Permian bimodal dyke of Tarim Basin, NW China: Geochemical characteristics and tectonic implications

This study reports for the first time the occurrence of bimodal dyke in the Shuigongtuan area of Bachu County, Tarim Basin, NW China. Here, quartz syenite porphyry and diabase dykes occur in direct contact showing bimodal feature. The quartz syenitic porphyry is metaluminous, enriched in K₂O + Na₂O (10–11 wt.%) and total rare earth elements (REE), with low Mg/(Mg + Fe) ratios, high LREE/HREE, and negative Eu anomalies. The chemical characteristics and tectonic discriminative diagrams show that the rocks have geochemical affinity with A-type granites. The diabase dyke shows 45–52 wt.% SiO₂ and Mg/(Mg + Fe) ratio in the range of, with high total REE, high LREE/HREE ratios and lack of Eu anomalies, broadly corresponding to tholeiitic composition. Based on low Y/Nb (as low as 0.4, and less than 1.2), enrichment in LILE and HFSE, and uniform Nb-enrichment patterns in spider diagram for the quartz syenitic porphyry, together with the geochemical patterns of the diabases, this biomodal association is interpreted to be derived from a mantle source and formed under typical within-plate environment. The quartz syenitic porphyry and diabase have Daly gap of 46 wt.%–67 wt.% in SiO₂, which is explained through formation under bimodal rifting. The quartz syenitic dyke probably formed during Early Permian (277 Ma) and has geochemical affinity with the Xiaohaizi syenitic body. We propose that magmas sourced from the mantle intruded into middle–upper crust and were emplaced as dykes, which indicate large-scale extension during the Permian in Tarim Basin. The bimodal dyke has genetic affinity with the huge volume of Permian basalts and igneous rocks (248–292 Ma) that occur in the Tarim Basin. The magmatism manifests the culmination of the major thermal event in the Tarim Basin.     

海底热液系统高温流体的稀土元素组成及其控制因素

研究稀土元素在流体中的地球化学行为及其控制因素,对利用稀土示踪与流体有关的地球化学过程具有重要意义。海底高温流体稀土组成研究表明,不同背景、岩性热液系统喷口流体的稀土含量差别较大,与海水之间可达几个数量级,但配分模式却非常类似,即普遍具有LREE富集、高的正Eu异常特征。流体的稀土组成与岩石或矿物的蚀变程度、结构构造有关,同时受流体的温压、pH值、Eh值、络合介质种类等因素的影响,其配分模式是流体循环、迁移过程中络合、吸附、矿物沉淀等不同因素共同作用而再次调整的结果。正Eu异常作为高温流体的特征标志,可以用来示踪与高温流体有关的地球化学作用过程,同时Y/Ho比值、负Ce异常可以用来示踪与流体/海水混合有关的化学过程。     

Metallogenesis of the Carajás Mineral Province, Southern Amazon Craton, Brazil: Varying styles of Archean through Paleoproterozoic to Neoproterozoic base- and precious-metal mineralisation

The Itacaiúnas Belt of the highly mineralised Carajás Mineral Province comprises ca. 2.75 Ga volcanic rocks overlain by sedimentary sequences of ca. 2.68 Ga age, that represent an intracratonic basin rather than a greenstone belt. Rocks are generally at low strain and low metamorphic grade, but are often highly deformed and at amphibolite facies grade adjacent to the Cinzento Strike Slip System. The Province has been long recognised for its giant enriched iron and manganese deposits, but over the past 20 years has been increasingly acknowledged as one of the most important Cu–Au and Au–PGE provinces globally, with deposits extending along an approximately 150 km long WNW-trending zone about 60 km wide centred on the Carajás Fault. The larger deposits (approx. 200–1000 Mt @ 0.95–1.4% Cu and 0.3–0.85 g/t Au) are classic Fe-oxide Cu–Au deposits that include Salobo, Igarapé Bahia–Alemão, Cristalino and Sossego. They are largely hosted in the lower volcanic sequences and basement gneisses as pipe- or ring-like mineralised, generally breccia bodies that are strongly Fe- and LREE-enriched, commonly with anomalous Co and U, and quartz- and sulfur-deficient. Iron oxides and Fe-rich carbonates and/or silicates are invariably present. Rhenium–Os dating of molybdenite at Salobo and SHRIMP Pb–Pb dating of hydrothermal monazite at Igarapé-Bahia indicate ages of ca. 2.57 Ga for mineralisation, indistinguishable from ages of poorly-exposed Archean alkalic and A-type intrusions in the Itacaiúnas Belt, strongly implicating a deep magmatic connection.A group of smaller, commonly supergene-enriched Cu–Au deposits (generally < 50 Mt @ < 2% Cu and < 1 g/t Au in hypogene ore), with enrichment in granitophile elements such as W, Sn and Bi, spatially overlap the Archean Fe-oxide Cu–Au deposits. These include the Breves, Águas Claras, Gameleira and Estrela deposits which are largely hosted by the upper sedimentary sequence as greisen-to ring-like or stockwork bodies. They generally lack abundant Fe-oxides, are quartz-bearing and contain more S-rich Cu–Fe sulfides than the Fe-oxide Cu–Au deposits, although Cento e Dezoito (118) appears to be a transitional type of deposit. Precise Pb–Pb in hydrothermal phosphate dating of the Breves and Cento e Dezoito deposits indicate ages of 1872 ± 7 Ma and 1868 ± 7 Ma, respectively, indistinguishable from Pb–Pb ages of zircons from adjacent A-type granites and associated dykes which range from 1874 ± 2 Ma to 1883 ± 2 Ma, with 1878 ± 8 Ma the age of intrusions at Breves. An unpublished Ar/Ar age for hydrothermal biotite at Estrela is indistinguishable, and a Sm–Nd isochron age for Gameleira is also similar, although somewhat younger. The geochronological data, combined with geological constraints and ore-element associations, strongly implicate a magmatic connection for these deposits.The highly anomalous, hydrothermal Serra Pelada Au–PGE deposit lies at the north-eastern edge of the Province within the same fault corridor as the Archean and Paleoproterozoic Cu–Au deposits, and like the Cu–Au deposits is LREE enriched. It appears to have formed from highly oxidising ore fluids that were neutralised by dolomites and reduced by carbonaceous shales in the upper sedimentary succession within the hinge of a reclined synform. The imprecise Pb–Pb in hydrothermal phosphate age of 1861 ± 45 Ma, combined with an Ar/Ar age of hydrothermal biotite of 1882 ± 3 Ma, are indistinguishable from a Pb–Pb in zircon age of 1883 ± 2 Ma for the adjacent Cigano A-type granite and indistinguishable from the age of the Paleoproterozoic Cu–Au deposits. Again a magmatic connection is indicated, particularly as there is no other credible heat or fluid source at that time.Finally, there is minor Au–(Cu) mineralisation associated with the Formiga Granite whose age is probably ca. 600 Ma, although there is little new zircon growth during crystallisation of the granite. This granite is probably related to the adjacent Neoproterozoic (900–600 Ma) Araguaia Fold Belt, formed as part of the Brasiliano Orogeny.Thus, there are two major and one minor period of Cu–Au mineralisation in the Carajás Mineral Province. The two major events display strong REE enrichment and strongly enhanced LREE. There is a trend from strongly Fe-rich, low-SiO₂ and low-S deposits to quartz-bearing and more S-rich systems with time. There cannot be significant connate or basinal fluid (commonly invoked in the genesis of Fe-oxide Cu–Au deposits) involved as all host rocks were metamorphosed well before mineralisation: some host rocks are at mid- to high-amphibolite facies. The two major periods of mineralisation correspond to two periods of alkalic to A-type magmatism at ca. 2.57 Ga and ca. 1.88 Ga, and a magmatic association is compelling.The giant to world-class late Archean Fe-oxide Cu–Au deposits show the least obvious association with deep-seated alkaline bodies as shown at Palabora, South Africa, and implied at Olympic Dam, South Australia. The smaller Paleoproterozoic Cu–Au–W–Sn–Bi deposits and Au–PGE deposit show a more obvious relationship to more fractionated A-type granites, and the Neoproterozoic Au–(Cu) deposit to crustally-derived magmas. The available data suggest that magmas and ore fluids were derived from long-lived metasomatised lithosphere and lower crust beneath the eastern margin of the Amazon Craton in a tectonic setting similar to that of other large Precambrian Fe-oxide Cu–Au deposits.     

U–Pb SHRIMP monazite ages of the giant Morro Velho and Cuiabá gold deposits, Rio das Velhas greenstone belt, Quadrilátero Ferrífero, Minas Gerais, Brazil

U–Pb SHRIMP results of 2672 ± 14 Ma obtained on hydrothermal monazite crystals, from ore samples of the giant Morro Velho and Cuiabá Archean orogenic deposits, represent the first reliable and precise age of gold mineralization associated with the Rio das Velhas greenstone belt evolution, in the Quadrilátero Ferrífero, Brazil. In the basal Nova Lima Group, of the Rio das Velhas greenstone belt, felsic volcanic and volcaniclastic rocks have been dated between 2792 ± 11 and 2751 ± 9 Ma, coeval with the intrusion of syn-tectonic tonalite and granodiorite plutons, and also with the metamorphic overprint of older tonalite–trondhjemite–granodiorite crust. Since cratonization and stable-shelf sedimentation followed intrusion of Neoarchean granites at 2612 + 3/− 2 Ma, it is clear that like other granite–greenstone terranes in the world, gold mineralization is constrained to the latest stages of greenstone evolution.     

Two Cu–Co sulfide phases and contrasting fluid systems in the Katanga Copperbelt, Democratic Republic of Congo

The Katanga Copperbelt is the Congolese part of the well-known Central African Copperbelt, the largest sediment-hosted stratiform Cu–Co province on Earth. Petrographic examination of borehole samples from the Kamoto and Luiswishi mines in the Katanga Copperbelt recognized two generations of hypogene Cu–Co sulfides and associated gangue minerals (dolomite and quartz). The first generation is characterized by fine-grained Cu–Co sulfides and quartz replacing dolomite. The second generation is paragenetically later and characterized by coarse-grained Cu–Co sulfides and quartz overgrown and partly replaced by dolomite. Fluid inclusion microthermometric data were collected from two different types of fluid inclusions: type-I fluid inclusions (liquid + vapor) in the quartz of the first generation and type-II fluid inclusions (liquid + vapor + halite) in the quartz of the second generation. The microthermometric analyses indicate that the fluids represented by type-I and type-II fluid inclusions had very different temperatures and salinities and were not in thermal equilibrium with the host rock.Petrographic and microthermometric data indicate the presence of at least two main hypogene Cu–Co sulfide phases in the Katanga Copperbelt. The first is an early diagenetic typical stratiform phase, which produced fine-grained sulfides that are disseminated in the host rock and frequently concentrated in nodules and lenticular layers. This phase is related to a hydrothermal fluid with a moderate temperature (115 to 220 °C, or less if reequilibration of inclusions has occurred) and salinity (11.3 to 20.9 wt.% NaCl equiv.). The second hypogene Cu–Co phase produced syn-orogenic coarse-grained sulfides, which also occur disseminated in the host rock but mainly concentrated in a distinct type of stratiform nodules and layers and in stratabound veins and tectonic breccia cement. This second phase is related to a hydrothermal fluid with high temperature (270 to 385 °C) and salinity (35 to 45.5 wt.% NaCl equiv.).A review of available microthermometric and ore geochronological data of the Copperbelt in both the Democratic Republic of Congo and Zambia supports the regional presence of the two Cu–Co phases proposed in our study. Future geochemical analyses in the Copperbelt should take into account the presence of, at least, these two Cu–Co phases, their contrasting fluid systems and the possible overprint of the first phase by the second one.     

Reconstruction of the hydrothermal history of the Cu–Ag vein-type mineralisation at Dikulushi, Kundelungu foreland, Katanga, D.R. Congo

The Kundelungu foreland, north of the Lufilian arc in the Democratic Republic of Congo, contains a number of various vein-type and stratiform copper mineralisations. The geodynamic context and metallogenesis of these mineral occurrences remain enigmatic. Currently, the vein-type Cu–Ag ore deposit at Dikulushi is the most significant deposit in the region. Mineralisation at Dikulushi comprises two major styles: 1) a polysulphide assemblage (Zn–Pb–Fe–Cu–As) within brecciated rocks along an anticlinal closure; and 2) a vein-hosted Cu–Ag assemblage. Petrographic and fluid inclusion studies indicate that the early Zn–Pb–Fe–Cu–As assemblage formed from a high-salinity Ca–Na–Cl fluid of modest temperature (135–172 °C). The later, economically more significant vein-related Cu–Ag mineralisation formed from intermediate salinity, lower temperature (46–82 °C) Na–Cl fluids. Weathering of the sulphide minerals resulted in a supergene enrichment with the formation of secondary Cu-minerals.     

Late Paleozoic underplating in North Xinjiang: Evidence from shoshonites and adakites

Shoshonitic series volcanic rocks (SSVR) and adakites are widely distributed in the Permian terrestrial volcanic strata of the Yishijilike–Awulale range of west Tianshan, north Xinjiang, China. Isotopic dating yields Permian ages of 280–250 Ma. The SSVR include absarokite, shoshonite and banakite which are characterized by enrichment of alkalis, particularly in K, combined with lower Ti, higher Al (A/NKC = 0.70–0.99, metaluminous) and Fe₂O₃ > FeO. The SSVR that are rich in LILE with high REE contents and Eu/Eu range from 0.59 to 1.30. They are rich in LREE ((La/Yb)_N 2.15–11.97) and depleted in Nb, Ta and Ti (TNT negative anomalies). The adakites are metaluminous to weakly peraluminous (A/NKC = 0.85-1.16) and belong to the high-SiO₂ type of adakite (HSA, SiO₂ = 62%–71%). They are characterized by lower ΣREE with strong LREE enrichment ((La/Yb)_N 13–35). Pronounced positive Eu anomalies (Eu/Eu = 1.02–1.27), very low Yb contents and distinct TNT-negative anomalies are evident. The SSVR have ε_Nd(t) (+ 1.28 to + 4.92) and (⁸⁷Sr/⁸⁶Sr)_i (0.7041–0.7057) that are similar to adakites in the regions which are characterized by ε_Nd(t) = 0.95 to + 5.69 and (⁸⁷Sr/⁸⁶Sr)_i = 0.7050–0.7053. Trace element, REE and Sr/Nd isotopic compositions suggest that both SSVR and adakites possess similar source regions associated with underplated mantle-derived basaltic materials. Lithosphere extension driven by magmatic underplating was responsible for the generation of both the SSVR and adakites. This magmatism serves as a petrological indicator of underplating during the Permian. Obviously thickened crust (62–52 km), a complex Moho discontinuity, high heat flow (~ 100 mw·m^− 2), widespread contemporary alkali-rich granites, basic dike swarms (K–Ar ages of 187–271 Ma, Ar–Ar ages of 174–270 Ma and Rb–Sr ages of 255 ± 28 Ma; ε_Nd(t) + 1.84 to + 10.1; (⁸⁷Sr/⁸⁶Sr)_i 0.7035 and 0.7065), and basic granulites (SHRIMP U–Pb age of 268–279 ± 5.6 Ma) provide additional evidences for the underplating event in this area during Permian.     

Geochemistry and geochronology of the Mkhondo suite, Swaziland: evidence for passive-margin deposition and granulite facies metamorphism in the Late Archean of Southern Africa

The Archean Mkhondo suite in southern Swaziland is a multiply deformed succession of metasediments intruded with amphibolite dykes and sills and granitoid gneisses. Mineral and textural relationships indicate an early period of granulite facies metamorphism, followed later by amphibolite facies metamorphism. Geothermobarometry indicates maximum temperatures of 700–900°C and burial depths of 25–3 km. Paragneisses and biotite quartzites have LREE enriched patterns with small negative Eu anomalies, whereas white quartzites show variable REE patterns and low REE concentrations. BIF has slight LREE enrichment and Eu anomalies. Amphibolites have moderate LREE enrichment and depletions in Ta---Nb and P. Unlike many Archean granitoids, the Mkhondo granitoid gneisses are high in K and other LILE, have large negative Eu anomalies and are not depleted in HREE.SHRIMP isotopic analyses of detrital zircons from a biotite quartzite define a source age of 3600–3460 Ma. A deformed granitoid in tectonic contact with the Mkhondo suite yields a zircon evaporation mean age of 3192±5 Ma, which is interpreted as the age of emplacement. A zircon evaporation age of a granitic melt patch in paragneiss, as well as whole-rock and garnet Sm---Nd isotopic ages, suggest that the peak of high-grade metamorphism in the Mkhondo suite occurred at about 2750 Ma. This is the first evidence for Late Archean high-grade metamorphism in the southeastern Kaapvaal craton. The age data of this study restrict deposition of the Mkhondo suite to between 3.2 and 2.75 Ga.Mkhondo paragneisses are interpreted as shales with biotite quartzites as iron- and quartz-rich detrital sediments. Geochemical mixing calculations indicate that the sediment sources were composed of basalt (±komatiite), TTG and Eu-depleted granitoids. The Mkhondo assemblage may have been deposited along a passive continental margin or in a continental interior basin. The presence of minor BIF with positive Eu anomalies suggests minor hydrothermal input into the sedimentary basin. Intense chemical weathering was probably most important in production of the relatively pure quartz sands.     

Fluid inclusion study of the Plomositas–Los Arcos polymetallic epithermal vein tract, Plomosas district, Sinaloa, Mexico

The most important deposit in the Plomosas–Rosario district, Sinaloa, is the vein tract named Plomositas–Plomosas–Los Arcos. These are NNW–SSE striking veins hosted in rocks of the Lower Volcanic Supergroup (LVS), and also in rocks at the bottom of the Upper Volcanic Supergroup (UVS). Both supergroups belong to the Sierra Madre Occidental. These veins evolved from an early intermediate sulfidation stage (1), rich in base metal sulfides, to a low sulfidation stage (2), rich in silver sulfides and sulfosalts. There is also a 45 m-wide stockwork with native silver and gold. Stage 1 is found in the deeper portion of the veins whereas stage 2 is found in the most shallow portion of the deposit. These stages record fluid inclusion salinities ranging from 7 to 12 wt.% NaCl equiv., and from 0.2 to 3.5 wt.% NaCl equiv., respectively. Homogenization temperatures range from 120 °C for surface samples to 200 °C at a depth of 320 m. The low homogenization temperatures recorded, and the dispersion of veins within host rocks as veinlets, suggest that this deposit formed at shallow depths and was probably blind.     

Geochemistry and geochronology of the Neoproterozoic Pan-African Transcaucasian Massif (Republic of Georgia) and implications for island arc evolution of the late Precambrian Arabian–Nubian Shield

The Transcaucasian Massif (TCM) in the Republic of Georgia includes Neoproterozoic–Early Cambrian ophiolites and magmatic arc assemblages that are reminiscent of the coeval island arc terranes in the Arabian–Nubian Shield (ANS) and provides essential evidence for Pan-African crustal evolution in Western Gondwana. The metabasite–plagiogneiss–migmatite association in the Oldest Basement Unit (OBU) of TCM represents a Neoproterozoic oceanic lithosphere intruded by gabbro–diorite–quartz diorite plutons of the Gray Granite Basement Complex (GGBC) that constitute the plutonic foundation of an island arc terrane. The Tectonic Mélange Zone (TMZ) within the Middle-Late Carboniferous Microcline Granite Basement Complex includes thrust sheets composed of various lithologies derived from this arc-ophiolite assemblage. The serpentinized peridotites in the OBU and the TMZ have geochemical features and primary spinel composition (0.35) typical of mid-ocean ridge (MOR)-type, cpx-bearing spinel harzburgites. The metabasic rocks from these two tectonic units are characterized by low-K, moderate-to high-Ti, olivine-hypersthene-normative, tholeiitic basalts representing N-MORB to transitional to E-MORB series. The analyzed peridotites and volcanic rocks display a typical melt-residua genetic relationship of MOR-type oceanic lithosphere. The whole-rock Sm–Nd isotopic data from these metabasic rocks define a regression line corresponding to a maximum age limit of 804 ± 100 Ma and εNd_int = 7.37 ± 0.55. Mafic to intermediate plutonic rocks of GGBC show tholeiitic to calc-alkaline evolutionary trends with LILE and LREE enrichment patterns, Y and HREE depletion, and moderately negative anomalies of Ta, Nb, and Ti, characteristic of suprasubduction zone originated magmas. U–Pb zircon dates, Rb–Sr whole-rock isochron, and Sm–Nd mineral isochron ages of these plutonic rocks range between  750 Ma and 540 Ma, constraining the timing of island arc construction as the Neoproterozoic–Early Cambrian. The Nd and Sr isotopic ratios and the model and emplacement ages of massive quartz diorites in GGBC suggest that pre-Pan African continental crust was involved in the evolution of the island arc terrane. This in turn indicates that the ANS may not be made entirely of juvenile continental crust of Neoproterozoic age. Following its separation from ANS in the Early Paleozoic, TCM underwent a period of extensive crustal growth during 330–280 Ma through the emplacement of microcline granite plutons as part of a magmatic arc system above a Paleo-Tethyan subduction zone dipping beneath the southern margin of Eurasia. TCM and other peri-Gondwanan terranes exposed in a series of basement culminations within the Alpine orogenic belt provide essential information on the Pan-African history of Gondwana and the rift-drift stages of the tectonic evolution of Paleo-Tethys as a back-arc basin between Gondwana and Eurasia.     

Geochronological framework of the Quadrilátero Ferrífero, with emphasis on the age of gold mineralization hosted in Archean greenstone belts

Archean terrains of the Quadrilátero Ferrífero comprise a greenstone belt association surrounded by granitoid–gneiss complexes, mainly composed of banded TTG gneisses whose igneous protoliths are older than 2900 Ma. This early continental crust was affected by three granitic magmatic episodes during the Neoarchean: ca. 2780 to 2760 Ma; 2720 to 2700 Ma; and 2600 Ma. Dating of felsic volcanic and volcaniclastic rocks defines a felsic magmatic event within the greenstone belt association around 2772 Ma, contemporaneous with emplacement of several of the granitic plutons and constrains a major magmatic and tectonic event in the Quadrilátero Ferrífero. Lead isotopic studies of lode–gold deposits indicate that the main mineralization episode occurred at about 2800 to 2700 Ma.Proterozoic evolution of the Quadrilátero Ferrífero comprises deposition of a continental-margin succession hosting thick, Lake Superior-type banded iron formations, at ca. 2500 to 2400 Ma, followed by deposition of syn-orogenic successions after 2120 Ma. The latter is related to the Transamazonian Orogeny. The western part of the Quadrilátero Ferrífero was also affected by the Brasiliano Orogeny (600 to 560 Ma).     

Fault–valve action and vein development during strike–slip faulting: An example from the Ribeira Shear Zone, Southeastern Brazil

Fluid inclusion microthermometry and structural data are presented for quartz vein systems of a major dextral transcurrent shear zone of Neoproterozoic–Cambrian age in the Ribeira River Valley area, southeastern Brazil. Geometric and microstructural constraints indicate that foliation–parallel and extensional veins were formed during dextral strike–slip faulting. Both vein systems are formed essentially by quartz and lesser contents of sulfides and carbonates, and were crystallized in the presence of CO₂–CH₄ and H₂O–CO₂–CH₄–NaCl immiscible fluids following unmixing from a homogeneous parental fluid. Contrasting fluid entrapment conditions indicate that the two vein systems were formed in different structural levels. Foliation–parallel veins were precipitated beneath the seismogenic zone under pressure fluctuating from moderately sublithostatic to moderately subhydrostatic values (319–397 °C and 47–215 MPa), which is compatible with predicted fluid pressure cycle curves derived from fault–valve action. Growth of extensional veins occurred in shallower structural levels, under pressure fluctuating from near hydrostatic to moderately subhydrostatic values (207–218 °C and 18–74 MPa), which indicate that precipitation occurred within the near surface hydrostatically pressured seismogenic zone. Fluid immiscibility and precipitation of quartz in foliation–parallel veins resulted from fluid pressure drop immediately after earthquake rupture. Fluid immiscibility following a local pressure drop during extensional veining occurred in pre-seismic stages in response to the development of fracture porosity in the dilatant zone. Late stages of fluid circulation within the fault zone are represented dominantly by low to high salinity (0.2 to 44 wt.% equivalent NaCl) H₂O–NaCl–CaCl₂ fluid inclusions trapped in healed fractures mainly in foliation–parallel veins, which also exhibit subordinate H₂O–NaCl–CaCl₂, CO₂–(CH₄) and H₂O–CO₂–(CH₄)–NaCl fluid inclusions trapped under subsolvus conditions in single healed microcracks. Recurrent circulation of aqueous–carbonic fluids and aqueous fluids of highly contrasting salinities during veining and post-veining stages suggests that fluids of different reservoirs were pumped to the ruptured fault zone during faulting episodes. A fluid evolution trending toward CH₄ depletion for CO₂–CH₄–bearing fluids and salinity depletion and dilution (approximation of the system H₂O–NaCl) for aqueous–saline fluids occurred concomitantly with decrease in temperature and pressure related to fluid entrapment in progressively shallower structural levels reflecting the shear zone exhumation history.     

Trace-element and Sr–Nd isotopic evidence for the origin of the Sardinian fluorite mineralization (Italy)

The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus ⁸⁷Sr/⁸⁶Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial ε_Nd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial ε_Nd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids.     

Rare earth element geochemistry of the Woxi W–Sb–Au deposit, Hunan Province, South China

The Woxi W–Sb–Au deposit in Hunan, South China, is hosted by Proterozoic metasedimentary rocks, a turbiditic sequence of slightly metamorphosed (greenschist facies), gray-green and purplish red graywacke, siltstone, sandy slate, and slate. The mineralization occurs predominantly (> 70%) as stratabound/stratiform ore layers and subordinately as stringer stockworks. The former consists of rhythmically interbedded, banded to finely laminated stibnite, scheelite, quartz, pyrite and silty clays, whereas the latter occurs immediately beneath the stratabound ore layers and is characterized by numerous quartz + pyrite + gold + scheelite stringer veins or veinlets that are typically either subparallel or subvertical to the overlying stratabound ore layers. The deposit has been the subject of continued debate in regard to its genesis. Rare earth element geochemistry is used here to support a sedimentary exhalative (sedex) origin for the Woxi deposit. The REE signatures of the metasedimentary rocks and associated ores from the Woxi W–Sb–Au deposit remained unchanged during post-depositional processes and were mainly controlled by their provenance. The original ore-forming hydrothermal fluids, as demonstrated by fluid inclusions in quartz from the banded ores, are characterized by variable total REE concentrations (3.5 to 136 ppm), marked LREE enrichment (La_N/Yb_N = 28–248, ∑LREE/∑HREE = 16 to 34) and no significant Eu-anomalies (Eu/Eu = 0.83 to 1.18). They were most probably derived from evolved seawater that circulated in the clastic sediment pile and subsequently erupted on the seafloor. The bulk banded ores are enriched in HREE (La_N/Yb_N = 4.6–11.4, ∑LREE/∑HREE = 3 to 14) and slightly depleted in Eu (Eu/Eu = 0.63 to 1.14) relative to their parent fluids. This is interpreted as indicating the influence of seawater rather than a crystallographic control on REE content of the ores. Within a single ore layer, the degree of HREE enrichment tends to increase upward while the total REE concentrations decrease, reflecting greater influence and dilution of seawater. There is a broad similarity in chondrite-normalized REE patterns and the amount of REE fractionation of the banded ores in this study and exhalites from other sedex-type polymetallic ore deposits, suggesting a similar genesis for these deposits. This conclusion is in agreement with geologic evidence supporting a syngenetic (sedex) model for the Woxi deposit.     

Partitioning of rare earth elements, yttrium, and some major elements among source rocks, liquid and vapor of Larderello-Travale geothermal field, Tuscany (Central Italy)

Rare earth elements (REE), yttrium and some major element concentrations have been measured in the high-enthalpy fluids (HEF) of several geothermal wells and the fluid′s source rocks in the Larderello-Travale area (Tuscany/Central Italy). The REE and Y abundances in the HEF range from 0.1 to about 10 pmol/kg and are slightly higher in the HEF originating from evaporite/carbonate sequences (Calcare Cavernoso) than in those from phyllites. The resulting REY distribution factors between HEF and source rocks, ^appKdsource-rockHEF defined as the ratios of REY/Ca in both phases, range from <0.01 to 0.03 and 0.03 to 0.1 for phyllites and evaporite-limestone sequences (Calcare Cavernoso), respectively. REE+Y are more retained by the source rocks than Ca. HEF show no inherited and, with exception of a small Y anomaly, no acquired anomalies. This indicates a static equilibrium between HEF and the source rocks. The absence of any Eu anomalies points to temperatures less than 250°C in the source region. The small negative Y anomalies are the result of Y depletion in the rock fractions taking part in the water-rock interaction.Due to depressurization of the HEF to about 120°C and 2 bars, a liquid and a vapor phase is produced, which were sampled for the determination of the REE+Y partitioning between the two phases. The apparent partition factors between vapor and liquid ^appDliquidvapor of REE+Y range between 0.05 to 0.2 and about 3 for HEF originating from the phyllites and evaporites/carbonates, respectively. Among all ionic species determined, only NH₄⁺ has an apparent partition factor ^appDliquidvapor above one. In general, REY partition more easily into the vapor phase than the earth alkaline and alkaline elements. No significant correlation of REE+Y in the vapor phase with any of the determined ionic species could be detected. This probably points to the dominant presence of ion pairing such as REY(OH)₃^o or REYO(OH)^o.     

High salinity fluid inclusions in the Yinshan polymetallic deposit from the Le–De metallogenic belt in Jiangxi Province, China: Their origin and implications for ore genesis

A fluid inclusion investigation of the polymetallic mineralization at Yinshan from the Le–De metallogenic belt in Jiangxi Province of China has been carried out using petrographic and microthermometric techniques. The data obtained here indicate that three major types of fluids were involved during the formation of the deposit. They are type I vapor-rich, type II liquid-rich and type III halite-bearing inclusions within the H₂O–NaCl system. The high salinity fluids represented by type III inclusions, being unusual to the distal part of an intrusion-centered ore-forming system such as Yinshan, have been interpreted as the product of direct exsolution of a crystallizing magma, rather than a result of fluid immiscibility from a low salinity fluid. Evidence used to support such an interpretation includes the mode of homogenization of type III inclusions exclusively via halite dissolution, spatial separation of type I and type III inclusions on microscopic scale, the consistent phase ratios within the inclusions concerned, and considerable deviation in homogenization temperature for both type I and type III inclusions. Trapping conditions for type I inclusions were estimated to be around 440 °C and 260 bars, while type III inclusions were constrained to be trapped at least above 900 bars and > 500 °C. The formation temperatures for type II inclusions range from 270 to 390 °C if a lithostatic pressure of 260 bars is assumed. Pressure fluctuation determined by this fluid inclusion study coupled with decreases in salinity and temperature as result of the potential fluid mixing are supposed to have played an important role in triggering the precipitation of ore minerals from the hydrothermal solution.     

Tracing element sources of hydrothermal mineral deposits: REE and Y distribution and Sr-Nd-Pb isotopes in fluorite from MVT deposits in the Pennine Orefield,England

Fluorite from Mississippi Valley Type (MVT) deposits in the South Pennine Orefield, England, displays significantly different distributions of rare earths and yttrium (REY) compared to fluorite from similar MVT deposits in the North Pennine Orefield. Samples from the South Pennine Orefield display negative Ce and positive Gd and Y anomalies but lack any Eu anomaly, indicating that the REY were mobilized from relatively pure marine sedimentary carbonates. In marked contrast, fluorite from the North Pennine Orefield lacks any Ce and Gd anomalies but shows a pronounced positive Eu anomaly, suggesting that the REY were provided by different source rock(s), that the mineralizing hydrothermal fluid had experienced higher temperatures prior to fluorite precipitation, and that it was derived from deeper crustal levels in the north compared to the south. The isotopic composition of Sr in Blue John fluorite from the South Pennine Orefield suggests that Sr was mobilized from Lower Carboniferous (Tournaisian) limestones, whereas Pb isotopes suggest that in contrast to REY and Sr, Pb was derived from aluminosilicate rocks. Neither Nd nor Sr or Pb isotopes can be used to radiometrically date the formation of Blue John fluorite. All isotope systems studied indicate that the limestone host rock of this fluorite mineralization did not contribute to the trace element budget of the hydrothermal fluid. Our results show that different solutes in a natural water (hydrothermal fluid, groundwater, etc.) may be derived from different sources, and that the study of a small set of elements or isotope ratios may not provide full insight into the genesis or history of a mineralization or a hydrothermal fluid. Our data provide evidence for the uncoupling of Sr, Nd and Pb during fluid-rock interaction and fluid migration, and show that the use of plots such as ⁸⁷Sr/⁸⁶Sr vs. _Nd. to learn about mixing relationships (as is commonly done in igneous geochemistry) is unreliable when applied to natural waters and their precipitates.Editorial handling: B. Lehmann     

Alkaline-ultrabasic mantle-derived magmas, their sources, and crystallization features: Data of melt inclusion studies

To find out the reasons responsible for the diversity of igneous rocks forming the alkaline-ultrabasic carbonatite Krestovskiy massif (the Maimecha–Kotui province, Russia) we have studied melt inclusions in clinopyroxene of trachydolerites, porphyric melanephelinites, and tholeiites. It was established that the homogenization temperatures of inclusions in these rocks are rather close: 1140–1180 °C, 1190–1230 °C, and 1150–1210 °C, respectively. Compositions of melt inclusions in clinopyroxenes from different rocks are significantly different. The chemical composition of clinopyroxene of trachydolerites corresponds to that of trachybasalts and their derivatives. The inclusions are enriched in Sr, Ba, P, and S and their total sum of alkalies (at K ≥ Na) is never less than 5–6 wt.%. Inclusions from the rims of clinopyroxene phenocrysts in porphyric melanephelinites are similar in composition also to inclusions in trachydolerites. But in the cores of clinopyroxene phenocrysts the composition of inclusions corresponds to nephelinite melt. The composition of some melt inclusions in the intermediate and cores zones of clinopyroxene from porphyric melanephelinite has high SiO₂ (53–55 wt.%), MgO (8–9 wt.%) and a low (1–2 wt.%) total sum of alkalies (at Na ≥ K) and is depleted in Al₂O₃ (6–7 wt.%), which is similar to the composition of basaltic komatiites. The composition of inclusions in tholeiites is also basic, highly magnesian, and low-alkaline, Sr and Ba are rare to absent. Compared to the inclusions of basaltic komatiite composition, the inclusions in tholeiites are enriched in Al and depleted in Ca, Ti, and P. The melts trapped in clinopyroxenes from different rocks contain low (0.014–0.018 wt.%) water but they are enriched in F: from 0.37 wt.% in nephelinite melts to 0.1–0.06 wt.% in tholeiite and basaltic komatiite melts. Inclusions in all the rocks under study, host clinopyroxene, and the rocks themselves are significantly enriched in incompatible elements (1–2 orders of magnitude relative to the mantle norm). In tholeiites, the partitioning of these elements is rather uniform, while in trachydolerites and especially in melanephelinites it is contrasting with a drastic depletion in HREE relative to LREE, MREE, and HFSE. A conclusion is made that the Krestovskiy massif was formed by no less than three mantle-derived magmas: melanephelinite, tholeiite and basaltic komatiite. Magmas were generated in different magma sources at different depths with various degrees of enrichment in incompatible elements. These magmas were, most likely, dominated by melanephelinite magma. In intermediate chambers this magma differentiated to form derivative melts of nephelinite, trachydolerite–trachyandesite–trachyte compositions. Komatiite-basalt melts were, most likely, derivatives of primitive meimechite magmas.     

Nature of fluids and regional implications for Lesser Himalayan carbonates and associated mineralization

Fluid inclusion data are presented for the successive stages of limestone, dolomite, magnesite and sulphide-bearing quartz veins in Proterozoic carbonate rocks of the Lesser Himalaya. Subsurface fluids were H₂O–NaCl–KCl ± MgCl₂ ± CaCl₂ and showed successive increase in salinity and temperature. The salinity of the pore fluid during limestone diagenesis was in the range of 7.5–15 eq wt.% NaCl and the magnesite-forming fluids had a salinity of about 9 to 19 eq wt.% NaCl. This progressive rise in salinity is attributed to a more saline fluid in the deeper zones. The inverse relation between homogenization temperatures and final melting temperatures suggests mixing of the fluids during diagenesis, and highly depleted δ¹⁸O values rule out participation of magmatic fluid in the mixing. A late stage carbonic fluid is linked with talc formation. The low temperature of sulphide-forming epigenetic solutions, as obtained from fluid inclusions, is also substantiated by the chemical data from these sulphides. δ³⁴S values in galena infer that magmatic sulphur was probably not involved, and the sulphur of the galena is derived from an isotopically heavy source.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).