ABSTRACT
The Allalin gabbro of the Zermatt-Saas meta-ophiolite consists of variably metamorphosed Mg- to Fe-Ti-gabbros, troctolites, and anorthosites, which are crosscut by basaltic dykes. Field relationships of the various rock types and petrographic studies together with bulk rock and mineral chemical composition data allow the reconstruction of the complete geological history of the Allalin gabbro. With increasing magmatic differentiation, the incompatible element content in clinopyroxene increases (e.g., REEs and Zr by a factor of 5), whereas the Mg# decreases (from 86.4 to 74.6) as do the compatible element contents (e.g., Cr and Ni by factors of 3.5 and 5, respectively). Exhumation to shallower depths led to subsolidus ductile deformation and cooling of the gabbro followed by the intrusion of fine-grained basaltic dykes, which display chilled margins. Bulk rock data of these dykes reveal strong similarities in fluid-immobile trace element patterns to tholeiitic pillow basalts of the Zermatt-Saas and nearby meta-ophiolites. The recalculated REE patterns of the melt in equilibrium with igneous clinopyroxene is very similar to the REE patterns of the mafic dykes, indicating a cogenetic origin of pillow basalts, dykes, and gabbros. Together with the previously determined Jurassic intrusion age of the gabbro, our observations demonstrate that the Allalin gabbro intruded as a tholeiitic magma in a slow spreading MOR environment of the Piemonte-Ligurian ocean of the Alpine Tethys. Subduction of the Allalin gabbro resulted in different eclogitization extents of the Mg-gabbros as a function of variable hydration degrees. Metagabbros with low extents of hydration record incomplete eclogitization; the magmatic mineralogy (olivine + clinopyroxene + plagioclase) is preserved together with disequilibrium textures in the form of reaction coronae surrounding mineral boundaries. Metagabbros with high extents of hydration are completely eclogitized and display pseudomorphic replacement textures of magmatic minerals by eclogite-facies mineral assemblages, which required significant major to trace element transport across mineral domains. The locally variable extents of hydration took place near the sea floor, as recorded by the presence of Cl-apatite (6.28 wt% Cl), and an increase in B concentrations of minerals pseudomorphically replacing olivine (e.g., chlorite with 0.20-0.31 µg/g B and omphacite with 0.22-0.25 µg/g B) compared to magmatic olivine (0.12-0.16 µg/g B). Moreover, the chemical zonation pattern of metamorphic garnet coronae is different in completely eclogitized gabbros and gabbros with relic igneous minerals, in agreement with a main hydration event prior to subduction. The Allalin gabbro therefore represents a classical example of an oceanic gabbro formed in a slow spreading setting in the mid Jurassic that experienced heterogeneous hydration near the sea floor. Paleogene subduction of the gabbro to 70-80 km depth produced variably equilibrated gabbroic eclogites. In eclogite-facies Mg-gabbros, the water-rich minerals chlorite, talc, and chloritoid pseudomorphing magmatic olivine remained stable to these depths, revealing the potential relevance of hydrated Mg-gabbros as a fluid source at subarc depths in subduction zones. Supplementary Information: The online version contains supplementary material available at 10.1186/s00015-024-00461-8.
ABSTRACT
Oxide minerals contained in ultramafic rocks are useful tools to assess the redox conditions of the rock and fluids liberated upon progressive serpentinite dehydration during subduction, as these minerals contain a relevant redox-sensitive element, iron. Previous studies have revealed that magnetite predominates across the antigorite-out reaction. However, the fate of magnetite and other oxides at higher pressure and temperature conditions has remained underexplored. We present a comprehensive petrological and geochemical study of oxide-sulfide-silicate mineral assemblages in metaperidotites beyond antigorite- and chlorite-out reactions (T = 650-850 °C and P = 1-3 GPa). Several ultramafic lenses, covering different bulk rock compositions and extents of oxidation upon oceanic serpentinization, were investigated from the Central Alps, Switzerland. Results point to two endmember scenarios: (i) Most frequently, metaperidotites have olivine with a Mg# of 89-91 (defined as molar Mg/(Mg + Fetot) × 100) and contain low oxide modes (0.06-1.41 vol.%), hematite is absent, and redox conditions are weakly oxidized and buffered by orthopyroxene-olivine-magnetite. (ii) Rare occurrence, high olivine Mg# > 94.5 metaperidotites display coexisting hematite and magnetite, high oxide modes (up to 4 vol.%), and redox conditions are hematite-magnetite (HM) buffered (Δlog10fO2,QFM of + 3 to + 4). Spinel displays evolving compositions from magnetite over chromite to Al-Cr-spinel, roughly correlating with increasing temperature. Most of the samples buffered by the olivine-orthopyroxene-magnetite assemblage contain coexisting pentlandite ± pyrrhotite, thus identifying stable sulfides beyond antigorite dehydration for these weakly oxidized samples (Δlog10fO2,QFM < 2.5). No sulfides were recognized in the highly oxidized sample. The transition of magnetite to chromite at around 700 °C goes along with a shift in fO2 to lower values. At the prevailing oxygen fugacity in the weakly oxidized metaperidotites sulfur in a coexisting fluid is always present in its reduced form. However, oxidized sulfur can be stable in the dehydration fluids released from highly oxidized serpentinites. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-023-02032-w.
ABSTRACT
Recent research has shown that certain Li-oxide garnets with high mechanical, thermal, chemical, and electrochemical stability are excellent fast Li-ion conductors. However, the detailed crystal chemistry of Li-oxide garnets is not well understood, nor is the relationship between crystal chemistry and conduction behavior. An investigation was undertaken to understand the crystal chemical and structural properties, as well as the stability relations, of Li(7)La(3)Zr(2)O(12) garnet, which is the best conducting Li-oxide garnet discovered to date. Two different sintering methods produced Li-oxide garnet but with slightly different compositions and different grain sizes. The first sintering method, involving ceramic crucibles in initial synthesis steps and later sealed Pt capsules, produced single crystals up to roughly 100 µm in size. Electron microprobe and laser ablation inductively coupled plasma mass spectrometry (ICP-MS) measurements show small amounts of Al in the garnet, probably originating from the crucibles. The crystal structure of this phase was determined using X-ray single-crystal diffraction every 100 K from 100 K up to 500 K. The crystals are cubic with space group Ia3Ì d at all temperatures. The atomic displacement parameters and Li-site occupancies were measured. Li atoms could be located on at least two structural sites that are partially occupied, while other Li atoms in the structure appear to be delocalized. (27)Al NMR spectra show two main resonances that are interpreted as indicating that minor Al occurs on the two different Li sites. Li NMR spectra show a single narrow resonance at 1.2-1.3 ppm indicating fast Li-ion diffusion at room temperature. The chemical shift value indicates that the Li atoms spend most of their time at the tetrahedrally coordinated C (24d) site. The second synthesis method, using solely Pt crucibles during sintering, produced fine-grained Li(7)La(3)Zr(2)O(12) crystals. This material was studied by X-ray powder diffraction at different temperatures between 25 and 200 °C. This phase is tetragonal at room temperature and undergoes a phase transition to a cubic phase between 100 and 150 °C. Cubic "Li(7)La(3)Zr(2)O(12)" may be stabilized at ambient conditions relative to its slightly less conducting tetragonal modification via small amounts of Al(3+). Several crystal chemical properties appear to promote the high Li-ion conductivity in cubic Al-containing Li(7)La(3)Zr(2)O(12). They are (i) isotropic three-dimensional Li-diffusion pathways, (ii) closely spaced Li sites and Li delocalization that allow for easy and fast Li diffusion, and (iii) low occupancies at the Li sites, which may also be enhanced by the heterovalent substitution Al(3+) â 3Li.
ABSTRACT
Fluids and melts liberated from subducting oceanic crust recycle lithophile elements back into the mantle wedge, facilitate melting and ultimately lead to prolific subduction-zone arc volcanism. The nature and composition of the mobile phases generated in the subducting slab at high pressures have, however, remained largely unknown. Here we report direct LA-ICPMS measurements of the composition of fluids and melts equilibrated with a basaltic eclogite at pressures equivalent to depths in the Earth of 120-180 km and temperatures of 700-1,200 degrees C. The resultant liquid/mineral partition coefficients constrain the recycling rates of key elements. The dichotomy of dehydration versus melting at 120 km depth is expressed through contrasting behaviour of many trace elements (U/Th, Sr, Ba, Be and the light rare-earth elements). At pressures equivalent to 180 km depth, however, a supercritical liquid with melt-like solubilities for the investigated trace elements is observed, even at low temperatures. This mobilizes most of the key trace elements (except the heavy rare-earth elements, Y and Sc) and thus limits fluid-phase transfer of geochemical signatures in subduction zones to pressures less than 6 GPa.
ABSTRACT
Microanalysis of major and trace elements in sulfide and silicate melt inclusions by laser-ablation inductively coupled plasma mass spectrometry indicates a direct link between a magmatic sulfide liquid and the composition of porphyry-type ore deposits. Copper (Cu), gold (Au), and iron (Fe) are first concentrated in a sulfide melt during magmatic evolution and then released to an ore-forming hydrothermal fluid exsolved late in the history of a magma chamber. The composition of sulfide liquids depends on the initial composition and source of the magma, but it also changes during the evolution of the magma in the crust. Magmatic sulfide melts may exert the dominant direct control on the economic metal ratios of porphyry-type ore deposits.
