, contributed greatly to the composition of the various microfacies. Dolomite, where present, is finely crystalline and an early replacement product. Anhydrite occurs as nodular, chickenwire and massive textures indicating supratidal sabkha deposition. Compaction, micr it i zat ion , dolomit izat ion , recrystallization, cementation, and dissolution resulted in alteration and obliteration of primary sedimentary structures of the Beda Formation microfacies. The study area is located in the Gerad Trough which developed as a NE-SW trending extensional graben. The Gerad trough was characterized by deep-shallow water conditions throughout the deposition of the Beda Formation sediments. The study area is marked by several horsts and grabens; as a result of extent ional tectonism. The area was tectonically active throughout the Tertiary period. Primary porosity is intergranular and intragranular, and secondary processes are characterized by dissolution, intercrystalline, fracture and fenestral features. Diagenesis, through solution leaching and dolomitization, contributed greatly to porosity development. Reservoir traps of the Beda Formation are characterized by normal fault blocks and the general reservoir characteristics/properties appear to be facies controlled.

Diagenesis and geochemical stratigraphy of Upper Pennsylvanian madera brachiopods, New Mexico

Owing to the fact that low-Mg calcite fossil shells are so important in paleoceanographic research, 249 brachiopod, cement and matrix specimens from two neighboring localities (Jemez Springs and Battleship Rock), of the Upper Pennsylvanian Madera Formation were analyzed. Of which, about 86% of the Madera brachiopods are preserved in their pristine mineralogy, microstructure and geochemistry. Cement and matrix samples, in contrast, have been subjected to complete but variable post-deposition~1 alteration. It is confirmed that the stable isotope data of brachiopods are much better than that of matrix material in defining depositional parameters. Because there is no uniform or constant relationship between the two data bases (e.g., from 0.1 to 3.0%0 for 0180 and from 0.2 to 6.7%0 for 013C in this study), it is not possible to make corrections for the matrix data. Regarding the two stratigraphic sections, elemental and petrographic analyses suggest that Jemez Springs is closer to Penasco Uplift than Battleship Rock. Seawater at Jemez Springs is more aerobic, and the water chemistry is more influenced by continental sources than that at Battleship Rock. In addition, there is a relatively stronger dolomitization in the mid-section of the Battleship Rock. Results further suggest that no significant biogenic fractionation or vital effects occurred during their shell secretion, suggesting that the Madera brachiopods incorporated oxygen and carbon isotopes in equilibrium with the ambient seawater. This conclusion is not only drawn from the temporal and spatial analyses, but also supported by brachiopod inter-generic comparison (Composita and Neospirifer) and statistical analysis ( t-test).

Paragenetic history of the Ordovician Trenton Group carbonates, Southwestern Ontario

Geochemical examination of the rock matrix and cements from core material extracted from four oil wells within southwestern Ontario suggest various stages of diagenetic alteration and preservation of the Trenton Group carbonates. The geochemical compositions of Middle Ordovician (LMC) brachiopods reflect the physicochemical water conditions of the ambient depositional environment. The sediments appear to have been altered in the presence of mixed waters during burial in a relatively open diagenetic microenvironment. Conodont CAl determination suggests that the maturation levels of the Trenton Group carbonates are low and proceeded at temperatures of about 30 - 50°C within the shallow burial environment. The Trenton Group carbonates are characterized by two distinct stages of dolomitization which proceeded at elevated temperatures. Preexisting fracture patterns, and block faulting controlled the initial dolomitization of the precursor carbonate matrix. Dolomitization progressed In the presence of warm fluids (60 75°C) with physicochemical conditions characteristic of a progressively depleted basinal water. The matrix is mostly Idiotopic-S and Idiotopic-E dolomite, with Xenotopic-A dolomite dominating the matrix where fractures occur. The second stage of dolomitization involved hydrothermal basinal fluid(s) with temperatures of about 60 - 70°C. These are the postulated source for the saddle dolomite and blocky calcite cements occurring in pore space and fractures. Rock porosity was partly occluded by Idiotopic-E type dolomite. Late stage saddle dolomite, calcite, anhydrite, pyrite, marcasite and minor sphalerite and celestite cements effectively fill any remaining porosity within specific horizons. Based on cathode luminescence, precipitation of the different diagenetic phases probably proceeded in open diagenetic systems from chemically homogeneous fluids. Ultraviolet fluorescence of 11 the matrix and cements demonstrated that hydrocarbons were present during the earliest formation of saddle dolomite. Oxygen isotope values of -7.6 to -8.5 %0 (PDB), and carbon isotope values of - 0.5 and -3.0 %0 (PDB) from the latest stage dog-tooth calcite cement suggest that meteoric water was introduced into the system during their formation. This is estimated to have occurred at temperatures of about 25 - 40°C. Specific facies associations within the Trenton Group carbonates exhibit good hydrocarbon generating potential based on organic carbon preservation (1-3.5%). Thermal maturation and Lopatin burial-history evaluations suggest that hydrocarbons were generated within the Trenton Group carbonates some time after 300 Ma . Progressively depleted vanadium trends measured from hydrocarbon samples within southwestern Ontario suggests its potential use as a hydrocarbon migration indicator on local (within an oilfield) and on regional scales.

Contribuição da catodoluminescência para o entendimento da diagênese da formação Jandaíra: áreas do campo de petróleo da fazenda Belém e Lajedo do Rosário

The general objective of this study was to contribute to the understanding of the chemical evolution of fluids that percolate through carbonate rocks of the Jandaíra Formation. The oxidation and reduction conditions in which grains, source and cement were formed was investigated using the cathodoluminescence technique (CL). The study area is located in the west part of the Potiguar Basin (Fazenda Belém field) and Rosário Ledge (Felipe Guerra municipality, State of Rio Grande do Norte, Brazil). The analysis of thin sections of carbonate rocks under CL revealed that grains (allochemical or not) and diagenetic products (micritization, dolomitization, neomorphism and cementation) exhibit since absence of luminescence the various luminescence colors (yellow, orange, red, brown, and blue) in a variety of intensities. As pure calcite shows dark blue luminescence, the occurrence of different luminescence colors in calcite crystals suggest one or more punctual crystal defects such as free electron, free space and impurity. The dyeing of thin sections with alizarin and potassium ferrocyanide revealed the absence of ferrous carbonate in the different lithotypes of Jandaíra Formation. Therefore, the different colors and intensities of CL observed in these rocks are probably caused by the presence of ion activators such as Mn2+ and is not an activator/inhibitor combination. In the same way, the absence of luminescence is very probably caused by the absence of activator ions and not due to the low concentration of inhibitor ions such as Fe2+. The incorporation of Mn2+ in the different members of the Jandaíra Formation must have been controlled by the redox state of the depositional environment and diagenesis. Therefore, it is possible that the luminescent members have been formed (e.g.,ooids) or have been modified (gastropod neomorphism) under reduction conditions in the depositional environments, in subsurface during the burial, or, in the case of Rosario Ledge samples , during the post-burial return to surface conditions. As regards the sudden changes from low to moderate and to strong luminescence, these features should indicate the precipitation of a fluid with chemical fluctuations, which formed the frequent zonations in the block cement of the Rosario Ledge samples. This study suggests that the different intensities and colors of CL should be correlated with the Mn2+ and Fe2+ contents, and stable isotopes of samples to determine the salinity, temperature, pH e Eh conditions during deposition

Evolução tectono-estrutural do Campo de Xaréu (Sub-bacia de Mundaú, Bacia do Ceará - NE do Brasil: abordagem multiescala e pluriferramental

The Xaréu Oil Field, located in the center-southern portion of the Mundaú Sub-Basin (eastern portion of the Ceará Basin), is characterized by a main Iramework of NW-trending and NE-dipping faults. The faults in the Xaréu Oil Field, among which the Xaréu Fautt stands out, are arranged according to an extensional-listriclan, rooted on a detachment surface corresponding to the Mundaú Fault, the border fautt of Mundaú Sub-Basin. During the tectonic-structural evolution of the Xaréu Oil Field and the Mundaú Sub-Basin, the Mundaú Fault played a crucial role on the control of the geometry of both compartments. The main carbonatic unit in the Xaréu Oil Field, named the Trairí Member(Paracuru Formation of Late Aptian to Early Albian age), contains the largest oil volume in the field, concentrated in structurally-controlled accumulations. The Trairí Member is composed by a variety of carbonatic rocks (massive, bedded or laminated calcilutites, ostracodites, calcarenites and carbonatic rudites, all of them presenting variable degrees of dolomitization). The carbonatic rocks are interbedded into thick packages of black shales and marls, besides local beds of siliciclastic conglomerates, sandstones, siltnes and argillites. From the spatial association and the genetic relationships between the carbonatic and siliciclastic units, it is possible to group them in three lithofacies associations (Marginal Plain, Ramp and Lacustrine Interior) that, together, were developed in a lacustrine system associated to a marginal sabkha. Structural studies based on drill coresthat sample the Trairí Member in the Xaréu Oil Field allowed to characterize two generations of meso- to microscale structures: the D1 group presents a typical hydroplastic character, being characterized by intra/interstratal to oblique-bedding shear zones. The hydroplastic character related to these structures allowed to infer their development at an early-lithilication stage of the Trairí Member, leading to infer an Early Cretaceous age to them. The second group of structures identified in the drill cores, nominated D2 and ascribed to a Neogene age, presents a strictly brttle character, being typilied by normal faults and slickenfibers of re-crystallized clayminerals, ali olthem displaying variable orientations. Although the present faults in the Xaréu Oil Field (and, consequently, in the Mundaú Sub-Basin) were classically relerred as struetures of essentially normal displacement, the kinematics analysis of the meso-to microscaie D1 struetures in the drill cores led to deline oblique displacements (normal with a clockwise strike-slip component) to these faults, indicating a main tectonic transport to ENE. These oblique movements would be responsible for the installation of a transtensive context in the Mundaú Sub-Basin, as part of the transcurrent to translormant opening of the Atlantic Equatorial Margin. The balancing of four struetural cross-sections ofthe Xaréu Oil Field indicates that the Mundaú Fault was responsible for more than 50% of the total stretching (ß factor) registered during the Early Aptian. At the initial stages of the "rifting", during Early Aptianuntil the Holocene, the Mundaú Sub-Basin (and consequently the Xaréu Oil Fleld) accumulated a total stretching between 1.21 and 1.23; in other words, the crust in this segment of the Atlantic Equatorial Margin was subjeeted to an elongation of about 20%. From estimates of oblique displacements related to the faults, it ws possible to construct diagrams that allow the determination of stretching factors related to these displacements. Using these diagrams and assuming the sense 01 dominant teetonictransport towards ENE, it was possible to calculate the real stretching lactors related to the oblique movement 0 of the faults in the Mundaú Sub-Basin. which reached actual values between 1.28 and 1.42. ln addnion to the tectonic-structural studies in the Xaréu Oil Field, the interpretation of remote sensing products, coupled wnh characterization of terrain analogues in seleeted areas along the northern Ceará State (continental margins of the Ceará and Potiguar basins), provided addnional data and constraints about the teetonic-structural evolution of the oil lield. The work at the analogue sites was particularly effective in the recognition and mapping, in semidetail scale, several generations of struetures originated under a brittle regime. Ali the obtained information (from the Xaréu Oil Field, the remote sensor data and the terrain analogues) were jointly interpreted, culminating with the proposnion of an evolutionary model lor this segment of the Atlantic Equatorial Margin; this model that can be applied to the whole Margin, as well. This segmentof the Atlantic Equatorial Margin was delormedin an early E-W (when considered lhe present-day position of the South American Plate) transcurrent to transform regime with dextral kinematics, started Irom, at least, the Early Aptian, which left its record in several outcrops along the continental margin of the Ceará State and specilically in the Xaréu off Field. The continuous operation of the regime, through the Albian and later periods, led to the definitive separation between the South American and African plates, with the formation of oceanic lithosphere between the two continental blocks, due to the emplacement off spreading centers. This process involved the subsequent transition of the transcurrent to a translorm dextral regime, creating lhe Equatorial Atlantic Oceano With the separation between the South American and African plates already completed and the increasing separation between lhe continental masses, other tecton ic mechanisms began to act during the Cenozoic (even though the Cretaceous tectonic regime lasted until the Neogene), like an E-W compressive stress líeld (related to the spreading olthe oceanic floor along lhe M id-Atlantic Ridge and to the compression of the Andean Chain) effective Irom the Late Cretaceous, and a state of general extension olthe horizontal surface (due to the thermal uplift ofthe central portion of Borborema Province), effective during the Neogene. The overlap of these mechanisms during the Cenozoic led to the imprint of a complex tectonic framework, which apparently influenced the migration and entrapment 01 hydrocarbon in the Ceará Basin

Anthropogenic impacts on mineral weathering: A statistical perspective

Correspondence Analysis was adopted as tool for investigating the statistical structure of hydrochemical and weathering datasets of groundwater samples, with the main purpose of identifying impacts on mineral weathering caused by anthropogenic activities, namely fertilizing of farmlands. The hydrochemical dataset comprised measured concentrations of major inorganic compounds dissolved in groundwater, namely bicarbonate, silica (usually by-products of chemical weathering), chloride, sulphate and nitrate (typically atmospheric plus anthropogenic inputs). The weathering dataset consisted of calculated mass transfers of minerals being dissolved in loess sediments of a region located in SW Hungary (Szigetvár area), namely Na-plagioclase, calcite and dolomite, and of pollution-related concentrations of sodium, magnesium and calcium. A first run of Correspondence Analysis described groundwater composition in the study area as a system of triple influence, where spots of domestic effluents-dominated chemistries are surrounded by areas with agriculture-dominated chemistries, both imprinted over large regions of weathering dominated chemistries. A second run revealed that nitrification of N-fertilizers is promoting mineral weathering by the nitric acid reaction (anthropogenic pathway), in concurrence with the retreating of weathering by carbonic acid (natural pathway). It also indicated that dolomite and calcite are being players in a dedolomitization process driven by dissolution of gypsum fertilizers and nitrification of N-fertilizers. © 2013 Elsevier Ltd.

Paleoambiente e diagênese da formação Itaituba, carbonífero da bacia do Amazonas, com base em testemunho de sondagem, região de Uruará, Pará

A Formação Itaituba de idade carbonífera representa a sedimentação carbonática de depósitos transgressivos do Grupo Tapajós da Bacia do Amazonas. A sucessão Itaituba é interpretada como depósitos de planície de maré mista, constituídos de calcários fossilíferos, dolomitos finos, arenitos finos a grossos e subordinadamente siltitos avermelhados, evaporitos e folhelhos negros. A análise de fácies e microfácies do testemunho de sondagem da região de Uruará, Estado do Pará, permitiu individualizar dezenove fácies agrupadas em cinco associações: planície de maré (AF1), canal de maré (AF2), laguna (AF3), barra bioclástica (AF4) e plataforma externa (AF5). AF1 é composta por arenito fino com rip-up clasts e gretas de contração, marga com grãos de quartzo e feldspato, dolomudstone laminado com grãos terrígenos e dolomito fino silicificado, com intercalação de argilito com grãos de quartzo disseminados, dolomitizado e localmente com sílica microcristalina. AF2 consiste em arenito médio a grosso com estratificação cruzada acanalada, recoberta por filmes pelíticos nos foresets, arenito muito fino a fino com acamamento wavy, siltito laminado com falhas sinsedimentares e acamamento convoluto. AF3 é constituída de siltito vermelho maciço, mudstone com fósseis, floatstone com braquiópodes e pirita disseminada e mudstone maciço com frequentes grãos de quartzo. AF4 e AF5 exibem abundantes bioclastos representados por espinhos e fragmentos de equinodermas, conchas, fragmentos e espinhos de braquiópodes, ostracodes, foraminíferos, algas vermelhas e conchas de bivalves. AF4 é formada por grainstone oolítico fossilífero e grainstone com terrígenos principalmente grãos de quartzo monocristalino e AF5 se compõe de wackestone fossilífero, wackestone com terrígenos e mudstone maciço com grãos de quartzo monocristalino. Subarcósios (AF1), arcósios (AF2) e arcósios líticos (AF2) são os tipos de arenitos da sucessão Itaituba e apresentam como principais constituintes grãos de quartzo monocristalino e policristalino, K-feldspato, plagioclásio, pirita, muscovita detrítica, fragmento de rocha pelítica, metamórfica e chert e raros bioclastos. O cimento é de calcita espática não ferrosa, óxido/hidróxido de ferro e sobrecrescimento de sílica. A porosidade é intergranular, móldica e às vezes alongada, sem permeabilidade perfazendo até 11% da rocha. Os processos diagenéticos dos arenitos são compactação física, sobrecrescimento de sílica, cimentação de calcita, formação de matriz diagenética, compactação química, substituição de grãos, autigênese de pirita, formação de óxido/hidróxido de ferro e alteração do plagioclásio. Os processos diagenéticos dos carbonatos são: micritização, neomorfismo, colomitização, fraturamento, compactação química, cimentação de calcita, dissolução secundária e autigênese de minerais. A sucessão da Formação Itaituba representa um sistema de laguna/planície de maré ligada a uma plataforma marinha carbonática. Planícies de maré desenvolveram-se nas margens das lagunas e eram periodicamente supridas por influxos de terrígenos finos (silte) que inibiam a precipitação carbonática. Barras bioclásticas eram cortadas por canais de maré (inlet) que conectavam a laguna com a plataforma rasa rica em organismos bentônicos.

A seção-tipo da Formação Serra do Quilombo, Grupo Araras, Neoproterozoico da Faixa Paraguai Norte, Mato Grosso

Após a última glaciação criogeniana (ca. 635 Ma), extensas plataformas carbonáticas desenvolveram-se sobre diversas regiões cratônicas da Terra e, apesar da intensa dolomitização desses depósitos, muitas informações paleoambientais e paleoceanográficas estão preservadas. Um dos exemplos mais importantes deste período no Brasil são os dolomitos da Formação Serra do Quilombo, pertencente à porção superior do Grupo Araras, no segmento norte da Faixa Paraguai, sul do Cráton Amazônico. A reavaliação estratigráfica da seção-tipo da formação e de uma seção de referência na região de Nobres, com base na análise de fácies e estratigráfica, permitiu ampliar as interpretações paleoambientais e elaborar um modelo deposicional. A sucessão estudada, de 140 m de espessura, inclui a Formação Serra do Quilombo em contato basal brusco com os calcários da Formação Guia e a passagem gradual para os dolomitos arenosos da Formação Nobres, no topo. A Formação Serra do Quilombo representa um megaciclo de raseamento ascendente, constituído por duas associações de fácies: 1) plataforma carbonática profunda à moderadamente rasa, composta por um dolomito fino laminado rico em matéria orgânica e outro maciço a laminado; e 2) face litorânea influenciada por tempestades, constituída por dolomito arenoso com estratificação cruzada hummocky/swaley associada com estratificação plano-paralela, dolomito arenoso/oolítico com laminações produzidas por ondas e brecha dolomítica com matriz. A Formação Serra do Quilombo representa o registro progradante de um trato do sistema de mar alto, em um contexto de rampa carbonática homoclinal instalada no sul do Cráton Amazônico durante o Ediacarano.