Carbonate Minerals in the Warrawoona Group, Pilbara Craton: Implications for Continental Crust, Life, and Global Carbon Cycle in the Early Archean

Abstract: The occurrences of the Early Archean carbonate minerals are compiled and their precipitation processes are investigated for the Warrawoona Group, Pilbara Craton. Sedimentary carbonate rocks such as limestone and dolostone are very rare, and only a small amount of sedimentary carbonate minerals are sometimes contained in the hydrothermal bedded chert, implying that a sink of CO₂ was minor in the Early Archean sediments. Moreover, it is very likely that the activity of cyanobacteria forming stromatolites was considerably low in the Early Archean. Microfossils and carbonaceous matter in the hydrothermal cherts are probably derived from a non-photosynthetic microorganisms related to the seafloor hydrothermal activity. Their preservation in sediments may play a very minor role in carbon sink of the Earth's surface.
On the other hand, carbonatized volcanic rocks subjected to seafloor hydrothermal alteration occur ubiquitously in the Early Archean greenstone belts such as the Warrawoona Group, suggesting that the hydrothermally altered oceanic crust had large amounts of CO₂ as carbonate minerals. Global carbon cycle in the Early Archean is considered to have been controlled by the intense seafloor hydrothermal alteration. Large amounts of CO₂ were sunk into the oceanic crust by the alteration. The carbonatized oceanic crust was partly accreted to the continents and/or island–arcs, and partly subducted into the mantle without decomposition. Significant amounts of carbonate minerals in the carbonatized oceanic crust were very likely to store in the accretionary prisms and mantle, consequently giving rise to a decrease of atmospheric and oceanic CO₂.     

Highly alkaline,high-temperature hydrothermal fluids in the early Archean ocean

Based on the petrology of hydrothermally altered Archean basaltic greenstones, thermodynamic calculations of phase equilibria were conducted to estimate the composition of a high-temperature (∼350 °C) hydrothermal fluid in an Archean subseafloor basalt-hosted hydrothermal system. The results indicate that the hydrothermal fluid was highly alkaline attributed to the presence of calcite in the alteration minerals under a high-CO₂ condition, and predict a generation of SiO₂-rich, Fe-poor hydrothermal fluids in the Archean subseafloor hydrothermal system. The chemically reactive mixing zones between alkaline hydrothermal fluids and slightly acidic-neutral seawater are characterized by inverse pH and chemical polarity to modern hydrothermal systems, leading to extensive precipitation of silica and iron oxyhydroxides on/under the seafloor. Such processes can be responsible for the abiotic formation of voluminous chert and subseafloor silica dike, the mechanism of silicification, and the pH-controlled generation of banded iron formation that has been arising mainly from the redox chemistry in the Archean ocean. Such high-temperature alkaline fluids could have had a significant role not only in the early ocean geochemical processes but also in the early evolution of life.     

Insights into C and H storage in the altered oceanic crust: Results from ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with δD values from −64‰ to −25‰. All samples are enriched in water relative to fresh basalts. The δD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO₂, extracted by step-heating technique, ranges between 564 and 2823 ppm with δ¹³C values from −14.9‰ to −26.6‰. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with δ¹³C = −4.5‰ and (2) an organic compound with δ¹³C = −26.6‰. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO₂ yield after H₃PO₄ attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO₂ degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO₂ is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when “fresh” oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO₂, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ∼ −4.7‰, similar to the δ¹³C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 × 10¹² molC/yr.     

Structural control and hydrothermal alteration at the BIF-hosted Raposos lode-gold deposit,Quadrilátero Ferrífero,Brazil

In the Raposos orogenic gold deposit, hosted by banded iron-formation (BIF) of the Archean Rio das Velhas greenstone belt, the hanging wall rocks to BIF are hydrothermally-altered ultramafic schists, whereas metamafic rocks and their hydrothermal schistose products represent the footwall. Planar and linear structures at the Raposos deposit define three ductile to brittle deformational events (D₁, D₂ and D₃). A fourth group of structures involve spaced cleavages that are considered to be a brittle phase of D₃. The orebodies constitute sulfide-bearing D₁-related shear zones of BIF in association with quartz veins, and result from the sulfidation of magnetite and/or siderite. Pyrrhotite is the main sulfide mineral, followed by lesser arsenopyrite and pyrite. At level 28, the hydrothermal alteration of the mafic and ultramafic wall rocks enveloping BIF define a gross zonal pattern surrounding the ore zones. Metabasalt comprises albite, epidote, actinolite and lesser Mg/Fe–chlorite, calcite and quartz. The incipient stage includes the chlorite and chlorite-muscovite alteration zone. The least-altered ultramafic schist contains Cr-bearing Mg-chlorite, actinolite and talc, with subordinate calcite. The incipient alteration stage is subdivided into the talc–chlorite and chlorite–carbonate zone. For both mafic and ultramafic wall rocks, the carbonate–albite and carbonate–muscovite zones represent the advanced alteration stage.Rare earth and trace element analyses of metabasalt and its alteration products suggest a tholeiitic protolith for this wall rock. In the case of the ultramafic schists, the precursor may have been peridotitic komatiite. The Eu anomaly of the Raposos BIF suggests that it was formed proximal to an exhalative hydrothermal source on the ocean floor. The ore fluid composition is inferred by hydrothermal alteration reactions, indicating it to having been H₂O-rich containing CO₂ + Na⁺ and S. Since the distal alteration halos are dominated by hydrated silicate phases (mainly chlorite), with minor carbonates, fixation of H₂O is indicated. The CO₂ is consumed to form carbonates in the intermediate alteration stage, in halos around the chlorite-dominated zones. These characteristics suggest variations in the H₂O to CO₂-ratio of the sulfur-bearing, aqueous-carbonic ore fluid, which interacted at varying fluid to rock ratios with progression of the hydrothermal alteration.     

Mineralogical and geochemical characteristics of hydrothermal alteration of basalt in the Kuroko mine area, Japan: implications for the evolution of a Back Arc Basin hydrothermal system

Basalt in the Furutobe District of the Kuroko mine area in Japan is characterized by abundant chlorite and epidote. Fluid inclusion studies indicate that chlorite is formed at lower temperatures (230–250°C) than epidote (250–280°C). The seawater/basalt mass ratio for the early chlorite-rich alteration was high (max. 40), but that for the later alteration was low (0.1–1.8). The CaO, Na₂O and SiO₂ of the bulk rock correlate negatively with MgO, while FeO and Σ Fe correlate positively with MgO. These changes in the characteristic features of hydrothermal alteration from early to late are generally similar to those for a mid-ocean ridge geothermal system accompanying basalt alteration.The MgO/FeO ratios of chlorite and actinolite and the Fe₂O₃ concentration of epidote from the basalt are greater than those of mid-ocean ridge basalt probably owing to the differences in the Fe₂O₃/FeO and MgO/FeO ratios of the parent rocks. The lower CaO concentration and the higher Na₂O concentration of the bulk rock compared with altered mid-ocean ridge basalt can be interpreted in terms of the difference in original bulk rock compositions.The Furutobe basalt, as well as other submarine back arc basalts, contains more vesicles filled with hydrothermal minerals (epidote, calcite, quartz, chlorite, pyrite) than do the mid-ocean ridge basalts. The abundance of vesicles plays an important role in controlling the secondary mineralogy and geochemistry of hydrothermally altered submarine back arc basin basalts.     

Isotope systematics of secondary minerals from the Prospect Intrusion,New South Wales

The differentiated Mesozoic alkali dolerite Prospect Intrusion contains a wide range of secondary minerals, including carbonates (primarily calcite), laumontite, prehnite and heulandite, whose stability relationships imply a formation temperature of <200°C. The δ¹⁸O data for carbonates define a higher temperature (160 – 195°C) suite, and a lower temperature (51 – 73°C) suite. The δ¹³C, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr isotope systematics for these carbonates suggest derivation of the higher temperature group from magmatic fluids, whereas the other group had a major meteoric component that probably originated from porewater in the country rock. Source fluids for prehnite were meteoric rather than magmatic in origin based on their δD and δ¹⁸O ratios. Early in the intrusion's emplacement, CO₂-rich hydrothermal fluids formed a carbonate rind sealing the upper part of the hydrothermal system and produced the higher temperature carbonates (calcite) and laumontite. Later, cooler fluids with a meteoric component infiltrated vesicles and fractures, depositing the lower temperature carbonates (calcite, aragonite), heulandite and prehnite.     

Multistage Carbonatization and Mineral Geochemistry of a Skarn—type Copper Deposit at Tongshan ,Guichi

The Tongshan copper deposit at Guichi can be considered as a skarn-type copper deposit. Multi-stage carbonatization was well developed in the skarn zone and copper-bearing orebodies. Mineralogy, mineral chemistry and stable isotope data allow it to be divided into five stages: (1) carbonatization of single calcite crystals in the skarn stage; (2) calcite carbonatization in the oxide stage; (3) carbonatization in the early sulfide stage; (4) carbonatization in the late sulfide stage; and (5) carbonatization in the post-sulfide stage. Carbonatization in the early sulfide stage is, among other things, closely related to copper mineralization and is one of the alteration indicators of copper mineralization of this type. C. O, Rb and Sr isotopic studies indicate that the calcites of skarn and oxide stages were formed from hydrothermal solutions predominated by magmatic water, and those of sulfide stage were formed from hydrothermal solutions mainly involving heated meteoric water. The former was formed in the environment wherefO ₂ (fO ₂ < 10⁻³³ and 10⁻³³< fO₂>10⁻³⁶)(pH = 7–8) is high as compared with the latter (10⁻³⁵< fO₂< 10⁻³⁸; pH = 5–7).     

P_{CO_2 } -T-Evolution and origin of zoning in melilite during the regressive stage of contact metamorphism in carbonate-bearing rocks

The article describes the thermal metamorphism of siliceous carbonate rocks near the dolerite intrusive body in Eastern Siberia. The mineral associations at the immediate contact with dolerite are the following: wollastonite+rankinite, rankinite+spurrite (+melilite?), spurrite+melilite+merwinite+calcite and merwinite+monticellite+melilite+calcite. The melilite in these associations is usually unzoned; its composition being essentially gehlenitic. During the regressive stage of contact metamorphism new akermanite-rich melilite and calcite were formed by replacement of merwinite and earlier gehlenitic melilite through participation of CO₂. The newly forming melilite grains have sharp compositional zoning. The origin of zoning was connected with the fall of temperature and decrease of the mole fraction of CO₂ in the fluid equilibrated with the minerals.     

Structural control and hydrothermal alteration at the BIF-hosted Raposos lode-gold deposit, Quadrilátero Ferrífero, Brazil

In the Raposos orogenic gold deposit, hosted by banded iron-formation (BIF) of the Archean Rio das Velhas greenstone belt, the hanging wall rocks to BIF are hydrothermally-altered ultramafic schists, whereas metamafic rocks and their hydrothermal schistose products represent the footwall. Planar and linear structures at the Raposos deposit define three ductile to brittle deformational events (D₁, D₂ and D₃). A fourth group of structures involve spaced cleavages that are considered to be a brittle phase of D₃. The orebodies constitute sulfide-bearing D₁-related shear zones of BIF in association with quartz veins, and result from the sulfidation of magnetite and/or siderite. Pyrrhotite is the main sulfide mineral, followed by lesser arsenopyrite and pyrite. At level 28, the hydrothermal alteration of the mafic and ultramafic wall rocks enveloping BIF define a gross zonal pattern surrounding the ore zones. Metabasalt comprises albite, epidote, actinolite and lesser Mg/Fe–chlorite, calcite and quartz. The incipient stage includes the chlorite and chlorite-muscovite alteration zone. The least-altered ultramafic schist contains Cr-bearing Mg-chlorite, actinolite and talc, with subordinate calcite. The incipient alteration stage is subdivided into the talc–chlorite and chlorite–carbonate zone. For both mafic and ultramafic wall rocks, the carbonate–albite and carbonate–muscovite zones represent the advanced alteration stage.Rare earth and trace element analyses of metabasalt and its alteration products suggest a tholeiitic protolith for this wall rock. In the case of the ultramafic schists, the precursor may have been peridotitic komatiite. The Eu anomaly of the Raposos BIF suggests that it was formed proximal to an exhalative hydrothermal source on the ocean floor. The ore fluid composition is inferred by hydrothermal alteration reactions, indicating it to having been H₂O-rich containing CO₂ + Na⁺ and S. Since the distal alteration halos are dominated by hydrated silicate phases (mainly chlorite), with minor carbonates, fixation of H₂O is indicated. The CO₂ is consumed to form carbonates in the intermediate alteration stage, in halos around the chlorite-dominated zones. These characteristics suggest variations in the H₂O to CO₂-ratio of the sulfur-bearing, aqueous-carbonic ore fluid, which interacted at varying fluid to rock ratios with progression of the hydrothermal alteration.     

Hydrothermal alteration in metasedimentary rock-hosted orogenic gold deposits,Reefton goldfield,South Island,New Zealand

Orogenic or mesothermal quartz lodes in lower Palaeozoic Greenland Group metasedimentary rocks of the Reefton area have produced 67 tonnes (t) of gold prior to 1951, and recent exploration has identified new gold resources in several deposits, including the largest past producers, Blackwater and Globe-Progress. The metasedimentary rocks consist of alternating sandstone and mudstone beds that were metamorphosed to lower greenschist facies prior to being hydrothermally altered adjacent to the quartz lodes. The sandstones are feldspathic litharenites averaging Q₆₅-F₁₀-R₂₅, with detrital grains of quartz, rock fragments, muscovite, and plagioclase and biotite that were altered to albite and chlorite, respectively, during metamorphism. Accessory minerals are graphite, apatite, zircon, tourmaline and titanite. Hydrothermal alteration of the sandstones has developed a mineral assemblage of K-mica, carbonate (dolomite, ankerite, ferroan magnesite and magnesian siderite), chlorite, pyrite and arsenopyrite. The abundance of hydrothermal chlorite is greater at Blackwater than at the other prospects studied. Hydrothermal alteration associated with the quartz lodes is marked by bleaching, magnesian siderite spots, disseminated arsenopyrite and pyrite and thin carbonate, quartz and sulphide veins. These trends are accompanied by increasing concentrations of S, As and Sb and decreasing Na, and a decrease of Fe and Mg in K-mica. The alkali alteration indices 3K/Al (representing K-mica) and Na/Al (representing albite) generally show antipathetic trends, with 3K/Al increasing near the lodes and Na/Al decreasing. These trends reflect the replacement of albite by K-mica. Carbonate alteration indices CO₂/(Ca + Mg +Fe) and CO₂/[Ca + Mg + Fe -0.5(S + As)] quantify the abundance of hydrothermal carbonates, but they show variable correlation with the lodes. They increase the width of the alteration halo in the hanging wall of the lodes at the Globe-Progress and General Gordon prospects, but the peak values are as far as 150 m from the lodes. By contrast, peak values of the carbonate alteration indices are within 10 and 2 m of the lodes, respectively, at the Merrijigs and Blackwater deposits. Data show that for deposits with wide hydrothermal alteration halos, such as at the Globe-Progress and General Gordon prospects, the use of a suite of geochemical indicators can assist exploration by indicating trends in hydrothermal alteration that provide vectors to mineralisation. They also increase the size of the exploration target. By contrast, the alteration halo of the Blackwater deposit is restricted to within less than 5 m of the quartz lode and, therefore, the geochemical indicators are of more limited assistance to exploration.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.     

Initial behavior of granite in response to injection of CO2-saturated fluid

To understand the initial reactions of granite in a CO₂-saturated hydrothermal system, experiments were conducted using a batch-type autoclave over a temperature range of 100–350 °C at up to 250 bar and numerical computations of phase equilibria based on the experimental results were carried out. The experiments showed that the dissolution of granite and the deposition of secondary minerals were encouraged by the addition of CO₂. Solution chemistry and examination of the granite’s surface texture suggested that its initial dissolution is characterized by the release of Na and Ca (from the dissolution of plagioclase) and that initial precipitation occurs by deposition of some secondary minerals on to plagioclase and/or biotite in the CO₂-saturated system. However, the effect of CO₂ was small at 350 °C owing to the low activity of H₂CO₃. According to EDX analysis and numerical phase equilibrium calculations, the secondary minerals formed might be kaolinite, muscovite, smectite and calcite. That is, the granite as a whole might have the potential to take-up dissolved CO₂. The results suggest that the alteration of granite under CO₂-saturated hydrothermal conditions has the potential to capture CO₂ when it is injected at moderate temperatures (150–250 °C) into granite-hosted rock masses.     

New constraints on carbonation associated with brecciation in hyperextended margins (example of Iberia and Newfoundland margins)

The sequestration of CO₂ occurs naturally in (ultra)‐mafic rocks by carbonation processes and is commonly noted in areas of the seafloor where mantle lithologies are exhumed. As well as carbonation, mantle exhumation is also responsible for rock brecciation. The relationship between carbonation and brecciation is not well constrained. A temporal evolution from syn‐ to post‐tectonic carbonation and brecciation is proposed in line with progressive mantle exhumation. Using a petrological study of brecciated material from IODP drill cores of the Iberia–Newfoundland conjugated margins, we relate crack–seal veins to tectonic brecciation, authigenic calcite with scalenohedral structure to hydraulic brecciation and reworked clasts within cement to (tectono)‐sedimentary processes. Oxygen isotope compositions reveal late‐staged < 50°C carbonate generation in the proximal part of the ocean–continent transition, which have followed an earlier phase of sub‐seafloor carbonate generation. The results are crucial to understand CO₂ exchange within the reworked sub‐seafloor in passive margins and oceanic systems.     

Reaction mechanisms,physical conditions,and mass transfer during hydrothermal alteration of mica and feldspar in granitic rocks from south-central Maine,USA

Samples of granitic rock from south-central Maine contain primary igneous minerals altered by hydrothermal fluids. The reaction mechanisms (by which the over-all mineralogical change during the alteration was accomplished) involve several different mineral-fluid reactions at different reaction sites in the rock. The reactions involve both molecular and charged species in solution. The different reaction sites correspond to alteration of different primary igneous minerals. Biotite is partially converted to chlorite+sphene; microcline to muscovite; plagioclase to various combinations of muscovite, epidote, and calcite. The different reaction sites are linked by exchange of ions: some reaction sites produce ions consumed at other sites and vice versa. Physical conditions during the hydrothermal event are estimated from mineralogical and thermochemical data: P = 3,500 (±300) bars; T =425 ° (± 25 °)C. The fluid was characterized by X _{CO 2} = 0–0.13; ln([K⁺]/[H⁺ ]) = 10.0; ln([Ca²⁺]/[H⁺]²)=9.1; ln([Na⁺]/[H⁺]) = 10.5; Fe/(Fe+Mg) = 0.95. Amounts of secondary minerals in altered rock, when compared to the inferred mineral reactions that formed them, indicate that small but significant amounts (0.01–0.3mol/ 1,000cm³ altered rock) of CO₂, H₂O, H⁺, and K⁺ were added to the granites by fluids during the alteration, as well as lesser amounts (< 0.01–0.03 mol/1,000cm³ altered rock) of Mg²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Na⁺, and Ti⁴⁺. The sole element leached from the granitic rocks during alteration was Ca in amounts 0.1–0.3 mol/1,000 cm³ rock. By estimating the composition of the hydrothermal fluids before and after reaction with the granites and by measuring the amount of material added to or subtracted from the granites during the alteration, the amount and volume of hydrothermal fluid involved can be calculated. Two independent calculations require minimum volumes in the range 100–1,000 cm³ fluid/1,000cm³ altered rock to participate in the hydrothermal event.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

The Sensitivity of the Phanerozoic Inorganic Carbon System to the Onset of Pelagic Sedimentation

The onset of pelagic sedimentation attending the radiation of pelagic calcifiers during the Mesozoic was an important divide in Earth history, shifting the locus of significant carbonate sedimentation from the shallow shelf environments of the Paleozoic to the deep sea. This shift would have impacted the CO₂ cycle, given that decarbonation of subducted pelagic carbonate is an important return flux of CO₂ to the atmosphere. Coupled with the fact that the mean residence time of continental platform and basin sedimentary carbonate exceeds that of the oceanic crust, it thus becomes unclear whether carbon cycling would have operated on a substantially different footing prior to the pelagic transition. Here, we examine this uncertainty with sensitivity analyses of the timing of this transition using a coupled model of the Phanerozoic atmosphere, ocean, and shallow lithosphere. For purposes of comparison, we establish an age of 250 Ma (i.e., after the Permo-Triassic extinctions) as the earliest opportunity for deposition of extensive biogenic pelagic carbonate on the deep seafloor, an age that predates known occurrences of pelagic calcifiers (and intact seafloor). Although an approximate boundary, we do show that attempts to shift this datum either significantly earlier or later in time produce model results that are inconsistent with observed trends in the mass–age distribution of the rock record and with accepted trends in seawater composition as constrained by proxy data. Significantly, we also conclude that regardless of the timing of the onset of biogenic pelagic carbonate sedimentation, a carbon sink involving seawater-derived dissolved inorganic carbon played a critical role in carbon cycling, particularly in the Paleozoic. This CaCO₃ sink may have been wholly abiogenic, involving calcium derived either directly from seawater (thus manifest as a direct seafloor deposit), or alternatively from basalt–seawater reactions (represented by precipitation of CaCO₃ in veins and fissures within the basalt). Despite the uncertainty in the source and magnitude of this abiogenic CaCO₃ flux, it is likely a basic and permanent feature of global carbon cycling. Subduction of this CaCO₃ would have acted as a basic return circuit for atmospheric CO₂ even in the absence of biogenically derived pelagic carbonate sedimentation. Lastly, model calculations of the ratio of dissolved calcium to carbonate ion (Ca²⁺/CO₃ ^2?) show this quantity underwent significant secular evolution over the Phanerozoic. As there is increasing recognition of this ratio’s role in CaCO₃ growth and dissolution reactions, this evolution, together with progressive increases in nutrient availability and saturation state, may have created a tipping point ultimately conducive to the appearance of pelagic calcifiers in the Mesozoic.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

The main causes of the occurrence of carbonate cementation zones in the strata of oil- and gas-bearing basins

The results of studies of sedimentary strata carbonatization in oil- and gas-bearing basins are generalized. The sources of CO₂, H₂CO₃, and organic acids, which regulate the carbonate balance in stratum waters at the stages of diagenesis and catagenesis, as well as under the influence of superposed processes, including those with the participation of microorganisms, are considered. The scale of secondary carbonatization of deposits in the zone of water-oil contacts and in the interval of hydrothermal action is estimated.