Deep crustal carbonates as CO2 fluid sources: Evidence from metasomatic reaction zones

Metasomatic reaction zones which developed at marble-pelitic schist contacts in a granulite facies terrane in West Greenland contain a consistent sequence of five mineralogical zones. Outward from the carbonates the zones are characterized by the assemblages grossular-diopside-meionite (I), meionite-anorthite-diopside (II), anorthite-diopside-edenitic hornblende (III), anorthite-enstatite (IV), plagioclase-almandine-sillimanite (V). Sphene is superceded by ilmenite between zones (II) and (III); quartz is present in all zones except zone I. Scapolite, plagioclase, clinopyroxene and mica exhibit a small degree of compositional variation which correlates with distance from the carbonate. These small compositional variations are superimposed on a strong CaO chemical potential gradient. Compositional features, zone distributions and CaO activity calculations demonstrate that the zones developed in response to CaO diffusion along a chemical potential gradient of 2 kcal/m. The CaO source appears to be carbonate rocks which release calcium as decarbonation reactions proceed. The maximum volume of CO₂ released in this process, and that released during discontinuous reactions in the marbles, will contribute a total volume of CO₂ approximately equivalent to the volume of carbonate in the rock. Calculations demonstrate that a terrane consisting of as little as 8% carbonate will release sufficient CO₂ to result in complete dehydration of an amphibolite terrane, at deep crustal conditions. Dehydration through CO₂ release will be accomplished either through rapid burial, which would prevent both equilibration of mineral assemblages and CO₂ release at intermediate crustal levels, or through diffusion-driven metasomatic reactions which would lead to CO₂ release primarily at the high temperatures of deep crustal environments. The latter process would be the dominant CO₂ source at deep crustal levels if carbonate rocks occur predominately as relatively thin layers.     

The problem of CO2 recycling in subduction zones

In connection with the imbalance between the carbon dioxide absorbed in the carbonate minerals in subduction zones and that emitted during island arc volcanism, the problem of redistribution the rest of the CO₂ from the plate to the mantle arises. Experimental modeling of the interaction between model analogs of the oceanic crust and the mantle wedge was performed for two systems: glaucophane schist-olivine and glaucophane schist-silicate marble-olivine under high pressure and varying temperature conditions that correspond to the oceanic crust-mantle transition zone in the subduction zone beneath the Cascade Mountains. The experiments carried out showed that there is a possibility that intensive CO₂ degassing occurs from the plate in the forearc area, which is controlled by carbonate dissolution in an aqueous fluid. As a result of this process, carbonates can redeposit in the form of magnesite in the overlying mantle rocks according to the vertical temperature gradient. It is assumed that part of the carbon dioxide bonded in mantle rocks can be transported by viscous flow from the forearc area to the deep mantle horizons within the field of the thermodynamic stability of magnesite. In addition, the experiments we carried out showed that between marble and olivine in the ultrahigh pressure a metasomatic column consisting of four zones develops: Fe-Mg-Ca carbonate|dolomite|diopside|magnesite.     

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.     

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.     

俯冲带碳酸盐化对深部碳循环的启示:以中国西南天山碳酸盐化云母片岩为例

俯冲带可将地球表层碳输送至深部地幔,同时也记录着俯冲板片来源碳质流体的迁移沉淀机制,对地球深部碳循环具有重大影响。近年来,俯冲带脱碳机制的研究表明流体溶解脱碳作用是冷的大洋俯冲板片释放COH流体的重要方式,而上覆板块(尤其地幔楔)则被认为是缓冲这些COH流体的重要场所,甚至是俯冲带CO_2的唯一"归宿"。事实上,俯冲带岩石本身的固碳能力却受到了忽视,而对俯冲带岩石捕获和固存CO_2(carbon capture and storage,CCS)能力的评估对全球碳通量的估算尤为重要。本文以中国西南天山高压-超高压变质带中碳酸盐化云母片岩为例,探讨俯冲带岩石的碳酸盐化对深部碳循环的影响。西南天山长阿吾子一带的碳酸盐化云母片岩记录了俯冲板片起源的碳质流体对俯冲带云母片岩的交代作用,地球化学特征表明蛇纹岩释放的富水流体溶解俯冲洋壳中的碳酸盐可能是产生COH流体的重要机制。基于碳质流体对多硅白云母(Si(a.p.f.u.)=3.58～3.73)的交代及相对高压的碳酸盐矿物(主要为白云石和菱镁矿)与金红石的共生,结合区域上碳酸盐化云母片岩与高压碳酸盐化蛇纹岩(HP-ophidolomite)的伴生,我们认为云母片岩的碳酸盐化作用可能发生在俯冲板片峰期稍后的高压折返阶段。俯冲带云母片岩的固碳作用表明除了上覆板块,俯冲带岩石本身对于碳质流体也具有很好的吸收能力。初步估算表明俯冲带云母片岩的碳酸盐化每年可固存至少2.46～6.68Mt/yr,约占俯冲板片每年进碳量的4%～17%。     

Alteration Patterns Related to Hydrothermal Gold Mineralizaition in Meta-andesites at Dungash Area, Eastern Desert, Egypt

Abstract: The hydrothermal alteration patterns associating with the gold prospect hosted by metavolcanics in the Dungash area, Eastern Desert of Egypt, were investigated in order to assign their relationship to mineralization. The metavolcanics of andesitic composition are generated by regional metamorphism of greenschist facies superimposed by hydrothermal activity. Epidote and chlorite are metamorphic minerals, whereas sericite, carbonates, and chlorite are hydrothermal alteration minerals. The auriferous quartz vein is of NEE‐SWW trend and cuts mainly the andesitic metavolcanics, but sometimes extends to the neighbouring metapyroclastics and metasediments. Quartz‐sericite, sericite, carbonate‐sericite, and chlorite‐sericite constitute four distinctive alteration zones which extend outwards from the mineralized quartz vein. The quartz‐sericite and sericite zones are characterized by high contents of SiO₂, K₂O, Rb, and As, the carbonate‐sericite zone is by high contents of CaO, Au, Cu, Cr, Ni, and Y, and the chlorite‐sericite zone is by high contents of MgO, Na₂O, Zn, Ba, and Co. Gold and sulphide minerals are relatively more abundant in the carbonate‐sericite zone followed by the sericite one. The geochemistry of the alteration system was investigated using volume‐composition and mass balance calculations. The volume factors obtained for the different alteration zones, mentioned above (being 1.64, 1.19, 1.17, and 1.07, respectively), indicate that replacement had taken place with a volume gain. The mass balance calculations revealed addition of SiO₂, K₂O, As, Cu, Rb, Ba, Ni, and Y to the system as a whole and subtraction of Fe2O3 from the system. Initial high aK+ and aH+ for the invading fluids is suggested. As the fluids migrated into wallrocks, they became more concentrated in Mg, Ca, and Na with increasing activities of CO₂ and S. The calculated loss‐gain data are in agreement with the microscopic observations. Breakdown of ferromagnesian minerals and feldspars in the quartz‐sericite, sericite, and chlorite‐sericite zones accompanied by loss in Mg, Fe, Ca, and Na under acidic conditions and low CO2/H2O ratio may obstruct the formation of carbonates and sulphides, and the precipitation of gold in these zones. The role of metamorphic fluids in the area is expected to be restricted to the liberation of Au and some associated elements from their hosts.     

Open to closed system transition traced through the TDIC isotopic signature at the aquifer recharge stage, implications for groundwater C dating

¹⁴C dating models are limited when considering recent groundwater for which the carbon isotopic signature of the total dissolved inorganic carbon (TDIC) is mainly acquired in the unsaturated zone. Reducing the uncertainties of dating thus implies a better identification of the processes controlling the carbon isotopic composition of the TDIC during groundwater recharge. Geochemical interactions between gas, water and carbonates in the unsaturated zone were investigated for two aquifers (the carbonate-free Fontainebleau sands and carbonate-bearing Astian sands, France) in order to identify the respective roles of CO₂ and carbonates on the carbon isotopic signatures of the TDIC; this analysis is usually approached using open or closed system terms. Under fully open system conditions, the seasonality of the ¹³C values in the soil CO₂ can lead to important uncertainties regarding the so-called “initial ¹⁴C activity” used in ¹⁴C correction models. In a carbonate-bearing unsaturated zone such as in the Astian aquifer, we show that an approach based on fully open or closed system conditions is not appropriate. Although the chemical saturation between water and calcite occurs rapidly within the first metre of the unsaturated zone, the carbon isotopic contents (δ¹³C) of the CO₂ and the TDIC evolve downward, impacted by the dissolution-precipitation of the carbonates. In this study, we propose a numerical approach to describe this evolution. The δ¹³C and the A¹⁴C (radiocarbon activity) of the TDIC at the base of the carbonate-bearing unsaturated zone depends on (i) the δ¹³C and the A¹⁴C of the TDIC in the soil determined by the soil CO_2, (ii) the water’s residence time in the unsaturated zone and (iii) the carbonate precipitation-dissolution fluxes. In this type of situation, the carbonate δ¹³C-A¹⁴C evolutions indicate the presence of secondary calcite and permit the calculation of its accretion flux, equal to . More generally, for other sites under temperate climate and with similar properties to the Astian sands site, this approach allows for a reliable determination of the carbon isotopic composition at the base of the unsaturated zone as the indispensable “input function” data of the carbon cycle into the aquifer.     

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.     

Origin of authigenic carbonates in sediment from the deep Bering Sea

Forty beds of authigenic carbonate were identified from the deep Bering Sea in cores taken on Leg 19 of the Deep Sea Drilling Project. Carbonate minerals were mainly high-magnesium calcite and protodolomite, less commonly siderite, rhodo-chrosite, low-magnesium calcite, and manganosiderite. Authigenic carbonates cement and replace diatom ooze, ash and bentonite beds, and, less commonly, clastic beds. Replacement zones are as much as 60 cm thick. Eighty-five per cent of carbonate beds occurred below 400 m sub-bottom depth and 70% in sediment older than 4 m.y. δ¹³C values averaged -17.20^0/00 PDB and δ¹⁸O ranged from 18.59 to 34–11^0/00SMOW. The carbon was derived from oxidation of organic matter under anaerobic conditions during bacterial reduction of sulphate, or from CO₂ produced in concert with CH₄ during degradation of organic matter. The cations (Ca, Mg, Fe, Mn) were derived from alteration of ash beds. In Bering Sea deposits, ash beds altered to smectite within about 3–5 m.y. Carbonate precipitated simultaneously at different stratigraphic levels within the 627–1057 m sections at temperatures of 7–85°C. No apparent calcite precursor of biogenic origin was found for these authigenic carbonates.     

Alteration processes of cement induced by CO2-saturated water and its effect on physical properties: Experimental and geochemical modeling study

The objective of this study is to understand cement alteration processes with the evolution of porosity and hardness under geologic CO₂ storage conditions. For this study, the cylindrical cement cores (class G) were reacted with CO₂–saturated water in a vessel (40 °C and 8 MPa) for 10 and 100 days. After the experiment, the CO₂ concentration and Vickers hardness were measured in the hydrated cement core to estimate the carbonation depth and to identify the change in hardness, respectively. Diffusive-reactive transport modeling was also performed to trace the alteration processes and subsequent porosity changes. The results show that cement alteration mainly results from carbonation. With alteration processes, four different reaction zones are developed: degradation zone, carbonation zone, portlandite depletion zone, and unreacted zone. In the degradation zone, the re-dissolution of calcite formed in the carbonation zone leads to the increase of porosity. In contrast, the carbonation zone is characterized by calcite formation resulting mainly from the dissolution of portlandite. The carbonation zone acts as a barrier to CO₂ intrusion by consuming dissolved CO₂. Especially in this zone, although the porosity decreases, the Vickers hardness increases. Our results show that cement alteration processes can affect the physical and hydrological properties of the hydrated cement under CO₂-saturated conditions. Further long-term observation is required to confirm our results under in-situ fluid chemistry of a CO₂ storage reservoir. Nonetheless, this study would be helpful to understand alteration processes of wellbore cements under CO₂ storage conditions.     

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.     

BIF-hosted iron mineral system: A review

The BIF-hosted iron ore system represents the world's largest and highest grade iron ore districts and deposits. BIF, the precursor to low- and high-grade BIF hosted iron ore, consists of Archean and Paleoproterozoic Algoma-type BIF (e.g., Serra Norte iron ore district in the Carajás Mineral Province), Proterozoic Lake Superior-type BIF (e.g., deposits in the Hamersley Province and craton), and Neoproterozoic Rapitan-type BIF (e.g., the Urucum iron ore district).The BIF-hosted iron ore system is structurally controlled, mostly via km-scale normal and strike-slips fault systems, which allow large volumes of ascending and descending hydrothermal fluids to circulate during Archean or Proterozoic deformation or early extensional events. Structures are also (passively) accessed via downward flowing supergene fluids during Cenozoic times.At the depositional site the transformation of BIF to low- and high-grade iron ore is controlled by: (1) structural permeability, (2) hypogene alteration caused by ascending deep fluids (largely magmatic or basinal brines), and descending ancient meteoric water, and (3) supergene enrichment via weathering processes. Hematite- and magnetite-based iron ores include a combination of microplaty hematite–martite, microplaty hematite with little or no goethite, martite–goethite, granoblastic hematite, specular hematite and magnetite, magnetite–martite, magnetite-specular hematite and magnetite–amphibole, respectively. Goethite ores with variable amounts of hematite and magnetite are mainly encountered in the weathering zone.In most large deposits, three major hypogene and one supergene ore stages are observed: (1) silica leaching and formation of magnetite and locally carbonate, (2) oxidation of magnetite to hematite (martitisation), further dissolution of quartz and formation of carbonate, (3) further martitisation, replacement of Fe silicates by hematite, new microplaty hematite and specular hematite formation and dissolution of carbonates, and (4) replacement of magnetite and any remaining carbonate by goethite and magnetite and formation of fibrous quartz and clay minerals.Hypogene alteration of BIF and surrounding country rocks is characterised by: (1) changes in the oxide mineralogy and textures, (2) development of distinct vertical and lateral distal, intermediate and proximal alteration zones defined by distinct oxide–silicate–carbonate assemblages, and (3) mass negative reactions such as de-silicification and de-carbonatisation, which significantly increase the porosity of high-grade iron ore, or lead to volume reduction by textural collapse or layer-compaction. Supergene alteration, up to depths of 200 m, is characterised by leaching of hypogene silica and carbonates, and dissolution precipitation of the iron oxyhydroxides.Carbonates in ore stages 2 and 3 are sourced from external fluids with respect to BIF. In the case of basin-related deposits, carbon is interpreted to be derived from deposits underlying carbonate sequences, whereas in the case of greenstone belt deposits carbonate is interpreted to be of magmatic origin. There is only limited mass balance analyses conducted, but those provide evidence for variable mobilization of Fe and depletion of SiO₂. In the high-grade ore zone a volume reduction of up to 25% is observed.Mass balance calculations for proximal alteration zones in mafic wall rocks relative to least altered examples at Beebyn display enrichment in LOI, F, MgO, Ni, Fe₂O_3total, C, Zn, Cr and P₂O₅ and depletions of CaO, S, K₂O, Rb, Ba, Sr and Na₂O. The Y/Ho and Sm/Yb ratios of mineralised BIF at Windarling and Koolyanobbing reflect distinct carbonate generations derived from substantial fluid–rock reactions between hydrothermal fluids and igneous country rocks, and a chemical carbonate-inheritance preserved in supergene goethite.Hypogene and supergene fluids are paramount for the formation of high-grade BIF-hosted iron ore because of the enormous amount of: (1) warm (100–200 °C) silica-undersaturated alkaline fluids necessary to dissolve quartz in BIF, (2) oxidized fluids that cause the oxidation of magnetite to hematite, (3) weakly acid (with moderate CO₂ content) to alkaline fluids that are necessary to form widespread metasomatic carbonate, (4) carbonate-undersaturated fluids that dissolve the diagenetic and metasomatic carbonates, and (5) oxidized fluids to form hematite species in the hypogene- and supergene-enriched zone and hydroxides in the supergene zone.Four discrete end-member models for Archean and Proterozoic hypogene and supergene-only BIF hosted iron ore are proposed: (1) granite–greenstone belt hosted, strike-slip fault zone controlled Carajás-type model, sourced by early magmatic (± metamorphic) fluids and ancient “warm” meteoric water; (2) sedimentary basin, normal fault zone controlled Hamersley-type model, sourced by early basinal (± evaporitic) brines and ancient “warm” meteoric water. A variation of the latter is the metamorphosed basin model, where BIF (ore) is significantly metamorphosed and deformed during distinct orogenic events (e.g., deposits in the Quadrilátero Ferrífero and Simandou Range). It is during the orogenic event that the upgrade of BIF to medium- and high-grade hypogene iron took place; (3) sedimentary basin hosted, early graben structure controlled Urucum-type model, where glaciomarine BIF and subsequent diagenesis to very low-grade metamorphism is responsible for variable gangue leaching and hematite mineralisation. All of these hypogene iron ore models do not preclude a stage of supergene modification, including iron hydroxide mineralisation, phosphorous, and additional gangue leaching during substantial weathering in ancient or Recent times; and (4) supergene enriched BIF Capanema-type model, which comprises goethitic iron ore deposits with no evidence for deep hypogene roots. A variation of this model is ancient supergene iron ores of the Sishen-type, where blocks of BIF slumped into underlying karstic carbonate units and subsequently experienced Fe upgrade during deep lateritic weathering.     

Melting phase relation of nominally anhydrous,carbonated pelitic-eclogite at 2.5–3.0 GPa and deep cycling of sedimentary carbon

We have experimentally investigated melting phase relation of a nominally anhydrous, carbonated pelitic eclogite (HPLC1) at 2.5 and 3.0 GPa at 900–1,350°C in order to constrain the cycling of sedimentary carbon in subduction zones. The starting composition HPLC1 (with 5 wt% bulk CO₂) is a model composition, on a water-free basis, and is aimed to represent a mixture of 10 wt% pelagic carbonate unit and 90 wt% hemipelagic mud unit that enter the Central American trench. Sub-solidus assemblage comprises clinopyroxene + garnet + K-feldspar + quartz/coesite + rutile + calcio-ankerite/ankerite_ss. Solidus temperature is at 900–950°C at 2.5 GPa and at 900–1,000°C at 3.0 GPa, and the near-solidus melt is K-rich granitic. Crystalline carbonates persist only 50–100°C above the solidus and at temperatures above carbonate breakdown, carbon exists in the form of dissolved CO₂ in silica-rich melts and as a vapor phase. The rhyodacitic to dacitic partial melt evolves from a K-rich composition at near-solidus condition to K-poor, and Na- and Ca-rich composition with increasing temperature. The low breakdown temperatures of crystalline carbonate in our study compared to those of recent studies on carbonated basaltic eclogite and peridotite owes to Fe-enrichment of carbonates in pelitic lithologies. However, the conditions of carbonate release in our study still remain higher than the modern depth-temperature trajectories of slab-mantle interface at sub-arc depths, suggesting that the release of sedimentary carbonates is unlikely in modern subduction zones. One possible scenario of carbonate release in modern subduction zones is the detachment and advection of sedimentary piles to hotter mantle wedge and consequent dissolution of carbonate in rhyodacitic partial melt. In the Paleo-NeoProterozoic Earth, on the other hand, the hotter slab-surface temperatures at subduction zones likely caused efficient liberation of carbon from subducting sedimentary carbonates. Deeply subducted carbonated sediments, similar to HPLC1, upon encountering a hotter mantle geotherm in the oceanic province can release carbon-bearing melts with high K₂O, K₂O/TiO₂, and high silica, and can contribute to EM2-type ocean island basalts. Generation of EM2-type mantle end-member may also occur through metasomatism of mantle wedge by carbonated metapelite plume-derived partial melts.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

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.     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80 GPa and 1,600–3,200 K, corresponding to depths within the Earth of approximately 800–2,200 km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO₃ (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO₃ (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO₂ + perovskite via reactions with SiO₂. Magnesite is not the only host phase for subducted carbon—solid CO₂ also carries carbon in the lower mantle. Furthermore, CO₂ itself breaks down to diamond and oxygen under geotherm conditions over 70 GPa, which might imply a possible mechanism for diamond formation in the lower mantle.     

Geochemistry of carbonated mineral waters from the Fadeevskoe deposit of the Primorye region

The geochemical study of bed rocks, underground and surface waters, and associated gases in the Fadeevskoe deposit of carbonated waters (Sikhote Alin, Primorye region) revealed that the chemical composition of these waters is formed in the zone of active water exchange in the limited area of the discharge zone, where hydro carbonate calcic waters with mineralization of up to 1 g/1 are formed in largely potassic-sodic rocks. Calculations of the saturation indices show that the mineral waters are characterized by the early stage of Ca saturation, being undersaturated with carbonates and aluminosilicates. The main factors that influence the water mineralization are the excess carbon dioxide in water and the circulation time. The oxygen and carbon isotope ratios indicate the atmospheric genesis of the aqueous component (δ²H = —117; δ¹⁸O = —15.4%o) and the carbon isotope content in the CO₂ implies the mantle nature of the carbon dioxide (δ¹³C = -9.9%o).     

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.     

Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

The continent is the second largest carbon sink on Earth’s surface. With the diversification of vascular land plants in the late Paleozoic, terrestrial organic carbon burial is represented by massive coal formation, while the development of soil profiles would account for both organic and inorganic carbon burial. As compared with soil organic carbon, inorganic carbon burial, collectively known as the soil carbonate, would have a greater impact on the long-term carbon cycle. Soil carbonate would have multiple carbon sources, including dissolution of host calcareous rocks, dissolved inorganic carbon from freshwater, and oxidation of organic matter, but the host calcareous rock dissolution would not cause atmospheric CO₂ drawdown. Thus, to evaluate the potential effect of soil carbonate formation on the atmospheric pCO₂ level, different carbon sources of soil carbonate should be quantitatively differentiated. In this study, we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop, consisting of limestone of the early Paleogene Guanzhuang Group in North China. Based on the C and Mg isotope data, we developed a numerical model to quantify the carbon source of calcite veins. The modeling results indicate that 4–37 wt% of carbon in these calcite veins was derived from atmospheric CO₂. The low contribution from atmospheric CO₂ might be attributed to the host limestone that might have diluted the atmospheric CO₂ sink. Nevertheless, taking this value into consideration, it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO₂ within 2000 years, i.e., soil carbonate alone would sequester all atmospheric CO₂ within 1 million years. Finally, our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.