Bulk Rock Research Articles

Tracing Lower Crustal Contamination in Continental Arc Magmas Using Sr–Nd–Hf Isotopes: A Combined In Situ and Bulk Rock Approach Applied to the Adamello Batholith

Abstract The incremental construction of plutons characterises magmatic activity in arc settings, where new continental crust is produced. This polyphasic growth entails interactions with one or more crustal components, which modulate the geochemical and isotopic compositions of the newly formed crust. However, the early stages of magmatism are not always preserved due to obliteration by later magmatic pulses. Spatial migration of magmatism during the construction of the Adamello batholith (Northern Italy) enables the examination of the early pulses of pluton formation, thus allowing a time-integrated study of the relative importance of crystallisation-differentiation and contamination in a continental arc setting. We conducted a detailed textural, major and trace element and Sr isotopic study of plagioclase from the first intrusive pulses of the Adamello batholith, combined with new major, trace element and Sr–Nd isotopic analyses of bulk rock samples across the entire Adamello batholith. We selected well-characterised samples with published CA-ID-TIMS 206Pb-238U ages and Hf isotopic composition for zircons. Strontium isotopes in plagioclase from the same samples were determined by laser ablation multi-collector ICP-MS. The tonalitic samples in the early magmatic stages show elevated but constant Sr isotopic compositions despite large variations in anorthite contents (An90 to An13), indicating that crustal contamination occurred before significant differentiation. Invariant bulk-rock 87Sr/86Sr with variable SiO2 in all superunits of the Adamello batholith further supports contamination preceding significant melt differentiation. Contamination by lower crustal basement lithologies is due to the increasing thermal anomaly triggered by consecutive magmatic injections coupled with the heterogeneous and less restitic nature of the basement in the early stage of the magmatic system (i.e., before consumption of fusible components). In addition, we observe significant variability in crustal contamination proxies (e.g., 87Sr/86Srplag, 87Sr/86Srbulk, εNdbulk, εHfzircon) during the initial phases of magmatism. This variability likely reflects the uneven distribution of positive thermal anomalies in the lower crust during early magmatic stages as well as the diverse lithological and isotopic makeup of the lower crust. The processes identified in our case study are pertinent to continental arc magmatism, particularly where magmas interact with a metapelitic lower crust.

Alkaline Devonian magmatism of the Menorca Island: Tracking the mantle isotopic sources in the realm of the western Paleo-Tethys Ocean

Several locations with alkaline magmatism are recognised in Silurian-Devonian basins along the southern variscan autochthon units (e.g. Central Iberian Zone) of the northern Gondwana margin. The origin of the Devonian basins and their magmatism has not been studied in the context of the passive margin of Gondwana. The basement of Menorca, Balearic Islands, consists of a deep Devonian-Carboniferous basin with mafic igneous rocks, the Tramuntana Gabbros. In this study, we trace the geodynamic setting and isotopic sources of the Tramuntana Gabbros through elemental geochemistry, isotopic geochemistry (SrNd) and UPb geochronology in zircons. These gabbros are the product of an intraplate alkaline magmatism with immobile trace element and REE contents similar to those of Ocean Island Basalts. Average 87Sr/86Sr(370) of 0.708456 and εNd(370) of +4.0 indicate a source similar to a Type-2 enriched mantle with average TDM of 665 Ma, suggesting a relatively old metasomatized mantle. Concordant UPb ages of c. 597 Ma (Ediacaran, radiometric age) from a single population of 31 zircons separated from the Tramuntana Gabbros (Devonian, biostratigraphic age) reinforce the presence of older units in the corresponding lithospheric mantle. The Tramuntana Gabbros and the Devonian-Carboniferous sequences of Menorca limit the westward extension of the Paleo-Tethys Ocean, whose development never reached these westernmost regions. Assuming a common sublithospheric mantle source for the peri-Gondwanic Devonian alkaline rocks and considering the previous Cadomian (Neoproterozoic) subduction to be the most favourable origin of the separated zircons, the bulk rock TDM and zircon UPb data obtained from the Tramuntana Gabbros track the mixing, recycling, and mantle accretion in this peri-Gondwanic section from Precambrian to Devonian times.

Finding and identifying platinum group elements in the Eastman layered mafic intrusion

Platinum group elements (PGEs) are commonly hosted by base metal sulfides (BMSs, e.g. chalcopyrite or pentlandite) or platinum group minerals (PGMs). PGE-bearing phases are generally small, ranging from tens of nanometres to a few micrometres. In addition, PGEs can be hosted in PGMs, either intimately associated with BMSs or spatially separated. This poses a difficulty in their detection and analysis, and leads to uncertainty in identification of their mineral hosts. Their erratic occurrence introduces a substantial nugget effect in bulk rock assays, used to evaluate deposit economics on a larger scale. Knowledge of PGE hosts has a direct influence on resource management and extraction efficiency, making the understanding of mineral distribution important for processing. The Eastman Ultramafic Intrusion is a layered mafic–ultramafic intrusive complex in the Eastern Kimberley of Western Australia. Samples from Cu–Co–Ni–PGE exploration drilling at Eastman were bulk-assayed and found to contain up to 2.39 ppm PGEs. The rocks have been strongly altered and no longer represent their primary magmatic mineral assemblage and textures. To better understand the Eastman PGE mineralogy, we applied a multi-method approach of quantitative analytical electron microscopy, 3D scanning and in situ mass spectrometry. We find that Pt is primarily hosted in sperrylite, whereas Pd is mainly associated with kotulskite, pseudomertieite, testibiopalladite, sudburyite and michenerite. Additionally, minor Pt and Pd occur in solid solution within cobaltite, as well as Rh-rich cobaltite (hollingworthite). Spatially, PGMs and cobaltite are mostly clustered on a millimetric scale, and BMSs on a micrometric scale.

Syndepositional and diagenetic processes in the pigmentation of Middle Ordovician carbonate red beds in South China

Marine red beds (MRBs) are often attributed to specific redox environments during syndepositional and early diagenetic phases. During the Middle Ordovician, a succession of reddish, deeper-water nodular argillaceous limestones (i.e., Zitai and Kuniutan formations) were deposited along the margin of Yangtze Platform in South China. However, the origin of their color remains enigmatic. In this study, we investigated the Middle Ordovician MRBs from a borehole core newly drilled in the Lower Yangtze area of South China whose stratigraphy frameworks are constrained by carbon isotope and biostratigraphy. This study investigates the pigmentation of these MRBs by integrating petrographic observations, elemental geochemistry, diffusive reflectance spectrometry (DRS), and scanning electron microscope (SEM) coupled with energy dispersive X-ray spectrometry (EDS). DRS results show that the red pigment is caused by hematite particles in submicron- to micron-level size. SEM demonstrates that the hematite grains are either detrital grains with traces of physical transport from terrestrial source, or flaky amorphous hematite aggregates situated within the calcite crystal interstices, implicating both syndepositional and early diagenetic origins, respectively. In terms of the geochemical result of the bulk rocks, the close positive correlation between Al2O3 and Fe2O3 indicates that the iron pigment materials may mainly originate from terrestrial Fe-bearing phyllosilicates. These observations are also consistent with the distribution patterns of rare earth elements (REEs) in carbonate leachates. The MRB limestones are characterized by MREE-bulged patterns and close to ~1 Ce anomalies, suggesting active reductive dissolution and subsequent reprecipitation of iron oxides during diagenesis in pore systems. This study proposes that the coloration of Middle Ordovician MRBs in Lower Yangtze Platform was linked to the enhanced input of terrestrial clay minerals rich in iron. The reductive dissolution released iron ions from terrestrial detrital and allowed subsequent reprecipitation of iron-oxides in pore water system during the fluid-buffered diagenesis. In this light, hematites formed during both the syndepositional and diagenetic processes thus could have involved the coloration of the Middle Ordovician carbonate red beds in this case.

Evidence for isotopically light Fe mobility under oxidising conditions in subduction zone fluids: A record of Monviso meta-serpentinites, Western Alps

The isotopically light Fe signature of arc magmas relative to mid-oceanic ridge basalts (MORB) is expected to be related to the redox state of their source. This implies a link between Fe mobility and redox variations across subduction zones. Here we address slab chemical variations during prograde metamorphism through a comprehensive geochemical study, including major, trace elements and Fe stable isotope (δ56Fe) analyses, of meta-serpentinites composing the eclogitic meta-ophiolite of the Monviso massif (Western Alps, Italy). These rocks partly preserve mantle related geochemical heterogeneities, as supported by negative correlations between fluid immobile elements (High Field Strong Elements) and LREE/HREE (Light – Heavy Rare Earth Elements) ratios. They are however characterized by large Cs enrichments relative to U or alkali elements suggesting that abyssal fluid mobile elements signature was overprinted by subduction related processes. Meta-serpentinites display large δ56Fe variations, from -0.20 ± 0.05 ‰ to +0.09 ± 0.03 ‰. Mineral separate analyses of olivine bearing veins show low Δ56Fe between olivine and magnetite (∼ 0.4 ‰), which according to Fe isotope thermometry correspond to high temperature equilibration, estimated between 530 and 550 °C, compatible with Monviso metamorphic climax (520–570 °C and 2.6–2.7 GPa). These results, in combination with geochemical modelling, confirm a reset of δ56Fe signature of abyssal serpentinites during prograde metamorphism in subduction zones. The bulk rock δ56Fe values of Monviso meta-serpentinites are negatively correlated with their Fe3+/∑Fe and As concentrations (a redox-sensitive and fluid mobile element). These correlations can be attributed to a metasomatism by external fluids derived from slab serpentinites during subduction. It also concords with the oxygen fugacity (fO2) record in meta-serpentinites, with meta-serpentinites equilibrated at high fO2 displaying the lowest δ56Fe values while samples equilibrated at low fO2 display mantle like δ56Fe signatures. These results highlight that oxidising conditions during serpentinite dehydration are likely to boost isotopically light Fe mobility in slab derived fluids.

Dolomite occurrence within drift deposits, Maldives archipelago

Considerable attention has been dedicated to the sedimentological processes associated with carbonate drift and contourite deposits, but a noticeable gap exists in the understanding of the diagenetic aspects of those deposits, especially dolomitization. This study presents an examination of dolomites from Middle to Late Miocene drift deposits collected during IODP Expedition 359 to the Maldives archipelago. Multiple geochemical parameters and petrographic analysis are used to explore the potential role of closed versus open system dolomitization in the two oldest drift sequences, which are overlain by a multimillion year-long hiatus. Overall, dolomite abundance is variable, but 50 % to nearly 100 % in a 30 m thick interval below the unconformity surface at one of the examined sites. The dolomite in the study interval consists of very fine-to-fine-sized crystalline dolomite cements and mimetically replaced dolomite grains. All dolomite is non-stoichiometric (mean 42.7 ± 2.0 mol% MgCO3) and mostly poorly ordered. Geochemical attributes include relatively invariant δ13C (+1.3 ‰ to +1.7 ‰ VPDB) and relatively high Sr concentrations in dolomite cements (mean 505 ppm) and dolomitized grains (mean 784 ppm). δ18O values and the constraints of burial histories indicate dolomitization in normal marine seawater at burial depths of 0 to 300 m and temperatures of ∼10 °C–14 °C below an ocean water column 100 to 400 m deep. Sr-isotope ages suggest dolomitization of the most extensively dolomitized interval below the unconformity occurred between 12.3 Ma and 6.7 Ma. Overall, the geochemical data and previously published δ34SCAS data suggest a closed, diffusion-dominated system created most of the dolomite. However, the youngest dolomite's age and bulk rock Sr isotope ages of calcitic rocks at the base of the drift deposits can only be explained by the advective flux of seawater through all the drift deposits. Furthermore, the geological context, including permeable facies, ocean current patterns, and other indicators, such as the absence of hardground or permeability barriers, suggests that some open system dolomitization may have also occurred.

Intraplate alkali basalts related to end-Cretaceous Deccan magmatism: implications for tectonomagmatic processes

This study aims to investigate the earliest imprint of Deccan rift magmatism as preserved in alkali basalts from the northwestern Indian shield. The alkali basalts are petrographically classified as nephelinites and basanites. They are silica undersaturated and their high Mg numbers, CaO/Al 2 O 3 , Cr and Ni indicate their primitive character. Geochemically, they are similar to global ocean island basalts; their bulk rock trace elements and Sr–Nd–Hf isotopic signatures suggest their derivation from a garnet-bearing peridotite field. However, their elevated values of Sr/Sm, Sm/Hf, Zr/Hf, Nb/Ta; positive Ba, Sr and negative Zr, Hf spikes suggest that the magma source represents a mixture of garnet peridotites and carbonated melts. Estimated primary melt compositions closely follow the trajectory defined by the high-pressure experimental partial melting trend of a low-carbonated peridotite source. The melting environment approximates to a high mantle potential temperature. A low 87 Sr/ 86 Sr ratio and a negative correlation between 176 Hf/ 177 Hf and 143 Nd/ 144 Nd of the alkali basalts suggest that the mantle source is a mixture of a depleted Indian MORB-type mantle and an enriched mantle type 2. We correlate this event with the melting of the leading edge of the Réunion plume head during Gondwana break-up in a relatively short span of the Cretaceous/Paleogene boundary.

Middle Triassic Cu–Pb–Zn Skarn mineralization in the Wulonggou gold ore field, Eastern Kunlun Orogen, NW China: Insights from phlogopite Ar–Ar and zircon U–Pb dating and Sr–Nd–Pb–Hf isotopes

The skarn is one of the most significant Cu–Pb–Zn mineralization worldwide. The timing of the magmatic-hydrothermal activity is of importance for understanding the Cu–Pb–Zn mineralization process. The Cu–Pb–Zn skarn mineralization has been recognized in the northwestern section of the Wulonggou gold ore field, Eastern Kunlun Orogen (EKLO), NW China. However, no precise geochronological data has been measured for the Cu–Pb–Zn mineralization, and the source of ore-forming materials is also not well studied. In this study, we present new LA-ICPMS U–Pb ages and Sr–Nd–Hf isotopic compositions for granodiorite and diorite in the northern section of the Wulonggou gold ore field, as well as an Ar–Ar age for phlogopite and Pb isotopic compositions for sulfides and intrusions, further to constrain the ages of mineralization and magmatism, and the source of ore-forming materials. Two granodiorite samples yield mean ages of 245 ± 2 to 243 ± 2 Ma and a diorite has a mean age of 245 ± 2 Ma. A phlogopite sample, which is associated with Cu–Pb–Zn mineralization, has been chosen to precisely date the formation of Cu–Pb–Zn ores by Ar–Ar method and yields a well–defined plateau age of 240.4 ± 1.2 Ma. These results indicate that the Cu–Pb–Zn skarn mineralization formed in the Middle Triassic and is closely related to the coeval magmatism. The εHf(t) values of the ore-related granodioritic and dioritic rocks range from −2.8 to +2.5, whereas an un-mineralized granodiorite sample (WHFG–1) shows lower εHf(t) values of –9.3 to –3.4, indicating that these magmatic rocks are derived from the mixing of magma with different proportions of mantle- and crust-components. A mixing model with ∼40–70 % mantle contribution involved in the formation of ore-related granodiorite and diorite was revealed by Sr–Nd–Hf isotopic compositions. Combined with Pb isotopic compositions for sulfides, feldspar, and bulk rocks, we consider a common source for the ore-forming materials and magmatism. In addition, higher εHf(t) and εNd(t) values for ore-related magmatism implicate that mantle-derived melts show a vital role in the Cu–Pb–Zn skarn mineralization process.

The Role of Latent Heat Buffering in the Generation of High-Silica Rhyolites

Abstract The physical process of crystal-melt separation is responsible for the accumulation of small to very large volumes (>100 km3) of eruptible rhyolitic melt in the shallow crust. Granitic intrusions, although providing a terminal, time-integrated image of melt segregation processes, host an unmatched record of the physical properties controlling mechanisms and rates of interstitial melt extraction from a crystal-rich source. We applied mass balance calculations and thermodynamic modeling simulations to an extensive bulk rock geochemistry dataset (>150 samples) collected in a Permian upper-crustal granitoid intrusion of the Italian Southern Alps. Textural and geochemical evidence indicate that this intrusion constituted a single, zoned magma body, with a crystal-rich base and a thick (~2 km), high-silica cap (75–77 wt% SiO₂). The large compositional variability of the crystal-rich materials suggests variable degrees of melt extraction efficiency and corresponding terminal porosities. Specifically, the loosely bimodal distribution of porosity values (φ) indicates that at least two distinct melt segregation mechanisms were operating in this system, which produced both high (0.65–0.45) and low terminal porosities (0.45–0.25) in the crystal-rich, cumulate materials. Modeling of latent heat budget shows that coexistence of cumulate products with differing terminal porosity signature can be explained by melt segregation processes taking place at different depths across a thick, interconnected magmatic reservoir with an initial homogenous water content (~4 wt% H2O). Deep in the mush column, low water activities (aH₂O < 0.5) promoted thermal buffering of cooling magma at high crystallinities, enabling residual melt extraction by percolation through a crystalline framework accompanied by compaction. Instead, at shallower depths, high water activities (aH₂O > 0.5) ensured prolonged magma residence at porosities that promoted crystal melt separation via hindered settling. Distinct melt extraction processes, acting synchronously but at different depths in vertically extensive silicic mush columns, can account for the large volumes of residual, haplogranitic melt mobilized during the relatively short lifespan of upper crustal magma reservoirs (~105 years).

U-Mo-Ba mineralizace na uranovém výskytu Soseň-Kosobody u Jesenice

This paper presents new mineralogical data from the small uranium occurrence Soseň-Kosobody near Jesenice in the Rakovník District in the western part of the Czech Republic. The uranium anomaly, discovered in early 50th, was explored by two shafts No 33 and No 36 in 1954–1959 and subsequently by boreholes and exploration trenches in 1970–1972 (Mrázek 1972). The host rock of the mineralization is Neoproterozioc phyllite of the Teplá-Barrandian Zone or Bohemicum (Fig. 1); the contact with granite and granodiorite of the Čistá-Jesenice Composite Pluton is exposed in the proximity. The studied samples were collected in 2019–2020 and analysed by XRF and ICP-MS for bulk rock chemistry, and by EMPA and XRD for mineralogy (see Table 1 and 2). The samples with primary hydrothermal mineralization were collected in a dump of a shaft No 33(Fig. 2a, b, f), and those with supergene mineralization at a shaft No 36 (Fig. 2c, d). The mineralization occurs in cm thick, discordant brecciated veinlets with sharp contacts (Fig. 3a, b) composed of quartz, K-Ba-feldspar (potassium feldspar to hyalophane), with minor spessartine garnet, pyrite, TiO2 and kaolinite or dickite (Fig. 4a–f). The presence of carbonates and/or baryte mentioned by Mrázek (1972) was not confirmed. The primary mineralization is rather weak and dispersed. An inhomogeneous U-Ca-Pb phosphate phase represents the sole primary uranium carrier. Molybdenum or Mo-S bearing phase forms tiny intergrowths with this phase. Associated ore mineralization is also low-grade, being represented by sphalerite, galena and chalcopyrite (see Figs. 4g–h, Tables 3–5). The samples of supergene mineralization contain common metatorbernite (with minor torbernite) and corkite, accompanied by kaolinite and abundant “limonite” (goethite). The mineralogical and compositional data indicate the origin of mineralization from silica-K-Ba-U-P-Mn-rich fluids poor in sulphate anion. Although the ore mineralization (Pb, Zn, Cu, As and Mo) accompanying uranium is of a low grade, especially the elevated Mo content indicates genetic connection with the Hůrky Mo-REE deposit, which is also associated with the Čistá-Jesenice Composite Pluton (see Klomínský 1962, Kopecký et al. 1997).

Biochemically induced diagenesis of Jurassic micrite: evidence from phase analysis, carbon, oxygen, and strontium isotopes (Franconian Alb, Germany)

The marine Upper Jurassic rocks of the Franconian Alb consist largely of micritic carbonate of partly dolomitized reef mounds and bedded basinal limestone. All carbonates were lithified in the shallow (centimeters, meters) subsurface and have a wide range of ∂13C (≤ + 3‰ to − 10‰VPDB) but always negative ∂18O (− 1 to − 6‰VPDB). Dolomite and reef limestone show the highest ∂18O and ∂13C values. The most negative ∂13C (≥ − 10‰) occurs mainly as cement in dolomite of a basinal, partly dolomitic, biostrome interval. Basinal limestone shows intermediate ∂13C values. Because freshwater diagenesis and elevated temperatures cannot explain the observed isotope values, pH is here considered a major factor influencing the isotope signal of micritic limestone. The bulk sediment isotope signal was reset to lower values, from an original lime mud with ∂13C ≥ 3‰ and a ∂18O of ≥ + 1‰, as a result of biochemically induced diagenesis. Carbonate, probably mostly aragonite but occasionally including dolomite, was dissolved in a zone where low pH developed as a result of organic matter degradation. Dissolved carbonate was translocated by diffusion and re-precipitated as cement (ca. 50vol%) in a zone with elevated pH where all in situ lime mud ∂18O was reset. Imported cement carbonate precipitated in equilibrium with the pore fluid with negative isotope values, whereas ∂13C of the in situ lime mud remained unmodified. The negative shift of the bulk ∂13C and ∂18O is variable and depends on pH and the contribution of 12C from anaerobic sulfate reduction in the zone of cement precipitation. This produced an ubiquitous covariance of ∂18O and ∂13C. Incorporation of seawater-derived Mg2+ during recrystallization of carbonate can account for the local dolomitization. Elevated 87Sr/86Sr ratios are explained as a result of interaction of clay minerals with the stationary pore fluids. This study shows that the isotopic signal produced by biochemically induced shallow submarine subsurface carbonate diagenesis can be indistinguishable from freshwater diagenesis, that ∂18O and ∂13C of the bulk rock are always reset, and that carbonates can show, in the presence of clay minerals, elevated 87Sr/86Sr ratios even when the pore fluids were never exchanged.Graphical

Bulk Rock and Olivine Chemistry and Isotopes of 106–58 Ma Basalts from Liaodong Peninsula and its Adjacent Areas: Implications for Secular Evolution of the Big Mantle Wedge in Eastern China

Abstract The subducting Pacific slab stagnates in the mantle transition zone and creates a big mantle wedge (BMW) system in East Asia. A similar BMW structure may have already existed since the Early Cretaceous (>120 Ma), but how such a structure evolved from Early Cretaceous to the present day remains unclear. We address this issue by comparing compositions and source heterogeneity of the 106–58 Ma basalts from Liaodong Peninsula and its adjacent areas (LPAA) in eastern China, with those formed in the modern BMW setting. The LPAA basalts display oceanic island basalts–like trace element patterns. Elemental and isotopic compositions of these basalts and their olivine phenocrysts point to peridotite and two recycled components in their source. One recycled component is altered lower oceanic crust given the low δ18Oolivine (2.8–5.2‰) of the ~99 Ma Liaoyuan alkali basalts. The second component consists of altered upper oceanic crust and pelagic sediments indicated by high δ18Oolivine (>6.0‰), represented by the ~58 Ma Luanshishanzi alkali basalts. The depleted mantle-like isotopes of these two components suggest derivation from a young HIMU source with characteristics of the Izanagi plate (e.g. Indian Ocean-type Sr-Nd-Pb-Hf isotopes), which may have resided in the mantle transition zone at that time. Our results reveal strong similarities between chemical and source characteristics of the mantle sampled by the 106–58 Ma LPAA basalts and those derived from the modern BMW. This implies that the BMW structure has been present since the Early Cretaceous, probably having lasted more than 120 Myr, and modulating the chemical properties of the upper mantle and influencing a variety of geological processes.

Magmatic genesis, hydration, and subduction of the tholeiitic eclogite-facies Allalin gabbro (Western Alps, Switzerland)

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.

Petrographic and Geochemical Evidence for a Complex Magmatic Plumbing System beneath Bagana Volcano, Papua New Guinea

Abstract Bagana is a persistently active stratovolcano located on Bougainville Island, Papua New Guinea. Characteristic activity consists of prolonged lava effusion over months to years, with occasional shifts to explosive vulcanian or sub Plinian eruptions that threaten surrounding communities. Satellite observations have shown that Bagana is a major SO2 emitter, particularly during eruptive intervals. Despite persistent and potentially hazardous activity, no previous geophysical, petrological, or geochemical studies have constrained the magma storage conditions and reservoir processes at Bagana. To address this knowledge gap, we present new bulk rock major, trace element, and radiogenic isotope data, plus mineral phase major element compositions, for Bagana lavas erupted in 2005 and 2012 and ash erupted in 2016. We use our new data to understand the magmatic processes controlling the typical effusive activity and provide the first estimates of magma storage conditions beneath Bagana. The basaltic andesite bulk rock compositions (56–58 wt% SiO2) of our Bagana lavas reflect accumulation of a plagioclase + clinopyroxene + amphibole + magnetite + orthopyroxene crystal cargo by andesitic-dacitic (57–66 wt% SiO2) carrier melts. Constraints from clinopyroxene and amphibole thermobarometry, amphibole hygrometry, and experimental petrology suggest that the high-An plagioclase + clinopyroxene + amphibole + magnetite assemblage crystallizes from basaltic-basaltic andesite parental magmas with >4 wt% H2O, over a temperature interval of ~1100–900°C, at pressures of ~130–570 MPa, corresponding to ~5–21 km depth. Continued crystallization in the magma storage region at ~5–21 km depth produces andesitic to dacitic residual melts, which segregate and ascend towards the surface. These ascending melts entrain a diverse crystal cargo through interaction with melt-rich and mushy magma bodies. Degassing of carrier melts during ascent results in crystallization of low-An plagioclase and the formation of amphibole breakdown rims. The radiogenic isotope and trace element compositions of Bagana lavas suggest that parental magmas feeding the system derive from an enriched mantle source modified by both slab fluids and subducted sediments. Our findings suggest that the prolonged lava effusion and persistently high gas emissions that characterise Bagana’s activity in recent decades are sustained by a steady state regime of near-continuous ascent and degassing of magmas from the crustal plumbing system. Our characterisation of the Bagana magmatic plumbing system during effusive activity provides a valuable framework for interpreting ongoing monitoring data, and for identifying any differences in magmatic processes during any future shift to explosive activity.

Boron sources of tourmaline-rich Nb-Y-F-pegmatites in south Norway: Implications for pegmatite melt origin

Tourmaline is common in rare element pegmatites of the Nb-Y-F (NYF) type in the south-central part of the Proterozoic Sveconorwegian orogen in southern Norway. In the global context, however, tourmaline appears rare in this type of pegmatite. This study aims to explain the unusual tourmaline abundance in these pegmatites and the origin of boron (B) in the respective melts, and to raise awareness of tourmaline in NYF pegmatites generally. Tourmalines from six pegmatites in three Sveconorwegian lithotectonic units: Bamble, Kongsberg and Idefjorden, were investigated in terms of their mineral chemistry and δ11B values, in addition to bulk rock analyses of pegmatites and host rocks. Tourmalines in pegmatites from Bamble and Kongsberg record B isotopic compositions (δ11B = -1.0 to + 9.9 ‰) that are heavy relative to continental crust and mantle sources. In contrast, tourmaline in pegmatites and host rocks from Idefjorden have light B isotopic ratios (δ11B = -14.8 to −12.5 ‰) that are typical crustal values. We suggest that the latter melts were sourced from orthogneisses at depth. We relate the heavy B isotopic composition of Bamble and Kongsberg pegmatites to regional Na-metasomatism by fluids sourced from Mesoproterozoic shallow marine sediments. This is supported by previously published δ11B ratios from metasomatized Bamble host rocks. The spatial association of pegmatites with Na-metasomatism in the basement rocks suggests that metasomatism enhanced the fertility and B-concentration in the affected lithologies, favouring partial melting and the formation of tourmaline-bearing pegmatites.These findings contribute to understanding the petrogenesis of Sveconorwegian pegmatites but they also imply that B can play a greater role in the formation of NYF pegmatites than previously thought and that tourmaline has value as a petrogenetic tool in this type of pegmatites as well as in the Li-Cs-Ta (LCT) type to which is it is more commonly applied.

Coupled δ56Fe and δ18O analysis of the Frere iron formation, Western Australia, and Paleoproterozoic ocean circulation

The Paleoproterozoic (ca.1.89 Ga) Frere Formation is a ca. 300-m-thick sedimentary succession of five stacked, Fe- and silicate-rich shallowing upwards cycles or parasequences that were deposited during marine transgression. Deposition in an oxygen-stratified water column is supported by the occurrence of magnetite-rich mudstones (anoxic and distal) beneath shallower, hematite- and chert-rich grainstones (suboxic and proximal). Minor (LREE/HREE)PAAS depletion and positive Ce anomalies in grainstones support this interpretation. Sequence stratigraphic relationships suggest that the Frere Formation accumulated on an unrimmed continental shelf associated with coastal upwelling of Fe.Large variations in oxygen isotope ratios (δ18O) of magnetite (–0.6 ‰ ≤ δ18O ≤ +2.8 ‰, n = 12) and quartz (+8.8 ‰ ≤ δ18O ≤ +20.1 ‰, n = 11) from lithofacies composing the Frere Formation indicate that pristine δ18O of minerals were overprinted by diagenesis. Highly variable δ18O values calculated at 200 °C in equilibrium with quartz (–3.0 to + 8.3 ‰) and magnetite (+8.0 to + 12.7 ‰) suggest that fluids with heterogeneous δ18O evolved through oxygen isotope exchange between minerals and porewater in accumulating sediment during diagenesis.The Fe isotope ratios (δ56Fe) of bulk rock (–0.50 ‰ ≤ δ56Fe ≤ +1.55 ‰, n = 20) and magnetite separates (–0.09 ‰ ≤ δ56Fe ≤ +2.06 ‰, n = 11) from deeper anoxic and shallow suboxic paleoenvironments define a decreasing trend through stratigraphically stacked parasequences. The high δ56Fe values of magnetite (+0.7 ‰ to + 2.06 ‰) characterizing the base of the Frere Formation is interpreted to reflect equilibrium isotopic fractionation between dissolved Fe2+aq and freshly precipitated Fe-(oxyhydr)oxide (Fe(OH)3) resulting from sluggish recharge of Fe2+aq from deeper shelf environments. These high δ56Fe values of magnetite from shallow paleoenvironments may also reflect microbial dissimilatory Fe reduction at the seafloor. As sea level rose, continued deepening and encroachment of a well-mixed water mass increased the oxidation of Fe2+aq, which ultimately increased the influence of kinetic isotopic fractionation between Fe2+aq and Fe(OH)3. Such a process produced δ56Fe compositions of magnetite that gradually decrease through the stratigraphic thickness of the Frere Formation (+2‰ to −0.1 ‰). Thus, Fe isotopic data framed in a sequence stratigraphic context provides greater insight into water column processes on Fe-rich, oxygen stratified Paleoproterozoic and Mesoproterozoic shelves, as well as geologically younger restricted basins with a redox gradient.

Links between Calcite Kimberlite, Aillikite and Carbonatite in West Greenland: Numeric Modeling of Compositional Relationships

Abstract Textural, mineralogical and mineral compositional observations in a suite of Neoproterozoic aillikite and calcite kimberlite dykes from southern West Greenland point to consistent variations in melt major element compositions amongst these silica-undersaturated magma types. The aillikites have notably higher bulk SiO2/CO2, H2O/CO2 and K2O compared to calcite kimberlite. Bulk rock arrays, together with field and petrographic observations, emphasize that flow sorting of olivine and other crystalline phases during magma emplacement is important in controlling the compositions of individual samples from these ultramafic dykes. Flow sorting together with variable overall proportions of entrained lithospheric mantle material result in scatter on element–element plots, which makes the interpretation of regional scale major and trace element geochemical datasets difficult. We argue that a significant proportion of the regional Ni–MgO variation in the ultramafic dyke suite of SW Greenland is due to variation in the proportion of an entrained refractory lithospheric mantle component. Therefore, ratios of elements to MgO can be used as proxies for melt compositions. Ratios of SiO2, TiO2, Al2O3, FeO and K2O over MgO are systematically higher, and CO2/MgO lower, in aillikites compared to calcite kimberlites. The trace element patterns of the calcite kimberlite and aillikite dykes show strong similarities in incompatible element concentrations, resulting in overlapping ratios for the highly to moderately incompatible elements. However, differences in Zr-Hf concentrations between rock types imply differences in mantle source mineralogy. Guided by our observations, we present mixing models that demonstrate that partial flux-melting of phlogopite–ilmenite metasomes within the cratonic mantle lithosphere is capable of produce the geochemical characteristics of aillikites and mela-aillikites in West Greenland. Fusion of cratonic metasomes was initiated by infiltrating asthenosphere-derived carbonatitic melts previously identified as the parental liquids to calcite kimberlite.

Changes in the magmatic plumbing system associated with the Gotemba sector collapse at Mount Fuji, Japan

It is well known that magmatic plumbing systems change over time, but there is much debate as to why and how. We studied volcanic ejecta continuously deposited in an outcrop at Kagosaka Pass at the eastern base of Mount Fuji to investigate the factors responsible for changes in the magmatic plumbing system. The sample consisted of pyroclastic sediments from explosive eruptions for approximately 3000 y, which sandwiched the time of the Gotemba sector collapse at approximately 2500 BP. Chemical analyses of whole rocks, minerals, and matrix glasses, as well as mode measurements of glass and bubbles, were performed on samples collected from approximately 30 layers; significant changes were observed before and after the collapse. For example, before and after the collapse, matrix glass area increased around 60% to over 80% and anorthite content (Ca / (Ca + Na) * 100) of phenocryst plagioclase decreased from over 80 to below 65. For a period after the collapse, possibly hundreds of years, the plagioclase and olivine phenocrysts exhibited characteristics indicative of crystallization at low temperatures and pressures, and the pyroclast matrix became highly vitreous. Eruptions with ejecta of these characteristics continued more than a dozen times, lasting about 500 years. In addition, the trend in the distribution of the bulk rock chemical composition changed significantly, showing a differentiation trend with only plagioclase and clinopyroxene crystal separation. An investigation using the MELTS software revealed that the phenomenon of direct eruptions from deep magma chambers to the surface, bypassing shallow magma reservoirs, continued for several hundred years after the collapse. This can be interpreted as a decrease in confining pressure associated with the collapse, facilitating the eruption of magma from the depths. Furthermore, based on an examination of the water content in the magma during this period, we posit that the trigger for the rise of magma from the deep magma chamber of Mount Fuji is the acquisition of excess pressure by the injection of magma from a deeper level.

Origin and thermal evolution of Cr-V-Ti magnetites (lodestones) from Coorg massif, southern India

This study deals with petrology, textural, thermometry, and geochemical characterization of naturally magnetized Cr-V-Ti magnetite deposits within the layered mafic-ultramafic intrusions in Coorg massif of southern India using ore petrography and mineral/whole rock geochemistry. These deposits, also known as ‘lodestones’, occur as rhythmic layers within the lateritized host rock, with the underlying basement distinguished by the presence of charnockites and layered gabbro-anorthosites and pyroxenites, delineating a stratified intrusive setting. Lodestones exhibit complex mineral assemblage involving magnetite, ilmenite, ulvöspinel, spinel, corundum, hematite, goethite, pyrite, pyrrhotite, and amphiboles. The bulk rock chemistry of the lodestone is analogues to Fe-Ti magnetite iron ore deposits with elevated vanadium and chromium contents. Their resemblance to tholeiitic magma-type suggests their formation in a layered intrusive setting, evolved through multiple fractional crystallization under oxidizing conditions. Thermometric and fugacity calculations using different textural associations estimate the magmatic fractional crystallization stage at elevated temperatures (601–704 °C) and low fO2 (−18.6 to −15.3), succeeded by the exsolution stage during subsolidus cooling at lower temperatures (379–540 °C) and high fO2 (−38.2 to −22.1). The whole sequence of formation and evolution of lodestone encompasses primary magmatic crystallization, subsolidus re-equilibration, metamorphism, and secondary weathering. The study also suggests a genetic linkage of lodestone with the associated mafic-ultramafic units, depicting two possible magmatic processes either through slab melting and fractional crystallization associated with subduction or due to plume magmatism and associated rifting.

Ferric Iron in Eclogitic Garnet and Clinopyroxene from the V. Grib Kimberlite Pipe (NW Russia): Evidence of a Highly Oxidized Subducted Slab

Abstract Estimates of oxygen fugacity of eclogitic rocks are linked to the redox evolution of the oceanic protolith during subduction and its residence in the lithospheric mantle, and, based on knowledge of pressures and temperatures, allow modelling of the speciation of volatile elements and diamond (or graphite) versus carbonate stability. To date, the oxygen fugacity of mantle eclogites has been shown to vary between −6 (Kasai, Congo and Udachnaya, Siberia) and −0.1 (Udachnaya, Siberia) log units (relative to the fayalite–magnetite–quartz buffer, FMQ), linked to the low Fe3+ contents of garnets. In this study, we investigated the Fe oxidation state of coexisting garnet and clinopyroxene hand-picked out of 17 diamond-free high-MgO and low-MgO mantle eclogites (dated at 2.84 Ga) from the Grib kimberlite pipe (East-European platform). Measured Fe3+/∑Fe values range between 0.03 and 0.19 for garnet and 0.18–0.38 for clinopyroxene, the former being higher than what was measured previously in garnets equilibrated at mantle conditions. The Fe3+/∑Fe of the reconstructed bulk rock ranges between 0.10 and 0.15 for high-MgO eclogites and 0.10 and 0.24 for low-MgO eclogites (with uncertainties of ± 0.02 and ± 0.03 in both cases). Thermobarometric calculations result in equilibration pressures and temperatures of 3.0–5.2 (± 0.4) GPa and 720–1050 (± 60) °C for both high-MgO and low-MgO eclogites, slightly lower than previous P–T estimates of mantle eclogites from the Udachnaya kimberlite pipe (Siberian craton). At these conditions, ∆logfo2 (FMQ) calculated using the available oxythermobarometric model varies from −1.7 to −0.6 log units for high-MgO eclogites and from −2.9 to 0.9 log units for low-MgO eclogites. Samples recording ∆logfo2 (FMQ) ≤ −1 log units overlap with North Slave, West Africa and Udachnaya eclogites, with no difference among eclogite types. The average values of −1.2 (± 0.4) log units for high-MgO and −0.6 (± 1.1) log units for low-MgO eclogites suggest different redox conditions of basaltic protoliths during subduction worldwide. Previous geochemical studies on the same rock samples reported evidence of cryptic metasomatism in both garnet and clinopyroxene that we demonstrate being not recorded by their major elements, while modal metasomatism evidenced by the presence of phlogopite as a product of interaction with a kimberlitic melt only affects the MgO of the bulk rock. Therefore, we suggest that high Fe3+/∑Fe ratios for garnet (> 0.10) and for reconstructed bulk rocks in the case of both low-MgO and high-MgO samples cannot be due to metasomatic interaction with an oxidized fluid, but rather are the consequence of Fe3+ redistribution in an unusually oxidized mafic protolith upon metamorphism. Our results highlight the redox variability of eclogites of Archaean age at conditions more oxidized than present-day mid-ocean ridge basalts (MORBs) and imply an oxidizing nature of the convective mantle source where magma was formed with consequent speciation of C in the form of carbonate fluid explaining, therefore, the lack of eclogitic diamonds in V. Grib kimberlite pipe.