Search

The volatile transfer in subduction zones and the role of sulfate as a vector for the mobilization of oxidized components from down-going slabs remain hotly debated issues. Orogenic spinel and garnet peridotite lenses from the Ulten Zone (Eastern Alps, Italy), exhumed as part of felsic metamorphic terranes in continental collision zones, bear witness to mass transfer processes in these pivotal environments. In this study, we carried out a multi-method investigation of mantle sulfides coexisting with four generations of carbonates, indicating coupled sulfur and carbon mobility throughout the peridotites’ metamorphic evolution as part of the Variscan subduction architecture. Detailed petrography, bulk rock measurements, in situ chemical and geochemical analyses of sulfides as well as Sr isotope analyses of associated clinopyroxene and amphibole are combined with the aim to constrain the origin, nature and effect of multiple C-O-H-S-bearing fluids and melts the peridotites interacted with. The first, pre-peak, metasomatic pulse (Stage 1) is represented by an H2S-CO2-bearing melt from the subduction-modified hot mantle wedge, which formed a pyroxenite layer hosting matrix pentlandite with δ34S of +2.77‰. Matrix carbonates occasionally occur in the coarse-grained peridotite under eclogite-facies conditions (Stage 2), with heavier δ34S (up to +3.43‰), radiogenic Sr (87Sr/86Srclinopyroxene > 0.7052) and elevated Pb abundances. These are ascribed to interaction with isotopically heavy melts carrying recycled crustal component, permissive of, but not requiring, involvement of oxidized S species. Conversely, isotopically lighter matrix pentlandite (δ34S = −1.62 to +0.67‰), and radiogenic Sr in amphibole (87Sr/86Sr = 0.7056) and associated dolomite (published data) from fine-grained garnet-amphibole peridotites may point to involvement of H2S-CO2-bearing crustal fluids, which variably equilibrated with the mantle before interacting with the peridotites. The post-peak Stage 3 marks the entrapment of peridotites into a tectonic melange. Here, kelyphitization of garnet is catalyzed by further ingress of a S-bearing fluid (δ34S = −0.38‰), while carbonate veining with occasional sulfides bear witness to channelized fluid flow. Sulfide and amphibole grains in retrogressed spinel peridotites reveal the highest contents of fluid-mobile elements (As, Sb) and 87Sr/86Sramphibole up to 0.7074, suggesting late interactions with isotopically heavy crustal fluids at high fluid-rock ratios. Textural observations indicate that, during Stage 4, serpentinization of peridotites at low ƒS2 played an active role not only in CO2 release by conversion of dolomite to calcite + brucite intergrowths, but also in local removal of 32S during the final exhumation stage. Late channelized sulfur remobilization is evidenced by the serpentine + magnetite (±millerite ± calcite) vein carrying > 300 ppm S. Overall, the relatively narrow range of sulfur isotope composition (δ34S = −1.62 to +3.76‰) is indicative of limited interaction with isotopically heavy crustal liquids, and points to a subordinate role of subduction-derived sulfate throughout the extended fluid(melt)/rock evolution of the Ulten Zone peridotites, first in the mantle wedge and then as part of a tectonic melange.

Understanding the physical basics of tectonic events, related fluid flow and ore deposition represents one of the great challenges in modern geosciences. In this contribution, Sm-Nd ages of hydrothermal fluorites and U-Pb ages of carbonates and iron oxides from unconformity-related vein type deposits in the Schwarzwald next to the Upper Rhinegraben rift in SW Germany are used to distinguish different pulses of hydrothermal fluid activity and to understand their relation to large-scale tectonics and magmatism. While the fluorites are of Early Jurassic to Oligocene age, carbonate (calcite, dolomite, siderite) and hematite dated by U-Pb small-scale isochrons records formation from Permian to Quaternary with a clear culmination in the Neogene. These new age-data in combination with microthermometry data of primary fluid inclusions from growth zones in the fluorites and carbonates are used to constrain the timing of fluid signatures. This contribution shows that the ages are correlated with changes in fluid properties and/or tectonic events in the evolving continental crust. Comparison with published thermochronological data, apparent ages of URG-related volcanic rocks and the tectono-sedimentary evolution of the Upper Rhinegraben rift show clear correlations between the intensity of hydrothermal mineralization (and, hence, the intensity of fracture-bound fluid flow) with the U-Pb carbonate ages. This method accordingly provides an excellent tool to date rift-related processes like fluid flow, ore deposition and tectonic activation or reactivation of fractures. Fluid properties changed after the deposition of Middle Triassic Muschelkalk evaporites from low salinity, high temperature (1–6 wt.% NaCleq, 200–270 °C, cooling late-metamorphic basement fluids) to high salinity, moderate temperature (20–26 wt.% (NaCl + CaCl2), 50–170 °C, mixture of a modified bittern brine (“basement brine”) with halite dissolution brine). This change led to large scale ore deposition (fluorite-barite-quartz with Pb-Zn-Cu, Bi-Co-Ni-Ag-U, Fe-Mn ores). During the Paleogene and Neogene, previously separated aquifers from various sedimentary units were connected by juxtaposition of the fluid source rocks during Rhinegraben rifting, which resulted in variable salinity and temperature fluids (1–26 wt. % (NaCl + CaCl2), 50–350 °C) by a multi-component fluid mixing process. Typical mineralization related to this shows barren or Pb-Zn-Cu veins with large amounts of barite.

The majority of hydrothermal vein systems of economic interest occur at relatively shallow crustal levels, although many of them formed at significantly greater depths. Their present position is a consequence of uplift and erosion. Although, many aspects of their formation are well constrained, the temporal chemical evolution of such systems during uplift and erosion is still poorly understood. These vein minerals comprise calcite, dolomite-ankerite, siderite-magnesite, anhydrite and gypsum forming the last gangue assemblages in Jurassic and Tertiary sulphide-fluorite-quartz-barite veins of the Schwarzwald mining district, SW Germany. Mineral textures of samples from nine localities reveal that in these sequences, mineral precipitation follows a recurring pattern: early calcite is followed by anhydrite or gypsum, siderite and/or dolomite. This succession may repeat up to three times. In-situ (LA-ICP-MS) U-Pb age dating of 15 carbonates from three subsequent generations of the late-stage vein assemblage yield robust ages between 20 and 0.6 Ma. Each mineral sequence forms in a distinctive period of about 2–5 Ma. These ages clearly relate these late-stage mineral phases to the youngest geological episode of the Schwarzwald, which is associated with the Cenozoic Rhine Graben rifting and basement uplift. Based on thermodynamic modelling, the formation of the observed mineral assemblages required an deeply sourced Mg-, Fe- and SO4-rich fluid (b), which was episodically mixed with a shallow crustal HCO3-rich fluid (a). As a consequence of fluid mixing, concentrations of Mg, Fe and SO4 temporarily increased and initiated the formation of the observed sulphate-carbonate mineral sequences. This discontinuous large-scale vertical fluid mixing was presumably directly related to episodes of active tectonics associated with the Cenozoic strike-slip regime of the Upper Rhine Graben. Analogously, episodic fluid mixing is a major key in the formation of older (Jurassic to early Tertiary) Pb-Zn-fluorite-quartz-barite assemblages in the same specific vein systems, albeit involving different fluid compositions. Late-stage hydrothermal (∼20–70 °C) vein assemblages reported in this study record the transition from deep (>2 km) to very shallow (0–1 km) crustal conditions. As a consequence of successive uplift, increasing proportions of shallower and cooler (∼50–70 °C) fluids could take part in such mixing processes. Associated changes in the fluid composition caused the vein mineralogy to change from sulphide-quartz-fluorite-barite to calcite-anhydrite/gypsum-siderite-dolomite, as the system passively ascended closer to the surface.

The Troodos igneous complex (Cyprus) is a ca. 90 Ma old, well preserved supra-subduction zone ophiolite. Troodos is unique in that it shows evidence of fluid-saturation throughout the complex, from its base (i.e. podiform chromitites) to its uppermost units – the upper pillow lavas (UPL). However, it is unclear what the source of dissolved water in UPL tholeiites is, with possibilities including shallow seawater infiltration, assimilation of altered Troodos oceanic crust, recycled serpentinized oceanic crust, or subducted pelagic sediments. In order to identify and characterize these components we have carried out a detailed high-resolution study on tholeiitic lavas on orbicular structures and glasses from the UPL in Troodos. Basaltic orbicules were measured for their Sr–Nd–Hf–Pb isotope compositions, and in situ for their B isotopes using LA-MC-ICP-MS. UPL orbicules display a very narrow range in ∊∊Nd and ∊∊Hf (+7 to +8 and +13 to +15, respectively) indicating melting of a depleted mantle source. Lead isotopes, specifically 207Pb/204Pb vs. 206Pb/204Pb, form a mixing array with pelagic sediments. Furthermore, high-resolution characterization of individual orbicules revealed that UPL tholeiites display strong variability in 87Sr/86Sr (0.7039–0.7060) at the outcrop scale. Samples display δ11δ11B between −8.2 (±±0.5)‰ and +5.9 (±±1.1)‰ with an average B content of ca. 5 μg/g. Contrary to expectation, altered orbicules and their associated hyaloclastite matrixes display lower δ11δ11B (down to −10‰) and higher B contents (max. 200 μg/g) when compared to fresh glass. Furthermore, the orbicules studied here show little or no evidence of interaction with seawater, which is supported by their trace element contents and isotope compositions. When all isotope systems are taken into account, UPL lavas reflect melting of a depleted mantle source that was overprinted by hydrous sediment melts, and potentially, fluid-like subduction components that in part originate from serpentinized oceanic crust. Subsequent low-temperature alteration then drove δ11δ11B to lower values coupled with increased B uptake due to its adsorption into palagonite.

Diamond- and kyanite-bearing eclogites from the Lace kimberlite on the Kaapvaal craton have common picritic to gabbroic oceanic protoliths with bimineralic eclogites, lying on arrays of Eu∗ and ∑REE that are consistent with accumulation and fractionation of plagioclase and olivine. However, they also show significant compositional differences, such as more grossular-rich garnet and aluminous clinopyroxene (cpx), which require the operation of additional processes. Their nature is elucidated using mineral major- and trace-element compositions, as well as Sr isotope ratios determined by in situ techniques. Highly variable major-element compositions across the co-genetic eclogite suites exert a strong effect on the trace-element distribution between garnet and cpx, whereby Sc, Ge, Sr, Y, Cd, REE, Th and U partition more strongly into garnet with increasing grossular-content. Thus, significant differences between the trace-element compositions of garnet can ensue from crystal-chemical effects alone, making their use as petrogenetic indicators potentially ambiguous. After correcting for these compositional effects, garnet in kyanite-/diamond eclogites, and in eclogites devoid of accessory minerals but with similar signatures, shows depletion (or dilution) in Sc, Ge, Y, In, Zr, Hf and the HREE, and enrichment in the LREE and Th compared to garnet in bimineralic eclogites. This is interpreted as the signature of a pelite-derived melt, which was transferred by addition of aluminous cpx that later exsolved kyanite and garnet, as observed in other aluminous eclogite suites. Continental input can explain initial (at 2.9 Ga) 87Sr/86Sr ⩾ 0.714 measured in cpx in eleven samples with low 87Rb/86Sr ( This model of sediment melt–oceanic crust interaction reconciles evidence for both low- and high-pressure igneous processes in some aluminous eclogites. We suggest that a subduction melange is a favourable setting for the transfer of a sediment-derived signature into oceanic crust, leading to formation of diamondiferous kyanite–eclogites from bimineralic eclogites. Diapirism, fluxed by the presence of partial melt, may have facilitated dispersal of the eclogites in the lithosphere column, consistent with their widely varying equilibration pressures ranging from ∼5 to 8 GPa.

Results from laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS) and isotope dilution (ID) analyses of minerals and rocks from a single outcrop of the Venetia Klippe of the Limpopo Belt indicate that the U–Pb and Hf isotope system homogenized on the decimetre scale under amphibolite-facies conditions of ⩽645 ± 25 °C and ⩽7.0 ± 1.1 kbar, i.e. in the presence of an aqueous fluid phase. For a metabasite sample, homogenization is supported by isotope analyses of metamorphic zircon, garnet, and whole rock, which yield a six-point Lu–Hf isochron age of 2039.7 ± 3.4 Ma, with initial 176Hf/177Hf of 0.28126 ± 0.00001, and a U–Pb zircon age of 2042 ± 10 Ma. The occurrence of a few inherited magmatic zircon cores with ages up to 2705 Ma, and with significantly lower initial 176Hf/177Hf of 0.28112, however, indicate that homogenization was incomplete. For a chlorite–biotite–garnet schist isotope homogenization is reflected by within error identical zircon and monazite U–Pb ages of 2045 ± 10 Ma and 2041 ± 8 Ma, respectively, and by a zircon-garnet-whole rock Lu–Hf isochron age of 2083 ± 63 Ma, with an initial 176Hf/177Hf of 0.28140 ± 0.00003. Contemporaneous formation of metamorphic zircon, monazite and garnet in the chlorite schist is not only supported by the isotope data, but also by chlorite inclusions in all three minerals, and by inclusions of metamorphic zircon in garnet. The inclusion textures and the identical initial 176Hf/177Hf support the conclusion that metamorphic zircon grains precipitated from an aqueous fluid phase, after dissolution of zirconium-bearing phases elsewhere, followed by a major HFSE transport, and Hf isotope homogenization. This fluid perhaps was Ca-bearing, as is suggested by the fact that garnet in the schist sample is the only Ca-bearing phase, and that metamorphic monazite, dating the metamorphic peak, is partially replacement by apatite. The fact that the metamorphic zircon rims in the metabasite sample have significantly lower initial 176Hf/177Hf than expected from the Lu–Hf isotope analyses of relic zircon cores and whole rock additionally hint that Ca-HFSE-bearing fluids infiltrated from surrounding quartzo-feldspathic gneisses, which had much lower 176Hf/177Hf at the time of metamorphism.

Subcalcic garnets carry the major inventory of most trace elements of their host harzburgites and are thus proxies of the bulk composition. We used single garnet grains from heavy mineral concentrates from the Kaapvaal craton (Roberts Victor and Lace mine) to determine the major and trace elements and the Sm–Nd and Lu–Hf isotope systematics of these highly depleted members of the peridotitic suite. The combination of the results with previous work from the Finsch mine (Lazarov et al., 2009a) allowed us to reconstruct the formation and evolution of the mantle underneath the Kaapvaal craton. Several lines of evidence from major and trace elements suggest that mantle melting was mainly at shallow pressures followed by subduction into the garnet stability field. A 3.22 Ga metasomatic event underneath the East block occurred in a previously depleted mantle (eHf = +16) which was sufficiently stabilized by that time to hold a crust with tonalite–trondhjemite–granodiorite (TTG’s) and greenstone belts. Such high eHf values can be produced within a few hundred million years by 25% non-modal fractional melting in the spinel stability field. This is the first prove of a mantle underneath the East block with an age similar to a 3.65 Ga crustal age. Before the amalgamation around 2.88 Ga, oceanic lithosphere was created between the W- and E-block around 2.95 Ga (group RV1 samples from the Roberts Victor) and subducted underneath the W-block. Another mantle portion (group RV2 garnets) from Roberts Victor yielded a seeming age of 3.27 ± 0.15 Ga with eHf = +17.6. It actually results from an enrichment process in a highly depleted mantle about 2.8–2.9 Ga ago. This may have been the depleted mantle wedge above the subduction and final collision between the West and the East block. The creation of a cratonic nucleus for the West-block is unknown until 3.2 Ga when the oldest mantle TRD and oldest crustal zircon ages are reported. Such ages were not directly obtained from the study of the subcalcic garnets but the high positive eHf value (+25) of the 2.62 Ga enrichment age from Finsch and the existence of a highly depleted mantle wedge before 2.8–2.9 Ga at Roberts Victor suggests that the depletion occurred several hundred million years earlier. Subsequently, the 2.6–2.8 Ga old voluminous Ventersdoorp volcanics poured over a major part of the unified Kaapvaal craton, an event which also may have modified portions of the mantle underneath Finsch. The attachment of the Kheis–Magondi belt to the Kaapvaal craton from the West caused further modification around 1.90 Ga. The latest stages of craton-scale metasomatism recorded in the subcalcic garnets lie between 0.9 and 1.3 Ga as can be seen in the Sm–Nd isotope systematic. This age range coincides with the Namaqua–Natal belt orogeny. The present study and previous work on subcalcic garnets show that they can be excellent recorders of multiple mantle events which can be correlated with the tectonomagmatic evolution of the craton.

Hafnium isotope analyses of a large number of metamorphic zircon grains of two garnet-kyanite-staurolite schist samples from the Shackleton Range yielded 176Hf/177Hf of 0.28160 ± 0.00003 and 0.28142 ± 0.00003, respectively. The variations of these analyses are less than ±1.2 epsilon units and indicate that all metamorphic zircon grains in the two rocks formed in environments with nearly homogenous Hf isotopic composition. The metamorphic origin of the zircon grains is constrained by textures as well as by their low Th/U (

Detrital zircon grains from Beit Bridge Group quartzite from the Central Zone of the Limpopo Belt near Musina yield mostly ages of 3.35–3.15 Ga, minor 3.15–2.51 Ga components, and numerous older grains grouped at approximately 3.4, 3.5 and 3.6 Ga. Two grains yielded concordant Late Hadean U–Pb ages of 3881 ± 11 Ma and 3909 ± 26 Ma, which are the oldest zircon grains so far found in Africa. The combined U–Pb and Lu–Hf datasets and field relationships provide evidence that the sedimentary protolith of the Beit Bridge Group quartzite was deposited after the emplacement of the Sand River Gneisses (3.35–3.15 Ga), but prior to the Neoarchean magmatic-metamorphic events at 2.65–2.60 Ga. The finding of abundant magmatic zircon detritus with concordant U–Pb ages of 3.35–3.15 Ga, and 176Hf/177Hf of 0.28066 ± 0.00004 indicate that the Sand River Gneiss-type rocks were a predominant source. In contrast, detrital zircon grains older than approximately 3.35 Ga were derived from the hinterland of the Limpopo Belt; either from a so far unknown crustal source in southern Africa, possibly from the Zimbabwe Craton and/or a source, which was similar but not necessarily identical to the one that supplied the Hadean zircons to Jack Hills, Western Australia. The Beit Bridge Group zircon population at >3.35 Ga shows a general eHft increase with decreasing age from eHf3.9Ga = −6.3 to eHf3.3–3.1Ga = −0.2, indicating that Hadean crust older than 4.0 Ga (TDM = 4.45–4.36 Ga) was rejuvenated during magmatic events between >3.9 and 3.1 Ga, due to a successive mixing of crustal rocks with mantle derived magmas. The existence of a depleted mantle reservoir in the Limpopo’s hinterland is reflected by the ∼3.6 Ga zircon population, which shows eHf3.6Ga between −4.6 and +3.2. In a global context, our data suggest that a long-lived, mafic Hadean protocrust with some tonalite–trondhjemite–granodiorite constituents was destroyed and partly recycled at the Hadean/Archean transition, perhaps due to the onset of modern-style plate tectonics.

In this study, we link mineral inclusion data, trace element analyses, U–Pb age and Hf isotope composition obtained from distinct zircon domains of complex zircon to unravel the origin and multi-stage metamorphic evolution of amphibolites from the Sulu ultrahigh-pressure (UHP) terrane, eastern China. Zircon grains separated from amphibolites from the CCSD-MH drill hole (G12) and Niushan outcrop (G13) were subdivided into two main types based on cathodoluminescence (CL) and Laser Raman spectroscopy: big dusty zircons with inherited cores and UHP metamorphic rims and small clear zircons. Weakly zoned, grey-white luminescent inherited cores preserve mineral inclusions of Cpx + Pl + Ap ± Qtz indicative of a mafic igneous protolith. Dark grey luminescent overgrowth rims contain the coesite eclogite-facies mineral inclusion assemblage Coe + Grt + Omp + Phe + Ap, and formed at T = 732–839 °C and P = 3.0–4.0 GPa. In contrast, white luminescent small clear zircons preserve mineral inclusions formed during retrograde HP quartz eclogite to LP amphibolite-facies metamorphism (T = 612–698 °C and P = 0.70–1.05 GPa). Inherited zircons from both samples yield SHRIMP 206Pb/238U ages of 695–520 Ma with an upper intercept age of 800 ± 31 Ma. The UHP rims yield consistent Triassic ages around 236–225 and 239–225 Ma for G12 and G13 with weighted means of 229 ± 3 and 231 ± 3 Ma, respectively. Small clear zircons from both samples give 206Pb/238U ages around 219–210 Ma with a weighted mean of 214 ± 3 Ma, interpreted as the age of retrograde quartz eclogite-facies metamorphism. Matrix amphibole from both samples indicate Ar–Ar ages of 209 ± 0.7 and 207 ± 0.7 Ma, respectively, probably dating late amphibolite-facies retrogression. The data suggest subduction of Neoproterozoic mafic igneous rocks to UHP conditions in Middle Triassic (∼230 Ma) times and subsequent exhumation to an early HP (∼214 Ma) and a late LP stage (∼208 Ma) over a period of ∼16 and 6 Myr, respectively. Thus, early exhumation from a mantle depth of 120–100 km to about 60 km occurred at an average rate of 0.3 cm/y, while subsequent exhumation to a middle crustal level took place at approximately 0.54 cm/y. These exhumation rates are considerably slower than those obtained for UHP rocks in the Dora Maira and Kokchetav massifs (2–3 cm/y). Based on similar P–T estimates and trace element and Hf isotope compositions, Sulu amphibolites can be identified as retrograde UHP eclogites. The eHf(800) of +8 implies a significant input from the depleted mantle to the Sulu–Dabie terrane during the middle Neoproterozoic. Overgrown rims are characterized by a distinct trace element composition with low Lu/Hf and Th/U and significantly higher 176Hf/177Hf ratios than inherited cores, consistent with formation during/after garnet (re-)crystallization and fractionation of the Lu–Hf system during UHP metamorphism. The combined dataset suggests homogenization of the 176Hf/177Hf ratio within the metamorphic mineral assemblage and during protolith formation. Observed variations are explained by mixing of material from both domains during laser ablation, e.g., due to partial recrystallization of inherited cores.

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the 238U/235U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed 236U–233U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ238U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ238U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ238U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ238U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ238U (−0.41‰ to −0.16‰) compared to seawater, which has δ238U of −0.41 ± 0.03‰. Granites define a range of δ238U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ238U = −0.29‰). Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble UVI to insoluble UIV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that 238U/235U varies in nature also has implications for the precision and accuracy of U–Pb dating. The total observed range in U isotope compositions would produce variations in 207Pb/206Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.