Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Significance of ancient sulfide PGE and Re–Os signatures in the mantle beneath Calatrava,Central Spain

Spinel lherzolite and wehrlite xenoliths from the Cenozoic Calatrava volcanic field carry the geochemical imprint of metasomatic agents that have affected the subcontinental lithospheric mantle beneath Central Iberia. Some xenoliths (mainly wehrlites) were enriched in REE, Sr, P, and CO₂ by silicic-carbonate-rich metasomatic melts/fluids, while others record the effects of subduction-related hydrous silicate fluids that have precipitated amphibole and induced high Ti/Eu in primary clinopyroxene. The petrographic observations and geochemical data suggest that interstitial glass in the xenoliths represent the quenched products of Si-rich melts that infiltrated the mantle peridotite shortly before the entrainment of the xenoliths in the host magmas that erupted ca 2 million years ago. During their infiltration, the metasomatic melts reacted with peridotite, resulting in silica enrichment, while remobilizing grains of iron-rich monosulfide solid solution (Fe-rich Mss) initially enclosed in, or intergranular to, primary olivine and pyroxenes. In situ laser ablation inductively coupled plasma-mass spectrometry analysis of single sulfide grains reveals that the Fe-rich Mss in glass shows platinum-group element (PGE) patterns and ¹⁸⁷Os/¹⁸⁸Os compositions identical to the Fe-rich Mss occurring as inclusions in, or at grain boundaries of primary silicates. Moreover, independent of its microstructural position, Fe-rich Mss exhibits PGE and ¹⁸⁷Os/¹⁸⁸Os signatures typical of Mss either residual after partial melting or crystallized directly from sulfide melts. Our findings reveal that young metasomatic melt(s)/fluid(s) may carry remobilized sulfides with PGE and Os-isotopic signatures identical to those of texturally older sulfides in the peridotite xenolith. These sulfides thus still provide useful information about the timing and nature of older magmatic events in the subcontinental mantle.     

Dissolution–precipitation processes governing the carbonation and silicification of the serpentinite sole of the New Caledonia ophiolite

The weathering of mantle peridotite tectonically exposed to the atmosphere leads commonly to natural carbonation processes. Extensive cryptocrystalline magnesite veins and stock-work are widespread in the serpentinite sole of the New Caledonia ophiolite. Silica is systematically associated with magnesite. It is commonly admitted that Mg and Si are released during the laterization of overlying peridotites. Thus, the occurrence of these veins is generally attributed to a per descensum mechanism that involves the infiltration of meteoric waters enriched in dissolved atmospheric CO₂. In this study, we investigate serpentinite carbonation processes, and related silicification, based on a detailed petrographic and crystal chemical study of serpentinites. The relationships between serpentine and alteration products are described using an original method for the analysis of micro-X-ray fluorescence images performed at the centimeter scale. Our investigations highlight a carbonation mechanism, together with precipitation of amorphous silica and sepiolite, based on a dissolution–precipitation process. In contrast with the per descensum Mg/Si-enrichment model that is mainly concentrated in rock fractures, dissolution–precipitation process is much more pervasive. Thus, although the texture of rocks remains relatively preserved, this process extends more widely into the rock and may represent a major part of total carbonation of the ophiolite.     

Enrichments of the mantle sources beneath the Southern Volcanic Zone (Andes) by fluids and melts derived from abraded upper continental crust

Mafic basaltic-andesitic volcanic rocks from the Andean Southern Volcanic Zone (SVZ) exhibit a northward increase in crustal components in primitive arc magmas from the Central through the Transitional and Northern SVZ segments. New elemental and Sr–Nd-high-precision Pb isotope data from the Quaternary arc volcanic centres of Maipo (NSVZ) and Infernillo and Laguna del Maule (TSVZ) are argued to reflect mainly their mantle source and its melting. For the C-T-NSVZ, we identify two types of source enrichment: one, represented by Antuco in CSVZ, but also present northward along the arc, was dominated by fluids which enriched a pre-metasomatic South Atlantic depleted MORB mantle type asthenosphere. The second enrichment was by melts having the characteristics of upper continental crust (UCC), distinctly different from Chile trench sediments. We suggest that granitic rocks entered the source mantle by means of subduction erosion in response to the northward increasingly strong coupling of the converging plates. Both types of enrichment had the same Pb isotope composition in the TSVZ with no significant component derived from the subducting oceanic crust. Pb–Sr–Nd isotopes indicate a major crustal compositional change at the southern end of the NSVZ. Modelling suggests addition of around 2 % UCC for Infernillo and 5 % for Maipo.     

Amphibole as an archivist of magmatic crystallization conditions: problems,potential, and implications for inferring magma storage prior to the paroxysmal 2010 eruption of Mount Merapi,Indonesia

Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO₂, melt H₂O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO₂ and melt SiO₂ content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H₂O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H₂O, and ~58–71 wt% melt SiO₂. We interpret the variations in calculated temperature, fO₂, and melt SiO₂ content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km³ Ongatiti and ~1.0 Ma ~1,200 km³ Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km³ Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE³⁺)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.     

Building zoned ignimbrites by recycling silicic cumulates: insight from the 1,000 km<Superscript>3</Superscript> Carpenter Ridge Tuff,CO

The ~1,000 km³ Carpenter Ridge Tuff (CRT), erupted at 27.55 Ma during the mid-tertiary ignimbrite flare-up in the western USA, is among the largest known strongly zoned ash-flow tuffs. It consists primarily of densely welded crystal-poor rhyolite with a pronounced, highly evolved chemical signature (high Rb/Sr, low Ba, Zr, Eu), but thickly ponded intracaldera CRT is capped by a more crystal-rich, less silicic facies. In the outflow ignimbrite, this upper zone is defined mainly by densely welded crystal-rich juvenile clasts of trachydacite composition, with higher Fe–Ti oxide temperatures, and is characterized by extremely high Ba (to 7,500 ppm), Zr, Sr, and positive Eu anomalies. Rare mafic clasts (51–53 wt% SiO₂) with Ba contents to 4,000–5,000 ppm and positive Eu anomalies are also present. Much of the major and trace-element variations in the CRT juvenile clasts can be reproduced via in situ differentiation by interstitial melt extraction from a crystal-rich, upper-crustal mush zone, with the trachydacite, crystal-rich clasts representing the remobilized crystal cumulate left behind by the melt extraction process. Late recharge events, represented by the rare mafic clasts and high-Al amphiboles in some samples, mixed in with parts of the crystal cumulate and generated additional scatter in the whole-rock data. Recharge was important in thermally remobilizing the silicic crystal cumulate by partially melting the near-solidus phases, as supported by: (1) ubiquitous wormy/sieve textures and reverse zoning patterns in feldspars and biotites, (2) absence of quartz in this very silicic unit stored at depths of >4–5 km, and (3) heterogeneous melt compositions in the trachydacite fiamme and mafic clasts, particularly in Ba, indicating local enrichment of this element due mostly to sanidine and biotite melting. The injection of hot, juvenile magma into the upper-crustal cumulate also imparted the observed thermal gradient to the deposits and the mixing overprint that partly masks the in situ differentiation process. The CRT provides a particularly clear perspective on processes of in situ crystal-liquid separation into a lower crystal-rich zone and an upper eruptible cap, which appears common in incrementally built upper-crustal magma reservoirs of high-flux magmatic provinces.     

Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples

Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V–Nb partitioning and dependence on oxygen fugacity (expressed as fO₂) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains (n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7–1,200 ppm) and V concentrations (50–3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of ^RtD_V and V valence with ?QFM, we suggest that the priority order of V incorporation into rutile is V⁴⁺ > V³⁺ > V⁵⁺. The inferred Nb–V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO₂ due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V³⁺ (expressed as V³⁺/∑V) and attendant decrease in ^RtD_V is suggested to lead to an increase in rutile lattice sites available for Nb⁵⁺. A similar effect may be observed under more oxidizing conditions. When V⁵⁺/∑V increases, ^RtD_V shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica–amphibole–rutile–ilmenite–diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V–Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5–15). This relationship is mainly controlled by a change in Nb concentrations, suggesting that the indirect dependence of ^RtD_Nb on fO₂, which is not mirrored in ^RtD_Ta, can exert considerable influence on rutile Nb–Ta fractionation.     

Jurassic plume-origin ophiolites in Japan: accreted fragments of oceanic plateaus

The Mikabu and Sorachi–Yezo belts comprise Jurassic ophiolitic complexes in Japan, where abundant basaltic to picritic rocks occur as lavas and hyaloclastite blocks. In the studied northern Hamamatsu and Dodaira areas of the Mikabu belt, these rocks are divided into two geochemical types, namely depleted (D-) and enriched (E-) types. In addition, highly enriched (HE-) type has been reported from other areas in literature. The D-type picrites contain highly magnesian relic olivine phenocrysts up to Fo_93.5, and their Fo–NiO trend indicates fractional crystallization from a high-MgO primary magma. The MgO content is calculated as high as 25 wt%, indicating mantle melting at unusually high potential temperature (T _p) up to 1,650 °C. The E-type rocks represent the enrichment in Fe and LREE and the depletion in Mg, Al and HREE relative to the D-type rocks. These chemical characteristics are in good accordance with those of melts from garnet pyroxenite melting. Volcanics in the Sorachi–Yezo belts can be divided into the same types as the Mikabu belt, and the D-type picrites with magnesian olivines also show lines of evidence for production from high T _p mantle. Evidence for the high T _p mantle and geochemical similarities with high-Mg picrites and komatiites from oceanic and continental large igneous provinces (LIPs) indicate that the Mikabu and Sorachi–Yezo belts are accreted oceanic LIPs that were formed from hot large mantle plumes in the Late Jurassic Pacific Ocean. The E- and D-type rocks were formed as magmas generated by garnet pyroxenite melting at an early stage of LIP magmatism and by depleted peridotite melting at the later stage, respectively. The Mikabu belt characteristically bears abundant ultramafic cumulates, which could have been formed by crystal accumulation from a primary magma generated from Fe-rich peridotite mantle source, and the HE-type magma were produced by low degrees partial melting of garnet pyroxenite source. They should have been formed later and in lower temperatures than the E- and D-type rocks. The Mikabu and Sorachi Plateaus were formed in a low-latitude region of the Late Jurassic Pacific Ocean possibly near a subduction zone, partially experienced high P/T metamorphism during subduction, and then uplifted in association with (or without, in case of Mikabu) the supra-subduction zone ophiolite. The Mikabu and Sorachi Plateaus may be the Late Jurassic oceanic LIPs that could have been formed in brotherhood with the Shatsky Rise.     

Emplacement ages and sources of kimberlites and related rocks in southern Africa: U–Pb ages and Sr–Nd isotopes of groundmass perovskite

Groundmass perovskite has been dated by LA-ICPMS in 135 kimberlites and related rocks from 110 localities across southern Africa. Sr and/or Nd isotopes have been analysed by LA-MC-ICPMS in a subset of these and integrated with published data. The age distribution shows peaks at 1,600–1,800, 1,000–1,200, 500–800 and 50–130 Ma. The major “bloom” of Group I kimberlites at ca 90 ± 10 Ma was preceded by a slow build-up in magmatic activity from ca 180 Ma. The main pulse of Group II kimberlites at 120–130 Ma was a distinct episode within this build-up. Comparison of the isotopic data with seismic tomography images suggests that metasomatized subcontinental lithospheric mantle (SCLM) with very low ε _Nd and high ⁸⁷Sr/⁸⁶Sr, (the isotopic signature of Group II kimberlites) was focused in low-Vs zones along translithospheric structures. Such metasomatized zones existed as early as 1,800 Ma, but were only sporadically tapped until the magmatic build-up began at ca 180 Ma, and contributed little to the kimberlitic magmas after ca 110 Ma. We suggest that these metasomatized volumes resided in the deep SCLM and that their low-melting point components were “burned off” by rising temperatures, presumably during an asthenospheric upwelling that led to SCLM thinning and a rise in the ambient geotherm between 120 and 90 Ma. The younger Group I kimberlites therefore rarely interacted with such SCLM, but had improved access to shallower volumes of differently metasomatized, ancient SCLM with low ⁸⁷Sr/⁸⁶Sr and intermediate ε _Nd (0–5). The kimberlite compositions therefore reflect the evolution of the SCLM of southern Africa, with metasomatic-enrichment events from as early as 1.8 Ga, through a major thermal and compositional change at ca 110 Ma, and the major kimberlite “bloom” around 90 Ma.