H2O-rich rutile as an indicator for modern-style cold subduction.

The trace-element and isotope geochemistry of rutile are robust tools to determine metamorphic temperatures, age, and host-/source lithologies. The use of rutile as single grain indicator for pressure, temperature, time and composition (P-T-t-X) of the host rock, which is vital in the use of detrital rutile to trace plate-tectonic regimes throughout Earth's history, requires the identification of a pressure dependent trace element in rutile. We investigate the pressure dependence of hydrogen in rutile using polarized in-situ Fourier Transform Infrared (FTIR) spectroscopy. H2O contents in rutile vary between < 10-2500 µg/g H2O with higher contents in samples with higher peak metamorphic pressures, making H2O-in-rutile a viable pressure indicator. The highest H2O contents at ~ 450-2000 µg/g are observed in mafic low temperature eclogite-facies rutile related to modern-style cold subduction conditions. Hydrogen zoning in FTIR maps indicates that H+ is retained at temperatures below 600-700 °C. Ratios of H2O/Zr, using H2O as pressure indicator and Zr as temperature proxy, are a proxy for thermal gradients of metamorphic rutile (i.e. P/T). Low temperature eclogite samples are also characterized by high Fe contents and therefore Fe/Zr-ratios might be used as a first order approximation for H2O/Zr-ratios to identify mafic low temperature eclogite facies rutile. Based on common discrimination diagrams, Nb, W, and Sn can be used to distinguish different host/source rock lithologies of rutile. Combining both H2O/Zr-ratios and Nb, W, and Sn contents can thus identify modern-style cold subduction signatures in rutile. The developed systematics can consequently be used to trace cold-subduction features in the (pre-Proterozoic) detrital record. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-024-02107-2.

Tracing fluid infiltration into oceanic crust up to ultra-high-pressure conditions.

Fluid-rock interaction within the altered oceanic crust and across the slab-mantle boundary during subduction facilitates element transfer, but the dynamics of fluid transport and fluid-rock exchange during upward fluid migration are still unclear. A study of metamorphic fluid-rock interaction within a section of subducted oceanic crust was carried out on eclogites and metasediments of the ultra-high-pressure Lago di Cignana Unit (NW Italian Alps). The P-T modeling of a quartzschist shows that garnet grew during the prograde and sporadically during the retrograde path and that phengite mainly records the peak to retrograde conditions. Microscale geochemical analysis of garnets has revealed a systematic evolution of oxygen isotopic composition with garnet major element zonation, with extreme within-sample core-rim variations in δ18O between 18 and 4‰ providing evidence for external fluid influx. Garnet in eclogites and calcschists, as well as garnet cores in quartz-rich lithologies, shows normal compositional zoning, as expected for prograde garnet growth, and a relatively constant oxygen isotopic composition. The outer garnet growth zones within a few metasediments show reverse or discontinuous zoning and progressively lower δ18O. Despite major element zoning, the isotopic composition of mica is homogeneous across chemical zoning in one eclogite and one quartzschist, but shows 6‰ variability in another quartzschist. In the underlying Zermatt-Saas serpentinites, antigorite from nine serpentinite samples shows some variation in δ18O, with average δ18O values for individual samples ranging from 1 to 6‰. These results provide evidence for two main stages of external fluid infiltration: (i) fluids from the dehydration of mafic lithologies entered the sequence at peak conditions around 3 GPa, as indicated by the oxygen composition of intermediate zones of mica and garnet, and (ii) low δ18O fluids from serpentinites infiltrated parts of the sedimentary package during exhumation prior to 1.5 GPa, as recorded by the 4‰ garnet outer rims. Samples recording external fluid infiltration are concentrated in the lower part of the sequence, indicating channelized fluid flow, suggesting focused fluid infiltration due to permeability contrasts between metasedimentary and eclogitic lithologies. Channelized fluid flow in the ultra-high-pressure metasediments of Lago di Cignana has not resulted in systematic decarbonation of the metasediments. Supplementary Information: The online version contains supplementary material available at 10.1007/s00410-023-02060-6.

Surface Analysis by Secondary Ion Mass Spectrometry (SIMS): Principles and Applications from Swiss laboratories.

Secondary Ion Mass Spectrometry (SIMS) extracts chemical, elemental, or isotopic information about a localized area of a solid target by performing mass spectrometry on secondary ions sputtered from its surface by the impact of a beam of charged particles. This primary beam sputters ionized atoms and small molecules (as well as many neutral particles) from the upper few nanometers of the sample surface. The physical basis of SIMS has been applied to a large range of applications utilizing instruments optimized with different types of mass analyzer, either dynamic SIMS with a double focusing mass spectrometer or static SIMS with a Time of Flight (TOF) analyzer. Here, we present a short review of the principles and major applications of three different SIMS instruments located in Switzerland.

The behaviour of monazite from greenschist facies phyllites to anatectic gneisses: An example from the Chugach Metamorphic Complex, southern Alaska.

Monazite is a common accessory mineral in various metamorphic and magmatic rocks, and is widely used for U-Pb geochronology. However, linking monazite U-Pb ages with the PT evolution of the rock is not always straightforward. We investigated the behaviour of monazite in a metasedimentary sequence ranging from greenschist facies phyllites into upper amphibolites facies anatectic gneisses, which is exposed in the Eocene Chugach Metamorphic Complex of southern Alaska. We investigated textures, chemical compositions and U-Pb dates of monazite grains in samples of differing bulk rock composition and metamorphic grade, with particular focus on the relationship between monazite and other REE-bearing minerals such as allanite and xenotime. In the greenschist facies phyllites, detrital and metamorphic allanite is present, whereas monazite is absent. In lower amphibolites facies schists (~ 550-650 °C and ≥ 3.4 kbar), small, medium-Y monazite is wide-spread (Mnz1), indicating monazite growth prior and/or simultaneous with growth of garnet and andalusite. In anatectic gneisses, new low-Y, high-Th monazite (Mnz2) crystallised from partial melts, and a third, high-Y, low-Th monazite generation (Mnz3) formed during initial cooling and garnet resorption. U-Pb SHRIMP analysis of the second and third monazite generations yields ages of ~ 55-50 Ma. Monazite became unstable and was overgrown by allanite and/or allanite/epidote/apatite coronas within retrograde muscovite- and/or chlorite-bearing shear zones. This study documents polyphase, complex monazite growth and dissolution during a single, relatively short-lived metamorphic cycle.

The evolution of the Sesia Zone (Western Alps) from Carboniferous to Cretaceous: insights from zircon and allanite geochronology.

Microscale dating of distinct domains in minerals that contain relics of multiple metamorphic events is a key tool to characterize the polyphase evolution of complex metamorphic terranes. Zircon and allanite from five metasediments and five metaintrusive high-pressure (HP) rocks from the Eclogite Micaschist Complex of the Sesia Zone were dated by SIMS and LA-ICP-MS. In the metasediments, zircon systematically preserves detrital cores and one or two metamorphic overgrowths. An early Permian age is obtained for the first zircon rim in metasediments from the localities of Malone Valley, Chiusella Valley and Monte Mucrone (292 ± 11, 278.8 ± 3.6 and 285.9 ± 2.9 Ma, respectively). In the Malone Valley and Monte Mucrone samples, the early Permian ages are attributed to high-temperature metamorphism and coincide with the crystallization ages of associated mafic and felsic intrusions. This implies that magmatism and metamorphism were coeval and associated to the same tectono-metamorphic extensional event. In the Malone Valley, allanite from a metasediment is dated at 241.1 ± 6.1 Ma and this age is tentatively attributed to a metasomatic/metamorphic event during Permo-Triassic extension. Outer zircon rims with a late Cretaceous age (67.4 ± 1.9 Ma) are found only in the micaschist from Monte Mucrone. In metagabbro of the Ivozio Complex, zircon cores yield an intrusive age for the protolith of 340.7 ± 6.8 Ma, whereas Alpine allanite are dated at 62.9 ± 4.2 and 55.3 ± 7.3 Ma. The Cretaceous ages constrain the timing of the HP metamorphic stage. The presence of zircon overgrowth only in the central area of the Eclogite Micaschist Complex is attributed to local factors such as (1) multiple fluid pulses at HP that locally enhanced zircon dissolution and recrystallization, and (2) slightly higher temperatures reached in this area during HP metamorphism.

Ediacaran 2,500-km-long synchronous deep continental subduction in the West Gondwana Orogen.

The deeply eroded West Gondwana Orogen is a major continental collision zone that exposes numerous occurrences of deeply subducted rocks, such as eclogites. The position of these eclogites marks the suture zone between colliding cratons, and the age of metamorphism constrains the transition from subduction-dominated tectonics to continental collision and mountain building. Here we investigate the metamorphic conditions and age of high-pressure and ultrahigh-pressure eclogites from Mali, Togo and NE-Brazil and demonstrate that continental subduction occurred within 20 million years over at least a 2,500-km-long section of the orogen during the Ediacaran. We consider this to be the earliest evidence of large-scale deep-continental subduction and consequent appearance of Himalayan-scale mountains in the geological record. The rise and subsequent erosion of such mountains in the Late Ediacaran is perfectly timed to deliver sediments and nutrients that are thought to have been necessary for the subsequent evolution of sustainable life on Earth.