Serpentine minerals in natural samples are dominated by lizardite and antigorite. In spite of numerous petrological experiments, the stability fields of these species remain poorly constrained. This paper presents the petrological observations and the Raman spectroscopy and XRD analyses of natural serpentinites from the Alpine paleo-accretionary wedge. Serpentine varieties are identified from a range of metamorphic pressure and temperature conditions from sub-greenschist (P < 4 kbar, T ~ 200-300°C) to eclogite facies conditions (P > 20 kbar, T > 460°C) along a subduction geothermal gradient. We used the observed mineral assemblage in natural serpentinite along with the T max estimated by Raman spectroscopy of the carbonaceous matter of the associated metasediments to constrain the temperature of the lizardite to antigorite transition at high pressures. We show that below 300°C, lizardite and locally chrysotile are the dominant species in the mesh texture. Between 320 and 390°C, lizardite is progressively replaced by antigorite at the grain boundaries through dissolutionprecipitation processes in the presence of SiO 2 enriched fluids and through a solid-state transition in the cores of the lizardite mesh. Above 390°C, under high-grade blueschist to eclogite facies conditions, antigorite is the sole stable serpentine mineral until the onset of secondary olivine crystallization at 460°C.
International audienceOlivine mineral replacement by serpentine is one major alteration reaction of oceanic hydrothermalism. In the present experimental study, olivine grains were replaced by chrysotile and brucite under high alkaline conditions. In our study, olivine replacement implied a spatial and temporal coupling of dissolution and precipitation reactions at the interface between olivine and chrysotile-brucite minerals. Coupled dissolution-precipitation led to the alteration of starting olivine grains (so-called primary or parent mineral) to a porous mineral assemblage of chrysotile and brucite with preservation of the initial olivine morphology. This mineral replacement reaction of olivine (serpentinization) has been characterized using XRD, FESEM and FTIR measurements. Moreover, a simple and novel method is here proposed to quantify the mineral replacement rate (or serpentinization rate) of olivine by using thermogravimetric (TG) and differential TG (DTG) analyses. Serpentinization extent depends on the grain size: it is complete after 30 days of reaction for the smallest olivine grains (<30µm), after 90 days of reaction for the intermediate olivine grains (30 µm-56 µm) and reaches 55% of olivine replacement after 90 days for the largest fraction (56-150 µm). Based on the fitting of the serpentinization extent (t) versus time (t) by using a kinetic pseudo-second-order model, the serpentinization rates vary from 3.6x10-6 s-1 to 1.4x10-7 s-1 depending on the olivine grain size. An additional correlation between FTIR spectra analysis and TG measurements is proposed. The mineral replacement reactions frequently observed in natural alteration processes could be a powerful synthesis route to design new porous and/or nanostructured materials
13 pagesInternational audienceThe present study reports original experiments in order to investigate the simultaneous serpentinization and carbonation of olivine with relevance in Earth systems (e.g. functioning of hydrothermal fields) or in engineered systems (e.g. ex-situ and in-situ mineral sequestration of CO2). For this case, specific experimental conditions were examined (200°C, saturated vapor pressure ≈ 16bar, solution/solid weight ratio = 15, olivine grain size < 30µm and high-carbonate alkalinity ≈ 1M NaHCO3). Under these conditions, competitive precipitation of magnesite and serpentine (preferentially lizardite type) were clearly determined by using conventional analytic tools (XRD, FESEM, FTIR and TGA); excluding the fate of the iron initially contained in olivine, the alteration reaction for olivine under high-carbonate alkalinity can be expressed as follows: 2〖Mg〗_2 SiO_4+2H_2 O+H〖CO〗_3^-→Mg〖CO〗_3+〖Mg〗_3 〖Si〗_2 O_5 〖(OH)〗_4+〖OH〗^- This reaction mechanism implied a dissolution process, releasing Mg and Si ions into solution until supersaturation of solution with respect to magnesite and/or serpentine. The released iron contained in the olivine has not implied any precipitation of iron oxides or (oxy)hydroxides; in fact, the released iron was partially oxidized (about 50%) via a simple reduction of water (2〖Fe〗^(2+)+〖2H〗_2 O→2〖Fe〗^(3+)+H_2+2〖OH〗^-). In this way, the released iron was incorporated in serpentine (Fe(II) and Fe(III)) and in magnesite (Fe(II). This latter was clearly determined by FESEM/EDS chemical analysis on the single magnesite crystals. The nucleation and epitaxial growth processes at the olivine-fluid interfaces cannot be excluded in our investigated system. The experimental kinetic data fitted by using a kinetic pseudo-second-order model have revealed a retarding process of serpentine formation with respect to magnesite (about three times slower); in fact, the magnesite seems to reach an apparent stabilization after about 20 days of reaction while the serpentine follows a progressive slower evolution. We assumed that the magnesite has reached a fast apparent equilibrium with solution because the available carbonate species are not renewed from fluid phase as typically constrained in aqueous carbonation experiments where a given CO2 pressure is imposed in the system. On the other hand, the reactivity of serpentinized olivine (chrysotile+brucite+small amount of residual olivine) and high-purity chrysotile at the same above investigated conditions; and the olivine serpentinization in initial acid pH ≈ 0.66 are also reported as complementary information in this study. These novel experimental results concerning simultaneous serpentinization and aqueous carbonation of olivine expand the thermodynamic conditions where serpentine and magnesite can simultaneously precipitate; this could contribute to a better understanding of fluid-rock interactions in natural active hydrothermal fields on Earth
In two companion papers, we report the detailed geological and mineralogical study of two emblematic serpentinized ultramafic bodies of the western North Pyrenean Zone (NPZ), the Urdach massif (this paper) and the Saraillé massif (paper 2). The peridotites have been exhumed to lower crustal levels during the Cretaceous rifting period in the future NPZ. They are associated with Mesozoic pre-rift metamorphic sediments and small units of thinned Paleozoic basement that were deformed during the mantle exhumation event. Based on detailed geological cross-sections and microprobe mineralogical analyses, we describe the lithology of the two major extensional fault zones that accommodated: (i) the progressive exhumation of the lherzolites along the Cretaceous basin axis; (ii) the lateral extraction of the continental crust beneath the rift shoulders and; (iii) the decoupling of the pre-rift cover along the Upper Triassic (Keuper) evaporites and clays, allowing its gliding and conservation in the basin center. These two fault zones are the (lower) crust-mantle detachment and the (upper) cover décollement located respectively at the crust-mantle boundary and at the base of the detached pre-rift cover. The Urdach peridotites were exposed to the seafloor during the Late Albian and underwent local pervasive carbonation and crystallization of calcite in a network of orthogonal veins (ophicalcites). The carbonated serpentinized peridotites were partly covered by debris-flows carrying fragments of both the ultramafics and Paleozoic crustal rocks now forming the polymictic Urdach breccia. The mantle rocks are involved in a Pyrenean overturned fold together with thin units of crustal mylonites. Continent-derived and mantle-derived fluids that circulated along the Urdach crust-mantle detachment led to the crystallization of abundant metasomatic rocks containing quartz, calcite, Cr-rich chlorites, Cr-rich white micas and pyrite. Two samples of metasomatized material from the crust-mantle detachment yielded in situ zircon U/Pb ages of 112.9 ± 1.6 Ma and 109.4 ± 1.2 Ma, thus confirming the Late Albian age of the metasomatic event. The cover décollement is a 30-m thick fault zone which also includes metasomatic rocks of greenschist facies, such as serpentine-calcite association and listvenites, indicating large-scale fluid-rock interactions implying both ultramafic and continental material. The lowermost pre-rift cover is generally missing along the cover décollement due to tectonic disruption during mantle exhumation and continental crust elision. Locally, metasomatized and strongly tectonized Triassic remnants are found as witnesses of the sole at the base of the detached pre-rift cover. We also report the discovery of a spherulitic alkaline lava flow emplaced over the exhumed mantle. These data collectively allow to propose a reconstruction of the architecture and fluid-rock interaction history of the distal domain of the upper Cretaceous northern Iberia margin now inverted in the NPZ.
The occurrence of the quartz–carbonate alteration assemblage (listvenite) in ophiolites indicates that ultramafic rock represents an effective sink for dissolved CO2. However, the majority of earlier studies of ultramafic rock carbonation had to rely on the surface exposure of reaction textures and field relationships. Here we present the first observations on ultramafic rock alteration obtained from the 300 m deep BT1B drill hole, ICDP Oman Drilling Project, allowing for a continuous and high-resolution investigation. Hole BT1B recovered continuous drill core intersecting surface alluvium, 200 meters of altered ultramafic rock comprising mainly listvenite and minor serpentinite bands at 90 m and 180 m depth, and 100 meters of the underlying metamorphic sole. Textural evidence suggests that the carbonation of fully serpentinized harzburgite commenced by non-equilibrium growth of spheroidal carbonate characterized by sectorial zoning resulting from radially oriented low-angle boundaries. In the serpentinite, carbonate spheroids are composed of alternating magnesite cores and dolomite rims, whereas texturally similar carbonate in the listvenite is composed of Fe-rich magnesite cores and Ca-Fe-rich magnesite rims. The distinct compositions and mineral inclusions indicate that the carbonation extent was controlled by fluid accessibility resulting in the simultaneous formation of limited carbonate in the serpentinite bands and complete carbonation in the listvenite parts of BT1B. The presence of euhedral magnesite overgrowing spheroidal carbonate in the listvenite suggests near-equilibrium conditions during the final stage of carbonation. The carbonate clumped isotope thermometry constrains carbonate crystallization between 50°C and 250°C, implying repeated infiltration of reactive fluids during ophiolite uplift and cooling.
In two companion papers we report the detailed geological and mineralogical study of two emblematic serpentinized ultramafic bodies of the western North Pyrenean Zone (NPZ), the Urdach massif (paper 1) and the Saraillé massif (this paper). The peridotites have been uplifted to lower crustal levels during the Cretaceous rifting period in the future NPZ. They are associated with Mesozoic pre-rift metamorphic sediments and small units of thinned Paleozoic basement that were deformed during the mantle exhumation event. In the Saraillé massif, both the pre-rift cover and the thin Paleozoic crustal lenses are involved in a Pyrenean recumbent fold having the serpentinized peridotites in its core. Based on detailed geological cross-sections microscopic observations and microprobe mineralogical analyses, we describe the lithology of the two major extensional fault zones that accommodated: (i) the progressive uplift of the lherzolites upward the Cretaceous basin axis, (ii) the lateral extraction of the continental crust beneath the rift margins and, (iii) the decoupling of the pre-rift cover along the Upper Triassic (Keuper) evaporites and clays, allowing its gliding and conservation in the basin center. These two fault zones are the (lower) crust-mantle detachment and the (upper) cover décollement located respectively at the crust-mantle boundary and at the base to the detached pre-rift cover. The Saraillé peridotites were never exposed to the seafloor of the Cretaceous NPZ basins and always remained under a thin layer of crustal mylonites. Field constraints allow to reconstruct the strain pattern of the mantle rocks in the crust-mantle detachment. A 20–50 m thick layer of serpentinized lherzolites tectonic lenses separated by anastomosed shear zones is capped by a thin upper damage zone made up of strongly sheared talc-chlorite schists invaded by pyrite crystallization. The cover décollement is a few decameter-thick fault zone resulting from the brecciation of Upper Triassic layers. It underwent strong metasomatic alteration in the greenschist facies, by multi-component fluids leading to the crystallization of quartz, dolomite, talc, Cr-rich chlorite, amphiboles, magnesite and pyrite. These data collectively allow to propose a reconstruction of the architecture and fluid-rock interaction history of the distal domain of the upper Cretaceous northern Iberia margin now inverted in the NPZ.
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