Hydrothermal Stage Research Articles

Hyper-enrichment of heavy rare earth elements in highly evolved granites through multiple hydrothermal mobilizations

Abstract Highly evolved granites can be important hosts of rare earth element (REE) resources, and more importantly, they commonly serve as the protolith for regolith-hosted REE deposits to form during weathering. Highly evolved granites in the Zudong pluton, South China, are extremely rich in the heavy (H)REE (up to 8000 ppm total HREE), and display significant REE fractionation. Moreover, the HREE enrichment is positively correlated with the degree of REE fractionation, indicating a unique process in preferentially enriching the HREE during the evolution of the granites. Multiple stages of hydrothermal re-mobilization of the REE can account for the HREE mineralization, and these are recorded in the texture and composition of the zircon. In these processes, fluctuations in the F activity of the fluid caused alternating dissolution-reprecipitation and continuous growth of the zircon. REE were repeatedly mobilized and enriched in the fluid to precipitate the major HREE mineral synchysite-(Y), and partially incorporated into the growth zone of zircon, while other elements were largely lost to the fluid during the extensive dissolution of the rock-forming minerals. LREE were also likely substantially mobilized in the late hydrothermal stage and lost through complexation with Cl, causing the significant LREE depletion and, thus REE fractionation. This process continuously enriched host granites in the HREE to a potentially economic grade, making them favorable protoliths for subsequent supergene regolith-hosted HREE deposits.

Petrology, mineral chemistry and geochemistry of chloritite associated with Neoproterozoic ophiolitic ultramaficsin the Eastern Desert of Egypt, Arabian-Nubian Shield

This study presents for the first time, the field observations, petrography, mineral chemistry and geochemistry of chloritite hosted in the Al-Barramiya Neoproterozoic ophiolite of the Eastern Desert of Egypt, Arabian-Nubian Shield (ANS). The Al-Barramiya ophiolite is one of the most important ophiolitic sequences exposed in the ANS. It is affected by different types of alterations including carbonatization, listvenitization, chloritization and rodingitization. The Al-Barramiya chloritite occurs as thin layers associated with highly serpentinized peridotite. It is a fine-grained rock entirely composed of chlorite (85–95 vol.%) with minor talc and accessory minerals (epidote, rutile, titanite, corundum and opaque minerals). The chlorite minerals in the chloritite are represented mainly by diabantite, while those in the serpentinites include ripidolite. Depending on the chemical composition of the chlorites, the chlorite in chloritite formed at temperatures ranging between 200 and 250°C, which are lower than those of the disseminated chlorite in the serpentinite (310–345oC), indicating their formation in different hydrothermal stages. The chloritite samples are rich in total REE contents (17.9–27.3 ppm) compared with the associated serpentinites (0.69–0.87 ppm). They are characterized by slightly depleted LREE relative to HREE [(La/Lu)n = 0.8–0.9], with a moderately negative Eu-anomaly [(Eu/Eu*)n = 0.4–0.5]. The negative Eu-anomalies are derived from chloritization fluids or reflect the presence of talc in the chloritite. Based on field work, petrography, mineralogical and geochemical data, the studied chloritite has been interpreted as being derived from the associated serpentinized ultramafics by hydrothermal alterations. This is supported by an enrichment of chloritite in compatible trace elements (Cr = 2031–2534 ppm, Ni = 1264–1988 ppm, Co = 76–101 ppm) similar to that which is observed in the associate serpentinite.

Fluid overprints and mineralization of the Zhuguangshan granite-related U district in China: Recorded by cathodoluminescence textures and chemistry of quartz

Most high-grade U ores are mined from quartz veins hosted in granites. The veins formed at shallow depths during episodic hydrothermal activity, however, the evolution of multiple stage fluids is not well constrained. In this study, we collected 56 quartz samples from the world-class, granite-related, Zhuguangshan U district (>17,000 t U from seven deposits) in southern China. Their textures and compositions were analyzed using scanning electron microscope cathodoluminescence (SEM-CL, n = 98) and laser ablation-induction coupled plasma-mass spectrometry (LA–ICP–MS, n = 643). Four types of quartz were identified, including magmatic quartz, early hydrothermal euhedral quartz, ore stage hydrothermal quartz (U-rich), and late hydrothermal quartz. New quartz textures and chemical compositions show that the transition of early hydrothermal quartz from the magmatic to hydrothermal stages is discontinuous, unlike the continuous trend observed in most magmatic-hydrothermal systems. Ore stage quartz is CL dark (with a peak at 650 nm), occurs as rims on early barren quartz, and has high contents of Mn, Al, and Sb. Altered textures of magmatic quartz developed through fluid-rock reactions at low temperatures, while rimmed textures of hydrothermal quartz formed during subsequent late-stage U-bearing fluid events, which played a crucial role in U mineralization. Quartz in the Zhuguangshan U district has distinct features compared to other magmatic-hydrothermal systems that can guide exploration for high-grade ore in this, and perhaps other, granite-related U systems.

Titanite from the NYF-type pegmatites of Szklarska Poręba Huta quarry, Karkonosze granite massif, SW Poland

Titanite, an accessory mineral of pegmatite related to aplogranite, was identified in the Szklarska Poręba Huta quarry within the Karkonosze granite massif in Lower Silesia, Poland. It formed during pegmatitic to hydrothermal stages. Besides the isovalent substitution Sn → Ti, the chemical composition of the mineral is characterized by three coupled substitutions: (1) (Al, Fe, Sc)3+ + (OH, F)- → YTi + ZO, (2) XREE3+ + Y(Al, Fe, Sc)3+ →X)Ca2+ + YTi4+, and (3) (Al, Fe, Sc)3+ + (Nb, Ta)5+ → 2YTi. These substitutions are strongly dependent on the composition of the magma in terms of its Al2O3/TiO2 activity ratio, with the first one also influenced by the H2O/HF fugacity ratio. Fluorine, which induced the most common substitution (1), had its source in high-temperature F-bearing fluids released from rocks of the metamorphic envelope adjacent to the intruding granite. These fluids mobilized and transported various rock components (Sc, REE, Nb, Ta, etc.) among others in the form of fluoride complexes, enriching the aplogranite magma with some metallic elements. The substitution of Sn for Ti developed with decreasing temperature to the extent that in thin ore-mineralized quartz veins cutting aplogranite, titanite reaches Sn-bearing compositions up to the prevalence of Sn corresponding to malayaite.

­Two-Stage Hydrothermal Synthesis of TiO<sub>2</sub> Nanotubes with Variations of TiO<sub>2</sub>/NaOH Molar Ratio

TiO2 nanomaterial is a semiconductor material that exhibits promising photocatalysis activity. TiO2 nanomaterials can be converted into several forms, including TiO2 nanotubes, which have a larger surface area and more applications. In this study, TiO2 nanotubes were synthesized hydrothermally using TiO2 micro powder precursors. The synthesis involved two hydrothermal stages: the first to synthesize TiO2 nanoparticles from TiO2 micro powder precursors, and the second to synthesize TiO2 nanotubes from TiO2 nanoparticle precursors. TiO2 micro powder was added to the synthesis of TiO2 nanoparticles by hydrothermal at mole ratios of TiO2/NaOH of 0.01, 0.025, and 0.04, respectively. The TiO2 nanoparticles obtained exhibit a morphology in the form of short fibers, with particle sizes increasing as the mole ratios are added. Furthermore, they possess an anatase crystal structure at all mole ratios of TiO2/NaOH. Subsequently, the TiO2 nanoparticles are calcined at 450°C. The results of the TiO2 nanoparticle calcination show that the morphology is in the form of short fibers, which are smaller than those of the uncalcinated sample. The calcinated sample also has larger particle sizes and an anatase crystal structure, compared to the uncalcinated sample. The TiO2 nanotubes obtained exhibit an elongated tube morphology with outer diameters ranging from 3.93 to 11.44 nm, inner diameters ranging from 2.5 to 4.25 nm, and a wall thickness of 1.09 to 3.4 nm. The surface area of the TiO2 nanotubes is 256.744 m2/g.

The gold content of mafic to felsic potassic magmas

Many epithermal gold and gold-rich porphyry-type ore deposits are associated with potassic magmas. Hence, potassic magmas are commonly assumed to have been unusually Au-rich or to have contained high Au/Cu ratios. However, these hypotheses remain poorly tested. Here, we report Au concentrations and Au/Cu ratios in silicate melt inclusions analyzed in potassic rocks worldwide. The results suggest that mafic potassic magmas generally contain only 2‒7 ng/g Au, despite common sulfide exhaustion during partial mantle melting. Both the absolute Au concentrations and Au/Cu ratios are comparable to those of mafic calc-alkaline magmas, and they vary little during subsequent magma differentiation because magmatic sulfide precipitation is strongly dominated by monosulfide solid solution that is relatively poor in Au and Cu. We thus suggest that the close association of Au-rich deposits with potassic magmas is not due to Au enrichment in the magma, but rather due to selective Au precipitation at the hydrothermal stage.

Genesis of LCT Pegmatites during Early Paleozoic Orogeny of the North Qinling Orogenic Belt, China: Emplacement Conditions and Structural Control

AbstractThe Guanpo pegmatite field in the North Qinling orogenic belt (NQB), China, hosts the most abundant LCT pegmatites. However, their emplacement conditions and structural control remain unexplored. In this contribution, we investigated it combining pegmatite orientation measurement with oxygen isotope geothermometry and fluid inclusion study. The orientations of type A1 pegmatites (Pf < σ2) are predominantly influenced by P‐ and T‐fractures due to simple shearing in Shiziping dextral thrust shear zone during D2 deformation, whereas type A2 pegmatites (contemporaneous with D4) are governed by hydraulic fractures aligned with S0 and S0+1 stemming from fluid pressure (Pf < σ2). Additionally, type B pegmatites (Pf ≤ σ2) exhibit orientations shaped by en echelon extensional fractures in local ductile shear zones (contemporaneous with D3). The albite‐quartz oxygen isotope geothermometry and microthermometric analysis of fluid inclusions in elbaites from the latest pegmatites (including types B and A2) suggest that the crystallization P‐T for late magmatic and hydrothermal stages are 527.5–559.2°C, 320°C, 3.1–3.6 kbar and 2.0 kbar, respectively. Our observations along with previous studies suggest that the genesis of the LCT pegmatites was a long‐term, multi‐stage event during early Paleozoic orogeny (including the collision stage) of the NQB, and was facilitated by various local fractures.

Insights into the indium enrichment of the Ashele VMS Cu-Zn deposit, Altay, NW China

Indium (In) is a critical metal used in the photovoltaic and semiconductor industries, which have exhibited extraordinary growth in demand. Indium is produced as a by-product of mining from different ore deposits (e.g., epithermal, sediment-hosted, and skarn). Volcanogenic massive sulfide (VMS) deposits are an important source of In; however, the mechanism of In enrichment is not fully understood. Here, we combine mineralogy with in situ trace element and S-Pb isotope geochemistry to reveal the enrichment of indium in the Ashele VMS Cu-Zn deposit (1.08 Mt. Cu, 0.43 Mt. Zn) located in Altay, NW China. The Ashele deposit is hosted in the metamorphosed Devonian felsic-bimodal volcanic rocks. This deposit consists of seafloor hydrothermal, metamorphic hydrothermal, and supergene stages. The seafloor hydrothermal stage comprises macro-scale Cu-rich bands (chalcopyrite, pyrite, and minor sphalerite) and Zn-rich bands (sphalerite, pyrite, and minor chalcopyrite). Indium is mainly hosted by chalcopyrite (mean 178 ppm) and sphalerite (mean 214 ppm) and occurs in the lattice. Mineral assemblages and trace element geochemistry suggest that the Cu-rich bands were deposited under high temperatures (> 300–350 °C) and sulfur fugacity (−7.2 to −4.9), whereas the Zn-rich bands were formed under lower temperatures (180–220 °C) and sulfur fugacity (−15.7 to −11.5). The interlayered Cu-rich and Zn-rich bands may reflect the oscillating temperature and sulfur fugacity variations. In situ S isotopic compositions of sulfides cluster within two ranges: 1–3 ‰ and 3–6 ‰, suggesting two endmembers: volcanic origin and reduced seawater sulfate. Pb isotopic ratios are similar to those of the host volcanic rocks, indicating that the metals may be derived from the felsic volcanic system. During metamorphism, the indium may be retained, but Cu contents of sphalerite become more homogeneous. Most In-rich VMS deposits worldwide are hosted by the felsic-dominant system in island arc and back-arc settings. These tectonic settings are conducive to the production of felsic volcanic systems, which are more likely to contain In mineralization. This study highlights the enrichment mechanism of indium in VMS deposits and suggests that the South Altay could become an important source of In.

Mesozoic orogenic gold metallogenesis at the Bangong–Nujiang suture belt, central Tibet: Constraints from pyrite textures, composition and sulfur isotope of the Shangxu gold deposit

Pyrite is a good carrier to provide gold within a hydrothermal mineralization system. Under prograde metamorphism, recrystallization of sedimentary and diagenetic pyrite and transformation of pyrite into pyrrhotite in a metamorphic terrane lead to the release of trace elements from the pyrite carrier into an upward migrating liquid phase carrier. In this case study, we report the in situ trace element and δ34S compositions of the pyrite from four different stages, which chronologically comprise sedimentary Py1, diagenetic Py2, metamorphic Py3a, Py3b and hydrothermal Py4a, Py4b, Py5, and the dominant sulfides from the hydrothermal stage at Shangxu, an Early Cretaceous turbidite-hosted orogenic gold deposit in the middle Bangong–Nujiang suture belt (BNSB) in central Tibet, in order to decipher the ore-forming material source and the metallogenesis of the Mesozoic orogenic gold mineralization in the BNSB. Concentrations of trace elements, i.e., Au, Co, Cu, Zn, Mo, Ag, Sb, Te, Hg, Tl, Pb and Bi, that are easy to dissolve during pyrite recrystallization, show a general progressive decline from Py1 to Py4b (excepting in Py3b and Py4a, which have a sudden rise in trace element composition) and a plunge in Py5, indicating that Py1 and Py2 supply the parent source minerals for mineralization, and that the main ore-forming stage are contemporary with the deposition of Py3b and Py4a, ending up with the precipitation of Py5. The δ34S values of pyrite narrow from −46.7 ‰–19.3 ‰ (Py1, Py2), through −7.6 ‰–0.2 ‰ (Py3a, Py3b), to − 3.6 ‰–5.7 ‰ (Py4a, Py4b) and −7.7 ‰–5.6 ‰ (Cp, Gn), indicating that a probable coeval seawater sulfate sulfur source for Py1 and Py2 (by bacterial sulfate reduction), and an inherited sulfur source from Py1 and Py2 for Py3 and Py4. We highlight that contributions from the magmatic materials to the hydrothermal gold mineralization are limited at Shangxu, and the widely distributed Lower–Middle Jurassic pyrite-rich turbidite of the Mugagangri Group is a highly potential primary source rock for the regional gold mineralization.

REE-phosphate mineralization stages and conditions of monazite formation in the ore veins in the northern part of Ditrău Alkaline Massif (Eastern Carpathians, Romania)

In terms of rare earth potential, the Ditrău Alkaline Massif (Romania) is one of the most prospective formations in Europe. The REE mineralization occurs as mineralized ore veins and is most prominent in the northern (Jolotca) and eastern (Belcina) parts of the Massif. The ore veins of Jolotca area outcrop over a larger area than the Belcina ones, and are predominantly rich in LREE minerals. The most important REE minerals in the Jolotca veins are phosphates, of which monazite (Mnz) (group) is by far the most abundant, while xenotime (Xtm) occur only sporadically. The monazite-xenotime mineral assemblages are the products of at least three successive mineralization stages: (1) Mnz1 followed by Xtm1 (the vast majority of REE phosphates formed in this stage); (2) Mnz2 + Xtm2 (as inclusions in apatite) and Mnz3 + Xtm3 (as interstitial phases), the two assemblages are texturally distinct but their synchronous formation is likely; (3) Mnz4 scattered in magnetite veins (no xenotime formed in this stage). The chemical composition of the phases formed in each stage supports their hydrothermal origin. The alteration characteristics, reaction patterns and internal textural features of the monazite-xenotime assemblages reflect the metasomatizing effect of each hydrothermal stage. Three fluid types with different compositions were identified in the earliest Mnz1 phase: An H2O-NaCl-CO2 type (2–4 mol% CO2, 10–22 wt% NaCleq., Th: 225–350 °C), an H2O-NaCl type (10–22 wt% NaCleq., Th: 160–330 °C) and an H2O-NaCl-CaCl2 type (23–25 wt% NaCleq., Th: 150–250 °C). Combining Y-in monazite thermometry data with isochores of primary originated fluid inclusions indicate <500 MPa pressures and 200–420 °C temperature conditions for formation of Mnz1. The observed REE patterns of monazites were most probably resulted by a temperature derived fractionation of REEs carried as carbonate complexes in hydrothermal fluids by the effect of successive metasomatic flushing.

Mineralogy and Geochemistry of Jasperoid Veins in Neoproterozoic Metavolcanics: Evidence of Silicification, Pyritization and Hematization

The Wadi Ranga sulfidic jasperoids in the Southern Eastern Desert (SED) of Egypt are hosted within the Neoproterozoic Shadli metavolcanics as an important juvenile crustal section of the Arabian Nubian Shield (ANS). This study deals with remote sensing and geochemical data to understand the mechanism and source of pyritization, silicification, and hematization in the host metavolcanics and to shed light on the genesis of their jasperoids. The host rocks are mainly dacitic to rhyolitic metatuffs, which are proximal to volcanic vents. They show peraluminous calc-alkaline affinity. These felsic metatuffs also exhibit a nearly flat REE pattern with slight LREE enrichment (La/Yb = 1.19–1.25) that has a nearly negative Eu anomaly (Eu/Eu* = 0.708–0.776), while their spider patterns display enrichment in Ba, K, and Pb and depletion in Nb, Ta, P, and Ti, reflecting the role of slab-derived fluid metasomatism during their formation in the island arc setting. The ratios of La/Yb (1.19–1.25) and La/Gd (1.0–1.17) of the studied felsic metatuffs are similar to those of the primitive mantle, suggesting their generation from fractionated melts that were derived from a depleted mantle source. Their Nb and Ti negative anomalies, along with the positive anomalies at Pb, K, Rb, and Ba, are attributed to the influence of fluids/melt derived from the subducted slab. The Wadi Ranga jasperoids are mainly composed of SiO2 (89.73–90.35 wt.%) and show wide ranges of Fe2O3t (2.73–6.63 wt.%) attributed to the significant amount of pyrite (up to 10 vol.%), hematite, goethite, and magnetite. They are also rich in some base metals (Cu + Pb + Zn = 58.32–240.68 ppm), leading to sulfidic jasperoids. Pyrite crystals with a minor concentration of Ag (up to 0.32 wt.%) are partially to completely converted to secondary hematite and goethite, giving the red ochre and forming hematization. Euhedral cubic pyrite is of magmatic origin and was formed in the early stages and accumulated in jasperoid by epigenetic Si-rich magmatic-derived hydrothermal fluids; pyritization is considered a magmatic–hydrothermal stage, followed by silicification and then hematization as post-magmatic stages. The euhedral apatite crystals in jasperoid are used to estimate the saturation temperature of their crystallization from the melt at about 850 °C. The chondrite (C1)-normalized REE pattern of the jasperoids shows slightly U–shaped patterns with a slightly negative Eu anomaly (Eu/Eu* = 0.43–0.98) due to slab-derived fluid metasomatism during their origin; these jasperoids are also rich in LILEs (e.g., K, Pb, and Sr) and depleted in HFSEs (e.g., Nb and Ta), reflecting their hydrothermal origin in the island arc tectonic setting. The source of silica in the studied jasperoids is likely derived from the felsic dyke and a nearby volcanic vent, where the resultant Si-rich fluids may circulate along the NW–SE, NE–SW, and E–W major faults and shear zones in the surrounding metavolcanics to leach Fe, S, and Si to form hydrothermal jasperoid lenses and veins.

Geology and in-situ S-Pb isotopes of the Luoboshan carbonate-hosted Pb-Zn deposit in Yunnan Province, SW China

The Luoboshan Pb-Zn deposit (0.2 Mt Pb + Zn metal reserves, @ 0.94 % Pb and 5.33 % Zn) is located in the Lanping-Simao Basin in the southern part of the Sanjiang Tethys metallogenic domain in Yunnan Province, SW China. The deposit comprises three ore bodies hosted in the lower Permian bioclastic and micritic limestone. Ore body I is stratiform (mineralization is small in scale and ores have been mined out), with average grades of 0.02–1.44 % Pb and 1.5–14.88 % Zn. Ore bodies II and III are lens-like, the average grades of them are 0.10–5.07 % Pb and 1.68–12.39 % Zn, and 0.10–1.71 % Pb and 1.14–11.79 % Zn, respectively. Two hydrothermal stages were identified in the Luoboshan deposit: Pyrite-I-sphalerite-galena-calcite (stage I) and Pyrite-II-calcite (stage II). The in-situ δ34S values of pyrite and sphalerite reveals a medium range of −8.80 ‰ to +10.1 ‰. Furthermore, Py-I and sphalerite exhibit low δ34S values from −8.80 ‰ to −3.04 ‰, but Py-II displays high δ34S values (+2.37 ‰ to +10.0 ‰). These results suggest distinct formation mechanism for reduced sulfur during different stages of Pb-Zn mineralization. A reasonable explanation is that a transition from bacterial sulfate reduction (BSR) in the early stage to thermochemical sulfate reduction (TSR) in the late stage as the likely mechanism for the formation of reduced sulfur. In addition, the in-situ Pb isotopes exhibit a narrow range (206Pb/204Pb = 18.660–18.672, 207Pb/204Pb = 15.665–15.677 and 208Pb/204Pb = 38.940–38.980), indicating that the metals originated from either a single source or a uniform mixture of different sources. Comparison of geological charateristics and isotopic geochemical data (S and Pb) indicates that the basin sedimentary strata (wall rocks) is the only and most probable source. Hence, we propose that the formation of the Luoboshan deposit involved biogenic in-situ acid generation of marine sulfates, which subsequently mixed with Pb-and-Zn-rich hydrothermal fluids, initiating TSR and resulting in Pb-Zn mineralization.

Degassing-Driven Oxidation Promotes HREE Enrichment in South China Granites

Abstract Heavy rare earth elements (HREEs) are critical metals in advanced technologies. Here, we report unusual REE patterns and O–Hf–Nd isotopic compositions of composite granites from the Zhaibei HREE deposit. The complex consists of two Mesozoic granites with ages of 188 and 170 Ma. The older granites are characterized by higher HREE contents and negative Ce anomaly and contain cerianite veinlets. Their REE-rich minerals also show strong Ce depletion, indicating a high oxidation state. Magmatic zircons have variables δ18O (6.1–9.4‰) and εHf(t) (−6 to 0), towards a depleted mantle contribution. Lower δ18O (~5.4 vs 6.6‰) and higher εNd(t) (approximately −3 vs −11) values in the altered apatite rim compared to the core and primary phase result from subduction-derived fluids. In contrast, the younger granites have lower REE contents and lack a Ce anomaly. They show mantle-derived Nd (apatite εNd(t) = 1–2), Hf (zircon εHf(t) = 3–8), and O (zircon and apatite δ18O = 4.6–5.7‰) isotopic compositions. Therefore, we infer that a REE-rich fluid migrated from the flat subducting slab and flushed the subsolidus granitic mush in the Early Jurassic. This caused volatile saturation and degassing, leading to the generation of highly oxidized fluids. These processes may cause temporary oxidizing conditions in post-magmatic hydrothermal stages, resulting in the oxidation of Ce3+ to Ce4+. The resulting Ce fractionation from other REE3+ promoted HREE enrichment in the granites.

Formation of the giant Maoping Mississippi Valley-type Pb–Zn (Ge) deposit via fluid mixing: Evidence from trace element and sulfur isotope geochemistry of pyrite

The SYG (Sichuan–Yunnan–Guizhou) area is one of the most economically significant Mississippi Valley Type (MVT) ore provinces, providing approximately 27 % of the Pb–Zn resources in China. The Pb-Zn deposits in this region are renowned for their high grade, and the Maoping deposit with 20.3 % Pb-Zn grade is one prime example. However, the mechanism of such high-grade mineralization remains unclear, and pyrite may record valuable ore-forming information before and during Pb-Zn mineralization. Based on field geology and petrography, three hydrothermal stages were identified in the Maoping deposit: dolomite–pyrite vein (stage I), dolomite–sphalerite–galena vein (stage II), and calcite vein (stage III). Three types of pyrite are recognized: Py1 and Py2 occur in stage I, and Py3 is closely associated with sphalerite and galena in stage II. Py1 exhibits the highest concentrations of S, Pb, Sb, Cu, Co, Ni, V, Ag, Mn, Se, and Mo, and Py3 shows the highest Fe and As contents but the lowest levels of S, Pb, Sb, Cr, Ti, Co, Ni, Mn, and Mo. The element composition of Py2 shows transitional characteristics between those of Py1 and Py3. The Co and Ni contents gradually decrease from Py1 through Py2 to Py3, while their ratios remain within the range of 0.1–1.0. Compared with Py1 and Py2, Py3 exhibits suddenly elevated As levels and apparent acicular structures, indicating that a rapidly precipitating environment was likely triggered by an abrupt temperature decrease. Py1 exhibits δ34S values of 19.7–21.5 ‰, followed by Py2 between 18.6 and 21.1 ‰; both indicate that the sulfur was sourced from sulfates by thermochemical sulfate reduction (TSR). In contrast, Py3 exhibits lower δ34S values ranging from 7.5 to 11.0 ‰, potentially attributed to bacterial sulfate reduction (BSR). The differences in mineral structure, element composition, and sulfur isotopes among the three pyrite types indicate the involvement of two distinct fluids: metal-bearing basin brine and fluid containing reduced sulfur. The former was derived from basin brine that extracted ore metals (Pb2+ and Zn2+) from host sedimentary piles. The latter originated from carbonate strata in the Maoping area containing reduced sulfur formed by BSR. We propose that the ore-bearing basin brine reacted with organic matter in the wallrock through TSR to generate Py1 and Py2 in stage I and then mixed with the positioned fluid containing reduced sulfur via BSR to precipitate Py3, sphalerite, and galena in stage II. Hence, fluid mixing is the primary ore-forming mechanism and effectively accounts for the high-grade Pb–Zn ores in the Maoping deposit.

The sources and physical–chemical conditions of gold mineralization in the Qi189 porphyry deposit, Qiyugou gold orefield, Eastern Qinling

The Qiyugou gold orefield is situated in the Eastern Qinling. It is a magmatic hydrothermal system, which includes cryptoexplosive breccia-type, vein-type, and porphyry gold deposits. However, the gold sources and physical–chemical conditions of precipitation of the newly discovered porphyry gold deposit, the Qi189, have not yet been well studied. It also hinders the comprehensive understanding of magmatic–hydrothermal gold systems in the Qiyugou gold orefield. Thus, detailed field and microscopic observations, C–O–He–Ar isotopic analysis, in situ major/trace element analysis, and thermodynamic studies on the Qi189 porphyry gold deposit have been carried out in this study. This deposit has three hydrothermal stages: the (I) early quartz–K-feldspar–molybdenite–magnetite stage, (II) middle quartz–sericite–pyrite–Te–Bi-mineral stage, as well as (III) late calcite–quartz stage. The carbon and He–Ar isotopic compositions suggest deep-seated sources of ore-forming fluids with mantle component proportions of up to 37 %. Oxygen isotopic compositions indicate the gradual involvement of more meteoric water in ore-forming fluids during stages I–III. The meteoric water input and reduction in temperature and pressure in the early stage II increased oxygen fugacity and decreased the pH values of ore-forming fluids. Then, in hematite and sulfides formation during late stage II, the oxygen and sulfur fugacities of ore-forming fluids gradually decreased. Precipitation of native gold and Au-bearing telluride grains with quartz-sericite alteration in stage II is significant for Au enrichment, which occurred under acidic (pH = 3.64–5.71), low-logfO2 (<-34.86), low-logfS2 (−13.07 to −11.13) and low-logfTe2 (−15.55 to −10.32) conditions. Therefore, abundant mantle components and changes in the pH, logfO2, logfS2, and logfTe2 of the ore-forming fluids play important roles in gold enrichment. Combined with previous studies, this work also provides some new evidence for identifying a magmatic-hydrothermal gold system in this district, including similar sulfide trace elements, δ13CV-PDB compositions, and changes in logfO2 and logfS2 of various types of gold deposits in a gold orefield.

Recycling carbonated hydrous sediments into the mantle source of carbonatite-associated rare-earth-element deposits

Decoding the petrogenesis of carbonatites is of great importance for our understanding of the Earth’s deep carbon cycling and formation of rare-earth-element (REE) deposits. Among global carbonatites, the Cenozoic Mianning-Dechang (MD) carbonatites in the western Yangtze Craton are unique because of their development in a post-collisional zone and host numerous giant-large REE deposits. However, most of previous studies have focused on the late magmatic to hydrothermal stages, while the nature of the mantle source and early-stage magmatic evolution remain largely unexplored. Here we present a combined petrographic, chemical and Sr-Nd-Pb isotopic study on the MD lamprophyres to address these issues. A genetic linkage is revealed between these lamprophyres and the MD carbonatites and syenites by their geochemical similarities and close spatial and temporal associations. Our data suggest a phlogopite-rich carbonated subcontinental lithospheric mantle (SCLM) source metasomatized by subducted carbonated hydrous sediment-derived melts/fluids. Significant fractional crystallization of olivine, clinopyroxene and biotite (±Ti-Fe oxides) from hydrous, K-rich and carbonated primary melts caused the carbonate–silicate liquid immiscibility in the highly evolved melts and thus formation of the MD carbonatites and syenites at shallow depths. Melting of subducted carbonated hydrous sediments not only provides carbonatitic liquids for the SCLM carbonation, but also supplies sufficient water and alkalis that are critical for accumulating and transporting REE in carbonatitic fluids. Post-collisional lithospheric thinning also played a critical role in the formation of carbonatites via triggering the melting of the carbonated SCLM. This study provides new insights into the deep processes during the formation of carbonatites and associated REE deposits in post-collisional zones.

Magmatic–hydrothermal stage recorded by mica zonation and Nb–Ta–W–Sn mineralization: New insight into the genesis of highly evolved Songshugang Nb–Ta deposit (Jiangxi, SE China)

The role of magmatic and hydrothermal processes in niobium-tantalum mineralization is still controversial and has been limited by a lack of mineralogical records in the evolving magmatic–hydrothermal system. Micas as essential rock-forming minerals and comprise the amount of elements (especially rare-metal elements), become one of the ideal indicator. The Songshugang rare-metal granite (RMG) located in the southern part of Jiangxi Province, China, is renowned as the largest tantalum reservoir in South China. The albite–topaz–K-feldspar granite is the major granite, with layers of pegmatite, topaz-K-feldspar granite, and greisen overlay on it. It is the typical highly evolved peraluminous with low phosphorous RMGs (PLP-type) according to geochemistry. The Songshugang pluton preserves analogical characters in topaz-albite-K feldspar granites and topaz-K feldspar granite, and partly reserves in greisen. Detailed petrographic, mineralogy, and chemical composition study of zoned mica and accessory Nb–Ta minerals suggest that zinnwaldite and Nb-Ta oxides have experienced magmatic fractionation with gradually decrease of K/Rb and Nb/Ta ratio in prismatic zinnwaldite and columbite-(Fe). The leap of Rb (Rb2O up to 4.08 wt%) and Ta (Ta# up to 0.29) at the rim of zinnwaldite and columbite is likely attributed to supersaturation. Afterwards the overgrowth of Rb-deficit zinnwaldite (0.56–0.72 wt% Rb2O) is coeval with the Ta-highest wodginite, taking place during the magmatic-hydrothermal transition associated with a fluid-melt interaction in hydrosaline melt. The ascent of fluxing elements contributes to the formation of hydrothermal zinnwaldite and cassiterite through greisenization. The systemic coupling mineralization of zinnwaldite and Nb–Ta oxides altogether record the both the melt-driven and fluid-driven processes in highly evolved Songshugang deposit that is critical for rare-metal mineralization. The Songshugang displays a great similarity to the typical PLP RMGs Cínovec cupola in geochemistry, which are metaluminous to peraluminous, containing low phosphorous, intermediate REE, Zr, Hf, and Th content. But Songshugang has experienced strong supersaturation; the latter is more akin to highly evolved melts alike Yichun or Beauvoir. The strong supersaturation and crystallization demonstrate its discrepant mineralization mechanism in Songshugang RMGs.

Mineralogy and a New Fertility Index of Alunite in the Fanshan Lithocap, Luzong Basin, Anhui Province, China

Alunite is used as a representative mineral for indicating deposits in lithocaps, and lithocaps are generally related to the porphyry–(high-sulfidation) epithermal mineralization system. The study of alunite is of theoretical and exploration significance for prospecting potential underlying porphyry and epithermal deposits. Studies on alunite geochemistry have made breakthroughs, but there is little research on alunite mineralogy, for example, using scanning electron microscopy (SEM) images, differential thermal analysis (DTA), and Fourier-transform infrared spectroscopy (FT-IR). This study mainly focuses on alunite micromorphological characteristics, weight loss changes with temperature, and ionic group structure, aiming to identify the relationship between these features and indications for prospecting. The Fanshan lithocap is located in the northwest part of the Luzong basin, Anhui province of China, and it can potentially be used for exploring porphyry and epithermal deposits. Fanshan alunite is formed in two stages with three types of alunite. IA alunite is formed in the early hydrothermal stage and replaces felsic minerals in the Zhuanqiao Formation, IB alunite is formed in the later hydrothermal stage and fills in open spaces with bladed particles, and II alunite is the product of pyrite oxidation and reaction with other minerals in the supergene stage. Alunite electron microprobe data and energy-dispersive spectroscopy data further confirm temperature decreases with hydrothermal evolution, and the presence of a high-sulfidation epithermal system in the Luzong basin. Aside from the forming environment, SWIR, and geochemistry of alunite, there are other indication indexes; for example, the larger peak values at 3480 cm−1 and smaller peak values at 1080 cm−1 in FT-IR spectra and the deeper exothermic valleys at 750 °C and steeper weight loss slopes in the DTA curve suggest a favorable formation environment for alunite and provide valuable indications for deposit exploration and assessments of mineralization potential.

Metals pre–enrichment during the syn–sedimentary period of Mengxing Pb–Zn Deposit, western Yunnan, SW China: Evidence on LA–ICP–MS trace elements and S isotopes of lamellar sphalerite

The Mengxing Pb–Zn deposit, which contains up to 1.02 Mt of Pb + Zn metal with an average Pb + Zn grade of ca. 12.13 %, is a representative of sedimentary–reworked deposit in western Yunnan. The orebodies, which are strata–bound and veined, occur in the Silurian Shangrenheqiao formation. The mineralization process has been divided into sedimentary stage and hydrothermal stage. Previous research has primarily focused on the economic ores enriched during the hydrothermal stage. However, the formation of syn–sedimentary ore, responsible for metal pre–enrichment, has been largely ignored. To solve the issue above, the in–situ trace elements and mapping, as well as in–situ S isotopes analyses, were conducted on lamellar sphalerite ore, which retains the characteristics of the syn–sedimentary ore. Analysis of the trace elements revealed that the sphalerite at Mengxing are rich in Ge, Cd, As, Sb and poor in Fe, Mn, In, Sn and Co overall, suggesting a metallogenic environment of medium–low temperature. The LA–ICP–MS trace elemental mapping graph indicated that colloidal sphalerite exhibits the obvious oscillation belts. The dark zonal band of sphalerite is more enriched in Fe, Mn, Cu, Ge, As, Ag, Sb, and Pb, and depleted in Ga, Cd, and Sn, compared to the light zonal band, suggesting the various formation temperature. Based on the equation of the first principal component (PC1*) relating trace elements to mineral formation temperature, it is estimated that ore in the sedimentary stage occurred at relatively lower temperatures (174.74℃ – 203.18℃), while that of the hydrothermal stage occurred at higher temperatures (209.78℃ – 240.18℃). The S isotopic composition of sphalerite indicated a significant distinction between the sedimentary stage (δ34SVCDT = 13.29 ‰ – 37.06 ‰, with an average value of 27.97 ‰) and the hydrothermal stage (δ34SVCDT = −6.45 ‰ – 31.57 ‰, with an average of 9.01 ‰). It is hypothesized that sulfur during the early stage originated primarily from thermochemical sulfate reduction (TSR) of seawater sulfate, while sulfur during the hydrothermal stage was likely influenced by hydrothermal fluid from the deep. In conclusion, the early lamellar ores formed during the Silurian period exhibit characteristics consistent with SEDEX type mineralization, leading to initial metal pre–enrichment, followed by further enrichment of ore grade by superimposed fluid during the hydrothermal stage.

Hydrothermal extraction of antioxidants from Camellia sinensis fruit husks: Experimental design in the development of enriched gels

The phenolic and saccharidic fractions from Camellia sinensis seed husks were extracted under selected conditions of hydrothermal treatment and further concentrated with membranes and nonionic polymeric resins. The fraction extracted heating up to 160 °C contained 30 % oligomers, being concentrated by ultrafiltration up to 1.4 times. The waste solids were further processed up to 220 °C to extract an additional phenolic fraction. Both the permeate from ultrafiltration membranes and the extract obtained in the second hydrothermal stage were concentrated by nanofiltration and by resin adsorption (SP-700). The refined extracts after elution in ethanol contained 75 % and 50 % phenolics, respectively and exhibited antiradical properties comparable to synthetic antioxidants. The xylooligosaccharide (XOS) and the phenolic (Ph) containing fractions were used to formulate starch-based hydrogels and a Box-Behnken experimental design was used to optimize the relative content of each fraction and the gelling temperature to maximize the rheological and color parameters of the hydrogels. Evaluating the multiple response of the effect of the formulation conditions on the viscoelastic behavior through tan δ and the luminosity of the gels through L*, the maximum values were observed for gels prepared in the absence of XOS and 29.8% of E160 at 63.5 °C.