Replacement Dolomite Research Articles

Hydrothermal Dolomitization of Upper Ordovician Limestone, Central-East Canada: Fluid Flow in a Craton-Interior Wrench-Fault System Likely Driven by Distal Taconic Tectonism

Narrow (tens of meters) vertical bodies of dolomite replace a nonporous Upper Ordovician (lower Chatfieldian) limestone along the leading limb of an asymmetric faulted anticline well inboard (∼300 km) of the northern Appalachian orogen, central-east Canada. Patterns of geometry, texture, and geochemistry suggest that dolomitizing fluids were focused (possibly along microfractures) within a paleosinistral transpressive stress field generated with reactivation of an underlying Neoproterozoic fault system. Strike-slip failure of the developing anticline resulted in fracture- and fault-controlled fluid flow from which precipitated saddle dolomite. A paragenetic succession of Fe-poor planar-e to ferroan planar-s dolostone marks the peak phase of replacement dolomitization. A subsequent increase (20%–30%) in porosity created through local dissolution of relict limestone was partially occluded by ferroan planar dolomite that, geochemically, is similar to later fracture-fill saddle dolomite. Replacement dolomitization is associated with a slight rise in Sr-isotope ratios (to 0.71085) from Late Ordovician–early Silurian marine signatures. Isotope (C, O, Sr) signatures support influx and mixing of burial fluids that had interacted with local Mg-rich (gabbro, anorthosite, syenite) crystalline basement with a background fluid similar to Late Ordovician seawater or dissolved marine limestone. Dolomitization predated maximum burial in the Late Paleozoic. Fluid inclusion and isotope paleothermometry suggest that dolomitizing temperatures (100°–120°C) were 20°–30°C warmer than associated with prior limestone diagenesis. The dolomitized limestone is an archival record of structure, hydrology, and heat flux that best fits with Taconic tectonism in the latest Ordovician through earliest Silurian.

Near-surface diagenesis of ophiolite-derived conglomerates of the Barzaman Formation, United Arab Emirates: a natural analogue for permanent CO 2 sequestration via mineral carbonation of ultramafic rocks

Abstract Carbon capture and storage by mineralization is a potential method for storing anthropogenic CO 2 emissions, and is based on the reaction between Mg silicate and CO 2 to form Mg carbonate. The conglomerates of the Barzaman Formation exposed in the eastern United Arab Emirates represent an excellent natural analogue of this process. These conglomerates were deposited as a series of alluvial fans along the western margin of the Hajar Mountains, part of the Oman-UAE Ophiolite, and are composed largely of ultramafic and lesser-mafic clasts. The clasts and matrix have been extensively altered to dolomite during diagenetic processes. Analysis and interpretation of rock textures provide evidence for the various factors that influenced the diagenetic processes and shed light on the silicate–carbonate transformation process. All the reactions have taken place in the near-surface environment; the silicate–carbonate conversion reaction is exothermic and occurs spontaneously at near-ambient pressure and temperature, probably no greater than 50 °C. Estimates of the amount of CO 2 stored in this way can be obtained from considerations of outcrop area, formation thickness and percentage of dolomite replacement, and show that c. 150 billion tonnes (equivalent to about 4 years of worldwide CO 2 emissions at current rates) are stored.

The Jabali nonsulfide Zn–Pb–Ag deposit, western Yemen

The Jabali Zn–Pb–Ag deposit is located about 110km east of Sana'a, the capital of Yemen, along the western border of the Marib-Al-Jawf/Sab'atayn basin. The economic mineralization at Jabali is a nonsulfide deposit, consisting of 8.7milliontons at an average grade of 9.2% zinc, derived from the oxidation of primary sulfides. The rock hosting both primary and secondary ores is a strongly dolomitized carbonate platform limestone of the Jurassic Shuqra Formation (Amran Group). The primary sulfides consist of sphalerite, galena and pyrite/marcasite. Smithsonite is the most abundant economic mineral in the secondary deposit, and is associated with minor hydrozincite, hemimorphite, acanthite and greenockite. Smithsonite occurs as two main generations: smithsonite 1, which replaces both host dolomite and sphalerite, and smithsonite 2, occurring as concretions and vein fillings in the host rock. At the boundary between smithsonite 1 and host dolomite, the latter is widely replaced by broad, irregular bands of Zn-bearing dolomite, where Zn has substituted for Mg. The secondary mineralization evolved through different stages: 1) alteration of original sulfides (sphalerite, pyrite and galena), and release of metals in acid solutions; 2) alteration of dolomite host rock and formation of Zn-bearing dolomite; 3) partial dissolution of dolomite by metal-carrying acid fluids and replacement of dolomite and Zn-bearing dolomite by a first smithsonite phase (smithsonite 1). To this stage also belong the direct replacement of sphalerite and galena by secondary minerals (smithsonite and cerussite); 4) precipitation of a later smithsonite phase (smithsonite 2) in veins and cavities, together with Ag- and Cd-sulfides.The δ18O composition of Jabali smithsonite is generally lower than in other known supergene smithsonites, whereas the carbon isotope composition is in the same range of the negative δ13C values recorded in most supergene nonsulfide ores. Considering that the groundwaters and paleo-groundwaters in this area of Yemen have negative δ18O values, it can be assumed that the Jabali smithsonite precipitated in different stages from a combination of fluids, possibly consisting of local groundwaters variably mixed with low-temperature hydrothermal waters. The carbon isotope composition is interpreted as a result of mixing between carbon from host rock carbonates and soil/atmospheric CO2.The most favorable setting for the development of the Jabali secondary deposit could be placed in the early Miocene (~17Ma), when supergene weathering was favored by major uplift and exhumation resulting from the main phase of Red Sea extension. Low-temperature hydrothermal fluids may have also circulated at the same time, through the magmatically-induced geothermal activity in the area.

Zebra and boxwork fabrics in hydrothermal dolomites of northern Canada: Indicators for dilational fracturing, dissolution or in situ replacement?

AbstractZebra and boxwork fabrics in Manetoe and Presqu'ile hydrothermal dolomites provide critical data for discrimination between hypotheses for their origin. In a unique occurrence, sets of weakly imbricated, decimetre‐sized curvilinear lenticles of white dolospar are developed within sub‐metre sized tongues of greyish‐white dolomitized crinoidal packstone and grainstone. This nascent zebra fabric has developed along wavy to nodular intra‐bed sedimentary partings. Primary bedding can be traced through dolomitized masses containing these fabrics, into the surrounding undolomitized limestone. All zebra and boxwork fabrics are confined within single beds, consistent with an early burial time of origin. No change in bed thickness occurs across zebra or boxwork fabrics within beds; this indicates a dissolutional, rather than a dilational, origin for the creation of pore space partly cemented with white dolospar. The dolomitized groundmass displays an abruptly gradational or sharp transition to centripetal saddle dolomite cement, which partially to nearly completely, occludes vugs. Circulation of geothermally heated hypersaline Devonian Elk Point basinal sea water brines led to dissolution and replacive dolomitization of limestone adjacent to vugs, and near‐contemporaneous precipitation of white dolospar within dissolutional vugs, consistent with geochemical simulations. The presence of downward‐extending galleries of white dolospar‐cemented solution‐collapse breccia provides further support for an interpretation of regional thermally driven convection of hydrothermal evaporative sea water brines across a broad area of northern Canada. The absence of gases under pressure in vacuoles within fluid inclusions from Manetoe and Presqu'ile dolospars is also more consistent with a dissolutional and contemporaneous dolomitization origin for these fabrics, rather than an origin involving dilational fracturing for space creation and dolospar precipitation. The ubiquitous presence of zebra and boxwork fabrics in hydrothermal dolomite reservoirs indicates that they are not confined fault zones and instead occur wherever precursor limestones had relatively greater porosity and permeability prior to dolomitization.

Multiphase partial and selective dolomitization of Carnian reef limestone (Transdanubian Range, Hungary)

AbstractPartially dolomitized carbonate successions provide a good opportunity to understand the commonly multistage process of dolomitization. Petrographic methods, fluid inclusion microthermometry and stable isotope measurements were applied to reconstruct the diagenetic evolution and dolomitization of a partially dolomitized Carnian reef limestone from the Transdanubian Range, Hungary. The diagenetic history began with reef diagenesis and formation of dolomite micro‐aggregates in microbial fabric elements; this was followed by the development of euhedral porphyrotopic dolomite crystals through overgrowths around the previously formed dolomite micro‐aggregates during the earliest burial stage. Increasing burial resulted in the extension of the dolomite patches via formation of finely crystalline replacement dolomite. From the Late Norian, when the Carnian reef carbonates reached the depth of 1·0 to 1·8 km, the diagenetic evolution continued in an intermediate to deep‐burial setting. Contemporaneously, an extensional regime was established, leading to fracturing. The progressive burial resulted in the recrystallization of the pre‐existing dolomite with increasing temperature, while saddle dolomite cement was precipitated in fractures. In connection with the Alpine Orogeny, intense denudation took place during the Late Cretaceous, accompanied by fracturing. Similar tectonically controlled denudation and fracturing occurred in several stages during the Cenozoic. As a result of these processes, the studied Carnian carbonates were raised to a near‐surface position or became subaerially exposed, leading to dedolomitization of the last dolomite phase and precipitation of calcite cement in cavities and fractures. This study revealed that by investigating partially and selectively dolomitized rock types, it is possible to document and understand those stages of the multiple dolomitization process which can barely be detected in the completely dolomitized rock bodies. Recognition of the dolomitization phases could provide the basis for the analysis of their relations with the depositional, diagenetic and tectonic processes, and stages of basin evolution.

The relationship between dolomite textures and their formation temperature: a case study from the Permian-Triassic of the Sichuan Basin and the Lower Paleozoic of the Tarim Basin

Study of dolomite texture can contribute to understanding the process of dolomitization. This research reports textures and homogenization temperatures of dolomites from the Permian-Triassic strata in the Sichuan Basin and the Lower Paleozoic strata in the Tarim Basin, which provided insights into relationships between dolomite textures and their formation temperatures. Our results are summarized as follows: 1) dolomites with well-preserved texture indicate low dolomitization temperature. However, in certain diagenetic environments, the hydrothermal dolomitization may completely or partially preserve the original texture of dolomites. 2) The formation temperatures of non-planar dolomites are always higher than those of planar dolomites. 3) The formation temperatures of dolomite cements are generally higher than those of replacive dolomites. 4) Although the formation temperatures of saddle dolomite cements have a wide range, they show higher values than those of the planar subhedral to euhedral dolomite cements. Thus, saddle dolomites could generally be an indicator of high precipitation temperature. 5) The fluid Mg/Ca ratio is another element controlling dolomite morphology. Micritic dolomites, which precipitate from hypersaline fluids with a high Mg/Ca ratio in a subaerial environment could also have features of non-planar anhedral crystal shape because of rapid nucleation and crystallization during dolomitization.

Characteristics and Dolomitization of Upper Cambrian to Lower Ordovician Dolomite from Outcrop in Keping Uplift, Western Tarim Basin, Northwest China

Abstract:Late Cambrian to Early Ordovician sedimentary rocks in the western Tarim Basin, Northwest China, are composed of shallow‐marine platform carbonates. The Keping Uplift is located in the northwest region of this basin. On the basis of petrographic and geochemical features, four matrix replacement dolomites and one type of cement dolomite are identified. Matrix replacement dolomites include (1) micritic dolomites (MD1); (2) fine–coarse euhedral floating dolomites (MD2); (3) fine–coarse euhedral dolomites (MD3); and (4) medium–very coarse anhedral mosaic dolomites (MD4). Dolomite cement occurs in minor amounts as coarse saddle dolomite cement (CD1) that mostly fills vugs and fractures in the matrix dolomites. These matrix dolomites have δ18O values of −9.7‰ to −3.0‰ VPDB (Vienna Pee Dee Belemnite); δ13C values of −0.8‰ to 3.5‰ VPDB; 87Sr/86Sr ratios of 0.708516 to 0.709643; Sr concentrations of 50 to 257 ppm; Fe contents of 425 to 16878 ppm; and Mn contents of 28 to 144 ppm. Petrographic and geochemical data suggest that the matrix replacement dolomites were likely formed by normal and evaporative seawater in early stages prior to chemical compaction at shallow burial depths. Compared with matrix dolomites, dolomite cement yields lower δ18O values (−12.9‰ to −9.1‰ VPDB); slightly lower δ13C values (−1.6‰–0.6‰ VPDB); higher 87Sr/86Sr ratios (0.709165–0.709764); and high homogenization temperature (Th) values (98°C–225°C) and salinities (6 wt%−24 wt% NaCl equivalent). Limited data from dolomite cement shows a low Sr concentration (58.6 ppm) and high Fe and Mn contents (1233 and 1250 ppm, respectively). These data imply that the dolomite cement precipitated from higher temperature hydrothermal salinity fluids. These fluids could be related to widespread igneous activities in the Tarim Basin occurring during Permian time when the host dolostones were deeply buried. Faults likely acted as important conduits that channeled dolomitizing fluids from the underlying strata into the basal carbonates, leading to intense dolomitization. Therefore, dolomitization, in the Keping Uplift area is likely related to evaporated seawater via seepage reflux in addition to burial processes and hydrothermal fluids.

Dolomite textures in the Upper Cretaceous carbonate-hosted Pb–Zn deposits, Zakho, Northern Iraq

In the northeast of Zakho City, Northern Iraq, the host rocks of Pb–Zn deposits are composed predominantly of dolomites with subordinate dolomitic limestone intervals. This study is focused on the dolomites of the Bekhme Formation (Upper Campanian) carbonate-hosted Pb–Zn deposits. The amount of dolomites, however, increases toward the mineralized zone. Dolomites are dominated by replacement dolomite with minor dolomite cements. Petrography study allowed identification of six different dolomite textures. These are (1) fine crystalline, planar-s (subhedral) dolomite, RD1; (2) medium to coarse crystalline, planar-e (euhedral) to planar-s (subhedral) dolomites, RD2; (3) medium crystalline, planar-s (subhedral) to nonplanar-a (anhedral) dolomites, RD3; (4) coarse crystalline, planar-s (subhedral) to nonplanar-a (anhedral) dolomites, RD4; (5) planar (subhedral) void-filling dolomite cements, CD1; and (6) nonplanar (saddle) void-filling dolomite, CD2. The RD1, RD2, RD3, and RD4 dolomite textures are replacive in origin and are volumetrically the most important types, whereas CD1 and CD2 dolomites with sparry calcite are commonly cements that fill the open spaces. Although the dolomites of the Bekhme Formation are not macroscopically observed in the field, their different types are easily distinguished by petrographic examination and scanning electron microscopy. It was observed that the dolomites of the Bekhme Formation are formed in two different diagenetic stages: the early diagenetic from mixing zone fluids at the tidal–subtidal (reef) environments and the late diagenetic from basinal brines which partially mixed with hydrothermal fluids at the shallow-deep burial depths. The latter occurs often with sphalerite, galena, and pyrite within mineralized zone. These dolomite types are associated base-metal mineralization (Mississippi Valley type).

Diagenetic processes in a partially dolomitized carbonate reservoir: Casablanca oil field, Mediterranean Sea, offshore Spain

Mesozoic and Neogene carbonates located in the Valencia Trough (offshore Spain, western Mediterranean Sea) are oil reservoirs. This paper investigates the diagenetic evolution of the Upper Jurassic limestones, currently dolomitized, that constitute the main reservoir of the Casablanca oil field. Core samples from Casablanca-1A well have been studied to determine the diagenetic products and their relation with porosity evolution, and to reconstruct the fluid flow history prior to and during oil emplacement. On the basis of petrological observations and geochemical analyses (major, minor and trace element composition and oxygen, carbon and strontium isotope composition), a major dolomitization event is recognized postdating subaerial exposure, erosion and karstification. The dolomitization event originated two replacive dolomites (RD1 and RD2) and two dolomite cements (saddle dolomite cement, SDC, and milky-white dolomite cement, MDC) which are partially cogenetic. RD1, RD2 and SDC precipitated at increasing temperatures (over 60oC and below 110oC), probably from meteoric water mixed with marine water. The last dolomite type (milky-white dolomite cement) precipitated with increasing burial conditions and by arrival of hydrothermal fluids during the Miocene. The post-dolomitization sequence comprises precipitation of calcite cement and partial calcitization of all previous dolomites. The oxygen, carbon and strontium isotope compositions suggest that this calcite cementation occurred from meteoric waters mixed with Burdigalian - Langhian marine waters trapped in the sediments and expelled by compaction in the moderate to deep burial realm. Normal faults were the conduits for upward migration of these fluids as well as for later oil expulsion from the Burdigalian - Langhian source rocks. Late corrosion associated with organic acid-enriched fluids took place prior or simultaneously to oil migration during the Pliocene, enhancing porosity and increasing reservoir quality.

Diagenetic evolution and associated mineralization in Middle Devonian carbonates, southwestern Ontario, Canada

Abstract The Middle Devonian Lucas Formation of southwestern Ontario, Canada, forms the main hydrocarbon reservoir rocks in the region. Integrated field, petrographic, fluid inclusion and isotope geochemistry reveal a variety of diagenetic processes that include the formation of dolomite, calcite, celestine and fluorite under diverse geochemical conditions. The host carbonate strata display two types of replacive dolomite fabrics: 1) fine-crystalline matrix dolomite (5–20 μm); and 2) medium-crystalline dolomite (50–150 μm) with an average size of 100 μm. Stable oxygen and carbon isotope results for both dolomite fabrics show a wide range of values (δ18O = −9.4‰ to −3.9‰ VPDB, δ13C = 0.4‰ to 3.4‰ VPBD). For late fracture-filling calcite, δ 18O and δ 13C values range from −9.4 to −5.9‰ VPDB and −7.7‰ to −0.04‰ VPDB, respectively. The 87Sr/86Sr ratios of selected dolomite and calcite samples range from 0.70798–0.70838, preserving Middle Devonian seawater values while some samples have slightly more radiogenic ratios than contemporaneous seawater. Field and petrographic evidence and Sr isotope ratios of dolomite suggest early dolomitization from evaporated seawater in a sabkha setting (shallow seepage reflux or evaporitive pumping). However, the depletion in δ18O (varying from −3.9 to −9.4‰ VPDB), and radiogenic Sr isotope values of the Lucas Formation dolomite are considered to be the result of recrystallization, which is interpreted to occur at elevated temperatures in a burial environment. The 18O-depleted values and slightly radiogenic 87Sr/86Sr ratios of calcite cements suggest precipitation from hot, saline basinal/hydrothermal brines. In addition, the 13C-depleted calcites indicate that carbon was possibly formed by oxidation of organic matter. Fluid inclusions in some of the late calcite cements fluoresce under UV light, indicating the presence of hydrocarbons. Homogenization temperatures of these inclusions vary from 87.1°C to 171.9°C with an average value of 126°C. Average salinity of fluid inclusions is 19.7 wt. % NaCl eq. Celestine samples have lower salinities relative to calcite, averaging 14.5 wt. % NaCl eq. with an average homogenization temperature of 219.5°C. Based on the geochemical and fluid inclusion results, hot, saline basinal/hydrocarbon bearing brines originated from central part of the basin and migrated to Devonian carbonates via fractures and faults. Celestine is a product of thermochemical sulfate reduction and formed due to mixing of saline, Sr and sulfate bearing brines and meteoric waters.

Dedolomitization and reservoir quality: insights from reactive transport modelling

AbstractDedolomitization or calcitization, the replacement of dolomite by calcite, modifies the porosity and permeability of carbonate rocks. This study evaluates the effects of dedolomitization on the porosity of carbonates by means of geochemical and reactive transport simulations. The obtained results indicate that dedolomitization is a slow process that may be triggered by cold meteoric water but also by warm groundwater at temperatures of ≤50°C. Dedolomitization is more efficient with fluid fluxes on the order of tens of metres per year. Most of the simulations performed in this study resulted in a loss of porosity due to calcitization. The rate of the dedolomitization reaction increases significantly when calcium‐bearing minerals with faster dissolution kinetics and smaller molar volume than calcite, such as anhydrite, are present in the system. In such situations, the porosity of the rock increases significantly (approximately 10%) during a time span of hundreds of thousands of years. Therefore, depending on its original composition, fluid flow conditions and fluid composition, the porosity of a tight dolostone can be enhanced and reach porosity values of reservoir rocks after being calcitized.

Hydrothermal dolomitization of the carbonate Jurassic succession in the Provençal and Subbriançonnais Domains (Maritime Alps, North-Western Italy)

The present article illustrates a straightforward case of hydrothermal dolomitization, affecting Jurassic platform limestones of the Provençal and Subbriançonnais Domains (Maritime Alps, North-Western Italy). Dolomitized bodies are randomly distributed within the host limestone, and are commonly associated with dolomite vein networks and tabular bodies of dolomite-cemented breccias discordant with respect to bedding. Main dolomite types are a finely to medium-crystalline replacive dolomite and a coarsely-crystalline saddle dolomite occurring both as replacive and as cement. Stratigraphic constraints indicate that dolomitization occurred during the Cretaceous, in a shallow burial context, and was due to the circulation of hot fluids (temperature about 200°C, as indicated by fluid inclusion microthermometry) through faults and related fracture networks. Hydrothermal dolomitization therefore indirectly documents a Cretaceous fault activity in the Maritime Alps segment of the European Tethyan passive margin.

Origin of dolomite in the Late Jurassic platform carbonates, Bolkar Mountains, Central Taurides, Turkey: Petrographic and geochemical evidence

The Late Jurassic-early Senonian Cehennemdere Formation extending in an E-W direction in a wide area at the south of the Bolkar Mountains (Central Taurides, Turkey) is composed of platform carbonates. The formation was deposited in an environment that was being transformed from a shallow carbonate platform to an open shelf and a continental slope, and was buried until late Paleocene uplift. The formation, with a thickness of about 360m, was chiefly developed as textures consisting of mudstone and wackestone and has been commonly dolomitized. Based on petrographic and geochemical properties, four types of replacement dolomites and two types of dolomite cements were distinguished. Replacement dolomite (RD), which is cut by low-amplitude stylolites developed as (1) fine crystalline planar-s dolomite (RD1); (2) medium crystalline planar-s dolomite (RD2); (3) medium-coarse crystalline planar-e dolomite (RD3) and; (4) coarse crystalline planar-s (e) dolomite (RD4). Two types of dolomite cements (CD) observed in low abundance and overlie low-amplitude stylolites: (1) coarse crystalline dolomite cement (CD1) filling dissolution voids and fractures in RD1 dolomites, and; (2) rim dolomite cement (CD2) that commonly develops on the space-facing surfaces of RD4 dolomite. Replacement dolomites are non-stoichiometric (Ca54–59Mg41–46), have similar geochemical properties, and are generally dull red/non luminescent in appearance. Replacement dolomite is represented by δ18O values from −4.5 to −0.5‰ VPDB, δ13C values of −0.7 to 2.7‰ VPDB, and 87Sr/86Sr ratios ranging from 0.707178 to 0.707692. Petrographic and geochemical data indicate that replacement dolomite (particularly RD2, RD3, and RD4 dolomite) was formed at shallow-intermediate burial depths during the Late Jurassic-Early Cretaceous, from seawater and/or from slightly modified seawater. The replacement dolomite (RD) was then recrystallized at increased burial depths and temperatures. Dolomite cements are similar to replacement dolomites in that they are non-stoichiometric (Ca55Mg45) and have similar trace element compositions. CD1 dolomite, which cuts low-amplitude stylolites, was formed during intermediate to deep burial following stylolite development. CD2 dolomite was precipitated in intercrystal pores in association with RD4 dolomite. Remaining pore space was filled with bitumen.

High-grade iron ore at Windarling, Yilgarn Craton: a product of syn-orogenic deformation, hypogene hydrothermal alteration and supergene modification in an Archean BIF-basalt lithostratigraphy

Banded iron formation (BIF)-hosted iron ore deposits in the Windarling Range are located in the lower greenstone succession of the Marda–Diemals greenstone belt, Southern Cross domain, Yilgarn Craton and constitute a total hematite–martite–goethite ore resource of minimum 52 Mt at 60 wt.% Fe (0.07 P). Banded iron formation is interlayered with high-Mg basalts at Windarling and precipitated during episodes of volcanic quiescence. Trace element content and the rare earth element (REE) ratios Y/Ho (42 to 45), Sm/Yb (1.5), together with positive La and Gd anomalies in ‘least-altered’ hematite–magnetite–metachert–BIF indicate the precipitation from Archean seawater that was fertilised by hydrothermal vent fluids with a basaltic HREE-Y signature. Hypogene iron ore in sub-greenschist facies metamorphosed BIF formed during three distinct stages: ore stage 1 was a syn- to post-metamorphic, syn-D1, Fe–Ca–Mg–Ni–Co–P–REE metasomatism that produced local Ni–REE-rich Fe–dolomite–magnetite alteration in BIF. Hydrothermal alteration was induced by hot fluid flow controlled by brittle–ductile reactivation of BIF-basalt margins and crosscutting D1 faults. The Ni–Co-rich content of dolomite and a shift in REE ratios in carbonate-altered BIF towards Archean mafic rock signature (Y/Ho to 31 to 40, Sm/Yb to 1 to 2 and Gd/Gd* to 1.2 to 1.4) suggest that high-Mg basalts in the Windarling Range were the primary source of introduced metals. During ore stage 2, a syn-deformational and likely acidic and oxidised fluid flow along BIF-basalt margins and within D1 faults leached carbonate and precipitated lepidoblastic and anhedral/granoblastic hematite. High-grade magnetite–hematite ore is formed during this stage. Ore stage 3 hydrothermal specular hematite (spcH)–Fe–dolomite–quartz alteration was controlled by a late-orogenic, brittle, compressional/transpressional stage (D4; the regional-scale shear-zone-related D3 is not preserved in Windarling). This minor event remobilised iron oxides, carbonate and quartz to form veins and breccia but did not generate significant volumes of iron ore. Ore stage 4 involved Mesozoic(?) to recent supergene oxidation and hydration in a weathering environment reaching down to depths of ∼100 to maximum 200 m below surface. Supergene ore formation involved goethite replacement of dolomite and quartz as well as martitisation. Important ‘ground preparation’ for supergene modification and upgrade were mainly the formation of steep D1 to D4 structures, steep BIF/basalt margins and particularly the syn-D1 to syn-D2 carbonate alteration of BIF that is most susceptible to supergene dissolution. The Windarling deposits are structurally controlled, supergene-modified hydrothermal iron ore systems that share comparable physical, chemical and ore-forming characteristics to other iron ore deposits in the Yilgarn Craton (e.g. Koolyanobbing, Beebyn in the Weld Range, Mt. Gibson). However, the remarkable variety in pre-, syn- and post-deformational ore textures (relative to D1 and D2) has not been described elsewhere in the Yilgarn and are similar to the ore deposits in high-strain zones, such as of Brazil (Quadrilatero Ferrifero or Iron Quadrangle) and Nigeria. The overall similarity of alteration stages, i.e. the sequence of hydrothermal carbonate introduction and hypogene leaching, with other greenstone belt-hosted iron ore deposits supports the interpretation that syn-orogenic BIF alteration and upgrade was crucial in the formation of hypogene–supergene iron ore deposits in the Yilgarn Craton and possibly in other Archean/Paleoproterozoic greenstone belt settings worldwide.

Dolomitization of the Miocene carbonates in Gebel Abu Shaar El Qiblie and Salum area, Egypt: a petrographical and geochemical comparative study

The shallow marine Miocene carbonates of Gebel Abu Shaar El Qiblie and Salum escarpment, Egypt have been extensively dolomitized. Different dolomite textures are identified in the two areas: mimic replacive dolomite with uni- to polymodal size distribution and high preservation of the grain fabrics, non-mimic replacive crystalline dolomite with relatively uniform crystal size distribution, and partial dolomitization with polymodal size distribution and planar crystal boundaries. Minor cavity-filling dolomite cement is also observed. The development of non-planar crystal boundaries, stoichiometric characteristic, Sr content (92–245 ppm), negative δ18O values (−9.34 to 1.59 ‰) of Abu Shaar dolomites and their association with Fe–Mn ore deposits suggest that these dolomites formed from partial recrystallization and modification of early formed normal marine dolomites by the influence of hydrothermal fluid evolved during rifting of Red Sea. However, recrystallization by freshwater-dominated fluid during meteoric water diagenesis can be supposed. Alternatively, the non-stoichiometric composition, δ18O values (2.15–3.19 ‰) of marine signature and Sr content (73–204 ppm) of Salum dolomites indicate that dolomitization was probably mediated by seawater or slightly modified seawater within the subtidal zone during early stage of diagenesis. The δ13C values (–1.03 to 0.7 ‰ for Abu Shaar, and –0.23 to 1.69 ‰ for Salum dolomites) reflect normal marine-derived carbon source and are probably inherited from the precursor marine limestones. The negative values of some Abu Shaar dolomites may be attributed to minimal contribution of carbon derived from soil-derived CO2 or from oxidation of methane derived from deep hydrocarbon reservoir via fractures during rifting of Red Sea.

Zincian dolomite related to supergene alteration in the Iglesias mining district (SW Sardinia)

One of the main effects of supergene alteration of ore-bearing hydrothermal dolomite in areas surrounding secondary zinc orebodies (Calamine-type nonsulfides) in southwestern Sardinia (Italy) is the formation of a broad halo of Zn dolomite. The characteristics of supergene Zn dolomite have been investigated using scanning electron microscopy and qualitative energy-dispersive X-ray spectroscopy, thermodifferential analysis, and stable isotope geochemistry. The supergene Zn dolomite is characterized by variable amounts of Zn, and low contents of Pb and Cd in the crystal lattice. It is generally depleted in Fe and Mn relative to precursor hydrothermal dolomite (Dolomia Geodica), which occurs in two phases (stoichiometric dolomite followed by Fe-Mn-Zn-rich dolomite), well distinct in geochemistry. Mg-rich smithsonite is commonly associated to Zn dolomite. Characterization of Zn-bearing dolomite using differential thermal analysis shows a drop in temperature of the first endothermic reaction of dolomite decomposition with increasing Zn contents in dolomite. The supergene Zn dolomites have higher δ18O but lower δ13C values than hydrothermal dolomite. In comparison with smithsonite-hydrozincite, the supergene Zn dolomites have higher δ18O, but comparable δ13C values. Formation of Zn dolomite from meteoric waters is indicated by low δ13C values, suggesting the influence of soil-gas CO2 in near-surface environments. The replacement of the dolomite host by supergene Zn dolomite is interpreted as part of a multistep process, starting with a progressive “zincitization” of the dolomite crystals, followed by a patchy dedolomitization s.s. and potentially concluded by the complete replacement of dolomite by smithsonite.

Dolomitization of the lower Ordovician Catoche formation: Implications for hydrocarbon exploration in western Newfoundland

The lower Ordovician St. George Group in Western Newfoundland consists of a sequence of subtidal and peritidal carbonates, which are extensively dolomitized. The current study investigates the diagenetic evolution of the Catoche Formation from the Port aux Choix and Port au Port peninsulas in order to study the controls on reservoir quality in western Newfoundland. The Catoche Formation dolomites are classified into three main generations. Early and pervasive replacement dolomite (D1) indicates that dolomitization began during early stages of diagenesis. Stable isotope and trace element data indicate significant variations between D1 dolomite on the Port aux Choix and Port au Port peninsulas. The depleted δ 18O signature of D1 dolomite fluids (−8.7 ± 1.3‰ VPBD) on the Port aux Choix Peninsula is consistent with partial dolomitization associated with mixing of seawater and meteoric waters on the flanks of structural highs. In contrast δ 18O values (−6.1 ± 0.7‰ VPBD) and trace element data from the Port au Port Peninsula indicate that pervasive D1 was associated with mixing of possibly post evaporitic brines with meteoric waters. Later-stage replacement dolomites (D2) are associated with enhancement in porosity through the development of intercrystalline pores, while latest stage saddle dolomite (D3), significantly occluded the pores in some horizons. D2 dolomite formed due to the influx of warm (>100 °C), saline (>15 eq. wt% NaCl) fluids. Intercrystalline porosity in D2 formed due to the dolomitization of precursor calcite, due to the lower molar volume of dolomite compared to calcite. Therefore porosity development is lower on the Port au Port Peninsula, with no significant volume change during the recrystallization of the pervasive early (D1) dolomicrite. Similarly, extensive porous horizons on the Port aux Choix Peninsula are related to the limited extent of D1 dolomitization. This suggests that the quality of a potential dolomite reservoir is strongly controlled by tectonic and diagenetic history of host carbonates.

Hydrothermal dolomitization in platform and basin carbonate successions during thrusting: A hydrocarbon reservoir analogue (Mesozoic of Venetian Southern Alps, Italy)

The Early Jurassic dolomitized carbonates in the Venetian Alp, represent a surface analogue of the hydrocarbon exploration targets in Adriatic offshore and Po Plain, Italy. Dolomitization affected the carbonate platform of Monte Zugna Formation (Lower Jurassic) and the Neptunian dikes breccia in the pelagic Maiolica Formation (Uppermost Jurassic–Lower Cretaceous) improving the poro-perm characteristics. Petrography, stable isotope, strontium isotope ratio, trace element and fluid inclusion analyses were carried out on samples from the Monte Grappa Anticline, which is the direct analogue for subsurface. The petrographic analyses showed a first pervasive, replacement dolomitization phase (D1) followed by volumetrically less important dolomite cement precipitation phases (D2, D3, DS). The same, quite wide range of oxygen isotope (−9 to −2‰ V-PDB) is observed in all dolomite types. The δ 13C range is in the positive field of marine derived carbonate (from +0.5 to +3.2‰ PDB). The trace element analysis showed a slight enrichment in Fe and Mn contents in the Monte Zugna dolostones with respect the original limestone. The same dolomite precipitation temperature (up to 105 °C Th) was observed in the replacement and cement dolomites, suggesting a unique dolomitization event. This temperature, largely higher than the maximum burial temperature (about 50 °C), supports a hydrothermal origin of the dolomitizing fluids, which had a seawater to brackish composition. The data collected suggest a hydrothermal dolomitization occurring during to the South Alpine thrusting according to the “squeegee model”. The interpretation is consistent with the dolomitization model proposed for similar Jurassic successions in the Central Southern Alps. This study indicates that the deformed foreland and thrust fold belts carbonates in Po Plain and Adriatic offshore are suitable to be dolomitized, and therefore reflect an efficient hydrocarbon exploration play.

Chemical mass transfer during hydrothermal alteration of carbonates: Controls of seafloor subsidence, sedimentation and Zn–Pb mineralization in the Irish Carboniferous

Petrographic and geochemical data were acquired to evaluate models for the formation of hydrothermal dolomite breccias that host zinc–lead orebodies in the Rathdowney Trend of the Irish orefield and assess element mobility during hydrothermal alteration of carbonates. Macroscopic and microscopic textures indicate that the breccias largely formed by a pseudobrecciation process involving dissolution and replacement of precursor Waulsortian dolomite of diagenetic origin during subseafloor hydrothermal fluid flow. Geochemical analyses show that, compared with the Waulsortian dolomite precursor, breccia “clasts” and “matrix” contain respectively higher concentrations of Al, Ti and light rare earth elements which are linearly correlated, indicative of mass loss during hydrothermal interaction. Bulk rock mass loss estimates average 33% indicating extensive dissolution of carbonate although petrographic evidence and limited clast rotation or translation rule out the development of significant open space. This supports a mechanism of alteration whereby hydrothermal fluids, migrating along grain boundaries, microcracks and solution seams, drove dissolution and replacement of the surrounding host rock with partial collapse of the transient microporosity produced. Progressive interaction led to the gradual isolation of domains (“clasts”) surrounded by replacement dolomite (“matrix”). Massive sulfide mineralization formed subsequently by stratabound replacement of the dolomite pseudobreccia by hydrothermal fluids preferentially focused within the more permeable and possibly more reactive lithology. This process involved further volume loss (30% of the replaced rock). Quantitative mass transfer analysis indicates that during hydrothermal interaction, net loss of Na, P, Mn, Sr and sometimes Cu, and net gain in Li, K, Fe as well as the ore-associated elements typically occurred. Marked fractionation of the REE is observed: Eu was added, implicating elevated temperature, acidic and reduced hydrothermal fluids; Ce was also added, possibly derived from remobilization of pre-sulfide oxide mineralization; the LREE were typically immobile or partially removed; and the HREE were preferentially mobilized and transported beyond the scale of sampling. Thus, the HREE, together with Na, P, Mn, Sr and possibly Cu, may form a distal chemical anomaly at the base of the Waulsortian Limestone Formation. The net addition of Li, K and Be in dolomite breccia matrix samples, combined with their increase in concentration due to dolomite dissolution, produced a broad anomaly of these elements extending for at least 1.5 km from the center of the Lisheen deposit. These various geochemical anomalies have potential utility in mineral exploration. A total volume loss of up to 68% at Lisheen is consistent with a marked thinning of the Waulsortian biomicrite facies above massive sulfide. The observed thickening of upper and supra-Waulsortian facies in the trough developed above this zone is interpreted to reflect infill of a seafloor depression up to ~ 90 m deep, developed in response to underlying hydrothermal dissolution. This model implies mineralization initiated during the latter stages of Waulsortian deposition in the late Courceyan/early Chadian at a depth of approximately 150 m below the seafloor.

Toolstone constraints on knapping skill: Levallois reduction with two different raw materials

Lithic raw material constraints are widely assumed to be a determining factor of flaked stone tool morphology, but this assumption remains largely untested. We conducted a controlled experiment to determine whether a knapper’s growing replication skills would be hindered if the toolstone used was switched from large flakes of an easily worked chert to nodules of less tractable one. Two batches of Preferential Levallois cores were knapped, an earlier series made from standardised large flakes of sediments dominated by chalcedonic quartz followed by a more challenging one using variably-shaped, cortical nodules of microcrystaline quartz that varies in the completeness of quartz replacement of calcite and dolomite. Skill level markers were designed to measure the knapper’s ability to achieve a series of set goals. These were quantified and subjected to statistical testing. In all but one test, significant increases in skill could be detected from the earlier to the later batch of reductions, despite the drop in toolstone quality. Significant improvements in the consistency of the knapper’s output could also be detected. However, the switch to a more challenging, nodular chert did require extra shaping, which resulted in more waste. This masked visible progress towards producing a less costly core. Overall, our results do not support the assumed primacy of toolstone constraints over other factors in influencing the morphology of flaked stone tools.