Water contents of the Cenozoic lithospheric mantle beneath the western part of the North China Craton: Peridotite xenolith constraints

Nominally anhydrous phases (clinopyroxene (cpx), orthopyroxene (opx), and olivine (ol)) of peridotite xenoliths hosted by the Cenozoic basalts from Beishan (Hebei province), and Fansi (Shanxi province), Western part of the North China Craton (WNCC) have been investigated by Fourier transform infrared spectrometry (FTIR). The H₂O contents (wt.) of cpx, opx and ol are 30–255 ppm, 14–95 ppm and ~ 0 ppm, respectively. Although potential H-loss during xenolith ascent cannot be excluded for olivine, pyroxenes (cpx and opx) largely preserve the H₂O content of their mantle source inferred from (1) the homogenous H₂O content within single pyroxene grains, and (2) equilibrium H₂O partitioning between cpx and opx. Based on mineral modes and assuming a partition coefficient of 10 for H₂O between cpx and ol, the recalculated whole-rock H₂O contents range from 6 to 42 ppm. In combination with previously reported data for other two localities (Hannuoba and Yangyuan from Hebei province), the H₂O contents of cpx, opx and whole-rock of peridotite xenoliths (43 samples) hosted by the WNCC Cenozoic basalts range from 30 to 654 ppm, 14 to 225 ppm, and 6 to 262 ppm respectively. The H₂O contents of the Cenozoic lithospheric mantle represented by peridotite xenoliths fall in a similar range for both WNCC and the eastern part of the NCC (Xia et al., 2010, Journal of Geophysical Research). Clearly, the Cenozoic lithospheric mantle of the NCC is dominated by much lower water content compared to the MORB source (50–250 ppm). The low H₂O content is not caused by oxidation of the mantle domain, and likely results from mantle reheating, possibly due to an upwelling asthenospheric flow during the late Mesozoic–early Cenozoic lithospheric thinning of the NCC. If so, the present NCC lithospheric mantle mostly represents relict ancient lithospheric mantle. Some newly accreted and cooled asthenospheric mantle may exist in localities close to deep fault.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Fluid inclusion and stable isotopic constraints on fluid sources and evolution of the Luojiahe Cu deposit in the southern margin of the North China Craton

The Luojiahe Cu deposit in the Zhongtiaoshan region is located in the southern margin of the North China Craton. The orebodies are hosted in the mafic volcanic-sedimentary sequences of the metamorphosed (greenschist-facies) Neoarchean Songjiashan Group. The Luojiahe Cu mineralization can be divided into the primary volcanogenic massive sulfide (VMS) mineralization stage (Stage I, banded or stockwork ores) and the subsequent metamorphic remobilization stage (Stage II, coarse-vein ores).Three types of quartz selected for fluid inclusion (FI) studies were collected from the Stage I banded (Q1) and stockwork (Q2) ores and Stage II coarse-vein (Q3) ores. Four types of FIs were identified: (1) liquid-rich FIs (L-type), (2) pure vapor and vapor-rich FIs (V-type), (3) daughter mineral-bearing FIs (S-type), and (4) CH₄-H₂O FIs (C-type). Systematical microthermometric and H-O isotopic studies show that the Stage I ore-forming fluids consist predominantly of high salinity evolved seawater (125–220 °C; 23.9–27.9 wt.% NaCl equiv.) and some magmatic-hydrothermal fluids (249–339 °C; 34.5–42.2 wt.% NaCl equiv.). The two fluid end-members are represented by the L-type FIs in Q1 and the S- and V-type FIs in Q2. The temperature- and salinity variation trends of the L-type FIs in Q1 indicate a mixing process between the hot evolved seawater and cold seawater at Stage I. Furthermore, the V- and S-type FI coexistence in Q2 and their microthermometric data suggest that fluid unmixing has occurred in original magmatic fluids at Stage I. In contrast, the Stage II ore-forming fluids consist of CH₄-rich metamorphic fluids (192–350 °C; 10.6–43.2 wt.% NaCl equiv.). Carbon isotopic analysis of the Stage II calcite (− 4.58 to − 10.83‰) and graphite (− 32.01 to − 39.16‰) in the ore-hosting chlorite schist indicates that the metamorphic ore-forming fluids had exchanged carbon isotope with graphite. The generation of CH₄ may have resulted from the interaction between H₂O (released by metamorphic devolatilization) and graphite. The continuous consumption of H₂O in the hydrothermal fluid system may have increased the fluid salinity and triggered fluid unmixing in the CH₄-NaCl-H₂O system. In addition, the VMS metallogenic environment is generally favorable for microbial communities. It is considered that the graphite at Luojiahe may have been derived from sedimentary organic matter formed in seafloor hydrothermal vent systems, as also supported by carbon isotopic data.We propose that at Stage I, the main mineralization may have been resulted from 1) fluid mixing of hot evolved seawater and cold seawater in the near-surface environment; and 2) fluid unmixing caused by the percolation of magmatic fluids into syn-volcanic faults, forming the stockwork ores. At Stage II, the interaction between H₂O and graphite may have resulted in the reduction of ore-forming fluids and Cu precipitation, and fluid unmixing in the CH₄-NaCl-H₂O system may have further promoted the Cu mineralization.     

Heterogeneous distribution of water in the mantle beneath the central Siberian Craton: Implications from the Udachnaya Kimberlite Pipe

The paper presents new petrographic, major element and Fourier transform infrared (FTIR) spectroscopy data and PT-estimates of whole-rock samples and minerals of a collection of 19 relatively fresh peridotite xenoliths from the Udachnaya kimberlite pipe, which were recovered from its deeper levels. The xenoliths are non-deformed (granular), medium-deformed and highly deformed (porphyroclastic, mosaic-porphyroclastic, mylonitic) lherzolites, harzburgite and dunite. The lherzolites yielded equilibration temperatures (T) and pressures (P) ranging from 913 to 1324 °C and from 4.6 to 6.3 GPa, respectively. The non-deformed and medium-deformed peridotites match the 35 mW/m² conductive continental geotherm, whereas the highly deformed varieties match the 45 mW/m² geotherm. The content of water spans 2 ± 1–95 ± 52 ppm in olivine, 1 ± 0.5–61 ± 9 ppm in orthopyroxene, and 7 ± 2–71 ± 30 ppm in clinopyroxene. The amount of water in garnets is negligible. Based on the modal proportions of mineral phases in the xenoliths, the water contents in peridotites were estimated to vary over a wide range from < 1 to 64 ppm. The amount of water in the mantle xenoliths is well correlated with the deformation degree: highly deformed peridotites show highest water contents (64 ppm) and those medium-deformed and non-deformed contain ca. 1 ppm of H₂O. The high water contents in the deformed peridotites could be linked to metasomatism of relatively dry diamondiferous cratonic roots by hydrous and carbonatitic agents (fluids/melts), which may cause hydration and carbonation of peridotite and oxidation and dissolution of diamonds. The heterogeneous distribution of water in the cratonic mantle beneath the Udachnaya pipe is consistent with the models of mantle plume or veined mantle structures proposed based on a trace element study of similar xenolithic suits. Mantle metasomatism beneath the Siberian Craton and its triggered kimberlite magmatism could be induced by mantle enrichment in volatiles (H₂O, CO₂) supplied by numerous subduction zones which surrounded the Siberian continent in Neoproterozoic-Cambrian time.     

Chemical variations of abyssal peridotites in the central Oman ophiolite: Evidence of oceanic mantle heterogeneity

Basal peridotites above the metamorphic sole outcropped around Wadi Sarami in the central Oman ophiolite give us an excellent opportunity to understand the spatial extent of the mantle heterogeneity and to examine peridotites−slab interactions. We recognized two types of basal lherzolites (Types I and II) that change upward to harzburgites. Their pyroxene and spinel compositions display severely variations at small scales over < 0.5 km, and encompass the entire abyssal peridotite trend; clinopyroxenes (Cpxs) show wide ranges of Al₂O₃, Na₂O, Cr₂O₃ and TiO₂ contents. Primary spinels show a large variation of Cr# [= Cr/(Cr + Al)] from 0.04 to 0.53, indicating various degrees of partial melting. Trace-element compositions of peridotites and their pyroxenes also show a large chemical heterogeneity in the base of the Oman mantle section. This heterogeneity mainly resulted from variations of partial-melting degrees due to the change of a mantle thermal regime and a distance from the spreading ridge or the mantle diapir. It was overlapped with subsolidus modification during cooling and fluid metasomatism prior and/or during emplacement. The studied peridotites are enriched in Rb, Cs, Ba, Sr and LREE due to fluid influx during detachment and emplacement stages. Chondrite (CI)-normalized REE patterns for pyroxenes are convex upward with strong LREE depletion due to their residual origin, similar to abyssal peridotites from a normal ridge segment. The Cpxs are enriched in fluid mobile elements (e.g., B, Li, Cs, Pb, Rb) and depleted in HFSE (Ta, Nb, Th, Zr) + LREE, suggesting no effect of melt refertilization. Their HREE contents, combined with spinel compositions, suggest two melting series with 1–5% melting for type II lherzolites, 3– < 10% melting for type I lherzolites and ~ 15% for harzburgites. Hornblendes are enriched in fluid-mobile elements relative to HFSE + U inherited from their precursor Cpx. The clinopyroxenite lens crosscuts the basal lherzolites, forming small-scale (< 5 cm) mineralogical and chemical heterogeneities. It was possibly formed from fractional crystallization of interstitial incremental melt that formed during decompression melting of a normal MORB mantle source. The studied peridotites possibly represent a chemical heterogeneity common to the mantle at an oceanic spreading center.     

Post-collisional ultrapotassic rocks and mantle xenoliths in the Sailipu volcanic field of Lhasa terrane,south Tibet: Petrological and geochemical constraints on mantle source and geodynamic setting

Post-collisional ultrapotassic magmatic rocks (15.2–18.8 Ma), containing mantle xenoliths, are extensively distributed in the Sailipu volcanic field of the Lhasa terrane in south Tibet. They could be subdivided into high-MgO and low-MgO subgroups based on their petrological and geochemical characteristics. The high-MgO subgroup has olivine-I (Fo_87–92), phlogopite and clinopyroxene as phenocryst phases, while the low-MgO subgroup consists mainly of phlogopite, clinopyroxene and olivine-II (Fo_77–89). These ultrapotassic magmatic rocks have high MgO (4.6–14.5 wt%), Ni (145–346 ppm), Cr (289–610 ppm) contents, and display enrichment in light rare earth element (REE) over heavy REE and enriched large ion lithophile elements (LILE) relative to high field strength elements (HFSE) with strongly negative Nb-Ta-Ti anomalies in primitive mantle-normalized trace element diagrams. They have extremely radiogenic (⁸⁷Sr/⁸⁶Sr)_i (0.7167–0.7274) and unradiogenic (¹⁴³Nd/¹⁴⁴Nd)_i (0.5118–0.5120), high (²⁰⁷Pb/²⁰⁴Pb)_i (15.740–15.816) and (²⁰⁸Pb/²⁰⁴Pb)_i (39.661–39.827) at a given (²⁰⁶Pb/²⁰⁴Pb)_i (18.363–18.790) with high δ¹⁸O values (7.3–9.7‰). Strongly linear correlations between depleted mid-ocean ridge basalt-source mantle (DMM) and the Indian continental crust (HHCS) in Sr-Nd-Pb-O isotopic diagrams indicate that the geochemical features could result from reaction between mantle peridotite and enriched components (fluids and melts) released by the eclogitized Indian continental crust (HHCS) in the mantle wedge. The high-MgO (13.7–14.5 wt%) subgroup displays higher (¹⁴³Nd/¹⁴⁴Nd)_i, lower (⁸⁷Sr/⁸⁶Sr)_i and (²⁰⁶Pb/²⁰⁴Pb)_i ratios and lower δ¹⁸O values compared with the low-MgO (4.6–8.8 wt%) subgroup. High Ni (850–4862 ppm) contents of olivine phenocrysts and high whole-rock SiO₂, NiO, low CaO contents indicate that the low-MgO ultrapotassic magmatic rocks are derived from partial melting of olivine-poor mantle pyroxenite. However, lower Ni concentrations of olivine phenocryst and lower whole-rock SiO₂, NiO, higher CaO contents of the high-MgO ultrapotassic rocks may indicate their peridotite mantle source. This could be attributed to different amounts of silicate-rich components added into the mantle sources of the parental magmas in the mantle wedge caused by the northward subduction of the Indian continental lithosphere. The reaction-formed websterite xenoliths, reported for the first time in this study, are made up of anhedral and interlocking clinopyroxene (45–65 vol%) and orthopyroxene (30–50 vol%) with minor phlogopite (< 3 vol%) and quartz (< 2 vol%) and are suggested to be formed by silicate metasomatism of the mantle peridotite. The harzburgites, another major type of mantle xenolith in south Tibet, have a mineral assemblage of olivine (60–75 vol%), orthopyroxene (20–35 vol%), clinopyroxene (< 3 vol%), phlogopite (< 2 vol%) and spinel (< 2 vol%) and may have experienced subduction-related metasomatism. Combined with two types of ultrapotassic magmas, we propose that compositions of mantle wedge beneath south Tibet may gradually evolve from harzburgite through lherzolite to websterite with strong metasomatism of silicate-rich components in their mantle source region. Partial melting of the enriched mantle sources could be triggered by rollback of Indian continental slab during 25–8 Ma in south Tibet.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Phase separation,fluid mixing,and origin of the greisens and potassic episyenite associated with the Água Boa pluton,Pitinga tin province,Amazonian Craton,Brazil

Based on petrographical data, three types of greisen have been characterized at the western border of Água Boa pluton: siderophyllite–topaz–quartz greisen (greisen 1), fluorite–phengite–quartz greisen (greisen 2) and quartz–chlorite–phengite greisen (greisen 3). Episyenites were also identified.Two fluids of independent origin interacted with the same protolith – a hornblende-biotite alkali feldspar granite – and produced both the greisens and potassic episyenite: (1) an acid, low-salinity (4–12 wt.% NaCl eq.), F-rich, relatively hot (400–350 °C) reduced aqueous-carbonic fluid (CH₄–H₂O–NaCl–FeCl₂ ± KCl), which by immiscibility gave rise to fluid IA (aqueous) and IC (carbonic); and (2) a lower salinity (2–4 wt.% NaCl eq.) and temperature (200–150 °C) aqueous fluid (H₂O–NaCl), which was responsible for all dilution processes. Fluid 1 seems to have had a magmatic-hydrothermal origin, while fluid 2 is probably surface-derived (meteoric water?). An alkaline, F-poorer and diluted equivalent of fluid IA was interpreted to have caused the episyenitization of the granite host rock as well as the formation of phengite-rich greisen 3. The continuos interaction of this fluid with the potassic episyenite produced a moderate- to high-salinity (20–24 wt.% NaCl eq.), low-temperature (200–100 °C) fluid (H₂O–NaCl–CaCl₂ ± KCl), leading to the formation of chlorite-rich zone of greisen 3 and late silicification of potassic episyenite.In the greisen 1, decreasing F-activity and increasing oxygen fugacity, as the system cooled down, favored the formation of a topaz-rich inner zone, which grades into a siderophyllite-rich zone outwardly. Greisen 2 was formed under more oxidizing conditions by fluids poorer in F than those trapped in the siderophyllite-rich zone.The oxidation of aqueous-carbonic fluid took place at three distinct stages: (i) below the FMQ buffer; (ii) between the FMQ and NNO buffers; and (iii) above the NNO buffer.The dissolution cavities generated during the episyenitization process increased the permeability of the altered rocks, resulting in an increase of the fluid/rock ratios at the potassic episyenite and greisen 3 sites.All these fluids were trapped under pressure conditions of <1.0 kbar, representing shallow crustal levels and are consistent with those that have been estimated for the Pitinga tin–granites.The oxygen fugacity, F-activity gradients and salinity variations that occurred during the cooling of the hydrothermal system, in addition to differences in permeability, were important factors in the formation of distinct greisens. They not only controlled the fluid compositional changes, but also caused the cassiterite and sulfide precipitation at the greisen sites.     

Water content in minerals of mantle xenoliths from the Udachnaya pipe kimberlites (Yakutia)

Distribution of water among the main rock-forming nominally anhydrous minerals of mantle xenoliths of peridotitic and eclogitic parageneses from the Udachnaya kimberlite pipe, Yakutia, has been studied by IR spectroscopy. The spectra of all minerals exhibit vibrations attributed to hydroxyl structural defects. The content of H₂O (ppm) in minerals of peridotites is as follows: 23–75 in olivine, 52–317 in orthopyroxene, 29–126 in clinopyroxene, and 0–95 in garnet. In eclogites, garnet contains up to 833 ppm H₂O, and clinopyroxene, up to 1898 ppm (~ 0.19 wt.%). The obtained data and the results of previous studies of minerals of mantle xenoliths show wide variations in H₂O contents both within different kimberlite provinces and within the Udachnaya kimberlite pipe. Judging from the volume ratios of mineral phases in the studied xenoliths, the water content varies over narrow ranges of values, 38–126 ppm. At the same time, the water content in the studied eclogite xenoliths is much higher and varies widely, 391–1112 ppm.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Decarbonation of subducting slabs: Insight from petrological–thermomechanical modeling

Subduction of heterogeneous lithologies (sediments and altered basalts) carries a mixture of volatile components (H₂O ± CO₂) into the mantle, which are later mobilized during episodes of devolatilization and flux melting. Several petrologic and thermodynamic studies investigated CO₂ decarbonation to better understand carbon cycling at convergent margins. A paradox arose when investigations showed little to no decarbonation along present day subduction geotherms at subarc depths despite field based observations. Sediment diapirism is invoked as one of several methods for carbon transfer from the subducting slab. We employ high-resolution 2D petrological–thermomechanical modeling to elucidate the role subduction dynamics has with respect to slab decarbonation and the sediment diapirism hypothesis. Our thermodynamic database is modified to account for H₂O–CO₂ binary fluids via the following lithologies: GLOSS average sediments (H₂O: 7.29 wt.% & CO₂: 3.01 wt.%), carbonated altered basalts (H₂O: 2.63 wt.% & CO₂: 2.90 wt.%), and carbonated peridotites (H₂O: 1.98 wt.% & CO₂: 1.50 wt.%). We include a CO₂ solubility P–x[H₂O wt.%] parameterization for sediment melts. We parameterize our model by varying two components: slab age (20, 40, 60, 80 Ma) and convergence velocity (1, 2, 3, 4, 5, 6 cm year^− 1). 59 numerical models were run and show excellent agreement with the original code base. Three geodynamic regimes showed significant decarbonation. 1) Sedimentary diapirism acts as an efficient physical mechanism for CO₂ removal from the slab as it advects into the hotter mantle wedge. 2) If subduction rates are slow, frictional coupling between the subducting and overriding plate occurs. Mafic crust is mechanically incorporated into a section of the lower crust and undergoes decarbonation. 3) During extension and slab rollback, interaction between hot asthenosphere and sediments at shallow depths result in a small window (~ 12.5 Ma) of high integrated CO₂ fluxes (205 kg m^− 3 Ma^− 1).     

Geology,mineralization, and fluid inclusion characteristics of the Lermontovskoe reduced-type tungsten (±Cu,Au, Bi) skarn deposit,Sikhote-Alin,Russia

The Lermontovskoe deposit (∼48 Kt WO₃; average 2.6% WO₃, 0.24% Cu, 0.23 g/t Au) is situated in a W-Sn-Au metallogenic belt that formed in a collisional tectonic environment. This tungsten skarn deposit has a W-Au-As-Bi-Te-Sb signature that suggests an affinity with reduced intrusion-related Au deposits. The deposit is associated with an intrusion that is part of the ilmenite-series, high-K peraluminous granitoid (granodiorite to granite) suite. These rocks formed via mantle magma-induced melting of crustal sources.The deposit comprises reduced-type, pyroxene-dominated prograde and retrograde skarns followed by hydrosilicate (amphibole-chlorite-pyrrhotite-scheelite-quartz) and phyllic (muscovite/sericite-carbonate-albite-quartz-scheelite-sulfide, with abundant apatite) alteration assemblages. Fluid inclusions from the skarn assemblages indicate high-temperature (>500 °C), high-pressure (1400–1500 bars) and high-salinity (53–60 wt% NaCl-equiv.) magmatic-hydrothermal fluids. They were post-dated by high-carbonic, methane-dominate, low-salinity fluid at the hydrosilicate alteration stage. These fluids boiled at 360–380 °C and 1300–1400 bars. The subsequent phyllic alteration started again with a high-temperature (>450 °C), high-pressure (1000–1100 bars) and high-salinity (42–47 wt% NaCl-equiv.) fluid, with further incursion of high-carbonic, methane-dominated, low-salinity fluid that boiled at 390–420 °C and 1150–1200 bars. The latest phyllic alteration included the lower-temperature (340–360 °C), lower pressure (370–400 bars) high-carbonic, methane-dominated (but with higher CO₂ fraction), low-salinity fluid, and then the low-temperature (250–300 °C) H₂O-CO₂-CH₄-NaCl fluid, with both fluids boiled at the deposit level. The high-salinity aqueous fluids are interpreted to have come from crystallizing granitoid magma, whereas the reduced high-carbonic fluids probably came from a deeper mafic magma source. Both of these fluids potentially contributed to the W-Au-As-Bi-Te-Sb metal budget. Decreasing temperatures coupled with high aCa²⁺ and fluid boiling promoted scheelite deposition at all post-skarn hydrothermal stages.The deposit is characterized by limited downdip extent of mineralized zones and abundant coarse-grained muscovite-quartz (+apatite, scheelite) aggregates that formed at the phyllic alteration stage. Together with presence of high-temperature, high-pressure and high-salinity fluids directly exsolving from crystallizing magma, this suggests a root level of the mineralized magmatic-hydrothermal system of reduced W skarn deposits.     

Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

Refertilization of lithospheric mantle beneath the Yangtze craton in south-east China: Evidence from noble gases geochemistry

The Yangtze craton (YC), in eastern China, is one of the oldest cratons in the world and is characterized by a complex tectonic and geodynamic evolution. This evolution regards most of the eastern China craton, which since Mesozoic time has undergone significant thinning (> 200 km) of Archean lithosphere. This thinning favored the refertilization of the old refractory subcontinental lithospheric mantle (SCLM) by the upwelling of younger fertile asthenosphere. Whether this feature is localized only beneath certain areas of eastern China or is a more widespread characteristic of the mantle, including the YC, is a matter of debate.In order to constrain the history of the YC SCLM, we have measured the He- and Ar-isotopic compositions of fluid inclusions hosted in mantle xenoliths in the Lianshan area, which is part of the poorly investigated YC in south-east China. We also report new mineral chemistry and trace element compositions of clinopyroxenes from the same suite of samples, for comparison with noble gases. Two distinct types of xenoliths can be identified: Type 1, characterized by mantle-like He-isotopic (³He/⁴He) ratios (up to 9.1 Ra), represents fragments of a fertile lithospheric mantle; Type 2, showing ³He/⁴He values in the SCLM range (³He/⁴He < 7 Ra), represents shallow relicts of a refractory mantle. The patterns of rare-earth elements as well as the Y and Yb concentrations in the clinopyroxenes normalized to primitive mantle (Y_N and Yb_N, respectively) indicate that fractional partial melting might have affected the local mantle by < 3% in Type 1 and up to 20% in Type 2 xenoliths from Lianshan, respectively. The range of ⁴He/⁴⁰Ar* (⁴⁰Ar* is corrected for atmospheric contamination) ranges from 4.9 × 10^− 4 to 3.6 × 10^− 1, which is below the typical production ratio of the mantle (⁴He/⁴⁰Ar* = 1–5); this range is however compatible with this fractional partial melting. The variable ³He/⁴He and ⁴He/⁴⁰Ar* values in Lianshan xenoliths suggest that the local mantle source was also influenced by kinetic fractionation, possibly triggered by metasomatic melts. Metasomatism associated with carbonatitic melts, together with fluxing by CO₂-rich fluids, have permeated the mantle beneath Lianshan, generating the observed decoupling between noble gases and trace elements. The interpretative framework is also applicable for other mantle xenoliths from eastern China, indicating that the refertilization of the SCLM by ascending mantle-like melts is common also to YC, which can be identified using noble gases.     

Geodynamics of rapid voluminous felsic magmatism through time

Two end member geodynamic settings produce the observed examples of rapid voluminous felsic (rhyolitic) magmatism through time. The first is driven by mantle plume head arrival underneath a continent and has operated in an identifiable and regular manner since at least 2.45 Ga. This style produces high temperature (≤ 1100 °C), low aspect ratio rheoignimbrites and lavas that exhibit high SiO₂/Al₂O₃ ratios, high K₂O/Na₂O ratios, and where available data exists, high Ga/Al₂O₃ ratios (> 1.5) with high F (in thousands of parts per million) and low water content. F concentration is significant as it depolymerizes the silicate melt, influencing the magmas' physical behavior during development and emplacement. These rhyolites are erupted as part of rapidly emplaced (10–15 Myr) mafic LIPs and are formed primarily by efficient assimilation-fractional crystallization processes from a mafic mantle parent. The second is driven by lithospheric extension during continental rifting or back arc evolution and is exclusive to the Phanerozoic. SLIPs (silicic large igneous provinces) develop over periods < 40 Myr and manifest in elongate zones of magmatism that extend up to 2500 km, contrasting with the mafic LIP style. Some of the voluminous felsic magmas within SLIPs appear to have a very similar geochemistry and petrogenesis to that of the rhyolites within mafic LIPs. Other voluminous felsic magmas within SLIPs are sourced from hydrous lower crust, and contrast with those sourced from the mantle. They exhibit lower temperatures (< 900 °C), explosive ignimbrites with lower SiO₂/Al₂O₃ ratios, and lower K₂O/Na₂O ratios. Rapid voluminous felsic magmatism represents both extreme examples of continental growth since the Archean, and also dramatic periods of crustal recycling and maturation during the Phanerozoic.     

Melting phase relations of the Udachnaya-East Group-I kimberlite at 3.0–6.5 GPa: Experimental evidence for alkali-carbonatite composition of primary kimberlite melts and implications for mantle plumes

Experiments on the origin of the Udachnaya-East kimberlite (UEK) have been performed using a Kawai-type multianvil apparatus at 3–6.5 GPa and 900–1500 °C. The studied composition represents exceptionally fresh Group-I kimberlite containing (wt.%): SiO₂ = 25.9, TiO₂ = 1.8, Al₂O₃ = 2.8, FeO = 9.0, MgO = 30.1, CaO = 12.7, Na₂O = 3.4, K₂O = 1.3, P₂O₅ = 1.0, Cl = 0.9, CO₂ = 9.9, and H₂O = 0.5. The super-solidus assemblage consists of melt, olivine (Ol), Ca-rich (26.0–30.2 wt.% CaO) garnet (Gt), Al-spinel (Sp), perovskite (Pv), a CaCO₃ phase (calcite or aragonite), and apatite. The low pressure assemblage (3–4 GPa) also includes clinopyroxene. The apparent solidus was established between 900 and 1000 °C at 6.5 GPa. At 6.5 GPa and 900 °C Na–Ca carbonate with molar ratio of (Na + K)/Ca ≈ 0.44 was observed. The UEK did not achieve complete melting even at 1500 °C and 6.5 GPa, due to excess xenogenic Ol in the starting material. In the studied P–T range, the melt has a Ca-carbonatite composition (Ca# = molar Ca/(Ca + Mg) ratio = 0.62–0.84) with high alkali and Cl contents (7.3–11.4 wt.% Na₂O, 2.8–6.7 wt.% K₂O, 1.6–3.4 wt.% Cl). The K, Na and Cl contents and Ca# decrease with temperature. It is argued that the primary kimberlite melt at depths > 200 km was an essentially carbonatitic (< 5 wt.% SiO₂), but evolved toward a carbonate–silicate composition (up to 15–20 wt.% SiO₂) during ascent. The absence of orthopyroxene among the run products indicates that xenogenic orthopyroxene was preferentially dissolved into the kimberlite melt. The obtained subliquidus phase assemblage (Ol + Sp + Pv + Ca-rich Gt) at P–T conditions of the UEK source region, i.e. where melt was in the last equilibrium with source rock before magma ascent, differs from the Opx-bearing peridotitic mineral assemblage of the UEK source region. This difference can be ascribed to the loss of substantial amounts of CO₂ from the kimberlite magma at shallow depths, as indicated by both petrological and experimental data. Our study implies that alkali-carbonatite melt would be a liquid phase within mantle plumes generated at the core–mantle boundary or shallower levels of the mantle, enhancing the ascent velocity of the plumes. We conclude that the long-term activity of a rising hot mantle plume and associated carbonatite melt (i.e. kimberlite melt) causes thermo-mechanical erosion of the subcontinental lithosphere mantle (SCLM) roots and creates hot and deformed metasomatic regions in the lower parts of the SCLM, which corresponds to depths constrained by P–T estimates of sheared Gt-peridotite xenoliths. The sheared Gt-peridotites undoubtedly represent samples of these regions.     

On the origin of saline fluids in the KTB (Continental Deep Drilling Project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ Ca–Na–Cl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of ³⁶Cl. The Na–Cl–(K-, SO₄) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

Evidence of Mid-ocean ridge and shallow subduction forearc magmatism in the Nagaland-Manipur ophiolites,northeast India: constraints from mineralogy and geochemistry of gabbros and associated mafic dykes

We discuss here the mineralogical and geochemical characteristics of mafic intrusive rocks from the Nagaland-Manipur Ophiolites (NMO) of Indo-Myanmar Orogenic Belt, northeast India to define their mantle source and tectonic environment. Mafic intrusive sequence in the NMO is characterized by hornblende-free (type-I) and hornblende-bearing (type-II) rocks. The type-I is further categorized as mafic dykes (type-Ia) of tholeiitic N-MORB composition, having TiO₂ (0.72–1.93 wt.%) and flat REE patterns (La_N/Yb_N = 0.76–1.51) and as massive gabbros (type-Ib) that show alkaline E-MORB affinity, having moderate to high Ti content (TiO₂ = 1.18 to 1.45 wt.%) with strong LREE-HREE fractionations (La_N/Yb_N = 4.54–7.47). Such geochemical enrichment from N-MORB to E-MORB composition indicates mixing of melts derived from a depleted mantle and a fertile mantle/plume source at the spreading center. On the other hand, type-II mafic intrusives are hornblende bearing gabbros of SSZ-type tholeiitic composition with low Ti content (TiO₂ = 0.54 wt.%–0.86 wt.%) and depleted LREE pattern with respect to HREE (La_N/Yb_N = 0.37–0.49). They also have high Ba/Zr (1.13–2.82), Ba/Nb (45.56–151.66) and Ba/Th (84.58–744.19) and U/Th ratios (0.37–0.67) relative to the primitive mantle, which strongly represents the melt composition generated by partial melting of depleted lithospheric mantle wedge contaminated by hydrous fluids derived from subducting oceanic lithosphere in a forearc setting. Their subduction related origin is also supported by presence of calcium-rich plagioclase (An_16.6–32.3). Geothermometry calculation shows that the hornblende bearing (type-II) mafic rocks crystallized at temperature in range of 565°–625 °C ± 50 (at 10 kbar). Based on these available mineralogical and geochemical evidences, we conclude that mid ocean ridge (MOR) type mafic intrusive rocks from the NMO represent the section of older oceanic crust which was generated during the divergent process of the Indian plate from the Australian plate during Cretaceous period. Conversely, the hornblende-bearing gabbros (type-II) represent the younger oceanic crust which was formed at the forearc region by partial melting of the depleted mantle wedge slightly modified by the hydrous fluids released from the subducting oceanic slab during the initial stage of subduction of Indian plate beneath the Myanmar plate.     

Fluid compositions and P-T conditions of vein-type uranium mineralization in the Beaverlodge uranium district,northern Saskatchewan,Canada

The Beaverlodge district in northern Saskatchewan is known for “vein-type” uranium mineralization. Most of the uranium deposits are spatially related to major structures, and hosted by ca. 3.2–1.9 Ga granitic rocks (and albitite derived from them) and by ca. 2.33 Ga Murmac Bay Group amphibolite, all of which are unconformably overlain locally by deformed but unmetamorphosed redbeds of the ca. 1.82 Ga Martin Group, and by the flat-lying ca. 1.75–1.5 Ga Athabasca Group. The uranium mineralization is mainly hosted in fault rocks (breccias) and carbonate ± quartz ± albite veins, referred to as breccia-style and vein-style mineralization, respectively, with the latter being the focus of this study. Most of the mineralized veins occur in the basement rocks, although some crosscut the Martin Group. This study examines the field, petrographic, fluid inclusion and C-O isotope characteristics of mineralized and non-mineralized veins from 19 deposits/occurrences as well as from the Martin Group, with an aim to better understand the mineralizing environment and processes.The coexistence of liquid-dominated (L + V), vapour-dominated (V + L) and vapour-only (V) fluid inclusions within individual fluid inclusion assemblages (FIAs) in the veins suggests fluid immiscibility and heterogeneous trapping. The L + V inclusions with the lowest homogenization temperatures (T_h) within individual FIAs are interpreted to represent homogeneous trapping of the liquid phase, which yield T_h values from 78° to 330 °C (mainly 100° to 250 °C), and salinities from 0.2 to 30.8 wt.% NaCl equivalent. Mass spectrometric analysis of bulk fluid inclusions shows that the volatiles are dominated by H₂O (average 97.2 mol%), with minor amounts of CO₂, CH₄, H₂, O₂, N₂, Ar and He. Fluid pressures were estimated to be < 200 bars based on the inference of fluid immiscibility, fluid temperatures of 100° to 250 °C, and low concentrations of non-aqueous volatiles (< 3 mol%). The δ¹⁸O_VPDB and δ¹³C_VPDB of carbonate minerals associated with mineralization range from − 20.5 to − 8.9‰ and − 10.1 to − 0.9‰, respectively. The δ¹⁸O_VSMOW values of the parent fluids calculated using the T_h values range from − 9.6 to + 17.0‰, with the majority from 0 to + 5.0‰. O isotopes of paired equilibrium quartz and calcite, analyzed by secondary ion mass spectrometry (SIMS), yield temperatures from 161° to 248 °C, which are consistent with the fluid inclusion data.The new fluid inclusion and stable isotope data are inconsistent with a metamorphic or magmatic-hydrothermal model as proposed in some previous studies (for breccia-style and vein-style mineralization), but rather support a model in which the vein-type uranium mineralization took place at relatively low temperature (100° to 250 °C) and shallow (< 2 km) conditions, with fluid pressure fluctuating between hydrostatic and sub-hydrostatic regimes, possibly related to episodic faulting. The mineralizing fluids were mainly sourced from the Martin Lake Basin, and uraninite was precipitated as a result of mixing between this basin-derived fluid and fluids carrying reducing agents (Fe^2 +, CH₄) derived from the basement, although fluid-rock reactions and fluid immiscibility may have also played a role.     

Cenozoic high-K alkaline magmatism and associated Cu–Mo–Au mineralization in the Jinping–Fan Si Pan region,southeastern Ailao Shan–Red River shear zone,southwestern China–northwestern Vietnam

The Jinping–Fan Si Pan (JFP) Cenozoic magmatic and Cu–Mo–Au metallogenic belt in the southeastern part of the Ailao Shan shear zone host the Tongchang, Chang′an, Habo, and Chinh Sang Cu–Mo–Au deposits. These deposits form an integrated epithermal-porphyry regional mineralization system associated with 40–32 Ma high-K alkaline magmatism. The magmatic rocks in the belt have relatively low TiO₂ (<0.73 wt%), P₂O₅ (<0.29 wt%), and FeO^* (<4.99 wt%), and high Na₂O (2.86–4.75 wt%) and K₂O (4.01–7.98 wt%). They also have high contents of incompatible trace elements, and are enriched in LILE (Rb, Ba, K, Sr) and LREE. They have marked Nb, Ta, Ti and P depletion in primitive mantle-normalized spidergrams, and plot close to the EMII mantle field in the Sr–Nd isotopic diagram. These characteristics are similar to those of the Eocene high-K alkaline rocks along the northern Ailao Shan belt, eastern Tibet plateau. The sulfur and lead isotope analyses of sulfide minerals from both the ores and related magmatic rocks confirm the involvement of a magmatic ore fluid. The Cenozoic alkaline intrusions and Cu–Mo–Au mineralization in the JFP were formed prior to the initiation of left-lateral shearing along the Ailao Shan shear zone. The magmas appear to have been derived from enriched mantle, possibly with mixing of materials from the buried Tethyan oceanic lithosphere, and/or crust.