Episodes Of Metasomatism Research Articles

Altered spinels act as a mirror of multi-episodic fluid metasomatism in the forearc mantle: An example from the Minhe ophiolite in Qilian Orogen, NW China

Forearc mantle peridotites commonly undergo complex melt/fluid metasomatism, which inevitably has a considerable influence on their geochemical compositions at the whole-rock scale. Serpentinites predominantly comprise the Minhe ophiolite, which is a fragment of the Proto-Tethys Ocean that outcrops in the Qilian Orogen in NW China. These serpentinites contain zoned spinels that vary compositionally from the centers to the margins, with a spinel core overgrown by ferritchromite layer and magnetite at the outermost rim. The mineral chemistry of the spinel cores (i.e., Cr#, Mg#, Cr2O3, and Al2O3) suggests that the protolith of the serpentinites was an oceanic mantle remnant in a forearc setting. Moreover, the ferritchromite exhibited increases in Fe, Mn, Sc, and Ni contents and decreases in Mg, Cr, Al, V, Zn, and Ga contents. Considering the linear correlation among elements (e.g., Co, Ni, and Zn) and the absence of mineral inclusions, the ferritchromite likely formed through ionic substitutions induced by slab fluids. The magnetite was enriched in Cr, Ni, V, Zn, Co, and Cu, but did not have a magmatic origin owing to low V concentrations. All evidence indicates that the peridotites underwent at least two episodes of fluidic metasomatism in the subduction zone. During early slab subduction, aqueous fluids released from the dehydration of the subducted slab directly serpentinized the forearc mantle peridotites, thereby altering the olivine and orthopyroxene to lizardite/chrysotile. During this process, certain mobile elements (e.g., Fe, Ni, and Mn) in the fluids and/or olivine serpentinization were incorporated into existing spinels, favoring ferritchromite growth. The second fluidic episode was dependent on prograde metamorphism at greater depths in the subduction channel, which not only produced antigorite via the recrystallization of lizardite and chrysotile, but also drove the fluids towards a more oxidizing state, thereby facilitating the growth of Cr-magnetites. Subsolidus re-equilibration controlled by fluid infiltration further promoted the inter-diffusion of elements (e.g., Cr, V, Co, Ni, Cu, and Zn) in the zoned spinels.

Gold and sulfide-bearing listvenite in the mantle section of the Tays ophiolite in the Arabian Shield, Saudi Arabia

The mantle section of the Late Neoproterozoic Tays ophiolite in the Arabian Shield consists principally of thoroughly serpentinized peridotite with characteristics typical of depleted mantle protoliths from a fore-arc environment. The serpentinite is altered along shear zones and thrust planes to gold-bearing listvenite bodies of various sizes. These bodies are divided into carbonate listvenite and silica‑carbonate listvenite; they may be dyke-like or lenticular in form, and are yellowish-brown, reddish-brown, or greyish in outcrop. Carbonate listvenite expresses schistose deformation fabrics concordant to fabric in the host serpentinite, whereas silica‑carbonate listvenite is undeformed at field scale and contains a generation of undeformed minerals at thin-section scale. Silica‑carbonate listvenite contains Cr-rich muscovite (fuchsite) and base-metal sulfides and is enriched in Zn, Pb, Cu, Ag, and Au along with SiO2. The transformation of serpentinite along shear zones to different types of listvenite reflects successive episodes of fluid-mediated metasomatism. Carbonate listvenite develops first, driven by infiltration of CO2–bearing fluids during serpentinization of the original fore-arc peridotite. Silica‑carbonate listvenite marks a later episode associated with infiltration of K-bearing, SiO2-saturated fluids released during emplacement of the ophiolite. Listvenitization in the Tays serpentinite concentrated gold in sub-economic to economic extents, with concentrations increasing from host serpentinite (2–4 ng/g) to carbonate listvenite (267–937 ng/g) to silica‑carbonate listvenite (1717–3324 ng/g).

Multiple growth of zirconolite in marble (Mogok metamorphic belt, Myanmar): evidence for episodes of fluid metasomatism and Zr–Ti–U mineralization in metacarbonate systems

Abstract. Fluid infiltration into (meta-)carbonate rocks is an important petrologic process that induces metamorphic decarbonation and potential mineralization of metals or nonmetals. The determination of the infiltration time and the compositional features of reactive fluids is essential to understand the mechanism and process of fluid–rock interactions. Zirconolite (ideal formula: CaZrTi2O7) is an important U-bearing accessory mineral that can develop in metasomatized metacarbonate rocks. In this study, we investigate the occurrence, texture, composition, and chronology of various types of zirconolite from fluid-infiltrated reaction zones in dolomite marbles from the Mogok metamorphic belt, Myanmar. Three types of zirconolite are recognized: (1) the first type (Zrl-I) coexists with metasomatic silicate and oxide minerals (forsterite, spinel, phlogopite) and has a homogeneous composition with high contents of UO2 (21.37 wt %–22.82 wt %) and ThO2 (0.84 wt %–1.99 wt %). (2) The second type (Zrl-II) has textural characteristics similar to those of Zrl-I. However, Zrl-II shows a core–rim zonation with a slightly higher UO2 content in the rims (average of 23.5 ± 0.4 wt % (n=8)) than the cores (average of 22.1 ± 0.3 wt % (n=8)). (3) The third type (Zrl-III) typically occurs as coronas around baddeleyite and coexists with polycrystalline quartz. Zrl-III has obviously lower contents of UO2 (0.88 wt %–5.3 wt %) than those of Zrl-I and Zrl-II. All types of zirconolite have relatively low rare earth element (REE) contents (< 480 µg g−1 for ΣREE). Microtextures and compositions of the three zirconolite types, in combination with in situ zirconolite U–Pb dating using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), reveal episodic fluid infiltration and element mobilization in the dolomite marbles. The first-stage infiltration occurred at ∼ 35 Ma, leading to the formation of Mg-rich silicates and oxides and accessory minerals (Zrl-I, baddeleyite, and geikielite). The reactive fluid was characterized by high contents of Zr, Ti, U, and Th. After that, some Zrl-I grains underwent a local fluid-assisted dissolution–precipitation process, which produced a core–rim zonation (i.e., the Zrl-II type). The final stage of fluid infiltration, recorded by the growth of Zrl-III after baddeleyite, took place at ∼ 19 Ma. The infiltrating fluid of this stage had relatively lower U contents and higher SiO2 activities than the first-stage infiltrating fluid. This study illustrates that zirconolite is a powerful mineral that can record repeated episodes (ranging from 35 to 19 Ma) of fluid influx, metasomatic reactions, and Zr–Ti–U mineralization in (meta-)carbonates. This mineral not only provides key information about the timing of fluid flow but also documents the chemical variation in reactive fluids. Thus, zirconolite is expected to play a more important role in characterizing the fluid–carbonate interaction, orogenic CO2 release, and the transfer and deposition of rare metals.

Serpentinization and Deserpentinization of the Mantle Wedge at a Convergent Plate Margin: Evidence of Orogenic Peridotites from a Composite Oceanic–Continental Subduction Zone

AbstractSerpentinites of the mantle wedge were identified from a composite oceanic–continental subduction zone that occurs as the Hong’an orogen in east–central China. They were comprehensively investigated by an integrated approach of whole-rock major and trace elements, mineral major and trace elements, whole-rock and olivine O isotopes, and phase equilibrium modeling as well as zircon U–Pb ages, trace elements, and Hf-O isotopes. These serpentinites show high Mg# and MgO/SiO2 ratios but low Al2O3/SiO2 ratios as well as low Ti contents, resembling those from the mantle wedge rather than the subducting oceanic slab. Petrographic observations were combined with CIPW norm calculations to suggest that the protoliths of these serpentinites are refractory peridotites in the mantle wedge. Whole-rock and mineral compositions indicate that these serpentinites experienced multiple episodes of metamorphism and metasomatism during the tectonic development from oceanic subduction in the Carboniferous to continental collision in the Triassic. The enrichments of Th, U, light rare earth elements and high field strength elements in the whole rock and the finding of zircon inside them indicate their formation through metasomatism of the mantle wedge peridotites by subducting crust-derived fluids. The ca. 310 Ma zircon domains exhibit positive εHf(t) values of 4.5 to 19.1 and variable δ18O values similar to those of oceanic-type eclogites in the Hong’an orogen but different trace element compositions, indicating their formation through metasomatism by fluids from the subducting Paleotethyan oceanic crust. The ca. 430 Ma zircons exhibit U–Pb ages, trace elements and Hf-O isotopes similar to those of the protolith magmatic zircons in the oceanic-type eclogites. The older zircon domains also exhibit similar element and isotope compositions to inherited zircons from the high- to ultrahigh-pressure metamorphic rocks in the Hong’an orogen. Thus, these relict zircons would be physically transferred into the serpentinites by metasomatic fluids originating from the subducting Paleotethyan oceanic crust. High Th/U ratios for the ca. 310 Ma zircons imply their formation through the metasomatic reaction rather than direct precipitation from the subducting oceanic crust-derived fluids. The metasomatic zircons of Triassic age show negative εHf(t) values of −16.0 to −2.7, indicating their formation through metasomatic overprinting by deeply subducting continental crust-derived fluids in the continental subduction channel during the Triassic continental collision. In this context, the mantle wedge peridotites were first metasomatized in the Carboniferous by the subducting oceanic crust-derived fluids. Afterwards, part of the metasomatized peridotites were off-scrapped into the oceanic subduction channel, where they were hydrated by further subducting oceanic crust-derived fluids to form antigorite serpentinite at forearc depths. The antigorite serpentinite was carried to deeper depths during subsequent continental subduction and underwent dehydration there. This gave rise to metamorphic olivine with extremely high Fo values of 96.7 to 97.6 and higher MnO but lower NiO contents than common mantle olivine. The coexistence of lizardite, brucite and magnesite in the serpentinites indicates their retrograde processes of serpentinization and carbonation on the subsurface. Therefore, the present observations and interpretations of orogenic serpentinites provide insights into the multistage fluid metasomatism at different depths during the tectonic transition from oceanic subduction to continental collision.

Mineralogical alteration of a type A CAI from Allende CV3 chondrite: Formation of secondary dmisteinbergite and its phase transition to anorthite

AbstractDmisteinbergite, a hexagonal form of CaAl2Si2O8, was found in a compact type A Ca‐Al‐rich inclusion (CAI) in the Allende CV3 chondrite. Scanning and transmission electron microscopic observations show that dmisteinbergite was always in contact with grossular and grossular was in contact with melilite. In addition, there is a crystallographic relationship between dmisteinbergite and anorthite. Based on the textural and crystallographic evidence, the following mineralogical alteration processes are proposed to have occurred in the CAI. (1) Melilite was replaced by grossular. High densities of vesicles in the grossular indicate that hydrogrossular might have been the primary alteration phase and dehydrated by later metamorphism. (2) Dmisteinbergite formed from (hydro)grossular through a reaction with Si‐rich fluid. (3) Nano‐sized minerals are formed within dmisteinbergite. (4) Dmisteinbergite was transformed to anorthite. (5) Both anorthite and dmisteinbergite were altered to nepheline. (6) Hydrogrossular was dehydrated to grossular. (Hydro)grossular, dmisteinbergite, anorthite, and nepheline in the CAI seem to have formed in the course of metasomatism that occurred in the Allende parent body. Except for the hydrogrossular dehydration, these reactions could have occurred at moderate temperature (200–250°C) in high pH fluids (pH 13–14) according to past experimental studies. Episodic changes in fluid composition seem to have occurred before reactions (2), (4), and (5), because these reactions were not completed before the next reaction started. Higher temperature is required for reactions (5) and (6) to occur. Our observation of the CAI suggests that it experienced multiple episodes of metasomatism as temperatures were rising in the Allende parent asteroid.

Discovery of Variscan orogenic peridotites in the Pelvoux Massif (Western Alps, France)

Small bodies of mantle-derived peridotites and other ultramafic rocks are commonly found in exhumed lower crustal units of collisional orogens. They provide a direct record of the complex evolution of the upper mantle before and during an orogeny, and are therefore key markers of the geodynamic evolution of an orogen. We report here the discovery of such mantle-derived peridotites, which occur as fragmented enclaves in migmatites of the high-grade Variscan lower crust exposed in the Pelvoux Massif (external Western Alps). A wide petrographic diversity has been observed, from very fertile, garnet-bearing lherzolites, to more depleted spinel/chromite-bearing harzburgites. Thermobarometric calculations on a garnet lherzolite indicate an initial stage at 3.0–4.0 GPa and 970–1140 °C, followed by exhumation to 0.8–1.3 GPa and 800–850 °C, while the harzburgites do not show any evidence of equilibration in the garnet field. Petrological observations, whole-rock geochemistry and in situ mineral compositions suggest the peridotites have undergone a complex history prior to their incorporation in the lower crust during the Variscan Orogeny. They derive from a refractory mantle, which has experienced variable degrees of melt depletion, and has then been extensively refertilized. Cryptic metasomatism is observed in all samples. It is characterized by an enrichment in large-ion lithophile elements (LILE, in particular Cs, Rb, U and Pb) relative to high field strength elements (HFSE), in particular Nb and Ta. This cryptic metasomatism is presumably related to percolation of subduction-related fluids or melts in the mantle. In addition, modal metasomatism occurred in some samples, where crystallization of phlogopite, pargasite, chromite and apatite has been observed. This modal metasomatism resulted in significant enrichment in K2O, P2O5 and Cr2O3 of the bulk rock, together with a strong enrichment in incompatible LREE relative to HREE. These geochemical characteristics are strikingly similar to that of syn-collisional, Mg–Cr–LILE rich mantle-derived (ultra)-potassic magmas such as durbachites and vaugnerites, which are ubiquitous in the Variscan metamorphic allochthons of Massif Central, external Alps, Vosges and Bohemian Massif. We therefore suggest that this metasomatism results from dynamic percolation of the peridotites by K2O–P2O5–Cr2O3-rich melts from which the durbachites and vaugnerites are primarily derived. These geochemical characteristics are in line with whole-rock Nd isotopic compositions, which indicate enrichment of the mantle by a continental crust component, presumably related to Variscan subductions. This evolution is consistent with that of other Variscan peridotites in the Eastern Alps (Ulten) and the Bohemian Massif, where multiple metasomatic episodes related to melts or fluids released in Variscan subduction zones have been documented.

Mineralogical and geological characteristics of the Nui Phao tungsten deposit and its resource in the Dai Tu area, northeastern Vietnam

Typically, granitic intrusions that document the lengthy and intricate history of the magmatic-hydrothermal system are linked to tungsten deposits. Uncertainty persists about the genetic relationship between tungsten mineralization and magmatic-hydrothermal development. The primary tungsten deposit in the Dai Tu region, known as the Nui Phao deposit, has been the subject of a petrographical and microscopic examination. Tungsten mineralization in the Dai Tu area often occurs in association with the formation of skarn and greisen bodies, and it has drawn much attention from geoscientists. Based on microscopic observations, tungsten ores can be divided into three mineralization stages, namely skarnisation, greisenization, and hydrothermal stage. To examine the geochemical features of the tungsten ores, the SEM-EDS and Microscope analytical methods were performed in this study. Research results indicate that the Nui Phao tungsten deposit was formed due to different tectonic and magmatism episodes. Accordingly, the Nui Phao tungsten deposit is relatively complicated with the multi-sources of ore components. Most of the tungsten ore was accumulated in association with the metasomatism between the Ordovician-Silurian carbonate-terrigenous sedimentary rocks of the Phu Ngu formation and the Cretaceous two-mica granite of the Pia Oac complex. The research results indicate that tungsten resources obtained at levels 122 and 333 are about 227.6 thousand tons. Moreover, the hydrothermal alteration and metasomatism in the study area are influenced by at least three metasomatic episodes, including skarnisation, greisenisation, and the late hydrothermal alteration of medium to a low temperature that is genetically related to fluorite-polymetallic mineralization.

Fractionation and Enrichment Patterns in White Mica from Li Pegmatites of the Wekusko Lake Pegmatite Field, Manitoba, Canada

ABSTRACTThe Wekusko Lake pegmatite field in central Manitoba, Canada, is known for its multiple pegmatite dike occurrences, most remarkably its Li-rich pegmatites of economic importance. The Li-rich pegmatites from Wekusko Lake are the focus of this study and belong to the Green Bay group of the Wekusko Lake pegmatite field. These dikes were dated at ca. 1.78 Ga and were emplaced early during the D4 brittle–ductile deformational event. The results presented here describe in detail the pegmatite mineralogy, textures, and zonation of the Li-rich dikes of the Green Bay group, with emphasis on white mica chemistry. The aim of this study is to establish the nature and evolution of white micas from the Li-rich pegmatites of the Wekusko Lake pegmatite field in Manitoba. We aim to understand the differentiation mechanisms that allowed the high level of trace element enrichment observed in the white micas of the studied Li-rich pegmatites. Major and trace elements in white micas from a representative and well studied pegmatite dike were analyzed by electron microprobe and LA-ICP-MS. White mica compositions and textural evidence were used to define two different populations that seem to have been affected by magmatic processes (fractional crystallization) and a secondary episode of metasomatism. Fractional crystallization modeling of a granitic melt can explain some of the trace element enrichment, but extreme Cs enrichment cannot be explained via this mechanism. We interpret that many metasomatic white micas crystallized in boundary layers. Their compositions are controlled by the local melt composition, but aqueous fluids likely contributed to the development of the white mica textures. The substitution mechanisms at play depend on the type of trend and on the stage of evolution. Li enrichment without M2+ enrichment in metasomatic white mica grains is observed, and it is postulated that Fe3+ in white mica explains this behavior. The K/Rb ratio decreases in white micas with fractionation, whereas the concentrations of incompatible elements, such as Cs, Rb, Tl, Ta, and Li, increase. At Wekusko Lake, the Nb and Ta contents seem to be controlled in part by the presence of columbite group minerals and in part by crystallization in boundary layers.

Vein and Wehrlite Formation in the Lithospheric Mantle Below the West Eifel Volcanic Field: Modelling the Effects of Pressure, Temperature and Peridotite/Melt Ratio on Magma-Peridotite Interaction Using pMELTS and a Melt Infiltration Experiment

Abstract The mantle peridotite xenoliths of the West Eifel Volcanic Field in Germany preserve evidence of multiple phases of metasomatism. The most recent metasomatic episode produced a variety of veins in the peridotite: high temperature (>1150°C), phlogopite–clinopyroxenite intermediate temperature (~1150°C), olivine clinopyroxenite and relatively low temperature (<1100°C) hornblendite together with marginal reaction zones of wehrlite and dunite. The veins and associated reaction zones have been interpreted as products of crystallization of magmas similar to those that transported the xenoliths to surface. We describe a high temperature melt infiltration experiment and thermodynamic (pMELTS) models that examine the origin of high temperature phlogopite–clinopyroxenite veins and the evolution of the wall rock adjacent to the veins and compare the result to the major and trace element signatures of the minerals in the veins. The infiltration experiment replicates the common reaction textures such as partially dissolved orthopyroxene and sieved secondary clinopyroxene that are found associated with veins. In the thermodynamic model, we calculated the equilibrium assemblages and mineral compositions for peridotite–melt mixtures ranging from peridotite only to melt only over the range of 1150 to 1350°C and 1 GPa to 2 GPa. The models reproduce the composition of vein minerals at a small peridotite/melt ratio, whereas at larger peridotite/melt ratios they produce wehrlite/dunite assemblages that are similar both in modal mineralogy and composition to the natural samples. The models show that olivine clinopyroxenite veins may have been produced at a higher pressure than the phlogopite–clinopyroxenite veins. Our models show that interaction of magma with a trace element signature indicative of a garnet-bearing source with spinel facies mantle will result in a dilution of the trace element garnet signature with little to no variation in the major oxide composition.

The Coles Hill Uranium Deposit, Virginia, USA: Geology, Geochemistry, Geochronology, and Genetic Model

Abstract The Coles Hill uranium deposit, with an indicated resource of about 130 Mlb of U3O8, is the largest unmined uranium deposit in the United States. The deposit is hosted in the Taconian (approx. 480–450 Ma) Martinsville igneous complex, which consists of the Ordovician Leatherwood Granite (granodiorite) and the Silurian Rich Acres Formation (diorite). The host rock was metamorphosed to orthogneiss during the Alleghanian orogeny (approx. 325–260 Ma), when it also underwent dextral strike-slip movement along the Brookneal shear zone. During the Triassic, extensional tectonics led to the development of the Dan River Basin that lies east of Coles Hill. The mineralized zone is hosted in brittle structures in the footwall of the Triassic Chatham fault that forms the western edge of the basin. Within brittle fracture zones, uranium silicate and uranium-bearing fluorapatite with traces of brannerite form veins and breccia-fill with chlorite, quartz, titanium oxide, pyrite, and calcite. Uranium silicates also coat and replace primary titanite, zircon, ilmenite, and sulfides. Sodium metasomatism preceded and accompanied uranium mineralization, pervasively altering host rock and forming albite from primary feldspar, depositing limpid albite rims on igneous feldspar, altering titanite to titanium oxide and calcite, and forming riebeckite. Various geothermometers indicate temperatures of less than ~200°C during mineralization. In situ U-Pb analyses of titanite, Ti-oxide, and apatite, along with Rb/Sr and U/Pb isotope systematics of whole-rock samples, resolve the timing of geologic processes affecting Coles Hill. The host Leatherwood Granite containing primary euhedral titanite is dated at 450 to 445 Ma, in agreement with previously obtained ages from zircon in the Martinsville igneous complex. A regional metamorphic event at 330 to 310 Ma formed anhedral titanite and some apatite, reequilibrated whole-rock Rb/Sr and U-Pb isotopes, and is interpreted to have coincided with movement along the Brookneal shear zone. During shearing and metamorphism, primary refractory uranium-bearing minerals including titanite, zircon, and uranothorite were recrystallized, and uranium was liberated and mixed locally with hematite, clay, and other fine-grained minerals. Uranium mineralization was accompanied by a metasomatic episode between 250 and 200 Ma that reset the Rb-Sr and U-Pb isotope systems and formed titanium oxide and apatite that are associated and, in places, intimately intergrown with uranium silicate dating mineralization. This event coincides with rifting that formed the Dan River Basin and was a precursor to the breakup of Pangea. The orientation of late-stage tectonic stylolites is compatible with their formation during Late Triassic to Early Jurassic basin inversion, postdating the main stage of uranium mineralization and effectively dating mineralization as Mesozoic. Based on the close spatial and temporal association of uranium with apatite, we propose that uranium was carried as a uranyl-phosphate complex. Uranium was locally reduced by coupled redox reactions with ferrous iron and sulfide minerals in the host rock, forming uranium silicates. The release of calcium during sodium metasomatic alteration of primary calcic feldspar and titanite in the host rock initiated successive reactions in which uranium and phosphate in mineralizing fluids combined with calcium to form U-enriched fluorapatite. Based on the deposit mineralogy, oxygen isotope geochemistry, and trace element characteristics of uranium silicate and gangue minerals, the primary mineralizing fluids likely included connate and/or meteoric water sourced from the adjacent Dan River Basin. High heat flow related to Mesozoic rifting may have driven these (P-Na-F-rich) fluids through local aquifers and into basin margin faults, transporting uranium from the basin or mobilizing uranium from previously formed U minerals in the Brookneal shear zone, or from U-enriched older basement rock.

Depletion and refertilisation of the lithospheric mantle below the Kapsiki plateau (Northern Cameroon Volcanic Line) deduced from trace element and H2O systematics in mantle xenoliths

Clinopyroxene bearing spinel harzburgites recovered from Cenozoic alkaline basalts from the Kapsiki plateau were investigated with the aim of understanding depletion and enrichment processes in the subcontinental mantle below a major tectonic line. Concentrations of major and trace elements (including H) were determined in-situ in olivine, orthopyroxene, clinopyroxene and spinel by EPMA, LA-ICP-MS and FTIR. The xenoliths are refractory with high olivine (0.91–0.92) and orthopyroxene (0.92–0.93) Mg# coupled with relatively high modal proportions of clinopyroxene (5–8%) and a remarkably wide range in clinopyroxene Mg# (0.91–0.94), interpreted to reflect high degrees of partial melting followed by modal and chemical metasomatic refertilization. A fractional partial melting model of orthopyroxene trace elements in a depleted mantle indicates 20–30% of melting. Clinopyroxenes show two groups based on their CaO contents (18.7–18.9 and 20.6–22.6 wt %) suggesting a secondary origin and modal metasomatism. The low Ca clinopyroxenes were the latest to be formed, and the wide range of clinopyroxene Mg# shows a lack of equilibrium with the coexisting minerals. The high Ca clinopyroxenes record ancient metasomatic events that are also documented in orthopyroxene. Cryptic metasomatism is shown by strong progressive enrichments in LREEs and MREEs of orthopyroxene and clinopyroxene. Th vs La and Sr vs Nd of clinopyroxene are used to identify different generations of metasomatism. Ti/Eu vs (La/Yb)N and Zr/Hf systematics indicate that the metasomatising agent has both a carbonatite and a silicate component. The structural hydroxyl contents of the different mineral phases are very low (<1 ppm for olivine, 40–48 ppm for orthopyroxene and 164–277 ppm for clinopyroxene). The very low water contents compared to typical sub-continental peridotites could be attributed to the depleted nature of the xenoliths or reflect lower water activities of carbonatitic melts relative to alkaline melts. Estimated fO2 values expressed as ΔlogFMQ, (where FMQ corresponds to the fayalite magnetite-quartz oxygen buffer) range from -0.42 to -0.26 and are consistent with minor OH stretching regions of 3520 cm-1 in orthopyroxene, related to a ferric iron defect.The combination of textural investigations, major, and trace element and H2O data suggests that a refractory subcontinental mantle was affected by several episodes of intraplate metasomatism dominated by silicate-carbonatite melts above the North-Eastern end of the Cameroon Volcanic Line.

Uraninite from the Guangshigou Pegmatite-Type Uranium Deposit in the North Qinling Orogen, Central China: Its Occurrence, Alteration and Implications for Post-Caledonian Uranium Circulation

The Guangshigou deposit is the largest pegmatite-type uranium deposit in the Shangdan domain of the North Qinling Orogenic Belt, which is characterized by the enrichment of uraninite hosted in biotite granitic pegmatites. At Guangshigou, uraninite commonly occurs as mineral inclusions in quartz, K-feldspar and biotite or in interstices of these rock-forming minerals with magmatic characteristics (e.g., U/Th &lt; 100, high ThO2, Y2O3 and REE2O3 contents and low concentrations of CaO, FeO and SiO2). It crystallized at 407.6 ± 2.9 Ma from fractionated calc-alkaline high-K pegmatitic melts under conditions of 470–700 °C and 2.4–3.4 kbar as deduced by the compositions of coexisting peritectic biotite. The primary uranium mineralization took place during the Late Caledonian post-collisional extension in the North Qinling Orogen. After this magmatic event, uraninite has experienced multiple episodes of fluid-assisted metasomatism, which generated an alteration halo of mineral assemblages. The alteration halo (or radiohalo) was the result of the combined effects of metamictization and metasomatism characterized by an assemblage of goethite, coffinite and an unidentified aluminosilicate (probably clay minerals) around altered uraninite. This fluid-assisted alteration was concomitant with the albitization of K-feldspar subsequently followed by the coffinitization of uraninite during the major period of 84.9–143.6 Ma, as determined by U-Th-Pb chemical ages. Further investigations revealed that the metasomatic overprinting on uraninite initially and preferentially took place along microcracks or cavities induced by metamictization and promoted their amorphization, followed by the release of U and Pb from structure and the incorporation of K, Ca and Si from the fluids, finally resulting in various degrees of uraninite coffinitization. The released U and Pb were transported by alkali-rich, relatively oxidizing fluids and then re-precipitated locally as coffinite and an amorphous U-Pb-rich silicate under low to moderate temperature conditions (85–174 °C). The compositional changes in primary uraninite, its structure amorphization together with the paragenetic sequence of secondary phases, therefore, corroborate a combined result of intense metamictization of uraninite and an influx of alkali–metasomatic fluids during the Late Mesozoic Yanshanian magmatic event in the region. Hence, the remobilization and circulation of uranium in the North Qinling Orogen was most likely driven by post-Caledonian magmatism and hydrothermal activities related to large-scale tectonic events. In this regards, Paleozoic pegmatite-type uranium mineralization may represent a significant uranium source for Mesozoic hydrothermal mineralization identified in the Qinling Orogenic Belt.

Re-Os Isotope Systematics of Sulfides in Chromitites and Host Lherzolites of the Andaman Ophiolite, India

Laser ablation MC-ICP-MS was used to measure the Os-isotope compositions of single sulfide grains, including laurite (RuS2) and pentlandite [(Fe,Ni)9S8], from two chromitite bodies and host lherzolites from ophiolites of North Andaman (Indo-Burma-Sumatra subduction zone). The results show isotopic heterogeneity in both laurite (n = 24) and pentlandite (n = 37), similar to that observed in other chromitites and peridotites from the mantle sections of ophiolites. Rhenium-depletion model ages (TRD) of laurite and pentlandite reveal episodes of mantle magmatism and/or metasomatism in the Andaman mantle predating the formation of the ophiolite (and the host chromitites), mainly at ≈0.5, 1.2, 1.8, 2.1 and 2.5 Ga. These ages match well with the main tectonothermal events that are documented in the continental crustal rocks of South India, suggesting that the Andaman mantle (or its protolith) had a volume of lithospheric mantle once underlaying this southern Indian continental crust. As observed in other oceanic lithospheres, blocks of ancient subcontinental lithospheric mantle (SCLM) could have contributed to the development of the subduction-related Andaman–Java volcanic arc. Major- and trace-element compositions of chromite indicate crystallization from melts akin to high-Mg IAT and boninites during the initial stages of development of this intra-oceanic subduction system.

Petrology and geochemistry of the Mesoproterozoic Vattikod lamproites, Eastern Dharwar Craton, southern India: evidence for multiple enrichment of sub-continental lithospheric mantle and links with amalgamation and break-up of the Columbia supercontinent

Numerous lamproite dykes are hosted by the Eastern Dharwar Craton, southern India, particularly towards the northwestern margin of the Cuddapah Basin. We present here a comprehensive mineralogical and geochemical (including Sr and Nd isotopic) study on the lamproites from the Vattikod Field, exposed in the vicinity of the well-studied Ramadugu lamproite field. The Vattikod lamproites trend WNW–ESE to NW–SE and reveal effects of low-temperature post-magmatic alteration. The studied lamproites show porphyritic texture with carbonated and serpentinized olivine, diopside, fluorine-rich phlogopite, amphibole, apatite, chromite, allanite, and calcite. The trace-element geochemistry (elevated Sr and HFSE) reveals their mixed affinity to orogenic as well as anorogenic lamproites. Higher fluorine content of the hydrous phases coupled with higher whole-rock K2O highlights the role of metasomatic phlogopite and apatite in the mantle source regions. Trace-element ratios such as Zr/Hf and Ti/Eu reveal carbonate metasomatism of mantle previously enriched by ancient subduction processes. The initial 87Sr/86Sr-isotopic ratios (calculated for an assumed emplacement age of 1350 Ma) vary from 0.7037 to 0.7087 and ɛNd range from − 10.6 to − 9.3, consistent with data on global lamproites and ultrapotassic rocks. We attribute the mixed orogenic–anorogenic character for the lamproites under study to multi-stage metasomatism. We relate the (1) earlier subduction-related enrichment to the Paleoproterozoic amalgamation of the Columbia supercontinent and the (2) second episode of carbonate metasomatism to the Mesoproterozoic rift-related asthenospheric upwelling associated with the Columbia breakup. This study highlights the association of lamproites with supercontinent amalgamation and fragmentation in the Earth history.

Petrology, physical volcanology and geochemistry of a Paleoproterozoic large igneous province: The Hekpoort Formation in the southern Transvaal sub-basin (Kaapvaal craton)

The ∼2.23 Ga Hekpoort Formation (Transvaal sub-basin) and the ∼2.43 Ga Ongeluk Formation (Griqualand West sub-basin) represent voluminous Paleoproterozoic igneous events on the Kaapvaal craton of South Africa that predate the emplacement of the ∼2.055 Ga Bushveld Complex, and probably covered most of the craton at the time of their extrusion. In this contribution, we present field, petrological and geochemical studies of the Hekpoort Formation and compare it with the Ongeluk Formation. The Hekpoort Formation consists of a thick subaerial volcanic sequence in which volcanoclastic rocks occur mainly at the base. Rare, localized hyaloclastites and variolitic rocks record the presence of ponded water, while interbedded sedimentary rocks and paleo-weathered flow tops suggest prolonged time-breaks in volcanic activity. The Hekpoort rocks underwent metamorphism up to greenschist facies but also episodes of metasomatism and silicification. Preserved primary magmatic minerals are clinopyroxene (pigeonite, augite and diopside), and rarely plagioclase (labradorite). Both the variable whole rock Mg# (evolving from 69 to 50) and the changes in clinopyroxene composition attest to magmatic fractionation. Lava units of both the Hekpoort and Ongeluk formations are mostly basalts, with silicification responsible for increased SiO2 contents. Lava units of both formations also display remarkably similar trace elements patterns, which is noteworthy for units separated by 200 million years, and unique among the Precambrian mafic magmatic units of the Kaapvaal craton that we evaluated.Similar to other Precambrian mafic magmatic units of the Kaapvaal craton, the Hekpoort Formation shows an arc-like trace element signature, mainly represented by negative Nb-Ta anomalies (in normalized trace element patterns). The Hekpoort (and Ongeluk), together with three other Paleoproterozoic mafic units of the craton older than 2.2 Ga, exhibit relatively high contents of Th and U, which sharply contrasts with Archean units. The data suggest that a subduction process marked the Archean-Proterozoic boundary on the Kaapvaal craton.

Eclogites and garnet pyroxenites from Kimberley, Kaapvaal craton, South Africa: their diverse origins and complex metasomatic signatures

We describe the petrography and mineral chemistry of sixteen eclogite and garnet pyroxenite xenoliths from the reworked Boshof road dump (Kimberley) and define three groups that stem from different depths. Group A, the shallowest derived, has low HREE (heavy rare earth element) abundances, flat middle to heavy REE patterns and high Mg# [= 100·Mg/(Mg + Fe)]. Their protoliths probably were higher pressure cumulates (~ 0.7 GPa) of mainly clinopyroxene (cpx) and subordinate orthopyroxene (opx) and olivine (ol). Group B1 xenoliths, derived from the graphite/diamond boundary and below show similarities to present-day N-MORB that were modified by partial melting (higher Mg# and positively inclined MREE (middle REE) and HREE (heavy REE) patterns of calculated bulk rocks). Group B2 samples from greatest depth are unique amongst eclogites reported so far worldwide. The calculated bulk rocks have humped REE patterns with very low La and Lu and prominent maxima at Sm or Eu and anomalously high Na2O (up to 5 wt%) which makes protolith identification difficult. The complex trace element signatures of the full spectrum of Kimberley eclogites belie a multi-stage history of melt depletion and metasomatism with the introduction of new phases especially of phlogopite (phlog). Phlogopite appears to be characteristic for Kimberley eclogites and garnet peridotites. Modelling the metasomatic overprint indicates that groups A and B1 were overprinted by volatile- and potassium-rich melts probably by a process of chromatographic fractionation. Using constraints from other metasomatized Kimberley mantle rocks suggest that much of the metasomatic phlogopite in the eclogites formed during an intense episode of metasomatism that affected the mantle beneath this region 1.1 Gyr ago.

Crustal Metasomatism at the Slab‐Mantle Interface in a Continental Subduction Channel: Geochemical Evidence From Orogenic Peridotite in the Sulu Orogen

AbstractTo understand crust‐mantle interactions in a continental subduction channel, we carried out a combined study of whole‐rock elements and Sr‐Nd isotopes, mineral elements, and whole‐rock and mineral O isotopes in orogenic peridotite and its host gneiss from the Sulu orogen in China. The results indicate that the peridotite originated from highly depleted subcontinental lithospheric mantle beneath the North China Craton and underwent three episodes of metasomatism via crustally derived fluids. The peridotite was offscraped from the subcontinental lithospheric mantle wedge base and experienced petrographic transformation from a spinel peridotite to a garnet peridotite during continental subduction from forearc to subarc depths. The peridotite underwent the first episode of metasomatism via aqueous solutions at high‐pressure conditions. Afterward, the peridotite underwent a second episode of metasomatism by carbonate melts at ultrahigh‐pressure conditions and a third episode of metasomatism by aqueous solutions at high‐pressure conditions. While the aqueous solution was derived from the metamorphic dehydration of the subducting/exhuming continental crust at the forearc depths, the carbonate melts were produced by partial melting of the ultrahigh‐pressure metasedimentary rocks in the exhuming continental crust at subarc depths. These metasomatic agents did not originate from the gneiss directly hosting the peridotite but from another part of the deeply subducted continental crust that was not in direct contact with the peridotite. Therefore, the orogenic peridotite recorded the geochemical transfer from the subducting crust into the mantle in the continental subduction zone.

Timescales between mantle metasomatism and kimberlite ascent indicated by diffusion profiles in garnet crystals from peridotite xenoliths

Rare garnet crystals from a peridotite xenolith from the Wesselton kimberlite, South Africa, have distinct zones related to two separate episodes of mantle metasomatism. The garnet cores were firstly depleted through melt extraction, then equilibrated during metasomatism by a potentially diamond-forming carbonate-bearing or proto-kimberlitic fluid at 1100–1300 °C and 4.5–5.5 GPa. The garnet rim chemistry, in contrast, is consistent with later overgrowth in equilibrium with a kimberlite at around 1025±25°C and 4.2±0.5 GPa. This suggests that the rock was physically moved upwards by up to tens of kilometres between the two metasomatic episodes. Preserved high Ca, Al and Cr contents in orthopyroxenes suggest this uplift was tectonic, rather than magmatic. Diffusion profiles were measured over the transitions between garnet cores and rims using electron microprobe (Mg, Ca, Fe for modelling, plus Cr, Mn, Ti, Na, Al) and nano Secondary Ion Mass Spectrometry (NanoSIMS; 89Y, along with 23Na, Ca, Cr, Fe, Mn and Ti) analyses. The short profile lengths (generally <10 μm) and low Y concentrations (0.2–60 ppm) make the NanoSIMS approach preferable. Diffusion profiles at the interface between the zones yield constraints on the timescale between the second metasomatic event and eruption of the kimberlite magma that brought the xenolith to the surface. The time taken to form the diffusion profiles is on the order of 25 days to 400 yr, primarily based on modelling of Y diffusion along with Ca, Fe and Mg (multicomponent diffusion) profiles. These timescales are too long to be produced by the interaction of the mantle xenolith with the host kimberlite magma during a single-stage ascent to the crust (hours to days). The samples offer a rare opportunity to study metasomatic processes associated with failed eruption attempts in the cratonic lithosphere.

Graphite‐bearing mineral assemblages in the mantle beneath Central Aldan superterrane of North Asian craton: combined confocal micro‐Raman and electron microprobe characterization

Mantle‐derived lherzolitic and harzburgitic Cr‐pyropes from lamprophyres of the Chompolo field (Central Aldan superterrane, North Asian Craton) were studied using micro‐Raman spectroscopy and electron microprobe microanalysis. These garnets enclose graphite coexisting with forsterite, diopside, Ba‐Cl‐phlogopite, tschermakite, rutile, magnesiochromite, Mg‐ilmenite, apatite, chalcopyrite, dolomite, magnesite and lindsleyite inclusions. The PT conditions of residence of graphite‐bearing assemblage in the mantle were estimated, using a combination of mineral thermometers and barometers, to be as high as 2.87–3.55 GPa and 710–770 °C. Generally, graphite within inclusions is well ordered; D1 and D2 disordered bands in its spectra are restricted to inclusion edges. The residual pressure up to 2.1 GPa was inferred for graphite assuming pressure dependence of the G‐band upshift (1580 cm−1 at ambient conditions vs 1588.6 cm−1 at 2.1 GPa). Disordered graphite most likely appears due to the stress‐induced distortion of the fully ordered graphite crystal structure. The distortion results from difference in the thermoelastic properties of graphite inclusions and their garnet hosts exposed to decompression during ascent to the surface with lamprophyre magma. The mineralogy of inclusions in the studied garnets strongly suggests an episode(s) of metasomatism by carbon‐rich agent(s) (COH‐fluid or carbonatitic melt) in the lithospheric mantle of the Central Aldan superterrane, which was coeval with the formation of graphite inclusions and the host pyropes. Copyright © 2017 John Wiley &amp; Sons, Ltd.

Geochemistry and oxygen isotopic composition of olivine in kimberlites from the Arkhangelsk province: Contribution of mantle metasomatism

The paper presents data on the composition of olivine macrocrysts from two Devonian kimberlite pipes in the Arkhangelsk diamond province: the Grib pipe (whose kimberlite belongs to type I) and Pionerskaya pipe (whose kimberlite is of type II, i.e., orangeite). The dominant olivine macrocrysts in kimberlites from the two pipes significantly differ in geochemical and isotopic parameters. Olivine macrocrysts in kimberlite from the Grib pipe are dominated by magnesian (Mg# = 0.92–0.93), Ti-poor (Ti < 70 ppm) olivine possessing low Ti/Na (0.05–0.23), Zr/Nb (0.28–0.80), and Zn/Cu (3–20) ratios and low Li concentrations (1.2–2.0 ppm), and the oxygen isotopic composition of this olivine δ18O = 5.64‰ is higher than that of olivine in mantle peridotites (δ18O = 5.18 ± 0.28‰). Olivine macrocrysts in kimberlite from the Pionerskaya pipe are dominated by varieties with broadly varying Mg# = 0.90–0.93, high Ti concentrations (100–300 ppm), high ratios Ti/Na (0.90–2.39), Zr/Nb (0.31–1.96), and Zn/Cu (12–56), elevated Li concentrations (1.9–3.4 ppm), and oxygen isotopic composition δ18O = 5.34‰ corresponding to that of olivine in mantle peridotites. The geochemical and isotopic traits of low-Ti olivine macrocrysts from the Grib pipe are interpreted as evidence that the olivine interacted with carbonate-rich melts/fluids. This conclusion is consistent with the geochemical parameters of model melt in equilibrium with the low-Ti olivine that are similar to those of deep carbonatite melts. Our calculations indicate that the variations in the δ18O of the olivine relative the “mantle range” (toward both higher and lower values) can be fairly significant: from 4 to 7‰ depending on the composition of the carbonate fluid. These variations were formed at interaction with carbonate fluid, whose δ18O values do not extend outside the range typical of mantle carbonates. The geochemical parameters of high-Ti olivine macrocrysts from the Grib pipe suggest that their origin was controlled by the silicate (water–silicate) component. This olivine is characterized by a zoned Ti distribution, with the configuration of this distribution between the cores of the crystals and their outer zones showing that the zoning of the cores and outer zones is independent and was produced during two episodes of reaction interaction between the olivine and melt/fluid. The younger episode (when the outer zone was formed) likely involved interaction with kimberlite melt. The transformation of the composition of the cores during the older episode may have been of metasomatic nature, as follows from the fact that the composition varies from grain to grain. The metasomatic episode most likely occurred shortly before the kimberlite melt was emplaced and was related to the partial melting of pyroxenite source material.