A planet in transition: The onset of plate tectonics on Earth between 3 and 2 Ga?

Many geological and geochemical changes are recorded on Earth between 3 and 2 Ga.Among the more important of these are the following:(1)increasing proportion of basalts with"arc-like"mantle sources;(2)an increasing abundance of basalts derived from enriched(EM)and depleted(DM)mantle sources;(3)onset of a Great Thermal Divergence in the mantle;(4)a decrease in degree of melting of the mantle;(5)beginning of large lateral plate motions;(6)appearance of eclogite inclusions in diamonds;(7)appearance and rapid increase in frequency of collisional orogens;(8)rapid increase in the production rate of continental crust as recorded by zircon age peaks;(9)appearance of ophiolites in the geologic record,and(10)appearance of global LIP(large igneous province)events some of which correlate with global zircon age peaks.All of these changes may be tied directly or indirectly to cooling of Earth's mantle and corresponding changes in convective style and the strength of the lithosphere,and they may record the gradual onset and propagation of plate tectonics around the planet.To further understand the changes that occurred between 3 and 2 Ga,it is necessary to compare rocks,rock associations,tectonics and geochemistry during and between zircon age peaks.Geochemistry of peak and inter-peak basalts and TTGs needs to be evaluated in terms of geodynamic models that predict the existence of an episodic thermal regime between stagnant-lid and plate tectonic regimes in early planetary evolution.     

Hydrosulfide/sulfide complexes of zinc to 250 °C and the thermodynamic properties of sphalerite

The solubility of synthetic ZnS_(cr) was measured at 25–250 °C and P = 150 bars as a function of pH in aqueous sulfide solutions (~ 0.015–0.15 m of total reduced sulfur). The solubility determinations were performed using a Ti flow-through hydrothermal reactor. The solubility of ZnS_(cr) was found to increase slowly with temperature over the whole pH range from 2 to ~ 10. The values of the Zn–S–HS complex stability constant, β, were determined for Zn(HS)₂⁰_(aq), Zn(HS)₃^?, Zn(HS)₄^2?, and ZnS(HS)^?. Based on the experimental values the Ryzhenko–Bryzgalin electrostatic model parameters for these stability constants were calculated, and the ZnS_(cr) solubility and the speciation of Zn in sulfide-containing hydrothermal solutions were evaluated. The most pronounced solubility increase, about 3 log units at m(S_total) = 0.1 for the temperatures from 25 to 250 °C, was found in acidic solutions (pH ~ 3 to 4) in the Zn(HS)₂⁰_(aq) predominance field. In weakly alkaline solutions, where Zn(HS)₃^? and Zn(HS)₄^2? are the dominant Zn–S–HS complexes, the ZnS_(cr) solubility increases by 1 log unit at the same conditions. It was found that ZnS(HS)^? and especially Zn(HS)₄^2? become less important in high temperature solutions. At 25 °C and m(S_total) = 0.1, these species dominate Zn speciation at pH > 7. At 100 °C and m(S_total) = 0.1, the maximum fraction of Zn(HS)₄^2? is only 20% of the total Zn concentration (i.e. at pH_t ~ 7.5), whereas at 350 °C and 3 <pH_t <10, the fraction of Zn(HS)₄^2? and ZnS(HS)^? is less than 0.05% and 2.5% respectively, of the total Zn concentration and Zn(HS)₂⁰ and Zn(HS)₃^? predominate. The measured equilibrium formation constants were combined with the literature data on the stability of Zn–Cl complexes in order to evaluate the concentration and speciation of Zn in chloride solutions. It was found that at acidic pH, and in more saline fluids having total chloride > 0.05 m, Zn–Cl complexes are responsible for hydrothermal Zn transport with no significant contribution of Zn–S–HS complexes. The hydrosulfide/sulfide complexes will play a more important role in lower salinity (< 0.05 m chloride) hydrothermal solutions which are characteristic of many epithermal ore depositing environments. The value of Δ_fG° (β-ZnS_(cr)) = ? 198.6 ± 0.2 kJ/mol at 25 °C was determined via solubility measurements of natural low-iron Santander (Spain) sphalerite.     

Genetic link between saline and carbonatitic mantle fluids: The system NaCl-CaCO3-MgCO3 ± H2O ± Fe0 at 6 GPa

Melt inclusions in kimberlitic minerals and diamonds indicate that chlorides are important constituents of mantle carbonatite melts. Besides, alkaline chlorides are important constituents of saline high-density fluids (HDFs) found in diamonds from kimberlites and placers around the world. Continuous compositional variations suggest that saline and carbonatitic HDFs could be genetically linked. However, the essence of this link remains unclear owing to the lack of data on phase relations in the chloride-carbonate systems under pressure. Here we studied subsolidus and melting phase relations in the system NaCl–CaCO₃–MgCO₃ at 6 GPa and 1000–1600 °C using a Kawai-type multianvil press. We found that at 1000 °C, subsolidus assemblage consists of halite, magnesite, and aragonite. At higher temperatures, the stabilization of dolomite splits the subsolidus area into two partial ternary fields: halite + magnesite + dolomite and halite + dolomite + aragonite. The minimum on the liquidus surface corresponds to the halite-dolomite-aragonite ternary eutectic, situated at 1100 °C. The eutectic melt has Ca# 89 and contains 30 wt.% NaCl (26 mol% 2NaCl). The system has two ternary peritectics: halite + dolomite = magnesite + liquid located near the ternary eutectic and magnesite + dolomite = Mg-dolomite + liquid situated between 1300 and 1400 °C. Although under dry conditions incipient melting yields carbonate-dominated melt, the addition of water facilitates the fusion of NaCl and expands the liquid field to NaCl-rich compositions with up to 70 wt.% NaCl. The obtained results favor the idea that hydrous saline melts/fluids (brines) found as inclusions in diamonds could be a lower temperature derivative of mantle carbonatite melts and disagree with the hypothesis on chloride melt generation owing to the chloride-carbonate liquid immiscibility since no such immiscibility was established. We also studied the interaction of the NaCl–CaCO₃–MgCO₃ system with iron metal and found that carbonate reduction produces C-bearing species (Fe⁰, Fe-C melt, Fe₃C, Fe₇C₃, C⁰) and wüstite containing Na₂O, CaO, and MgO. Besides, a carbonate chloride compound, Ca₂Cl₂CO₃, was established among the reaction products. The interaction between NaCl-bearing carbonate melt shifts its composition toward Mg-poor and NaCl-rich. Given the above, an alternative hypothesis can be proposed, according to which the interaction of alkaline chloride-bearing carbonate melts formed in the subduction zones with the reduced mantle should be accompanied by diamond crystallization and shift the composition of the melt from carbonatitic to alkali-rich saline.     

Relationship among titanium,rare earth elements,U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.     

Kyanite far from equilibrium dissolution rate at 0–22 °C and pH of 3.5–7.5

Acta Geochimica - Kyanite is an important and slow-dissolving mineral. Earlier work has measured its dissolution rate at high temperature and acidic pH, but experimental measurements at low...     

Paragonite stability at 700°C in the presence of H<Subscript>2</Subscript>O–NaCl fluids: constraints on H<Subscript>2</Subscript>O activity and implications for high pressure metamorphism

We carried out reversed piston-cylinder experiments on the equilibrium paragonite = jadeite + kyanite + H₂O at 700°C, 1.5–2.5 GPa, in the presence of H₂O-NaCl fluids. Synthetic paragonite and jadeite and natural kyanite were used as starting materials. The experiments were performed on four different nominal starting compositions: X(H₂O)=1.0, 0.90, 0.75 and 0.62. Reaction direction and extent were determined from the weight change in H₂O in the capsule, as well as by optical and scanning electron microscopy (SEM). At X(H₂O)=1.0, the equilibrium lies between 2.25 and 2.30 GPa, in good agreement with the 2.30–2.45 GPa reversal of Holland (Contrib Miner Petrol 68:293–301, 1979). Lowering X(H₂O) decreases the pressure of paragonite breakdown to 2.10–2.20 GPa at X(H₂O)=0.90 and 1.85–1.90 GPa at X(H₂O)=0.75. The experiments at X(H₂O) = 0.62 yielded the assemblage albite + corundum at 1.60 GPa, and jadeite + kyanite at 1.70 GPa. This constrains the position of the isothermal paragonite–jadeite–kyanite–albite–corundum–H₂O invariant point in the system Na₂O–Al₂O₃–SiO₂–H₂O to be at 1.6–1.7 GPa and X(H₂O)~0.65±0.05. The data indicate that H₂O activity, a(H₂O), is 0.75–0.86, 0.55–0.58, and <0.42 at X(H₂O)=0.90, 0.75, and 0.62, respectively. These values approach X(H₂O)², and agree well with the a(H₂O) model of Aranovich and Newton (Contrib Miner Petrol 125:200–212, 1996). Our results demonstrate that the presence or absence of paragonite can be used to place limits on a(H₂O) in high-pressure metamorphic environments. For example, nearly pure jadeite and kyanite from a metapelite from the Sesia Lanzo Zone formed during the Eo-Alpine metamorphic event at 1.7–2.0 GPa, 550–650°C. The absence of paragonite requires a fluid with low a(H₂O) of 0.3–0.6, which could be due to the presence of saline brines.     

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.     

Combined U–Pb and Lu–Hf isotope data on turbidites of the Paleozoic basement of NW Argentina and petrology of associated igneous rocks: Implications for the tectonic evolution of western Gondwana between 560 and 460 Ma

New combined U–Pb and Lu–Hf isotope analyses on zircon from three turbidite deposits, and petrologic data for associated igneous rocks were used to study the evolution of the Paleozoic basement of Eastern Cordillera, NW Argentina. Maximum and minimum ages for turbidite deposits, considered to be part of the Puncoviscana Fm., are reported. In the Tastil area, turbidites were deposited in a fore-arc setting after 560 Ma and intruded at 534 Ma by the Tastil batholith. In the El Niño Muerto Hill area turbidites with maximum depositional age of 496 ± 11 Ma were intruded by high-K dacites at 483 ± 3 Ma. In the Río Blanco Valley, the turbiditic/hemipelagitic sediments, with maximum depositional age of 463 ± 11 Ma were contemporaneous with E-MORB/OIB volcanism. The U–Pb and Lu–Hf data permitted to distinguish two major periods of magmatic activity during Late Mesoproterozoic–Early Neoproterozoic (0.95 to 1.2 Ga) and Late Neoproterozoic–Early Paleozoic (0.75 to 0.46 Ga) times, the former dominated by the input of juvenile crust and the latter by arc magmatism and recycling of Meso- to Paleoproterozoic crust. On the basis of new data we suggest that western margin of Gondwana was controlled by subduction processes and accretion of small terrains during Neoproterozoic–Early Paleozoic times.     

Coupled alkali-feldspar dissolution and secondary mineral precipitation in batch systems: 1. New experiments at 200 °C and 300 bars

Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

Neoendemic ground beetles and private tree haplotypes: two independent proxies attest a moderate last glacial maximum summer temperature depression of 3–4 °C for the southern Tibetan Plateau

Previous findings regarding the Last Glacial Maximum LGM summer temperature depression (maxΔT in July) on the Tibetan Plateau varied over a large range (between 0 and 9 °C). Geologic proxies usually provided higher values than palynological data. Because of this wide temperature range, it was hitherto impossible to reconstruct the glacial environment of the Tibetan Plateau. Here, we present for the first time data indicating that local neoendemics of modern species groups are promising proxies for assessing the LGM temperature depression in Tibet. We used biogeographical and phylogenetic data from small, wingless edaphous ground beetles of the genus Trechus, and from private juniper tree haplotypes. The derived values of the maxΔT in July ranged between 3 and 4 °C. Our data support previous findings that were based on palynological data. At the same time, our data are spatially more specific as they are not bound to specific archives. Our study shows that the use of modern endemics enables a detailed mapping of local LGM conditions in High Asia. A prerequisite for this is an extensive biogeographical and phylogenetic exploration of the area and the inclusion of additional endemic taxa and evolutionary lines.     

Thermal behaviour of pyrope at 1000 and 1100 °C: mechanism of Fe<Superscript>2+</Superscript> oxidation and decomposition model

The mechanism of thermally induced oxidation of Fe²⁺ from natural pyrope has been studied at 1000 and 1100 °C using ⁵⁷Fe Mössbauer spectroscopy in conjunction with XRD, XRF, AFM, QELS, TG, DTA and electron microprobe analyses. At 1000 °C, the non-destructive oxidation of Fe²⁺ in air includes the partial stabilization of Fe³⁺ in the dodecahedral 24c position of the garnet structure and the simultaneous formation of hematite particles (15–20 nm). The incorporation of the magnesium ions to the hematite structure results in the suppression of the Morin transition temperature to below 20 K. The general garnet structure is preserved during the redox process at 1000 °C, in accordance with XRD and DTA data. At 1100 °C, however, oxidative conversion of pyrope to the mixed magnesium aluminium iron oxide, Fe-orthoenstatite and cristoballite was observed. During this destructive decomposition, Fe²⁺ is predominantly oxidized and incorporated into the spinel structure of Mg(Al,Fe)₂O₄ and partially stabilized in the structure of orthoenstatite, (Mg,Fe)SiO₃. The combination of XRD and Mössbauer data suggest the definite reaction mechanism prevailing, including the refinement of the chemical composition and quantification of the reaction products. The reaction mechanism indicates that the respective distribution of Fe²⁺and Fe³⁺ to the enstatite and spinel structures is determined by the total content of Fe²⁺ in pyrope.     

Polymetallic (Pb-Zn-Cu-Ag ± Au) vein-type deposits in brittle-ductile transtensional shear zones,Eastern Sierras Pampeanas (Argentina): Age constraints and significance for the Late Paleozoic tectonic evolution and metallogenesis

This paper discusses new structural, kinematic and geochronological data from polymetallic (Pb-Zn-Cu-Ag ± Au) vein-type deposits hosted in the metamorphic basement of the southern Sierras de Córdoba. A Carboniferous age was established for the hydrothermal event between ∼329 and 315 Ma (Late Mississippian-Early Pennsylvanian) by the K/Ar fine-fraction dating method of sericitic alteration related to metallic ore deposition in the Las Guindas and Oro districts. The obtained ages postdate the spatially associated Devonian magmatism and overlap the A-type Early Carboniferous magmatism defined for the Eastern Sierras Pampeanas. The presence of non-exhumed granitic bodies at shallow depths, possibly related to mineralization, is supported by available geophysical and field evidence.The strain fabric and 3-D kinematic analyses constitute first kinematic data for the Carboniferous basement of the Southern Sierras Pampeanas demonstrating that mineralization was controlled by NNW- and ENE-trending brittle-ductile transtensional shear zones that overprint the earlier high-strain deformation fabrics of the basement. Transtensional deformation has accommodated large amounts of strike-slip movements and subordinated extensional components. The calculated kinematic axes indicate a coherent kinematic pattern of the mineralized systems in the two studied districts, with a maximum extension direction oriented NNE- to NE and maximum shortening direction oriented WNW- to NW. This deformation regime, active during mineralization, point to a non-compressive setting at the Late Mississippian-Early Pennsylvanian boundary. In line with other regional evidence, we propose a distinctive Carboniferous deformational phase in the Eastern Sierras Pampeanas, dominated by transtension. This period would have occurred after the transition with the Devonian compressional/transpressional orogenic regime.     

High-P (P = 1.5–1.8 GPa) blueschist from Elba: Implications for underthrusting and exhumation of continental units in the Northern Apennines

The Acquadolce Subunit on the Island of Elba, Italy, records blueschist facies metamorphism related to the Oligocene–early Miocene stages of continental collision in the Northern Apennines. The blueschist facies metamorphism is represented by glaucophane- and lawsonite-bearing metabasite associated with marble and calcschist. These rock types occur as lenses in a schistose complex representing foredeep deposits of early Oligocene age. Detailed petrological analyses on metabasic and metapelitic protoliths, involving mineral and bulk-rock chemistry coupled with P–T and P–T–X(Fe₂O₃) pseudosection modelling using PERPLE_X, show that the Acquadolce Subunit recorded nearly isothermal exhumation from peak pressure–temperature conditions of 1.5–1.8 GPa and 320–370°C. During exhumation, peak lawsonite- and possibly carpholite- or stilpnomelane-bearing assemblages were overprinted and partially obliterated by epidote-blueschist and, subsequently, albite-greenschist facies metamorphic assemblages. This study sheds new light on the tectonic evolution of Adria-derived metamorphic units in the Northern Apennines, by showing (a) the deep underthrusting of continental crust during continental collision and (b) rapid exhumation along ‘cold’ and nearly isothermal paths, compatible with syn-orogenic extrusion.     

Reaction between basaltic melt and orthopyroxene at 3.0–4.5 GPa:Implications for the evolution of ocean island basalts in the mantle

Interactions between basaltic melt and orthopyroxenite(Opx)were investigated to gain a better understanding of the consequences of the residence and transport of ocean island basalts(OIBs)within the mantle.The experiments were conducted using a DS-3600 six-anvil apparatus at 3.0–4.5 GPa and 1300–1450℃.The basaltic melt and Opx coexisted at local equilibrium at these pressures and temperatures;the initial melts dissolved Opx,which modified their chemical composition,and clinopyroxene(Cpx)precipitated with or without garnet(Grt).The trace-element contents of Grt,Cpx,and melt were measured and the mineral–melt distribution coefficients(D)of Cpx–melt and Grt–melt were calculated,which can be used to assess the distribution of trace elements between basalt and minerals in the mantle.Two types of reaction rim were found in the experimental products,Cpx,and Cpx+Grt;this result indicates that residual rocks within the mantle should be pyroxenite or garnet pyroxenite.Both rock types are found in mantle xenoliths from Hawaii,and the rare-earth-element(REE)pattern of Cpx in these mantle pyroxenites matches those of Cpx in the experimental reaction rims.Furthermore,residual melts in the experimental products plot in similar positions to Hawaiian high-SiO₂OIBs on major-element Harker diagrams,and their trace-element patterns show the signature of residual Grt,particularly in runs at1350℃ and 4.0–4.5 GPa.Trace-element concentrations of the experimental residual melts plot in similar positions to the Hawaiian OIBs on commonly used discrimination diagrams(Ti vs.Zr,Cr vs.Y,Cr vs.V,Zr/Y vs.Zr,and Ti/Y vs.Nb/Y).These results indicate that reaction between basaltic melt and pyroxenite might contribute to the generation of Hawaiian high-SiO2 OIBs and account for their chemical variability.     

Alteration of nuclear glass in contact with iron and claystone at 90 °C under anoxic conditions: Characterization of the alteration products after two years of interaction

The present study investigates the alteration of a fractured glass block in contact with iron and Callovo-Oxfordian claystone at 90 °C under anoxic and water-saturated conditions. The alteration rates and the nature of glass alteration products at the different compact interfaces (glass-clay, glass-iron) and in cracks were assessed by solution chemistry and microscopic-scale techniques (scanning electron microscopy coupled with energy-dispersive X-ray microscopy, microRaman spectroscopy, and X-ray absorption fine structure spectroscopy). A significant but modest (two-fold) increase in glass alteration in contact with steel was observed, leading to an average alteration rate over the experiment of about 0.007–0.014 g/m²/d. This rate is significantly lower than forward rate r₀ in clay-equilibrated groundwater (1.7 g/m²/d), indicating that a decrease of the alteration rate was not hindered by the steel presence. The corrosion–alteration interface was made up of successive layers of corrosion products in contact with iron, a layer of Fe silicates, and an altered glass layer enriched in Fe. Characterization of the glass block in direct contact with claystone revealed that the thickness of altered glass was much more important than at the glass-iron interface. The altered glass layer in contact with clay was slightly enriched in Fe and Mg, and depleted in alkali cations. Altered glass layers in cracks were usually limited to fringes thinner than 2 μm, with a thickness decreasing from the crack mouth, indicating that alteration is controlled by transport in the cracks. The fractures were partially filled with calcite and lanthanide hydroxocarbonate precipitates. These results contribute to the understanding of nuclear vitrified waste-iron-corrosion products interactions in a deep geological repository.