Carbonate rocks and related facies with vestiges of biomarkers: Clues to redox conditions in the Mesoproterozoic ocean

The Raipur Group of the Chattisgarh Basin preserves two major Late Mesoproterozoic carbonate platforms. The lower platform is about 490-m thick, separated from the upper platform (~ 670 m thick) by a 500-m thick calcareous shale. Carbonate strata cover almost 40% of the Chattisgarh Basin outcrop and represent two major platform types: a) a non-stromatolitic ramp (the Charmuria/Sarangarh Limestone) and b) a platform developed chiefly in the intertidal to shallow subtidal environment with prolific growth of stromatolites (the Chandi/Saradih Limestone). The first platform consists primarily of the black Timarlaga limestone that is locally replaced by early diagenetic dolomite. This carbonate platform experienced strong storm waves and was subsequently drowned by a major transgression, during which extensive black limestone–marl rhythmite was deposited, followed by deposition of the Gunderdehi Shale. The carbonate factory was later re-established with development of an extensive stromatolite-dominated Charmuria/Sarangarh platform that ranged from restricted embayment to open-marine conditions. Sea-level change played a major role in controlling the broad facies pattern and platform evolution. The δ¹³C signatures of the Chattisgarh limestones, falling within a relatively narrow range (0 to + 4‰) are typical for Upper Mesoproterozoic carbonate rocks. δ¹⁸O values, however, have a greater range (− 5.7 to − 13.3‰) indicating significant diagenetic alteration of some samples. Likely dysoxic or anoxic conditions prevailed during deposition of the black Timarlaga limestone and well-oxygenated conditions during deposition of the Gunderdehi Shale and Saradih/Chandi stromatolite. The lack of 17β,21α (moretanes) and high T_max values suggest mature organic matter in the non-stromatolitic ramp. A paucity of diagnostic eukaryotic steroids indicates that algae were rare in the Chattisgarh Basin. A high content of hopanes supports a generally bacterially-dominated Proterozoic ocean in which various stromatolites flourished.     

Diagenesis of silica-rich mound-bedded chalk,the Coniacian Arnager Limestone,Denmark

The Coniacian Arnager Limestone Formation is exposed on the Danish island of Bornholm in the Baltic Sea. It is composed of mound-bedded siliceous chalk, and X-ray diffraction and scanning electron microscopy indicate a content of 30–70% insoluble minerals, including authigenic opal-CT, quartz, clinoptilolite, feldspars, calcite, dolomite, and barite. Opal-CT and clinoptilolite are the most common and constitute 16–53% and 2–9%, respectively. The content of insoluble minerals varies laterally both within the mounds and in planar beds, and the opal-CT content varies by up to 10% vertically. The mounds consist of two microfacies, spiculitic wackestone and bioturbated spiculitic wackestone, containing 10–22% and 7–12% moulds after spicules, respectively.Subsequent to deposition and shallow burial, dissolution of siliceous sponge spicules increased the silica activity of the pore water and initiated precipitation of opal-CT. The opal-CT formed at temperatures around 17 °C, the precipitation lowered the silica activity and the Si/Al ratio of the pore water, resulting in precipitation of clinoptilolite, feldspar and smectite. Calcite formed synchronously with the latest clinoptilolite. Minor amounts of quartz precipitated in pore water with low silica activity during maximum burial, probably to depths of 200–250 m. The dissolution of sponge spicules and decomposition of the sponge tissue also resulted in the release of Ba²⁺, Sr²⁺, Mg²⁺, Ca²⁺ and CO₃^2?, facilitating precipitation of barite and dolomite. Precipitation of especially opal-CT reduced the porosity to an average of 40% and cemented the limestone. The study highlights the diagenetic pathways of bio-siliceous chalk and the effects on preservation of porosity and permeability.     

Monitoring groundwater flow and chemical and isotopic composition at a demonstration site for carbon dioxide storage in a depleted natural gas reservoir

Between March 2008 and August 2009, 65,445 tonnes of ∼75 mol% CO₂ gas were injected in a depleted natural gas reservoir approximately 2000 m below surface at the Otway project site in Victoria, Australia. Groundwater flow and composition were monitored biannually in two overlying aquifers between June 2006 and March 2011, spanning the pre-, syn- and post-injection periods. The shallower (∼0–100 m), unconfined, porous and karstic aquifer of the Port Campbell Limestone and the deeper (∼600–900 m), confined and porous aquifer of the Dilwyn Formation contain valuable fresh to brackish water resources. Groundwater levels in either aquifer have not been affected by the drilling, pumping and injection activities that were taking place, or by the rainfall increase during the project. In terms of groundwater composition, the Port Campbell Limestone groundwater is brackish (electrical conductivity = 801–3900 μS cm⁻¹), cool (temperature = 12.9–22.5 °C), and near-neutral (pH = 6.62–7.45), whilst the Dilwyn Aquifer groundwater is fresher (electrical conductivity = 505–1473 μS cm⁻¹), warmer (temperature = 42.5–48.5 °C), and more alkaline (pH = 7.43–9.35). Carbonate dissolution, evapotranspiration and cation exchange control the composition of the groundwaters. Comparing the chemical and isotopic composition of the groundwaters collected before, during and after injection shows no statistically significant changes; even if they were statistically significant, they are mostly not consistent with those expected if CO₂ addition had taken place. The monitoring program reveals no impact on the groundwater resources attributable to the C storage demonstration project.     

A remarkable sea-level drop and relevant biotic responses across the Guadalupian–Lopingian (Permian) boundary in low-latitude mid-Panthalassa: Irreversible changes recorded in accreted paleo-atoll limestones in Akasaka and Ishiyama,Japan

The Capitanian (Upper Guadalupian) to Wuchiapingian (Lower Lopingian) shallow-marine limestones at Akasaka and Ishiyama in central Japan record unique aspects of the extinction-related Guadalupian–Lopingian boundary (G-LB) interval. The ca. 140 m-thick Akasaka Limestone consists of the Capitanian black limestone (Unit B; 112 m) and the Wuchiapingian light gray dolomitic limestone (Unit W; 21 m), with a black/white striped limestone (Unit S; 9 m) between them. The G-LB horizon is assigned at the base of Unit W, on the basis of the first occurrence of the Wuchiapingian fusulines. The Capitanian Unit B and the Wuchiapingian Unit W were deposited mostly in the subtidal zone of a lagoon, whereas the intervened Unit S and the lowermost Unit W were in the intertidal zone. A hiatus with a remarkable erosional feature was newly identified at the top of Unit S. These records indicate that the sea-level has dropped significantly around the G-LB to have exposed the top of the atoll complex above the sea-level. The Ishiyama Limestone, located ca. 10 km to the north of the Akasaka limestone, retains almost the same depositional records. The extinction of large-tested fusuline (Yabeina) and large bivalves (Alatoconchidae) occurred in the upper part of Unit B, and the overlying 20 m-thick limestone (the uppermost Unit B and Unit S) below the hiatus represents a unique barren interval. The upper half of the barren interval is more depleted in fossils than the lower half, and this likely represents a duration of the severest environmental stress(es) for the shallow-marine protists/animals on the mid-oceanic paleo-atoll complex. Small-tested fusulines re-appeared at the base of Unit W above the hiatus. These facts prove that the elimination of shallow-marine biota occurred during the Capitanian shallowing of Akasaka paleo-atoll before the subaerial exposure/erosion across the G-LB. The overall shallowing and the development of such a clear hiatus at the top of a mid-oceanic seamount, in accordance with the contemporary sea-level curve based on continental shelf records, indicates that a remarkable sea-level drop has occurred globally during the latest Capitanian. This further suggests that a cool climate likely has appeared even in the low-latitude domains in Panthalassa to cause the decline of the Middle Permian shallow-water protists/animals that adapted to warmer seawater. The Wuchiapingian biota first appeared immediately after this erosional episode, i.e., during the onset of warming after the G-LB.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Chronostratigraphy of Campanian–Maastrichtian platform carbonates and rudist associations of Salento (Apulia,Italy)

Late Cretaceous platform carbonates from the Salento peninsula (south Italy) were studied by strontium-isotope stratigraphy to improve their chronostratigraphy. Forty-three samples from nine localities were collected and the numerical ages were derived from fifteen geochemically well-preserved samples of rudist shells that were analyzed for ⁸⁷Sr/⁸⁶Sr values. Strontium isotope stratigraphy yielded new ages for the base of the Ciolo Limestone. The oldest successions studied in Salento are 85.9 Ma (+/− 0.6) and assigned to the Melissano Limestone. The youngest Cretaceous limestones observed at the Ciolo Limestone type locality (Ciolo cove) are 66.4 Ma (+/− 1.5), and the base of this formation is older than 72.8 Ma (+/− 0.4). Karstic cavities observed at the Cava Cocumola in the mid-Campanian S. Cesarea Limestone are tentatively interpreted to be linked to an intra-Campanian event which is related to a sea-level lowstand inferred also on the island of Brač (Adriatic coast of Croatia) and in the Boreal realm at 75–77 Ma. A new large recumbent rudist similar to Sabinia and Pseudosabinia is observed in the Ciolo and S. Cesarea Limestone and appears to be characteristic of the Apulian platform carbonates. Rudist associations from the S. Cesarea Limestone and the overlying Ciolo Limestone are remarkably similar, although they range over a time interval of more than 12 Ma.     

Post-Chicxulub depositional and diagenetic history of the northwestern Yucatan Peninsula,Mexico

The Chicxulub Sedimentary Basin of the northwestern Yucatan Peninsula, Mexico, which was formed because of the largest identified Phanerozoic bolide impact on Earth, became a site of deposition of dominantly marine carbonate sediments during most of the Cenozoic Era. This is a study of the filling and diagenetic history of this basin and surrounding areas. The study makes use of lithologic, biostratigraphic, petrographic, and geochemical data obtained on core samples from boreholes drilled throughout the northwestern Yucatan Peninsula.The core sample data indicate that: 1) The Chicxulub Sedimentary Basin concentrated the deposition of pelagic and outer-platform sediments during the Paleocene and Eocene, and, in places, during the Early Oligocene, as well, and filled during the Middle Miocene, 2) deeper-water limestone also is present within the Paleocene and Lower Eocene of the proposed Santa Elena Depression, which is located immediately south of the Basin, 3) shallow-water deposits are relatively more abundant outside the Basin and Depression than inside, 4) the autigenic and allogenic silicates from the Paleogene formations are the most abundant inside the Depression, 5) sediment deposition and diagenesis within the Basin also were controlled by impact crater topography, 6) the abundance of the possible features of subaerial exposure increases upward and outward from the center of the Basin, and 7) the formation of replacive low-magnesium calcite and dolomite, dedolomitization, dissolution, and precipitation of vug-filling calcite and dolomite cement have been more common outside the Basin than inside.δ¹⁸O in whole-rock (excluding vug-filling) calcite from core samples ranges from − 7.14‰ to + 0.85‰ PDB. δ¹³C varies from − 6.92‰ to + 3.30‰ PDB. Both stable isotopes correlate inversely with the abundance of subaerial exposure features indicating that freshwater diagenesis has been extensive especially outside and at the edge of the Chicxulub Sedimentary Basin.δ¹⁸O and δ¹³C in whole-rock (excluding vug-filling) dolomite ranges from − 5.54‰ to + 0.87‰ PDB and − 4.63‰ to + 3.38‰ PDB, respectively. Most dolomite samples have negative δ¹⁸O and positive δ¹³C suggesting that replacive dolomitization involved the presence of a fluid dominated by freshwater and/or an anomalously high geothermal gradient.Most dolomite XRD-determined mole percent CaCO₃ varies between 51 and 56. Replacive dolomite is larger, more euhedral, and less stoichiometric inside the Chicxulub Sedimentary Basin than outside.     

Early Carboniferous paleomagnetic results from the northeastern margin of the Qinghai–Tibetan plateau and their implications

We conducted paleomagnetic investigations on limestone from the Lower Carboniferous Huaitoutala Formation in the Qaidam Basin near Delingha City, Qinghai Province, China. The characteristic remanent magnetization (D = 5.8°, I = − 25.7°, k = 114.3, α₉₅ = 4.8°) passes a fold test and indicates a paleopole position of − 39.2°N, 90.4°E and a paleolatitude of 13.5°N for the Qaidam Block for the early Carboniferous. Based on global tectonic reconstructions and paleontological evidence, we suggest that the Qaidam Block was adjacent to, but independent from, the North China, South China, Alashan–Hexi and Tarim blocks at this time. This result suggests that Pre-Carboniferous sutures reported around the Qaidam Basin represent collisional events within Gondwana, rather than the final sutures that gave rise to the present tectonic configuration.     

Analysis of limestone micromechanical properties by optical microscopy

Four dense Scandinavian limestones were analyzed to determine their mechanical properties. The generation of dust (? 10 μm) and fines (? 90 μm) during a closed circuit vertical roller mill comminution process was correlated with the calcite crystal size distributions of each limestone. Thin sections were analyzed and by means of stereology the calcite crystal size distributions for each limestone was measured. The dust generation of limestones is governed by a surface abrasive mechanism (R² = 0.99) and the production of fines is governed by the mechanical strength of limestones (R² = 0.99). The overall limestone degradation mechanism is predominantly controlled by the calcite cleavage planes which reduce the power consumption during the comminution process. This study is the first step in determining the influence of limestone texture on the wear rates in heterogenous raw mixes used in closed circuit comminution equipment.     

Organic geochemistry and depositional environment of the Aptian bituminous limestone in the Kale Gümüşhane area (NE-Turkey): An example of lacustrine deposits on the platform carbonate sequence

The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average T_max value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The T_max values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C₂₆–C₃₀) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C₂₉ is the dominant sterane, with C₂₉ > C₂₇ > C₂₈. The bituminous limestone samples have low C₂₂/C₂₁ ratios, high C₂₄/C₂₃ tricyclic terpane ratios and very low C₃₁R/C₃₀ hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.     

Noble gas,CFC and other geochemical evidence for the age and origin of the Bath thermal waters,UK

The city of Bath is a World Heritage site and its thermal waters, the Roman Baths and new spa development rely on undisturbed flow of the springs (45 °C). The current investigations provide an improved understanding of the residence times and flow regime as basis for the source protection. Trace gas indicators including the noble gases (helium, neon, argon, krypton and xenon) and chlorofluorocarbons (CFCs), together with a more comprehensive examination of chemical and stable isotope tracers are used to characterise the sources of the thermal water and any modern components. It is shown conclusively by the use of ³⁹Ar that the bulk of the thermal water has been in circulation within the Carboniferous Limestone for at least 1000 years. Other stable isotope and noble gas measurements confirm previous findings and strongly suggest recharge within the Holocene time period (i.e. the last 12 kyr). Measurements of dissolved ⁸⁵Kr and chlorofluorocarbons constrain previous indications from tritium that a small proportion (<5%) of the thermal water originates from modern leakage into the spring pipe passing through Mesozoic valley fill underlying Bath. This introduces small amounts of O₂ into the system, resulting in the Fe precipitation seen in the King’s Spring. Silica geothermometry indicates that the water is likely to have reached a maximum temperature of between 69–99 °C, indicating a most probable maximum circulation depth of ∼3 km, which is in line with recent geological models. The rise to the surface of the water is sufficiently indirect that a temperature loss of >20 °C is incurred. There is overwhelming evidence that the water has evolved within the Carboniferous Limestone formation, although the chemistry alone cannot pinpoint the geometry of the recharge area or circulation route. For a likely residence time of 1–12 kyr, volumetric calculations imply a large storage volume and circulation pathway if typical porosities of the limestone at depth are used, indicating that much of the Bath-Bristol basin must be involved in the water storage.     

Geostatistical techniques application to dissolved radon hazard mapping: An example from the western sector of the Sabatini Volcanic District and the Tolfa Mountains (central Italy)

Dissolved Rn was determined in 192 samples collected from cold shallow volcanic and sedimentary aquifers, deep thermal aquifers and from waters associated with bubbling gases in the western sector of the Sabatini Volcanic District and the Tolfa Mountains (central Italy). Shallow aquifers hosted in the Quaternary volcanic complexes show values ranging from 1.0 to 352 Bq/L (median value 55 and inter-quartile distance 62 Bq/L), while waters circulating within the permeable horizons of the sandy-to-clayey sediments of the Tolfa flysch have values from 1.0 to 44 Bq/L (median value 6.9 and inter-quartile distance 8.1 Bq/L). Thermal waters are hosted in the Mesozoic carbonate formations and move towards the surface along faults. Here, dissolved Rn values range from 0 to 37 Bq/L (median value 3.0 and inter-quartile distance 9.5 Bq/L). Waters associated with bubbling gases show dissolved Rn contents ranging from 2.0 to 48 Bq/L (median value 6.2 and inter-quartile distance 23 Bq/L). Those results suggest that lithology is the main factor affecting the Rn contents in shallow aquifers, due to the high levels of Rn progenitors U and Ra in the volcanic rocks relative to sedimentary units. The influence of other factors such as the presence of a fracture network, seasonal flow variations, type of discharge (from well or spring) was also investigated. Radon contents of thermal waters result from mixing with shallow waters (from both volcanic and sedimentary rock aquifers) and decrease of Rn solubility with temperature, while for bubbling pools the effects of strong degassing were also considered.In terms of health hazard from direct ingestion of Rn-rich waters, 20.8% of those circulating within the volcanic aquifer show values higher than the recommended value of 100 Bq/L, while none of those circulating within the sedimentary aquifers exceed the threshold value. Geostatistical techniques were used for the elaboration of contour maps by using variogram models and kriging estimation aimed at defining the areas where a potential health hazard due to the direct ingestion of Rn-rich waters and to inhalation of air following degassing of Rn from waters may be expected.     

“Dedolomitization reactions” driven by anthropogenic activity on loessy sediments,SW Hungary

In the Szigetvár area, SW Hungary, shallow groundwaters draining upper Pleistocene loess and Holocene sediments are considerably contaminated by domestic effluents and leachates of farmland fertilizers. The loess contains calcite and dolomite, but gypsum was not recognized in these sediments. The anthropogenic inputs contain significant amounts of Ca and SO₄. The Ca from these anthropogenic inputs is promoting calcite growth, with concomitant consumption of carbonate alkalinity, undersaturation of the system with respect to dolomite, and dolomite dissolution; in brief, is driving “dedolomitization reactions”. Geochemical arguments supporting the occurrence of “dedolomitization reactions” in the area are provided by the results of mass balance and thermodynamic analyses. The mass balances predicted the weather sequence dolomite > calcite > plagioclase > K-feldspar, at odds with widely accepted sequences of weatherability where calcite is the first mineral in the weathering sequence. The exchange between calcite and dolomite can be a side effect of “dedolomitization reactions” because they cause precipitation of calcite. The thermodynamic prerequisites for “dedolomitization reactions” are satisfied by most local groundwaters (70%) since they are supersaturated (or in equilibrium) with respect to calcite, undersaturated (or in equilibrium) with respect to dolomite, and undersaturated with respect to gypsum. The Ca vs. SO₄ and Mg vs. SO₄ trends are also compatible with homologous trends resulting from “dedolomitization reactions”.     

Rapid Eocene erosion,sedimentation and burial in the eastern Himalayan syntaxis and its geodynamic significance

The lower Bomi Group of the eastern Himalayan syntaxis comprises a lithological package of sedimentary and igneous rocks that have been metamorphosed to upper amphibolite-facies conditions. The lower Bomi Group is bounded to the south by the Indus–Yarlung Suture and to the north by unmetamorphosed Paleozoic sediments of the Lhasa terrane. We report U–Pb zircon dating, geochemistry and petrography of gneiss, migmatite, mica schist and marble from the lower Bomi Group and explore their geological implications for the tectonic evolution of the eastern Himalaya. Zircons from the lower Bomi Group are composite. The inherited magmatic zircon cores display ²⁰⁶Pb/²³⁸U ages from ~ 74 Ma to ~ 41.5 Ma, indicating a probable source from the Gangdese magmatic arc. The metamorphic overgrowth zircons yielded ²⁰⁶Pb/²³⁸U ages ranging from ~ 38 Ma to ~ 23 Ma, that overlap the anatexis time (~ 37 Ma) recorded in the leucosome of the migmatites. Our data indicate that the lower Bomi Group do not represent Precambrian basement of the Lhasa terrane. Instead, the lower Bomi Group may represent sedimentary and igneous rocks of the residual forearc basin, similar to the Tsojiangding Group in the Xigaze area, derived from denudation of the hanging wall rocks during the India–Asia continental collision. We propose that following the Indian–Asian collision, the forearc basin was subducted, together with Himalayan lithologies from the Indian continental slab. The minimum age of detrital magmatic zircons from the supracrustal rocks is ~ 41.5 Ma and their metamorphism had happened at ~ 37 Ma. The short time interval (< 5 Ma) suggests that the tectonic processes associated with the eastern Himalayan syntaxis, encompassing uplift and erosion of the Gangdese terrane, followed by deposition, imbrication and subduction of the forearc basin, were extremely rapid during the Late Eocene.     

Sampling oxygenated Archean hydrosphere: Implications from fractionations of Th/U and Ce/Ce* in hydrothermally altered volcanic sequences

Hydrothermally altered Archean igneous suites erupted in the submarine environment record variable excursions of Ce/Ce* and Th/U from primary magmatic values of 1 and ~ 4 respectively. Rhyolites of the 2.96 Ga bimodal basalt–rhyolite sequence of the Murchison Domain, Yilgarn Craton, Western Australia, hosting the Golden Grove VMS deposit, are enriched in MnO up to ten fold over primary values. Th/U ratios span 2.6–4.7, Ce/Ce* = 2.5–16, and Eu/Eu* = 1.3–3. The 2.8 Ga Lady Alma ultramafic–mafic subvolcanic complex of the same domain features highly dispersed MREE and LREE due to intense hydrothermal alteration. Th/U ratios span 0.005–0.16 from preferential addition of U, with Ce/Ce* = 0.6–2.2, and Eu/Eu* = 1–1.4. The eastern Dharwar Craton, India, includes greenstone terranes dominantly 2.7–2.6 Ga. Adakites of the Gadwal terrane preserve near primary magmatic Th/U, Ce/Ce*, and Eu/Eu*. In contrast, igneous lithologies of the Hutti greenstone terrane are characterized by total ranges of Th/U = 2–5.8, Ce/Ce* = 1.01–1.28, and Eu/Eu* = 0.82–1.26, and counterparts of the Sandur terrane have Th/U = 0.4–6.0, Ce/Ce* = 0.9–1.25, and Eu/Eu* = 0.8–1.8. Coexistence of Ce and Eu anomalies may reflect a two-stage process: low-temperature hydrothermal alteration at high water–rock ratios by oxidizing fluids, with evolution of the hydrothermal systems to high temperature, low water–rock ratios, under reducing conditions. Uranium is dominantly added to these lithologies over Th in common with Recent altered ocean crust. Iron-rich shales in the Sandur terrane record U-enrichment where Th/U = 2–4. Three shales record true negative Ce anomalies and Eu/Eu* = 0.8–2.4: true negative Ce anomalies, present in some other Archean iron formations, are interpreted as a signature of precipitates from the ocean water column whereas Eu anomalies are hydrothermal in origin. Volcanic flows of the 2.7 Ga Blake River Group, Abitibi greenstone terrane, Canada, preserve Th/U = 1.5–8.5, the conjunction of low Th/U values with Ce/Ce* = 1.4 in two samples, and Eu/Eu* = 0.15–1.3. Mobility of U and Ce in these hydrothermally altered Archean lithologies is in common with their mobility in Phanerozoic counterparts by oxygenated fluids.     

Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

REE and their relevance to the development of the Kupferschiefer copper deposit in Poland

Over one hundred samples, representing mainly clayey-organic- and carbonate-rich shales (Kupferschiefer) but also other members of different ore sections, including hangingwall dolomites (Z1 Werra) and footwall Weissliegend sandstone (Lower Permian), have been collected in different mines of the Lubin–Głogów mining district, mainly near the contact (transitional zone) between the copper-mineralized zone and secondarily oxidized (Rote Fäule = RF) zone. In general, the Polish Kupferschiefer shales are enriched in MREE in comparison to NASC. In a typical copper-rich ore section the REE amounts and patterns depend on lithologies, being generally similar in shales and dolomite. ∑REE vary among sandstones, shales and dolomites (average 73, 143 and 85 ppm, respectively), probably reflecting mainly their clay contents. Sandstones have strongly convex REE patterns with positive Eu and negative Gd anomalies and depletion in LREE and enrichment in MREE relative to HREE. The REE patterns of shale and dolomite are similar to one another and rather flat, with strong negative Eu anomalies, and a small positive Gd anomaly in the case of shales.The REE patterns of shales from the mineralized Cu-zone are generally convex (MREE enriched) and have negative Eu anomalies. However, in a section with Cu-, Zn- and Pb-shales the REE pattern of Pb-bearing shales shows a positive Eu anomaly, in contrast to other shales and overlying dolomite. More oxidizing conditions of deposition can be assumed for Pb-shales.No significant differences between REE distributions in transitional and oxidized zones have been observed. Their REE patterns are more convex and are much higher (av. 247 ppm) than those in the mineralized zone and they do not show Eu anomalies. The strongly convex pattern may suggest either enrichment in MREE or relative depletion in LREE due to localized precipitation of light REE minerals, both in shales and in the uppermost part of the sandstones.Two unique sections, one Cu-rich and one Cu-lean (partly oxidized), comprising three shale beds interbedded with dolomites have been compared. Generally ∑REE contents are similar in these two sections. Also similar are changes in contents of REE between beds in both sections, which decrease significantly upwards (from 157–171 ppm to 54–60 ppm). The REE patterns of the lowermost beds (directly overlying sandstones) are ramp-like, with LREE enrichments. The upper beds have concave REE patterns. Comparison between sections shows generally stronger negative Eu and positive Gd anomalies in the highly-mineralized section.There is a highly significant positive relationship between Cu and ∑ REE contents in Cu-rich shales and slightly less significant negative relationship for their concentration in oxidized and transitional shales. There is a moderate significant positive correlation between P₂O₅ and ∑ REE contents in Cu-rich shales.The observed differences in REE contents cannot be provenance dependent but have been caused by diagenetic processes, possibly related to mineralization and oxidation processes. Europium anomalies, generally reflecting different Eh conditions in the deposit, can be eliminated by the prolonged oxidation. Strong enrichment of the RF zones in REE may result from their desorption from large volumes of oxidizing, including mineralizing, solutions which probably emerged from the underlying molasse lithologies into the Rote Fäule areas. Higher contents of REE in the lowermost shales suggest upward movement of solutions from the underlying sandstones also far away from the RF areas.     

Electromagnetic emissions during dilating fracture of a rock

A lot of experiments on electromagnetic emissions (EMEs) have been reported under axial compressive fracture, shear fracture, indentation fracture and stick–slip (friction) in lab and blasting in situ, but there are rare reports on the in-lab experimental work on EMEs during dilating fracture of a rock which is helpful in studying and understanding EMEs related to slow earthquakes and the earthquakes due to volcanic activities and water level changes of reservoirs. Therefore, in the present paper in order to check whether there are detectable EMEs during dilating fracture of a rock in lab, dilating fracture experiments were conducted. The dry cuboid specimens of initially intact granodiorite and limestone were tested inside magnetic field free space (MFFS) at room temperature. We arranged evenly 20 EME antennas whose resonance frequencies range from 2.5 kHz to 540 kHz close to rock specimens. Our experimental results strongly indicate that detectable EMEs could generate during dilating fracture of a rock. They were recorded only associated with some but not all phases of fracture. Their waveforms often took on the trend that a peak arrived at first and then attenuated sharply and followed by a series of low-amplitude oscillations. The electromagnetic (EM) signals after eliminating the effects of EME antennae via deconvolution had the maximum peak-to-peak amplitudes of about 80.0 mV and 40.5 mV for granodiorite and limestone, respectively. Their main spectral components often concentrated in the band of several kHz to ∼60 kHz and of several kHz to ∼280 kHz. The emission of electrons and charged particles from fracture surfaces and/or micro-fracture electrification could be possible mechanisms for our experimental results.     

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

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

The Jabali Zn–Pb–Ag deposit is located about 110 km 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 8.7 million tons 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 (~ 17 Ma), 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.