Pre-existing Calcite Research Articles

“Roll-Front” Mass Transfer of Carbonate Cations in Carlin-Type Gold Deposits: Insights from UV-Fluorescent Calcite Veins

Abstract Hydrothermal fluids dissolve and precipitate vast quantities of carbonate during the formation of Carlin-type gold deposits. This mass transfer results in extensive volumes of decarbonatized rock and hydrothermal calcite with distinct δ18O and δ13C signatures, occurring as both veins and wall-rock pseudomorphs. However, the processes which cause the fluids to switch between carbonate-dissolving and carbonate-precipitating are not well understood. Here, we present a model for the formation of ore-stage calcite through the pseudomorphic replacement of pre-existing calcite based on a detailed study of UV-fluorescent (UVF) calcite veins from the Nadaleen trend Carlin-type gold deposits in Yukon. The UV fluorescence in the veins is a visual indicator of their high-Mn, low-Fe chemistry, which we use to develop our model. The proximity of UVF calcite veins to ore-stage alteration and the realgar within the veins indicate that they formed during Au mineralization. Vein orientation and crosscutting relationships with faults and dikes suggest they formed by replacing pre-existing calcite veins that developed during folding. Cathodoluminescence responses, showing the selective replacement of pre-ore calcite by Mn-rich calcite, support this hypothesis. We propose that differences in Mn, Sr, and Mg content between pre-existing calcite and UVF calcite drive this replacement reaction as the fluids approach calcite saturation. UVF calcite veins have fluid-dominated δ13C and δ18O compositions, suggesting that the fluids dissolved fluid-buffered hydrothermal carbonate upstream along the flow path. In our model, unreactive and high-permeability decarbonatized rock allows upstream fluids to reach reactive calcite at the edge of the dissolution zone, where they replace the calcite with ore-stage calcite pseudomorphs. Over several iterations of this process, the fluids repeatedly precipitate and dissolve ore-stage calcite, moving it downstream as a roll front, which concentrates Mn at the edge of the dissolution zone. We suggest that this mass transfer also occurs at the deposit scale to form zoned carbonate alteration along the flow path. Additionally, we present carbonate clumped isotope thermometry results that indicate UVF calcite veins formed at temperatures of ~140°C, although higher temperatures of up to 300°C are possible if the veins exhumed slowly after their formation. Calculated fluid δ13C and δ18O values at these temperatures suggest a meteoric fluid source, although the isotopic data are not inconsistent with a magmatic source if fluid temperatures were ≥200°C because less isotopic fractionation occurs at higher temperatures.

Carbonation reactivity enhancement of γ-C2S through biomineralization

Most of the calcium silicates exhibit high carbonation reactivity, and thus start to be utilized in the production of low carbon concrete due to the growing pressure of carbon mitigation in the cement industry. In this study, powdered γ-C2S, with limited hydraulicity, is preconditioned in a suspension consisting of urease-producing bacterium and urea. This biomineralization process induces the precipitation on the γ-C2S surface of calcite crystals with spherical shape, the size of which is dependent on the urea suspension concentration. The effect of the pre-existing calcite crystals on the carbonation behavior, mechanical and micro-morphology of γ-C2S compacts is investigated. Results indicate the compressive strength are significantly improved with the pre-existing calcite crystals, and the increasing percentage is 43.66 % at 30 min carbonation and 0.25 mol/L urea concentration. The strength enhancement is found to be associated with the pre-existing calcite crystals acting as nucleation seeds which accelerate the carbonation at the early stage. In addition, the pre-existing calcite seeds induce the preferential formation of calcite in the crystalline carbonation products of γ-C2S, which may be beneficial to the enhancement of the carbonated products.

Reaction path modelling of in-situ mineralisation of CO2 at the CarbFix site at Hellisheidi, SW-Iceland

Results from injection of 175 tonnes of CO2 into the basaltic subsurface rocks at the CarbFix site in SW-Iceland in 2012 show almost complete mineralisation of the injected carbon in less than two years (Matter et al., 2016; Snæbjörnsdóttir et al., 2017). Reaction path modelling was performed to illuminate the rate and extent of CO2-water-rock reactions during and after the injection. The modelling calculations were constrained by the compositions of fluids sampled prior to, during, and after the injection, as reported by Alfredsson et al. (2013) and Snæbjörnsdóttir et al. (2017). The pH of the injected fluid, prior to CO2 dissolution was ∼9.5, whereas the pH of the background waters in the first monitoring well prior to the injections was ∼9.4. The pH of the sampled fluids used in the modelling ranged from ∼3.7 at the injection well to as high as 8.2 in the first monitoring well. Modelling results suggest that CO2-rich water-basalt interaction is dominated by crystalline basalt dissolution along a faster, high permeability flow path, but by basaltic glass dissolution along a slower, pervasive flow path through which the bulk of the injected fluid flows. Dissolution of pre-existing calcite at the onset of the injection does not have a net effect on the carbonation, but does contribute to a rapid early pH rise during the injection, and influences which carbonate minerals precipitate. At low pH, Mg, and Fe are preferentially released from crystalline basalts due to the higher dissolution rates of olivine, and to lesser extent pyroxene, compared to plagioclase and glass (Gudbrandsson et al., 2011). This favours the formation of siderite and Fe-Mg carbonates over calcite during early mineralisation. The model suggests the formation of the following carbonate mineral sequences: siderite at pH < 5, Mg-Fe-carbonates and Ca-Mg-Fe-carbonates at pH > 5, and calcite at higher pH. Other minerals forming with the carbonates are Al- and Fe-hydroxides and chalcedony, and zeolites and smectites at elevated pH. The most efficient carbonate formation is when the pH is high enough for formation of carbonates, but not so high that zeolites and smectites start to form, which compete with carbonates over both cations and pore space. The results of reaction path modelling at the CarbFix site in SW-Iceland indicate that this “sweet spot” for mineralisation of CO2 is at pH from ∼5.2 to 6.5 in basalts at low temperature (20–50 °C).

Sabkha and Burrow-Mediated Dolomitization in the Mississippian Debolt Formation, Northwestern Alberta, Canada

Dolomitized burrows in the Mississippian (Visean) Debolt Formation of northwestern Alberta, Canada form the primary reservoir intervals in the Dunvegan gas field. Sedimentological and ichnological analyses suggest a carbonate ramp setting that includes subenvironments such as sabkhas, hypersaline lagoons, restricted subtidal lagoons, intertidal mud flats, and peloidal shoals. Dolomitization occurs primarily within oxidized muds and highly bioturbated sediments, with the primary mode being sabkha-associated precipitation. In this context, dolomitization within the burrows also appears to be mediated by sulfate-reducing bacteria. δ18O values for dolomite within burrows (mean 2.4‰) are enriched by 1.3‰ relative to calcite values (mean 1.1‰) within the burrows. This degree of fractionation is similar for dolomite and calcite that have precipitated from the same solution. It is therefore suggested that the protodolomite precipitated in equilibrium with calcite rather than by replacement of pre-existing calcite. Isotopic values of δ13C measured for dolomite associated with burrows (mean 3.4‰) and matrix (mean 3.5‰) is slightly enriched relative to measured calcite values (mean 3.2‰ for matrix; mean 3.1‰ for burrows). These isotopic trends are common for modern dolomite that has precipitated in equilibrium with seawater where concomitant sulfate reduction and organic carbon-oxidation is inferred to occur near the surface.

Mineralogy and origin of rhizoliths on the margins of saline, alkaline Lake Bogoria, Kenya Rift Valley

A wide range of rhizoliths occurs around the margins of Lake Bogoria, Kenya. These include root casts, moulds, tubules, rhizocretions, and permineralised root systems. These rhizoliths are variably composed of opaline silica, calcite, zeolites (mainly analcime), fluorite, and possibly fluorapatite, either alone or in combinations. Some rhizoliths are infilled moulds with detrital silicate grains. Most rhizoliths are in situ, showing both vertical and horizontal orientations. Reworked rhizoliths have been concentrated locally to form dense rhizolites. Hot-spring fluids, concentrated by evapotranspiration and capillary evaporation, have provided most of the silica for the permineralisation of the plant tissues. Precipitation involved the growth of silica nanospheres and microspheres that coalesced into homogeneous masses. Calcite rhizoliths formed following evaporative concentration, evapotranspiration, and (or) CO 2 degassing of Ca-bearing runoff water that infiltrated the sediment, or by mixing of runoff with saline, alkaline groundwater. Fluorite precipitated in areas where mixing of hot-spring and meteoric waters occurred, or possibly where hot-spring fluids came into contact with pre-existing calcite. Zeolitic rhizoliths formed during a prolonged period of aridity, when capillary rise and evaporative pumping brought saline, alkaline waters into contact with detrital silicate minerals around roots.

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO2 components—atmospheric CO2 and CO2 from in situ oxidation of organic matter. The δ13C values measured for the Fe(CO3)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most 13C-rich Fe(CO3)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO2 components. δ13C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco2 value of about 1 × PAL, but the scatter in the measured δ13C values of organic matter permits a calculated maximum Pco2 of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO3)OH in MCGoeth and SAP correspond to soil CO2 concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO2 concentrations are similar to modern soils in warm, wet environments.The average δ13C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ13C value for all profiles of −5.4‰. Thus, the value of Δ13C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco2 and organic matter δ13C values were the same for both paleosol types. Furthermore, the atmospheric Pco2 calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco2 (permitted by one standard deviation of the organic matter δ13C value) of ∼5 × PAL.If, however, measured average δ13C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of 13C-depleted, labile organic compounds, calculated Permian atmospheric Pco2 using these 13C-enriched organic values would underestimate the actual atmospheric Pco2 using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO2 concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO2.The Fe(CO3)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in 13C relative to Fe(CO3)OH in goethites from soils in which there are mixtures of two isotopic CO2 components. Field-relationships and the δ13C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO2 components at the time of goethite crystallization. The three components were probably atmospheric CO2, CO2 from in situ oxidation of organic matter and CO2 from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO2 components, as recorded by Fe(CO3)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco2.

Evolution of the structural fault permeability in argillaceous rocks in a polyphased tectonic context

Deep argillaceous formations have petrophysical and hydrodynamic properties favourable to long-term radioactive waste confinement (very low intrinsic permeability, high sorption capacity,…). However, these properties may be modified by the development of discontinuities in the host-rock. The tectonic activity is responsible on the one hand for creating the fractures and on the other hand for reactivating them. Today, the calcite crystallisations in faults give evidence of paleofluid flows during the tectonic deformation. The microstructural study shows that faults were alternately and temporarily impermeable, permeable or “semi-permeable” during the tectonic activity. These “hydraulic states” were controlled by the nature and the architecture of the microstructures and by variations in the petrophysical properties of the rock in the core zone (CZ) and damage zone (DZ) of the faults. Within DZ, the structural fault permeability evolution is associated with (1) microcracking and (2) a probable ductile behaviour of the shales. Within CZ, the structural fault permeability is associated with the development of cavities generated by (1) dilation, (2) shearing and openings in extensional stepover and (3) microcracking in pre-existing calcite fillings. During the tectonic evolution, the development of a new structural porosity both in CZ and DZ gave up the faults permeable. The crystallisation sealing of the total structural porosity gave up the faults impermeable. But, when only the CZ was sealed, the fault was “semi-permeable”. Finally, we show that (1) the fluid transfers occurred principally from the DZ to the CZ, (2) the DZ constituted a “storage zone” in fluids for the CZ, (3) the DZ then remained longer permeable than the CZ and became permeable with weaker stress intensity and (4) the sealed discontinuities constituted zones of weakness (fracture reactivation with or without shearing) in the argillaceous material.

Conservation of ornamental stone by Myxococcus xanthus-induced carbonate biomineralization.

Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO(3) polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone.

Discrimination of Multiple Episodes of Meteoric Diagenesis in a Kimmeridgian Reefal Complex, North Iberian Range, Spain

ABSTRACT Stratigraphic relations, detailed petrography, and fine-scale geochemical and isotopic analysis of diagenetic phases formed within Kimmeridgian-age reefal carbonates of the Torrecilla en Cameros Formation of Northern Iberian Ranges in Spain indicate a complex history of alteration in marine, meteoric, burial, and uplift-related settings. The reefal succession is separated from the overlying Tithonian-Berriasian fluvial and lacustrine continental deposits by a single unconformity, which is marked by brecciation and karstification. Nevertheless, a record of three distinct stages of alteration associated with this unconformity is preserved in the succession of calcite cements present within the reefal carbonates. Recognition of temporally distinct episodes of meteoric diagenesis associated with a single unconformity is atypical in carbonate rocks, but this study illustrates how such complex systems can be deconvoluted. The first episode of subaerial exposure and meteoric alteration resulted in neomorphism of marine allochems and precipitation of a first generation of nonferroan clear calcite (NFC) cement. Following local faulting and brecciation, a second NFC precipitated throughout the reefal unit. Although similar in petrographic character, this phase of cementation is distinct in its isotopic composition, reflecting changes in the regional climate of the Iberian Peninsula during the early Tithonian. Another phase of meteoric alteration of the reefal unit is recorded by renewed corrosion, including dissolution of preexisting calcite cements and precipitation of prismatic calcite, prior to the deposition of Tithonian-Berriasian lacustrine and continental sediments. These continental units, in turn, record yet another episode of alteration by meteoric waters as NFC cements formed within intragranular and dissolution porosity in the lacustrine limestones. Notably, these cements are also distinct on the basis of their petrographic and geochemical character. Following subsidence and burial during Aptian to late Cretaceous times, migration of regionally derived fluids (perhaps in response to the onset of tectonic deformation to the north) led to cementation of saddle ankerite and ferroan calcite throughout the sedimentary sequence. Alteration of these burial-related diagenetic phases has subsequently taken place in response to the regional uplift during the Tertiary. This final episode of meteoric alteration is indicated by replacement of the ferroan calcite and ankerite by a cloudy nonferroan calcite.

Phase equilibrium and stable isotope constraints on the formation of metasomatic garnet-vesuvianite veins (SW Adamello, N Italy)

Metasomatic garnet-vesuvianite veins occur within the contact metamorphic marble sequence of the Lower Triassic Prezzo formation in a narrow, 1–5 m wide zone along an intrusive marble-granodiorite contact at the southwestern border of the Tertiary Adamello batholith. The metasomatic mineral assemblage is comprised of garnet, vesuvianite, clinopyroxene, wollastonite, and pyrrhotite, which were precipitated from the vein-forming fluid in a preexisting calcite matrix at conditions of about 2800 bars and 630° C. The veins are enriched in silicon, aluminum, iron, magnesium, titanium and depleted in calcium with respect to the unaltered contact metamorphic marble. Graphite, which is present in the unaltered Prezzo Marble is absent in the veins. Irregularly shaped mineralogically distinct zones with different degrees of silicification can be distinguished within the veins. The isotopic compositions of calcite (cc) in the unaltered marble are about δ18O (SMOW; Standard mean Ocean Water)=21.0‰ and δ13C(PDB; Peedee belemnite)=0.0‰. They are reset to significantly lower values within the veins, where δ18Occ is 15.0 to 16.0‰ and δ13Ccc is −4.5 to −3.5‰. The isotopic front coincides with an abrupt change in the microscopic texture of matrix carbonate which occurs at the sharp boundary between graphite-bearing and graphite-free material. Within the veins the oxygen isotope fractionation between calcite and garnet (gar) varies systematically with distance from highly silicified zones. The variations in Δ18Occ-gar are as large as 2‰, on a millimeter scale, indicating garnet-calcite isotopic disequilibrium. Vein formation was due to the infiltration of a water rich fluid of magmatic provenance into the carbonate country rock along fractures. Removal of graphite from the wall rock by dissolution through the metasomatic fluid induced recrystallization of matrix calcite. Permeability was enhanced during calcite recrystallization facilitating material transport into the wall rock and metasomatic alteration. Vein garnet was precipitated in isotopic equilibrium with the metasomatic fluid. The isotopic composition of preexisting calcite was initially out of equilibrium with the vein-forming fluid and it was shifted towards equilibrium by surface-reaction controlled calcite-fluid isotopic exchange during calcite recrystallization. Due to the short lifetime of the metasomatic system, calcite-fluid isotopic equilibrium was generally not attained. Within the veins, oxygen and carbon transport was fast relative to mineral-fluid exchange of their isotopes and the geometry of the isotopic pattern is largely controlled by the kinetics of mineral-fluid exchange.

Authigenic Dolomite in a Saline Soil in Alberta, Canada

AbstractThe formation of dolomite is poorly understood and highly controversial, since well‐ordered dolomite has never been synthesized under earth surface conditions and natural occurrences of modern dolomite have been reported only rarely from restricted sedimentary environments. It is generally accepted that dolomite does not form in soils. This study investigates the characteristics and origin of dolomite in a sulfatic saline soil in east‐central Alberta, Canada, in which dolomite makes up more than half of the &lt;2‐µm fraction. X‐ray diffraction analysis shows that the dolomite is stoichiometric and ordered, with only slight deviations in unit cell parameters relative to ideal dolomite. The clay‐sized dolomite is enriched in 18O and depleted in 13C relative to detrital dolomite and dolomite present in larger size fractions, and has a radiocarbon age ranging from 1270 to 5270 yr before present, clearly indicating an authigenic origin. The very small dolomite particle size and differences in isotope content from coexisting calcite suggests that the dolomite formed by direct precipitation in the soil rather than by dolomitization of a preexisting calcite.

The genesis and isotopic composition of carbonates associated with some Permian Australian coals

Siderite and calcite are the two forms of carbonate commonly associated with Permian Australian coals. The former occurs as disseminated spherulites and is a product of the early post-depositional environment. Isotopic measurements show that the CO 2 fixed as siderite did not result from the direct oxidation of photosynthetically derived materials, but rather from the anaerobic fermentation of these. The higher concentrations of calcite are generally found towards the roofs of coal seams and are characterized by isotopic enrichments to δ 13C values of +25‰ PDB. Isotopic exchange between CO 2 and CH 4 within the coal seam is postulated as the mechanism which leads to the formation of isotopically heavy CO 2. At sites along the seam margins where the CO 2 escapes, interaction with circulating metal ions or preexisting calcite results in the deposition of “heavy” calcite. With increasing alteration of coal by thermal metamorphism, the 13C content of calcites and finally siderites decreases so that it more nearly approaches that of the associated coal.

Possible Natural Mechanism for Protodolomite Formation

IT is commonly believed that solutions with a Mg2+/Ca2+ molar ratio (abbreviated to Mg/Ca in this communication) greater than that of seawater (⋍5) are a prerequisite for the formation of early diagenetic dolomite from pre-existing calcite at low temperatures in the various sedimentary environments1–3. But as a result of our laboratory experiments it seems that large Mg/Ca ratios and calcite are not necessary for the formation of a protodolomite.

Oxygen Isotope Fractionation between Coexisting Calcite and Dolomite in the Freshwater Upper Carboniferous Freeport Formation

HYDROTHERMAL experiments of Epstein, Graf and Degens1 have suggested that dolomite forms from pre-existing calcite by a replacement mechanism in which the 18O/16O ratio of the original calcite remains unchanged. In an investigation of natural sedimentary dolomite-calcite rocks, Degens and Epstein2 observed no fractionation of the oxygen isotopes between coexisting calcite and dolomite in relatively young deposits and concluded that all dolomite is secondary, that is a replacement product of pre-existing calcite. Older carbonate rocks examined by those authors, however, did contain dolomite which was enriched in oxygen-18 with respect to the associated calcite. This phenomenon was explained by possible isotopic equilibration of the calcite with intrastratal fluids (which are generally enriched in oxygen-16). Dolomite is believed to be more resistant to equilibration. Hence, according to Degens and Epstein, such calcite rocks are partly replaced by diagenetic dolomite without alteration of the isotopic composition of the carbonate. With time, oxygen isotope exchange between formation waters and the calcite, but to a negligible extent between the waters and the dolomite, results in a higher 18O/16O ratio in the dolomite. Thus the difference in δ18Odol and δ18Oct observed in ancient carbonate rocks does not represent original isotopic equilibrium between these two minerals.