Mineralogy of high-field-strength elements (Y,Nb, REE) in the world-class Vergenoeg fluorite deposit,South Africa

The Vergenoeg fluorite deposit in the Bushveld Complex in South Africa is hosted by a volcanic pipe-like body. The distribution characteristics, composition and formation conditions of high-field-strength element (HFSE)-rich minerals in different lithological units of the deposit were investigated by optical and cathodoluminescence microscopy, scanning electron microscopy, X-ray fluorescence, inductively-coupled plasma mass-spectrometry and electron-probe microanalysis. The Vergenoeg host rocks comprise a diverse silica-undersaturated assemblage of fayalite–magnetite–fluorite with variably subordinate apatite and mineral phases enriched in rare-earth elements (REEs). The Sm–Nd isotope systematics of the fluorite from the various lithological units of the pipe support the model that the HFSE budget of the Vergenoeg pipe was likely derived from a Lebowa-type granitic magma. Isotopically, there is no evidence for other REE sources. Formation of the pipe, including development of the fluorite mineralization, occurred within the same time frame as the emplacement of other magmatic rock units of the Bushveld Complex (Sm–Nd isochron age for fluorite separates: 2040 ± 46 Ma). Hydrothermal alteration is manifested in strongly disturbed Rb–Sr isotope systematics of the Vergenoeg deposit, but did not affect its HFSE and REE budget. Whole-rock chondrite-normalized REE + Y distribution patterns of two types were observed: (i) flat patterns characteristic of magnetite–fluorite unit, gossan, metallurgical-grade fluorite (“metspar”) plugs and siderite lenses, and (ii) U-shaped patterns showing enrichment towards the heaviest REE (Tm–Lu) observed in the fayalite-rich units. Common HFSE minerals are complex Nb-rich oxides (samarskite, fergusonite), REE phosphates and fluorocarbonates. Additionally, fluocerite and REE silicates, whose identification requires further work, were found. Most of the HFSE-rich minerals are spatially associated with Fe-rich phases (e.g., pyrite, magnetite, greenalite and hematite). To a smaller extent, they are found finely disseminated or healing micro-fractures in fluorite. The whole-rock REE + Y distribution patterns of the individual lithological units are mainly controlled by the distribution of Yb-rich and Y-rich xenotime in these rocks. The common occurrence of bastnäsite-(Ce) in the gossan, “metspar” plugs and especially in the rhyolitic carapace at the pipe–wall-rock contact, controls the REE + Y distribution patterns of these rocks. HFSE minerals in the Vergenoeg pipe rocks have formed in several stages. Samarskite and coarse fluorapatite belong to the primary mineral assemblage. Fergusonite and Yb-rich xenotime formed during high- to moderate-temperature hydrothermal activity. Significant remobilization of the HFSE from the early-crystallized minerals (breakdown of fluorapatite and possibly allanite with release of REE + Y) and subsequent partial redistribution of these elements into near surface rocks are inferred. The late-stage assemblages are characterized by the presence of fine-grained REE fluorocarbonates, monazite-(Ce), monazite-(La) and xenotime-(Y).     

Volcanic evolution of the back-arc Pleistocene Payun Matru volcanic field (Argentina)

For the first time, about 30 volcanic formations of the back-arc Payun Matru volcanic field (Payun Matru volcanic field, Argentina, 36°S, 69°W) have been sampled for K–Ar geochronology and geochemistry in order to reconstruct the eruptive history of this key province in the Andean back-arc. The Payun Matru volcanic field has been built since final Pleistocene until present with ages ranging from 280 ± 5 to 7 ± 1 ka. Erupted lavas belong to calc-alkaline series, with characteristics of both arc and intraplate magmas. From previous studies, three main units are distinguished: (1) a basaltic field (Los Volcanes), which covers a large surface of the Payun Matru volcanic field, composed of strombolian cones and associated lava flows emitted from 300 ka to Holocene times, (2) the stratovolcano Payun, with intermediate compositions, built around 265 ka, and (3) the shield volcano Payun Matru s.s. characterized by trachytic compositions and a large summit caldera. The earlier stages of the Payun Matru volcano are not dated, but we constrain the major explosive event, related to the eruption of a widespread ignimbrite and to the formation of the caldera, between 168 ± 4 ka (internal wall of caldera) and 82 ± 1 ka (flow within the caldera). Based on the geochemical similarities of the ignimbrite and the upper lava flow of the pre-caldera cone, we suggest that the age of this event is most probably at the older end of this interval. Numerical modeling using a GIS program has been used to reconstruct the morphological evolution for Payun Matru volcano before and after the caldera collapse. The ancient edifice could be modeled as a flattened cone, 2300 m high, with a volume of about 240 km³. The ignimbrite eruption associated with the Payun Matru caldera formation could be related to the regional tectonic environment, which is characterized by multiple Plio-Pleistocene extensional stages during the last 5 Myr. The evolution of the Nazca plate subduction from a flat slab to a normal dip induced an input of fluid mobile elements and asthenosphere plume-like mantle source beneath the Patagonian lithosphere, which yields the observed intraplate signature. We also interpret this geodynamic evolution as the influence of extensive processes in the upper crust leading to caldera-forming eruptions as observed throughout this province.     

Relationships between major and trace elements during weathering processes in a sedimentary context: Implications for the nature of source rocks in Douala,Littoral Cameroon

In Douala (Littoral Cameroon), the Cretaceous to Quaternary formation composed of marine to continental sediments are covered by ferrallitic soils. These sediments and soils have high contents of SiO₂ (≥70.0 wt%), intermediate contents of Al₂O₃ (11.6–28.4 wt%), Fe₂O₃ (0.00–20.5 wt%) and TiO₂ (0.04–4.08 wt%), while K₂O (≤0.18 wt%), Na₂O (≤0.04 wt%), MgO (≤0.14 wt%) and CaO (≤0.02 wt%) are very low to extremely low. Apart from silica, major oxides and trace elements (REE included) are more concentrated in the fine fraction (<62.5 μm) whose proportions of phyllosilicates and heavy minerals are significant. The close co-associations between Zr, Hf, Th and ∑REE in this fraction suggest that REE distribution is controlled by monazite and zircon. CIA values indicate intense weathering. Weathering products are characterized by the association Al₂O₃ and Ga in kaolinite; the strong correlation between Fe₂O₃ and V in hematite and goethite; the affinity of TiO₂ with HFSE (Hf, Nb, Th, Y and Zr) in heavy minerals. The ICV values suggest mature sediments. The PCI indicates a well-drained environment whereas U/Th and V/Cr ratios imply oxic conditions. La/Sc, La/Co, Th/Cr, Th/Sc and Eu/Eu* elemental ratios suggest a source with felsic components. Discrimination diagrams are consistent with the felsic source. The REE patterns of some High-K granite and granodiorite of the Congo Craton resemble those of the samples, indicating that they derive from similar source rocks.     

Luminescence dating of fluvial and coastal red sediments in the SE coast,India, and implications for paleoenvironmental changes and dune reddening

The Holocene and late Pleistocene environmental history of the teri (‘sandy waste’ in local parlance) red sands in the southeast coastal Tamil Nadu was examined using remote sensing, stratigraphy, and optically stimulated luminescence (OSL) dating. Geomorphological surveys enabled the classification of the teri red sands as, 1) inland fluvial teri, 2) coastal teri and, 3) near-coastal teri dunes. The inland teri sediments have higher clay and silty-sand component than the coastal and near-coastal teri, suggesting that these sediments were deposited by the fluvial process during a stronger winter monsoon around > 15 ka. The coastal teri dunes were deposited prior to 11.4 ± 0.9 ka, and the near-coastal dunes aggraded at around 5.6 ± 0.4 ka. We interpret that the coastal dunes were formed during a period of lower relative sea level and the near-coastal dunes formed during a period of higher sea level. Dune reddening is post deposition occurred after 11.4 ± 0.9 ka for the coastal teri dunes and after 5.6 ± 0.4 ka for the near-coastal teri dunes. Presence of microlithic sites associated with the coastal dunes suggest that the cultures existed in the region during 11.4 ± 0.9 ka and 5.6 ± 0.4 ka.     

The Lamandau IOCG deposit,southwestern Kalimantan Island,Indonesia: Evidence for its formation from geochronology,mineralogy, and petrogenesis of igneous host rocks

The Lamandau region of Kalimantan Island, Indonesia is located in Sandaland, in the southern part of the Kuching tectonic belt. A series of Cenozoic epithermal gold deposits and Fe–Cu–Au deposits are located in the Kuching belt. The Lamandau Fe–Cu–Au deposit is hosted by diorite porphyry. In-situ zircon U–Pb dating of the diorite porphyry shows that it formed between 82.1 ± 1.7 Ma and 78.7 ± 2.3 Ma. Geochemical data indicate a depletion of high field strength elements (HFSE) in the diorite porphyry and related basalt is similar to that of arc-related igneous rocks. The diorite porphyry and basalt were probably derived from typical arc magmas related to continental margin subduction and thus are characterized by light rare earth element (REE) enrichment and HFSE depletion. The sub-chondritic Nb/Ta ratios for the basalt in the Lamandau region indicate that the subducted Pacific slab began partial melting at depths where amphibole was the major residual phase, with some residual rutile. The basalt was derived from a depleted mantle source. The composition of apatite and zircon in the diorite porphyry indicates that the dioritic magma was produced from the subcontinental mantle after it was metasomatized by slab-derived fluids. The magma had a high oxygen fugacity, thus and therefore it was particularly conducive to the precipitation of Cu, Au and other ore-forming elements. The composition of magnetite indicates that it was of volcanic origin. The magnetite has a low REE content, and a high Cu–Au content. The deposit may be classified as an IOCG mineral system. In summary, the ore-related diorite porphyry in the Lamandau region might have formed in an extensional environment during rollback of the subducting western Pacific plate. The convergent velocity between the Philippine Sea and Eurasian plates was at a minimum during the rollback, so that the margin of East Asian began to undergo rifting with associated magmatism.     

Amphibole and phlogopite in “hybrid” metasomatic bands monitor trace element transfer at the interface between felsic and ultramafic rocks (Eastern Alps,Italy)

Ultramafic rocks in contact to gneisses in the Mt. Hochwart HP mélange (Eastern Italian Alps) preserve a series of metasomatic mineral zones. A phlogopitite with minor tremolite and accessory zircon and apatite forms close to the gneiss (Zone 1). Zone 2 consists of tremolite, phlogopite and anthophyllite followed by Zone 3 with anthophyllite plus minor chlorite and talc. Zone 3 grades into an amphibole–garnet peridotite lens. This reaction zone has been generated by infiltration of hydrous fluids at T of 660–700 °C and P < 1.2 GPa, which occurred during exhumation of coupled continental crust and mantle peridotites.The reaction zone between a trace element-rich (gneiss) and a trace element depleted reservoir (peridotite) allows assessment of local trace element mobility in aqueous fluids. We present the results of in situ LA-ICP-MS trace element analysis of minerals from the reaction zone. Phlogopite is the main host for Large Ion Lithophile Elements (LILE) and contributes significantly to the Li, Ti, Nb, Ta, Pb and Sc budget. Anthophyllite is the main host for Li whereas all other trace elements including Rare Earth Elements (REE) are preferentially incorporated into tremolite. Combined with the abundance of these minerals over the contact zone, the mineral trace element data suggests that the LILE and REE were mobile on a small scale of a few centimetres only. Limited mobility of Ta, which is generally regarded as barely mobile in fluids, is documented in elevated contents of Ta in anthophyllite coupled with low Nb/Ta. The high Li content in minerals throughout the reaction zone suggests that Li was the most mobile element.The studied metasomatic zones mirror geochemical processes occurring in subduction zones at the slab–mantle interface. Phlogopite crystallization at the slab–mantle interface is an efficient mechanism to filter LILE from the aqueous fluid. Thus, such reaction zones, forming at temperatures < 660–700 °C, likely prevents that the typical slab signature with enriched LILE is transported by aqueous fluids over long distances in the mantle wedge. However, if coupled to the downgoing slab, phlogopite- and tremolite-rich rocks from such reaction zones might be able to act as carriers of trace elements and water into deeper parts of the subduction zone.     

Petrological and geochemical characteristics of Zhaibei granites in Nanling region,Southeast China: Implications for REE mineralization

Mineralization with ion adsorption rare earth elements (REEs) in the weathering profile of granitoid rocks from Nanling region of Southeast China is an important REE resource, especially for heavy REE (HREE) and Y. However, the Jurassic granites in Zhaibei which host the ion adsorption light REE (LREE) ores are rare. It is of peraluminous and high K calc-alkaline composition, which has similar geochemical features of high K₂O + Na₂O and Zr + Nb + Ce + Y contents and Ga/Al ratio to A-type granite. Based on the chemical discrimination criteria of Eby [Geology 20 (1992) 641], the Zhaibei granite belongs to A1-type and has similar source to ocean island basalts. The rock is enriched in LREE and contains abundant REE minerals including LREE-phosphates and halides. Minor LREE was also determined in the feldspar and biotite, which shows negligible and negative Eu anomalies, respectively. This indicates that the Zhaibei granite was generated by extreme differentiation of basaltic parent magmas. In contrast, granites associated with ion adsorption HREE ores contain amounts of HREE minerals, and show similar geochemical characteristics with fractionated felsic granites. Note that most Jurassic granitoids in the Nanling region contain no REE minerals and cannot produce REE mineralization. They belong to unfractionated M-, I- and S-type granites. Therefore, accumulation of REE in the weathering profile is controlled by primary REE mineral compositions in the granitoids. Intense fractional crystallization plays a role on REE enrichment in the Nanling granitoid rocks.     

Middle Paleozoic mafic magmatism and ocean plate stratigraphy of the South Tianshan,Kyrgyzstan

The tectonic history of the Kyrgyz South Tianshan in the western Central Asian Orogenic Belt (CAOB) remains controversial, first of all, due to the limited amount of geochemical and isotope data. Our paper presents the first results of a detailed geochemical study (major and trace elements, Sr, Nd and Pb isotopes) of Middle Paleozoic mafic volcanic and subvolcanic rocks of the Ferghana and Atbashi–Kokshaal accretionary belts of the South Tianshan orogen in Kyrgyzstan, which formed during the evolution of the Turkestan Ocean. A special focus is given to the relation between magmatic rocks and sedimentary units of marine origin, chert, siliceous shale/mudstone, volcanogenic–carbonate clastics, seamount carbonates, and turbidites, which we consider as elements of Ocean Plate Stratigraphy (OPS). The age range of marine sediments is Late Silurian to Early Carboniferous, but the age of the most volcanic rocks associated with fossil-bearing OPS sediments is Devonian. The magmatic rocks have geochemical affinity to oceanic island basalts (OIB-type) and, to a lesser extent, mid-oceanic ridge (MORB-type) basalts associated with hemipelagic siliceous mudstone and pelagic chert. The rocks with OIB-type affinity are associated with chert, siliceous shale and carbonaceous clastics and carbonates. They are enriched in TiO₂, LREE (La/Sm_n = 1.9), and Nb (Zr/Nb_av. = 10), have differentiated HREE (Gd/Yb_n = 2.0), medium to low εNd (~ 5.7) and are characterized by clear Nb positive anomalies in normalized multi-element plots (Nb/Th_pm = 1.3, Nb/La_pm = 1.1). The OIBs formed by relatively low degrees of melting (< 5%) of mantle sources in the garnet stability field and erupted in an oceanic island setting. The MORB-type samples associated with siliceous mudstone and chert are less enriched in incompatible elements, possess flat REE and multi-element pattern, and show higher εNd values (~ 9.1); they were probably produced by high-degree melting of spinel lherzolite and/or harzburgite and erupted in a mid-oceanic ridge setting. The geological, lithological and geochronological data suggest that the OPS units with dominantly OIB-type basalts formed at one or several seamount chains of the Turkestan Ocean, which were accreted to the Kazakhstan continent, and thus contribute to our understanding of the Paleozoic tectonic evolution of the western CAOB during the Serpukhovian–Bashkirian.     

Geology,geochemistry and 40Ar/39Ar dating of Sevan ophiolites (Lesser Caucasus,Armenia): Evidence for Jurassic Back-arc opening and hot spot event between the South Armenian Block and Eurasia

In the Lesser Caucausus the Sevan-Akera ophiolites of N Armenia have lithological features of a slow-spreading oceanic lithosphere: serpentinites are frequently exposed and hydrothermalized at sea-floor level, plutonic rocks and dykes are rare. A complete differentiation trend is observed from mafic norites evolving to diorites and plagiogranites. Normal faults have exposed some of the deep magmatic rocks at sea-floor level. Geochemically, two distinct lava flow series have been distinguished: (1) a contaminated Mid-Oceanic Ridge Basalt (MORB) series evolving from gabbros to plagiogranites and from basalts to basaltic andesites, exhibiting slight calc-alkaline features (enrichments in Large Ion Lithophile Elements (LILE); negative anomalies in Nb–Ta and Ti relative to N-MORB); (2) an alkaline series evolving from basanites to trachy-andesites (on anhydrous basis). ⁴⁰Ar/³⁹Ar age on amphibole-bearing gabbros evidence a Middle Jurassic age (165.3 ± 1.7 Ma, 2σ) for oceanic crust formation. Structural data, including geological cross-sections and logs of the ophiolite along the northern part of Sevan Lake allow discussing the geodynamic evolution of that segment of the Amassia-Sevan-Akera ophiolitic suture zone.     

Arc magmatism in the Delhi Fold Belt: SHRIMP U–Pb zircon ages of granitoids and implications for Neoproterozoic convergent margin tectonics in NW India

The northwestern region of Peninsular India preserves important records of Precambrian plate tectonics and the role of Indian continent within Proterozoic supercontinents. In this study, we report precise SHRIMP zircon U–Pb ages from granitoids from the Sirohi terrane located along the western fringe of the Delhi Fold Belt in Rajasthan, NW India. The data reveal a range of Neoproterozoic ages from plagiogranite of Peshua, foliated granite of Devala, and porphyritic granite of Sai with zircon crystallization from magmas at 1015 ± 4.4 Ma, 966.5 ± 3.5 and 808 ± 3.1 respectively. The plagiogranite shows high SiO₂, Na₂O and extremely low K₂O, Rb, Ba, comparable with typical oceanic plagiogranites. These rocks possess low LREE and HREE concentrations and a relatively flat LREE–HREE slope, a well-developed negative Eu-anomaly and conspicuous Nb and Ti anomalies. Compared to the plagiogranite, the foliated Devala granite shows higher SiO₂ and moderate Na₂O, together with high K₂O and comparatively higher Rb, Ba, Sr and REE, with steep REE profiles and a weak positive Eu anomaly. In contrast to the plagiogranite and foliated granite, the porphrytic Sai granite has comparatively lower SiO₂ moderately higher Na₂O, extremely high Y, Zr, Nb and elevated REE. The geochemical features of the granitoids [HFSE depletion and LILE enrichment, Nb- and Ta-negative anomalies], and their plots in the fields of Volcanic Arc Granites and those from active continental margins in tectonic discrimination diagrams suggest widespread Neoproterozoic arc magmatism with changing magma chemistry in a protracted subduction realm. Our results offer important insights into a long-lived active continental margin in NW India during early and mid Neoproterozoic, consistent with recent similar observations on Cryogenian magmatic arcs widely distributed along the margins of the East African Orogen, and challenge some of the alternate models which link the magmatism to extensional tectonics associated with Rodinia supercontinent breakup.     

Geochronology and geochemistry of submarine volcanic rocks in the Yamansu iron deposit,Eastern Tianshan Mountains,NW China: Constraints on the metallogenesis

The Yamansu skarn iron deposit is hosted in Early Carboniferous submarine lava flow and volcaniclastic rocks of the Yamansu Formation in Eastern Tianshan Mountains, NW China. The lava flows are predominantly basaltic, with minor andesites. Laser ablation inductively coupled plasma mass spectrometry (LAICP-MS) U–Pb zircon dating of the basalts and skarns yields almost coeval ages of 324.4 ± 0.94 and 323.47 ± 0.95 Ma, respectively. The basalts contain clinopyroxene and plagioclase phenocrysts with a considerable amount of Fe–Ti oxide minerals in the groundmass as interstitial phases, probably suggesting that olivine–, clinopyroxene- and plagioclase fractionated within the magma chamber. Geochemically, the basalts are characterized by slight variations in SiO₂ (42.90–46.61 wt.%), P₂O₅ (0.08–0.12 wt.%), MnO (0.35–0.97 wt.%) and TiO₂ (0.74–0.82 wt.%), and relatively large variations in CaO (6.93–15.13 wt.%), Al₂O₃ (14.71–19.93 wt.%), total Fe₂O₃ (8.14–12.66 wt.%) and MgO (4.96–8.52 wt.%). They possess flat to light rare earth element (REE)-depleted patterns and display variable degrees of depletions in high field-strength elements (HFSE), suggesting a transitional feature between MORB and arc volcanic rocks, and indicating a back-arc tectonic setting. Furthermore, the geochemical signature also suggests that the volcanic rocks of Yamansu Formation were produced by partial melting of the spinel-facies, asthenospheric mantle peridotite which had been metasomatized by slab-derived fluids. The broadly overlapping ages of the basalts and skarn mineralization suggests that the skarn formation in the Yamansu deposit is related to subaqueous volcanism. In combination with the available information including fluid inclusions and stable isotope data, we infer that the hydrothermal fluids that generated the skarns could be a mixture of evolved magma-derived fluids and convecting sea water driven by the heat from the shallow active magma chamber. The Yamansu basalts provided the source of iron for the skarn mineralization. We envisage the submarine volcanism, skarn alteration and iron mineralization in the Yamansu iron deposit as a continuous process, different from either conventional intrusion-related skarn type or submarine volcanic exhalation sedimentation type.     

Geochemistry,provenance, and tectonic setting of Neoproterozoic metavolcanic and metasedimentary units,Werri area,Northern Ethiopia

Major, trace and rare earth element (REE) compositions of upper Proterozoic metavolcanic and metasedimentary rocks from the Tsaliet and Tembien Groups in the Werri district of northern Ethiopia were determined to examine their tectonic setting of eruption, provenance and source area weathering conditions. Tsaliet Group metavolcanic rocks in the Werri area have sub-alkaline chemistry characterized by low to intermediate SiO₂ contents, high Al₂O₃, low MgO and very low Cr and Ni. High field strength element (HFSE) abundances are highly variable. ∑REE abundances vary from 66.7 to 161.3 ppm, and chondrite-normalized REE patterns are moderately fractionated, with La_N/Yb_N values of between 3.1 and 9.0. Europium anomalies are variable (Eu/Eu* 0.80–1.21) but are generally positive (average Eu/Eu* 1.06). On tectonic discrimination diagrams, most samples have either volcanic-arc chemistry or fall in the overlap field with mid-oceanic ridge basalt (MORB). However, primitive mantle-normalized trace element abundances are comparable with sub-alkaline basalts from developed island arcs. ¹⁴⁷Sm/¹⁴⁴Nd ratios range from 0.1167 to 0.1269 (n = 3), yielding initial εNd_(800 Ma) of +3.8 to +4.9 and mean T_DM model age of 0.96 Ga, indicative of derivation from juvenile Neoproterozoic mantle. Metasediments from three locations (Werri1, Werri2 and Tsedia) in the Werri and Tsedia Slates have similar Al₂O₃, TiO₂ and HFSE contents but variable and low Na₂O, CaO and K₂O. Cr and Ni are slightly enriched in the Werri2 and Tsedia suites. SiO₂ is very variable, with average values of 70.75, 72.2 and 66.4 wt.% in the Werri1, Werri2 and Tsedia suites, respectively. ∑REE abundances in the metasediments (14.74–108.1) are lower than in the metavolcanics, and are slightly less fractionated, with La_N/Yb_N ratios of 0.8–5.9. Europium anomalies vary (Eu/Eu* 0.80–1.21) but are insignificant on average (Eu/Eu* 0.96). High values for the Chemical Index of Alteration (generally 70–90), and Plagioclase Index of Alteration (>75) in the Werri metasediments indicate moderate to severe chemical weathering in their source. Average major and trace element compositions of the metasediments and their REE patterns are comparable with the metavolcanics. ¹⁴⁷Sm/¹⁴⁴Nd ratios of the metasediments range from 0.1056 to 0.1398 (n = 4), with initial εNd_(800 Ma) of +3.4 to +5.0 and mean T_DM model age of 0.97 Ga, indicating derivation from juvenile Neoproterozoic crust similar to the underlying metavolcanics, with minimal (4–10%) contribution from older crust. The most sensitive tectonic setting discriminators indicate the Werri metasediments represent developed oceanic island arc sediments. The chemical similarity of the Werri metavolcanics to the nearby Adwa metavolcanics, Nakfa terrane in Eritrea, and volcanic units in central Saudi Arabia imply that juvenile Neoproterozoic Arabian Nubian Shield crust extended south at least as far as the Werri area of northern Ethiopia. The comparable geochemistry of the metasediments and their underlying lithologies attests to their derivation from this juvenile crustal material.     

Mineralogical and geochemical studies of brecciated ores in the Dalucao REE deposit,Sichuan Province,southwestern China

The Dalucao deposit, located in western Sichuan Province, southwestern China, in the western part of the Yangtze Craton, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE belt. Moreover, the Dalucao deposit is the only deposit identified in the southern part of the belt. The Dalucao deposit contains the No. 1, 2, and 3 orebodies; the No. 1 and 3 orebodies are both hosted in two breccia pipes, located in syenite–carbonatite host rocks. Both pipes have elliptical cross-sections at the surface, with long-axis diameters of 200–400 m and short-axis diameters of 180–200 m; the pipes extend downwards for > 450 m. No. 1 and No. 3 have total thickness varying between 55 and 175 m and 14 to 58 m respectively. The REE mineralization is associated with four brecciation events, which are recorded in each of the pipes. The ore grades in the No. 1 and 3 orebodies are similar, and consist of 1.0%–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a Type I mineral assemblage (fluorite + barite + celestite + bastnäsite), whereas the No. 3 orebody is characterized by a Type II assemblage (fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite). Argon (⁴⁰Ar/³⁹Ar) dating of hydrothermal muscovite intergrown with REE minerals in typical ores from the No. 1 and 3 orebodies yielded similar ages of 12.69 ± 0.13 and 12.23 ± 0.21 Ma, respectively, which suggest that both mineral assemblages formed coevally, rather than in paragenetic stages. Both ages are also similar to the timing of intrusion of the syenite–carbonatite complex (12.13 ± 0.19 Ma). The ore-mineral assemblages occur in breccias, veinlets, and in narrow veins. The ore veinlets, which usually show a transition to mineralized breccia or brecciated ores, are commonly enveloped by narrow veins and stringer zones with comparable mineral assemblages. The brecciated ores form 95% of the volume of the deposit, whereas brecciated ores are only a minor constituent of other deposits in the Mianning–Dechang REE belt. The carbonatite in the syenite–carbonatite complexes contains high concentrations of S (0.07–2.32 wt.%), Sr (16,500–20,700 ppm), Ba (3600–8400 ppm), and light REEs (LREE) (2848–10,768 ppm), but is depleted in high-field-strength elements (HFSE) (Nb, Ta, P, Zr, Hf, and Ti). The syenite is moderately enriched in large-ion lithophile elements (LILE), Sr (155–277 ppm), and Ba (440–755 ppm). The mineralized, altered, and fresh syenites and carbonatites exhibit similar trace element compositions and REE patterns. Brecciation events, and the Dalucao Fault and its secondary faults around the deposit, contributed to the REE mineralization by facilitating the circulation of ore-forming fluids and providing space for REE precipitation. Some hydrothermal veins composed of coarse-grained fluorite and quartz are distributed in the syenite–carbonatite complex. The oxygen isotope compositions of ore-forming fluids in equilibrium with quartz at 215 °C are − 4.95‰ to − 7.45‰, and the hydrogen isotope compositions of fluid inclusions in coarse-grained quartz are − 88.4‰ to − 105.1‰. The syenite–carbonatite complex and carbonatite are main contributors to the mineralization in the geological occurrence. Thus, the main components of the ore-forming fluids were magmatic water, meteoric water, and CO₂ derived from the decarbonation of carbonatite. According to the petrographic studies, bastnäsite mineralization developed during later stages of hydrothermal evolution and overprinted the formation of the brecciated fluorite–quartz hydrothermal veins. As low-temperature isotope exchange between carbonates of the carbonatite and water-rich magmatic fluids will lead to positive shifts in δ¹⁸O values of the carbonates, C–O isotopic compositions from the bulk primary carbonatite to hydrothermal calcite and bastnäsite changed (δ¹⁸O_V-SMOW from 8.0‰ to 11.6‰, and δ¹³C _V-PDB from − 6.1 to − 8.7‰). According to the chemical composition of syenite and carbonatite, REE chloride species are the primary complexes for the transport of the REEs in the hydrothermal fluids, and the presence of bastnäsite and parisite means the REE were precipitated as fluorocarbonates. High contents of Sr, Ba and S in the syenite–carbonatite complex led to the deposition of large amount of barite and celestite.     

A review of the genesis of the world class Bayan Obo Fe–REE–Nb deposits,Inner Mongolia,China: Multistage processes and outstanding questions

The Bayan Obo Fe–REE–Nb deposit is the world's largest rare earth element (REE) resource and with the increasing focus on critical metal resources has become a focus of global interest. The deposit is hosted in the Palaeoproterozoic Bayan Obo Group, mainly concentrated in the H8 dolomite marble. The ores consist of light REE enriched monazite and bastnäsite, with a wide array of other REE minerals. Niobium mineralisation is hosted primarily in aeschynite and pyrochlore, although there are a wide range of other Nb-minerals. The origin of the host dolomite and ore bodies has been a subject of intense debate. The host dolomite has been proposed to be both of sedimentary origin and an igneous carbonatite. Carbonatite dykes do occur widely in the area, and consideration of the textural, geochemical and isotopic composition of the dolomite suggests an origin via intrusion of magmatic carbonatite into meta-sedimentary marble, accompanied by metasomatism. The origin of the ore bodies is complex, indicated most strongly by an ~ 1 Ga range in radiometric age determinations. Compilation of available data suggests that the ores were originally formed around 1.3 Ga (Sm–Nd isochron ages; Th–Pb ages of zircon), close in time to the intrusion of the carbonatite dykes. The ores were subsequently subjected to several stages of deformation and hydrothermal overprint, culminating in deformation, metamorphism and fluid flow related to the Caledonian subduction of the Mongolian Plate under the North China Craton from ~ 450 to 420 Ma (Th–Pb ages of monazite). This stage resulted in the formation of the strong foliation (‘banding’) of the ore. The presence of undeformed veins with alkali mineral fills, and the overprinting of the foliation by Nb minerals suggest that secondary fluid flow events may also have contributed to the metal endowment of the deposits, as well as remobilising the original Fe and REE mineralisation. The alteration mineralogy and geochemistry of the ores are comparable to those of many REE mineralised carbonatites. Initial Nd isotope ratios at 450 Ma, however, suggest crustal sources for the metals. These conflicting lines of evidence can be reconciled if a (at least) two stage isotopic evolution is accepted for the deposits, with an original mantle-sourced, carbonatite-related metal accumulation forming around 1.3 Ga with εNd close to 0. The ore was remobilised, with associated re-equilibration of Th–Pb isotope systematics during deformation at ~ 450 Ma. A further stage of alkaline hydrothermal fluid was responsible for Nb mineralisation at this stage. The complex geological history, with multiple stages of alkaline, high field strength element-rich, metasomatic fluid flow, is probably the main reason for the exceptional metal endowment of the Bayan Obo area.     

Delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex,North China Craton and its geological implications

Through detailed studies we have delineated a suite of banded TTG gneisses from the Zanhuang Complex. The protolith of the gneisses, predominantly tonalite, has undergone intensive metamorphism, deformation and anatexis and in a banded structure is intimately associated with melanocratic dioritic gneiss and leucocratic trondhjemitic veins. SHRIMP Zircon U–Pb data show that the tonalite was formed ca. 2692 ± 12 Ma ago. The tonalitic gneiss has the features of high SiO₂ (67.76–73.31%), high Al₂O₃ (14.38–15.83%), rich in Na₂O (4.48–5.07%) and poor in K₂O (0.77–1.93%). The gneiss is strongly fractioned in REE ((La/Yb)_N = 12.02–24.65) and shows a weak positive Eu anomaly (Eu/Eu^* = 1.05–1.64). It has high contents of Ba (199–588 ppm) and Sr (200–408 ppm), low contents of Yb (0.32–1.00 ppm) and Y (3.41–10.3 ppm) with high Sr/Y ratios (21.77–96.77) and depletion in HFSE Nb, Ta and Ti. These characteristics are similar to those of the high-Si adakitic rocks. The melanocratic dioritic gneiss has low SiO₂ (59.81%), high MgO (6.34%), high Al₂O₃ (14.02%) contents, rich in Na₂O (3.7%) and poor in K₂O (1.79%), with high Mg index (Mg^# = 67). REE and trace elements are on the whole similar to that of the tonalitic gneiss, but compatible element abundances V (116 ppm), Cr (249 ppm), Co (37 ppm) and Ni (179 ppm) are higher. The leucocratic felsic bands (approximating trondhjemite in composition) have major oxides similar to that of the TTG gneisses but the REE and compatible elements are extremely low, which are indicative of the products of anatexis. The tonalitic gneiss has positive ε_Nd(t) (2.37–3.29) and low initial Sr (0.69719–0.70068) values with depleted mantle Nd model age of ca. 2.8 Ga, suggesting its generation from partial melting of mantle-derived juvenile crust. The dioritic gneiss was also derived from subduction environment, but has undergone significant metasomatism of mantle wedge. The delineation of the ca. 2.7 Ga TTG gneisses in the Zanhuang Complex further proves that the North China Craton experienced large-scale continental crustal accretion in early Neoarchean, and gives new constraints on the subdivision of the early blocks and greenstone belts of the craton.     

Geochronological,geochemical and mineralogical constraints on the petrogenesis of appinites from the Laoniushan complex,eastern Qinling,central China

Appinites are commonly derived from a mantle source and are potentially significant in constraining the tectonic nature and evolution of ancient orogens, yet they have received little attention because of their limited outcrop. Here we investigate the newly identified appinitic rocks from the Laoniushan complex in the eastern Qinling Orogen. The appinites are composed of coarse-grained hornblendite, medium- and fine-grained hornblende-gabbro, and diorite porphyrite in the field occurrence. Winthin the appinitic rocks, the hornblendite displays features of cumulates. This study presents LA-ICP-MS zircon U-Pb data, mineral chemistry and whole rock geochemistry of the appinites. Zircons in the mafic to ultramafic rocks yield a U-Pb age of 152 ± 1Ma. The geochemistry of the rocks displays: lower SiO₂, higher Fe₂O₃^T and MgO contents, relatively flat chondrite normalized REE patterns with slight enrichment in light REE and a minor negative Eu anomaly; enrichment in large-ion lithophile elements(LILE, e.g. Rb, Ba, Sr and P), and depletion in high field strength elements(HFSE, e.g. Nb, Zr, Hf and Ti). Such geochemical features, together with crust-like bulk Sr-Nd isotopic compositions(initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7057–0.7072, ε_Nd(t) = −17.2 to −9), suggest that the Laoniushan appinites likely originated from an ancient metasomatised mantle, followed by fractional crystallization in the petrogenetic process. The studied appinites were most likely generated in an intracontinental extensional environment in the Late Mesozoic.     

Trace-element composition and zoning in clinopyroxene- and amphibole-group minerals: Implications for element partitioning and evolution of carbonatites

The present work is a first comprehensive study of the trace-element composition and zoning in clinopyroxene- and amphibole-group minerals from carbonatites, incorporating samples from 14 localities worldwide (Afrikanda, Aley, Alnö, Blue River, Eden Lake, Huayangchuan, Murun, Oka, Ozernaya Varaka, Ozernyi, Paint Lake, Pinghe, Prairie Lake, Turiy Mys). The new electron-microprobe data presented here significantly extend the known compositional range of clinopyroxenes and amphiboles from carbonatites. These data confirm that calcic and sodic clinopyroxenes from carbonatites are not separated by a compositional gap, instead forming an arcuate trend from nearly pure diopside through intermediate aegirine–augite compositions confined to a limited range of CaFeSi₂O₆ contents (15–45 mol%) to aegirine with < 25 mol% of CaMgSi₂O₆ and a negligible proportion of CaFeSi₂O₆. A large set of LA-ICPMS data shows that the clinopyroxenes of different composition are characterized by relatively low levels of Cr, Co and Ni (≤ 40 ppm) and manifold variations in the concentration of trivalent lithophile and some incompatible elements (1–150 ppm Sc, 26–6870 ppm V, 5–550 ppm Sr, 90–2360 ppm Zr, and nil to 150 ppm REE), recorded in some cases within a single crystal. The relative contribution of clinopyroxenes to the whole-rock Rb, Nb, Ta, Th and U budget is negligible. The major-element compositional range of amphiboles spans from alkali- and Al-poor members (tremolite) to Na–Al-rich Mg- or, less commonly, Fe-dominant members (magnesiohastingsite, hastingsite and pargasite), to calcic–sodic, sodic and potassic–sodic compositions intermediate between magnesio-ferrikatophorite, richterite, magnesioriebeckite, ferri-nyböite and (potassic-)magnesio-arfvedsonite. In comparison with the clinopyroxenes, the amphiboles contain similar levels of tetravalent high-field-strength elements (Ti, Zr and Hf) and compatible transition elements (Cr, Co and Ni), but are capable of incorporating much higher concentrations of Sc and incompatible elements (up to 500 ppm Sc, 43 ppm Rb, 1470 ppm Sr, 1230 ppm Ba, 80 ppm Pb, 1070 ppm REE, 140 ppm Y, and 180 ppm Nb). In some carbonatites, amphiboles contribute as much as 25% of the Zr + Hf, 15% of the Sr and 35% of the Rb + Ba whole-rock budget. Both clinopyroxenes and amphiboles may also host a significant share (~ 10%) of the bulk heavy-REE content. Our trace-element data show that the partitioning of REE between clinopyroxene (and, in some samples, amphibole) and the melt is clearly bimodal and requires a revision of the existing models assuming single-site REE partitioning. Clinopyroxenes and amphiboles from carbonatites exhibit a diversity of zoning patterns that cannot be explained exclusively on the basis of crystal chemistry and relative compatibility of different trace-element in these minerals. Paragenetic analysis indicates that in most cases, the observed zoning patterns develop in response to removal of selected trace elements by phases co-precipitating with clinopyroxene and amphibole (especially magnetite, fluorapatite, phlogopite and pyrochlore). With the exception of magnesiohastingsite–richterite sample from Afrikanda, the invariability of trace-element ratios in the majority of zoned clinopyroxene and amphibole crystals implies that fluids are not involved in the development of zoning in these minerals. The implications of the new trace-element data for mineral exploration targeting REE, Nb and other types of carbonatite-hosted rare-metal mineralization are discussed.     

Neoproterozoic nascent island arc volcanism from the Nubian Shield of Egypt: Magma genesis and generation of continental crust in intra-oceanic arcs

The Neoproterozoic Wadi Ranga metavolcanic rocks, South Eastern Desert of Egypt, constitute a slightly metamorphosed bimodal sequence of low-K submarine tholeiitic mafic and felsic volcanic rocks. The mafic volcanic rocks are represented by massive and pillow flows and agglomerates, composed of porphyritic and aphyric basalts and basaltic andesites that are mostly amygdaloidal. The felsic volcanic rocks embrace porphyritic dacites and rhyolites and tuffs, which overlie the mafic volcanic rocks. The geochemical characteristics of Wadi Ranga volcanic rocks, especially a strong Nb depletion, indicate that they were formed from subduction-related melts. The clinopyroxene phenocrysts of basalts are more akin to those crystallizing from island-arc tholeiitic magmas. The tholeiitic nature of the Wadi Ranga volcanics as well as their LREE-depleted or nearly flat REE patterns and their low K₂O contents suggest that they were developed in an immature island arc setting. The subchondritic Nb/Ta ratios (with the lowest ratio reported for any arc rocks) and low Nb/Yb ratios indicate that the mantle source of the Wadi Ranga mafic volcanic rocks was more depleted than N-MORB-source mantle. Subduction signature was dominated by aqueous fluids derived from slab dehydration, whereas the role of subducted sediments in mantle-wedge metasomatization was subordinate, implying that the subduction system was sediment-starved and far from continental clastic input. The amount of slab-derived fluids was enough to produce hydrous magmas that follow the tholeiitic but not the calc-alkaline differentiation trend. With Mg# > 64, few samples of Wadi Ranga mafic volcanic rocks are similar to primitive arc magmas, whereas the other samples have clearly experienced considerable fractional crystallization.The low abundances of trace elements, together with low K₂O contents of the felsic metavolcanic rocks indicate that they were erupted in a primitive island arc setting. The felsic volcanic rocks are characterized by lower K/Rb ratios compared to the mafic volcanic rocks, higher trace element abundances (~ 2 to ~ 9 times basalt) on primitive arc basalt-normalized pattern and nearly flat chondrite-normalized REE patterns, which display a negative Eu anomaly. These features are largely consistent with fractional crystallization model for the origin of the felsic volcanic rocks. Moreover, SiO₂-REE variations for the Wadi Ranga volcanic rocks display steadily increasing LREE over the entire mafic to felsic range and enriched La abundances in the felsic lavas relative to the most mafic lavas, features which are consistent with production of the felsic volcanic rocks through fractional crystallization of basaltic melts. The relatively large volume of Wadi Ranga silicic volcanic rocks implies that significant volume of silicic magmas can be generated in immature island arcs by fractional crystallization and indicates the significant role of intra-oceanic arcs in the production of Neoproterozoic continental crust. We emphasize that the geochemical characteristics of these rocks such as their low LILE and nearly flat REE patterns can successfully discriminate them from other Egyptian Neoproterozoic felsic volcanic rocks, which have higher LILE, Zr and Nb and fractionated REE patterns.     

Relative sea level changes and regional tectonic evolution of seven coastal areas in NW Greece since the mid-Holocene

This study presents relative sea level (RSL) curves for seven coastal areas in Akarnania and the northwestern Peloponnese (NW Greece) since the mid-Holocene. RSL fluctuations are deduced from 48 ¹⁴C-AMS dated sedimentological sea level markers from 27 vibracores drilled in near-coast geological archives as well as from six geoarchaeological sea level indicators of known ages. Seven palaeo sea level curves including uncertainty bands are reconstructed for a coastal zone spanning a distance of 150 km. Considerable intra-regional differences in sea level evolution exist. These differences are mainly due to tectonic reasons. In general, RSL in northwestern Greece has never been higher than today. Rates of local sea level rise were highest until 5500–5000 cal BC (up to 12.3 m/ka) and lowest during 4000–500 cal BC (0.2–1.4 m/ka). During the past 2500 or so years, RSL has accelerated anew (0.7–2.7 m/ka). Calculating differences between local mean sea level curves provides quantitative information on intra-regional differences of tectonic activity. The coastal plains of Palairos and Elis show signs of uplift, whereas the Mytikas and Boukka plains are strongly subsiding. Compared to other areas of the eastern Mediterranean, northwestern Greece has been subject to significant net long-term subsidence. Regional tectonic events (RTEs) were detected for the time around 4000, 2500, 500 and 250 cal BC as well as around 250 and 1250 cal AD. RTEs are characterized by changes of uplift/subsidence rates or by the redirection of local tectonic movements. The question if some of the RTEs were of a supra-regional nature is still open. From a geodynamic point of view, the results presented show that Akarnania's southwestern fringe is being downwarped while the tectonic block as a whole is moving towards the southwest. Strongest subsidence rates are observed for central Akarnania. At Akarnania's fringes, subsidence is reduced by the influence of strong uplift of adjacent areas such as around Preveza and the northern Peloponnese.     

Mobility of elements in a continental subduction zone: evidence from the UHP metamorphic complex of the Kokchetav massif

We studied clastics of high-alumina garnet-kyanite-mica schists and garnet-kyanite-quartz granofelses, including diamond-bearing ones, found in the eluvial sediments near Lake Barchi. In contents of major elements the studied rocks correspond to argillaceous shales. The garnet-kyanite-quartz granofelses are poorer in K (0.49-1.35 wt.% K₂O) than the garnet-kyanite-mica schists (4.9-2.2 wt.% K₂O) but have the same contents of other major components. The REE patterns of most of the garnet-kyanite-phengite schists are similar to those of the Post-Archean Australian Shale (PAAS) (xLa/Yb = 13). All garnet-kyanite-quartz rocks are much stronger depleted in LREE (x_La/Yb = 1.4) and other incompatible elements. Our studies show that allanite and monazite are the main concentrators of LREE and Th in the garnet-kyanite-phengite rocks of the Barchi site. Monazite, occurring as inclusions in garnet, contains not only LREE but also Th, U, and Pb. Rutile of the nondepleted rocks is enriched in Fe and Nb impurities only. The garnet-kyanite-quartz granofelses bear rutile, apatite, and xenotime as accessory phases. Rutile of the depleted rocks shows wide variations in contents of Nb, Ta, and V impurities. In places, the contents of Nb and Ta reach 10.5 and 2.3 wt.%, respectively. The rutile decomposes into rutile with Nb (1.4 wt.%) and Fe (0.87 wt.%) impurities and titanium oxide rich in Fe (6.61 wt.%), Nb (up to 20.8 wt.%), and Ta (up to 2.81%) impurities. Based on the measured contents of incompatible elements in differently depleted high-alumina rocks, the following series of element mobility during UHP metamorphism has been established: Th > Ce > La > Pr > Nd > K > Ba > Rb > Cs > Sm > Eu. The contents of U, P, and Zr in the depleted rocks are similar to those in the nondepleted rocks. The studies have shown that metapelites subducted to the depths with diamond stability conditions can be depleted to different degrees. This might be either due to their exhumation from different depths of the subduction zone or to the presence of an external source of water controlling the temperature of dissolution of phengite and the formation of supercritical fluid/melt.