Carbonate Host Rocks Research Articles

Stylolites in Carbonate Rocks: Morphological Variability According to the Host Rock Texture

Stylolites are ubiquitous structures in carbonates that present a variety of morphologies. Besides being important structures in terms of rock compaction and deformation, stylolites control limestone permeability, which is influenced by their morphology and arrangement in connected networks. This study characterizes stylolite morphological parameters, such as length, thickness, filling by insoluble material, spacing and connectivity, to provide quantitative data on the relationships between stylolite morphology and carbonate host rock textures. A collection of thin sections from a variety of lithologies and geological settings was analyzed, showing that the stylolite length, thickness and morphology are interrelated and are controlled by the host rock textures. The results show that stylolite linearity, calculated as the ratio between the straight length and the length measured along the stylolite trace, varies according to the stylolite type. Higher stylolite thickness is observed in mud-dominated textures compared to grain-dominated ones but is independent of the stylolite type. There is no clear trend in terms of the amount of insoluble material collected by the stylolites and the rock texture or stylolite type. Analysis of stylolite spacing reveals that heterogeneity in grain size, grain sorting and composition controls stylolite formation.

Determining the age and origin of a Tertiary karstic system by in situ U-Pb geochronology on speleothems

Abstract Dating the onset of ancient (>1 Ma) karstification is a challenge. One approach is to date the earliest calcite cements in speleothems. We show the benefits of in situ U-Pb dating directly on thin sections from ancient (ca. 30 Ma) thin (<1 mm) speleothems in the karstified Lower Oligocene lacustrine-palustrine carbonates of the Paris Basin (France), which cannot be dated using other methods. We dated 32 calcite rafts (a type of speleothem), one geopetal cement, and 10 calcite cements precipitated along the karstic walls. The ages of the calcite rafts and cements at 29 ± 1 Ma (Lower Oligocene) fall within the age range of the host deposits (≈29 Ma) previously deduced from palaeontological evidence. We demonstrate that cementation of the carbonate host rock, its dissolution, and the speleothem precipitation occurred within 2 m.y. after deposition. Ostracods and intraclasts trapped within Rupelian calcite rafts clearly indicate that the karst developed deep underground shortly before a phase of lacustrine-palustrine sedimentation at the surface. This very early dissolution episode is attributed to the uplift of the Paris Basin as a result of the far-field intraplate deformation induced by the alpine orogenesis. This study shows that in situ U-Pb geochronology on ancient calcite rafts is a promising technique for the indirect dating of karstification and, more broadly, for dating geodynamic events and diagenetic evolution of sedimentary basins.

Pyroclastic component influence on the weathering indices assessment in marine sediments – Lessons from Upper Ordovician of the Baltic Basin

The chemical weathering indices of the sediments can serve as tools for estimating the intensity of weathering in the sediment source rock area and its changes in response to the dynamic interplay of climate, tectonics, and bioevolution. The siliciclastic terrigenous component, comprising sediment particles formed during weathering, carries information regarding weathering. Nevertheless, the presence of volcanic material with silicate composition in the sedimentary record can introduce bias to the weathering estimate by incorporating pyroclastic material that has not undergone weathering but is susceptible to diagenetic alteration. Therefore, a comprehensive understanding of the nature and significance of the volcanic component in sediments is imperative for accurately interpreting weathering derived from sedimentary successions. Our study focuses on investigating the presence of the volcanic component and its influence on weathering indices calculation in the Upper Ordovician sedimentary succession of the Baltic Basin. The results from geochemical massbalance mixing modelling reveal that volcanic material is not confined solely to discrete altered volcanic ash beds (bentonites), and a substantial amount of volcanic material is dispersed or re-deposited into the host rock. Within the interval containing discrete bentonite beds, the volcanic component in the carbonate host rock sections ranges from 50% to 90%, and significantly impacts the terrigenous fraction weathering index calculations. This underscores the necessity of considering the nature and significance of the volcanic component when interpreting geochemical-mineralogical signals.

Diagenetic evolution of secondary evaporites and associated host-rock dolostones in the Huron Domain (Michigan Basin): insights from petrography, geochemistry, and C-O-S-Sr isotopes

ABSTRACT In this study, we present a detailed investigation of C-O-S-Sr isotope systematics and elemental analysis of secondary sulfates and associated host-rock carbonates of Cambrian to Devonian sedimentary successions along the eastern flank of the Michigan Basin, Ontario. This study evaluates the diagenetic evolution of pore fluids and their sources in fracture-fill and replacement sulfate minerals in low-permeability carbonate units in the Michigan Basin. Secondary sulfates, represented by gypsum and anhydrite, contain various petrographic types, represented by vug- and fracture-filling fibrous anhydrite in the Cambrian (δ18O vary between 16.8 to 17.6‰ VPDB and δ34S 28.3 to 29.0‰ CDT, 87Sr/86Sr ratios vary from 0.70834 to 0.70991, respectively) and Ordovician fibrous anhydrite (δ18O 16.8‰, δ34S 28.2‰, 87Sr/86Sr ratios 0.70829). These phases display mainly uniform REE patterns with Y/Ho and Zr/Hf ratios, flat La*, Gd*, and Y*, and enriched LREEs. In the Silurian strata, idiotopic satin-spar δ18O values vary between 4.0 and 8.3‰, δ34S 23.4 and 31.4‰ with 87Sr/86Sr ratios 0.70816–0.70866, xenotopic porphyroblast gypsum δ18O values vary between 4.5 and 13.3‰, δ34S 22.6 to 33.1‰, with 87Sr/86Sr ratios of 0.70850–0.70880, alabastrine gypsum δ18O values vary between 4.2 and 11.7‰, δ34S 23.1 to 26.9‰, with 87Sr/86Sr ratios of 0.70816–0.70876 and felted anhydrite δ18O values of 11.1‰, δ34S 27.4‰, with a 87Sr/86Sr ratio of 0.70849. These geochemical proxies suggest a comparable sulfate-rich source for both age groups under similar geochemical conditions. Gypsum in the Silurian Salina Group displays a wide range of REE values with Y/Ho, and Zr/Hf ratios, Nd/YbN and Pr/YbN, flat to strong Ce/Ce*, and a flat to strong Eu/Eu* anomaly, Gd/LaN, Tb/LaN, and Sm/LaN. These sulfates formed at burial from fluids of variable isotope compositions, chemical compositions, and temperatures. The sources of these fluids range from brines migrating from a deeper part of the basin forming anhydrite in the Cambrian and Ordovician sequences which were also affected by dolomitization and later hydrothermal fluid influx, to rehydration of gypsum at shallower burial depths and affected by salt dissolution and incursion of meteoric water during and following the Alleghenian orogeny.

Mineralogical and geochemical characteristics of alteration minerals related to fossil geothermal activities in the Kızıldere geothermal field, Western Turkey

The Kızıldere geothermal field, located at the eastern part of the Büyük Menderes graben in Western Turkey, is the most important geothermal reservoir suitable for electricity generation. Fossil fumarole fields and alteration or mineralization zones are directly related to the tectonic zones influenced by N-S directional extension. Associated to fossil geothermal activities, calcite, dolomite, strontianite, quartz, gypsum, anhydrite, celestine, kaolinite, smectite, boehmite and goethite/limonite were occurred in the form of void or crack fill within the Paleozoic metamorphic and Miocene-Quaternary clastic and carbonate host rocks. The current mineralogical composition indicates temperature conditions of 100–250 °C which close to current reservoir temperatures. Some of minerals with fossil geothermal origin, i.e. calcite, anhydrite, dolomite, celestine, amorphous silica and quartz, are compatible for mineral precipitations estimated from mineral equilibrium modeling, and scale mineralogy of wells, as well. The formation order of the most common geothermal minerals is determined as calcite → gypsum → anhydrite → quartz direction indicating that alkaline conditions were followed by acidic conditions. The blade-like/prismatic rhombohedral calcites replaced by quartz occurrences in siliceous‑carbonate veins indicate the boiling was occurred in the field. The geothermal mineral zoning determined from drilling samples is anhydrite-dolomite-calcite from shallow to deeper parts. The lateral and vertical distribution of mineral zoning is related to the fact that geothermal waters are mainly affected by host rock compositions, i.e. dissolution from the host rocks and precipitation along the cracks/fractures and bedding planes. Mineralizations in the Kızıldere geothermal field mainly represent the direct precipitations from hot geothermal waters rather than transformations of minerals in the host rocks. Si, Al, Mg, K and Na concentrations in carbonate and sulfate minerals show a positive correlation relationship and are derived from metapelites. Whereas Ca is negatively related to these elements and it is derived from metacarbonate and/or carbonate host rocks. According to the current geothermal water composition, Ca enriches in the deeper parts, while Mg and B enrichment in shallow depths near the basin edge that indicates the different composition of the host rocks where minerals precipitated. The relatively high boron contents at shallow depth indicate that it is retained by the minerals precipitated this level and causes less release to the surface.

Quaternary periglacial silicifications in the Paris Basin

In this paper, and in previous works, quartzites within the Sable de Fontainebleau are clearly shown to occur only near outcrops in Plio-Pleistocene plateau landscapes and are related to groundwater flows. These arrangements, together with dating of encased calcites, led us to consider that silicification occurred during Plio-Pleistocene glacial stages. The precipitation of silica was most likely triggered by cooling of groundwaters as they approached cold zones in the regolith close to points of discharge. We describe the arrangement and morphologies of quartzites in Tertiary sand formations in the Paris Basin to demonstrate how cold climates could have influenced hydrologic regimes and promoted silicification. The coeval precipitation of calcite and silica in gypseous formations at the edges of plateaux-bordering valleys, along with the dissolution of gypsum, also points to interactions between silica-laden groundwater and carbonate host rocks during cold periods. In parallel, the distribution and micromorphology of silicifications in associated Tertiary limestone formations suggests that they formed during cold climates in the Quaternary. These are key pointers to the role of groundwater in regolith environments in controlling silicification processes. We detail a link to palaeosurfaces of the distinctive meulières facies in the Paris Basin. Geotropic structures and micromorphological organisations are the basis of new ideas about their origin in a combination of vadose and phreatic environments and proximity to impervious cold horizons. The active zone in a permafrost landscape is a good hydrological example. All silicifications in Tertiary formations in the Paris Basin can be linked to the hydrology of Quaternary periglacial environments in a single model. This could apply more widely to similar silicifications elsewhere and be tested using new analytical techniques that date silicifications and unravel the isotopic relationships between silicification, groundwater composition and the prevailing climate.

Miocene Volcanism in the Slovenský Raj Mountains: Magmatic, Space, and Time Relationships in the Western Carpathians

The Miocene volcanic-intrusive complex in the Slovenský Raj Mountains, middle Slovakia, comprises a swarm of subalkaline basalts and basaltic andesites with alkaline basalts, trachybasalts and basaltic trachyandesites. Basaltic to doleritic feeder dykes and sporadic hyaloclastite lavas are exposed in contact with the Triassic Bódvaszilas Formation of the Silica Nappe. The primary clinopyroxene, plagioclase, and Fe-Ti oxide assemblage also contains calcite spheroids inferred to represent carbonatitic melt. These spheroids are associated with subsolidus chlorite, actinolite, magnetite, titanite, calcite, and epidote. Micropoikilitic clinopyroxene, albite, and Ti-magnetite formed due to rapid quenching. There was an incorporation of host rock carbonate during the eruption. The erupted products are the result of magmatic differentiation of the parental basaltic tholeiitic magma with a redox of ∆QFM = +1 to +3, affected by varying degrees of 0%–50% fractionation and the assimilation of carbonate material in a shallow magmatic reservoir. REE geochemistry shows N-MORB-like type patterns with both LaN/YbN and LaN/SmN < 1 at near constant Eu/Eu* (~0.9). This is supported by εNd(t=13 Ma) values of +8.0 to +7.4 determined from the basaltic rocks. The REE values can be modeled by 1% fractional melting of garnet peridotite mixed with 7% melting of spinel peridotite of PM composition (1:9 proportions). SIMS and LA-ICP-MS U/Pb analysis of zircons yields a concordant age of 12.69 ± 0.24 Ma and a 13.3 ± 0.16 Ma intercept (Serravallian) age. The Middle Miocene volcanic activity was related to subduction-collision processes along the boundary of the Cenozoic ALCAPA (Alps–Carpathians–Pannonia) microplate and the southern margin of the European plate.

Origin of Hydrothermal Barite in Polymetallic Veins and Carbonate-Hosted Deposits of the Cyclades Continental Back Arc

Abstract Polymetallic veins and breccias and carbonate-replacement ore deposits in the Cyclades continental back arc, Greece, formed from a range of fluid and metal sources strongly influenced by the dynamics of the late Mesozoic-Cenozoic Hellenic subduction system. These complexities are recorded in the isotopic signatures of hydrothermal barite. We investigated 17 mineral occurrences on four Cycladic islands and from Lavrion on the mainland. Here, barite occurs in almost all deposit types of Miocene to Quaternary age. We used a multiple isotope and geochemical approach to characterize the barite in each deposit, including mineral separate analysis of δ34S and δ18O and laser ablation-inductively coupled plasma-mass spectrometry of 87Sr/86Sr and δ34S. Barite from carbonate-hosted vein and breccia Pb-Zn-Ag mineralization on Lavrion has a wide range of δ34S (2–20‰) and δ18O (10–15‰) values, reflecting a mix of magmatic and surface-derived fluids that have exchanged with isotopically heavy oxygen in the carbonate host rock. Sulfur (δ34S = 10–13‰) and oxygen (δ18O = 9–13‰) values of barite from the carbonate-hosted vein iron and barite mineralization on Serifos are permissive of a magmatic sulfate component. Barite from epithermal base and/or precious metal deposits on Milos has δ34S (17–28‰) and δ18O (9–11‰) values that are similar to modern seawater. In contrast, barite from vein-type deposits on Antiparos and Mykonos has a wide range of δ34S (16–37‰) and δ18O (4–12‰) values, indicating a seawater sulfate source modified by mixing or equilibration of the hydrothermal fluids with the host rocks. Strontium isotope ratios of barite vary regionally, with 87Sr/86Sr ≥ 0.711 in the central Cyclades and 87Sr/86Sr ≤ 0.711 in the west Cyclades, confirming the strong influence of upper crustal rocks on the sources of fluids, Sr, and Ba in the formation of ore.

Катодолюминесценция конодонтовых элементов

Conodont elements are used as a geochemical archive of seawater. Some compositional features of conodont elements reflect conodont ecology and trophic structure of Palaeozoic pelagic ecosystems. However, the screening of conodont elements prior to geochemical and/or isotopic studies is a real problem. This study evaluates SEM cathodoluminescence (SEM-CL), which is very sensitive to the REE and Mn content of apatite, for the detection of traces of secondary transformation in the composition of conodont bioapatite. The SEM-CL of conodont elements is similar to that of unaltered shark teeth (blue-violet), but differs significantly from that of fossil vertebrate teeth (orange-red). Thermal alteration has little effect on the SEM-CL. Elements with a CAI of 1—1.5 show a redder and more intense CL than elements with a CAI of 5. In the case of corrosion of the conodont element surface in carbonate host rocks, the CL of the outer parts of the conodont element become reddish due to invasion of the carbonate material. Conodont elements from the clay host rock show deep purple SEM-CL. Thus, SEM-CL allows detection of the results of secondary processes in conodont mineralised tissues, including enrichment by REE and/or Mn, corrosion and contamination by carbonate material. This method can be used to screen significantly altered samples prior to chemical and isotopic analyses.

Mineralization and Skarn Formation Associated with Alkaline Magma Chambers Emplaced in a Limestone Basement: A Review

The emplacement of shallow magma chambers within a carbonate basement is a typical feature of many volcanic systems around the world. The accompanying formation of exoskarns, endoskarns, cumulates, exsolved fluids and differentiated melts at the interface between the magma chamber and carbonate host-rock is well documented through mineralogical and geochemical studies of ejected skarns and cumulates and through fluid and melt inclusion studies. This review presents the current knowledge on the interaction of alkaline magma chambers with carbonate-bearing host-rocks, with a focus on the geochemical evolution and mineralization at the outer margins of the magma chamber and the accessory mineral phases at Somma-Vesuvius, Colli Albani and Merapi volcanic systems. Furthermore, we discuss how this interaction and its products, especially the CO2 released during the thermometamorphic decarbonation of the carbonate host-rock, impacts the eruptive behavior in all three systems.

Geology, geochemistry, fluid inclusion microthermometry and depositional environment of the Early Cretaceous Meymeh sub-seafloor replacement sideritic-ankeritic iron deposit, Malayer-Esfahan Metallogenic Belt, Iran

Meymeh sideritic-ankeritic iron deposit in the eastern part of Malayer-Esfahan Metallogenic Belt (MEMB) is formed in the sedimentary-volcanic rocks of the Early Cretaceous sequence. Ore mineralization in the study area based on stratigraphic location and type of host rocks divided in two ore horizons. Lower ore horizon located in the dolomitic-sandy limestone (Kc3) unit, which upper ore horizon is formed in thin-bedded limestone (Km) rocks. Petrographic studies indicates that mineralization comprises three ore facies: stockwork, bedded and massive ore facies. The most important primary minerals are siderite, ankerite, ferroan-dolomite, pyrite, pyrolusite, barite and minor chalcopyrite. The most frequent textures in the ore zones include laminae, replacement, vein-veinlet, massive and banded. Dolomitization and silicification are the main wall rock alteration styles; alteration intensity increases towards the ore zones. Based on relationships between ore minerals and rock forming minerals, ore mineralization (hypogene and supergene) in the Meymeh deposit formed during three main stages: fine-grained Fe-carbonate bands are intricately interlayered with dolomite beds. Sideritic-ankeritic bands exhibit classic sedimentary textures, such as laminations and bedding, indicative of a syn-sedimentary to early diagenesis origin. Coarser-grained stage two siderites and ankerites show breccia and vein-veinlet textures, and are considered to have formed by replacement during burial diagenetic sub-seafloor fluid flow. In stage three, siderite and ankerite were converted to secondary iron oxides such as oxide/hydroxide Fe minerals during meteoric water flow through the inverted normal and thrust faults and uplift. The primary two-phase fluid inclusions in the quartz-2 and ankerite-2 minerals that have been investigated from the ore mineralization section of the Meymeh deposit are homogenized at temperatures between 110.3 to 226.9 °C. Salinities of the primary fluid inclusions range from 3.39 wt.% to 14.77 % NaCl eq. This finding suggests that hydrothermal brine fluid mixing with seawater could be the primary mechanism that prompted ore formation. The similarity of REE patterns between siderite and ankerite in different ore facies and host rock carbonates indicates their derivation from the same ore fluids. The Meymeh deposit is considered a typical case of sedimentary hydrothermal diagenetic sideritic-ankeritic mineralization, in which minerals deposited when hydrothermal fluid was released from anoxic to suboxic water columns.

Regional Scale, Fault‐Related Fluid Circulation in the Ionian Zone of the External Hellenides Fold‐And‐Thrust Belt, Western Greece: Clues for Fluid Flow in Fractured Carbonate Reservoirs

AbstractWe combined field mapping, structural and microstructural analyses, stable‐clumped isotope geochemistry, and U‐Pb dating of calcite veins and syn‐tectonic slickenfibres, to assess the regional scale fault‐related fluid flow during the evolution of the External Hellenides fold‐and‐thrust belt. We show that fluid circulation during forebulge uplift was characterized by cold meteoric water‐derived fluids, from which calcite precipitated and sealed bed‐perpendicular joints. Fluid circulation during foreland flexuring and early layer‐parallel shortening was characterized by warm fluids buffered by the carbonate host rock, which circulated through normal faults and bed‐parallel veins. Mixing with meteoric‐derived fluids also occurred at this stage of tectonic evolution. Fluid circulation during the late stage of thrust wedge accretion and post‐orogenic extension at 1.6 ± 1 Ma was characterized by increasing dominance of cold meteoric water circulating in strike‐slip and normal faults. The ingress of meteoric‐derived fluids was controlled by throughgoing fault conduits, while host rock‐buffered fluids were confined in isolated structures such as minor faults and veins. We developed a conceptual model of fault‐related fluid circulation, which invokes a transition from an open fluid system during forebulge uplift, to a semi‐closed fluid system during foreland flexuring and early layer‐parallel shortening, and to an open system during late thrust wedge accretion and post‐orogenic extension. This type of fluid circulation may have impacted fluid migration/leakage, including hydrocarbons, into or outside potential reservoirs in the highly prospective Hellenides‐Albanides fold‐and‐thrust belt, a renovated frontier for hydrocarbon exploration in the Mediterranean area.

Distribution of silicification intervals throughout the Barra Velha and Itapema formations: Host rock controls and chronology of silica precipitation (Pre-Salt, Santos Basin, Brazil)

The Barra Velha and Itapema formations, Aptian, Santos Basin, constitute large hydrocarbon reservoirs, mainly in carbonate rocks. These rocks host up to centimeter-thick silica bodies with a variety of textures and geometries along different carbonate facies, suggesting syngenetic, diagenetic, and hydrothermal processes in their formation. The mineralogical and textural changes related to these processes can directly influence the porosity and permeability of the reservoir rocks, turning the study of the silicified intervals important in the exploration and production of these deposits. We present here a systematic macroscopic and microscopic description of the silica bodies and its distribution through the carbonate facies the of Barra Velha and Itapema formations from the Sapinhoá and Búzios fields. Data allow us to identify four geometric types of silica bodies: tabular, irregular, oval and disseminated, which are composed of chalcedony, microcrystalline and macrocrystalline quartz. Tabular, oval, and irregular silica bodies are cross-cutted by mechanical compaction structures such as vertical fractures, boudins and faults. In addition, these bodies include relicts of the host rock lamination, which in turn deflects around them. Thus, silica precipitation must have been penecontemporaneous or in the early stages of diagenesis, before the main mechanical compaction stage. These features were not observed in the disseminated silica type, in the contrary, this type involves and overlaps oval and irregular bodies, indicating that this silica precipitation probably occurred in latter stages in relation to other body types. The genesis of disseminated bodies can then be related to diagenetic or hydrothermal processes during diagenesis. Therefore, the geometry of silica bodies and their spatial distribution are influenced by the host carbonatic petrofabrics and the chronology of silica precipitation within the sedimentary to diagenetic evolution of the sedimentary package. Finally, we present a systematics that can be easily applied to recognize these silica types in other exploration fields of pre-salt interval. The results presented here have great potential to be applied in the research on pre-salt intervals from other Brazilian and African basins since the host carbonate rocks are very similar and favor the development of similar silicification processes and results.

Syn-tectonic contact aureole and metasomatic reaction zones in carbonate and pelitic host rocks (Elba Island, Italy)

Syn-tectonic contact aureole and metasomatic reaction zones in carbonate and pelitic host rocks (Elba Island, Italy)

The spatial characterization of stepovers along deeply-buried strike-slip faults and their influence on reservoir distribution in the central Tarim Basin, NW China

Strike-slip faults imaged on seismic reflection data from the central Tarim Basin clearly illustrate the spatial and geometrical characteristics of deeply buried (>6.8 km depth) stepovers and their influence on reservoir distributions in fractured Middle Ordovician carbonates. Characterization of along- and across-strike seismic profiles demonstrates that restraining and releasing stepovers characteristically produce pop-up and pull-apart structures, respectively, defined by systems of high-angle subsidiary faults with down-dip reverse or normal displacements. Along-strike vertical displacement and damage zone width measurements reveal that restraining stepovers typically exhibit much wider deformation zones and higher densities of fractures compared to releasing stepovers. Core samples and well logs show that the fractured reservoirs in restraining stepovers comprise stylolite meshes and mosaic breccias. Damage zones in narrower releasing stepovers are more prone to the development of cavities, dilational breccias, and high-angle open fractures. Both restraining and releasing stepovers are strongly asymmetric in the across-strike direction, except in the central part of fault overlap zones where the maximum vertical displacements are symmetrical. Restraining stepovers can typically be subdivided into four sectors separated by helicoidal intermediate-scale linking faults: two in the hanging walls and two in the footwalls. Hanging walls are normally wider, intensely fractured and exhibit better well performance compared to footwalls. Strain compartmentalization with localized zones of upward and downward displacement exist both within, and adjacent to releasing stepovers. The localized extensional zones are where cavities and open fractures are most likely best developed. Seismic reflection profiles and well logging show that certain intraclastic grainstone and packstone horizons in the Middle Ordovician carbonate host rock sequences are more favorable for fracture development. This leads to vertical partitioning of local fractured reservoirs due to the development of down-dip stepovers or bends localized close to major lithological boundaries. Thus interactions between lithological layering and tectonic processes cause further three-dimensional complexity in the reservoirs.

Origin and evolution of the ore-forming fluids in the southern Abbas Abad iron skarn deposit, NE Isfahan, Central Iran: Insights from geology, fluid inclusions, and C[sbnd]O isotopes

The southern Abbas Abad iron skarn deposit is located in the western part of the Central Iran zone, SW edge of the Urumieh˗Dokhtar magmatic arc. The skarn alteration occurred mainly at the contact of the Abbas Abad gabbro and Triassic Nayband Formation. The Triassic Nayband Formation in the southern Abbas Abad area consists of limestone, shale, siltstone, and marl with interlayers of tuff. The Abbas Abad gabbro is calc˗alkaline with adakitic signatures and continental arc setting affinity. Four iron ore bodies occur along the NW˗SE trending normal fault along the southern margin of Abbas Abad gabbro within sedimentary host rocks of the Nayband Formation. Three main paragenetic stages of skarnification and ore deposition have been recognized: i) prograde stage, ii) retrograde stage, and iii) supergene stage. Spinel, garnet, and pyroxene formed during the prograde stage. Epidote, tremolite˗actinolite, calcite and ore minerals, such as magnetite, hematite-I, pyrite, and minor chalcopyrite formed the retrograde stage assemblage. Magnetite is the main economic ore mineral, which is diverse in terms of fabric and texture, including massive, disseminated, needle˗like, blade˗like, prismatic, crustification, and cubes. Stable isotope data from Abbas Abad iron skarn deposit indicated that the interaction of non-magmatic brine (connate) fluids with Triassic carbonate host rocks at high temperature and its mixing with meteoric water has led to changes in the isotopic composition of the mineralizing fluid. Subsequently, garnet and magnetite with relatively high estimated fluid δ18O values (average 12.3 and 14.6 ‰, respectively) formed from this modified fluid. The estimated δ18O values of fluid in equilibrium with calcite decreased as a result of the greater influx of the meteoric water into the hydrothermal system in the late stages of ore formation. Fluid inclusion data from this iron skarn deposit are consistent with minor boiling during the prograde stage, although cooling and dilution seem to be principally responsible for Fe precipitation. The petrogenetic model proposed for the Southern Abbas Abad iron skarn deposit suggests that during the Eocene a gabbroic stock intruded the sedimentary rocks of the Nayband Formation and acted as a heat source for the non-magmatic brine (connate and meteoric) fluids convection cells, then reacted with cooler Triassic carbonate rocks. In this model, leaching of the gabbroic rock provided the iron, whereas carbon came from degassing and dissolution of carbonate rocks during contact metamorphism-metasomatism.

Origin of the Amensif Zn-Cu (Pb-Ag-Au) distal skarn deposit (Western High Atlas, Morocco): Constraints from C-O-S isotopes

The Amensif Zn-Cu (Pb-Ag-Au) ore deposit is located in the northern part of the western High Atlas. The deposit hosts 1 million tons (Mt) of Zn-Cu-Pb metal reserves at 3% Zn, 2% Cu, and 1% Pb. The lenticular sulfide ores are structurally controlled open-space fillings (fractures, faults) in the Lower Cambrian carbonates. The mineralogical paragenetic sequence consists of andradite-quartz-epidote-dolomite-calcite-sphalerite-chalcopyrite-pyrite-galena with subordinate amounts of barite. The pre-ore stage and ore stage I dolomite samples have δ13CPDB and δ18OSMOW values in the range of −10.2 to −2.6‰ and 17.4–26.8‰, respectively. The lower δ18O value of these dolomites suggests oxygen isotope exchange between the ore-forming fluids and the carbonate host rock whereas negative δ13CPDB values reveal the interaction between these hydrothermal fluids and black shales. The δ34S values of sulfides ore (sphalerite, chalcopyrite, and pyrite) are high, ranging from 6.4 to 14.4‰. These S isotopic values reveal that sulfur derived from the mixture of magmatic sulfur and lower Cambrian carbonate-derived sulfur in almost equal proportions. Sulfide ores precipitated from the mixing between the magmatic-hydrothermal fluids exsolved from a hidden magma or the nearby Azegour granite of Permian age and an external cooler fluid of unknown origin. Fluid-rock interactions with the carbonate host rock contributed in the precipitation of the ore. Mineralogical and geological features allow us to ascribe the Amensif Zn-Cu (Pb-Ag-Au) polymetallic ore as a distal skarn system which is spatially associated with the lower Permian granite intrusion.

Implications of multiple fluids in the deposition of Pb-Zn-Ba deposits in the Alvand Mountain, Golpayegan, Iran: Evidence from fluid inclusions and O, C, S isotopes

Middle Cretaceous sedimentary carbonates of Alvand Mountain host Pb-Zn-Ba veins. This mineralization occurs mainly as veins, breccia fillings, and to a lesser extent disseminated and host rock replacements. Ore mineralogy is simple and consists of sphalerite, galena, and barite, with minor pyrite, rare chalcopyrite, and tetrahedrite. Host rock dolomitization and hydrothermal silicification are typically associated with ore. Two types of primary liquid–vapor fluid inclusions were distinguished in sphalerite, quartz, and barite. Type I (salinity, 17–23 wt% NaCl; Th, 130 ± 30 °C) is dominant in sphalerite, whereas type II (salinity, 4.5–10 wt% NaCl, Th, 190 ± 40 °C) is dominant in quartz and barite; these fluids have characteristics of basinal brines and show a negative mixing trend in an evolving process of sulfide and gangue saturation. The δ18O and δ13C values for host rock and altered minerals range from 22.0 to 12.9 ‰ and 3.8 to −3.2 ‰, respectively, which suggest the influence of increased temperature fluids, presence of organic carbon, and fluid mixing. The δ34S values of sulfides and barite varies from 2 to 17 ‰ and 23 to 24 ‰, respectively, suggesting that reduced sulfur could be derived by thermochemical reduction of Paleogene seawater sulfate in the presence of organic matter; however, the wide ranges of δ34S sulfide values (15 ‰) exhibits that reduction of sulfur probably originated by different sulfur reduction processes. The data present in this study suggest that during increased tectonic activity in the late Cretaceous-Paleogene, mixing of basinal brines and water–rock interaction resulted in Pb-Zn-Ba deposition in carbonate host rocks. Therefore, it may represent low-temperature mineralization, possibly analogous to MVT depositional systems.

Chemical changes during endoskarn and porphyry‐style alteration and Cu—Fe exoskarn mineralization in the Tonglushan system, eastern China

AbstractElement mobility and chemical mass transfer are evaluated in the formation of Cu—Fe exoskarn deposits and endoskarn and minor porphyry‐style alteration in the Tonglushan quartz monzodiorite (QMD) system, eastern China. Endoskarn formation involved the migration of Ca into the QMD from the exoskarnification of carbonates (now marble) xenoliths and wall rocks, addition of Fe and Mn by magmatic‐hydrothermal fluids emanating from the interior of the QMD, and removal of alkali elements due to the replacement of feldspars and mica by prograde skarn minerals. Zirconium, Hf, U, and rare earth elements (REE) were added by hydrothermal fluids which were able to carry these often poorly mobile high field strength elements (HFSE) due to elevated F activity. Additions of Al were likely from Na‐rich fluids that also caused sodic alteration. Several factors favored mineralization within the exoskarns rather than endoskarns and QMD. The endoskarns were relatively oxidizing, as evidenced by a significant addition of Fe3+, which caused Cu to remain in magmatic‐hydrothermal fluids until they entered and precipitated sulphides in the more reducing environment of the exoskarns. Fluid migration from the QMD through the endoskarns and into the exoskarns was favored due to decarbonation of wall rock carbonates and related upwards migration of CO2 to produce a self‐sustaining chimney effect, which drew further fluids towards the carbonates to form, alter and mineralize the exoskarns. The higher porosity and permeability of the endoskarns compared with the QMD further promoted the lateral flow of Cu‐bearing fluids towards the exoskarns and limited porphyry‐style alteration and mineralization within the QMD. This proposed mechanism is only likely to be relevant for porphyry‐type systems developed predominantly within carbonate host rocks. Its significance for exploration models is that relatively poorly mineralized porphyry stocks in this setting may be associated with more substantive exoskarn deposits on their margins.

Organic matter governs weathering rates and microstructure evolution during early pedogenesis

Soil aggregation and the translocation of clay and organic matter are significant pedogenic processes that manifest in diagnostic horizons in mature soil. Yet, their onset might date to much earlier stages of soil development where host rock weathering is dominant and litter from pioneer vegetation is the only input of organic matter. We present a time-lapse experimental-pedogenesis study on early host rock weathering that shows the formation of aggregates and clay translocation in response to irrigation with and without organic matter released from a litter layer. The presence of organic matter increases total carbonate dissolution capacity and results in a characteristic surface morphology, while simultaneously slowing down the dissolution rate. With the dissolution of carbonates, clay minerals of the host rock and iron from pyrite are released. Controlled by the presence of organic matter, both are either transported with the seepage water or form crusts and aggregates from clay minerals and freshly precipitated secondary iron oxides. Our study shows that the interplay of dissolution, neoformation of secondary minerals, translocation, and aggregation of organic matter and clay-sized minerals shape soil structure evolution during early pedogenesis in carbonate host rocks.