Fracture sealing and fluid overpressures in limestones of the Jabal Akhdar dome,Oman mountains

Fractures are important conduits for fluid flow in the Earth's crust. To better understand the spatial and temporal relations among fracturing, fracture sealing, and fluid flow, we have studied fractures, faults, and veins in a large dome (Jabal Akhdar) in the Oman mountains. Our work combines the results of meso‐ and microstructural analyses and stable isotope analyses. Seven generations of fractures and veins have been identified in the carbonate‐dominated dome. The earliest generations of veins developed during extension and subsidence of the Mesozoic basin. These veins formed in the inclined segments of bedding‐parallel stylolites and in extensional fractures that are perpendicular to bedding (#1 and #2, respectively). These extension‐related veins are truncated by bedding‐parallel veins (#4) that formed during top‐to‐north bedding‐parallel shear of both the northern and southern limbs of the dome. These veins are consistent with a change in stress regime and may be related to an earlier generation of strongly deformed pinch‐and‐swell veins (#3) that are exposed locally on the southern limb of the dome. Normal faults contain a set of en‐echelon tension gashes (#5) and veins emplaced in dilational jogs along the fault planes (#6). In the northern part of the dome, veins (#7) associated with thrusts post‐date the normal faults. Samples of veins and their host rocks were analyzed to provide information on fluid‐rock interaction in the dome and the scale(s) of fluid movement. Oxygen isotope values range from +16.2 to +29.3‰; carbon isotope values range from 0 to +3.6‰. The results of the structural and isotopic analyses are consistent with the early veins (#2–#5) having precipitated from overpressured fluid in a isotopically rock‐buffered system. During normal faulting (#5 and #6), a more open system allowed external fluid to infiltrate the dome at drained conditions and precipitate the youngest sets of veins (#6 and #7).     

Fracture-fill calcite as a record of microbial methanogenesis and fluid migration: a case study from the Devonian Antrim Shale, Michigan Basin

The Devonian Antrim Shale is an organic‐rich, naturally fractured black shale in the Michigan Basin that serves as both a source and reservoir for natural gas. A well‐developed network of major, through‐going vertical fractures controls reservoir‐scale permeability in the Antrim Shale. Many fractures are open, but some are partially sealed by calcite cements that retain isotopic evidence of widespread microbial methanogenesis. Fracture filling calcite displays an unusually broad spectrum of δ¹³C values (+34 to ?41‰ PDB), suggesting that both aerobic and anaerobic bacterial processes were active in the reservoir. Calcites with high δ¹³C values (>+15‰) record cementation of fractures from dissolved inorganic carbon (DIC) generated during bacterial methanogenesis. Calcites with low δ¹³C values (13C values between ?10 and ?30‰ can be attributed to variable organic matter oxidation pathways, methane oxidation, and carbonate rock buffering. Identification of ¹³C‐rich calcite provides unambiguous evidence of biogenic methane generation and may be used to identify gas deposits in other sedimentary basins. It is likely that repeated glacial advances and retreats exposed the Antrim Shale at the basin margin, enhanced meteoric recharge into the shallow part of the fractured reservoir, and initiated multiple episodes of bacterial methanogenesis and methanotrophic activity that were recorded in fracture‐fill cements. The δ¹⁸O values in both formation waters and calcite cements increase with depth in the basin (?12 to ?4‰ SMOW, and +21 to +27‰ PDB, respectively). Most fracture‐fill cements from outcrop samples have δ¹³C values between ?41 and ?15‰ PDB. In contrast, most cement in cores have δ¹³C values between +15 and +34‰ PDB. Radiocarbon and ²³⁰Th dating of fracture‐fill calcite indicates that the calcite formed between 33 and 390 ka, well within the Pleistocene Epoch.     

Fluid dynamics and fluid‐structural relationships in the Red Lake mine trend,Red Lake greenstone belt,Ontario, Canada

The Red Lake mine trend, a deformation zone in the Archean Red Lake greenstone belt that hosts the world‐class Campbell‐Red Lake gold deposit, is characterized by abundant foliation‐parallel iron‐carbonate ± quartz veins with banded colloform‐crustiform structures and cockade breccias overprinted by silicification and gold mineralization. There is an apparent incompatibility between the cavity‐fill structures of the veins and breccias (typically developed at shallow crustal depths) and the upper greenschist to lower amphibole facies metamorphic conditions recorded in the host rocks (indicating relatively deep environments). This, together with the development of veins along the foliation plane, represents an enigmatic problem that may be related to the interplay between fluid dynamics and stress field. We approach this problem through systematic study of fluid inclusion planes (FIPs) in the vein minerals, including the orientations of the FIPs and the pressure–temperature conditions inferred from fluid inclusion microthermometry. We find that fluid inclusions in the main stage vein minerals (pregold mineralization ankerite and quartz and syn‐ore quartz) are predominantly carbonic without a visible aqueous phase, whereas many inclusions in the postore stage contain an aqueous phase. Most FIPs are subvertical, and many are subparallel to the foliation. High fluid pressure coupled with the high wetting angles of the water‐poor, carbonic fluids may have been responsible for the abundance of brittle deformation features. The development of subvertical FIPs is interpreted to indicate episodic switching of the maximum principal compressive stress (σ₁) from subhorizontal (perpendicular to the foliation) to subvertical (parallel to the foliation) orientation. The subvertical σ₁ is favorable for the formation of foliation‐parallel veins, as fractures are preferentially opened along the foliation in such a stress regime, the origin of which may be linked to the fluid source.     

Metamorphic and basin fluids in quartz–carbonate–sulphide veins in the SW Scottish Highlands: a stable isotope and fluid inclusion study

Metalliferous (Fe–Cu–Pb–Zn) quartz–carbonate–sulphide veins cut greenschist to epidote–amphibolite facies metamorphic rocks of the Dalradian, SW Scottish Highlands, with NE–SW to NW–SE trends, approximately parallel or perpendicular to regional structures. Early quartz was followed by pyrite, chalcopyrite, sphalerite, galena, barite, late dolomite–ankerite and clays. Both quartz–sulphide and carbonate vein mineralisation is associated with brecciation, indicating rapid release of fluid overpressure and hydraulic fracturing. Two distinct mineralising fluids were identified from fluid inclusion and stable isotope studies. High temperature (>350°C) quartz‐precipitating fluids were moderately saline (4.0–12.7 wt.% NaCl equivalent) with low (approximately 0.05). Quartz δ¹⁸O (+11.7 to +16.5‰) and sulphide δ³⁴S (?13.6 to ?1.1‰) indicate isotopic equilibrium with host metasediments (rock buffering) and a local metasedimentary source of sulphur. Later, low‐temperature (T_H = 120–200°C) fluids, probably associated with secondary carbonate, barite and clay formation, were also moderately saline (3.8–9.1 wt.% NaCl equivalent), but were strongly enriched in ¹⁸O relative to host Dalradian lithologies, as indicated by secondary dolomite–ankerite (δ¹⁸O = +17.0 to +29.0‰, δ¹³C = ?1.0 to ?3.0‰). Compositions of carbonate–forming fluids were externally buffered. The veins record the fluid–rock interaction history of metamorphic host rocks during cooling, uplift and later extension. Early vein quartz precipitated under retrograde greenschist facies conditions from fluids probably derived by syn‐metamorphic dehydration of deeper, higher‐grade rocks during uplift and cooling of the Caledonian metamorphic complex. Veins are similar to those of mesothermal veins in younger Phanerozoic metamorphic belts, but are rare in the Scottish Dalradian. Early quartz veins were reactivated by deep penetration of low‐temperature basin fluids that precipitated carbonate and clays in veins and adjacent Dalradian metasediments throughout the SW Highlands, probably in the Permo‐Carboniferous. This event is consistent with paragenetically ambiguous barite with δ³⁴S characteristic of late Palaeozoic basinal brines.     

Preparation of a new calcite layer from calcium glycolate for the conservation of sulfated limestone artifacts

A novel preparation method of calcite layer was explored for the conservation purpose of the surface sulfation limestone artifacts. In this method, the alcoholic solution of calcium glycolate was used as a precursor of calcite layer. After application on the surface of gypsum crust on limestone by spraying, calcium glycolate can combine with the carbon dioxide spontaneously and form a compact calcite layer. The obtained calcite layer can act as a shelter and can prevent the gypsum crust from the dissolution damage of the natural precipitation. The protective properties of the calcite layer were investigated by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD), infrared spectroscopy (FTIR), water erosion resistance, water absorption, colour difference, surface strength, and hardness test. The results revealed that the water erosion resistance, surface strength, and hardness of the treated sample were increased remarkably. Meanwhile, the intrinsic physical properties such as porosity, capillary absorption, and appearance were not affected obviously, indicating a good compatibility of the proposed protection method.     

Red calcite: an indicator of paleo‐karst systems associated with bauxitic unconformities

A unique red calcite generation, which fills fractures/cavities, is hosted by Mesozoic carbonates in the Transdanubian Range, Hungary. Solid inclusions are located along growth zones of calcite. Hematite, the most abundant solid inclusion, gives the red colour of it. Outcrop‐scale geometry, mineralogical features and detrital mineral assemblage (hematite, gibbsite, goethite, kaolinite, smectite, illite, Cr‐spinel, monazite, xenotime, zircon, apatite and Ti‐oxide) of calcite precipitates suggest strong correlation between the calcite and nearby karst bauxite deposits. Fluid inclusion petrography and microthermometry (T < 50°C; salinity from 0 to 0.17 NaCl eq. w%) of primary fluid inclusions, and the stable isotope trend of the calcite, following the meteoric water line, clearly indicate vadose and phreatic meteoric origin in a near‐surface karst system. The late Cretaceous to mid‐Eocene unconformity‐related cavity‐filling deposits occur close to the surface; indicating that the most recent Quaternary exhumation re‐exposed those surfaces that existed at the time of calcite mineralization. Thus, red calcite precipitates are interpreted as being speleothems, vestiges of the subterranean part of the pre‐Middle Eocene karst. The infiltrated, fine bauxite particles enclosed by the calcite are the witnesses of the once areally extensive pre‐Middle Eocene bauxitic blanket that became partially eroded by the time of the deposition of the cover beds. Red calcite when found in core samples may provide good evidence on bauxite formation associated with the overlying unconformity, even if it was later removed by erosion. Therefore, presence or absence of red calcite may be used as distinguishing criteria between karst episodes with or without bauxite formation.     

Oscillatory zoning and trace element incorporation in hydrothermal minerals: insights from calcite growth experiments

Oscillatory zoning and fine‐scale variations in trace element chemistry are commonly observed in hydrothermal minerals. It has been suggested that fine‐scale chemical variations are caused by extrinsic changes in the parent hydrothermal system, such as varying fluid composition, pressure or temperature, as well as changes in mineral growth rate. In this study, LA–ICP–MS (laser ablation, inductively coupled plasma mass spectrometer) analyses were carried out on calcite crystals grown in Ca–NH₃–Cl solutions doped with rare earth elements (REE). The variety of crystal morphologies observed (euhedral to acicular), likely relate to variations in trace element abundance and calcite supersaturation state. Crystals display oscillatory and sector zoning, with significant variations in REE concentrations among zones. Cyclic variations in REE concentrations (exceeding 10‐fold) occur over distances of <1 mm along the growth direction of acicular calcite crystals. In general, trace element concentrations decrease during progressive crystal growth, implying that the concentration of trace and REEs within crystals reflects the overall composition of the growth solution. However, bulk changes in crystal composition are modulated by fine‐scale (<1 mm) variations, which are inferred to be caused by growth‐rate‐controlled incorporation of trace elements. These results have important implications for using hydrothermal minerals to infer fluctuations in fluid compositions in ancient, exhumed hydrothermal systems.     

Absolute dating of hominids and palaeolithic artifacts of the cave of La Chaise-de-Vouthon (Charente), France

Two adjacent chambers of the cave of La Chaise, Grotte de Bourgeois-Delaunay (B-D) and Grotte Suard, have been studied. Both were partly filled with detrital sediments containing lower and middle Palaeolithic artifacts and skeletal remains of pre-Neanderthalian hominids. Layers of stalagmitic calcite occur interstratified in the sediments of both chambers. Dates obtained by ²³⁰Th/²³⁴U ratios have provided a time scale for hominid and cultural evolution as represented in this cave.In B-D the lower travertine rests on a breccia containing cranial remains of juvenile Neanderthals. The base of the travertine dates to 151 ± 15 Ky (Ky = 1000 years BP); the top of the travertine yields a date of 112±5 Ky. The travertine contains pollen of an interglacial flora. Overlying detrital sediments 1·2 m in thickness contain artifacts transitional from Acheulian to Mousterian industries. They are capped by a travertine (Layer 7) whose base is dated at 100±6 Ky, and which is capped by stalagmites ranging in age down to 58±7 Ky. Overlying the travertine is sediment containing first Mousterian, and then Aurignacian artifacts.Near the base of the sediments filling Grotte Suard is a stalagmite layer dated to 249±30 Ky. It contains interglacial pollen and presumably dates to the beginning of the isotope stage 7 interglacial. Neanderthaloid hominid teeth and cranial fragments are found scattered through the overlying sediments, up to a capping stalagmitic layer whose base is dated at 101±7 Ky. The best described hominids from Suard are from a section that was probably overlying the capping stalagmite. The capping stalagmite is temporally correlated with layer 7 of B-D.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.     

Fluid inclusion and stable isotope constraints on the genesis of the Jian copper deposit,Sanandaj–Sirjan metamorphic zone,Iran

The Jian copper deposit, located on the eastern edge of the Sanandaj–Sirjan metamorphic zone, southwest of Iran, is contained within the Surian Permo‐Triassic volcano‐sedimentary complex. Retrograde metamorphism resulted in three stages of mineralization (quartz ± sulfide veins) during exhumation of the Surian metamorphic complex (Middle Jurassic time; 159–167 Ma), and after the peak of the metamorphism (Middle to Late Triassic time; approximately 187 Ma). The early stage of mineralization (stage 1) is related to a homogeneous H₂O–CO₂ (XCO₂ > 0.1) fluid characterized by moderate salinity (<10 wt.% NaCl equivalent) at high temperature and pressure (>370°C, >3 kbar). Early quartz was followed by small amounts of disseminated fine‐grained pyrite and chalcopyrite. Most of the main‐ore‐stage (stage 2) minerals, including chalcopyrite, pyrite and minor sphalerite, pyrrhotite, and galena, precipitated from an aqueous‐carbonic fluid (8–18 wt.% NaCl equivalent) at temperatures ranging between 241 and 388°C during fluid unmixing process (CO₂ effervescence). Fluid unmixing in the primary carbonaceous fluid at pressures of 1.5–3 kbar produced a high XCO₂ (>0.05) and a low XCO₂ (<0.01) aqueous fluid in ore‐bearing quartz veins. Oxygen and hydrogen isotope compositions suggest mineralization by fluids derived from metamorphic dehydration (δ¹⁸O_fluid = +7.6 to +10.7‰ and δD = ?33.1 to ?38.5‰) during stage 2. The late stage (stage 3) is related to a distinct low salinity (1.5–8 wt.% NaCl equivalent) and temperatures of (120–230°C) aqueous fluid at pressures below 1.5 kbar and the deposition of post‐ore barren quartz veins. These fluids probably derived from meteoric waters, which circulated through the metamorphic pile at sufficiently high temperatures and acquire the characteristics of metamorphic fluids (δ¹⁸O_fluid = +4.7 to +5.1‰ and δD = ?52.3 to ?53.9‰) during waning stages of the postearly Cimmerian orogeny in Surian complex. The sulfide‐bearing quartz veins are interpreted as a small‐scale example of redistribution of mineral deposits by metamorphic fluids. This study suggests that mineralization at the Jian deposit is metamorphogenic in style, probably related to a deep‐seated mesothermal system.