Compatible Trace Elements Research Articles

Petrogenesis of Early Cretaceous granites and associated microgranular enclaves in the Xiabie Co area, central Tibet: Crust-derived magma mixing and melt extraction

Multiple petrogenesis models have been proposed for granitic rocks and the mafic microgranular enclaves (MMEs) hosted in them. The mantle and crust-derived magma mixing/mingling process was widely suggested for the formation of MMEs or the host granitoids. However, whether the mixing between magmas derived from different crustal sources may also form microgranular enclaves (MEs, not restricted to mafic) or the host granites remain unclear. Here, we report petrological, geochemical, and zircon in situ Hf-O isotopic data for MEs and their host granites in the northern Nyima area, southern Qiangtang terrane (SQT), central Tibet. The host granitic rocks consist of amphibole-bearing biotite granites and syenogranite, minor granodiorite and aplite veins, and MEs comprising diorite and granodiorite. Host rocks and MEs are contemporaneous and were generated in the Early Cretaceous (∼120 Ma). Host granitoid samples are high-K calc-alkaline rocks and have high SiO2 (66–78 wt%) and low MgO (<1.14 wt%). They have enriched whole-rock εNd(t) (−1.82 to −3.06), and variable zircon εHf(t) (+0.64 to +5.12) and δ18O (7.35 to 9.61‰) values. The host granodiorites contain some mafic mineral-rich clots and lower silica contents than the biotite granites. They exhibit distinctive geochemical patterns (such as high K2O > 5 wt%, high Zr >500 ppm with Zr/Hf ratios >45, and high Ba >400 ppm), implying biotite and zircon concentrations. Combining this information with embayed feldspars, curved biotites, and closely spaced feldspar grains, we suggest that liquid loss resulted from crystal compaction or filter pressing. Both the fine-grained syenogranites and aplite veins exhibit high SiO2 and Rb/Sr ratios in addition to low Zr/Hf ratios and Zr and Ba concentrations with remarkably negative Eu anomalies, indicating that they are highly differentiated melts extracted from felsic crystal mush. Such a crystal mush is possibly represented by the biotite granites. Gradual contact relationships between variable granitic phases indicate that melt extraction and crystal concentration were coeval. Residual melt extraction from the crystal mush was facilitated by mush remobilization resulting from magma replenishment. We suggest that for the host rocks, the biotite granites were mainly derived by partial melting of ancient crust, and the granodiorites most likely resulted from the magma mixing/mingling that might be accompanied with the loss of melts, the fine-grained syenogranites and aplites represent highly evolved residual melts. MEs are geochemically characterized by intermediate to felsic compositions (SiO2 = 56.3–67.8 wt%), with low MgO (<4 wt%) and Mg# (< 53) and low mantle compatible trace element (Cr and Ni) contents. They exhibit enriched whole-rock Nd (εNd(t) = −0.36 to −2.71), depleted zircon εHf(t) (+0.51 to +5.68) and high δ18O values (7.45 to 9.57‰), except for one sample with comparable whole-rock εNd(t) (−1.32), relatively high zircon εHf(t) (+5.05 to +7.11) and δ18O (6.09 to 7.10‰) values. MEs exhibit evidence for quenched magma crystallization, chemical exchange, mineral disequilibrium and mass transfer, indicating inefficient magma mixing/mingling. Mafic minerals from MEs were in equilibrium with evolved melts rather than mantle-derived primitive melts. Given the substantial absence of contemporaneous basaltic rocks from the SQT and the relatively high SiO2 and low MgO contents and crust-like zircon stable oxygen isotope of MEs, we propose that they most likely resulted from the mixing/mingling of diverse crust-derived magmas. Therefore, our study provides important evidence for crust-derived magma mixing and melt extraction from mush.

Geochemistry and fore-arc evolution of upper mantle peridotites in the Cryogenian Bir Umq ophiolite, Arabian Shield, Saudi Arabia

ABSTRACTThe Bir Umq ophiolite is one of the most important ophiolitic successions in the Arabian Shield, and represents an excellent case for the study of the tectonomagmatic evolution of the earliest Precambrian events in the juvenile part of the Arabian-Nubian Shield (ANS). It is a dismembered ophiolite, which includes a serpentinized peridotite with small amounts of gabbro and mélange, and is overlain by the Sumayir formation. The mantle section of the Bir Umq ophiolite has been pervasively sheared and folded during its emplacement and is extensively serpentinized, carbonated and silicified, resulting in the common development of magnesite and listwaenite along the shear zones. Listwaenite occurs in the form of upstanding ridges due to its resistance to erosion. Antigorite is the main serpentine mineral, which, however, has low amounts of lizardite and chrysotile, indicating that the present serpentinites formed by prograde metamorphism. The ophiolitic rocks of Bir Umq have undergone regional metamorphism up to the greenschist to amphibolite facies. The presence of mesh and bastite textures indicates harzburgite and dunite protoliths. The serpentinized peridotite preserves rare relicts of primary minerals such as olivine, pyroxene and Cr-spinel. The serpentinized ultramafics of Bir Umq have high Mg# [molar Mg/(Mg+Fe2+); 0.90–0.93), low CaO, and Al2O3 contents similar to that of the environment of the suprasubduction zone. Additionally, they are characterized by the depletion of some compatible trace elements (e.g., Nb, Sr, Ta, Zr, Hf and REE), but show a wide variation in the Rb and Ba. Moreover, they are enriched in some elements that have affinities for Mg-rich minerals such as Ni, Cr, V, and Co. Fresh relics of olivine have high Fo (av. 0.91) and NiO (av. 0.42) contents, similar to those in the mantle olivine. The fresh Cr-spinel has high Cr# (0.68) and low TiO2 content (av. 0.11), similar to those in modern fore-arc peridotites. The composition of both orth- and clinopyroxenes confirms the fore-arc affinity of the studied ultramafics. The present study indicates that the protoliths of the serpentinized ultramafics of Bir Umq have high partial melt degrees, which is consistent with the characteristics of ultramafic rocks formed in a subarc environment (fore-arc) within a suprasubduction zone system.

The effect of diffusive re-equilibration time on trace element partitioning between alkali feldspar and trachytic melts

We present new experimental data on major and trace element partition coefficients between alkali feldspar and trachytic melt. Experiments were conducted at 500 MPa, 870–890 °C to investigate through short disequilibrium and long near-equilibrium experiments the influence of diffusive re-equilibration on trace element partitioning during crystallization. Our data show that Ba and Sr behave compatibly, and their partition coefficients are influenced by re-equilibration time, orthoclase (Or) content, growth rate and cation order-disorder. High field strength elements (HFSE) and rare earth elements (except Eu) are strongly incompatible, but alkali feldspar efficiently fractionates light (LREE) from heavy rare earth elements (HREE).Our crystallization experiments reveal a strong influence of disequilibrium crystal growth on the partitioning of Ba and Sr. In particular, short-duration experiments show that rapid alkali feldspar crystal growth after nucleation, promotes disordered growth and less selectivity in the partitioning of compatible trace elements that easily enter the crystal lattice (e.g., Ba and Sr). This produces partition coefficients of compatible elements higher than those obtained through long-duration experiments, in which growth is slower and more selective. On approach to equilibrium, decreasing growth rate and timescales of diffusive re-equilibration facilitates the incorporation of compatible elements within the crystal lattice (through ordered growth), on the basis of the charge and size of the octahedral site, resulting in lower partition coefficients of Ba and Sr. Therefore, our results indicate that besides crystal-chemical effects, i.e. lattice strain, the substitution mechanisms during growth (with different degrees of ordering) of Ba and Sr in alkali feldspar are strongly influenced by diffusive re-equilibration and crystal growth kinetics. This implies that partition coefficients of Ba and Sr can be used to establish timescales of crystallization processes under pre- and syn-eruptive conditions. The application of our results to alkali feldspar in rocks from Campi Flegrei, constrain the magma residence time at subliquidus conditions in a reservoir to a maximum of 6 days under disequilibrium conditions and to a minimum of 9 days upon approaching near-equilibrium conditions.

Origin of dioritic magma and its contribution to porphyry Cu–Au mineralization at Pulang in the Yidun arc, eastern Tibet

The giant Pulang porphyry Cu–Au deposit in the Yidun arc, eastern Tibet, formed due to westward subduction of the Garze–Litang oceanic plate in the Late Triassic. The deposit is hosted in an intrusive complex comprising primarily coarse-grained quartz diorite and cored quartz monzonite. Here, we investigate a suite of simultaneous (216.6 ± 1.9 Ma) diorite porphyries within the complex. The diorite porphyries are geochemically similar to mafic magmatic enclaves (MME) hosted in coarse-grained quartz diorite, and both are characterized by low SiO2 (59.4–63.0 wt%) and high total alkali (Na2O + K2O = 7.0–9.2 wt%), K2O (3.5–6.4 wt%), MgO (3.2–5.5 wt%), and compatible trace element (e.g., Cr = 72–149 ppm) concentrations. They are enriched in large-ion lithophile and light rare earth elements (LILE and LREE, respectively), but depleted in high field-strength and heavy rare earth elements (HFSE and HREE, respectively), and yield variably high (La/Yb)N ratios (17–126, average 65) with weak to negligible Eu anomalies. Furthermore, they yield low (87Sr/86Sr)i ratios (0.7054–0.7067), weakly negative εNd(t) (−2.8 to −0.8) values, and variable zircon εHf(t) (−5.4 to +0.8) and δ18O (6.0‰–6.7‰) values. These geochemical features indicate that the diorite porphyry and MME formed through crustal assimilation of a magma produced during low-degree partial melting of metasomatized phlogopite-rich subcontinental lithospheric mantle. In contrast, the coarse-grained quartz diorite and quartz monzonite have relatively high concentrations of SiO2 (61.1–65.3 wt%), K2O (4.1–5.4 wt%), and total alkali (Na2O + K2O = 7.1–8.1 wt%), and low concentrations of MgO (generally <3.0 wt%) and compatible trace elements (e.g., Cr = 38–61 ppm). They yield high Sr/Y ratios (50–63) that indicate an adakitic affinity, and are enriched in LILE, depleted in HFSE, and yield lower (La/Yb)N values (13–20, average 17) than the diorite porphyry and MME. They yield low (87Sr/86Sr)i ratios (0.7046–0.7066), negative εNd(t) (−3.3 to −1.7) values, and zircon εHf(t) and δ18O values of −2.9 to −0.1 and 5.7‰–6.5‰, respectively, suggesting that they represent high-K calc-alkaline to shoshonitic adakitic magmas that were sourced from subduction-modified juvenile lower crust. Observations of the newly identified diorite porphyry and previously reported MME suggest that input of such dioritic magma into the upper crustal porphyry magma chamber would have contributed not only the necessary metals (e.g., Cu and Au), sulfur, but also H2O to the system, thus aiding in the generation of the giant Pulang porphyry Cu–Au deposit.

Mantle-derived trace element variability in olivines and their melt inclusions

Trace element variability in oceanic basalts is commonly used to constrain the physics of mantle melting and the chemistry of Earth's deep interior. However, the geochemical properties of mantle melts are often overprinted by mixing and crystallisation processes during ascent and storage. Studying primitive melt inclusions offers one solution to this problem, but the fidelity of the melt-inclusion archive to bulk magma chemistry has been repeatedly questioned. To provide a novel check of the melt inclusion record, we present new major and trace element analyses from olivine macrocrysts in the products of two geographically proximal, yet compositionally distinct, primitive eruptions from the Reykjanes Peninsula of Iceland. By combining these macrocryst analyses with new and published melt inclusion analyses we demonstrate that olivines have similar patterns of incompatible trace element (ITE) variability to the inclusions they host, capturing chemical systematics on intra- and inter-eruption scales.ITE variability (element concentrations, ratios, variances and variance ratios) in olivines from the ITE-enriched Stapafell eruption is best accounted for by olivine-dominated fractional crystallisation. In contrast, ITE variability in olivines and inclusions from the ITE-depleted Háleyjabunga eruption cannot be explained by crystallisation alone, and must have originated in the mantle. Compatible trace element (CTE) variability is best described by crystallisation processes in both eruptions. Modest correlations between host and inclusion ITE contents in samples from Háleyjabunga suggest that melt inclusions can be faithful archives of melting and magmatic processes. It also indicates that degrees of ITE enrichment can be estimated from olivines directly when melt inclusion and matrix glass records of geochemical variability are poor or absent. Inter-eruption differences in olivine ITE systematics between Stapafell and Háleyjabunga mirror differences in melt inclusion suites, and confirm that the Stapafell eruption was fed by lower degree melts from greater depths within the melting region than the Háleyjabunga eruption.Although olivine macrocrysts from Stapafell are slightly richer in Ni than those from Háleyjabunga, their overall CTE systematics (e.g., Ni/(Mg/Fe), Fe/Mn and Zn/Fe) are inconsistent with being derived from olivine-free pyroxenites. However, the major element systematics of Icelandic basalts require lithological heterogeneity in their mantle source in the form of Fe-rich and hence fusible domains. We thus conclude that enriched heterogeneities in the Icelandic mantle are composed of modally enriched, yet nonetheless olivine-bearing, lithologies and that olivine CTE contents provide an incomplete record of lithological heterogeneity in the mantle. Modally enriched peridotites may therefore play a more important role in oceanic magma genesis than previously inferred.

The origin and tectonic significance of the volcanic rocks of the Yeba Formation in the Gangdese magmatic belt, South Tibet

Zircon U-Pb geochronology, Hf isotope and whole-rock geochemistry were performed on the tuffs of the Yeba Formation in the Gangdese magmatic belt, South Tibet. The results are used to detail the age, source nature and tectonic processes that led to the formation of the Gangdese belt. Dating results indicate that the rhyolitic-andesitic tuffs were formed at 174-170 Ma. Positive and variable zircon e Hf(t) values of the rhyolitic tuffs reveal that the source was dominated by juvenile material, however, experienced crustal contamination. The basaltic tuffs have low HREEs, high contents of compatible elements (V and Cr) and no Eu anomaly. In contrast, the rhyolitic-andesitic tuffs show low compatible trace elements, depletion in Eu but enrichment in incompatible elements (Rb, Zr and Hf). According to the discrimination diagrams of P2O5-SiO2 and Th-Rb, the rhyolitic-andesitic tuffs show a close affinity to I-type granitoids. Moreover, these tuffs are marked by significant depletion in Nb, Ta and Ti, plotted in calc-alkaline field, and with the andesitic-rhyolitic tuffs falling into an active continental margin setting. We suggest that these tuffs of the Yeba Formation were probably generated in an active continental margin above the northward subduction of the Neo-Tethyan oceanic lithosphere.

Chemical homogeneity of high-Cr chromitites as indicator for widespread invasion of boninitic melt in mantle peridotite of Bir Tuluha ophiolite, Northern Arabian Shield, Saudi Arabia

The Bir Tuluha ophiolite is one of the most famous chromitite-bearing occurrences in the Arabian Shield of Saudi Arabia, where chromitite bodies are widely distributed as lensoidal pods of variable sizes surrounded by dunite envelopes, and are both enclosed within the harzburgite host. The bulk-rock geochemistry of harzburgites and dunites is predominately characterized by extreme depletion in compatible trace elements that are not fluid mobile (e.g., Sr, Nb, Ta, Hf, Zr and heavy REE), but variable enrichment in the fluid-mobile elements (Rb and Ba). Harzburgites and dunites are also enriched in elements that have strong affinity for Mg and Cr such as Ni, Co and V. Chromian spinels in all the studied chromitite pods are of high-Cr variety; Cr-ratio (Cr/(Cr+Al) atomic ratio) show restricted range between 0.73 and 0.81. Chromian spinels of the dunite envelopes also show high Cr-ratio, but slightly lower than those in the chromitite pods (0.73–0.78). Chromian spinels in the harzburgite host show fairly lower Cr-ratio (0.49–0.57) than those in dunites and chromitites. Platinum-group elements (PGE) in chromitite pods generally exhibit steep negative slopes of typical ophiolitic chromitite PGE patterns; showing enrichment in IPGE (Os, Ir and Ru), over PPGE (Rh, Pt and Pd). The Bir Tuluha ophiolite is a unimodal type in terms of the presence of Ru-rich laurite, as the sole primary platinum-group minerals (PGM) in chromitite pods. These petrological features indicates that the Bir Tuluha ophiolite was initially generated from a mid-ocean ridge environment that produced the moderately refractory harzburgite, thereafter covered by a widespread homogeneous boninitic melt above supra-subduction zone setting, that produced the high-Cr chromitites and associated dunite envelopes. The Bir Tuluha ophiolite belt is mostly similar to the mantle section of the Proterozoic and Phanerozoic ophiolites, but it is a “unimodal” type in terms of high-Cr chromitites and PGE-PGM distribution.

Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland

Melt inclusions formed during the early stages of magmatic evolution trap primitive melt compositions and enable the volatile contents of primary melts and the mantle to be estimated. However, the syn- and post-entrapment behaviour of volatiles in primitive high-anorthite plagioclase-hosted melt inclusions from oceanic basalts remains poorly constrained. To address this deficit, we present volatile and light lithophile element analyses from a well-characterised suite of nine matrix glasses and 102 melt inclusions from the 10ka Grímsvötn tephra series (i.e., Saksunarvatn ash) of Iceland’s Eastern Volcanic Zone (EVZ). High matrix glass H2O and S contents indicate that eruption-related exsolution was arrested by quenching in a phreatomagmatic setting; Li, B, F and Cl did not exsolve during eruption. The almost uniformly low CO2 content of plagioclase-hosted melt inclusions cannot be explained by either shallow entrapment or the sequestration of CO2 into shrinkage bubbles, suggesting that inclusion CO2 contents were controlled by decrepitation instead. High H2O/Ce values in primitive plagioclase-hosted inclusions (182–823) generally exceed values expected for EVZ primary melts (∼180), and can be accounted for by diffusive H2O gain following the entrainment of primitive macrocrysts into evolved and H2O-rich melts a few days before eruption. A strong positive correlation between H2O and Li in plagioclase-hosted inclusions suggests that diffusive Li gain may also have occurred. Extreme F enrichments in primitive plagioclase-hosted inclusions (F/Nd=51–216 versus ∼15 in matrix glasses) possibly reflect the entrapment of inclusions from high-Al/(Al+Si) melt pools formed by dissolution-crystallisation processes (as indicated by HFSE depletions in some inclusions), and into which F was concentrated by uphill diffusion since F is highly soluble in Al-rich melts. The high S/Dy of primitive inclusions (∼300) indicates that primary melts were S-rich in comparison with most oceanic basalts. Cl and B are unfractionated from similarly compatible trace elements, and preserve records of primary melt heterogeneity. Although primitive plagioclase-hosted melt inclusions from the 10ka Grímsvötn tephra series record few primary signals in their volatile contents, they nevertheless record information about crustal magma processing that is not captured in olivine-hosted melt inclusions suites.

Origin of the Eocene porphyries and mafic microgranular enclaves from the Beiya porphyry Au polymetallic deposit, western Yunnan, China: Implications for magma mixing/mingling and mineralization

The origin of magmas with high H2O, S and metals that are linked to porphyry economic mineralization in continental collisional belts is controversial. In this paper, we studied the host porphyries and associated microgranular enclaves (MMEs) including gabbroic enclaves and dioritic enclaves from the large Beiya porphyry Au deposit in Jinshajiang-Ailaoshan mineralization belt, which provide first hand evidence of crust–mantle hybridization in the formation of fertile magma for porphyry deposit. Zircon LA-ICPMS U–Pb ages indicate coeval formation for the MMEs and the felsic porphyries in Eocene time (~36Ma). The MMEs show spheroidal shapes, acicular apatites, and oscillatory zoning with repeated resorption surfaces in plagioclases, which suggest that the MMEs are globules of a more mafic magma that was injected into and mingled with the host felsic magma. One gabbroic enclave sample exhibits high MgO (5.6wt.%), high TiO2 (1.7wt.%), enriched in large-ion lithophile element (LILE) and depleted in high field strength element (HFSE), with negative Nb, Ta and Ti anomalies. This indicates that the gabbroic enclave is similar to those of the coeval potassic mafic rocks in the Western Yunnan, which originated from the enriched mantle metasomatized by the slab-derived fluids. The dioritic enclave exhibit both potassic and adakitic-like features, and are characterized by high contents of MgO (4.4–4.9wt.%), K2O (6.4–7.4wt.%), and compatible trace elements (e.g. Ni: 115–142ppm; Cr: 214–291ppm), as well as by high Sr/Y ratios. The dioritic enclave samples yield εHf (t) values (−1.9 to +3.6) similar to those of the host porphyries. Petrographic, elemental, and isotopic evidence suggests that the Beiya dioritic enclave were formed by mixing between potassic mafic and adakitc-like melts, derived from metasomatized lithospheric mantle and lower crust, respectively. In contrast, the Beiya host porphyries are characterized by high SiO2 (66.9–71.9wt.%) and Al2O3 (13.8–15.9wt.%) contents, high Sr/Y ratios (35–79), low compatible element contents (e.g. Ni=0.9–7.2ppm; Cr =1.0–8.2ppm), low Mg# values (0.19–0.35), positive LILE anomalies, marked negative high HFSE anomalies, negative εNd(t) values (−6 to −2), and high (87Sr/86Sr)i values (0.7071–0.7081). These features indicate that the host porphyries were mainly formed by partial melting of subduction-modified lower crust with a certain assimilation of mafic melts represented by MMEs. MMEs hosted in the Beiya porphyries, formed from a hydrous, mafic magma although they formed in a non-arc setting. High magmatic water content is probably related to an enriched mantle metasomatized by fluids from a Proterozoic subducted oceanic slab. High Cu (341–626ppm) and Au contents of the MMEs suggest they crystallized from a metal-rich mafic melt. Complex assemblages of pyrite–chalcopyrite–apatite–rutile with hornblende are observed in the least altered MME. We suggest that the mafic melt probably supplied part of water, and metal to the Beiya porphyry Au system.

The muscovite granites: Parental rocks to the Nanling Range tungsten mineralization in South China

Muscovite granites (MGs) in the Nanling Range (South China) occur as satellite intrusions within or surrounding batholitic biotite monzogranites (BMs). The MGs are massive and fine-grained with a porphyritic texture, and contain quartz, K-feldspar and albite in nearly equal portions. The accessory minerals in the MGs include alumina-rich minerals (e.g., Mn- and Fe-rich garnet, andalusite, topaz, and tourmaline), anatase, rutile, wolframite, cassiterite, xenotime, chalcopyrite, molybdenite, and volatile-rich minerals (e.g., microlite, topaz, tourmaline, fluorite, and calcite). Compared with the BMs, the MGs are geochemically enriched in major elements of Si, K, and Na, and incompatible trace elements of Rb, Cs, Y, U, Nb, Ta, W, Sn, Pb, Bi, Li, and Be, and depleted in major elements of Fe, Mg, Ca, Ti, and P, and compatible trace elements of Ba, Sr, Co, Ni, Cr, Cd, V as well as Zr and Hf. The chondrite-normalized REE patterns of the MGs are flat with large negative Eu anomalies. The mineralogical and geochemical features of the MGs indicate that they crystallized from highly fractionated granitic magmas. Zircons separated from the MG samples, which were collected from six different tungsten deposits, show characters of hydrothermal origin according to their morphologies, chemical compositions and inclusions. In-situ U–Pb dating of the zircons yields a weighted mean 206Pb/238U age of 133.4±1.0Ma. This age is similar to the mean age of the zircons from wolframite-bearing quartz veins (WQVs) in the Nanling Range (133.7±1.3Ma) reported from our previous study. Zircon Hf isotopes also reveal that the MGs and the WQVs are homologous. These mineralogical, geochemical and zirconological features indicate that the MGs are the parental rocks of the tungsten deposits in the Nanling Range. This study provides a new guidance for the exploration of magmatic-hydrothermal tungsten deposits.

Zircon U–Pb age, Hf isotope and geochemistry of Carboniferous intrusions from the Langshan area, Inner Mongolia: Petrogenesis and tectonic implications

Late Paleozoic was a critical period for the tectonic evolution of the northern margin of the Alxa-North China craton, but the evolutionary history is not well constrained. The Carboniferous intrusions in the Langshan area in the western part of the northern margin of the Alxa-North China craton are mainly composed of tonalite, quartz diorite, olivine gabbro and pyroxene peridotite. Zircon LA-ICP-MS U–Pb dating indicates that the Langshan Carboniferous intrusions were emplaced at ca. 338–324Ma. The quartz diorites are characterized by high amounts of compatible trace elements (Cr, Ni and V) and high Mg# values, which may suggest a significant mantle source. The positive Pb and negative Nb–Ta–Ti anomalies, the variable εHf(t) (−6.9 to 2.0) values and the old Hf model ages (1218–1783Ma) imply some involvement of ancient continental materials in its petrogenesis. The tonalite has relatively high Sr/Y ratios, low Mg#, Yb and Y contents, features of adakite-like rocks, negative εHf(t) values (−9.8 to −0.1) and older Hf model ages (1344–1953Ma), which suggest significant involvement of ancient crust materials and mantle-derived basaltic component in its petrogenesis. The high Mg# values, high Cr and Ni contents, and low Zr and Hf contents of the mafic–ultramafic rocks show evidence of a mantle source, and the relatively low zircon εHf(t) values (−5.9 to 3.2) might point to an enriched mantle. The trace element characteristics indicate the influence of subducted sediments and slab-derived fluids. In the tectonic discrimination diagrams, all the rocks plot in subduction-related environment, such as volcanic arc and continental arc. Considering the regional geology, we suggest that the Carboniferous intrusions in the Langshan area were likely emplaced during the late stage of the southward subduction of the Paleo-Asian Ocean plate, which formed a continental arc along the northern margin of the Alxa-North China craton.

Simple models for disequilibrium fractional melting and batch melting with application to REE fractionation in abyssal peridotites

Disequilibrium melting arises when the kinetics of chemical exchange between a residual mineral and partial melt is sluggish compare to the rate of melting. To better understand the role of a finite crystal–melt exchange rate on trace element fractionation during mantle melting, we have developed a disequilibrium melting model for partial melting in an upwelling steady-state column. We use linear kinetics to approximate crystal–melt mass exchange rate and obtain simple analytical solutions for cases of perfect fractional melting and batch melting. A key parameter determining the extent of chemical disequilibrium during partial melting is an element specific dimensionless ratio (ε) defined as the melting rate relative to the solid–melt chemical exchange rate for the trace element of interest. In the case of diffusion in mineral limited chemical exchange, ε is inversely proportional to diffusivity of the element of interest. Disequilibrium melting is important for the trace element when ε is comparable to or greater than the bulk solid–melt partition coefficient for the trace element (k). The disequilibrium fractional melting model is reduced to the equilibrium perfect fractional melting model when ε is much smaller than k. Hence highly incompatible trace elements with smaller mobilities in minerals are more susceptible to disequilibrium melting than moderately incompatible and compatible trace elements. Effect of chemical disequilibrium is to hinder the extent of fractionation between residual solid and partial melt, making the residual solid less depleted and the accumulated melt more depleted in incompatible trace element abundances relative the case of equilibrium melting.Application of the disequilibrium fractional melting model to REE and Y abundances in clinopyroxene in abyssal peridotites from the Central Indian Ridge and the Vema Lithospheric Section, Mid-Atlantic Ridge revealed a positive correlation between the disequilibrium parameter ε and the degree of melting, which can be explained by an increase in melting rate and a decrease in REE diffusion rate in the upper part of the melting column. Small extent of disequilibrium melting for LREE and equilibrium melting for HREE in the upper part of the melting column can explain the elevated LREE abundances or spoon-shaped REE patterns in clinopyroxene in more refractory abyssal peridotites. The latter has often been attributed to melt refertilization.

Provenance and composition of unusually chrome and nickel-rich bucket-shaped pottery from Rogaland (southwestern Norway)

We report results from FE-SEM–EDS, geochemical, mineralogical analyses and Raman spectroscopy of pottery of bucket-shaped ceramic from Rogaland (southwestern Norway) dated between the 5th and 6th Century. The study reveals a very rare pottery composition including asbestos-group minerals and an unusual enrichment in compatible elements like Cr (8–27× Post Archean average shale (PAS), McLennan et al., 2006), Ni (2–8× normal shale) and Co (2–3× PAS). X-Rray diffraction and Raman spectroscopy could pinpoint that Ni is introduced by specific Ni-rich talc mineral and chlorite minerals and Cr occurs in a rare Cr-rich talc, and possibly in a Cr-chlorite, these minerals are the most abundant in the pottery, which is supported by strong enrichment in Mg (10–20× PAS). The addition of Mg, Cr, Ni and Co and other compatible trace elements is to our current knowledge not caused by anthropogenic activity but related to the used materials, which are alteration products of mafic and ultramafic rocks or genetically related to mafic and ultramafic rocks. Rocks of this type are exposed in vicinity of the sampling areas in a region called Karmøy, hosting a world famous ophiolite complex, which is identified as the major source for the mafic and ultramafic component, as the next succession of a similar composition is far further north located in Norway and a number of rock types on Karmøy matches the chemical composition of the pottery. The here reported composition is spectacular and extremely rare – if ever found – in pottery. Our study shows that unusual material sources have been used in pottery production, and this opens for discussion whether the materials were deliberately selected by the manufacturers, thereby expressing a specific social function, in a time period where more functional clay types and additives, and certainly functional and sufficient for use in pottery, where abundant in areas of Rogaland closer to where the pots were found.

Petrogenesis of Mesoproterozoic lamproite dykes from the Garledinne (Banganapalle) cluster, south-western Cuddapah Basin, southern India

We report mineral chemistry and whole-rock major and trace-element geochemistry for a recent find of Mesoproterozoic (~1.4 Ga) lamproites from the Garledinne (Banganapalle) cluster, south-western part of the Paleo-Mesoproterozoic Cuddapah Basin, southern India. The Garledinne lamproites occur as WNW–ESE-trending dykes that have undergone varying degree of pervasive silicification and carbonate alteration. Nevertheless, their overall texture and relict mineralogy remain intact and provide important insights into the nature of their magmas. The lamproite dykes have porphyritic to weakly porphyritic textures comprising pseudomorphed olivine macrocrysts and microphenocrysts, titanian phlogopite microphenocrysts, spinel having a compositional range from chromite to rarely magnesiochromite, Sr-rich apatite and niobian rutile. The Garledinne and other Cuddapah Basin lamproites (Chelima and Zangamarajupalle) collectively lack sanidine, clinopyroxene, potassic richterite, and titanite and are thus mineralogically distinct from the nearby Mesoproterozoic lamproites (Krishna and Ramadugu) in the Eastern Dharwar Craton, southern India. The strong correlation between various major and trace elements coupled with high abundances of incompatible and compatible trace elements imply that alteration and crustal contamination have had a limited effect on the whole-rock geochemistry (apart from K2O and CaO) of the Garledinne lamproites and that olivine fractionation played an important role in their evolution. The Garledinne lamproites represent small-degree partial melts derived from a refractory (previously melt extracted) peridotitic mantle source that was subsequently metasomatised (enriched) by carbonate–rich fluids/melts within the garnet stability field. The involvement of multiple reservoirs (sub-continental lithospheric mantle and asthenosphere) has been inferred in their genesis. The emplacement of the Garledinne lamproites is linked to extensional events, across the various Indian cratons, related to the break-up of the Proterozoic supercontinent of Columbia.

High-Mg Diorite from Qulong in Southern Tibet: Implications for the Genesis of Adakite-like Intrusions and Associated Porphyry Cu Deposits in Collisional Orogens

We have investigated a suite of Miocene high-Mg diorite porphyries from Qulong in southern Tibet, the largest porphyry Cu–Mo deposit in China. Laser ablation inductively coupled plasma mass spectrometry zircon U–Pb dating shows that the high-Mg diorite porphyry was emplaced at 15.7±0.2 Ma, which is slightly younger than the Qulong adakite-like Rongmucuola pluton (c. 19.5–16.4 Ma). The Qulong high-Mg diorites have phenocrysts showing disequilibrium textures and include high-Mg# clinopyroxene (0.91–0.97). These porphyry rocks exhibit both ultrapotassic and adakite-like features, and are characterized by high contents of MgO (4.2–5.1 wt %), K2O (3.2–3.6 wt %), and compatible trace elements (e.g. Ni: 115–142 ppm; Cr: 214–291 ppm), as well as by high Sr/Y and La/Yb ratios. The rocks have highly radiogenic isotopic compositions with (87Sr/86Sr)i = 0.707004–0.707198, eNd(t)=-5.1 to -5.5, 207Pb/204Pb = 15.697–15.704, and 208Pb/204Pb = 39.082 – 39.116, as well as variable zircon eHf values of -3.0 to +5.9. Petrographic, elemental, and isotopic evidence suggests that the Qulong high-Mg diorites were formed by mixing between ultrapotassic and adakite-like melts, derived from metasomatized Tibetan lithospheric mantle and juvenile lower crust, respectively. In contrast, the Qulong pre-ore Rongmucuola pluton is characterized by high SiO2 (66.3–68.9 wt %) and Al2O3 (16.4–17.0 wt %) contents, high Sr/Y ratios (121–151), low compatible element contents (e.g. Ni = 16.0 – 17.4 ppm; Cr=14.5–20.2 ppm), low Mg# values (0.44–0.52), positive large-ion lithophile element (LILE) anomalies, marked negative high field strength element (HFSE) anomalies, positive eNd(t) values (+0.4 to +2.5), and low (87Sr/86Sr)i values (0.704847–0.705237). These features indicate that the Rongmucuola pluton was formed by partial melting of subduction-modified juvenile lower crust within the garnet stability field. The newly identified Qulong high-Mg diorite allows us to propose a mixing model for the origin of the Gangdese high-K, adakite-like rocks. In this model, the formation of these rocks occurred in two stages: (1) partial melting of highly metasomatized lithospheric mantle that generated ultrapotassic mafic melts; (2) underplating of such melts beneath thickened juvenile lower crust, which resulted in melting of the lower crust and the generation of adakite-like magmas. Mixing of the adakite-like melt with ultrapotassic magmas elevated the K2O, MgO, and other LILE (e.g. Rb and Ba) contents of the adakite-like melt. Exogenous water necessary for formation of the Gangdese porphyry Cu systems was mainly added during mixing of ultrapotassic magma with adakite-like melt at lower and/ or upper-crustal depths, reflecting the large decrease in the H2O solubility of the ultrapotassic mafic melt upon ascent and decompression. Upper-crustal fractionation of the Rongmucuola magma could also possibly increase the water content of mineralization-related, adakite-like porphyry intrusions at Qulong. Fluid exsolution from the ultrapotassic magma is likely to have been a key process in the generation of the Gangdese porphyry Cu deposits, as well as other porphyry Cu deposits in the Tibetan collisional orogens.

Consideraciones geoquímicas y petrogenéticas para establecer la evolución magmática del Complejo Volcánico Nevado del Huila

The Nevado del Huila Volcano Complex is made of rocks that have intermediate to acid composition, calc-alkaline affinity and middle content in K2O. According to SiO2 content, there are three geochemical types: andesites ss, dacitic andesites and dacites. Adakitic tendence in more recent lavas and more dacitic composition. Behaviors of mayor elements, REE, LFSE and HFSE are typical of orogenic andesites of active continental margin. Isotopic composition Sr-Nd resemble to volcanoes of ZVN Andes (Ecuador’s volcanoes, Galeras and Nevado del Ruiz volcanoes from Colombia). Homogeneous isotopic rate Sr-Nd (87Sr/86Sr = 0,7041-0,7042 and 143Nd/144Nd = 0,51279-0,51283) are typical of mantle melts, with limited taking part of derived components of subduced slab or continental crust. Compatible and incompatible trace elements indicate that fractional crystallization is petrogenetic process that has controlled magmatic evolution. Besides to reject others mechanisms: crustal contamination and magmas mixing. These rocks have probably been generated from partial melting of enriched mantle wedge by components of subduced slab. Later fractional crystallization drove magmatic differentiation of this volcano complex.

In-situ LA-ICP-MS trace elemental analyses of magnetite: Fe–Ti–(V) oxide-bearing mafic–ultramafic layered intrusions of the Emeishan Large Igneous Province, SW China

The Taihe, Baima, Hongge, Panzhihua and Anyi intrusions of the Emeishan Large Igneous Province (ELIP), SW China, contain large magmatic Fe–Ti–(V) oxide ore deposits. Magnetites from these intrusions have extensive trellis or sandwich exsolution lamellae of ilmenite and spinel. Regular electron microprobe analyses are insufficient to obtain the primary compositions of such magnetites. Instead, laser ablation ICP-MS uses large spot sizes (~40μm) and can produce reliable data for magnetites with exsolution lamellae. Although magnetites from these deposits have variable trace element contents, they have similar multi-element variation patterns. Primary controls of trace element variations of magnetite in these deposits include crystallography in terms of the affinity of the ionic radius and the overall charge balance, oxygen fugacity, magma composition and coexisting minerals. Early deposition of chromite or Cr-magnetite can greatly deplete magmas in Cr and thus Cr-poor magnetite crystallized from such magmas. Co-crystallizing minerals, olivine, pyroxenes, plagioclase and apatite, have little influence on trace element contents of magnetite because elements compatible in magnetite are incompatible in these silicate and phosphate minerals. Low contents and bi-modal distribution of the highly compatible trace elements such as V and Cr in magnetite from Fe–Ti oxide ores of the ELIP suggest that magnetite may not form from fractional crystallization, but from relatively homogeneous Fe-rich melts. QUILF equilibrium modeling further indicates that the parental magmas of the Panzhihua and Baima intrusions had high oxygen fugacities and thus crystallized massive and/or net-textured Fe–Ti oxide ores at the bottom of the intrusive bodies. Magnetite of the Taihe, Hongge and Anyi intrusions, on the other hand, crystallized under relatively low oxygen fugacities and, therefore, formed net-textured and/or disseminated Fe–Ti oxides after a lengthy period of silicate fractionation. Plots of Ge vs. Ga+Co can be used as a discrimination diagram to differentiate magnetite of Fe–Ti–(V) oxide-bearing layered intrusions in the ELIP from that of massif anorthosites and magmatic Cu–Ni sulfide deposits. Variable amounts of trace elements of magmatic magnetites from Fe–Ti–(P) oxide ores of the Damiao anorthosite massif (North China) and from Cu–Ni sulfide deposits of Sudbury (Canada) and Huangshandong (northwest China) demonstrate the primary control of magma compositions on major and trace element contents of magnetite.

Petrogenesis of Late Mesozoic granitoids and coeval mafic rocks from the Jiurui district in the Middle–Lower Yangtze metallogenic belt of Eastern China: Geochemical and Sr–Nd–Pb–Hf isotopic evidence

Large-scale Cu–Au mineralization is associated with the Late Mesozoic granitoids in the Jiurui district of the Middle–Lower Yangtze Mineralization Belt in Eastern China. To constrain the petrogenesis of these granitoids and coeval mafic rocks, a detailed geochemical and Sr–Nd–Pb–Hf isotopic study was performed. The Jiurui granitoids are made up primarily of granodiorite porphyry and quartz diorite porphyry. These granitoids are characterized by SiO2 and K2O contents of 58.8wt.% to 68.6wt.% and 1.9wt.% to 5.7wt.%, respectively. These granitoids show relatively high MgO contents (1.0wt.% to 3.1wt.%, average 2.1wt.%) and high Mg# values (39 to 70, average 54). The Jiurui granitoids are enriched in light rare earth elements (LREE), large ion lithophile elements (LILE), and compatible trace elements (Cr, Ni and V) but are relatively depleted in Nb, Ta, Y and Yb. These rocks show a negligible negative Eu anomaly (Eu/Eu⁎=0.76–1.13, average 0.91) and nearly no negative Sr anomaly. The whole-rock initial 87Sr/86Sr ratios range from 0.7060 to 0.7092, and the εNd(t) values vary from −5.4 to −2.0. The granitoids show radiogenic Pb isotopic ratios with values of 206Pb/204Pb (17.93–18.21), 207Pb/204Pb (15.55–15.58), and 208Pb/204Pb (38.16–38.56) for the plagioclases. The zircon Hf isotopic compositions show εHf(t) values from −11.8 to 2.4. The coeval mafic rocks consist of lamprophyre, diabase and fine-grained mafic dyke. These rocks are characterized by SiO2 contents ranging from 47.6wt.% to 54.8wt.%, with a negative Eu anomaly and a positive to negative Sr anomaly. The whole-rock initial 87Sr/86Sr ratios range from 0.7059 to 0.7071, and the εNd(t) values vary from −3.8 to −1.4. By comparing the geochemical and isotopic compositions of the Jiurui granitoids and the coeval mafic rocks, we conclude that the granitoids are similar to adakites that were likely related to the delamination processes, and the coeval mafic rocks may have originated directly from enriched lithospheric mantle. The thickened lower continental crust and underlying enriched lithospheric mantle may have been simultaneously delaminated into the asthenospheric mantle. This process led to the partial melting of the thickened lower crust and the enriched lithospheric mantle, and the melts experienced an interaction with the asthenospheric mantle during ascension. Mafic melts could be generated from the enriched lithospheric mantle, which was heated by the upwelling asthenospheric mantle. The geochemical and isotopic compositions of mafic rocks were most likely controlled by the AFC process. A geochemical and isotopic comparison of the granitoids in the Jiurui district with those of two other districts (e.g., Angui and Tongling) in the same mineralization belt indicates that a significant crust–mantle interaction played a crucial role in their petrogeneses and metallogeneses. From the southwest to northeast in this metallogenic belt, the proportion of mantle component that was involved in the granitic magma shows a decreasing trend from the Jiurui to the Angui and Tongling districts. It is suggested that the Juirui district has the highest potential for a significant amount of Cu–Au accumulation because the mantle is an important supply for these metals.

Geochronology, geochemistry, and mineralization of the granodiorite porphyry hosting the Matou Cu–Mo (±W) deposit, Lower Yangtze River metallogenic belt, eastern China

Porphyry and skarn Cu–Fe–Au–Mo deposits are widespread in the Middle and Lower Yangtze River metallogenic belt (MLYMB), eastern China. The Matou deposit has long been regarded as a typical Cu–Mo porphyry deposit within Lower Yangtze part of the belt. Recently, we identified scheelite and wolframite in quartz veins in the Matou deposit, which is uncommon in other porphyry and skarn deposits in the MLYMB. We carried out detailed zircon U–Pb dating and geochemical and Sr–Nd–Hf isotopic studies of the granodiorite porphyry at Matou to define any differences from other ore-related granitoids. The porphyry shows a SiO2 content ranging from 61.85wt.% to 65.74wt.%, K2O from 1.99wt.% to 3.74wt.%, and MgO from 1.74wt.% to 2.19wt.% (Mg# value ranging from 45 to 55). It is enriched in light rare earth elements and large ion lithophile elements, but relatively depleted in Nb, Ta, Y, Yb and compatible trace elements (such as Cr, Ni, and V), with slight negative Eu anomalies (Eu/Eu*=0.88–0.98) and almost no negative Sr anomalies. Results of electron microprobe analysis of rock-forming silicate minerals indicate that the Matou porphyry has been altered by an oxidized fluid that is rich in Mg, Cl, and K. The samples show relatively low εNd(t) values from −7.4 to −7.1, slightly high initial 87Sr/86Sr values from 0.708223 to 0.709088, and low εHf(t) values of zircon from −9.0 to −6.5, when compared with the other Cu–Mo porphyry deposits in the MLYMB. Zircon U–Pb dating suggests the Matou granodiorite porphyry was emplaced at 139.5±1.5Ma (MSWD=1.8, n=15), which is within the age range of the other porphyries in the MLYMB. Although geochemical characteristics of the Matou and other porphyries in the MLYMB are similar and all adakitic, the detrital zircons in the samples from Matou suggest that Archean lower crust (2543±29Ma, MSWD=0.25, n=5) was involved with the generation of Matou magma, which is different from the other porphyries in the belt. Our study suggests that the Matou granodiorite porphyry originated from partial melting of thickened lower crust that was delaminated into the mantle, similar to the other porphyries in the MLYMB, but it has a higher proportion of lower crustal material, including Archean rocks, which contributed to the formation of the porphyry and related W-rich magmatic-hydrothermal system.

Geochemical variability of MORBs along slow to intermediate spreading Carlsberg-Central Indian Ridge, Indian Ocean

We present new major and ICP-MS trace element data from the Carlsberg Ridge MORBs from two different locations (i.e., 3°35′N/64°05′E and 3°41′N/64°09′E). Using this data we reassess the intra-ridge geochemical variations of the Carlsberg Ridge- Central Indian Ridge MORBs. Trace element contents of the Carlsberg Ridge MORBs are similar to the Rodriguez Triple Junction MORBs [e.g., LIL and REE spidergrams and (La/Sm)N ratio etc.]; both closely resemble the average N-MORB. However, the MORBs from the northern- and southern Central Indian Ridge, significantly vary in composition from the average N- and E-MORBs. Most Carlsberg Ridge- Central Indian Ridge MORBs show significantly less fractionation in FeOt, in the MgO–CaO–FeOt diagram, compared to those of the Mid Atlantic- and East Pacific Rise MORBs. Furthermore, the depleted LREE and nearly flat HREE patterns of the Carlsberg Ridge–Central Indian Ridge MORBs (along with their low compatible trace element (Ni, Cr, Sr) variability compared with the increasing incompatible trace element (Y, Zr) contents in the log–log plots, as well as their increasing incompatible trace element ratios) favor partial melting dominated processes for their petrogenetic evolution. Our (Sr, Nd, Pb) isotope data review shows that the Carlsberg Ridge-Central Indian Ridge MORBs are derived from a depleted mantle source that was variously contaminated by continental crust, perhaps during the third stage of Gondwana break up between 155 and 135Ma. Such contamination could also have occurred later during the strike slip movement along a mega fracture (a member of the Davie Transform Faults in the Somali Basin that broke Gondwanaland into the East and West Gondwanas). The 208Pb/204Pb versus 206Pb/204Pb plot of above mentioned MORBs suggests that the depleted mantle source of the Rodriguez Triple Junction MORBs was contaminated by ∼21% lower continental crust, whereas the mantle source of the Central Indian Ridge MORBs was contaminated by upper continental crust, which are ∼19% for the Carlsberg Ridge and Northern Central Indian Ridge MORBs and ∼32% for the Southern Central Indian Ridge MORBs. The contaminated mantle sources were compositionally similar to the Al-depleted Komatiite basalt and significantly enriched in Rb, Ba, La and Ce over the depleted mantle.