Generations Of Dolomite Research Articles

Dolomitization in the Upper Paleozoic succession of the north-Ostaninsk field, Nyurolsk Basin, Western Siberia: Implications for hydrocarbon exploration

Paleozoic rocks in Western Siberia may contain significant hydrocarbon resources. However, effective methods for their exploration are poorly constrained. This study provides new insights into the causes of reservoir formation using the upper part of the Paleozoic succession of the North-Ostaninsk field in the Nyurolsk Basin as a case study. The carbonate rocks have been affected by dolomitization. Four dolomite generations have been identified: Floating in the matrix (D1), fracture-filling (D2.1), stylolite-associated (D2.2), partly replacive (D3) and, pervasive (D4). The last one replaces biogenic limestone in the upper part of the Paleozoic succession and coincides with the presence of a reservoir in the field. A systematic analysis petrographic, fluid inclusion, and carbon and oxygen isotope investigations suggest that the origin of dolomite is from the downward infiltration of meteoric water with higher Mg2+ and Fe2+ derived from the alteration of tuffaceous materials. The results, along with values of the magnetic field anomaly, reveal the relationship between dolomitization and the distribution of the oil and gas reserves in this Paleozoic succession within the basement of the West Siberian Basin. This new insight may be used to predict similar accumulations in poorly explored territories.

The Ediacaran Hiyam Formation: A zoom through the diagenetic and structural complexity of the metamorphic Hi2 Member, Saih Hatat Dome, Oman Mountains

This is the first diagenetic study of the metamorphic upper Hiyam Member “Hi2” of the Saih Hatat Dome. Despite metamorphism, texture and paragenesis of the Hi2 Member are so well preserved that it is possible to unravel its diagenetic evolution. We applied lithological and structural field methods, transmission and cathodoluminescence microscopy to establish the paragenetic sequence and vein-forming deformation. Our work reveals a complex diagenetic and structural history, including several alternating dolomitization, calcite precipitation, silicification and fracturing events. Most of the replacive dolomite and silica are linked to early diagenesis under intertidal to sabkha and restricted marine as well as to terrestrial conditions. Evaporation of sea water concentrated Mg2+ and triggered extensive early dolomitization while silica-bearing fluids caused local silicification. Various generations of dolomite and calcite cements pervasively occluded macropores, micropores and veins. Late burial is reflected by pressure solution seams/stylolites, non-ferroan to weakly ferroan saddle-type dolomite cement and non-ferroan blocky and drusy calcite cement, filling veins and macropores. The various generations of calcite cements (e.g., in veins) are considered to have formed during burial or possibly meteoric conditions. The latter potentially resulted from tectonic uplift, while late dolomite cement displays hydrocarbon residues from coeval oil migration. A later minor oil migration event has also been recognized. Initial fracture/fissure formation is most likely related to folding during the Early Cambrian Angudan Orogeny (open NW-SE fractures) and to divergence during the Late Paleozoic Pangean/Neo-Tethys rifting (open NW-SE fractures). Metamorphism impacted the Hi2 Member, resulting in phyllite formation, phyllosilicate crystallization and ductile shearing. Metamorphism occurred during shallow Late Cretaceous subduction. Striking lithological similarities between the Hi2 Member and that of the upper Kharus Formation of the Jabal Akhdar region could indicate their lateral equivalence.

Laterally-continuous dolomite layers of the Miocene Pisco Formation (East Pisco Basin, Peru): A window into past cyclical changes of the diagenetic environment

Along the Peruvian coast, the sedimentary succession of the East Pisco Basin is exposed in the Ica Desert. At Cerro Los Quesos, laterally continuous dolomite layers characterise the diatomaceous sediments of the P2 sequence of the Miocene Pisco Formation, where a large number of marine vertebrates are exceptionally preserved, many enclosed in dolomite nodules. In this work, cemented layers from this sequence were described and sampled for petrographic, chemical, microscopic and isotopic analyses. Dolomite occurs in continuous 10–50 cm thick well cemented layers, formed by sediment of different nature: biogenic, terrigenous, volcanoclastic, and phosphatic. The underlying sediments exhibit a yellow layer with sparse dolomite crystals, a black layer with abundant Mn-oxides, and a reddish layer rich in Fe-oxides, indicating redox-related fronts. Two generations of dolomite can be recognised: an early diagenetic microcrystalline one, and a sparry one, filling the large cavities. As observed in both thin sections and on broken surfaces, microcrystalline dolomite also fills the inner spaces of the diatom areolae replicating their finest ultrastructure, such as foramina and cribra and replace calcite shells of foraminifera. δ18O and δ13C values from the microcrystalline dolomite of two layers, selected based on the absence of other carbonate phases (e.g. calcite) and the lack of sparry cement, are in agreement with those reported for the Peru margin and fall in the fields of either sulphate-reduction or methanogenesis.All the data point to dolomite precipitation associated with low-temperature early diagenesis that typically occurs in upwelling settings, where high surface water productivity is responsible for high rates of organic carbon flux to the sea bottom and for the cyclical oxygen depletion at the bottom. Such conditions also promote high abundances of marine vertebrates and the exceptional preservation of their skeletons in the sediments.

In situ U-Pb dating and geochemical characterization of multi-stage dolomite cementation in the Ediacaran Dengying Formation, Central Sichuan Basin, China: Constraints on diagenetic, hydrothermal and paleo-oil filling events

Improved understanding of subsurface paleo-fluid circulation history can assist in reconstructing associated pore evolution of carbonate reservoirs. Multi-stage dolomite cements generated by basinal fluids over time were investigated using a combination of petrography, geochemistry, fluid-inclusion studies, LA-ICP-MS U-Pb geochronology, and seismic interpretation. This study aims to gain clues about diagenetic, hydrothermal and paleo-oil filling events within the Ediacaran Dengying Formation, Sichuan Basin, China.Four main phases of dolomite cementation were petrographically, geochemically and geochronologically distinguished that can be ascribed to major tectonic events throughout the basin evolution. The earliest dolomite generation occurs as fibrous dolomite crust (FDC) growing along the karst vug wall, interpreted as marine diagenetic cement formed in a submarine environment during the Late Ediacaran, most likely from the influx of seawaters following the uplift and subaerial exposure related to the Tongwang movement. In situ U-Pb ages obtained from the other three generations of cement dolomites are interpreted to coincide with the timing of repeated strike-slip fault movements as indicated by the seismic data, suggesting a direct link between cement emplacement and regional tectonic-thermal events. Sub-vertical extension dolomite veins (EDV), representing the second generation, are considered as being syntectonic, generated from slightly modified connate seawaters at a shallow to moderate burial depth in a transtensional stress regime during the Cambrian taphrogenesis. Two generations of saddle dolomite cements, SD1 and SD2, have recorded two major episodes of hot fluids circulating in the Dengying Formation. The SD1, filling in hydraulic fractures and vugs, formed during the third phase of cementation, as a result of a hydrothermal event associated with Caledonian exhumation. Deep-seated hot brines squeezed into the Dengying reservoirs along the sub-vertical strike-slip faults combined with some meteoric waters that percolated downward, are deemed responsible for precipitating SD1. The SD2 is the youngest cement present, which is interpreted to have formed during the ingress of deeper, hot, hypersaline brines arising from the late Permian hydrothermal activity likely triggered by the eruption of Emeishan flood basalts.Cross-cutting relationships between bitumen phases and different dolomite generations indirectly define the dates of two paleo-oil charging events. The first episode of paleo-oil charging occurred during the Late Ediacaran to Early Cambrian, likely sourced from underlying Ediacaran Doushantuo shales. Late oil emplacement occurred after the Late Permian, in agreement with the reported bitumen Re-Os age and the age inferred through fluid-inclusion analysis. Primary source rocks generating this phase of oil were considered as the Cambrian Qiongzhusi shales, because basin modeling-derived date of oil window matches with the second oil filling time.

Geochemical constraints of hydrothermal alteration of dolostones: An example of Lower Cretaceous Qamchuqa Formation, Kurdistan Region, northern Iraq

This paper integrates major, minor, trace and rare-earth element (REE) data into C-, O-, Sr-isotopes, fluid-inclusions microthermometry of replacive matrix dolomite and vug/fracture-filling saddle dolomite and calcite of the Lower Cretaceous Qamchuqe Formation, the Kurditan Region of Iraq, in order to get further insights into the origin and geochemical evolution of their parent diagenetic fluids. Multiple generations of dolomite have been observed. These dolomites constitute replacive matrix dolomite and saddle dolomite cement, dominantly poorly ordered, non-ferroan, non-stoichiometric, with an average of 59.4 and 60 mol% CaCO3, respectively, and have low Sr, Fe and Mn concentrations. Replacive matrix dolomites display fairly comparable REE patterns to saddle dolomite, but with light REE (LREE) enrichment, and moderate low (∑REEs) contents (18.9–1111.5 and 16.6–593.4 ppb, respectively). Saddle dolomite has moderately positive Eu anomalies while replacive matrix dolomite has slightly less positive Eu anomalies and negative Dy, Ho and Yb anomalies. Both dolomites are characterized by slightly radiogenic 87Sr/86Sr ratios ranging from 0.707702 to 0.707839, overlapping, wide-ranging and negative δ18O values from −10.43 to −4.47 and −12.87 to −7.79 ‰VPDB, and δ13C values ranging from 0.38 to 3.57 and −3.45 to 3.11‰VPDB, respectively. The primary fluid inclusions microthermometry of replacive matrix and saddle dolomites yield homogenization temperatures (Th) ranging from 71.3 to 228.3 °C and 82–188 °C, respectively, and salinity values ranging between 14.4 to 25.4 and 15.6 to 27.9 wt% NaCl eq., respectively. These data suggest multiple hydrothermal fluid fluxes during and post Zagros orogeny. The geochemical data also show that these fluids derived from similar source of mixed hydrothermal and marine fluids, which caused the dolomitization of host rock and precipitation of dolomite cements.

Dolomitization of Paleozoic Successions, Huron Domain of Southern Ontario, Canada: Fluid Flow and Dolomite Evolution

Integrated petrographic, isotopic, fluid inclusion microthermometry, and geochemical analyses of Paleozoic carbonate successions from multiple boreholes within the Huron Domain, southern Ontario were conducted to characterize the diagenetic history and fluid composition, on a regional scale, and evaluate the nature and origin of dolomitized beds. Multiple generations of non-stochiometric dolomite have been observed. These dolomites occur as both replacement (D1 and D2) and cement (saddle dolomite; SD) and formed either at near-surface to shallow burial zone (D1) or intermediate burial (D2 and SD). Petrographic and geochemical data of dolomite types and calcite cement suggest that these carbonates have experienced multiple fluid events that affected dolomite formation and other diagenetic processes. Cambrian and Ordovician strata have two possibly isolated diagenetic fluid systems; an earlier fluid system that is characterized by a pronounced negative shift in oxygen and carbon isotopic composition, more radiogenic Sr ratios, warm and saline signatures, higher average ∑REE compared to warm water marine brachiopods, negative La anomaly, and positive Ce anomaly; and a later Ordovician system, characterized by less negative shifts in oxygen and carbon isotopes, comparable Th, hypersaline, a less radiogenic, less negative La anomaly, and primarily positive Ce anomaly but also higher average ∑REE compared to warm water marine brachiopods. Ordovician, Silurian, and Devonian Sr isotopic ratios, however, show seawater composition of their respective age as the primary source of diagenetic fluids with minor rock/water interactions. In contrast, the isotopic data of the overlying Silurian and Devonian carbonates show overlaps between δ13C and δ18O values. However, δ18O values show evidence of dolomite recrystallization. D2 shows wide Th values and medium to high salinity values. Higher Th and salinity are observed in SD in the Silurian carbonates, which suggest the involvement of localized fluxes of hydrothermal fluids during its formation during Paleozoic orogenesis. Geochemical proxies suggest that in both age groups the diagenetic fluids were originally of coeval seawater composition, subsequently modified via water-rock interaction possibly related to brines, which were modified by the dissolution of Silurian evaporites from the Salina series. The integration of the obtained data in the present study demonstrates the linkage between fluid flux history, fluid compartmentalization, and related diagenesis during the regional tectonic evolution of the Michigan Basin.

Application of fluorescent light microscopy to enhanced lithofacies analysis of Jurassic carbonate rocks, SE Bohemian Massif

Upper Jurassic limestones and dolomites of the Vranovice Formation occur on the southeastern slopes of the Bohemian Massif below the Western Carpathian thrust belt. They represent a special type of reservoir rocks in the potential geothermal systems and exhibit highly variable porosity, permeability, and flow mechanisms due to different type of diagenesis and pervasive dolomitization. Fluorescence and translucent light microscopy was used for more detailed petrographic analysis of Vranovice limestones and dolomites. Isopachous, syntaxial and dolomitic cements were distinguished along with fossils recrystallization. Two generations of dolomite were identified – replacement dolomite and zonal cementation dolomite, what suggests a number of changes in the formation water chemistry during the dolomitization process. Extent of the observed dolomitization is inversely related to the porosity of the Jurassic rocks. Postdiagenetic generation of fissures cutting the strata due to tectonic deformation is documented by bright fluorescent color. In the studied samples of Vranovice limestones and dolomites the fissures represent the most important migration pathways, more than pore throats themselves. Further genetic information on petoleum migration is interpreted from intercrystalline porosity filled with precipitated solid bitumen. Present results provide basis for further investigations in pore-water-rock interactions and changes in chemical conditions during diagenesis.

Origin of Middle-Upper Cambrian dolomites in eastern Laurentia: A case study from Belle Isle strait, western Newfoundland

The Middle and Upper Cambrian Port au Port Group of western Newfoundland consists mainly of mixed carbonates and siliciclastics and is composed of the March Point, Petit Jardin, and Berry Head formations. Samples were collected from the core NF-02 that spans the uppermost Hawke Bay (40 m), the March Point (~83 m thick) and the lowermost Petit Jardin (~47 m). Petrographic examination of carbonates of the March Point and Petit Jardin carbonates reveals three generations of dolomite: (i) micritic to near-micritic (D1, 4 μm −35 μm) fabric-retentive dolomite, (ii) coarse crystalline sucrosic (D2, 60 μm−150 μm) fabric-destructive dolomite (sub-to euhedral zoned rhombs with clear rim and cloudy core), and (iii) coarse anhedral (D3, >0.5 mm) fracture-filling saddle dolomite. The microthermometric measurements of primary two-phased fluid inclusions retained in D2, and D3 samples yielded homogenization temperatures (Th) showing a general increase with burial. The mean values of Th and salinity are 89.1 ± 6.4 °C vs 21.2 ± 2.2 eq. wt% NaCl, and 110 ± 8.2 °C vs 21.1 ± 4.7 eq. wt% NaCl, respectively. The investigated dolomites show a decrease of Sr from D1 (102 ± 49 ppm) to D3 (47 ± 15 ppm) which reflects the influence of progressive burial. The mean δ18O values decrease from D1 (−6.3 ± −1.1‰ VPDB), to D3 (−9.7 ± 1.7‰ VPDB) where D2 (−7.6 ± 1.2‰ VPDB) is in the middle. The estimated δ18O values of the D1 parent fluid (−5 to −10‰ VSMOW) are bracketed by those suggested for the Middle Cambrian meteoric and seawaters. The fluid-inclusion gas analyses provided CO2/CH4 and N2/Ar ratios coherent with the conclusions from the petrographic examination and geochemical compositions.

Fracture dolomite as an archive of continental palaeo-environmental conditions

The origin of Quaternary dolomites in continental environments (e.g. karst and lakes) is barely constrained compared to marine dolomites in sedimentary records. Here we present a study of dolomite and aragonite formations infilling young fractures of the ‘Erzberg’ iron ore deposit, Austria, under continental-meteoric and low temperature conditions. Two dolomite generations formed shortly after the Last Glacial Maximum (~20 kyr BP): dolomite spheroids and matrix dolomite. Clumped isotope measurements and U/Th disequilibrium ages reveal formation temperatures of 0–3 °C (±6 °C) and 3–20 °C (±5 °C) for the both dolomite types, and depositional ages around 19.21 ± 0.10 kyr BP and 13.97 ± 0.08 kyr BP or younger, respectively. Meteoric solution and carbonate isotope compositions (δ18O, δ13C and 87Sr/86Sr) indicate the dolomites formed via aragonite and high-Mg calcite precursors from CO2-degassed, Mg-rich solutions. Our study introduces low temperature dolomite formations and their application as a sedimentary-chemical archive.

Petrological and geochemical constraints on the origin of dolomites: a case study from the early Cambrian Qingxudong Formation, Sichuan Basin, South China

Several types of dolomite had occurred pervasively in the lower Cambrian Qingxudong Formation in the Sichuan Basin. However, the origin of these dolomites remains particularly controversial until now. Here, we describe the petrographic and geochemical characteristics of dolomites from the lower Cambrian Qingxudong Formation in the southeastern Sichuan Basin, which can potentially provide useful information to constrain the origin and evolution of dolomitization fluid. Three fabric types and five dolomite generations were identified in this study: fabric-retentive dolomites (dolomicrite, Dol-1, and dolomitic microbialite, Dol-2), fabric-destructive dolomites (sucrosic dolomite, Dol-3) and pore-filling dolomites (medium- to coarse-crystalline dolomite, Dol-4, and saddle dolomite, Dol-5). The δ13C and δ18O values, 87Sr/86Sr ratios and rare earth element (REE) pattern of Dol-1, Dol-2 (except the δ13C values) and Dol-3 are approximately consistent with original seawater values, suggesting that the dolomitization fluids were mediated by seawater. The calculated dolomitization temperature (25.66 °C) and Z values (125.2) of Dol-1 with evaporite minerals indicate that the dolomitization fluid was high-salinity concentrated seawater derived from evaporation. The calculated dolomitization temperature (24.20 °C) and Z value (121.8) of Dol-2, and no traces of evaporite minerals in Dol-2 imply that the dolomitization fluid was slightly hypersaline seawater. The more negative δ13C and abundant microbial features of Dol-2 indicate that microbial mats were involved in dolomite formation. The dolomitization temperature (30.55 °C) and Z value (125) of Dol-3 also indicate that the dolomitization fluid was high-salinity concentrated seawater. However, Dol-3 is commonly distributed in reef and shoal facies (high porosity and permeability) throughout the Qingxudong Formation. Moreover, the abundant organic matters in the dolomitization fluid likely overcame the kinetic and thermodynamic barriers in the process of dolomitization. The geochemical data (except the δ18O values) of Dol-4 are approximately consistent with fabric-retentive dolomites, suggesting that the Dol-4 had been inherited from precursor carbonates. The negative δ18O values of Dol-4 revealed a further burial environment. High LREE/HREE ratios, positive europium anomalies and negative δ18O values of Dol-5 suggest that these dolomites were affected by hydrothermal fluids under deep burial conditions. Thus, Dol-1, Dol-2 and Dol-3 are likely attributed to sabkha, organogenic (microbial) and seepage-reflux dolomitization models during early-stage diagenesis, respectively. Dol-4 and Dol-5 are commonly attributed to burial and hydrothermal dolomitization models during deep burial diagenesis. This study provides new insights into the origin of dolomites and is especially useful for the further understanding of dolomite reservoir formation in the Qingxudong Formation.

Can crystal morphology indicate different generations of dolomites? Evidence from magnesium isotopes

Among various geochemical and petrographic approaches, dolomite crystal morphology and dolostone fabric have been widely applied in the study of ancient dolostones. It is proposed that dolomite crystal morphologies and the rock fabric may reflect the formation temperature, and thus can be used to distinguish different generations of dolomite. However, this scenario has also been challenged by some researchers. In order to test whether the dolomite crystal morphology can be used to differentiate different generations of dolomite, in this study, we measured the Mg isotopic compositions (δ26Mg) of dolomite with different crystal morphologies. δ26Mg of dolomite is controlled by a variety of factors, including temperature, magnesium isotopic composition of dolomitization fluids, and the flow rate of dolomitization fluids. If dolomite with distinct crystal morphologies were derived from different dolomitization processes, it is highly plausible that they would have different δ26Mg. Five types of dolomite with distinct crystal morphologies and rock fabric were recognized from three sampling intervals (S1, S2, and S3) in the middle Ordovician Majiagou Formation in North China. Different types of dolomite in the same sampling interval have similar δ26Mg values, suggesting that these dolomites might have derived during the same dolomitization event. Our study indicates that the crystal morphology alone may not unambiguously differentiate the generations of dolomites. We propose the following reasons: (1) the dolomite crystal morphology might be controlled by various factors rather than the formation temperature alone, or (2) the dolomite crystal morphology might be modified in diagenesis, but δ26Mg remains unchanged.

Structurally-controlled hydrothermal fluid flow in an extensional tectonic regime: A case study of Cretaceous Qamchuqa Formation, Zagros Basin, Kurdistan Iraq

Shallow water carbonate rocks of the Lower Cretaceous Qamchuqa Formation host a significant reserve of oil in the NNE Arabian plate-Southwestern Zagros Sutured Belt in the Kurdistan Region, Iraq. Such carbonates consist of several dolostone bodies with unique and complex arrays of saddle and zebra dolomite textures especially in fractured intervals. Integration of field, core description, microstructural analysis, petrographic, stable C, O and Sr isotopes, and fluid inclusion analyses reveals two main phases of multiple fluxes of hydrothermal fluid circulation during the Zagros Orogeny at the end of Cretaceous and Cenozoic times. An early regional non-focused hydrothermal dolomitization and a subsequent fault- and fracture- controlled hydrothermal fluid flow, which led to replacement and cementation by a range of saddle dolomite and zebra textures. Several generations of matrix dolomite, saddle dolomite and calcite cement were identified. The host dolostone has been affected by shortening, folding, fracturing, and thrust faulting. Saddle dolomite pipes, in particular, were found to be associated with en-échelon folding. The morphology and areal extent of the zebra dolomite are controlled by the pore geometry of the host dolostone in relationship to fracturing and faulting.Both matrix and saddle dolomite cements have comparable, overlapping stable isotopic values ranging from 0.39‰ to 3.57‰ and −0.12 to 3.11‰ VPDB, respectively for δ13C and δ18O values range from −10.53‰ to −4.47‰ and −12.87 to −7.79‰ VPDB, respectively. 87Sr/86Sr ratios of pervasive matrix dolomite range from 0.707702 to 0.707839, fall close to late Cretaceous seawater values. Slightly more radiogenic values of saddle dolomites ranging from 0.707759 to 0.708024 resulted from mixing of basinal brines with connate waters. Isotopic signatures of later calcite cements show more radiogenic Sr ratios from 0.707755 to 0.708198 and negative δ13C values 1.76 to −7.45‰, possibly related to late diagenetic processes due to incursion of meteoric waters during subaerial exposure.Fluid inclusion data of pervasive matrix dolomite and saddle dolomites show homogenization temperatures (Th) with a wide range from 71.3 to 169.7 °C and 82.3 to 188.2 °C, and salinity between 14.4 to 25.4 and 15.6 to 27.9 wt% NaCl eq., respectively. These values demonstrate the effect of hydrothermal fluid flow of the alteration of host dolomite and formation of saddle dolomite in fractures and faults.

Trace element geochemistry of carbonates in the Jurassic Lusitanian Basin records mineral-fluid interactions

Carbonate rocks in sedimentary basins are reactive and can record complex histories of events associated with fluid flow in these basins. These include processes of dolomitization and dedolomitization. In this work we provide some preliminary data where distinct calcite and dolomite generations in the Jurassic Lusitanian Basin were analysed by LA-ICP-MS for trace elements in order to characterize chemical signatures of fluid-mineral interaction. It was observed that different carbonate generations can preserve the range of certain trace metal concentrations, but later calcites have distinctly higher contents in REE, Th and U, and Ba. Dolomites also show distinct chemical signatures but lack of analytical and spatial resolution does not allow quantification of the precursor calcite relicts. However, these processes point to the action of basinal fluids triggered by distinct tectonic episodes and associated volcanic activity.

The Tonian Beck Spring Dolomite: Marine dolomitization in a shallow, anoxic sea

The reason for the abundance of dolomite lithologies in Earth's early geological record compared to modern environments remains contentious. This study provides new insight into this Precambrian “dolomite problem” by revisiting one of the most controversial dolomite localities, the Beck Spring Dolomite, of Death Valley, USA. Consistent with some previous studies, petrographic evidence indicates that although the Beck Spring Dolomite now consists almost entirely of dolomite, it was originally precipitated largely as aragonite and high-Mg calcite. Depositional constituents (microbialites and ooids) were likely originally aragonitic, and early marine length-fast cements (now dolomite) are suggested to have precipitated as high-Mg calcite then replaced syntaxially by dolomite. Based on petrographic and geochemical evidence, we suggest that marine dolomitization was the dominant synsedimentary diagenetic process in the unit, and for the most part, involved syntaxial and mimetic replacement. Further, a length-slow fibrous dolomite generation was precipitated during the later stages of marine diagenesis as a primary marine dolomite cement. This is indicated by the length-slow crystallographic structure of the cement and from its preserved geochemical and cathodoluminescence growth zonation. This new evidence for Tonian marine dolomite precipitation reinforces the idea of Precambrian marine environmental conditions, including the chemical composition of seawater, promoting dolomite formation at this time. The trace metal geochemical composition of well-preserved marine components, especially dolomite marine cements, reveals information about redox conditions in this Tonian shallow seawater. In terms of rare earth element geochemistry, the Beck Spring Dolomite has no significant Ce anomaly, and a ubiquitous positive Eu anomaly, consistent with widespread oceanic anoxia during deposition. Furthermore, the relatively low levels of iron and chalcophile elements Co, Cu, Pb and Zn in marine components compared to other Neoproterozoic carbonates suggest euxinic conditions (both anoxic and sulphidic) prevailed during deposition of the Beck Spring Dolomite.

Testing clumped isotopes as a reservoir characterization tool: a comparison with fluid inclusions in a dolomitized sedimentary carbonate reservoir buried to 2–4 km

Abstract Constraining basin thermal history is a key part of reservoir characterization in carbonate rocks. Conventional palaeothermometric approaches cannot always be used: fluid inclusions may be reset or not present, while δ 18 O palaeothermometry requires an assumption on the parent fluid composition. The clumped isotope palaeothermometer, however, is a promising technique for constraining the thermal history of basins. In this study, we test if clumped isotopes record temperatures of recrystallization in deeply-buried dolomitic reservoirs, through comparison with fluid-inclusion data. The studied reservoir is the Cretaceous Pinda Formation, offshore Angola, a deeply-buried dolomitized sedimentary carbonate hydrocarbon reservoir. It provides an ideal test case as samples from industry wells are available over a relatively wide burial depth range of c. 2000–4000 m below seafloor (mbsf) and the constituent dolomites are relatively homogeneous. Across this depth range, fluid-inclusion homogenization temperatures for the Pinda Formation record a range of temperatures from c. 110 to 170°C, increasing with depth. These closely match present-day ambient well temperatures, indicating recent resetting of the fluid inclusions. Clumped isotopes, however, record temperatures significantly ( c. 20–60°C) below fluid-inclusion and well temperatures for the seven samples analysed. The deepest five samples ( c. 2800–3700 mbsf) record clumped isotope temperatures of around 100–120°C, interpreted to represent a deep burial recrystallization event responsible for a massive (re)dolomitization of the reservoir. The lower clumped isotope temperatures (65 and 82°C) of the shallower (2055 and 2740 mbsf) samples are interpreted to represent physical mixing of two dolomite generations due to incomplete burial recrystallization of an early shallow dolomite. Determination of temperature through clumped isotopes allows calculation of the parent fluid δ 18 O values. In the five deepest samples, the fluid δ 18 O values of 3.7–6.5‰ cluster around the modern-day porewater composition (5‰), suggesting that burial dolomitization occurred in the presence of evolved brine. Mineral δ 18 O values of c . −7 to −4.5‰ are lower than pristine Cretaceous marine dolomite and are in accordance with burial recrystallization. Clumped isotopes are therefore interpreted to record temperatures corresponding to open-system burial recrystallization events. This study shows that clumped isotopes are a valuable tool in characterizing the thermal history of deeply-buried (>2000 m) carbonate hydrocarbon reservoirs.

Petrologic and geochemical attributes of calcite cementation, dolomitization and dolomite recrystallization: an example from the Mississippian Pekisko Formation, west-central Alberta

Abstract Carbonate rocks of the Pekisko Formation make up an important reservoir in west-central Alberta, especially in fields along the Pekisko subcrop edge. They represent a transgressive-regressive carbonate platform sequence comprised of upward shallowing facies, which subsequently underwent extreme erosion leading to the development of karst topography. As a result, diagenetic alteration, mainly through dolomitization and karstification, has affected reservoir characterization for most of the carbonate facies. Several generations of calcite cementation and dolomite are the result of complex diagenetic changes. Calcite cements include isopachous fibrous, equant drusy mosaic, pendant/meniscus, blocky spar, syntaxial, fibrous, and bladed. These cements formed during early and late diagenetic events; pre- syn- and post exposure in shallow and deeper burial realms. There are five types of dolomite identified in the Pekisko Formation, based on petrographic and geochemical analyses: 1) pervasive, fine to coarse crystalline, subhedral to anhedral replacive dolomite;2) void-filling, coarse crystalline, euhedral dolomite cement;3) selective, fine to coarse crystalline, euhedral to anhedral dolomite; 4) dissolution seam-associated, fine crystalline, euhedral dolomite; and 5) saddle dolomite. Dolomite types 1), 3) and 4) are interpreted to have formed early in the diagenetic history and subsequently recrystallized, whereas void-filling, coarse crystalline, euhedral dolomite and saddle dolomite formed later in deeper burial setting. Petrographic evidence for recrystallization of dolomite types, excluding void-filling and saddle dolomite, includes: etching, displayed mainly on euhedral crystals; dissolved cores on many crystals of varying shapes; non-planar crystal boundaries, exclusively in pervasive dolomites; and coarsening crystal size, evident in both pervasive and selective dolomite types. Geochemical evidence, such as pronounced negative shift in oxygen isotopes (by up to 8‰ VPDB) and enrichment of radiogenic Sr isotopes further support this interpretation. There is a definite negative trend whereby wells closest to the subcrop edge have the most negative isotopic values and those farthest away show the least depletion. This trend in δ18O isotope values points to recrystallization of the earlier formed dolomites.

Középső-triász dolomitok képződésének története és töréses deformációja a Szegedi-medence területén

A Pannon-medence aljzatának egyik részmedencéje a Szegedi-medence, mely szénhidrogén-földtani szempontból hazánk egyik kiemelt fontosságú területe. A prekainozoos aljzat legelterjedtebb mezozoos képződményei a középső-triász dolomitok, melyek fontos szerepet töltenek be a terület szénhidrogén-rendszerének felépítésében. Jelen tanulmány célja, hogy az évtizedek óta nem vizsgált képződmények képződéséről és deformációtörténetéről új, korszerű leírást nyújtson. Értelmezésünket általános petrográfiai leírásra, fluoreszcens és katódlumineszcens vizsgálati módszerekre, valamint a területről szóló szakirodalomra alapozzuk.A vizsgált anisusi képződmények változatos partszegélyi, sekélytengeri környezetben ülepedtek le. Ezek a leülepedést követő süllyedés következtében, a sekély és közepes betemetődés után, a kora-krétára juthattak a mély betemetődési diagenezis zónájába. Ezen zónákban a képződmények feltehetően többfázisú, részben szövetmegőrző, részben szövet -romboló dolomitosodási folyamatokon mentek keresztül. A petrográfiai alapon elkülönített dolomit típusok közülközepes vagy mély betemetődési környezetet jeleznek a porfirotópos és cukorszövetű dolomitok, valamint a póruskitöltő nyeregdolomit, de ezek szerepe alárendelt a korábbi dolomitosodási folyamatokhoz viszonyítva. A középső-miocént megelőzően a kőzeteket többször is töréses deformáció érte, melynek hatására breccsa, ezt követően pedig üreg- és repedéskitöltő nyeregdolomit képződött. A nyeregdolomit kristályai több esetben kőolajtartalmú fluidumzárványokat csapdáztak. A dolomittestek felszínközeli helyzetét középső-miocén, abráziósparti kör -nyezetben leülepedett fedőkőzetek jelzik, továbbá dedolomitosodás is kapcsolódhat ehhez a szakaszhoz. A Pannon-medence kialakulásával párhuzamos süllyedés és eltemetődés hatására a képződmények ismét nagy mélységbe kerültek, mely során újabb töréses deformáció és cementáció folyt. A legfiatalabb repedéskitöltő ásványegyüttest fluoreszcens tulajdonságú dolomit, valamint pirit és szilárd bitumen alkotja.A vizsgált dolomitok többfázisú diagenezis- és deformációtörténetéhez többfázisú szénhidrogén-migrációs események kapcsolhatóak, melyek pontosabb megismerése és elhelyezése a medence fejlődéstörténetében kulcsfontosságú. Az erősen átalakult nyeregdolomit tartalmú minták további vizsgálata rezervoárgeológiai szempontból a jövőben szintén fontos feladat.

Dissolving dolomite in a stable UHP mineral assemblage: Evidence from Cal-Dol marbles of the Dora-Maira Massif (Italian Western Alps)

In deep and cold subduction such as that experienced by the UHP Units of the Western Alps, carbon dissolution is a relevant mechanism for carbon transfer from the slab into the mantle. The UHP impure Cal-Dol-marbles from the Dora-Maira Massif are studied to investigate the poorly known evolution of dolomite during deep subduction. Dolomite shows four stages of growth, from pre-Alpine to early-retrograde Alpine, coupled with chemical variations and distinct included mineral assemblages. To explain the evidence for growth and partial reabsorption of dolomite through HP prograde, UHP peak, and UHP early-retrograde Alpine metamorphism, a chemically simple marble (Cal, Dol, Di, Fo, and retrograde Atg, Tr, Mg-Chl) has been studied in detail. Microstructural relationships, coupled with mineral chemistry, indicate the growth of the assemblage dolomite+diopside+forsterite±aragonite during HP prograde, UHP peak, and UHP early-retrograde evolution. Mixed-volatile P-T projection modeled in the simple CaO-(FeO)-MgO-SiO 2 -H 2 O-CO 2 system and T - P - X CO 2 petrogenetic grids and pseudosections predict the prograde (1.7 GPa, 560 °C) growth of dolomite in equilibrium with diopside and forsterite through the breakdown of antigorite+aragonite. In a H 2 O-CO 2 -saturated system, the subsequent HP-UHP evolution is predicted in the Di+Fo+Dol+Arg stability field in equilibrium with a dominantly aqueous COH fluid [ 0 . 0003 X CO 2 0 . 0008 ], whose composition is internally buffered by the equilibrium assemblage. Thermodynamic modeling indicates that neither the consumption nor the growth of new dolomite generations at UHP conditions can have been induced by metamorphic reactions. The abundant primary H 2 O+Cal+Dol+Cl-rich Tr+Cl-rich Tlc±chloride fluid inclusions present in UHP Cpx indicate that a dominantly aqueous, saline (salinity >26.3 wt% of NaCl eq ) COH fluid, containing Ca, Mg, and Si as dissolved cations was present during the growth of the UHP assemblage Dol+Cpx+Ol+Arg. The complex zoning of dolomite is therefore interpreted as due to protracted episodes of dissolution and precipitation in saline aqueous fluids at HP/UHP conditions. Kinetics of dolomite dissolution in aqueous fluids is poorly known, and experimental and thermodynamic data under HP conditions are still lacking. Data on calcite indicate that dissolution at HP is enhanced by a prograde increase in both P and T , by high salinity in aqueous fluids, and/or low-pH conditions. In the studied marble, the P-T path and the occurrence of free high-saline fluids represent favorable conditions: (1) for the inferred dissolution-precipitation processes of the stable dolomite in a closed system, and (2) for possible migration of the dissolved carbonate, if the system would have been open during subduction.

Climate controlled, fabric destructive, reflux dolomitization and stabilization via marine- and synorogenic mixed fluids: An example from a large Mesozoic, calcite-sea platform, Croatia

The Jurassic–Cretaceous dolomites, Adriatic platform, Croatia resulted from climate-influenced post-depositional reflux dolomitization (as opposed to synsedimentary peritidal- and deeper burial dolomitization), and subsequent stabilization within a Mesozoic, “calcite sea” isolated platform. The dolomites are stratiform (10 to 200m thick), fabric destructive (20 to over 500μm crystals), nonluminescent, and zoned with respect to Ca. Bulk dolomites have low Mn (10 to 30ppm), moderate Sr (60 to over 200ppm), positive δ13C and δ18O values, only moderate ordering (0.25 to 0.6) and single-phase fluid inclusions (temperatures <50°C). High-Ca dolomite (HCD; ~53 to ~59mol% Ca; δ18O+1 to >+3‰ VPDB and Sr>100ppm) composes most Jurassic and 40% of Cretaceous dolomites, making up turbid dolomite cores and initial clear dolomite rims. A first generation of low-Ca dolomite (LCD-1; 50 to 53mol% Ca; δ18O+1 to >+3‰ VPDB; 100–180ppm Sr) forms cement and variably replaces (stabilizes) earlier HCD cores. HCD and LCD-1 formed in refluxing marine-dominated pore waters under semi-arid climate (<300m depth, 30 to ~40°C). 87/86Sr values of the HCD and LCD-1 dominantly were controlled by the refluxing seawater 87/86Sr with minor addition of 87/86Sr from ascending cooling fluids. During maturation of HCD, Sr loss was greatest from least stable, more calcic HCD (>55mol%) phases. A second generation of much younger, low-Ca dolomite (LCD-2; fracture-associated, more negative δ18O from −1.4 to +1‰ VPDB, Sr <100ppm, enriched in radiogenic 87Sr) overgrows and variably replaces earlier Cretaceous dolomites. It formed during Eocene–Oligocene deformation and uplift to <1km burial depths (<50°C) from synorogenic, mixed marine–meteoric pore fluids, circulating via faults, fractures and local permeable zones. Porosity loss by dolomite cementation coupled with localized, rapid Cenozoic uplift, variably arrested stabilization to LCD.

Origin of the Breno and Esino dolomites in the western Southern Alps (Italy): Implications for a volcanic influence

The Esino Limestone of the western Southern Alps represents a differentiated Ladinian-Lower Carnian (?) carbonate platform comprised of margin, slope and peritidal inner platform facies up to 1000 m thick. A major regional subaerial exposure event lead to coverage by another peritidal Lower Carnian carbonate platform (Breno Formation). Multiphase dolomitization affected the carbonate sediments. Petrographic examinations identified at least three main generations of dolomites (D1, D2, and D3) that occur as both replacement and fracture-filling cements. These phases have crystal-size ranges of 3–35 μm (dolomicrite D1), 40–600 μm (eu-to subhedral crystals D2), and 200 μm to 5 mm (cavity- and fracture-filling anhedral to subhedral saddle dolomite D3), respectively.The fabric retentive near-micritic grain size coupled with low mean Sr concentration (76 ± 37 ppm) and estimated δ18O of the parent dolomitizing fluids of D1 suggest formation in shallow burial setting at temperature ∼ 45–50 °C with possible contributions from volcanic-related fluids (basinal fluids circulated in volcaniclastics or related to volcanic activity), which is consistent with its abnormally high Fe (4438 ± 4393 ppm) and Mn (1219 ± 1418 ppm) contents. The larger crystal sizes, homogenization temperatures (D2, 108 ± 9 °C; D3, 111 ± 14 °C) of primary two-phase fluid inclusions, and calculated salinity estimates (D2, 23 ± 2 eq wt% NaCl; D3, 20 ± 4 eq wt% NaCl) of D2 and D3 suggest that they formed at later stages under mid-to deeper burial settings at higher temperatures from dolomitizing fluids of higher salinity, which is supported by higher estimated δ18O values of their parent dolomitizing fluids. This is also consistent with their high Fe (4462 ± 4888 ppm; and 1091 ± 1183 ppm, respectively) and Mn (556 ± 289 ppm and 1091 ± 1183 ppm) contents, and low Sr concentrations (53 ± 31 ppm and 57 ± 24 ppm, respectively).The similarity in shale-normalized (SN) REE patterns and Ce (Ce/Ce*)SN and La (Pr/Pr*)SN anomalies of the investigated carbonates support the genetic relationship between the dolomite generations and their calcite precursor. Positive Eu anomalies, coupled with fluid-inclusion gas ratios (N2/Ar, CO2/CH4, Ar/He), high F− concentration, high F/Cl and high Cl/Br molar ratios suggest an origin from diagenetic fluids circulated through volcanic rocks, which is consistent with the co-occurrence of volcaniclastic lenses in the investigated sequence.