Rutile is a common accessory mineral in subducted oceanic crust and its trace element geochemistry is frequently used to investigate subduction zone processes.To understand the evolution of subduction on Earth, sedimentary equivalents of missing Precambrian low-T high-P metamorphic rocks can be investigated.This requires the estimation of pressure, temperature, time of formation, and source lithologies (P-T-t-X) on detrital single grains.As rutile is one of the most likely minerals from subduction zone rocks to survive sedimentation, and single grain T-t-X estimates are possible, it is a prime candidate for the investigation of subduction processes through time.We present results from in-situ quantitative Fourier Transform Infrared (FTIR) spectroscopy of metamorphic rutile from various P-T conditions and bulk rock compositions that indicate a pressure dependence of H 2 O in rutile.H 2 O contents in rutile vary between < 10 μg/g in granulite facies rutile up to ~2500 μg/g in blueschist-and low-T eclogite facies rutile.Rutile from low pressure samples have H 2 O contents of < 400 μg/g, while rutile formed at higher pressures contain higher amounts of H 2 O.At temperatures < 600 °C, a trend of higher H 2 O contents in samples reaching higher peak pressures is identified.Samples with higher peak temperatures > 600 °C do not follow this trend, showing evidence of diffusive H + loss in FTIR maps of H 2 O in rutile.The substitution of H + and trivalent cations (e.g.Fe 3+ , Al 3+ ) is linked, and as subducted oceanic crust is saturated in Fe and Al, the incorporation of H + into rutile in these lithologies should depend only on H 2 O fugacity.As H 2 O fugacity is pressure dependent, H 2 O contents of rutile increase with increasing pressure.This pressure dependence of H + in rutile could aid in tracing modern-style cold subduction in the sedimentary record.Rutile from mafic rocks, with Zr contents < 150-200 μg/g, and H 2 O contents > 500 μg/g are interpreted to be derived from high pressure rocks related to modern-style cold subduction.Evidence from fluvial, detrital rutile suggests that this signature can be retained during sedimentation processes, opening the possibility of finding high-P signatures in detrital rutile.
Abstract Garnet is a fundamental expression of metamorphism and one of the most important minerals used to constrain the thermal conditions of the crust. We used innovative in situ laser-ablation ICP-MS/MS Lu-Hf geochronology to demonstrate that garnet in metapelitic rocks enclosing Cambrian eclogite in southern Australia formed during Laurentian Mesoproterozoic metamorphism. Garnet porphyroblasts in amphibolite-facies metapelitic rocks yielded Lu-Hf ages between 1286 ± 58 Ma and 1241 ± 16 Ma, revealing a record of older metamorphism that was partially obscured by metamorphic overprinting during ca. 510 Ma Cambrian subduction along the East Gondwana margin. Existing detrital zircon age data indicate the protoliths to the southern Australian metapelitic rocks were sourced from western Laurentia. We propose that the metapelitic rocks of southern Australia represent a fragment of western Laurentian crust, which was separated from Laurentia in the Neoproterozoic and incorporated into the East Gondwana subduction system during the Cambrian. The ability to obtain Lu-Hf isotopic data from garnet at acquisition rates comparable to those for U-Pb analysis of detrital zircon means, for the first time, the metamorphic parentage of rocks as expressed by garnet can be efficiently accessed to assist paleogeographic reconstructions.
Abstract Lu Hf geochronology is a powerful method to constrain the temporal evolution of geological systems. Traditional application of this dating method requires time-consuming chemical separation of the parent (176Lu) and daughter (176Hf) isotopes that is commonly accompanied by loss of textural context of the analysed minerals. In contrast, In-situ (laser-ablation based) Lu Hf geochronology offers a number of advantages including rapid analysis with high spatial resolution, as well as control on textural relationships of the analysed mineral. However, laser-ablation based Lu Hf geochronology has been hindered by isobaric interferences of 176Yb and 176Lu on 176Hf that have effectively masked reliable determination of 176Lu and 176Hf. We present a methodology that resolves these interferences using LA-ICP-MS/MS (laser ablation tandem inductively coupled mass spectrometry) and NH3 gas to separate Hf from Lu. Both Lu, Yb, and Hf react with NH3 to form a variety of product ions. By measuring high order reaction products (e.g. Hf(NH)(NH2)(NH3)3+), we demonstrate that 176Hf can be measured interference-free from 176Lu and 176Yb with sufficient sensitivity to yield useful geochronological age data. The novel in-situ Lu Hf technique has been successfully applied to a variety of Palaeozoic and Precambrian-aged garnet, apatite and xenotime samples, including published reference materials. The resulting age uncertainties are as low as ~0.5% (95% conf. interval). The technique has the potential to obtain spatially-resolved Lu Hf ages in garnet-bearing samples that would be difficult to obtain by conventional techniques. The method also offers the opportunity for rapid “campaign style” geochronology in complex terrains that record poly-metamorphic histories. In apatite, the expected higher closure temperature of the Lu Hf system compared to the commonly used U Pb system allows high-temperature thermal history reconstructions. In addition, Lu Hf dating of apatite allows dating of samples with low U and high common Pb (e.g. mafic and low-grade metamorphic rocks and ore deposits). Furthermore, apatite tends to incorporate little to no common Hf, allowing single grain ages to be calculated, which opens new doors for detrital provenance studies. In situ Lu Hf dating of xenotime offers an additional avenue to U Pb dating, and may be particularly beneficial to dating of rare earth element ore deposits that often have complex temporal records of development.
Abstract. The coupling behaviour of H+ and trace elements in rutile has been studied using in situ polarised Fourier transform infrared (FTIR) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) analysis. H2O contents in rutile can be precisely and accurately quantified from polarised FTIR measurements on single grains in situ. The benefits of this novel approach compared to traditional quantification methods are the preservation of textural context and heterogeneities of water in rutile. Rutile from six different geological environments shows H2O contents varying between ∼ 50–2200 µg g−1, with large intra-grain variabilities for vein-related samples with H2O contents between ∼ 500 and ∼ 2200 µg g−1. From FTIR peak deconvolutions, six distinct OH absorption bands have been identified at ∼ 3280, ∼ 3295, ∼ 3324, ∼ 3345, ∼ 3370, and ∼ 3390 cm−1 that can be related to coupled substitutions with Ti3+, Fe3+, Al3+, Mg2+, Fe2+, and Cr2+, respectively. Rutile from eclogite samples displays the dominant exchange reactions of Ti4+ → Ti3+, Fe3+ + H+, whereas rutile in a whiteschist shows mainly Ti4+ → Al3+ + H+. Trace-element-dependent H+ contents combined with LA–ICP–MS trace-element data reveal the significant importance of H+ for charge balance and trace-element coupling with trivalent cations. Trivalent cations are the most abundant impurities in rutile, and there is not enough H+ and pentavalent cations like Nb and Ta for a complete charge balance, indicating that additionally oxygen vacancies are needed for charge balancing trivalent cations. Valance states of multivalent trace elements can be inferred from deconvoluted FTIR spectra. Titanium occurs at 0.03 ‰–7.6 ‰ as Ti3+, Fe, and Cr are preferentially incorporated as Fe3+ and Cr3+ over Fe2+ and Cr2+, and V most likely occurs as V4+. This opens the possibility of H+ in rutile as a potential indicator of oxygen fugacity of metamorphic and subduction-zone fluids, with the ratio between Ti3+- and Fe3+-related H+ contents being most promising.
Abstract In this study, data from garnet‐kyanite metapelites in ultrahigh‐pressure (UHP) domains of the Western Gneiss Region (WGR), Norway, are presented. U–Pb geochronology and trace element compositions in zircon, monazite, apatite, rutile and garnet were acquired, and pressure–temperature ( P–T ) conditions were calculated using mineral equilibria forward modelling and Zr‐in‐rutile thermometry. Garnet‐kyanite gneiss from Ulsteinvik record a prograde evolution passing through ~690–710°C and ~9–11 kbar. Zircon and rutile age and thermometry data indicate these prograde conditions significantly pre‐date Silurian UHP subduction in the WGR and are interpreted to record early Caledonian subduction of continental‐derived allochthons. Minimum peak conditions in the Ulsteinvik metapelite occur at ~28 kbar, constrained by an inferred garnet+kyanite+omphacite+muscovite+rutile+coesite+H 2 O assemblage. The retrograde evolution passed through ~740°C and ~7 kbar, first recorded by the destruction of omphacite and followed by the partial replacement of kyanite and garnet by cordierite and spinel. Garnet‐kyanite metapelite from the diamond‐bearing Fjørtoft outcrop documents a polymetamorphic history, with garnet forming during the late Mesoproterozoic and limited preservation of high‐pressure Caledonian assemblages. Similar to the Ulsteinvik metapelite, zircon and rutile age data from the Fjørtoft metapelite also record pre‐Scandian Caledonian ages. Two potential tectonic scenarios are possible: (1) The samples were exhumed at different times during pre‐Scandian subduction of the Blåhø nappe, or (2) the samples do not share a history in the same nappe complex, instead the Ulsteinvik metapelite is a constituent of the Seve‐Blåhø Nappe, whilst the Fjørtoft metapelite shares its history within a separate nappe complex.
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