Concentrations Of High Field Strength Elements Research Articles

Systematic study of high field strength elements during liquid immiscibility between carbonatitic melt and silicate melt

Abstract Natural carbonatites exhibit a wide range of high field strength elements (HFSEs) and the highest Nb/Ta and Zr/Hf ratios among various rock types. However, primitive carbonatitic melts derived from carbonated peridotite do not display significant fractionation of Nb-Ta and Zr-Hf. To investigate this further, we conducted liquid immiscibility experiments to comprehend the differentiation of these HFSEs. Our experiments revealed substantial changes in partition coefficients for Nb, Ta, Zr, and Hf between carbonatite and silicate melts. We identified a positive correlation between the partition coefficients of these elements and Si, indicating that Si determines the differentiation of Nb-Ta and Zr-Hf during liquid immiscibility. The partition coefficients of Si increase as temperature increases and pressure decreases, resulting in higher HFSE concentrations during the early stages of liquid immiscibility. Liquid immiscibility is crucial in differentiating HFSEs in carbonatitic melts, explaining the association between super large carbonatite-related Nb deposits and Si-undersaturated silicate rocks.

Ages and geochemistry of garnet reveal multi-types of iron-copper mineralization in the Eastern Tianshan, NW China

The Aqishan-Yamansu Fe-Cu-Au metallogenic belt in the Eastern Tianshan, NW China, hosts numerous Fe and Fe-Cu deposits that may have different genetic models, such as volcanic-hosted and skarn/IOCG types. These variations in genetic models are attributed to whether the mineralization is associated with hydrothermal activity related to volcanic or intrusive rocks. This study primarily focuses on garnets formed during the early skarn alteration in the Shuanglong Fe-Cu and Shaquanzi Fe deposits within this belt. Garnets from the Shuanglong deposit can be divided into two types and exhibit general homogeneity, with SL-Grt1 being Fe-rich and subsequently replaced by the Fe-poor SL-Grt2. Garnets from the Shaquanzi deposit display complex zonation patterns, SQZ-Grt1 show core–oscillatory zoned rim and SQZ-Grt2 show core–mantle–oscillatory zoned rim. Laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) dating of SL-Grt1 and SL-Grt2 produced lower intercept 206Pb/238U ages ranging from 318.0 ± 6.4 Ma to 303.7 ± 16.4 Ma, coinciding with the multi-stage granite occurrence. In contrast, SQZ-Grt1 and SQZ-Grt2 yielded ages between 328.0 ± 2.6 Ma and 320.4 ± 1.7 Ma, corresponding to the timing of the hosted rhyolite. SL-Grt1 show light rare earth element (LREE) enrichment, and low concentrations of high field strength elements (HFSE), such as V and Zr, and appears to have formed rapidly within an open system. Conversely, SL-Grt2 is characterized by heavy rare earth element (HREE) enrichment and elevated HFSE contents, which could be formed slowly in a closed system. The variable composition in the SQZ-Grt1 and SQZ-Grt2 record cyclical changes in fluid kinetics (vigorous fluid flow vs. fluid stagnation). The cyclical zones in SQZ-Grt2 with HREE and HFSE concentrations below the detection limit indicate multiple inputs of external seawater. The distinct characteristics between Shuanglong and Shaquanzi garnets may reflect the difference between the single magma intrusion and complex volcanic activity. Combining previously published chronological data, this study elucidates a transition from the Middle Carboniferous volcanic-hosted Fe deposits (335–320 Ma) to the Late Carboniferous intrusion-related skarn or IOCG type Fe-Cu deposits (310–300 Ma) in the Aqishan-Yamansu belt.

Forearc magmatism in the Pannonian basin recorded by metasomatised skarnoid xenoliths in Pliocene basalt (Novohrad-Gemer Volcanic Field, Slovakia)

Anorthite-diopside-spinel-forsterite xenoliths occur in basaltic lava flow in northern part of the Pannonian basin in the Novohrad-Gemer Volcanic Field (NGVF). Several lines of geochemical evidence suggest that the typical skarn assemblage originated by multiple carbonatitic and alkaline silicate metasomatism of pristine basalt to picrobasalt protolith rather than by the modification of crustal carbonates around shallow magma chambers. Interaction with mantle-derived magnesite or dolomite carbonatite melt triggered the crystallization of neoformed forsterite at the expense of primary clinopyroxene. The alkaline silicate metasomatism resulted in the replacement of primary diopside and augite by neoformed aegirine and aegirine-augite accompanied by amphiboles (richterite, katophorite, arfvedsonite). Weakly metasomatised Group 1 xenoliths retained their fore-arc magmatic geochemical signatures: flat REE patterns, low concentrations of high-field strength elements (Ti, P, Zr) and Ni compared to MORB, low ratios of highly-to-less incompatible elements (Ti/V, Zr/Y) relative to MORB, low Na2O, low total REE, and supra-subduction affinity of primary clinopyroxenes, being thus analogues to fore-arc basalts (FAB). In contrast, strongly metasomatised Group 2 xenoliths exhibit LREE-enriched patterns sub-parallel with those of host trachybasalts. Some Group 1 xenoliths also exhibit large positive Eu anomalies and strongly depleted signatures diagnostic of low-pressure plagioclase-pyroxene cumulates. One xenolith with complementary negative Eu, Sr and positive Rb anomalies has been identified as high-Mg basaltic andesite melt residuum. Sr and Nd isotopes plot along the OIB-MORB array. The Group 1 converges at initial 87Sr/86Sr and 143Nd/144Nd ratios of 0.7038–0.7041 and 0.5127–0.5128, respectively, thus recording a 140–190 Ma old mantle source. Thermobarometry data on metasomatically unmodified pyroxenes have been arranged along decompression cooling trend, propagating from ∼1230 °C and ∼ 1 GPa and ending at ∼1160 °C around atmospheric pressure. The maximum pressure indicates the melt generation zone ∼35 km deep, reflecting thin lithospheric mantle. The FABs identified for the first time in the AlCaPa megaunit corroborate the affinity of the NGVF lithospheric segment to Dinarides.

Petrogenetic and geochemical constraints on ca. 1.89–1.88 Ga Bastanar mafic dyke swarm, Bastar craton, India: Insights into MORB- and OIB-type contributions and interactions with metasomatized subcontinental lithospheric mantle

The Bastar craton of the Indian Shield hosts several generations of mafic dyke swarms of various trends, compositions, and ages, which span from ca. 2.7 Ga to 1.42 Ga. This study focuses on geochemical attributes of the ca. 1.89–1.88 Ga NNW-trending Bastanar swarm, aiming to address a perceived discrepancy between its arc-like geochemistry and the influence of a heterogeneous mantle source. To resolve the intra-swarm geochemical variations, we conducted a comprehensive geochemical characterization and petrogenetic interpretation of the ca. 1.89–1.88 Ga Bastanar swarm. The samples from this swarm are categorized into two distinct groups, primarily based on their geochemical composition. The Group 1 samples exhibit higher TiO2 (1.06–1.86 wt%), (La/Yb)N (7.2–8.6), (Gd/Yb)N (2- 2.27), Nb (14.6–16.6 ppm), Th (1.23–3.03 ppm) and Zr (104–118.72 ppm) concentrations than the Group 2 samples. Furthermore, rare-earth element patterns and variations in high-field strength element contents in the Group 1 samples suggest derivation from a deeper, less depleted mantle source resembling an OIB/less MORB-type. This inference is further supported by higher TiO2/Yb, Zr/Nb, and Nb/Y ratios. In contrast, the Group 2 samples indicate derivation from a shallower, more MORB/less OIB-type depleted mantle source, as evidenced by lower TiO2/Yb, Zr/Nb, and Nb/Y ratios. Variations in Dy/Yb and Gd/Yb ratios confirm the involvement of variable mantle sources, implying the derivation of the Group 1 and 2 samples from garnet-rich and spinel-rich lherzolite mantle sources, respectively. The absence of consistent negative Nb-Ta-Ti anomalies in the Group 1 samples suggests an uncontaminated nature, ruling out any role of crustal contamination. On the other hand, the Group 2 samples display negative Nb-Ta-Ti anomalies with enriched LREE and LILE patterns, indicating the involvement of crustal components in their genesis. A trace-element modelling suggests that the ca. 1.89–1.88 Ga mafic dyke swarm exhibits significant intra-swarm variability, with at least two distinct source components contributing to its genesis – a depleted MORB-type and an enriched OIB-type mantle. Notably, the geochemical characteristics of the Group 2 samples suggest interaction with a metasomatized mantle source, possibly enriched by fluids from an earlier subducted slab. Geochemical evidence presented in this work supports Archean subduction-related processes for the crustal growth of the Bastar craton and highlight the enduring influence of a metasomatized sub-continental lithospheric mantle on subsequent magmatism over millions of years.

Petrogenesis of Paleozoic trachyte and rhyolite in the Haidewula area, East Kunlun Orogenic Belt, and their implications for uranium mineralization

Zircon U–Pb-Hf isotopic compositions, mineralogical chemistry, and whole-rock geochemistry analyses were performed on rhyolite and trachyte from the Haidewula deposit in the East Kunlun Orogen Belt (EKOB). These analyses aimed to elucidate the genetic relationship between trachyte and rhyolite and to investigate the role of these volcanic rocks in uranium mineralization. Zircon U–Pb isotope dating indicates that the Haidewula rhyolite and trachyte were contemporaneous with emplacement ages of 421 Ma to 428 Ma, respectively. The trachyte samples exhibit high K2O/Na2O and Fe# [FeO/(FeO + MgO)] ratios, and belong to metaluminous, ferroan volcanic rock; the rhyolite samples display high A/CNK and Fe# ratios, elevated high field strength element contents, and can be classified as strongly peraluminous A2-type magma. Trace and major elemental geochemical signatures demonstrate that the Haidewula trachyte originated from the high-temperature partial melting of a mafic lower crust, followed by fractional crystallization of plagioclase, pyroxene, magnetite, and/or K-feldspar. On the other hand, the rhyolite was likely generated by high-temperature melting of granodiorite in a low water and mid-crust pressure environment, followed by fractional crystallization of feldspar and ilmenite. The occurrence of A-type volcanic rocks at Haidewula suggests that the initial timing of crustal extension in the EKOB was not later than 428 Ma. Overall, Paleozoic igneous rocks in the EKOB revealed that a post-collisional extensional regime, resulting from the rewelding of the microcontinents in eastern Gondwana, was responsible for intensive magmatism during the Late Silurian period. In comparison to other volcanic complexes hosting uranium deposits in eastern China, the relatively U-rich rhyolite and trachyte had the potential to contribute to the formation of U mineralization. In particular, the rhyolitic tuffaceous U-rich glassy volcanic rocks in the Haidewula deposit may represent favorable U-source rocks for mineralization, with uranium released through volcanic glass devitrification processes and leaching by oxidizing hydrothermal fluids.

Petrogenesis of Late Devonian I- and A-type granitoids, and associated mafic microgranular enclaves in the northwestern North Qaidam Orogenic Belt, China: Implications for continental crust growth during the post-collisional stage

Post-collisional magmatic intrusions and their mafic microgranular enclaves (MMEs) can provide significant insights into granite petrogenesis, crust-mantle interaction, and the reworking and growth of the continental crust. A combined petrological and geochemical study was carried out on MMEs and their host Niubiziliang I-type felsic composite pluton (granite and granodiorite) and aluminous A 2 -type Datonggou biotite granite from the Niubiziliang batholith in the northwestern segment of the North Qaidam Orogenic Belt (NQOB), China. This study presents whole-rock major- and trace elements and Sr Nd isotopic compositions, electron probe microanalyses of plagioclase, hornblende, and biotite, and zircon U Pb dating and Hf isotopes. Zircon U Pb dating demonstrates that the studied rocks formed during the Late Devonian (ca. 382 Ma). The Niubiziliang composite felsic pluton samples yield a metaluminous calc-alkaline to high-K calc-alkaline I-type granitic composition. The MMEs from Niubiziliang composite felsic pluton have low SiO 2 (52–64 wt%) and high MgO (2.8–4.9 wt%) concentrations. Both MMEs and host granites are enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs) and are depleted in P and high field strength elements (HFSEs). All MMEs and host granitoids samples from Niubiziliang have indistinguishable Sr-Nd-Hf isotopic compositions characterized by initial Sr isotope ratios of 0.70545–0.70633 (MMEs), 0.70555–0.70742 (host rock), whole-rock ε Nd ( 382 Ma ) values of −2.95 to +1.6, −0.25 to +3.5, and zircon ε Hf( 382Ma ) values of +2.2 to +10.2, +1.3 to +10.4, respectively. The Niubiziliang composite felsic pluton is a product of mixing juvenile crust-derived and depleted mantle-derived melts in a 40:60 proportion. MMEs crystallized from the same source as the host granite, and they were formed by self-mixing with the earlier crystallized cumulates when they were affected by the emplacement of subsequent hot magmas. The Datonggou biotite granite has high TFe 2 O 3 /(TFe 2 O 3 + MgO), TiO 2 /MgO, Ga/Al, and Y/Nb ratios, high zircon saturation temperatures (802–846 °C), high HFSE concentrations (e.g., Zr, Nb, and Y), moderate (Na 2 O + K 2 O) concentrations, and low Eu and Sr concentrations. Interstitial biotite has high Fe 2 O 3 but low MgO concentrations, similar to those of aluminous A-type granite. The above-mentioned characteristics imply that the Datonggou biotite granite is an aluminous A 2 -type granite. Considering their high initial Sr isotopic composition (0.72218–0.72652), low ε Nd ( 382 Ma ) (−6.73 to −6.31), and comparatively old two-stage Nd model ages (1640–1674 Ma), we suggest the biotite granite was generated by partial melting of Ordovician-Silurian granitoids with tonalitic compositions at H T -L P conditions. The formation of coeval I- and aluminous A 2 -type granitoids in this region was probably related to the lithospheric mantle delamination and associated asthenospheric upwelling at ca. 390 Ma. The I-type granitoids and MMEs from the Niubiziliang area represent a net addition of juvenile mantle to the crust and, given the wide distribution of contemporaneous I-type granitoids, the post-collisional magmatism has significantly contributed to the growth of the continental crust in the NQOB. • The Niubiziliang granitoids, MMEs, and biotite granite were emplaced at 382 Ma. • Lithospheric delamination occurred at ca. 390 Ma in the North Qaidam belt. • The post-collisional granitoids contribute to the growth of the continental crust.

Effects of Mantle Hybridization by Interaction with Slab Derived Melts in the Genesis of Alkaline Lavas across the Back-Arc Region of South Shetland Subduction System

AbstractLate Miocene to Late Pleistocene alkaline lavas in the northernmost part of the Antarctic Peninsula and its off-lying islands are the latest stage of magmatic activity that took place in response to lithospheric extension in the back-arc region of the South Shetland subduction system. The alkaline magmatism occurred much later than the main pulse of Cretaceous arc magmatism and generated basaltic extrusive rocks during several sub-aqueous/sub-glacial and sub-aerial eruption periods. The suite consists primarily of alkali olivine basalts with oceanic island basalt (OIB)-like trace element signatures, characterized by elevated highly to less incompatible element ratios compared to MORB. The samples have higher 87Sr/86Sr (0.70301–0.70365), and lower 143Nd/144Nd (0.51283–0.51294) and 176Hf/177Hf (0.28291–0.28298) than depleted MORB mantle. Their lead isotope ratios vary within a limited range with 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb ratios of 18.797–18.953, 15.577–15.634, and 38.414–38.701, respectively. Sr, Nd, Hf and Pb isotope systematics suggest involvement of diverse source materials in the genesis of the alkaline magmas. Evaluation of radiogenic isotope and trace element data indicates that the source of the alkaline melts had a complex petrogenetic history, reflecting the effects of mantle hybridization along the slab mantle interface through interaction of mantle wedge peridotites with volatile-bearing, siliceous melts produced by melting of subducted sediments and basaltic oceanic crust. Hf-Nd isotope and trace element projections further demonstrate that the metasomatizing melt was likely generated by eclogite partial melting at sub-arc to post-arc depths, in equilibrium with a garnet-bearing residue and involved breakdown of high field strength elements (HFSE) retaining phases. Consumption of metasomatic amphibole during partial melting of hybridized peridotite at the wet solidus appears to have had a significant effect on the final melt compositions with high HFSE, Na and H2O contents.

Trace element partitioning in zoned clinopyroxene as a proxy for undercooling: Experimental constraints from trachybasaltic magmas

Sector-zoned clinopyroxene records kinetic effects imposed by variable degrees of magma undercooling, ΔT, and can be utilised to track the dynamics of magmatic systems. The partitioning of trace elements into sectors grown in different crystallographic orientations can be used as a proxy for ΔT. However, an experimental assessment of the relationship between trace element zoning and ΔT has been lacking to date. Here we present trace element data from a series of undercooling crystallisation experiments on a primitive trachybasalt from Mt. Etna (Italy), at conditions of crustal storage (400 MPa, NNO + 2), and ΔT ranging from 23 to 173 °C. Changes in ΔT were modulated by varying both resting and liquidus temperatures, the latter via the melt-H2O content of the experiments. The resting temperature was retained for 24 h to ensure the attainment of near-equilibrium conditions.High-resolution elemental mapping reveals the distribution of trace elements in individual clinopyroxene zones. Increasing ΔT drives a shift from polyhedral morphologies with Al-rich prism and Al-poor hourglass sectors (ΔT = 23–25 °C), to skeletal (ΔT = 75–123 °C) and dendritic (ΔT = 132–173 °C) crystals with Al-rich skeletons and Al-poor overgrowths. Aluminium-rich zones have higher concentrations of rare earth elements (REE) and high field strength elements (HFSE) than Al-poor zones across all investigated ΔT conditions, and overall, Al, REE and HFSE contents increase with ΔT. This indicates that tetrahedral aluminium (TAl) and associated charge-balancing mechanisms govern the incorporation of REE and HFSE within clinopyroxene. Lattice strain parameters for REE in the M2 site indicate the incorporation of light relative to heavy REE in clinopyroxene is controlled by competing effects between the strain-free partition coefficient, D0, and the optimum cation radius, r0. Critically, the middle and heavy REE switch from incompatible to compatible with increasing ΔT. Used to model fractional crystallisation, our data demonstrate that fractionation of clinopyroxene at low ΔT controls pre-eruptive melt evolution. Importantly, this indicates crystallisation of clinopyroxene in the deep portions of Mt. Etna’s plumbing system is not rapid and is unlikely to result in the early formation of dendrites.We develop a parameterisation of ΔT based on REE partitioning between experimental clinopyroxene and coexisting melt, which can be applied to sector-zoned augite crystallising from mafic alkaline magmas, to reconstruct dynamic processes and thermal pathways during magma transport and storage. Applied to sector-zoned clinopyroxene microphenocrysts and groundmass microcrysts from the 1974 eccentric eruption at Mt. Etna, our parameterisation tracks an increase in ΔT with magma ascent and eruption, following recharge of Cr-rich mafic magma at depth. Sector-zoned clinopyroxene can track ΔT variations leading to volcanism at Mt. Etna and could be applied to quantify magma dynamics in other active volcanoes.

Scavenging and release of REE and HFSE by Na-metasomatism in magmatic-hydrothermal systems

Exploitable or potentially exploitable deposits of critical metals, such as rare-earth (REE) and high-field-strength elements (HFSE), are commonly associated with alkaline or peralkaline igneous rocks. However, the origin, transport and concentration of these metals in peralkaline systems remains poorly understood. This study presents the results of a mineralogical and geochemical investigation of the Na-metasomatism of alkali amphiboles and clinopyroxenes from a barren peralkaline granite pluton in NE China, to assess the remobilization and redistribution of REE and HFSE during magmatic-hydrothermal evolution. Alkali amphiboles and aegirine-augites from the peralkaline granites show evolutionary trends from sodic-calcic to sodic compositions, with increasing REE and HFSE concentrations as a function of increasing Na-index [Na#, defined as molar Na/(Na+Ca) ratios]. The Na-amphiboles (i.e., arfvedsonite) and aegirine-augites can be subsequently altered, or breakdown, to form hydrothermal aegirine during late- or post-magmatic alteration. Representative compositions analyzed by in-situ LA-ICPMS show that the primary aegirine-augites have high and variable REE (2194–3627 ppm) and HFSE (4194–16,862 ppm) contents, suggesting that these critical metals can be scavenged by alkali amphiboles and aegirine-augites. Compared to the primary aegirine-augites, the presentative early replacement aegirine (Aeg-I, Na# = 0.91–0.94) has notably lower REE (1484–1972) and HFSE (4351–5621) contents. In contrast, the late hydrothermal aegirine (Aeg-II, Na# = 0.92–0.96) has significantly lower REE (317–456 ppm) and HFSE (6.44–72.2 ppm) contents. Given that the increasing Na# from aegirine-augites to hydrothermal aegirines likely resulted from Na-metasomatism, a scavenging-release model can explain the remobilization of REE and HFSE in peralkaline granitic systems. The scavenging and release of REE and HFSE by Na-metasomatism provides key insights into the genesis of globally significant REE and HFSE deposits. The high Na-index of the hydrothermal aegirine might be useful as a geochemical indicator in the exploration for these critical-metals.

Titanite geochemistry and textures: Implications for magmatic and post-magmatic processes in the Notch Peak and Little Cottonwood granitic intrusions, Utah

Abstract Textural and compositional variations in titanite constrain the roles of magma mixing and hydrothermal alteration in two plutons in central Utah: the Jurassic Notch Peak and the Oligocene Little Cottonwood stocks. In the Notch Peak intrusion, magmatic titanite grains usually have oscillatory zones combined with BSE-bright sector zones, in some cases surrounding simple unzoned cores. These grains are frequently overprinted by hydrothermal titanite with low concentrations of high field strength elements (HFSE). Magmatic titanite has an average δ18O of 6.0‰ and post-magmatic titanite is 6.2‰, as analyzed by SIMS. Average Zr-in-titanite temperatures are also similar, with 718 °C for magmatic and 711 °C for hydrothermal titanite. These observations indicate simple magmatic growth, followed by hydrothermal alteration by magmatic fluids. Titanite in aplite dikes and sills has lower concentrations of all trace elements except F. Many titanite grains in the aplites have late overgrowths of high-Fe titanite. This high-Fe titanite has δ18O of 6‰ and an average Zr-in-titanite temperature of 718 °C and likely precipitated from a last flush of exsolved magmatic water enriched in Cl and Fe. Titanite in the Little Cottonwood stock typically has distinct patchy cores with rounded and embayed ilmenite inclusions. Mafic enclaves have abundant titanite that is similar in texture and δ18O (5.1‰) to titanite in the host (δ18O = 4.9‰), but it has a slightly higher average Zr-in-titanite temperature (731 vs. 717 °C). The patchy cores in the enclaves have the highest average Zr-in-titanite temperature (759 °C) and distinctive REE patterns. The textural and compositional data indicate that a hotter, more reduced, ilmenite-bearing mafic magma mixed into an oxidized felsic magma, destabilizing existing ilmenite and allowing crystallization of titanite. In the granodiorite and in the enclaves, hydrothermal growth of titanite is evidenced by distinct narrow rims as well as anhedral titanite that grew between sheets of chloritized biotite. Secondary hydrothermal titanite typically has lower concentrations of most HFSE, but is relatively enriched in F, Mg, Mo, and U, and it has higher Nb/Ta and lower Th/U ratios. Post-magmatic titanite also has strikingly different REE patterns than magmatic titanite, including the absence of pronounced Eu anomalies and lower REE abundances. These chemical features are controlled by element solubilities in aqueous fluids. In most cases, hydrothermal titanite has δ18O values similar to magmatic titanite, indicating alteration and recrystallization from exsolved magmatic fluids. The involvement of meteoric water with low δ18O is evident locally; individual spots have δ18O as low as 1.7‰ in the Little Cottonwood stock. Titanite compositions and textures provide important insights into the origins of granitic rocks and can be used to distinguish separate batches of magma, gauge the evolution of magmatic rocks, assess mixing processes, and infer compositions of mixing components. Because titanite also forms hydrothermally, it retains hints about the composition, temperature, and oxygen fugacity of the hydrothermal fluids and reveals details about titanite-forming reactions. However, the Al-in-titanite geobarometer does not yield realistic pressures of crystallization and the use of titanite as a geochronometer is compromised by the development of U-rich hydrothermal titanite.

Sediment-Peridotite Reaction Controls Fore-Arc Metasomatism and Arc Magma Geochemical Signatures

Subduction of oceanic crust buries an average thickness of 300–500 m of sediment that eventually dehydrates or partially melts. Progressive release of fluid/melt metasomatizes the fore-arc mantle, forming serpentinite at low temperatures and phlogopite-bearing pyroxenite where slab surface reaches 700–900 °C. This is sufficiently high to partially melt subducted sediments before they approach the depths where arc magmas are formed. Here, we present experiments on reactions between melts of subducted sediments and peridotite at 2–6 GPa/750–1100 °C, which correspond to the surface of a subducting slab. The reaction of volatile-bearing partial melts derived from sediments with depleted peridotite leads to separation of elements and a layered arrangement of metasomatic phases, with layers consisting of orthopyroxene, mica-pyroxenite, and clinopyroxenite. The selective incorporation of elements in these metasomatic layers closely resembles chemical patterns found in K-rich magmas. Trace elements were imaged using LA-ICP-TOFMS, which is applied here to investigate the distribution of trace elements within the metasomatic layers. Experiments of different duration enabled estimates of the growth of the metasomatic front, which ranges from 1–5 m/ky. These experiments explain the low contents of high-field strength elements in arc magmas as being due to their loss during melting of sedimentary materials in the fore-arc.

Rare earth element enrichment in the ion-adsorption deposits associated granites at Mesozoic extensional tectonic setting in South China

Ion-adsorption type rare earth element mineralization occurs in weathered profile of three Mesozoic granites in the Bachi area, Guangdong Province, South China. In this study, we investigate the REE enrichment processes in these granites using geochemical and geochronological data. The three granites yield zircon U-Pb ages of ca. 189 Ma, 153 Ma and 94 Ma, respectively, and could be divided into Early Jurassic, Late Jurassic and Cretaceous granites. The Early Jurassic and Cretaceous granites show similar geochemical characteristics, i.e. high K2O and low CaO, Fe2O3, and MgO contents, low K2O/Na2O ratios, and depletion of Eu, Sr, Ba, Ti, and P. They are characterized by high HFSE (high field strength elements) contents and enriched isotopic compositions with εNd(t) values ranging from −5.4 to-2.7, and εHf(t) values ranging from −4.5 to 1.7. The Late Jurassic granite also shows Eu, Sr, Ba, Ti, and P depletion and high HFSE contents. It has, however, higher CaO, Fe2O3, MgO and lower K2O contents than the Early Jurassic and Cretaceous granites. The Late Jurassic granite also shows more enriched isotopic compositions with εNd(t) values ranging from −9.0 to −8.9, and εHf(t) values ranging from −11.1 to −6.1. In addition, the Late Jurassic granite comprises, in contrast to the Early Jurassic and Cretaceous granites, abundant inherited/captured zircons cores and accessory REE-rich minerals of allanite, titanite, apatite and fluorite. These Mesozoic granites have the geochemical affinity of A-type granite. The Zr saturation temperature is >820 °C for the Early Jurassic and Cretaceous granites, and ~900 °C for the Late Jurassic granite. The Early Jurassic and Cretaceous granites were derived from partial melting of felsic igneous rocks under high-temperature, low-pressure, and anhydrous conditions. The felsic igneous source could provide relatively high REE contents for the melts, and the high-temperature, low-pressure, and anhydrous conditions resulted in residual plagioclase and melting of REE-rich minerals in the source area, which favour to REE enrichment in the melt. The Late Jurassic granite, on the other hand, was derived from a more mafic source and associate with fast crustal magma generation as indicated by its abundant presence of inherited/captured zircon cores in the high-temperature condition. The fast magma generation of the Late Jurassic granite prevented the separation of REE-rich minerals from the melt resulting in REE enrichment. Further, the high-temperature, low-pressure, and anhydrous physicochemical conditions and fast magma generation, which favour to REE enrichment in the granites, are tightly associated with large-scale Mesozoic extension in South China.

The Generation of Arc Andesites and Dacites in the Lower Crust of a Cordilleran Arc, Fiordland, New Zealand

Abstract We present microbeam major- and trace-element data from 14 monzodiorites collected from the Malaspina Pluton (Fiordland, New Zealand) with the goal of evaluating processes involved in the production of andesites in lower arc crust. We focus on relict igneous assemblages consisting of plagioclase and amphibole with lesser amounts of clinopyroxene, orthopyroxene, biotite and quartz. These relict igneous assemblages are heterogeneously preserved in the lower crust within sheeted intrusions that display hypersolidus fabrics defined by alignment of unstrained plagioclase and amphibole. Trace-element data from relict igneous amphiboles in these rocks reveal two distinct groups: one relatively enriched in high field strength element concentrations and one relatively depleted. The enriched amphibole group has Zr values in the range of ∼25–110 ppm, Nb values of ∼5–32 ppm, and Th values up to 2·4 ppm. The depleted group, in contrast, shows Zr values <35 ppm and Nb values <0·25 ppm, and Th is generally below the level of detection. Amphibole crystallization temperatures calculated from major elements range from ∼960 to 830 °C for all samples in the pluton; however, we do not observe significant differences in the range of crystallization temperatures between enriched (∼960–840 °C) and depleted groups (∼940–830 °C). Bulk-rock Sr and Nd isotopes are also remarkably homogeneous and show no apparent difference between enriched (εNdi = 0·1 to –0·1; 87Sr/86Sri = 0·70420–0·70413) and depleted groups (εNdi = 0·3 to –0·4; 87Sr/86Sri = 0·70424–0·70411). Calculated amphibole-equilibrium melt compositions using chemometric equations indicate that melts were highly fractionated (molar Mg# <50), andesitic to dacitic in composition, and were much more evolved than bulk lower continental crust or primitive basalts and andesites predicted to have formed from hydrous melting of mantle-wedge peridotite beneath an arc. We suggest that melts originated from a common, isotopically homogeneous source beneath the Malaspina Pluton, and differences between enriched and depleted trace-element groups reflect varying contributions from subducted sediment-derived melt and sediment-derived fluid, respectively. Our data demonstrate that andesites and dacites were the dominant melts that intruded the lower crust, and their compositions mirror middle and upper bulk-continental crust estimates. Continental crust-like geochemical signatures were acquired in the source region from interaction between hydrous mantle-wedge melts and recycled subducted sediment rather than assimilation and/or remelting of pre-existing lower continental crust.

The Petrology of the Tarosero Volcanic Complex: Constraints on the Formation of Extrusive Agpaitic Rocks

Abstract The Quaternary Tarosero volcano is situated in the East African Rift of northern Tanzania and mainly consists of trachyte lavas and some trachytic tuffs. In addition, there are minor occurrences of extrusive basalts, andesites and latites, as well as peralkaline trachytes, olivine trachytes and phonolites. Some of the peralkaline phonolites contain interstitial eudialyte, making Tarosero one of the few known occurrences for extrusive agpaitic rocks. This study investigates the genetic relationships between the various rock types and focuses on the peculiar formation conditions of the extrusive agpaitic rocks using a combination of whole-rock geochemistry, mineral chemistry, petrography, thermodynamic calculations, and major and trace element modelling. The Tarosero rocks formed at redox conditions around or below the fayalite–magnetite–quartz buffer (FMQ). During multi-level magmatic fractionation at depths between ∼40 km and the shallow crust, temperature decreased from >1100 °C at near-liquidus conditions in the basalts to ∼700 °C in the peralkaline residue. Fractional crystallization models and trace element characteristics do not indicate a simple genetic relationship between the trachytes and the other rock types at Tarosero. However, the genetic relationships between the primitive basalts and the intermediate latites can be explained by high-pressure fractional crystallization of olivine + clinopyroxene + magnetite + plagioclase + apatite. Further fractionation of these mineral phases in addition to amphibole and minor ilmenite led to the evolution towards the peralkaline trachytes and phonolites. The eudialyte-bearing varieties of the peralkaline phonolites required additional low-pressure fractionation of alkali feldspar and minor magnetite, amphibole and apatite. In contrast to the peralkaline trachytes and phonolites, the peralkaline olivine trachytes contain olivine instead of amphibole, thus indicating a magma evolution at even lower pressure conditions. They can be modelled as a derivation from the latites by fractional crystallization of plagioclase, clinopyroxene, magnetite and olivine. In general, agpaitic magmas evolve under closed-system conditions, which impede the escape of volatile phases. In the case of the extrusive agpaitic rocks at Tarosero, the early exsolution of fluids and halogens was prevented by a low water activity. This resulted in high concentrations of rare earth elements (REE) and other high field strength elements (HFSE) and the formation of eudialyte in the most evolved peralkaline phonolites. Within the peralkaline rock suite, the peralkaline olivine trachytes contain the lowest HFSE and REE concentrations, consistent with mineralogical evidence for formation at a relatively high water activity. The lack of amphibole fractionation, which can act as a water buffer of the melt, as well as the evolution at relatively low-pressure conditions caused the early exsolution of fluids and loss of water-soluble elements. This prevented a strong enrichment of HFSE and REE before the magma was finally extruded.

TTG generation by fluid-fluxed crustal melting: Direct evidence from the Proterozoic Georgetown Inlier, NE Australia

Across the Archaean to Proterozoic transition, the composition of newly-formed felsic continental crust changed from tonalite–trondhjemite–granodiorite (TTG) to calc-alkaline granitoid, possibly coinciding with the emergence of plate tectonics. Nevertheless, TTG suites were sporadically produced in Proterozoic and Phanerozoic orogenic belts, and such occurrences may provide petrological and tectonic insights into the formation of ancient continents. Here we demonstrate that the ca 1560 Ma Forest Home TTG plutonic suite in the Georgetown Inlier, NE Australia, was derived from partial melting of spatially-associated mafic rocks in a post-collisional setting. The studied TTG rocks have a ‘high-pressure’ geochemical signature, with elevated Sr, low heavy rare earth element and low high field strength element contents. Established petrogenetic models suggest they were derived by partial melting either of hydrated basaltic crust at >70 km depth or enriched lithospheric mantle, or by fractionation of lower-pressure mafic magmas. Using phase equilibrium calculations and trace-element modelling, we show that the geochemical signature of the Georgetown TTG likely resulted from fluid-fluxed crustal melting at relatively shallow depths (25–35 km), consistent with field observations and the inferred metamorphic evolution of the inlier. Our results suggest that the chemical variability of TTGs can reflect the variable availability of fluids rather than depth of melting, which has implications for tectonic processes responsible for the formation of early continental crust.

Ultrapotassic magmatism in the heyday of the Variscan Orogeny: the story of the Třebíč Pluton, the largest durbachitic body in the Bohemian Massif

The Třebic Pluton (TP) comprises plutonic rocks of the ‘durbachite series’, i.e., ultrapotassic biotite–amphibole quartz melasyenites–melagranites with conspicuous K-feldspar phenocrysts and abundant mafic enclaves. The TP with its satellite bodies intruded the eastern Moldanubian Zone (orogenic root of the Variscan Bohemian Massif) at c. 338 Ma. Overall, the entire TP durbachite series (SiO2 = 52–67 wt%) remains highly magnesian, reduced, and (except when strongly contaminated) metaluminous. The durbachitic rocks are markedly enriched in lithophile elements (esp. Cs, Rb, Th, U, K and Pb) and LREE; in contrast, the contents of high-field strength elements (Nb, Ta, and Ti) and Sr are much lower, resulting in conspicuous negative anomalies in Primitive mantle-normalized multielement plots. The proposed petrogenetic model requires re-enrichment of the depleted, harzburgitic lithospheric mantle by deeply subducted crustal material of the Saxothuringian lower plate, directly and/or via (U)HP melt/fluid. This process produced phlogopite-rich metasomes (phlogopite harzburgites and/or glimmerites). The metasomes re-melted soon thereafter by a short thermal pulse caused by slab break-off or decompression melting of rising diapirs of the relatively light metasomatized mantle, yielding primary ultrapotassic melts (87Sr/86Sr337 > 0.712 and $$\varepsilon_{{{\text{Nd}}}}^{337}$$ ≤ 7.6). Upon their passage through the Moldanubian upper plate, ultrapotassic primary magmas mixed with felsic anatectic melts (87Sr/86Sr337 < 0.710; $$\varepsilon_{{{\text{Nd}}}}^{337}$$ > – 6.5). K-feldspar-driven fractional crystallization ± accumulation represented only a late modifying influence. The occurrence of such ultrapotassic enriched/crustally contaminated mantle-derived magmatism complicates any conventional mass-balance assessments of relative roles of crustal recycling vs. growth in hot collisional orogens, e.g., Variscides or Himalayas.

Generation of late Mesozoic felsic volcanic rocks in the Hailar Basin, northeastern China in response to overprinting of multiple tectonic regimes

We performed zircon U–Pb age dating and geochemical analyses of late Mesozoic felsic volcanic rocks in the Hailar Basin, NE China, with the aim of eclucidating their emplacement ages, origin and geodynamic significance. The volcanic rocks consist of dacites, rhyolites and rhyolitic tuffs. Laser ablation–inductively coupled plasma–mass spectrometry zircon U–Pb dating results suggest that the rocks were erupted during the Late Jurassic–Early Cretaceous (161–117 Ma). They belong to the high-K calc-alkaline series and can be divided into two groups. Group I rocks are metaluminous to weakly peraluminous, contain low concentrations of heavy rare earth elements (HREEs) and high field strength elements (HFSEs), and have low zircon saturation temperatures (average 786 °C), all of which indicate an I-type affinity. In contrast, Group II rocks have higher HREE and HFSE concentrations and zircon saturation temperatures (average 918 °C), suggesting an A-type affinity. All the felsic volcanic rocks have positive εHf(t) values of 1.43–12.32 with two-stage model ages of 1110–401 Ma. Our data indicate that the I-type felsic volcanic rocks formed from magmas generated by partial melting of a dominantly juvenile mica-bearing K-rich basaltic lower crust, whereas the A-type felsic volcanic rocks originated from the partial melting of a dry mafic–intermediate middle–lower crust that was dehydrated but not melt depleted. Based on the present results and previous research, we propose that the Late Jurassic I- and A-type felsic volcanic rocks in the Hailar Basin were formed in a post-collisional environment related to break-off of the subducted oceanic slab of the Mongol–Okhotsk Ocean and the subsequent gravitational collapse of the orogenically-thickened crust after closure of the ocean. In contrast, the Early Cretaceous I- and A-type felsic volcanic rocks were erupted in an extensional setting related to rollback of the subducted Paleo-Pacific Plate.

Trace element–enriched mid-Visean dikes in the New Carlisle area of Quebec, Canada: Unusual products of a tholeiitic melt sourced from metasomatized mantle rocks and fractionated in a brine-rich upper-crustal environment

Abstract Early Carboniferous tholeiitic dikes in the New Carlisle area of Quebec, Canada, are abnormally enriched in high field strength elements (HFSEs), including rare earth elements. The enrichment is systematic and was apparently caused by an enhanced incompatibility of HFSEs during a prolonged episode of crystal fractionation. As a result, HFSE concentrations are up to one order of magnitude higher than those of typical mafic rocks. Very high F and Cl contents suggest that halogen complexing was largely responsible for the trace-element enrichment. The high halogen contents are in part accounted for by a subcontinental lithospheric mantle source that had previously been enriched in these elements by prolonged subduction. Additional Cl enrichment is interpreted to have occurred in a magma chamber that developed within porous and brine-rich country rocks of the upper crust. This conclusion is supported by the observation that HFSE-enriched mafic plutons in the same magmatic province occur in nonmetamorphosed upper-crustal rocks, suggesting high buoyancy and therefore high temperatures. Such evidence for high heat in the late Paleozoic magmatic system of eastern Canada corroborates previous studies suggesting that the transtensional basin in which it evolved was overriding a mantle plume at the time. In the case of the New Carlisle dikes, which are more than twice as enriched in incompatible trace elements as slightly older mafic rocks of the same magmatic system, the regional paleoenvironmental setting suggests that the associated upper-crustal magma chamber may have evolved in rocks with saltier pore water due to long-lasting evaporitic conditions at the surface.

Petrogenesis of plagiogranites from the Troodos Ophiolite Complex, Cyprus

Small volumes of felsic melt, commonly known as oceanic plagiogranites, appear as melt pockets or dikes within the gabbroic section and the sheeted dikes root zone of the oceanic crust. Plagiogranites from the Troodos Ophiolite Complex on Cyprus are among the best exposures of felsic rocks that are embedded in a complete section of obducted oceanic lithosphere. Nevertheless, their exact petrogenesis is still a matter of debate, largely due to limited high-quality trace element and radiogenic isotope data. Previously proposed models for Troodos plagiogranites have included both low-pressure dehydration melting and fractional crystallisation at deeper levels of the oceanic crust. To evaluate both models, oceanic plagiogranites from the Troodos Ophiolite Complex were analysed in this study for their major and trace elements, and for the first time also for Hf–Nd–Sr isotope compositions. The trace element measurements also include for the first time high-precision measurements of high-field-strength element (HFSE) abundances that now permit to better unravel the petrogenesis of the Troodos plagiogranites and their possible mantle sources. In general, the Troodos plagiogranites exhibit a narrow range of Nb/Ta and Zr/Hf that overlap the compositions of mid-ocean ridge basalts (MORB). In line with earlier studies, three compositional groups can be identified: two groups formed by either fractional crystallisation or combined fractional crystallisation and wall rock assimilation, and one group derived from partial melting of slightly altered oceanic crust. The majority of the Troodos plagiogranites (Main Group) are the product of extensive fractional crystallisation of ambient arc-tholeiitic mafic melts. A second group of plagiogranites (Spilia Group) is generated by fractional crystallisation of boninitic precursor melts and the assimilation of arc-tholeiitic crustal material. Variable HFSE concentrations and diagnostic Hf–Nd isotope signatures that are unique to both suites allow discriminating between the two parental melts and fractionation processes. A small group of plagiogranites (Zoopigi Group) is interpreted to derive from partial melting in the conductive layer of active magma chamber lenses (AML). Elevated Nb/Ta, Zr/Hf, and light rare-earth element (LREE) enrichments in these rocks are in support of this model. Collectively, our data suggest that low-pressure fractional crystallisation (also in combination with assimilation of wall rocks) might be the predominant process controlling the formation of felsic rocks on Cyprus, whereas dehydration melting appears to be less important. If compared to Archean tonalitic–trondhjemitic–granodioritic suites (TTGs), compositions of plagiogranites from Cyprus mirror shallow-level processes in thin oceanic crust, which is illustrated by their narrow, MORB-like range of HFSE ratios and their distinct enrichment in heavy rare-earth elements (HREE) that distinguishes them from the Archean TTGs.

From Mantle to Motzfeldt: A genetic model for syenite-hosted Ta,Nb-mineralisation

A genetic model for the Motzfeldt Tantalum-Niobium-rich syenite in south-west Greenland, considered to be one of the world’s largest Ta prospects, is presented. The Motzfeldt primary magma formed early in regional Gardar (1273 ± 6 Ma) rifting. Isotope signatures indicate that the Hf had multiple sources involving juvenile Gardar Hf mixed with older (Palaeoproterozoic or Archaean) Hf. We infer that other High Field Strength Elements (HFSE) similarly had multiple sources. The magma differentiated in the crust and ascended before emplacement at the regional unconformity between Ketilidian basement and Eriksfjord supracrustals. The HFSE-rich magmas crystallised Ta-rich pyrochlore which formed pyrochlore-rich crystal mushes, and it is these pyrochlore-rich horizons, rich in Ta and Nb, that are the focus of exploration. The roof zone chilled and repeated sheeting at the roof provided a complex suite of cross-cutting syenite variants, including pyrochlore microsyenite, in a ‘Hot Sheeted Roof’ model. The area was subject to hydrothermal alteration which recrystallized alkali feldspar to coarse perthite and modified the mafic minerals to hematite, creating the friable and striking pink-nature of the Motzfeldt Sø Centre. Carbon and oxygen isotope investigation of carbonate constrains fluid evolution and shows that carbonate is primarily mantle-derived but late-stage hydrothermal alteration moved the oxygen isotopes towards more positive values (up to 21‰). The hydrothermal fluid was exceptionally fluorine-rich and mobilised many elements including U and Pb but did not transport HFSE such as Ta, Hf and Nb. Although the U and Pb content of the pyrochlore was enhanced by the fluid, the HFSE contents remained unchanged and therefore Hf isotopes were unaffected by fluid interaction. While the effect on hydrothermal alteration on the visual appearance of the rock is striking, magmatic processes concentrated HFSE including Ta and the hydrothermal phase has not altered the grade. Exploration for HFSE mineralisation commonly relies on airborne radiometric surveying which is particularly sensitive to the presence of U, Th. A crucial lesson from Motzfeldt is that the best target is unaltered pyrochlore which was identified less easily by radiometric survey. Careful petrological/mineral studies are necessary before airborne survey data can be fully interpreted.